Metal ionomer compositions and methods of making the same

Abstract

Metal ionomers and methods of making the same are provided.SOLUTION: Ionomers include neutralized blends of olefin-carboxylic acid copolymers with Group II, Group IIIA, and transition metal salts. A method of making an ionomer includes mixing an acid copolymer formed from an α - olefin monomer and an α, β - ethylenically unsaturated carboxylic acid having at least one carboxylic acid group with an amine-containing aqueous solution to form an aqueous dispersion containing an amine salt of the acid copolymer. The method further includes mixing the solution of the Group IIA, Group IIIA, or transition metal salt with an aqueous dispersion comprising an amine salt of an acid copolymer to exchange at least a portion of the amine salt with the Group IIA, Group IIIA, or transition metal salt, thereby forming the ionic copolymer.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application is a continuation of U.S. Provisional Patent Application No. 62 / 857,466, filed June 5, 2019. No. 60 / 699,999, filed on Dec. 1, 2003, the entire disclosure of which is incorporated herein by reference.

[0002] Embodiments of the present disclosure relate generally to ionomers, and in particular to metal ionomers, i.e. , acid compounds at least partially neutralized with Group IIA and Group IIIA metal salts Concerning polymers. Summary of the Invention [Problem to be solved by the invention]

[0003] The conventional process for making ionomers involves mixing neutral nonionic monomers with phenolic compounds. Copolymerization with a monomer containing a dant acid group to form a copolymer having an acid functional group and neutralizing it with a metal salt. However, certain metal salts can be used to form solutions of acid copolymers. The poor solubility of ionomers in the melt mix limits the synthesis of many types of ionomers. Alternative processes, such as the coking process, require a large amount of energy input to melt the polymer. There may be a need.

[0004] Therefore, there is a need for alternative processes for forming metal ionomers.

[0005] Disclosed in embodiments herein are metal ionomers and methods for making same. Metal ionomers are made by combining olefin-carboxylic acid copolymers with Group II , Group IIIA, or a neutralized blend with a transition metal salt. - an acid copolymer formed from an olefin monomer and an α,β-ethylenically unsaturated carboxylic acid The ionomer is mixed with an aqueous solution containing an amine-containing neutralizing agent to form an aqueous solution containing an amine-neutralized ionomer. The method further comprises forming a Group IIA, Group IIIA, or Group IIB dispersion. or a transition metal salt is mixed with an aqueous dispersion containing an amine-neutralized ionomer to form an amine-neutralized ionomer. The compound is at least partially composed of a Group IIA, Group IIIA, or transition metal salt and an ion. The method further includes exchanging to form a metal ionomer in an aqueous dispersion. [Brief explanation of the drawings]

[0006] [Figure 1] FIG. 1 is a schematic diagram of the reaction of Example 1. [Figure 2] FIG. 2 is a graph of the FTIR analysis of the reaction results of Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0007] Unless otherwise defined, all technical and scientific terms used herein are It has the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure pertains. In all cases, the present specification, including definitions, will control.

[0008] Methods and methods similar to, or equivalent to, those described herein Although suitable methods and materials may be used in the practice or testing of various embodiments, and materials are described herein.

[0009] Unless otherwise stated, all percentages, portions, ratios, etc. are by weight. or other value or parameter falls on the low and high ends of a range, preferred range, or preferred value. Where a range is given as either a list of lower and upper preferred values, the range is separately disclosed. This includes any lower range limit or preferred value and any Specify all ranges formed by any pair of upper range limits or preferred values. When a range of values ​​is recited herein, it should be understood that the range is disclosed in its entirety. , unless otherwise stated, ranges include their endpoints, and all integers and fractions within the range. The scope of the invention is not limited to the specific values ​​recited when defining a range. It is not intended to be a set of rules.

[0010] When the term "about" is used in describing values ​​or endpoints of a range, the present disclosure , should be understood to include the particular value or endpoint referred to.

[0011] As used herein, "comprises" and "compr ising), "includes", "including", " "Containing," "characterized by," "has," "having" The terms "compound" and "compounds," or any other variations thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that includes a listing of elements does not necessarily qualify as such. It is not limited to elements not expressly listed or to any process, method, or article. Additionally, the present invention may include other elements inherent in the product or device. Insofar as "or" refers to an inclusive or and not an exclusive or.

[0012] The transitional phrase "consisting essentially of" extends the claim to the specified material or substance. and those that do not materially affect the basic and novel characteristics of the present disclosure. If applicant defines an embodiment or portion thereof with open-ended language such as "comprising," Unless otherwise noted, the description will use the term "consisting essentially of" to refer to such implementations. The morphology should also be construed as descriptive.

[0013] The use of "a" or "an" to describe elements and components of various embodiments This is merely for convenience and to give a general sense of the various embodiments. This statement should be read to include one or at least one Unless it is clear that the singular refers otherwise, it also includes the plural.

[0014] In describing certain polymers, applicants sometimes use the The monomer used, or the amount of monomer used to make the polymer, determines the polymer. It should be understood that such a description refers to the final polymer. Does not include specific nomenclature used to describe or product-by-product May not contain process terminology, but may include such discretion on monomers and amounts. The intended reference is that the polymer contains copolymerized units of those monomers or the amount of those monomers. and the corresponding polymers and compositions thereof. be.

[0015] The term "copolymer" refers to a polymer formed by copolymerization of two or more monomers. Such copolymers essentially consist of two copolymerized comonomers. The dipolymer includes:

[0016] The term "acid copolymer" refers to an α-olefin, α,β-ethylenically unsaturated carboxylic acid copolymer. a carboxylic acid or anhydride thereof, and optionally other suitable comonomers, such as α,β-ethyl "Ethylene acid copolymer" refers to a polymer containing copolymerized units of ethylene unsaturated carboxylic acid ester. "polymer" refers to a compound obtained by condensing ethylene and an α,β-ethylenically unsaturated carboxylic acid or anhydride thereof. and at least 50 mole % of which is ethylene.

[0017] "(Meth)acrylic acid" includes methacrylic acid and / or acrylic acid, and "(meth)acrylic acid" includes methacrylic acid and / or acrylic acid. The term "methacrylate" includes methacrylate and / or acrylate.

[0018] The term "ionomer" refers to a polymer formed by dissolving a parent acid copolymer, as defined above, in one or more neutralizing agents. Polymers derived from parent acid copolymers by partial or complete neutralization with - refers to.

[0019] The term "amine-neutralized ionomer" refers to a compound in which the neutralizing agent contains at least one amine. It refers to ionomer.

[0020] The term "metal ionomer" refers to a polymer in which all or some of the carboxylic acid groups of a parent acid copolymer have been substituted. refers to an ionomer in which the moiety is in the form of a metal carboxylate.

[0021] Various embodiments are directed to a method of making a metal ionomer, which comprises: Acid copolymers formed from fin monomers and α,β-ethylenically unsaturated carboxylic acids with an aqueous solution containing an amine-containing neutralizing agent, An amine-neutralized ionomer that is at least 20 mole percent neutralized with an amine-containing neutralizing agent. The method further comprises the steps of: forming an aqueous dispersion comprising: a Group IIA, a Group IIIA, Alternatively, a transition metal salt may be mixed with an aqueous dispersion containing an amine-neutralized ionomer to form an amine-neutralized ionomer. at least partially ionically exchanged with a Group IIA, Group IIIA, or transition metal salt. and forming a metal ionomer in an aqueous dispersion.

[0022] Traditionally, ionomers are made by mixing neutral nonionic monomers with acrylic or methacrylic acid. was formed by copolymerizing with a monomer containing a pendant acid group, such as The resulting copolymer has acid functionality that is neutralized with a metal salt. This is typically Neutralize the acid with a basic metal salt by melt mixing or neutralize it by solution process. This is achieved in one of two ways: melt mixing and mixing. The metal salts are inactivated, taking care not to oxidize the carboxylic acid functional groups and produce color. It is melted in a neutral atmosphere (e.g., N2) at high temperatures (e.g., over 400°C depending on the metal salt). In the solution neutralization process, the acid copolymer is dissolved and converted into a basic salt containing a metal cation. (e.g., hydroxide basic salt) is added to the solution. However, Group IIA gold Hydroxide salts of metals (e.g., Mg, Ca, Sr, and Ba) are present in the acid copolymer solution. However, they are only soluble in water, which may limit ionomer synthesis.

[0023] Thus, in various embodiments, the method of forming a metal ionomer comprises: As will be explained in more detail, ions that are limited in conventional methods due to solubility considerations can be This is a two-step process that allows the use of metal salts in the monomers. The two-step process of one embodiment is a process that is similar to the conventional melt mixing process used to make metal ionomers. This can be done without adding large amounts of energy that may be required.

[0024] In various embodiments, the aqueous dispersion of the amine-neutralized ionomer is an α-olefin monomer, and an α,β-ethylenically unsaturated carboxylic acid having at least one carboxylic acid group Acid copolymers formed from carboxylic acids or carboxylic anhydrides are added with an amine-containing neutralizing agent. It is formed by mixing with an aqueous solution.

[0025] The α-olefin monomers of various embodiments are C2 to C20 α-olefin monomers. Any and all ranges between C2 and C20 are included herein and are not intended to be limiting unless otherwise specified. For example, in some embodiments, the α-olefin is a C2 to C8 Examples of α-olefins that can be used in various embodiments include: Examples of suitable olefins include, but are not limited to, ethylene, propylene, butadiene, styrene, 1-butene, 1- pentene, 1-hexene, 1-heptene, and 1-octene, among which preferred may be ethylene, propylene, styrene, butadiene, or mixtures thereof. In certain embodiments, the α-olefin comonomer is ethylene.

[0026] In various embodiments, the α-olefin monomer is the monomer present in the acid copolymer. It is present in an amount of more than 50% or more than 60% by weight based on the total weight of the monomer. For example, The α-olefin monomer content of the acid copolymer is 50% by weight to 95% by weight, 50% by weight It may be up to 90% by weight, 50% to 85% by weight, or 60% to 80% by weight.

[0027] In various embodiments, the α,β-ethylenically unsaturated carboxylic acid or carboxylic acid-free The ester is an α,β-ethylenically unsaturated monomer containing at least one carboxylic acid group. In some embodiments, the α,β-ethylenically unsaturated carboxylic acid or The α,β-ethyl carboxylic acid anhydride used in various embodiments has 3 to 8 carbon atoms. Examples of olefinically unsaturated carboxylic acid or carboxylic acid anhydride monomers include monobasic acids, e.g. For example, acrylic acid, methacrylic acid, crotonic acid, and acyloxypropionic acid, and Included are dibasic acid monomers such as maleic acid, fumaric acid, and itaconic acid. Monoesters of dibasic acid monomers, such as the monobutyl ester of maleic acid, may also be used. In some particular embodiments, the α,β-ethylenically unsaturated carboxylic acid may be , acrylic acid, methacrylic acid, maleic anhydride, and mixtures thereof. In certain embodiments, the acid copolymer is ethylene (meth)acrylic acid.

[0028] α,β-ethylenically unsaturated carboxylic acids or carboxylic anhydrides are present in the acid copolymers. 1% to 25% by weight, 1% to 20% by weight, based on the total weight of monomers present; Or it can be present in an amount of 5% to 15% by weight. The acid copolymer can be present in an amount of 0.900 g / cc to 1.2g / cc, 0.920g / cc~0.980g / cc, 0.930g / cc~0. 960 g / cc, or a density between 0.932 g / cc and 0.958 g / cc.

[0029] Before neutralization, the acid copolymer has a viscosity of less than about 2000 g / 10 min, less than about 1800 g / 10 min, Melt index less than approximately 1600g / 10min, or even less than approximately 1400g / 10min This can be measured according to ASTM D1238 (190°C, 2.16 kg load). Therefore, it is measured.

[0030] In various embodiments, the acid copolymer is purified by high temperature gel permeation chromatography (P Approximately 1-3% of the total mass was determined by using lymerChar GPC-IR. Acid number between 200 mg KOH and number average molecular weight between 500 and 10,000,000 g / mol In some embodiments, the acid copolymer has a molecular weight (Mn) of 500 to 5.0 00,000, 500-1,000,000, 500-500,000, 500-100 ,000, 500-50,000, 500-10,000, 500-5,000, 750 Number average molecular weight (Mn) of up to 3,000 or 1,000 to 2,000 g / mol Acid number is measured according to ASTM D-1386 and the values ​​given are based on titration. When measured by the formula, the amount of 1 gram of polymer required to neutralize the acid functional groups of the acid copolymer is This refers to the amount of KOH in milligrams per gram.

[0031] The acid copolymers disclosed herein can be obtained by radical copolymerization at high temperature and pressure. Examples of commercially available acid copolymers that can be used in some embodiments include SK Gl PRIMACOR (trademark) available from Obal Chemical Co., Ltd. ) (e.g., PRIMACOR 5890), The Dow in Midland, MI NUCREL™ (e.g., NU CREL™ 2806), and ExxonMobil Chemical Com Ethylene acid copolymers available under the ESCOR™ trademark available from Included.

[0032] Acid copolymers are prepared using standard free radical copolymerization techniques that utilize high pressure and are operated continuously. The monomers can be prepared by the following procedure: In this way, the amount of monomer units along the chain is increased. A uniform, nearly random distribution of the monomer positions is achieved. Unreacted monomer can be recycled. Additional information on the preparation of acid copolymers can be found in U.S. Pat. No. 3,264,272 and U.S. Pat. No. 4,766,174, each of which is incorporated herein by reference. will be incorporated into

[0033] In various embodiments, the acid copolymer is mixed with an aqueous solution containing an amine-containing neutralizing agent. Amine-containing neutralizing agents include, for example, ammonia or organic amines, such as monoethanolamines. Methanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA) ), dimethylaminoethanol (DMEA), or a mixture thereof. It is contemplated that other amine-containing neutralizing agents may be used depending on the embodiment, such as In some embodiments, a hydrophilic amine-containing neutralizing agent may be used. Without bundling, the use of a hydrophilic amine-containing neutralizing agent aids in the dispersion of the acid copolymer in solution. Furthermore, in various embodiments, certain amine-containing The neutralizing agent can be selected based on the pKa of the amine-containing neutralizing agent. For example, in some embodiments, In some embodiments, the amine-containing neutralizer may have a pKb of 8 to 13, or 9 to 12, The specific pKb of amine-containing neutralizers varies depending on the metal salt incorporated into the metal ionomer. possible.

[0034] The acid copolymer and the amine-containing neutralizing agent can be mixed by extrusion, high shear mixing, or in a reaction vessel. In some embodiments, the mixing can be carried out in a vessel at a temperature of 90°C to 150°C. The temperature is above the melting point or glass transition temperature (Tg) of the polymer. If desired, other temperatures may be used to ensure that a dispersion is produced.

[0035] When the acid copolymer is mixed with an amine-containing neutralizer, the five carboxylic acid groups of the acid copolymer are neutralized. Amine-neutralized ionomers are produced in which 100 mol % to 100 mol % of the ionomer is neutralized with an amine-containing neutralizing agent. In some embodiments, at least 20 mole percent of the carboxylic acid groups are amines. For example, amine-neutralized ionomers are those in which two of the carboxylic acid groups are neutralized by a neutralizing agent. 0 mol% to 100 mol% or 50 mol% to 100 mol% is neutralized by an amine-containing neutralizing agent It may be possible to reconcile.

[0036] In various embodiments, the resulting aqueous dispersion of amine-neutralized ionomer is Based on the total solids content, the composition contains 1% to 70% by weight of an amine-neutralized ionomer. The aqueous dispersion may contain 1% to 50% by weight or 1% to 30% by weight of an amine-neutralized ion. In various embodiments, the amine-neutralized ionomer in the aqueous dispersion may include It is understood that the particular amount will depend on the amount of acid groups in the acid copolymer.

[0037] In various embodiments, the resulting amine-neutralized ionomer dispersion has a particle size ranging from 5 nm to 10 Without being bound by theory, the particle size is 00 μm, 10 nm to 500 μm, or 25 nm to 50 μm. The lack of bundling and small particle size make the amine-neutralized ionomers easily dispersible in water. Furthermore, it is possible to use the amine-neutralized ionomer to impregnate porous materials. It is thought that this is the case.

[0038] Amine-neutralized ionomers are used to produce Group IIA, Group IIIA, or transition Metal ionomers can be produced by treatment with transition metal salts. Replaces amine groups in neutralized ionomers to produce metal ionomers by blending In some embodiments, a Group IIA or Group IIIA metal salt is used. The metal ionomers can be produced by the addition of the metal cations. Any convenient salt, including but not limited to halides, acetates, nitrates, or sulfates. In some embodiments, the metal salt is water soluble. As used herein, the term "water soluble" refers to a solubility in water of greater than 1 g / L.

[0039] In various embodiments, the amine-neutralized ionomer is selected from magnesium, calcium, It can be treated with one or more cations of barium, zinc, or aluminum. In some particular embodiments, the metal salt is Mg(OH)2 or Ca(OH)2. In embodiments, about 10% to about 100%, about 10% to about 100% of the total acid units of the amine-neutralized ionomer. % to about 80%, or about 10% to about 55%, is exchanged with metal cations.

[0040] In the context of this disclosure, percent neutralization data is calculated for each cation from its ionic charge. The formula is presented using the assumption that the maximum number of carboxylic acid groups present in the For example, Al 3+ reacts with three carboxylic acid groups, and Mg 2+ and Zn 2+ There are two reacts with Na + is assumed to react with one

[0041] In various embodiments, when metal ions are used, the neutralization level is determined by the following formula: Therefore, it can be calculated.

number

[0042] In various embodiments, the neutralization level when caustic or amine is used is: It can be calculated according to the formula:

number

[0043] Alternatively or additionally, the degree of neutralization can be determined, for example, as described in U.S. Pat. No. 3,328,367. As described, it can be measured directly via established analytical methods or by As described in US Patent No. 3,471,460, the infrared absorption spectrum of the copolymer can be calculated based on the change in

[0044] The blends can be produced by any means known to those skilled in the art. For example, a solution of metal salts is mixed with an aqueous dispersion containing an amine-neutralized ionomer in a reactor at room temperature or above. or other mixing vessel in an inert or air atmosphere. In an embodiment, the metal salt solution contains 0.01 wt % to 100 wt % based on the total weight of the solution. % of metal salts. Stir to ensure the solution is blended with the aqueous dispersion. Agitation may be used.

[0045] The blend contains plasticizers, stabilizers including viscosity stabilizers, hydrolysis stabilizers, primary and secondary acids. anti-oxidants, ultraviolet absorbers, anti-static agents, dyes, pigments or other colorants, inorganic fillers, Flame retardants, lubricants, reinforcing agents such as glass fibers and flakes, synthetic (e.g., aramid) fibers or pulp, foaming or blowing agents, processing aids, slip additives, silica or anti-blocking agents such as talc, release agents, tackifying resins, or a combination of two or more thereof Inorganic fillers such as calcium carbonate may also be included in the blend. It can be incorporated into the

[0046] These additives are used in an amount of 0.01 to 40% by weight, 0.01 to 25% by weight, 0.01 to 15% by weight, %, 0.01-10% by weight, or 0.01-5% by weight in the blend. The incorporation of additives can be achieved, for example, by dry blending, extrusion of a mixture of the various components. This can be done by any known process, such as conventional masterbatch technology. do.

[0047] In various embodiments, the resulting metal ionomer contains greater than 5 mole percent metal. For example, a metal ionomer may be present in an amount of 5 moles based on the total moles in the metal ionomer mixture. % to 20 mol %, or 6 mol % to 10 mol % of metal.

[0048] In some embodiments, the resulting dispersion containing the metal ionomer is filtered and to remove any remaining amines and / or metal salts from the metal ionomer. Depending on the particular embodiment, other processing steps may also be included. It can be done.

[0049] Without being bound by theory, the two-step process described herein is This is believed to allow for increased production of metal ionomers that would otherwise be hindered by the For example, Group IIA, Group IIIA, or Mg(OH)2 and Ca(OH)2 Transition metal hydroxides such as HCl, HCl, and HCl have limited solubility in acid copolymer solutions. Therefore, salts such as MgCl2 and CaCl2 are possible additives to dispersions containing amine-neutralized ionomers. It can be dissolved in water, thereby eliminating the solubility constraint and allowing it to be incorporated into ionomers. Additionally, various embodiments described herein may be used to neutralize amines. Instead of the heating step of 400°C or more required in conventional processes, It can be formed at temperatures below about 150°C, so it does not require the application of large amounts of energy. This allows the process to be carried out without [Example]

[0050] The following examples are provided to illustrate various embodiments, but are not intended to limit the scope of the claims. All parts and percentages are not intended to be limiting unless otherwise indicated. By weight unless otherwise noted. The approximate properties, characteristics, parameters, etc. of the materials used are provided below. The raw materials used in the examples are described below.

[0051] Example 1 Ethylene commercially available from SK Global Chemical Co., Ltd. PRIMACOR™ 5980, a polyethylene acrylic acid copolymer, is incorporated herein by reference in its entirety. Nos. 3,389,109, 5,206, 5,216, 5,389 ... 279, and U.S. Pat. No. 5,387,635. The copolymer was mixed with triethanolamine (TEA) to obtain a 60 mol % copolymer of acrylic acid. The resulting aqueous dispersion had a solids content of 24%, a pH of 7.79, and a pH of 18.5. The dispersion had an average particle size of 0.1 m.

[0052] A molar excess of aqueous calcium chloride (40 wt%) was added to the aqueous dispersion with mixing at room temperature. A white precipitate was formed. The aqueous phase was collected for further analysis. Filter the material under vacuum and wash the precipitate using deionized (DI) water to remove excess salt from the precipitate. The calcium chloride and potentially TEA (as the hydrochloride) were removed. The washed precipitate was then The resulting solid was collected and dried overnight in an oven at 60°C. The final dried white solid was analyzed by various methods. The samples were analyzed using analytical techniques.

[0053] The comparative example is a PRIM without neutralizing the EAA with an amine or forming an aqueous dispersion. It was prepared by mixing ACOR™ 5980 with a molar excess of aqueous calcium chloride. The EAA remained as a solid pellet and did not react with calcium chloride. Comparative examples include PRIMACOR™ 5980 in combination with TEA and calcium chloride, and a single In the comparative example, a homogeneous product was not obtained, and the amine was present in the final product as a neutralizing agent to interact with the acid.

[0054] In particular, infrared spectroscopic characterization and X-ray fluorescence (XRF) were used to characterize the solid state of the reaction. Both the water and the water layers were characterized. A Nicolet FTIR spectrometer with a 2% error and a KE ATR attachment was used. The infrared spectrum was obtained using a FTIR spectrophotometer. The proposed reaction pathway is shown in Figure 1. The IR results are shown in Figure 2.

[0055] Based on the FTIR spectrum, the aqueous layer showed strong evidence of TEA, and the solids showed salts. Form (COO - ) showed strong evidence of amine-neutralized ethylene acrylic acid ionomers. This analysis suggests the formation of EAA-TEA-CaCl2. Further evidence is found at 1560 cm -1 The peak around 2+ Salt form (COO - ) is an index of carboxylic acids.

[0056] XRF analysis was performed using Axios max from Malvern Panalytical The XRF analysis of the solids was performed using an advanced X-ray fluorescence spectrometer and is shown in Table 1 below.

[0057] [Table 1] ">

[0058] The XRF data in Table 1 indicates that the solid contains calcium in a calcium to chlorine ratio of 9:1. It was found that EAA contained small amounts of CaCl2 or TEA hydrochloride as impurities. Ca 2+ indicates the presence of ionic complexes.

[0059] Various embodiments provide methods for making metal ionomers suitable for use in a wide variety of applications. Such applications include, by way of example and not limitation, golf balls, ice Optical and / or medical devices such as contact lenses, and packaging such as cosmetic and food packaging In particular, various embodiments described herein may be incorporated into copolymers. The amount of metal can be increased to allow for metal ionomers, which in turn can be waterproof, functional, and The mechanical and adhesive properties can be increased.

[0060] Furthermore, terms such as "generally," "generally," and "typically" are used in the context of the claimed invention. To limit the scope of the invention or to limit the structure or scope of the invention in which certain features are claimed Critical, essential, or even important to the function Note that these terms are not used herein to imply otherwise. Rather, they are used to Alternative or alternative methods that may or may not be utilized in particular embodiments of the present disclosure. It is merely intended to highlight additional features.

Claims

1. 1. A method for making a metal ionomer, comprising: formed from an α-olefin monomer and an α,β-ethylenically unsaturated carboxylic acid mixing the acid copolymer with an aqueous solution containing an amine-containing neutralizing agent, and at least 20 mole percent of the carboxylic acid groups are neutralized with the amine-containing neutralizing agent. mixing to form an aqueous dispersion containing the amine-neutralized ionomer; A Group IIA, Group IIIA, or transition metal salt is added to the amine-neutralized ionomer. and mixing the amine with the aqueous dispersion containing the amine of Group I IA, Group IIIA, or transition metal salts to form the aqueous dispersion. forming the metal ionomer in a liquid.

2. The acid copolymer comprises at least 50 mole percent of an α-olefin, The method of claim 1 , wherein the fin is ethylene.

3. 10 mol % to 100 mol % of the amines are selected from the group IIA and group II 10. The method of any one of the preceding claims, wherein the IA is ion-exchanged with a metal salt of IA.

4. The metal of the Group IIA or Group IIIA metal salt is magnesium, Calcium, barium, zinc, and aluminum are selected from the group consisting of Item 10. The method according to any one of items 1 to 4.

5. At least 50 mole percent of the carboxylic acid groups of the acid copolymer are from the amine-containing copolymer.

10. The method of any one of the preceding claims, wherein the solution is neutralized by a neutralizing agent.

6. The α,β-ethylenically unsaturated carboxylic acid has 3 to 8 carbon atoms.

10. The method of claim 9 .

7. The α,β-ethylenically unsaturated carboxylic acid is acrylic acid, methacrylic acid, itaconic acid, or the like.

7. The method of claim 6, wherein the acid is crotonic acid, maleic acid, or fumaric acid.

8. 7. The method according to claim 1, wherein the acid copolymer is ethylene (meth)acrylic acid. The composition described in claim 1.

9. The amine-containing neutralizing agent is selected from the group consisting of ammonia, monoethanolamine (MEA), diethanolamine (DIA), and the like. diethanolamine (DEA), triethanolamine (TEA), dimethylaminoethanol ( DMEA), or mixtures thereof.

10. 10. The method of claim 9, wherein the metal ionomer is substantially free of amines. A metal ionomer produced from the method.

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