阅读说明：本技术 离聚物组合物 (Ionomer compositions ) 是由 姜贤 于 2019-07-15 设计创作，主要内容包括：本文中的实施例中描述了离聚物,其包含乙烯酸共聚物、脂肪族和单官能有机酸的中和共混物。按所述共混物的总重量计,所述共混物包括40wt％到95wt％的所述乙烯酸共聚物、5到50wt％的所述脂肪族单官能有机酸。按存在于所述乙烯酸共聚物中的单体的总重量计,所述乙烯酸共聚物为乙烯、1到25wt％单羧酸和1到40wt％丙烯酸烷基酯的聚合反应产物。所述脂肪族单官能有机酸的碳原子少于36个。在各种实施例中,至少70摩尔％的总酸单元经三价阳离子和一价或二价阳离子两者中和。(Ionomers are described in the examples herein that comprise neutralized blends of ethylene acid copolymers, aliphatic and monofunctional organic acids. The blend comprises from 40 to 95 weight percent of the ethylene acid copolymer, from 5 to 50 weight percent of the aliphatic monofunctional organic acid, based on the total weight of the blend. The ethylene acid copolymer is the polymerization reaction product of ethylene, 1 to 25 weight percent monocarboxylic acid, and 1 to 40 weight percent alkyl acrylate, based on the total weight of monomers present in the ethylene acid copolymer. The aliphatic monofunctional organic acid has less than 36 carbon atoms. In various embodiments, at least 70 mole% of the total acid units are neutralized with both a trivalent cation and a monovalent or divalent cation.)

1. An ionomer comprising a neutralized blend of an ethylene acid copolymer and an aliphatic monofunctional organic acid, wherein the blend comprises:

from 40 to 95 weight percent, based on the total weight of the blend, of the ethylene acid copolymer, which is the polymerization reaction product of:

ethylene, and

from 1 to 25 weight percent, based on the total weight of monomers present in the ethylene acid copolymer, of a monocarboxylic acid; and

1 to 40 wt%, based on the total weight of monomers present in the ethylene acid copolymer, of a softening comonomer; and

from 5 to 50 weight percent, based on the total weight of the blend, of the aliphatic monofunctional organic acid, wherein the aliphatic monofunctional organic acid has less than 36 carbon atoms;

wherein at least 70 mole% of the total acid units are neutralized by a cation source comprising (a) a trivalent cation and (b) a monovalent or divalent cation.

2. The ionomer of claim 1, wherein the monocarboxylic acid comprises one or more of acrylic acid, methacrylic acid, or a combination thereof.

3. The ionomer of any preceding claim, wherein the softening comonomer is an alkyl acrylate selected from the group consisting of: methyl acrylate, ethyl acrylate, n-butyl acrylate, or isobutyl acrylate, or combinations thereof.

4. The ionomer of any preceding claim, wherein the ionomer has a melt index I, as determined according to ASTM D1238(220 ℃, 2.16kg) of 0.1 to 30 grams/10 minutes₂。

5. The ionomer of any preceding claim, wherein the ionomer has a density of 0.920 to 0.980 g/cc.

6. The ionomer of any preceding claim, wherein the monovalent or divalent cation is selected from the group consisting of: magnesium cations, sodium cations, zinc cations, lithium cations, and potassium cations.

7. The ionomer of any preceding claim, wherein the blend comprises 60 to 80 wt% of the ethylene acid copolymer.

8. The ionomer of any preceding claim, wherein the blend comprises 15 to 35 wt.% of the aliphatic monofunctional organic acid.

9. The ionomer of any preceding claim wherein at least 90 mole% of the total acid units are neutralized by a cation source comprising (a) a trivalent cation and (b) a monovalent or divalent cation.

10. The ionomer of any preceding claim, wherein 100 mol% of the total acid units are neutralized using an amount of the cation source in excess of the amount required to neutralize 100% of the total acid units.

11. A molded article or foam comprising the ionomer of any one of the preceding claims.

12. The molded article or foam of claim 11, wherein the molded article exhibits creep resistance as defined by a dimensional change of less than 50% after 30 minutes at 100 ℃, a load of 30g, a stress of 46 kPa.

13. The molded article or foam of claim 11 or 12, wherein the molded article exhibits creep resistance as defined by a dimensional change of less than 200% after 30 minutes at 100 ℃, a load of 100g, a stress of 150 kPa.

14. The molded article or foam of any of claims 11 to 13, wherein the molded article exhibits creep resistance as defined by a dimensional change of less than 15% after 30 minutes at 100 ℃, a load of 100g, a stress of 150 kPa.

15. The molded article or foam of any of claims 11 to 14, wherein the molded article exhibits creep resistance as defined by a dimensional change of less than 500% after 96 hours at 50 ℃, a load of 400g, a stress of 600 kPa.

Technical Field

Embodiments of the present disclosure generally relate to ionomers, and in particular to ionomers comprising neutralized blends of ethylene acid copolymers and aliphatic monofunctional organic acids.

Background

Ionomers are known to have resiliency and foamability that makes them suitable for use as footwear midsoles and other foam applications. However, conventional ionomer compositions may lack dimensional stability and creep resistance at high temperatures, which may limit the practical applications in which they may be used. To improve creep resistance, ionomers have been blended with other high temperature materials. However, blends have limited elasticity and foamability.

Accordingly, there is a need for alternative ionomers that can be used in high temperature foam applications.

Disclosure of Invention

Ionomers are disclosed in the examples herein. The ionomer comprises a neutralized blend of an ethylene acid copolymer, an aliphatic monofunctional organic acid, and a neutralizing composition. The blend comprises from 40 to 95 weight percent of the ethylene acid copolymer, from 5 to 50 weight percent of the aliphatic monofunctional organic acid, based on the total weight of the blend. The ethylene acid copolymer is the polymerization reaction product of ethylene, 1 to 25 weight percent monocarboxylic acid, and 1 to 40 weight percent alkyl acrylate, based on the total weight of monomers present in the ethylene acid copolymer. The aliphatic monofunctional organic acid has less than 36 carbon atoms. In various embodiments, at least 70 mole% of the total acid units are neutralized with both a trivalent cation and a monovalent or divalent cation.

Drawings

FIG. 1 is a graph comparing the dimensional change (y-axis;%) of sample L and samples 1-5 at a load of 30g over a temperature range of 50 deg.C to 120 deg.C; and

FIG. 2 is a graph comparing the dimensional change (y-axis;%) of sample L and samples 1-7 at a load of 100g over a temperature range of 50 deg.C to 160 deg.C.

Detailed Description

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. In case of conflict, the present specification, including definitions, will control.

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

All percentages, parts, ratios, etc., are by weight unless otherwise indicated. When an amount, concentration, or other value or parameter is given as either a range, preferred range, or a list of lower preferable values and higher preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any lower limit or lower preferable value and any upper limit or higher preferable value for the range, regardless of whether ranges are separately disclosed. Where a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range. When defining a range, it is not intended that the scope of the invention be limited to the specific values recited.

When the term "about" is used to describe a value or range endpoint, the disclosure should be understood to include the specific value or endpoint referred to.

As used herein, the terms "comprises," "comprising," "includes," "including," "contains," "characterized by," "has/having," or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to those elements, and may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Further, unless expressly stated to the contrary, "or" means an inclusive or and not an exclusive or.

The transitional phrase "consisting essentially of … …" limits the scope of the claims to the specified materials or steps and those materials or steps that do not materially affect one or more of the basic and novel features of the disclosure. Where applicants have defined an embodiment, or a portion thereof, using open-ended terms such as "comprising," the description should be construed as also using the term "consisting essentially of … … to describe such embodiment, unless otherwise noted.

The use of "a" or "an" is employed to describe elements and components of various embodiments. This is for convenience only and to give a general sense of the various embodiments. This description should be read to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise.

In describing certain polymers, it is to be understood that sometimes applicants refer to a polymer by the monomer used to produce the polymer or the amount of monomer used to produce the polymer. While such description may not include specific terms for describing the final polymer or may not include process-defined product (product-by-process) terms, any such reference to monomers and amounts should be construed to mean that the polymer comprises copolymerized units of these monomers or the amounts of the monomers, as well as their corresponding polymers and compositions.

The term "copolymer" is used to refer to a polymer formed by the copolymerization of two or more monomers. Such copolymers include binary copolymers consisting essentially of two comonomers.

"(meth) acrylic acid" includes methacrylic acid and/or acrylic acid, and "(meth) acrylate" includes methacrylate and/or acrylate.

Various embodiments relate to an ionomer comprising a neutralized blend of an ethylene acid copolymer, an aliphatic and a monofunctional organic acid. The blend comprises from 40 to 95 weight percent of the ethylene acid copolymer, from 5 to 50 weight percent of the aliphatic monofunctional organic acid, based on the total weight of the blend. The ethylene acid copolymer is the polymerization reaction product of ethylene, 1 to 25 weight percent monocarboxylic acid, and 1 to 40 weight percent alkyl acrylate, based on the total weight of monomers present in the ethylene acid copolymer. The aliphatic monofunctional organic acid has less than 36 carbon atoms. In various embodiments, at least 70 mole% of the total acid units are neutralized with both a trivalent cation and a monovalent or divalent cation.

In various embodiments, the ionomers exhibit improved creep resistance at high temperatures while maintaining their elasticity and foamability. Molded articles comprising ionomers according to various embodiments described herein exhibit creep resistance, such as less than 50% after 30 minutes at 100 ℃, a load of 30g, a stress of 46 kPa; less than 200% after 30 minutes at 100 ℃, 100g load, 150kPa stress; less than 15% after 30 minutes at 100 ℃, 100g load, 150kPa stress; or a dimensional change of less than 500% after 96 hours at 50 ℃, 400g load, 600 kPa.

Ethylene acid copolymers are the polymerization reaction product of ethylene, a monocarboxylic acid, and a softening comonomer. The monocarboxylic acid can be, for example, acrylic acid, methacrylic acid, or a combination thereof. In various embodiments, the monocarboxylic acid is present in an amount of about 1 wt% to about 25 wt%, about 1 wt% to about 20 wt%, or about 5 wt% to about 15 wt%, based on the total weight of monomers present in the ethylene acid copolymer. In various embodiments, the ethylene acid copolymer has an ethylene content greater than about 40 wt%, greater than about 50 wt%, or greater than about 60 wt%. For example, the ethylene acid copolymer has an ethylene content of about 40 wt% to about 95 wt%, about 40 wt% to about 90 wt%, about 50 wt% to about 85 wt%, or about 60 wt% to about 80 wt%.

In various embodiments, the ethylene acid copolymer comprises a softening comonomer selected from the group consisting of: vinyl esters, alkyl vinyl esters, and alkyl (meth) acrylates. The softening comonomer can be present in an amount of about 1 wt% to about 40 wt% or about 1 wt% to about 30 wt%, based on the total weight of monomers present in the ethylene acid copolymer. In some embodiments, the softening comonomer is an alkyl acrylate. The alkyl acrylate may be present in an amount of from about 1 wt% to about 40 wt%, or from about 1 wt% to about 30 wt%, based on the total weight of monomers present in the ethylene acid copolymer. Suitable examples of alkyl acrylates include, but are not limited to, ethyl acrylate, methyl acrylate, n-butyl acrylate, isobutyl acrylate, or combinations thereof. In various embodiments, the alkyl acrylate has an alkyl group having 1 to 8 carbons. In a particular embodiment, the alkyl acrylate is n-butyl acrylate.

Ethylene acid copolymers can be prepared by standard free radical copolymerization processes, using high pressures, operating in a continuous manner. The monomers are fed to the reaction mixture in a ratio which is related to the reactivity of the monomers and the desired incorporation. In this way, a uniform, nearly random distribution of the monomer units along the chain is achieved. The unreacted monomer can be recovered. Additional information regarding the preparation of ethylene acid copolymers including softening monomers 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 in its entirety.

In various embodiments, the neutralized blend comprises from about 40 to about 95 weight percent of the ethylene acid copolymer or from about 50 to about 80 weight percent of the ethylene acid copolymer, based on the total weight of the blend.

Ethylene acid copolymers can be used to produce ionomers by treatment with monovalent or divalent cations. The source of monovalent or divalent metal cations may be any suitable derivative including, but not limited to, formates, acetates, hydroxides, nitrates, carbonates, and bicarbonates. In various embodiments, the ethylene acid copolymer can be treated with one or more cations of magnesium, sodium, or zinc ions. In embodiments, from about 1% to about 70%, from about 5% to about 60%, or from about 10% to about 55% of the total acid units of the ethylene acid copolymer are neutralized with a monovalent or divalent cation. Commercially available ionomers include those available under the trade nameThose obtained from DuPont (E.I.du Pont de Nemours and Company).

In various embodiments described herein, the ionomer is a Fatty Acid Modified Ionomer (FAMI). Specifically, according to various embodiments, the ethylene acid copolymer is modified with an aliphatic monofunctional organic acid. In various embodiments, the aliphatic monofunctional organic acid has fewer than 36 carbon atoms. For example, the fatty acid may include C₄To less than C₃₆E.g. C₃₄、C_4-26、C_6-22Or C_12-22Or a salt thereof. At high neutralization levels (e.g., at least 70% to 80%), nominal neutralization levels (i.e., sufficient metal compound is added so that all acid moieties in the copolymer and organic acid are nominally neutralizedAnd) volatility is not an issue and organic acids with lower carbon content can be used, but it is preferred that the organic acid (or salt) be non-volatile (non-volatile at the melt blending temperature of the agent and acid copolymer) and non-migratory (not accumulating to the polymer surface under normal storage conditions (ambient temperature). The fatty acid may be present in the blend from about 5 wt% to about 50 wt%, from about 5 wt% to about 40 wt%, or from about 15 wt% to about 35 wt%, based on the total weight of the blend. Examples of fatty acids include, but are not limited to, caproic acid, caprylic acid, capric acid, lauric acid, palmitic acid, stearic acid, isostearic acid, behenic acid, erucic acid, oleic acid, linoleic acid, isostearic acid, 12-hydroxystearic acid, or combinations of two or more thereof.

The salt of any of these fatty acids may include one or more alkali metal salts, including sodium salts, potassium salts, or both. In addition to the alkali metal salts, small amounts of salts of alkaline earth and/or transition metal ions may also be present. In some embodiments, the salt of the fatty acid can include a monovalent or divalent metal cation as described above, thereby modifying the ionomer during treatment with the metal cation to form a fatty acid modified ionomer ("FAMI").

In various embodiments, the FAMI can be further neutralized by blending a melt of the FAMI with a neutralizing composition that includes a metal cation, including a trivalent cation, such as an aluminum cation, a chromium cation, an iron cation, or a lanthanide metal cation. The metal cation may be present in the neutralizing composition in the form of a metal salt or other metal compound that provides the metal cation. In embodiments where the neutralization solution includes a metal salt, the metal cation is provided in the ionomer and the anion of the salt is evaporated from the polymer. In various embodiments, the neutralizing composition comprises aluminum cations. The source of aluminum cations may be any suitable derivative including, but not limited to, carboxylates, alkoxides, chelating compounds, and hydroxides. For example, the source of aluminum cations may be aluminum acetate, aluminum isopropoxide, or aluminum acetylacetonate. In embodiments where trivalent cations other than aluminum cations are used, suitable derivatives thereof may be employed.

Neutralization can be carried out by first neutralizing the blend with a trivalent cation, followed by a second neutralization step using a monovalent or divalent cation. Neutralization can also be carried out by first neutralizing the blend with a monovalent or divalent cation followed by a second neutralization step with a trivalent cation. While in various embodiments, the neutralization of the blend is described as a two-step neutralization process, it is also contemplated that, in some embodiments, the blend can be neutralized in a single-step neutralization process, wherein the neutralizing composition comprises (i) a monovalent or divalent cation and (ii) a trivalent cation, and then the neutralizing composition is used to neutralize the blend.

Thus, in various embodiments, up to 70 mole% of the total acid units are neutralized with trivalent cations, at least 80 mole% of the total acid units are neutralized with trivalent cations, at least 90 mole% of the total acid units are neutralized with trivalent cations, at least 95 mole% of the total acid units are neutralized with trivalent cations, or even 100 mole% of the total acid units are neutralized with trivalent cations.

In the context of the present disclosure, the following assumptions are used to present the neutralization data percentage: each cation will react with the maximum number of carboxylic acid groups calculated from its ionic charge. That is, assume, for example, Al³⁺Will react with three carboxylic acid groups, Mg²⁺And Zn²⁺Will react with two carboxylic acid groups and Na⁺Will react with one carboxylic acid group.

In various embodiments, 100 mole% of the total acid units are neutralized using an amount of cation source in excess of the amount required to neutralize 100 mole% of the total acid units. The level of neutralization can be calculated according to the following equation:

the blend may be produced by any means known to those skilled in the art. It is substantially melt processable and can be produced by combining one or more ethylene acid copolymers or ionomers of ethylene acid copolymers, one or more fatty acids or salts thereof, a basic metal compound, and a neutralizing composition comprising a trivalent metal cation to produce a mixture, and heating the mixture under conditions sufficient to produce the composition. The heating may be conducted at a temperature in the range of about 80 ℃ to about 350 ℃, about 120 ℃ to about 300 ℃, or about 160 ℃ to about 260 ℃ at a pressure that accommodates the temperature for a period of about 30 seconds to about 2 or 3 hours. The blend can be produced by melt blending the ethylene acid copolymer and/or ionomer thereof with one or more fatty acids or salts thereof and simultaneously or subsequently combining a sufficient amount of the basic metal compound and the trivalent metal cation. Salt blends of the components can be prepared or the components can be melt blended in an extruder. For example, the ethylene acid copolymer and organic acid (or salt) can be simultaneously mixed and processed with the metal compound using a Werner & Pfleiderer twin screw extruder.

The blend may additionally include minor amounts of additives including plasticizers, stabilizers (including viscosity stabilizers, hydrolytic stabilizers), primary and secondary antioxidants, ultraviolet light absorbers, antistatic agents, dyes, pigments or other colorants, inorganic fillers, flame retardants, lubricants, reinforcing agents (glass fibers and glass flakes), synthetic (e.g., aramid) fibers or pulps, foaming or blowing agents, processing aids, slip additives, antiblocking agents (e.g., silica or talc), mold release agents, tackifying resins, or combinations of two or more thereof. Inorganic fillers such as calcium carbonate may also be incorporated into the blend.

These additives may be present in the blend in an amount in the range of 0.01 to 40 weight percent, 0.01 to 25 weight percent, 0.01 to 15 weight percent, 0.01 to 10 weight percent, or 0.01 to 5 weight percent. Incorporation of the additives can be carried out by any known method, such as, for example, by dry blending, by extruding a mixture of the various ingredients, by conventional masterbatch techniques, and the like.

In various embodiments, the resulting ionomer has a melt index I of about 0.1 to about 30.0 grams/10 minutes as determined according to ASTM D1238(220 ℃, 2.16kg)₂. In some embodiments, the resulting ionomer has a melt index I of about 0.1 to about 20.0 grams/10 minutes as determined according to ASTM D1238(220 ℃, 2.16kg)₂. Further, the ionomer has from about 0.920 to about 0.980g as determined according to ASTM D792Density of/cc.

Without being bound by theory, it is believed that the at least partially neutralized trivalent cation-containing ionomers, particularly aluminum-containing ionomers, result in greatly improved foam properties as compared to neutralized ionomers containing only monovalent and divalent metal cations. For example, foams comprising at least partially neutralized trivalent cation-containing ionomers exhibit improved dimensional stability and creep resistance at elevated temperatures while maintaining elasticity and foamability, as compared to neutralized ionomers containing only monovalent and divalent metal cations.

According to various embodiments, the ionomer may be used to form a foam or molded article. For example, in embodiments, the ionomer may be combined with additives for controlling foam properties to form foams of various shapes. In some embodiments, the foam may be extruded, for example, from a twin screw extruder, as known to one of ordinary skill in the art.

The blowing agent (also referred to as a blowing agent) used to make the foam may be a physical blowing agent or a chemical blowing agent. As used herein, a "physical blowing agent" is a low boiling liquid that volatilizes under curing conditions to form a blowing gas. Exemplary physical blowing agents include hydrocarbons, fluorocarbons, hydrofluorocarbons, hydrofluoroolefins, hydrochlorofluoroolefins, and other halogenated compounds. Other suitable chemical blowing agents may include, for example, sodium bicarbonate, ammonium bicarbonate, azodicarbonamide, dinitrosopentamethylenediamine, and sulfonyl hydrazide. Blowing agents added in gaseous or liquid form, such as water or carbon dioxide, or generated in situ by the reaction of water with the polyisocyanate may also be used. The blowing agent may be used in the form of a mixture of two or more, and chemical and physical blowing agents may be used together to adjust the expansion-decomposition temperature and the foaming process.

The foam composition may further include a free radical initiator or cross-linking agent, a co-curing agent, an activator, and any other type of additive typically used in similar compositions, including but not limited to pigments, adhesion promoters, fillers, nucleating agents, rubbers, stabilizers, and processing aids.

The free radical initiator or crosslinking agent may include, for example, but is not limited to, organic peroxides, such as dialkyl organic peroxides. Suitable example organic peroxides include 1, 1-di-tert-butylperoxy-3, 3, 5-trimethylcyclohexane, tert-butylcumyl peroxide, dicumyl peroxide, 2, 5-dimethyl-2, 5-di (tert-butyl-peroxy) hexane, 1, 3-bis (tert-butyl-peroxy-isopropyl) benzene, or a combination of two or more thereof.

The co-curing agent comprises trimethylpropane triacrylate (and similar compounds), N-m-phenylene bismaleimide (N, N-m-phenylene bismaleimide), triallyl cyanurate, or a combination of two or more thereof.

The activator may comprise an activator for the blowing agent and may comprise one or more metal oxides, metal salts or organometallic complexes. Examples include ZnO, zinc stearate, MgO, or a combination of two or more thereof.

Foams can be produced by a variety of methods, such as compression molding, injection molding, and a mixture of extrusion and molding. The method may include mixing the components of the foam composition under heat to form a melt. The components may be mixed and blended using any technique known and used in the art, including Banbury (Banbury) machines, intensive mixers, twin roll mills, and extruders. The time, temperature and shear rate can be adjusted to ensure dispersion without premature crosslinking or foaming.

After mixing, shaping can be performed. Sheeting rolls or calendering rolls can be used to prepare the sheet in the appropriate size for foaming. An extruder may be used to shape the composition into pellets.

Foaming can be carried out in a compression mold at a temperature and time to complete decomposition of the peroxide and blowing agent. The pressure, molding temperature and heating time can be controlled. Foaming can be carried out using injection molding equipment by using pellets made from the foam composition. The resulting foam may be further shaped to the dimensions of the finished product by any means known and used in the art, including thermoforming and compression molding.

In various embodiments, the resulting polymer foam composition may be substantially closed cell and suitable for use in a variety of articles of manufacture, such as footwear applications including midsoles or insoles.

Examples of the invention

The following examples are provided to illustrate various embodiments and are not intended to limit the scope of the claims. All parts and percentages are by weight unless otherwise indicated. The following provides approximate characteristics, features, parameters, and the like with respect to various working examples, comparative examples, and substances used in the working and comparative examples. Further, the description of the raw materials used in the examples is as follows:

example 1 ionomer ("ex.1") is an ethylene/15 wt% methacrylic acid copolymer partially neutralized with zinc cations, the ionomer having 0.97g/cm measured according to ASTM D792³And a melt index I of 0.7 g/10 min as determined according to ASTM D1238(190 ℃, 2.16kg)₂。

Example 2 ionomer ("ex.2") is a blend of 62 wt% ethylene acid copolymer and 38 wt% oleic acid. The ethylene acid copolymer is the polymerization product of an ethylene/6.2 wt% acrylic acid/28 wt% n-butyl acrylate terpolymer. The total acid units are neutralized with magnesium cations.

The ionomers of ex.1 and ex.2 can be prepared by standard neutralization techniques, as disclosed in U.S. patent No. 3.264.272 (Rees), which is incorporated herein by reference. The ethylene acid copolymers, first ethylene acid copolymers, and second ethylene acid copolymers of the present disclosure can be prepared by standard free radical copolymerization methods, using high pressure, operating in a continuous manner. The monomers are fed to the reaction mixture in a ratio which is related to the reactivity of the monomers and the desired incorporation. In this way, a uniform, nearly random distribution of the monomer units along the chain is achieved. Polymerizations conducted in this manner are well known and are described in U.S. patent No. 4.351.931 (Armitage), which is incorporated herein by reference. Other polymerization techniques are described in U.S. Pat. No. 5,028,674 (Hatch et al) and U.S. Pat. No. 5,057,593 (Statz), which are also incorporated herein by reference.

Example 1

Table 1 below lists comparative samples a-K, which are eleven example examples of formulations including ex.1. The amounts reported in table 1 represent the actual amount of metal (Zn, Al) salt mixed with ex.1 and the corresponding additional degree of neutralization for each ionomer.

TABLE 1

Comparative samples A-K were prepared by compounding Ex.1 using a 26mm twin screw extruder. Barrel temperature was set at about 230-. The components were pre-mixed in a polyethylene bag by tumbling the mixing ingredients and then fed into a twin screw extruder. For comparative samples G-K, by Al in the table³⁺The calculated values for the additional percent neutralization achieved assume that all aluminum ions form trivalent salts with the ionomer carboxylic acid groups. For comparative samples B-F, Ex.1 was mixed with zinc acetylacetonate in Al³⁺The same neutralization level was mixed down for comparison and the possibility of characteristic changes that could result from different neutralization levels was excluded.

Table 2 lists the comparative samples A-K at high (2000 seconds)^-1) And low (10 seconds)^-1) Shear rate and melt viscosity measured at 220 ℃. Viscosity data were obtained using a Kayeness capillary rheometer. The cylindrical capillary die size was 30mm long and 1mm in diameter (L/D ═ 30). A pre-heat residence time of 5 minutes was used before the viscosity test was started. With Al at both lower and higher shear rates³⁺Viscosity (comparative samples G-K) ratio of neutralized comparative samples Zn²⁺The neutralized comparative sample had a much greater increase in viscosity. Without being bound by theory, it is believed that the increase in viscosity is a result of the formation of trivalent bonds.

TABLE 2

Example 2

Next, samples 1-7 were prepared by mixing ex.2 with aluminum acetylacetonate according to the method described above. Comparative sample L was ex.2 and no additional neutralization was performed. The amounts reported in table 3 represent the additional degree of neutralization of each ionomer when mixed with ex.2 and the actual amount of aluminum acetylacetonate.

TABLE 3

At a higher level (3000 seconds)^-1) And lower (10 seconds)^-1) The melt viscosities of comparative sample L and samples 2, 4 and 5 were measured at shear rate. The results are reported in table 4.

TABLE 4

As shown in Table 4, at both lower and higher shear rates, with Al³⁺The viscosity of the neutralized samples (samples 2-5) increased over that of the comparative sample L. In particular, the viscosity of the ionomer increased rapidly and significantly, indicating successful incorporation of Al³⁺A trivalent bond is formed.

The creep resistance of comparative sample L and samples 1-5 was measured by measuring the dimensional change (vertical) of a compression molded film (10 mils) attached to a static load in a heated oven. The load was 30g and the dimensional change was measured as the oven temperature increased by 10 ℃ every 30 minutes. If the film elongates to the point where it touches the bottom of the oven (i.e., 1200% dimensional change), then the test fails. The test results are reported in fig. 1.

Creep resistance was also measured for comparative sample L and samples 1-7 using a load of 100 g. The dimensional change was measured and the results are reported in figure 2.

As shown in fig. 1 and 2, including Al as compared to comparative sample L³⁺Cationic samples 1-7 exhibited much less dimensional change and the onset creep temperature was also much higher. Thus, Al is doped³⁺The cations improve the resistance to thermal creep.

Example 3

The creep resistance of comparative sample L and samples 6 and 7 at constant temperature were then measured. The test results at 50 ℃, 400g static load, 24 hours and 96 hours at 600kPa, the test results at 60 ℃, 400g static load, 24 hours and 48 hours at 600kPa, and the test results at 1 hour, 2 hours, 3 hours, 4 hours and 24 hours at 50 ℃, 1000g static load, 1500kPa are presented in table 5.

TABLE 5

As shown in Table 5, Al is included as compared with comparative sample L³⁺The cationic samples exhibited much smaller dimensional changes and could be modified by increasing Al³⁺The addition of (b) further improves creep resistance.

It is also noted that terms like "generally," "commonly," and "typically" are not utilized herein to limit the scope of the claimed invention or to imply that certain features are critical, essential, or even important to the structure or function of the claimed invention. Rather, these terms are merely intended to highlight alternative or additional features that may or may not be utilized in a particular embodiment of the present disclosure.