IONOMER POLYAMIDES, PRIMER, ARTICLES, AND METHODS FOR MAKING SAME - Patent application

Abstract

An ionomeric polyamide membrane is provided that includes a reaction product of a polymerizable composition that includes a first diacid that is a dimer acid, an ionomeric component, a first diamine that is an oxyalkylenediamine, at least one second diamine that includes a primary diamine and / or a secondary diamine, and optionally at least one second diacid. The ionomeric component is an ionomeric diacid, an ionomeric diester, or an ionomeric diamine. The present disclosure also provides a primer that includes an ionomeric polyamide dispersed in water and / or a lower alcohol. Additionally, an article is provided that includes a substrate and an ionomeric polyamide or primer disposed on the substrate. Methods are also provided, including methods of making the ionomeric polyamide and methods of making the article.

Description

[Technical field]

[0001] The present disclosure relates generally to ionomeric polyamides. Summary of the Invention

[0002] In a first aspect, an ionomeric polyamide is provided. The ionomeric polyamide comprises the reaction product of a polymerizable composition comprising: a) a first diacid that is a dimer acid; b) an ionomeric component that is an ionomeric diacid, an ionomeric diester, and / or an ionomeric diamine; c) a first diamine that is an oxyalkylenediamine; d) at least one second diamine that includes a primary diamine and / or a secondary diamine; and e) optionally at least one second diacid. The mole fraction of the dimer acid is 0.40 to 0.99, the mole fraction of the ionomeric component is 0.01 to 0.20, and the mole fraction of the at least one second diacid is 0 to 0.60, each based on the total moles of the combination of the dimer acid, the at least one second diacid, and any ionomeric diacid or diester used to form the ionomeric polyamide. The mole fraction of the oxyalkylenediamine is from 0.005 to 0.10 and the mole fraction of the at least one second diamine is from 0.70 to 0.995, each based on the total moles of the combination of oxyalkylenediamine, at least one second diamine, and optional ionomer diamine used to form the ionomeric polyamide.

[0003] In a second aspect, there is provided a primer comprising up to 20 weight percent of an ionomeric polyamide according to the first aspect.

[0004] In a third aspect, an article is provided. The article includes a substrate and a layer of ionomeric polyamide according to the first aspect disposed on a major surface of the substrate.

[0005] In a fourth aspect, another article is provided. The article includes a substrate and a layer of a primer according to the second aspect disposed on a major surface of the substrate.

[0006] In a fifth aspect, a method of making an ionomeric polyamide is provided. The method includes reacting the components of a polymerizable composition including: a) a first diacid that is a dimer acid; b) an ionomeric component that is an ionomeric diacid, an ionomeric diester, and / or an ionomeric diamine; c) a first diamine that is an oxyalkylenediamine; d) at least one second diamine that includes a primary diamine and / or a secondary diamine; and e) optionally at least one second diacid. The mole fraction of the dimer acid is 0.40 to 0.99, the mole fraction of the ionomeric component is 0.01 to 0.20, and the mole fraction of the at least one second diacid is 0 to 0.60, each based on the total moles of the combination of the dimer acid, the at least one second diacid, and any ionomeric diacids or diesters used to form the ionomeric polyamide. The mole fraction of the oxyalkylenediamine is from 0.005 to 0.10 and the mole fraction of the at least one second diamine is from 0.70 to 0.995, each based on the total moles of the combination of oxyalkylenediamine, at least one second diamine, and optional ionomer diamine used to form the ionomeric polyamide.

[0007] In a sixth aspect, there is provided a method of making an article, the method comprising coating a primer according to the second aspect on a major surface of a substrate and orienting the substrate.

[0008] The above summary of the present disclosure is not intended to describe each disclosed embodiment or every implementation of the present disclosure. The following description illustrates exemplary embodiments in more detail. In several places throughout this application, guidance is provided through lists of examples, which examples can be used in various combinations. In each instance, the recited list serves only as a representative group and should not be interpreted as an exclusive list. [Brief description of the drawings]

[0009] [Figure 1] 1 is a schematic cross-sectional view of an exemplary article according to the present disclosure.

[0010] [Diagram 2] 1 is a schematic cross-sectional view of another exemplary article according to the present disclosure.

[0011] [Diagram 3] 1 is a flow chart of an exemplary method of making an ionomeric polyamide according to the present disclosure.

[0012] [Figure 4] 1 is a flow chart of an exemplary method of making an article according to the present disclosure.

[0013] Although the above-identified figures set forth various embodiments of the present disclosure, other embodiments are also contemplated as noted herein. In all cases, the present disclosure presents the invention by way of representation and not by way of limitation. The figures are not necessarily drawn to scale. Like numbers used in the figures indicate like components. However, it will be understood that the use of a number to indicate a component in a given figure is not intended to limit the component in another figure that is indicated with the same number. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] Glossary

[0015] The thickness of a layer (coating, substrate, adhesive, etc.) should be understood to be its smallest dimension, which is commonly referred to as the "z" dimension and refers to the distance between the major surfaces of the layer.

[0016] As used herein, the term "curable" refers to a material that can be cured or hardened, for example, by heating to remove solvent, by heating to cause polymerization, chemical crosslinking, radiation-induced polymerization or crosslinking, etc. As used herein, "polymerizable composition" means a curable composition that can undergo addition polymerization upon initiation (e.g., free radical polymerization initiation) or condensation polymerization when co-reactive monomers are combined under appropriate conditions.

[0017] The term "backbone" refers to the main continuous chain of a polymer.

[0018] The term "aliphatic" refers to a C1-C40, preferably C1-C30, straight or branched chain alkenyl, alkyl, or alkynyl, which may or may not be interrupted or substituted by one or more heteroatoms, such as O, N, or S.

[0019] The term "alicyclic" refers to cyclic aliphatic C3-C30, preferably C3-C20, groups, including those interrupted by one or more heteroatoms, such as O, N, or S.

[0020] The term "alkyl" refers to a monovalent group that is a radical of an alkane, and includes straight-chain, branched-chain, cyclic, and bicyclic alkyl groups and combinations thereof, including both unsubstituted and substituted alkyl groups. Unless otherwise specified, alkyl groups typically contain 1 to 30 carbon atoms. In some embodiments, alkyl groups contain 1 to 20 carbon atoms, 1 to 10 carbon atoms, 1 to 6 carbon atoms, 1 to 4 carbon atoms, or 1 to 3 carbon atoms. Examples of "alkyl" groups include, but are not limited to, methyl, ethyl, n-propyl, n-butyl, n-pentyl, isobutyl, t-butyl, isopropyl, n-octyl, n-heptyl, ethylhexyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, and the like. As used herein, "Me" refers to a methyl group.

[0021] The term "alkylene" refers to a divalent group that is a radical of an alkane, including groups that are linear, branched, cyclic, bicyclic, or combinations thereof. Unless otherwise specified, alkylene groups typically have 1 to 30 carbon atoms. In some embodiments, alkylene groups have 1 to 20 carbon atoms, 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms. Examples of "alkylene" groups include methylene, ethylene, 1,3-propylene, 1,2-propylene, 1,4-butylene, 1,4-cyclohexylene, and 1,4-cyclohexyldimethylene.

[0022] "Alkenyl" and "ene" each refer to a monovalent linear or branched unsaturated aliphatic group having one or more carbon-carbon double bonds, e.g., vinyl.

[0023] The term "aromatic" refers to aromatic groups from C3 to C40, preferably C3 to C30, including both carbocyclic aromatic groups and heterocyclic aromatic groups containing one or more of the heteroatoms O, N, or S, and fused ring systems containing one or more of these aromatic groups fused together.

[0024] The term "aryl" refers to a monovalent group that is aromatic and optionally carbocyclic. An aryl has at least one aromatic ring. Any additional rings may be unsaturated, partially saturated, saturated, or aromatic. Optionally, the aromatic ring may have one or more additional carbocyclic rings fused to the aromatic ring. Unless otherwise indicated, an aryl group typically contains 6 to 30 carbon atoms. In some embodiments, an aryl group contains 6 to 20, 6 to 18, 6 to 16, 6 to 12, or 6 to 10 carbon atoms. Examples of aryl groups include phenyl, naphthyl, biphenyl, phenanthryl, and anthracyl.

[0025] The term "arylene" refers to a divalent group that is aromatic and optionally carbocyclic. An arylene has at least one aromatic ring. Optionally, the aromatic ring may have one or more additional carbocyclic rings fused to the aromatic ring. Any additional rings may be unsaturated, partially saturated, or saturated. Unless otherwise specified, arylene groups often have 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.

[0026] The term "aralkyl" refers to a monovalent group that is an alkyl group substituted with an aryl group, such as, for example, benzyl. The term "alkaryl" refers to a monovalent group that is an aryl group substituted with an alkyl group, such as, for example, tolyl. Unless otherwise specified, the alkyl portion in either group often has 1-10 carbon atoms, 1-6 carbon atoms, or 1-4 carbon atoms, and the aryl portion often has 6-20 carbon atoms, 6-18 carbon atoms, 6-16 carbon atoms, 6-12 carbon atoms, or 6-10 carbon atoms.

[0027] As used herein, "aralkylene" refers to a divalent group that is an alkylene group substituted with an aryl group or an alkylene group bonded to an arylene group. The term "alkarylene" refers to a divalent group that is an arylene group substituted with an alkyl group or an arylene group bonded to an alkylene group. Unless otherwise indicated, the alkyl or alkylene moieties in either group typically have 1 to 20 carbon atoms, 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms. Unless otherwise indicated, the aryl or arylene moieties in either group typically have 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.

[0028] As used herein, the term "(meth)acrylate" is shorthand for acrylate, methacrylate, or a combination thereof, "(meth)acrylic" is shorthand for acrylic, methacrylic, or a combination thereof, and "(meth)acryl" is shorthand for acrylic and methacrylic groups. "Acrylic" refers to derivatives of acrylic acid such as acrylate, methacrylate, acrylamide, and methacrylamide. "(Meth)acryl" means a monomer or oligomer having at least one acrylic or methacrylic group, linked by an aliphatic segment if it contains more than one group. As used herein, a "(meth)acrylate-functional compound" is a compound that includes, among others, a (meth)acrylate moiety.

[0029] As used herein, "amorphous polyamide" refers to a polyamide having a melting enthalpy from the second heat ramp of a heat-cool-heat cycle of 50 Joules per gram (J / g) or less as measured by differential scanning calorimetry (DSC). The melting enthalpy of the polyamide is measured by DSC on a differential scanning calorimeter (available under the trade designation Q200 SERIES DSC from TA Instruments, New Castle, DE) using a heat / cool / heat cycle procedure with the following parameters: equilibrate at (-30.00°C), then ramp to 200.00°C at 20.00°C / min, then ramp to (-30.00°C) at 20.00°C / min, then ramp to 200.00°C at 20.00°C / min, with a data collection rate of 1 data point per second. The enthalpy of fusion is evaluated by linear integration of the endothermic transition in the range 35° C. to 85° C. using commercial software (available from TA Instruments under the trade name UNIVERSAL ANALYSIS 2000 software).

[0030] As used herein, "resin" includes all polymerizable components (monomers, oligomers and / or polymers) present in a polymerizable composition. A resin may contain only one polymerizable component compound or a mixture of different polymerizable compounds.

[0031] As used herein, the “glass transition temperature” (T g The term β-polystyrene (β-styrene) refers to the transition from a glassy to a rubbery state of a polymer and can be measured using differential scanning calorimetry (DSC), for example at a heating rate of 10° C. per minute in a nitrogen stream. Suitable DSC methods and analysis modes are as described in Matsumoto, A. et.al., I. Polym. Sci. A., Polym. Chem. 1993, 31, 2531-2539.

[0032] The words "preferred" and "preferably" refer to embodiments of the present disclosure that may provide certain benefits, under particular circumstances. However, other embodiments may also be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, and is not intended to exclude other embodiments from the scope of the present disclosure.

[0033] In this application, terms such as "a," "an," and "the" are not intended to refer to only a singular entity, but include general classes, specific examples of which may be used for illustration. The terms "a," "an," and "the" are used interchangeably with the term "at least one." The phrases "at least one of" and "including at least one of" following a list refer to any one of the items in the list, and any combination of two or more items in the list.

[0034] As used herein, the term "or" is generally used in its ordinary sense including "and / or" unless the content clearly dictates otherwise. The term "and / or" refers to one or all of the listed elements or a combination of any two or more of the listed elements.

[0035] Also, all numbers herein are intended to be modified by the term "about", preferably the term "exactly". When used herein in the context of a measured quantity, the term "about" refers to the variation of the measured quantity as would be expected by one of ordinary skill in the art making the measurement and exercising a level of care commensurate with the purpose of the measurement and the precision of the measuring device used. Also, herein, the recitation of numerical ranges by endpoints includes all numbers subsumed within that range and the endpoints (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc.).

[0036] The term "generally," when used herein as a modifier to a characteristic or attribute, unless specifically defined otherwise, means that the characteristic or attribute is one that would be readily recognizable by one of ordinary skill in the art, but does not require absolute precision or perfect agreement (e.g., within ±20% for quantifiable characteristics). The term "substantially," unless specifically defined otherwise, means a high degree of approximation (e.g., within ±10% for quantifiable characteristics), but again does not require absolute precision or perfect agreement. Terms such as same, equal, uniform, constant, exactly, etc., are understood to not require absolute precision or perfect agreement, but rather within normal tolerances or measurement errors applicable to a particular situation.

[0037] As used herein, in the context of a composition being essentially free of a component, the term "essentially free" refers to the composition containing less than 1 weight percent (wt.%), 0.5 wt.% or less, 0.25 wt.% or less, 0.1 wt.% or less, 0.05 wt.% or less, 0.001 wt.% or less, or 0.0001 wt.% or less of the component based on the total weight of the composition.

[0038] One of the challenges presented by solventless processing of primer compositions is the difficulty of producing defect-free thin primer coatings substantially less than about 2 micrometers thick by extrusion processes. However, due to the popularity of solvent-based primers, there is coating equipment available to produce primer coatings less than 1 micrometer thick. Therefore, it would be useful to provide an alternative technique to deliver very thin primer coatings using such coating equipment.

[0039] Water-soluble polyamides based on oxyalkylenediamines among other polyamide-forming comonomers are known in the art (see, for example, U.S. Pat. No. 5,866,675 to Ahmed et al.). However, a drawback of such polyamides is that the oxyalkylene content makes the performance of such polyamides sensitive to humidity conditions during product use. Cationic charged water-soluble polyamides are also known in the art (see, for example, U.S. Pat. No. 3,058,873 to Keim et al.). A drawback of such polyamides is that such cationic water-soluble polyamides are known to be thermally unstable due to the presence of quaternary ammonium groups along the polyamide backbone. Polyamides having metal salts of sulfonate anions pendant from the backbone are known in the art and have been used to prepare hydrophilic compositions for dyeing nylon fibers with cationic dyes or to create water-soluble lithography compositions. For example, U.S. Patent No. 3,709,865 (Lofquist et al.) discloses that changing from nylon 6,6 monomers such as adipic acid and hexamethylenediamine used to prepare sulfonated polyamides to the less polar caprolactam monomer also results in insoluble metal salts of the sulfonated monomer. Unexpectedly, it has been discovered that sulfonated polyamide ionomers according to the present disclosure can be successfully prepared having a mole fraction of dimer acid of 0.40 or greater, resulting in significantly greater hydrophobicity than sulfonated polyamides prepared with caprolactam.

[0040] It has been discovered that water-dispersible, yet water-resistant, dimer acid-based ionomeric polyamides can be prepared that can function as effective primers for a variety of polymers and polar substrates (e.g., backings) with pendant carboxylic acid groups. The ionomeric polyamides described herein can be applied as thin layers (e.g., less than 2 micrometers) using common coating equipment.

[0041] Ionomeric polyamides according to the present disclosure preferably do not contain ester bonds in their backbones, making such polyamides more thermally and hydrolytically stable than sulfonated polyesters or sulfonated polyesteramides. The inclusion of dimer acid monomers results in amorphous branched polyamide ionomers that are characterized by being amorphous (e.g., having little or no crystalline phase) and having a polydispersity greater than 2 due to the trifunctionality in the dimer acid. The inclusion of dimer acid monomers also results in significant bio-based content in the ionomeric polyamides. The solvent-free synthesis, water-based coatings, and bio-based content provide an environmentally friendly primer technology. Furthermore, ionomeric polyamides may have the added benefit of acting as an improved barrier against hydrophobic materials such as mineral oils and plasticizers such as dioctyl phthalate.

[0042] Ionomer Polyamide In a first aspect, an ionomeric polyamide is provided. The ionomeric polyamide comprises:

[0043] a) a first diacid which is a dimer acid;

[0044] b) an ionomer component; and

[0045] c) a first diamine which is an oxyalkylenediamine; and

[0046] d) at least one second diamine comprising a primary diamine and / or a secondary diamine; and

[0047] e) optionally, at least one second diacid;

[0048] The mole fraction of the dimer acid is 0.40 to 0.99, the mole fraction of the ionomer component is 0.01 to 0.20, and the mole fraction of the at least one second diacid is 0 to 0.60, each based on the total moles of the combination of the dimer acid, the ionomer component, and the at least one second diacid used to form the ionomeric polyamide; and the mole fraction of the oxyalkylenediamine is 0.005 to 0.10, and the mole fraction of the at least one second diamine is 0.70 to 0.995, each based on the total moles of the combination of the oxyalkylenediamine, the at least one second diamine, and the optional ionomeric diamine used to form the ionomeric polyamide.

[0049] It should be understood that the sum of all mole fractions of a particular group of listed components (eg, diacids, diamines, etc.) add up to 1.0.

[0050] Preferably, the polymerizable composition is essentially free (e.g., free) of diols, resulting in an ionomeric polyamide that is essentially free of ester linkages. As noted above, the presence of ester linkages in a polymer reduces the thermal and hydrolytic stability of the polymer.

[0051] Each of components a) through d) of the polymerizable composition is described in detail below.

[0052] a) a first diacid

[0053] The polymerizable composition includes a first diacid. The first diacid is a dimer acid. A dimer acid is a dicarboxylic acid that is typically formed by dimerizing one or more unsaturated fatty acids.

[0054] In some embodiments, the dicarboxylic acid dimer acid may contain at least one alkyl or alkenyl group, may contain 12-100 carbon atoms, 16-100 carbon atoms, or 18-100 carbon atoms, and is characterized by having two carboxylic acid groups. The dimer acid may be saturated or partially unsaturated. In some embodiments, the dimer acid may be a dimer of a fatty acid. The phrase "fatty acid" as used herein means an organic compound composed of an alkyl or alkenyl group containing 5-22 carbon atoms and characterized by a terminal carboxylic acid group. Useful fatty acids are disclosed in "Fatty Acids in Industry: Processes, Properties, Derivatives, Applications", Chapter 7, pp 153-175, Marcel Dekker, Inc., 1989. In some embodiments, the dimer acid may be formed by dimerization of an unsaturated fatty acid having 18 carbon atoms, such as oleic acid or tall oil fatty acid. Dimer acids are often at least partially unsaturated and often contain 36 carbon atoms. The dimer acids may be of relatively high molecular weight or may be composed of mixtures containing various ratios of various large or relatively high molecular weight substituted cyclohexene carboxylic acids, primarily 36 carbon atom dicarboxylic acid dimer acids. The component structures may be acyclic, cyclic (monocyclic or bicyclic), or aromatic, as shown below. [ka] [ka]

[0055] Dimer acids may be prepared by condensing unsaturated monofunctional carboxylic acids such as oleic acid, linoleic acid, soybean acid, or tall oil acid through their olefinically unsaturated groups in the presence of a catalyst such as an acidic clay. The distribution of various structures in dimer acids (nominally C36 dibasic acids) depends on the unsaturated acid used in their production. Typically, oleic acid gives dicarboxylic acid dimers containing about 38% non-ring, about 56% mono-ring and bi-ring, and about 6% aromatics. Soybean acid gives dicarboxylic acid dimers containing about 24% non-ring, about 58% mono-ring and bi-ring, and about 18% aromatics. Tall oil acid gives dicarboxylic acid dimer acids containing about 13% non-ring, about 75% mono-ring and bi-ring, and about 12% aromatics. The dimerization procedure also produces trimer acids. In certain embodiments, the dimer acids contain less than 10 mole % triacid content. Commercial dimer acid products are typically purified by distillation to produce a range of dicarboxylic acid contents. Useful dimer acids contain at least 80% dicarboxylic acid, more preferably 90% dicarboxylic acid content, and even more preferably at least 95% dicarboxylic acid content. In certain applications, it may be advantageous to further purify the dimer acid by color reduction techniques including hydrogenation of unsaturation, as disclosed in U.S. Pat. No. 3,595,887, the entirety of which is incorporated herein by reference. Hydrogenated dimer acid may also achieve increased oxidative stability at high temperatures. Other useful dimer acids are disclosed in Kirk-Othmer Encyclopedia of Chemical Technology, Organic Chemicals: Dimer Acids (ISBN 9780471238966), copyright 1999-2014, John Wiley and Sons, Inc. Commercially available dicarboxylic acid dimer acids are available, for example, under the trade names EMPOE 1008 and EMPOL 1061 (both from BASF, Florham Park, New Jersey) and PRIPOL 1006, PRIPOL 1009, PRIPOL 1013, PRIPOL 1017 and PRIPOL 1025 (all from Croda Inc., Edison, New Jersey).

[0056] In some cases, the dimer acid has a number average molecular weight of 300 grams per mole (g / mol) or more, 350 g / mol, 400 g / mol, 450 g / mol, 500 g / mol, 550 g / mol, 600 g / mol, 650 g / mol, 700 g / mol, 750 g / mol, or 800 g / mol or more, and 1400 g / mol or less, 1350 g / mol, 1300 g / mol, 1250 g / mol, 1200 g / mol, 1150 g / mol, 1000 g / mol, 950 g / mol, 800 g / mol, 750 g / mol, or 700 g / mol or less. In other words, the dimer acid may have a number average molecular weight of 300 g / mol to 1400 g / mol, 300 g / mol to 1200 g / mol, 300 g / mol to 1000 g / mol, or 300 g / mol to 800 g / mol. The number average molecular weight may be measured using gel permeation chromatography (GPC). In some embodiments, the number of carbon atoms in the dimer acid may be 12 to 100, 20 to 100, 30 to 100, 12 to 80, 20 to 80, 30 to 80, 12 to 60, 20 to 60, or even 30 to 60.

[0057] The mole fraction of dimer acid, based on the total moles of the combination of dimer acid, at least one second diacid, and any ionomeric diacids or diesters (e.g., the sum of all diacids) used to form the ionomeric polyamide, is 0.40 or less, based on the total moles of the combination of dimer acid, at least one second diacid, and any ionomeric diacids or diesters used to form the ionomeric polyamide. or more and 0.99 or less, or 0.98, 0.97, 0.96, 0.95, 0.94, 0.93, 0.92, 0.91, 0.90, 0.87, 0.85, 0.82, 0.80, 0.77, 0.75, 0.72, 0.70, 0.67, 0.65, 0.62, or 0.60 or less. Stated another way, the mole fraction of dimer acid can be from 0.40 to 0.95, from 0.50 to 0.90, or from 0.60 to 0.85, based on the total moles of the combination of dimer acid, at least one second diacid, and any ionomeric diacids or diesters used to form the ionomeric polyamide.

[0058] b) Ionomer Component

[0059] The polymerizable composition includes an ionomeric component. The ionomeric component can be either an ionomeric diacid, an ionomeric diester, and / or an ionomeric diamine. The term "diacid" as used herein to refer to the total moles of diacid should be understood to encompass diesters. The reason is that both groups react with amines to form amide bonds. The difference between them is that acids react with amines to form amide bonds and a water by-product, whereas esters react with amines to form amide bonds and the corresponding alcohol. Typically, polymerizable compositions according to the present disclosure contain a 1.01-1.2 or 1.01-1.05 molar excess of amine, but in certain embodiments, instead, contain an equimolar ratio (1.0:1.0) or a molar excess (e.g., 1.05) of acid. A molar excess of acid monomers results in acid-terminated ionomeric polyamides, and a molar excess of amine monomers results in amine-terminated polyamides. The use of ionomeric diamines can contribute to the formation of amine-terminated polyamides.

[0060] Unexpectedly, it has been discovered that ionomeric polyamides incorporating an ionomeric component are suitable for use as primers due to the presence of an ionic charge on what are typically hydrophobic materials.

[0061] Suitable ionomeric diacids and ionomeric diesters include phthalate ionomers such as sodium sulfate isophthalate (SSIP). Ionomers typically contain one or more dicarboxylic acid or diester moieties derived from phthalate, isophthalate, terephthalate, and / or naphthalate. The counterion can be H+ or other metal ions such as potassium, lithium, zinc, magnesium, calcium, cobalt, iron, and / or antimony. In some embodiments, the ionomeric component comprises an aryl group. The ionomeric diacid or diester may preferably comprise the sodium salt of dimethyl 5-sulfoisophthalate (DMSSIP). Another suitable ionomeric diacid is represented by the following formula (V): [ka]

[0062] where R11 is selected from ammonium, sodium, lithium, and potassium.

[0063] Such ionomeric diacids having acid substituents at the 1,3 or 1,4 positions are described in detail in US Pat. No. 3,389,549 (David).

[0064] Suitable ionomer diamines include sulfone alkyl alkylene diamines, such as N-N(H)-R-NH-(CH 2 ) y -SO 3 Another suitable ionomer diamine has the following formula (VI): R10, where R9 is an alkylene or cycloalkylene having 2 to 12 carbon atoms, y is an integer from 4 to 6, and R10 is H or an alkali metal. [ka]

[0065] (wherein R12 and R13 are independently selected from H and lower alkyl, and R14 is selected from H, an ammonium radical, a Group I alkali metal, and a Group II alkaline earth metal). In some cases, R12 and R13 are the same.

[0066] Such ionomer diamines are described in detail in U.S. Pat. Nos. 3,454,535 (Bodesheim et al.) and 3,184,436 (Magat).

[0067] As noted above, the mole fraction of the ionomeric component is from 0.01 to 0.20 based on the total moles of either the combination of the dimer acid, at least one second diacid, and any ionomeric diacid or diester used to form the ionomeric polyamide, or the combination of the oxyalkylenediamine, at least one second diamine, and any ionomeric diamine used to form the ionomeric polyamide. Thus, the mole fraction of the ionomeric component is 0.01 or more, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, or 0.10 or more, and 0.20 or less, 0.19, 0.18, 0.17, 0.16, 0.15, 0.14, 0.13, 0.12, 0.11, or 0.10 or less.

[0068] c) a first diamine

[0069] The polymerizable composition includes a first diamine. The first diamine is an oxyalkylenediamine. In some embodiments, the oxyalkylenediamine includes each of ethylene oxide and propylene oxide. Suitable oxyalkylenediamines include those commercially available under the tradenames JEFFAMINE ED series (including ED-600, ED-900, and ED-2003) from Hunstman Corporation (The Woodlands, TX), and PPG-based diamines commercially available under the tradenames BAXXODUR EC (e.g., EC301, EC302, and EC303) from BASF (Florham Park, New Jersey). In selected embodiments, JEFFAMINE ED-2003 is preferred as the oxyalkylenediamine because of its molecular weight of approximately 2000 g / mol.

[0070] As noted above, the mole fraction of oxyalkylenediamine is 0.005 to 0.10, e.g., 0.01 to 0.03, based on the total moles of the combination of oxyalkylenediamine, at least one second diamine, and optional ionomer diamine (e.g., the sum of all diamines) used to form the ionomer polyamide. Thus, the mole fraction of oxyalkylenediamine is 0.005 or more, 0.006, 0.007, 0.008, 0.009, 0.010, 0.012, 0.015, 0.017, 0.020, 0.022, 0.025, 0.02, based on the total moles of the combination of oxyalkylenediamine, at least one second diamine, and optional ionomer diamine used to form the ionomer polyamide. 7, 0.030, 0.032, 0.035, 0.037, 0.040, 0.042, 0.045, 0.047, 0.050, 0.052, 0.055, 0.057, or 0.060 or more and 0.100 or less, 0.095, 0.090, 0.085, 0.080, 0.075, 0.070, 0.065, 0.060, 0.055, 0.050, 0.045, 0.040, 0.035, 0.030, or 0.025 or less.

[0071] In certain embodiments, the molar ratio of oxyalkylenediamine to ionomer component is preferably 0.10 moles of oxyalkylene to 1.0 moles of ionomer component (i.e., 0.10:1.0) to 2.0:1.0, such as 0.15:1.0 to 1.0:1.0, or even 0.20:1.0 to 0.50:1.0 moles of oxyalkylenediamine to ionomer component. If the molar ratio of oxyalkylenediamine to ionomer component is less than 0.10:1.0, the dispersion tends to contain large particles, and if the ratio is much greater than 1.0:1.0, the dispersion tends to have an excessively thick (e.g., hand lotion) consistency.

[0072] d) A second diamine

[0073] The polymerizable composition includes at least one second diamine. By "at least one second diamine" is meant that the polymerizable composition contains one or more diamine components different from the first diamine described in detail above as component c) and, if the ionomeric component is an ionomeric diamine described in detail above with respect to component b). Often, the at least one second diamine includes two or more different diamines, for example, two diamines, three diamines, four diamines, etc.

[0074] In some embodiments, the diamine component can include one or more secondary diamines or one or more hybrid secondary / primary diamines, and optionally one or more primary diamines, e.g., both primary and secondary diamines.

[0075] Optionally, the at least one second diamine comprises an alkyl group, an alkylene group, an aryl group, a cycloalkyl group, or any combination thereof. For example, the at least one second diamine can comprise each of an aliphatic diamine and an alicyclic diamine.

[0076] In some embodiments, suitable secondary or hybrid secondary / primary amines are Formula (IV): R7-NH-R8-NH-R7(IV)

[0077] (Wherein, R8 is

[0078] Alkylene (e.g., -CH 2 CH 2 CH 2 -),

[0079] Branched chain alkylene (-CH 2 CH(Me)CH 2 -),

[0080] Cycloalkylene (e.g., -cyclohexylene-CH 2 -cyclohexylene-),

[0081] substituted or unsubstituted arylene (e.g., -1,4-phenylene-);

[0082] Heteroalkylene (e.g., -CH 2 CH 2 -O-CH 2 CH 2 - or any other Jeffamine), or

[0083] Heterocycloalkylene (e.g., -CH 2 -Furan ring -CH 2 -) and

[0084] Each R7 is independently

[0085] Straight or branched chain alkyl (e.g., -Me, -isopropyl),

[0086] cycloalkyl (e.g., -cyclohexyl),

[0087] aryl (e.g., -phenyl);

[0088] Heteroalkyl (e.g., -CH 2 CH 2 -O-CH 3 ),

[0089] heteroaryl (e.g., -2-substituted-pyridyl), or

[0090] Hydrogen atom

[0091] (with the proviso that both R1 cannot be hydrogen atoms), or

[0092] The R7 groups may be alkylene or branched alkylene to form heterocyclic compounds (eg, piperazines).

[0093] Suitable secondary diamines can include, for example, piperazine, 1,3-di-4-piperidylpropane, 4,4'-methylenebis[N-sec-butylaniline], and cyclohexanamine, 4,4'-methylenebis[N-(1-methylpropyl)-. In some embodiments, suitable secondary / primary hybrid diamines (i.e., diamines having a secondary amine and a primary amine) can include, for example, 2-aminoethylpiperazine. In some embodiments, the secondary / primary hybrid diamine can be absent or can be present such that the mole fraction of the secondary / primary hybrid diamine is less than 0.50, 0.40 or less, 0.30, 0.20, 0.10, or 0.05 or less, based on the total moles of the second diamine. In some embodiments, suitable secondary diamines or secondary / primary hybrid diamines can have a number average molecular weight of 30 g / mol to 5000 g / mol, 30 g / mol to 500 g / mol, or 50 g / mol to 100 g / mol.

[0094] In some embodiments, the at least one second diamine component may include a primary diamine, such as an aliphatic or aromatic primary amine, in addition to an (optional) secondary or secondary / primary hybrid amine. Suitable primary amines include, for example, ethylenediamine, m-xylylenediamine, 1,6-hexanediamine, o-toluidine, or 1,3-benzenedimethaneamine. In some embodiments, suitable primary diamines may have a number average molecular weight of 30 g / mol to 5000 g / mol, 30 g / mol to 500 g / mol, or 50 g / mol to 100 g / mol.

[0095] In selected embodiments, the at least one second diamine has formula (III): R5-NH-R6-NH-R5(III)

[0096] wherein R5 is independently selected from straight or branched chain alkyl, cycloalkyl, aryl, heteroalkyl, heteroaryl, hydrogen, or the R5 groups are alkylene or branched chain alkylene to form a heterocyclic compound, provided that both R5 are not hydrogen;

[0097] R6 is alkylene, branched alkylene, cycloalkylene, substituted or unsubstituted arylene, or heteroalkylene.

[0098] As noted above, the mole fraction of the at least one second diamine is from 0.70 to 0.995, based on the total moles of the oxyalkylene diamine, the at least one second diamine, and the optional ionomeric diamine combined (e.g., the sum of all diamines) used to form the ionomeric polyamide. Thus, the mole fraction of the at least one second diamine is greater than or equal to 0.700, 0.710, 0.720, 0.730, 0.740, 0.750, 0.760, 0.770, 0.780, 0.790, 0.800, 0.810, 0.820, 0.830, 0.840, 0.850, 0.860, 0.870, 0.880, 0.890, 0.900, 0.910, 0.920, 0.930, 0.940, 0.950, 0.960, 0.970, 0.980, 0.990, 1000, 1010, 1020, 1030, 1040, 1050, 1060, 1070, 1080, 1090, 1100, 1110, 1120, 1130, 1140, 1150, 1160, 1170, 1180, 1190, 1200, 1210, 1220, 1230, 1240, 1250, 1260, 1270, 1280, 1290, 1300, 1310, 1320, 1330, 1340, 1350, 1360, 1370, 1380, 1390, 1400, 1410, 1420, 1430, 1440, 1450, 1460, 0.900, 0.905, 0.910, 0.915, 0.920, 0.925, 0.930, 0.935, 0.940, 0.945, 0.950, 0.955, or 0.960 or more and 0.995 or less, 0.995, 0.990, 0.985, 0.980, 0.975, 0.970, 0.965, 0.960, 0.955, 0.950, 0.945, 0.940, 0.935, 0.930, 0.910, 0.890, 0.870, 0.850, 0.830, 0.810, 0.790, 0.770, or 0.750 or less.

[0099] e) a second diacid

[0100] The polymerizable composition optionally includes at least one second diacid. By "at least one second diacid" is meant that the polymerizable composition contains one or more diacid components different from the first diacid (i.e., dimer acid) described in detail above as component a) and, in the case where the ionomeric component is an ionomeric diacid or ionomeric diester described in detail above with respect to component b).

[0101] Suitable exemplary diacids include, but are not limited to, for example, hexanedioic acid, nonanedioic acid, dodecanedioic acid, 1,3-benzenedicarboxylic acid, 1,4-benzenedicarboxylic acid, and 11-aminoundecanoic acid.

[0102] As noted above, the mole fraction of the at least one second diacid, based on the total moles of the combination of dimer acid, at least one second diacid, and any ionomeric diacids or diesters (e.g., the sum of all diacids) used to form the ionomeric polyamide, is from 0 to 0.60. Stated another way, the mole fraction of the at least one second diacid, based on the total moles of the combination of dimer acid, at least one second diacid, and any ionomeric diacids or diesters used to form the ionomeric polyamide, can be from 0 (i.e., absent), 0.01 or more, 0.02, 0.05, 0.07, 0.10, 0.12, 0.15, 0.20, 0.25, 0.30, 0.40, 0.45, 0.50, 0.60, 0.80, 0.90, 0.110, 0.120, 0.130, 0.140, 0.150, 0.160, 0.180, 0.190, 0.210, 0.220, 0.230, 0.240, 0.250, 0.350, 0.360, 0.380, 0.390, 0.410, 0.420, 0.430, 0.440, 0.450, 0.500, 0.510, 0.520, 0.530, 0.540, 0.550, 0.600, 0.600, 0.700, 0.850, 0.900, 0.950, 0.960, 0.17, 0.20, 0.22, 0.25, 0.27, 0.30, 0.32, or 0.35 or more and 0.60 or less, 0.58, 0.57, 0.56, 0.55, 0.54, 0.53, 0.52, 0.51, 0.50, 0.47, 0.45, 0.42, 0.40, 0.37, 0.35, 0.32, 0.30, 0.27, 0.25, 0.22, or 0.20 or less.

[0103] Reaction products of polymerizable compositions

[0104] As described above, the reaction product of the polymerizable composition is an ionomeric polyamide. Preferably, the ionomeric polyamide is acid-terminated or amine-terminated. The ionomeric polyamide typically does not contain ester groups. The ionomeric polyamide has a glass transition temperature of less than 25 degrees Celsius, 20°C or less, 15°C, 10°C, 5°C, 0°C, -5°C, -10°C, -15°C, -20°C, -25°C, -30°C or less, and -50°C or more.

[0105] In select embodiments, the ionomeric polyamide has Formula (I) or Formula (II): [ka]

[0106] where R1 is independently selected from the residue of a dimer acid (e.g., any of the dimer acids described above), the residue of an ionomeric diacid or diester (e.g., any of the ionomeric diacids or diesters described above), or any other diacid monomer (e.g., any of the at least one second diacid described above).

[0107] R2 is independently selected from the residue of a primary diamine or a secondary diamine (e.g., any of the primary or secondary diamines described above);

[0108] R3 is independently selected from an alkylene group or an arylene group;

[0109] R4 is independently selected from H, an alkyl group, an alkenyl group, an aryl group, a cycloalkyl group, or two R4 groups are alkylene or branched alkylene to form a heterocyclic compound.

[0110] In certain embodiments, at least one R2 is a residue of an oxyalkylenediamine and at least one R3 is an arylene group.

[0111] Primer In a second aspect, the present disclosure provides a primer, the primer comprising up to 20 weight percent of an ionomeric polyamide according to the first aspect detailed above. Optionally, the ionomeric polyamide is acid-terminated or amine-terminated, and the primer has a pH of 2-6 or 8-12.

[0112] Typically, the ionomeric polyamides according to at least certain embodiments of the present disclosure advantageously do not require a surfactant to remain dispersed in the aqueous composition, and therefore in certain embodiments the primer is essentially free of (e.g., does not include) a surfactant. In some cases, however, a surfactant may be included in the primer if the primer is to be used in a high speed coating process.

[0113] In some embodiments, the ionomeric polyamide is dispersed in a solvent comprising 80-90 weight percent water, 10-20 weight percent C2-C4 aliphatic alcohol (the sum of water and C2-C4 aliphatic alcohol equals 100 percent), and an optional pH adjuster. From such a solvent blend, it is unexpectedly possible to strip the C2-C4 aliphatic alcohol at elevated temperatures, such as, for example, 60-80 degrees Celsius. Thus, in some embodiments, the ionomeric polyamide is dispersed in water, advantageously providing an aqueous primer dispersion. Without wishing to be bound by theory, it is believed that the non-ionic portion of the ionomeric polyamide can form droplets of about 50 nanometers to 1000 nanometers in size, and the ionic portion of the ionomeric polyamide interacts with the water to help keep the ionomeric polyamide dispersed in water. It has been surprisingly discovered that aqueous dispersions containing ionomeric polyamides in amounts up to 20 weight percent can be stable for 1 month or more, 2 months, 3 months, 4 months, 5 months, 6 months, 7 months, 8 months, 9 months, 10 months, 11 months, or even 12 months or more.

[0114] Goods

[0115] In a third aspect, the present disclosure provides an article. Referring to Figure 1, a schematic cross-sectional view of an exemplary article 100 is shown. In an embodiment of the third aspect, the article 100 includes a substrate 110 and a layer 120 of an ionomeric polyamide (according to the first aspect described in detail above) disposed on a major surface 112 of the substrate 110. In select embodiments, the ionomeric polyamide may exhibit pressure sensitive adhesive (PSA) properties including a low shear modulus (e.g., between a substrate and an ionomeric polyamide) of 0.01 megapascals (MPa) or greater at 25 degrees Celsius, e.g., 0.02 MPa, 0.04 MPa, 0.06 MPa, 0.08 MPa, 0.10 MPa, 0.12 MPa, 0.14 MPa, 0.16 MPa, 0.18 MPa, 0.20 MPa, 0.25 MPa, 0.30 MPa, 0.35 MPa, 0.40 MPa, 0.45 MPa, 0.50 MPa, 0.60 MPa, 0.70 MPa, 0.80 MPa, 0.90 MPa, 1 MPa, 1.1 MPa, 1.2 MPa, 1.3 MPa, 1.4 MPa, 1.5 MPa, 1.6 MPa, 1.7 MPa, 1.8 MPa, 1.9 MPa, or 2 MPa or greater, and 3 MPa or less.

[0116] In a fourth aspect, the present disclosure provides another article. Referring again to Figure 1, in an embodiment of the fourth aspect, article 100 includes a substrate 110 and a layer 120 of an ionomeric primer (according to the second aspect described in detail above) disposed on a major surface 112 of substrate 110.

[0117] The article preferably exhibits a shear modulus (e.g., between the substrate and the ionomeric polyamide or primer) of greater than 5 megapascals (MPa) at 25 degrees Celsius, e.g., 6 MPa or more, 7 MPa, 8 MPa, 9 MPa, 10 MPa, 11 MPa, 12 MPa, 13 MPa, 14 MPa, 15 MPa, 16 MPa, 17 MPa, 18 MPa, 19 MPa, or even 20 MPa or more.

[0118] Optionally, the article of the third or fourth embodiment further comprises an adhesive. Referring to FIG. 2, a schematic cross-sectional view of an exemplary system 200 is shown. The article 200 comprises a substrate 210 and a layer 220 of ionomeric polyamide (according to the first embodiment described in detail above) or primer (according to the second embodiment described in detail above) disposed on a major surface 212 of the substrate 210. The article 200 further comprises an adhesive 230 disposed on a major surface 222 of the layer 220 of ionomeric polyamide or primer. The adhesive may comprise a polymer comprising at least one pendant carboxylic acid group. Additionally, an acrylic adhesive having acrylic acid as a comonomer is suitable for use in the exemplary article.

[0119] Advantageously, in any article according to the present disclosure, the layer of ionomeric polyamide or primer can have an average thickness of less than 1 micrometer, e.g., 0.9 micrometers or less, 0.8 micrometers, 0.7 micrometers, 0.6 micrometers, 0.5 micrometers, 0.4 micrometers, 0.3 micrometers, 0.2 micrometers, or 0.1 micrometers or less. In some cases, the dried primer (e.g., layer of ionomeric polyamide) has an average thickness of less than 1 micrometer, less than 0.5 micrometers, or less than 0.25 micrometers, and 0.05 micrometers or more.

[0120] Exemplary substrates may be at least one of metal, ceramic, or polymer, such as thermoplastic polymer. In the article of either the third or fourth aspect, the substrate optionally comprises a polar polymeric material. Advantageously, ionomeric polyamides may be particularly effective primers for various polymers having polar groups (e.g., pendant carboxylic acid groups).

[0121] The polymer substrate may comprise any of a variety of materials, including polyesters, such as polyethylene terephthalate, polyethylene naphthalate, copolyesters or polyester blends based on naphthalenedicarboxylic acid; polycarbonates; polystyrene; styrene-acrylonitrile; cellulose acetate; polyethersulfone; poly(meth)acrylates, such as polymethyl methacrylate; polyurethanes; polyvinyl chloride; polycyclo-olefins; polyimides; glass; paper; or combinations or blends thereof. Specific examples include polyethylene terephthalate, polymethyl methacrylate, polyvinyl chloride, and cellulose triacetate. Desirable examples include polyethylene terephthalate, polyethylene naphthalate, cellulose triacetate, polypropylene, polyester, polycarbonate, polymethyl methacrylate, polyimides, polyamides, or blends thereof. The substrate may also be an oriented film, such as a cast web substrate, which is coated prior to orientation in a tentering operation.

[0122] method

[0123] In a fifth aspect, the present disclosure provides a method of making an ionomeric polyamide, the method comprising:

[0124] a) a first diacid which is a dimer acid;

[0125] b) an ionomer component which is an ionomer diacid, an ionomer diester, and / or an ionomer diamine;

[0126] c) a first diamine which is an oxyalkylenediamine; and

[0127] d) at least one second diamine comprising a primary diamine and / or a secondary diamine; and

[0128] e) optionally reacting the components of the polymerizable composition including at least one second diacid;

[0129] The mole fraction of the dimer acid is 0.40 to 0.99, the mole fraction of the ionomer component is 0.01 to 0.20, and the mole fraction of the at least one second diacid is 0 to 0.60, each based on the total moles of the combination of the dimer acid, the at least one second diacid, and the optional ionomer diacid or diester used to form the ionomer polyamide; and the mole fraction of the oxyalkylenediamine is 0.005 to 0.10, and the mole fraction of the at least one second diamine is 0.70 to 0.995, each based on the total moles of the combination of the oxyalkylenediamine, the at least one second diamine, and the optional ionomer diamine used to form the ionomer polyamide.

[0130] The ionomeric polyamide is according to any embodiment of the first aspect described in detail above.

[0131] 3, a flow chart of an exemplary method of making an ionomeric polyamide is shown. In this method, step 310 includes reacting the components of a polymerizable composition including: a) a first diacid that is a dimer acid; b) an ionomer component that is an ionomeric diacid, ionomeric diester, and / or ionomeric diamine; c) a first diamine that is an oxyalkylene diamine; d) at least one second diamine including a primary diamine and / or a secondary diamine; and e) optionally at least one second diacid, wherein the dimer acid, the at least one second diacid, and any ionomeric diacids or diesters used to form the ionomeric polyamide are reacted together. The mole fraction of the dimer acid is 0.40 to 0.99, the mole fraction of the ionomeric component is 0.01 to 0.20, and the mole fraction of the at least one second diacid is 0 to 0.60, each based on the total moles of the combination of the oxyalkylenediamine, the at least one second diamine, and the optional ionomeric diamine used to form the ionomeric polyamide. The mole fraction of the oxyalkylenediamine is 0.005 to 0.10, and the mole fraction of the at least one second diamine is 0.70 to 0.995, each based on the total moles of the combination of the oxyalkylenediamine, the at least one second diamine, and the optional ionomeric diamine used to form the ionomeric polyamide.

[0132] The ionomeric polyamides may be formed according to a conventional condensation reaction between components a) through d) (and optionally e) of the polymerizable composition. In some embodiments, the reacting comprises refluxing the polymerizable composition, followed by distillation.

[0133] As mentioned above, U.S. Patent No. 3,709,865 (Lofquist et al.) discloses that changing from nylon 6,6 monomers such as adipic acid and hexamethylenediamine used to prepare sulfonated polyamides to less polar caprolactam monomers also results in insoluble metal salts of the sulfonated monomers. For example, too much sulfonated material makes synthesis difficult due to phase separation. It was therefore unexpected that ionomeric polyamides could be successfully synthesized using the above components, especially dimer acids which tend to be hydrophobic.

[0134] Acid-terminated ionomeric polyamide dispersions may be prepared with improved stability imparted by modifying the pH of the aqueous phase to a range of 8 to 12, more preferably to a range of 8 to 10, by adding one or more pH adjusters. The pH modification is accomplished by adding one or more Bronsted bases, such as sodium hydroxide or ammonium hydroxide, or an organic base, such as triethylamine, during the dispersion process itself. Amine-terminated ionomeric polyamide dispersions may be prepared with improved stability imparted by modifying the pH of the aqueous phase to a range of 2 to 6, more preferably to a range of 3 to 5, by adding one or more Bronsted acids, such as hydrochloric acid, or an organic acid, such as acetic acid, during the dispersion process itself. In certain embodiments, acetic acid is the preferred acid, and either sodium hydroxide or potassium hydroxide are the preferred bases. Furthermore, such pH adjusters may be flashed off when the coating is made, so that they no longer remain in the resulting layer of ionomeric polyamide or primer.

[0135] In a sixth aspect, there is provided a method of making an article, the method comprising:

[0136] Coating a major surface of a substrate with a primer according to the second aspect described in detail above;

[0137] and orienting the substrate.

[0138] Referring to FIG. 4, a flow chart of an exemplary method of making an article is shown. In this method, step 410 includes coating a primer according to the second embodiment on a major surface of a substrate, and step 420 includes orienting the substrate. Often, the substrate is oriented in the length (e.g., machine) direction before coating the primer on the substrate. Thus, if the substrate is biaxially oriented, the primer may only be present on the substrate for transverse orientation (e.g., tenter orientation). Alternatively, it is possible to coat the primer on the substrate before any orientation, i.e., either uniaxial or biaxial orientation.

[0139] Optionally, the method further includes at least one of heating or drying the primer, thereby obtaining a layer of ionomeric polyamide having an average thickness of less than 1 micrometer, e.g., 0.9 micrometers or less, 0.8 micrometers, 0.7 micrometers, 0.6 micrometers, 0.5 micrometers, 0.4 micrometers, 0.3 micrometers, 0.2 micrometers, or 0.1 micrometers or less. In some cases, the dried primer (e.g., layer of ionomeric polyamide) has an average thickness of less than 1 micrometer, less than 0.5 micrometers, or less than 0.25 micrometers, and greater than or equal to 0.05 micrometers.

[0140] An additional optional step, namely, applying a layer of adhesive onto a major surface of the layer of ionomeric polyamide, step 440, is shown in Figure 4. The adhesive can be any of the adhesives described above with respect to the third and fourth embodiments.

[0141] Exemplary embodiments In a first embodiment, the present disclosure provides an ionomeric polyamide. The ionomeric polyamide comprises the reaction product of a polymerizable composition comprising a diacid that is a dimer acid, an ionomeric component that is an ionomeric diacid, an ionomeric diester, and / or an ionomeric diamine, a first diamine that is an oxyalkylenediamine, at least one second diamine that includes a primary diamine and / or a secondary diamine, and, optionally, at least one second diacid. The mole fraction of the dimer acid is 0.40 to 0.99, the mole fraction of the ionomeric component is 0.01 to 0.20, and the mole fraction of the at least one second diacid is 0 to 0.60, each based on the total moles of the combination of the dimer acid, the at least one second diacid, and any ionomeric diacid or diester used to form the ionomeric polyamide. The mole fraction of the oxyalkylenediamine is from 0.005 to 0.10 and the mole fraction of the at least one second diamine is from 0.70 to 0.995, each based on the total moles of the combination of oxyalkylenediamine, at least one second diamine, and optional ionomer diamine used to form the ionomeric polyamide.

[0142] In a second embodiment, the present disclosure provides an ionomeric polyamide according to the first embodiment, wherein the oxyalkylenediamine comprises each of ethylene oxide and propylene oxide.

[0143] In a third embodiment, the present disclosure provides an ionomeric polyamide according to the first or second embodiment, wherein the mole fraction of oxyalkylenediamine is from 0.005 to 0.10 or from 0.01 to 0.03, based on the total moles of the combination of oxyalkylenediamine, at least one second diamine, and optional ionomeric diamine used to form the ionomeric polyamide.

[0144] In a fourth embodiment, the present disclosure provides an ionomeric polyamide according to the second or third embodiment, wherein the ionomeric polyamide is acid-terminated or amine-terminated.

[0145] In a fifth embodiment, the present disclosure provides an ionomeric polyamide according to any one of the first to fourth embodiments, wherein the at least one second diamine comprises an alkyl group, an alkylene group, an aryl group, a cycloalkyl group, or any combination thereof.

[0146] In a sixth embodiment, the present disclosure provides an ionomeric polyamide according to any one of the first to fifth embodiments, wherein the at least one second diamine comprises both a primary diamine and a secondary diamine.

[0147] In a seventh embodiment, the present disclosure provides an ionomeric polyamide according to any one of the first to sixth embodiments, wherein the at least one second diamine comprises an aliphatic diamine and a cycloaliphatic diamine.

[0148] In an eighth embodiment, the present disclosure provides a method for preparing a cycloaliphatic amine comprising the steps of: R5-NH-R6-NH-R5 (III) The present invention provides an ionomeric polyamide according to any one of the first to seventh embodiments, which is

[0149] R5 is independently selected from straight or branched chain alkyl, cycloalkyl, aryl, heteroalkyl, heteroaryl, hydrogen, or the R5 groups are alkylene or branched chain alkylene to form a heterocyclic compound, provided that both R5 are not hydrogen, and R6 is alkylene, branched chain alkylene, cycloalkylene, substituted or unsubstituted arylene, or heteroalkylene.

[0150] In a ninth embodiment, the present disclosure provides an ionomeric polyamide according to any one of the first to eighth embodiments, wherein the ionomeric component comprises an aryl group.

[0151] In a tenth embodiment, the present disclosure provides an ionomeric polyamide according to any one of the first to ninth embodiments, wherein the ionomeric component comprises the sodium salt of dimethyl 5-sulfoisophthalate.

[0152] In an eleventh embodiment, the present disclosure provides an ionomeric polyamide according to any one of the first to tenth embodiments, wherein the mole fraction of dimer acid is from 0.40 to 0.95, from 0.50 to 0.90, or from 0.60 to 0.85, based on the total moles of the combination of dimer acid, at least one second diacid, and any ionomeric diacids or diesters used to form the ionomeric polyamide.

[0153] In a twelfth embodiment, the present disclosure provides an ionomeric polyamide according to any one of the first to eleventh embodiments, wherein the dimer acid has a number average molecular weight from 300 g / mol to 1400 g / mol.

[0154] In a thirteenth embodiment, the present disclosure provides an ionomeric polyamide according to any one of the first to twelfth embodiments, wherein the dimer acid comprises 36 carbon atoms.

[0155] In a fourteenth embodiment, the present disclosure provides an ionomeric polyamide according to any one of the first to thirteenth embodiments, wherein the dimer acid comprises less than 10 mole % of a triacid content.

[0156] In a fifteenth embodiment, the present disclosure provides an ionomeric polyamide according to any one of the first to fourteenth embodiments, wherein the polymerizable composition does not comprise a diol.

[0157] In a sixteenth embodiment, the present disclosure provides an ionomeric polyamide according to any one of the first to fifteenth embodiments, wherein the ionomeric polyamide does not comprise an ester group.

[0158] In a seventeenth embodiment, the present disclosure provides an ionomeric polyamide according to any one of the first to sixteenth embodiments, wherein the ionomeric polyamide has a glass transition temperature less than 25 degrees Celsius.

[0159] In an eighteenth embodiment, the present disclosure provides an ionomeric polyamide having formula (I) or formula (II): [ka] The ionomeric polyamide according to any one of the first to seventeenth embodiments has the structure:

[0160] R1 is independently selected from the residue of a dimer acid, an ionomeric diacid or diester, or any other diacid monomer. R2 is independently selected from the residue of a primary or secondary diamine. R3 is independently selected from an alkylene or arylene group. R4 is independently selected from H, an alkyl group, an alkenyl group, an aryl group, a cycloalkyl group, or two R4 groups are alkylene or branched alkylene to form a heterocyclic compound.

[0161] In a nineteenth embodiment, the present disclosure provides an ionomeric polyamide according to the eighteenth embodiment, wherein at least one R2 is a residue of an oxyalkylenediamine and at least one R3 is an arylene group.

[0162] In a twentieth embodiment, the present disclosure provides an ionomeric polyamide according to any one of the first to nineteenth embodiments, wherein at least one second diacid is present and the mole fraction of the at least one diacid is from 0.01 to 0.50, based on the total moles of the combination of dimer acid, the at least one second diacid, and any ionomeric diacids or diesters used to form the ionomeric polyamide.

[0163] In a twenty-first embodiment, the present disclosure provides an ionomeric polyamide according to any one of the first to twentieth embodiments, wherein the molar ratio of oxyalkylenediamine to ionomer component is from 0.10 moles of oxyalkylene to 1.0 mole of ionomer component to 2.0:1.0, from 0.15:1.0 to 1.0:1.0, or from 0.20:1.0 to 0.50:1.0 moles of oxyalkylenediamine to ionomer component.

[0164] In a twenty-second embodiment, the present disclosure provides an ionomeric polyamide according to any one of the first to twenty-first embodiments, wherein the ionomeric component comprises an ionomeric diacid.

[0165] In a twenty-third embodiment, the present disclosure provides an ionomeric polyamide according to any one of the first to twenty-second embodiments, wherein the ionomeric component comprises an ionomeric diester.

[0166] In a twenty-fourth embodiment, the present disclosure provides an ionomeric polyamide according to any one of the first to twenty-third embodiments, wherein the ionomeric component comprises an ionomer diamine.

[0167] In a twenty-fifth embodiment, the present disclosure provides a primer, the primer comprising up to 20 weight percent of an ionomeric polyamide according to any one of the first to nineteenth embodiments.

[0168] In a twenty-sixth embodiment, the present disclosure provides the primer according to the twenty-fifth embodiment, wherein the ionomeric polyamide is dispersed in a solvent comprising 80 to 90 weight percent water, 10 to 20 weight percent C2 to C4 aliphatic alcohol, and an optional pH adjuster.

[0169] In a twenty-seventh embodiment, the present disclosure provides the primer according to the twenty-fifth embodiment, wherein the ionomeric polyamide is dispersed in water.

[0170] In a twenty-eighth embodiment, the present disclosure provides a primer according to any one of the twenty-fifth to twenty-seventh embodiments, wherein the ionomeric polyamide is acid-terminated or amine-terminated, and the primer has a pH of 2-6 or 8-11.

[0171] In a twenty-ninth embodiment, the present disclosure provides a primer according to any one of the twenty-fifth to twenty-eighth embodiments, essentially free of surfactant.

[0172] In a thirtieth embodiment, the present disclosure provides an article, comprising: a substrate; and a layer of the ionomeric polyamide according to any one of the first to nineteenth embodiments disposed on a major surface of the substrate.

[0173] In a thirty-first embodiment, the present disclosure provides an article according to the thirtieth embodiment, further comprising an adhesive disposed on a major surface of the layer of ionomeric polyamide.

[0174] In a thirty-second embodiment, the present disclosure provides an article according to the thirtieth or thirty-first embodiment, wherein the adhesive comprises a polymer comprising at least one pendant carboxylic acid group.

[0175] In a thirty-third embodiment, the present disclosure provides an article according to any one of the thirty-two embodiments, wherein the layer of ionomeric polyamide has an average thickness of less than 1 micrometer, less than 0.5 micrometer, or less than 0.25 micrometer.

[0176] In a thirty-fourth embodiment, the present disclosure provides an article according to any one of the thirty-third to thirty-third embodiments, wherein the ionomeric polyamide exhibits a shear modulus at 25 degrees Celsius of 0.01 to 3 megapascals (MPa).

[0177] In a thirty-fifth embodiment, the present disclosure provides an article. The article includes a substrate and a layer of the primer according to any one of the twentieth to twenty-third embodiments disposed on a major surface of the substrate.

[0178] In a thirty-sixth embodiment, the present disclosure provides the article according to the thirty-fifth embodiment, wherein the primer layer exhibits a shear modulus of greater than 5 MPa at 25 degrees Celsius.

[0179] In a thirty-seventh embodiment, the present disclosure provides an article according to any one of the thirty-sixth to thirty-sixth embodiments, wherein the substrate comprises a polar polymeric material.

[0180] In a thirty-eighth embodiment, the present disclosure provides a method of making an ionomeric polyamide comprising reacting the components of a polymerizable composition comprising a first diacid that is a dimer acid, an ionomer component that is an ionomeric diacid, an ionomeric diester, and / or an ionomeric diamine, a first diamine that is an oxyalkylenediamine, at least one second diamine that includes a primary diamine and / or a secondary diamine, and optionally at least one second diacid. The mole fraction of the dimer acid is between 0.40 and 0.99, the mole fraction of the ionomeric component is between 0.01 and 0.20, and the mole fraction of the at least one second diacid is between 0 and 0.60, each based on the total moles of the combination of the dimer acid, the at least one second diacid, and any ionomeric diacids or diesters used to form the ionomeric polyamide. The mole fraction of the oxyalkylenediamine is from 0.005 to 0.10 and the mole fraction of the at least one second diamine is from 0.70 to 0.995, each based on the total moles of the combination of oxyalkylenediamine, at least one second diamine, and optional ionomer diamine used to form the ionomer.

[0181] In a thirty-ninth embodiment, the present disclosure provides the method according to the thirty-eighth embodiment, wherein the ionomeric polyamide is according to any one of the first to twenty-fourth embodiments.

[0182] In a fortieth embodiment, the present disclosure provides a method according to the thirty-eighth or thirty-ninth embodiment, wherein the reacting comprises refluxing the polymerizable composition, followed by distillation.

[0183] In a 41st embodiment, the present disclosure provides a method according to any one of the 38th to 40th embodiments, further comprising adjusting the pH of the ionomeric polyamide-containing composition by adding one or more pH adjusters.

[0184] In a forty-second embodiment, the present disclosure provides a method of making an article, the method comprising coating a primer according to any one of the twenty-fifth to twenty-ninth embodiments onto a major surface of a substrate, and orienting the substrate.

[0185] In a forty-third embodiment, the present disclosure provides a method according to the forty-second embodiment, wherein the orienting comprises biaxial orientation.

[0186] In a forty-fourth embodiment, the present disclosure provides a method according to the forty-second or forty-third embodiment, further comprising at least one of heating or drying the primer, thereby obtaining a layer of ionomeric polyamide having an average thickness of less than 1 micrometer, less than 0.5 micrometer, or less than 0.25 micrometer.

[0187] In a forty-fifth embodiment, the present disclosure provides a method according to the forty-fourth embodiment, further comprising applying a layer of adhesive onto a major surface of the layer of ionomeric polyamide.

[0188] The advantages and embodiments of the present invention are further illustrated by the following examples, in which the particular materials and amounts thereof, as well as other conditions and details, are not to be construed as unduly limiting the invention. All parts and percentages are by weight unless otherwise indicated. EXAMPLES

[0189] Unless otherwise stated or apparent from the context, all parts, percentages, ratios, etc. in the examples and elsewhere in this specification are by weight. The Table of Materials (below) lists the materials used in the examples and their sources. [Table 1]

[0190] General Procedure for Polyamide Synthesis A 1-liter glass resin flask equipped with a mechanical stirrer, thermocouple, distillation head fitted with a 100 milliliter receiving flask, and nitrogen gas inlet / outlet ports was charged with all of the raw materials listed in Table 1, except for PS30. The contents of the flask were heated to 160°C using an electric mantle and controller while stirring under a nitrogen atmosphere. The reaction mixture was refluxed for 60 minutes, after which the cold finger on the distillation head condenser was switched to distillation. Once the rate of water evolution slowed, the batch temperature was increased to 225°C and held overnight with stirring under a nitrogen atmosphere. A 20-30 millimeter mercury vacuum was introduced into the flask over a period of 5-10 minutes. After the vacuum was held for 2 hours, nitrogen gas was introduced into the flask. After adding PS30 and stirring for 15 minutes, the reactor was disassembled and the contents poured into an aluminum tray lined with silicone release paper. The contents were allowed to cool naturally to room temperature and collected.

[0191] General procedure for the preparation of polyamide dispersions E1-E7 Dimer acid-based ionomer polyamide from Table 1, isopropanol, aqueous sodium hydroxide, and deionized water were charged to a flask equipped with a distillation head fitted with an overhead stirrer, thermocouple, and a 500 milliliter receiving flask, as described in Table 3. The mixture was heated to 84° C. with stirring under nitrogen for 2 hours to form a clear solution. The isopropanol was then distilled off under atmospheric conditions to yield milky white dispersions. The contents of the flask were allowed to cool to ambient temperature and were collected as E1-E7 (Table 3). The solids content of E1-E7 was measured for each dispersion according to the General Procedure for Determining Percent Solids.

[0192] General Procedure for Determining Percent Solids Approximately 1 gram of polyamide dispersion was placed into a tared aluminum pan. The exact weight of the dispersion was recorded. The aluminum pan was placed in a forced air oven with a temperature setting of 105° C. for 2 hours. After this time, the pan was removed from the oven and allowed to cool for at least 2 minutes. The weight of the pan and contents was recorded. The % solids was calculated according to the following formula:

number

[0193] General Procedure for the Preparation of Ionomeric Polyamide Primer Coatings Biaxially oriented PET films with ionomeric polyamide coatings were prepared using Mayer rod coating on cast (unoriented) PET films, after which the coated films were heated to temperatures above 70-80°C and above the intrinsic T of the PET film. g The coated PET cast film was batch oven dried in a forced air oven at a temperature below 150° C. Once dried, the coated PET cast film was then cut into 150 mm×250 mm sheets, which were then loaded into a laboratory-scale batch tenter oven (Karo IV lab stretcher, Brueckner Maschinenbau GmbH & Co. KG, Germany) (hereinafter referred to as “Karo”). The Karo has two ovens, one used to heat the film with or without the coating layer as described above, and the other to preheat the film to a temperature, determined by the film substrate, sufficient to stretch the film either uniaxially or biaxially to simulate the production tentering or production orientation of the polymer film as described above. Once the first stretching was completed, the oriented film and coating were then transferred to a second oven, which simulated the heat setting or annealing of the polymer film and coating at much higher temperatures typically found in the processing of oriented films as described above.

[0194] The temperature of the first preheat zone of the Karo film orienter is determined by the T g The preheating temperature was close to 90°C for PET films, between 90°C and 105°C for PET films, and the time for preheating the film depended on the amount of time required for the film and coating to reach a temperature sufficient to fully uniaxially and / or biaxially stretch the film as desired. Typical times in the preheat oven were 20 seconds to 60 seconds for cast PET films 250 micrometers to 1270 micrometers (10 to 50 mils) thick. Once the polymer film and / or coating was at sufficient temperature, the film was stretched in one or both directions, known as MD (machine direction) and TD (transverse direction), to a typical draw dimension, also known as the draw ratio, typical for PET films. Typical draw ratios were 1:1 to 2:1 in MD and 1:1 to 5:1 in TD relative to the original size, more typically 1.1 to 1:1.5 in MD and 3:1 to 4:1 in TD.

[0195] Once the polymer film was oriented in the Karo stretch zone, the film was then transferred to the annealing "heat set" oven or zone of the Karo film orienter. The temperatures in the Karo annealing zone are typical of conventional film manufacturing, ranging from 200°C to 260°C, more commonly 215°C to 255°C, thereby simulating the typical annealing, heat setting of oriented PET films and / or coatings that are typical of the manufacturing film orientation described above.

[0196] Wet, dry and stretch-dried (e.g., after Karo stretch) primer coating thicknesses were measured and reported. The stretch-dried primer coating thickness was calculated by dividing the dry coating thickness before stretching by the total Karo stretch.

[0197] Preparation of Pressure Sensitive Adhesive Transfer Tape A crosslinked removable pressure-sensitive adhesive layer approximately 56 micrometers thick was prepared from a blend of 83 / 15 / 2 parts w / w IOA / 2EHA / AA. The adhesive layer was prepared by in situ UV polymerization (photoinitiator, 2,4-triazine crosslinker and UV source up to 351 nm) to cure and crosslink on a removable silicone-coated release liner to obtain a pressure-sensitive adhesive transfer tape.

[0198] Preparation of Adhesive-Coated, Oriented, Primed Films A primer-coated oriented film measuring approximately 5 inches by 10 inches (12.7 centimeters by 25.4 centimeters) was placed on a flat surface with the primer coating side facing up (exposed). A PSA adhesive transfer tape was laminated to the exposed primer surface by manually rolling it back and forth twice using a 6 inch (15 centimeter) wide rubber roller, bringing its adhesive surface into contact with the primer surface. A structure was obtained having, in order, the oriented film, the primer coating, and the adhesive layer, and the embossed liner.

[0199] General Procedure for Preparation of Adhesive Samples A primer-coated oriented film measuring approximately 12.7 centimeters by 25.4 centimeters (5 inches by 10 inches) was placed on a flat surface with the primer coating side facing up (exposed). An adhesive transfer tape prepared according to Preparation of Pressure-Sensitive Adhesive Transfer Tape was laminated to the exposed primer surface by manually rolling it back and forth twice using a 15 centimeter (6 inch) rubber roller, bringing its adhesive surface into contact with the primer surface. A structure was obtained having, in order, the oriented film, the primer coating, and the adhesive layer, and the embossed liner.

[0200] General procedure for primer-PSA binding assay Adhesive samples were prepared according to the General Procedure for Preparation of Adhesive Samples. The adhesive samples were bonded to a flat anodized aluminum plate using a 4.5 pound (2.0 kilogram) roller with two passes at 12 inches per minute (0.51 centimeters per second). After lamination to the plate, the adhesive samples were removed at 12 inches per minute (0.51 centimeters per second) at a 90 degree angle using a Model 2000 / 2100 TL-2300 IMASS Peel Tester (IMASS Inc., Accord, MA). The average load over 3 inches (7.5 centimeters) of sample length was tested and recorded for each sample. Adhesion testing was performed in a controlled environment at 73°F (22.8°C) and 50% relative humidity (RH).

[0201] Preparation of ionomeric polyamides P1-P7 Ionomeric polyamides P1-P7 were prepared according to the general procedure for polyamide synthesis. The amounts of monomers and additives are specified in Table 1, and the mole fraction compositions are specified in Table 2. Typical yields were 600-700 grams. [Table 2] [Table 3]

[0202] Preparation of ionomeric polyamide dispersions E1-E7 Ionomeric polyamide dispersions E1-E7 were prepared according to the general procedure for the preparation of polyamide dispersions E1-E7. The amounts of materials are specified in Table 3. [Table 4]

[0203] Preparation of ionomeric polyamide coatings E8-E10 Examples E1-E3 were coated onto cast (unoriented) polyethylene terephthalate (PET) film, and the substrate PET was then biaxially oriented to obtain coatings E8-E10, respectively. The water-based polyamide dispersions from Table 3 were coated onto PET cast film using a Mayer rod to a wet coating thickness of 5 micrometers. The coatings and cast film were then dried in a forced air oven at 80° C. for 3 minutes, and the dried coatings and films were removed and cooled to room temperature.

[0204] Cast web pieces of film and coating were trimmed to 150 millimeters by 250 millimeters for loading into the Karo film orienter. The Karo film orienter was preheated as follows: preheat oven zone 100° C. and annealing oven zone 225° C. The coated and trimmed film samples were loaded into the Karo orienter frame loading position and clipped in place to hold them securely during heating and stretching. The Karo film samples were then preheated at 100° C. for 50 seconds and then stretched 1.5×3.8 times in the stretching oven zone. After stretching, the films and coatings were moved to the annealing zone (225° C.) and heat set for 15 seconds. The completed film and coating samples were then returned to the loading position of the Karo film stretcher and removed from the clips after the clips released the oriented film samples. The Karo film orienter settings are specified in Table 4. [Table 5]

[0205] This procedure was repeated until all samples were coated, stretched, and heat set. The samples were then trimmed to remove excess film remaining from the stretching process and were ready for adhesive coating. The final film size with coating after orientation is the initial film size multiplied by the stretch ratio. The target coating thickness after film stretching is calculated as follows: Dry Coating Thickness = (Ionomer Polyamide Dispersion Solids %) x (Wet Coating Thickness)

[0206] The stretch ratios of E8 to E10 were calculated according to the following formula:

number

[0207] Final coating thickness after Karo stretching of the film = (Dry coating thickness) / (Stretch ratio). [Table 6]

[0208] Adhesion performance test of ionomer polyamide coating Films E8-E10 were hand laminated to adhesive transfer tape following the general procedure for preparation of adhesive samples. The constructions were aged for 7 days at the conditions listed in Table 6. The adhesive samples were tested for PSA to primer bonding by peel testing following the general procedure for Primer-PSA Bonding Test Method. The results are summarized in Table 6. [Table 7]

[0209] Foreseeable modifications and variations of this invention will become apparent to those skilled in the art that do not depart from the scope and spirit of the invention. The present invention is not limited to the embodiments set forth in this application for illustrative purposes.

Claims

1. 1. An ionomeric polyamide comprising the reaction product of a polymerizable composition, the polymerizable composition comprising: a) a first diacid which is a dimer acid; b) an ionomer component which is an ionomer diacid, ionomer diester, and / or ionomer diamine; c) a first diamine which is an oxyalkylenediamine; and d) at least one second diamine comprising a primary diamine and / or a secondary diamine; and e) optionally at least one second diacid; and Including, the mole fraction of the dimer acid is 0.40 to 0.99, the mole fraction of the ionomer component is 0.01 to 0.20, and the mole fraction of the at least one second diacid is 0 to 0.60, each based on the total moles of the combination of the dimer acid, the at least one second diacid, and any ionomer diacid or diester used to form the ionomeric polyamide; an ionomeric polyamide, wherein the mole fraction of the oxyalkylenediamine is 0.005 to 0.10 and the mole fraction of the at least one second diamine is 0.90 to 0.995, each based on the total moles of the combination of the oxyalkylenediamine, the at least one second diamine, and the optional ionomeric diamine used to form the ionomeric polyamide.

2. 2. The ionomeric polyamide of claim 1, wherein the oxyalkylenediamine comprises each of ethylene oxide and propylene oxide.

3. 3. The ionomeric polyamide of claim 2, wherein the ionomeric polyamide is acid-terminated or amine-terminated.

4. 10. The ionomeric polyamide of claim 1, wherein the at least one second diamine comprises an aliphatic diamine and a cycloaliphatic diamine.

5. The at least one second diamine has the formula (III): 【Chemistry 1】 (In the formula, R5 is independently selected from straight or branched chain alkyl, cycloalkyl, aryl, heteroalkyl, heteroaryl, hydrogen atom, provided that both R5 cannot be hydrogen atoms; or the R5 groups are alkylene or branched alkylene to form a heterocyclic compound; R6 is alkylene, branched alkylene, cycloalkylene, substituted or unsubstituted arylene, or heteroalkylene.

2. The ionomeric polyamide of claim 1, wherein

6. The ionomeric polyamide of claim 1 , wherein the polymerizable composition is diol-free.

7. The ionomeric polyamide is represented by formula (I) or formula (II): 【Chemistry 2】 【Transformation 3】 (In the formula, R1 is independently selected from the residue of said dimer acid, the residue of said ionomeric diacid or diester, or the residue of any other diacid monomer; R2 is independently selected from the residue of a primary diamine or a secondary diamine; R3 is independently selected from an alkylene group or an arylene group; R4 is independently selected from H, an alkyl group, an alkenyl group, an aryl group, a cycloalkyl group, or two R4 groups are alkylene or branched alkylene to form a heterocyclic compound.

2. The ionomeric polyamide of claim 1, which is of the structure:

8. A primer comprising up to 20 weight percent of the ionomeric polyamide of any one of claims 1 to 7.

9. An article comprising a substrate and a layer of the ionomeric polyamide of any one of claims 1 to 7 disposed on a major surface of the substrate.

10. 10. The article of claim 9, further comprising an adhesive disposed on a major surface of the layer of ionomeric polyamide, the adhesive comprising a polymer containing at least one pendant carboxylic acid group.

11. 10. The article of claim 9, wherein the layer of ionomeric polyamide has an average thickness of less than 1 micrometer, less than 0.5 micrometer, or less than 0.25 micrometer.

12. An article comprising a substrate and a layer of the primer of claim 8 disposed on a major surface of the substrate.

13. The article of claim 9 , wherein the substrate comprises a polar polymeric material.

14. 1. A method for making an ionomeric polyamide, comprising: a) a first diacid which is a dimer acid; b) an ionomer component which is an ionomer diacid, ionomer diester, and / or ionomer diamine; c) a first diamine which is an oxyalkylenediamine; and d) at least one second diamine comprising a primary diamine and / or a secondary diamine; and e) optionally at least one second diacid; and reacting the components of a polymerizable composition comprising: the mole fraction of the dimer acid is 0.40 to 0.99, the mole fraction of the ionomer component is 0.01 to 0.20, and the mole fraction of the at least one second diacid is 0 to 0.60, each based on the total moles of the combination of the dimer acid, the at least one second diacid, and any ionomer diacid or diester used to form the ionomeric polyamide; the mole fraction of the oxyalkylenediamine is from 0.005 to 0.10 and the mole fraction of the at least one second diamine is from 0.70 to 0.995, each based on the total moles of the combination of the oxyalkylenediamine, the at least one second diamine, and the optional ionomer diamine used to form the ionomeric polyamide.

15. 1. A method of making an article, comprising: Coating a major surface of a substrate with the primer of claim 8; orienting the substrate; A method comprising:

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