Articles made from elastomeric polymer compositions

Abstract

A profile or article formed from a moisture-curable and / or thermosetting elastomeric polymer composition comprising: (A) at least one ethylene-olefin monomer-silane polymer having a melt index of 0.1 grams / 10 minutes to 10.0 grams / 10 minutes and a melting enthalpy of less than 85 J / g; and (B) at least one silanol condensation catalyst; molded articles made from said elastomeric polymer composition; and a method of making molded articles using said elastomeric polymer composition.

Description

[Technical field]

[0001] The present invention relates to articles or profiles comprising elastomeric polymer compositions, more particularly, the present invention relates to articles or profiles comprising moisture curable and / or thermosetting elastomeric polymer compositions useful for making automotive articles and parts such as automotive weather seals and automotive hoses. [Background technology]

[0002] Flexible ethylene propylene diene monomer (EPDM) rubber is used, for example, to manufacture automotive weatherstrips and coolant hoses. Automotive weatherstrips or weatherseals are typically attached to the automobile door along the periphery of the door and to the automobile body to provide a seal between the automobile door and the automobile body when they contact each other. Functions of automotive weatherseals include, but are not limited to, reducing wind noise, providing an air and water seal, and preventing dust and foreign objects from entering the automobile.

[0003] Typically, automotive weather seals are made with fully vulcanized EPDM profiles or extruded thermoplastic vulcanizate (TPV) profiles. Although TPV is a solution with a relatively low manufacturing cost, the performance of TPV is limited due to the high hardness characteristics of TPV and poor long-term dynamic sealing properties. Although vulcanized EPDM parts provide good static and dynamic sealing performance, vulcanized EPDM parts often suffer from, for example, (1) surface discoloration after aging, which is recognized as poor UV weather resistance, (2) poor long-term compression set, which results in poor long-term NVH (Noise, Vibration, Harshness) properties, and (3) poor automobile interior noise reduction performance. The manufacturing process and costs associated with the production of EPDM weather seals are typically complex and expensive due to, for example, (1) batch mixing of the composite compound of the composition, (2) extrusion of the composition, and (3) the long time required for several curing steps to cure the composition.

[0004] Automotive coolant hoses are used to transport aqueous coolants containing corrosion inhibitors under pressure conditions at continuous temperatures ranging from -40℃ to 150℃. One-third of the heat energy generated by an internal combustion engine ends up as waste heat in the cooling system. Therefore, EPDM coolant hoses (e.g., upper radiator hose, lower radiator hose, and heater hose) are the most important components in the entire engine cooling system of an automobile. Long-term high temperature resistance is considered to be the most important property for automotive coolant EPDM hoses. EPDM rubber hose formulations usually contain reinforcing fillers, extending fillers, process oils, stabilizers, curing agents, and other additives, and mixing the above ingredients with EPDM rubber is a critical step in the overall EPDM hose manufacturing process, as a uniform and well-mixed compound is required for consistent rubber compound properties.

[0005] Thermoset EPDM rubber coolant hoses for automotive thermal management systems have also undergone dramatic changes over the past decade. Compact and sophisticated engine designs for internal combustion engine (ICE) vehicles have resulted in increased temperature environments and durability requirements for automotive components under the hood compartment (e.g., under-hood coolant hoses, as well as wire and cable components). Improving the continued high temperature resistance of thermoset rubber is a challenging task due to the more stringent design criteria required to meet the increased high temperature environment and durability requirements of ICE. Industrial applications are following similar trends with higher service temperatures and longer service lives for rubber articles. As a result, many automotive and industrial applications now require rubber formulations with high temperature performance and long-term heat and weather resistance.

[0006] In addition, technology development trends in the automotive industry are constantly focused on next generation automotive sealing systems and thermal management systems that provide, for example, (1) lower part density or weight, (2) lower electrical conductivity, (3) lower volatile organic compound (VOC) levels to reduce fogging, and (4) better long-term heat and weather resistance.

[0007] US Patent No. 10040888(B1) refers to a weatherseal formulation containing silane-grafted polyolefin, which is different from the conventional weatherseal formulations containing EPDM or TPV. The manufacturing method of the weatherseal composition of the patent includes reactive extrusion, extrusion, molding, and curing. The advantages of the proposed composition containing silane-grafted polyolefin of the patent include: (1) the formulation of the patent uses fewer ingredients and is easy to compound all ingredients in a simple extrusion step without using complicated conventional rubber internal mixing equipment; (2) the formulation of the patent shows superior stress / strain behavior compared to conventional EPDM materials; (3) the formulation of the patent reduces the carbon footprint of the extrusion plant by eliminating the vulcanization process (e.g., the process using hot air / microwave oven or autoclave); and (4) The formulations of the above patents containing silane-grafted and crosslinked polyolefins have lower specific gravities compared to TPV and EPDM formulations. The production of parts using the above patented formulations having reduced specific gravities results in the ability to produce lighter weight parts compared to parts made from conventional formulations, thereby helping automobile manufacturers meet the increasing demand for automobiles with improved fuel economy.

[0008] US Patent No. 10253127(B2) refers to a weatherstrip composition comprising a silane-grafted polyolefin, which is different from conventional weatherstrip formulations containing EPDM or TPV. The composition of the patent also comprises a silane-grafted polyolefin and one or more additives, such as polypropylene (PP), TPV, olefin block copolymer (OBC), EPDM, ethyl vinyl acetate (EVA), ethylene-butyl acrylate (EBAC) copolymer, and ethylene methacrylate (EMA) copolymer. The patent also refers to the manufacturing process of the patent comprising reactive extrusion, extrusion, molding, and curing.

[0009] US Patent No. 10774168(B2) refers to a windshield wiper formulation containing a silane-grafted polyolefin, which is different from conventional weatherstrip formulations containing EPDM or TPV. The composition of the patent includes a silane-grafted polyolefin and one or more additives (e.g., PP, TPV, OBC, EPDM, EVA, EBAC copolymer, and EMA copolymer). The manufacturing method mentioned in the patent involves reactive extrusion, extrusion, molding, and curing.

[0010] US Patent No. 10100139(B2) refers to a hose composition containing silane-grafted polyolefin; and a manufacturing process involving reactive extrusion, extrusion, molding, and curing.

[0011] US Patent No. 6,624,254 (B1) refers to silane-functionalized olefin interpolymer derivatives. In the above patent, the silane-functional polymer has uniform silane distribution, long chain branching and / or tertiary silane functional groups. The conversion methods disclosed in the above patent are carried out by coupling, hydrolysis, hydrolysis and neutralization, condensation, oxidation or hydrosilylation.

[0012] US Patent No. 6,667,098 (B1) refers to a moisture-curable ethylene-alkyl(meth)acrylate vinyltrialkoxysilane terpolymer composition used to produce insulation and coating layers for electrical rubber cables. The alkyl(meth)acrylate comonomer constitutes more than 5 mole % in the terpolymer composition, and the trialkoxysilane termonomer constitutes 0.2% to 5% by weight of the terpolymer composition. The total polymer composition disclosed in the above patent for producing insulation and coating layers can contain 0% to up to 50% by weight of plasticizer, up to 60% by weight of filler, and up to 10% by weight of another additive.

[0013] The above prior art documents are silent about elastomeric polymer compositions that are particularly moisture curable and more specifically useful for making automotive articles and parts such as automotive hoses and automotive weather seals. Also, automotive original equipment manufacturers (OEMs) are keen to find better alternative solutions and replacements for the various elastomeric products currently in use, such as EPDM and TPV.

[0014] Therefore, it would be desirable to provide elastomeric polymer compositions for use in automotive applications, for example, by automotive OEMs in the automotive industry; and for use in wire and cable applications. Summary of the Invention

[0015] In one embodiment, the present invention relates to a profile or article comprising a moisture curable elastomeric polymer composition and / or a thermosetting elastomeric polymer composition, (A) at least one ethylene-olefin monomer-silane polymer, such as a terpolymer or tetrapolymer, having a melt index of 0.1 grams / 10 minutes to 10.0 grams / 10 minutes and a melt enthalpy of less than 85 J / g; (B) at least one cure catalyst that promotes moisture cure and / or thermal cure of the elastomeric polymer composition; and The present invention relates to a profile or article comprising a mixture, admixture or blend of

[0016] In one embodiment, at least one ethylene-olefin monomer-silane polymer, component (A) of the moisture and / or heat curable elastomeric polymer composition described above, includes, for example, an ethylene-ethyl acrylate-silane terpolymer or tetrapolymer.

[0017] In another embodiment, the at least one curing catalyst, component (B) of the above moisture and / or heat curable elastomeric polymer composition, includes, for example, at least one silanol condensation catalyst.

[0018] In another embodiment, the present invention relates to a method for preparing a profile or article comprising the moisture and / or heat curable elastomeric polymer composition described above.

[0019] The moisture and / or heat curable elastomeric polymer compositions are useful in a variety of applications, more particularly in automotive applications. For example, in other embodiments, the moisture and / or heat curable elastomeric polymer compositions include weather seal, hose, belt, or profile compositions.

[0020] In yet another embodiment, the present invention provides a method for producing a weatherseal, hose, belt, or profile product, comprising the steps of: (I) providing (A) at least one ethylene-olefin monomer-silane polymer and (B) at least one cure catalyst that promotes moisture cure and / or thermal cure of the elastomeric polymer; (II) mixing or blending (A) the at least one ethylene-olefin monomer-silane polymer from step (I) with (B) at least one cure catalyst that promotes moisture curing and / or thermal curing of the elastomeric polymer composition to form a moisture curable and / or thermally curable elastomeric polymer composition; (III) extruding the elastomeric polymer composition from step (II); (IV) forming the extruded elastomeric polymer composition from step (III) into the shape of a final (finished) part or article; (V) exposing the final part or article from step (IV) to moisture and / or heat to cure the final part or article from step (IV).

[0021] In some embodiments, the mixing or compounding step (II) of the method is carried out using conventional mixing or compounding equipment, such as a roll mill, an internal mixer, a single screw extruder, or a twin screw compounding extruder. In other embodiments, in step (II) of the process, the moisture and / or heat curable elastomeric polymer composition component (A) of the at least one ethylene-olefin monomer-silane polymer includes, for example, an ethylene-ethyl acrylate-silane terpolymer or tetrapolymer. In yet other embodiments, in step (II) of the method, the moisture and / or heat curable elastomeric polymer composition component (B) of the curing catalyst includes, for example, at least one silanol condensation catalyst.

[0022] In step (IV) of the above process, the ethylene-ethyl acrylate-silane terpolymer or tetrapolymer and silanol condensation catalyst composition is formed into the shape of a final part or article, such as a weatherseal, hose, belt, profiled article, and the like.

[0023] In another preferred embodiment, the article is a weatherseal, a hose, a belt, or a profile article manufactured by the above process.

[0024] The present invention develops a technical solution for various crosslinked / thermo-cured automotive parts without the need for a conventional sulfur or peroxide curing step. The fully formulated compound exhibits the required compound hardness and can be fully vulcanized, for example, by a moisture curing process. Thus, significant manufacturing cost reductions can be achieved compared to conventional sulfur and peroxide cured EPDM systems. In essence, the moisture cured crosslinked network that forms the profile or article of the present invention imparts excellent color stability, long-term high temperature resistance, long-term weatherability, and long-term sealing performance to the profile or article. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0025] Temperatures used herein are in degrees Celsius (°C).

[0026] As used herein, "room temperature (RT)" means a temperature between 20° C. and 26° C., unless otherwise specified.

[0027] By "ambient temperature" herein is meant the temperature of the environment that exists without the application of a heating or cooling system, particularly for the purpose of promoting moisture bridging. In a broad embodiment, the ambient temperature contemplated in the present disclosure may be, for example, 0°C to 50°C.

[0028] As used herein, "ambient humidity" refers to the humidity of the environment that exists without the application of techniques specifically for the purpose of promoting moisture bridging. In a broad embodiment, the ambient humidity contemplated in the present disclosure may be, for example, 5% to 100%.

[0029] The phrase "ambient conditions" refers to the temperature and humidity of the environment that exists without the application of techniques for heating, cooling, or providing humidity, particularly for the purpose of promoting moisture bridging. The term "ambient conditions" in one embodiment is an air atmosphere having a temperature between 0°C and 50°C and a relative humidity between 5% and 100%.

[0030] By "vulcanization" herein is meant the formation of a three-dimensional crosslinked (cured) network.

[0031] As used herein, the term "composition" refers to a mixture of materials that comprise the composition, as well as reaction products and decomposition products formed from the materials of the composition.

[0032] By "elastomer" or "elastomeric material" or "elastomeric polymer" herein is meant a polymer that has elastic properties and is capable of recovering its original shape after being stretched significantly.

[0033] The phrase "moisture curable elastomeric polymer composition" as used herein refers to an elastomeric polymer composition that can be chemically crosslinked by reaction with water, where alkoxysilanes react with water in a hydrolysis step to form silanols. Condensation of adjacent silanol groups in the elastomeric polymer composition forms siloxane bonds, resulting in a three-dimensionally crosslinked network.

[0034] A "terpolymer" is a polymer (such as a composite resin) that results from the copolymerization of three distinct monomers (or comonomers).

[0035] A "tetrapolymer" is a polymer (such as a composite resin) that results from the copolymerization of four separate monomers (or comonomers).

[0036] A "condensation catalyst" is a catalyst that promotes alkoxysilane hydrolysis reactions and / or silanol condensation reactions to form siloxane crosslinks.

[0037] In this specification, "long-term" with respect to properties such as "long-term heat resistance," "long-term weather resistance," "long-term dynamic sealability," "long-term compression set characteristics," and "long-term NVH (Noise, Vibration and Harshness) characteristics" means longer than one month.

[0038] The terms "comprising," "including," "having," and their derivatives are not intended to exclude the presence of any additional components, steps, or procedures, whether or not they are specifically disclosed. For the avoidance of doubt, all compositions claimed through the use of the term "comprising" may include any additional additives, adjuvants, or compounds, whether polymeric or not, unless stated to the contrary. In contrast, the term "consisting essentially of" excludes from the scope of any preceding description any other component, step, or procedure, except those that are not essential to operability. The term "consisting of" excludes any component, step, or procedure not specifically delineated or listed. The term "or" refers to the listed members individually and in any combination, unless otherwise stated. The use of the singular includes the use of the plural, and vice versa.

[0039] Numerical ranges disclosed herein include all values ​​between the lower limit and the upper limit (inclusive). In the case of ranges containing explicit values ​​(e.g., ranges 1, or 2, or 3-5, or 6, or 7), any subranges between any two explicit values ​​are included (e.g., the range 1-7 above includes the subranges 1-2, 2-6, 5-7, 3-7, 5-6, etc.).

[0040] As used throughout this specification, the following abbreviations have the following meanings unless the context clearly dictates otherwise: "=" means "equal to" or "equal to", "<" means "less than", ">" means "greater than", "≦" means "less than or equal to", "≧" means "greater than or equal to", "@" means "at", "and / or" means including the term "and" or the term "or", ppm = parts per million, ppb = parts per billion, ppt = parts per trillion, "BV / hr" = bed volume per hour, "MT" = metric ton, g = grams, mg = milligram, Kg = kilogram, J / g = joules per gram, L = liter, g / L = grams per liter, μL = microliter, g / cm 3 " or "g / cc" = grams per cubic centimeter, g / 10min = grams per 10 minutes, mg / mL = milligrams per milliliter, "kg / m 3 = kilograms per cubic meter, ppm = parts per million by weight, pbw = parts by weight, rpm = revolutions per minute, m = meters, mm = millimeters, cm = centimeters, μm = microns or micrometers, nm = nanometers, min = minutes, s = seconds, ms = milliseconds, hr = hours, Pa = pascals, MPa = megapascals, Pa s = pascal seconds, mPa s = millipascal seconds, g / mol = grams per mole, g / eq = grams per equivalent, M n = number average molecular weight, M w = weight average molecular weight, pts = parts by weight, 1 / s or seconds -1 = reciprocal of seconds [s -1 ], °C = degrees Celsius, °C / min = degrees Celsius per minute, psi = pounds per square inch, kPa = kilopascals, % = percent, vol% = volume percent, mol% = mole percent, and wt% = weight percent.

[0041] Specific embodiments of the present invention are described herein below. These embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the inventive subject matter to those skilled in the art.

[0042] Unless otherwise stated, implied from the context, or customary in the art, all percentages, parts, ratios, and similar amounts are by weight, all temperatures are in degrees Celsius, and all test methods are current as of the filing date of this disclosure.

[0043] Generally, the elastomeric polymer compositions described in this disclosure are useful for preparing, for example, automotive parts / articles / profiles, and the elastomeric polymer compositions useful in the present invention include (A) at least one ethylene-olefin monomer-silane polymer, and (B) at least one curing catalyst. Other optional additives or agents, or compounds, optional component (C), can be added to the elastomeric polymer composition, if desired.

[0044] In some embodiments, the ethylene-olefin monomer-silane polymer, component (A), may include a terpolymer. Alternatively, in other embodiments, component (A) may include a tetrapolymer. In some embodiments, component (A) is selected from one or more tetrapolymers, such as ethylene-alkyl(meth)acrylate-silane, ethylene-glycidyl(meth)acrylate-silane, ethylenemaleic anhydride-alkyl(methacrylate)silane, ethylene-glycidyl(meth)acrylate alkyl(meth)acrylate silane, ethylene vinyl acetate-silane, ethylene-alkyl(meth)acrylate-vinyl acetate-silane, ethylene carbon monoxide-silane, ethylene alkyl(meth)acrylate carbon monoxide-silane, and mixtures thereof. In a preferred embodiment, component (A) is a terpolymer, such as an ethylene-olefin monomer-silane terpolymer.

[0045] In one embodiment, the at least one ethylene-olefin monomer-silane terpolymer, component (A), can be an ethylene-alkyl(meth)acrylate-silane terpolymer. The olefin monomer component of the terpolymer can be an alkyl(meth)acrylate monomer, which can be represented by the general formula CH2:C(R1)CO2(R2). In the above general formula, R1 is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, which may have a branch, a ring, and / or an unsaturated bond. R2 is a hydrocarbon group having 1 to 30 carbon atoms, which may have a branch, a ring, and / or an unsaturated bond. If the carbon number of R1 is more than 11, the polymerization activity tends to be suppressed. Therefore, R1 is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, and in a preferred embodiment, the alkyl(methacrylate) monomer component can be, for example, a (meth)acrylate in which R1 is hydrogen or a hydrocarbon group having 1 to 5 carbon atoms. In another preferred embodiment, the alkyl (meth)acrylate may be a (meth)acrylate in which R1 is a methyl group, or an acrylate in which R1 is hydrogen. Similarly, when the carbon number of R2 is more than 30, the polymerization activity tends to be suppressed. Therefore, the carbon number of R2 is 1 to 30 in a broad embodiment, 1 to 12 in another embodiment, and 1 to 8 in still another embodiment.

[0046] Alkyl (meth)acrylate monomers useful in the ethylene-olefin monomer-silane terpolymers for preparing elastomeric polymer compositions include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, phenyl (meth)acrylate, toluoyl (meth)acrylate, benzyl (meth)acrylate, and mixtures thereof. Useful additional comonomers include heteroatom-containing olefin monomers, including vinyl acetate, maleic anhydride, glycidyl (meth)acrylate, carbon monoxide, hydroxyethyl (meth)acrylate, 1-aminopropyl (meth)acrylate, 2-aminopropyl (meth)acrylate, 3-aminopropyl (meth)acrylate, and mixtures thereof.

[0047] Examples of the ethylene-alkyl(meth)acrylate-silane terpolymer, component (A), include ethylene-ethyl(meth)acrylate-silane terpolymer, ethylene-methylacrylate-silane terpolymer, ethylene-ethylacrylate-silane terpolymer, ethylene-propylacrylate-silane terpolymer, ethylene-butylacrylate-silane terpolymer, and mixtures thereof.

[0048] In one preferred embodiment, component (A) of the elastomeric polymer composition comprises, consists essentially of, or consists of ethylene-methyl(meth)acrylate-silane terpolymer, ethylene-ethylacrylate-silane terpolymer, ethylene-butylacrylate-silane terpolymer, and mixtures thereof.

[0049] In other embodiments, the olefin monomer component (component (A)) of the at least one ethylene-olefin monomer-silane terpolymer useful in the present invention may be, for example, an ethylene-methyl acrylate silane terpolymer, an ethylene-ethyl acrylate silane terpolymer, an ethylene-propyl acrylate silane terpolymer, an ethylene-n-butyl acrylate silane terpolymer, an ethylene-i-butyl acrylate silane terpolymer, an ethylene-2-ethylhexyl acrylate silane terpolymer, an ethylene-isobornyl acrylate silane terpolymer, an ethylene-pentyl acrylate-silane terpolymer, an ethylene-hexyl acrylate-silane terpolymer. , ethylene-octyl acrylate silane terpolymer, ethylene-methyl methacrylate silane terpolymer, ethylene-ethyl methacrylate silane terpolymer, ethylene-propyl methacrylate silane terpolymer, ethylene-n-butyl methacrylate silane terpolymer, ethylene-i-butyl methacrylate silane terpolymer, ethylene-2-ethylhexyl methacrylate silane terpolymer, ethylene-isobornyl methacrylate silane terpolymer, ethylene-pentyl methacrylate-silane terpolymer, ethylene-hexyl methacrylate-silane terpolymer or ethylene-octyl methacrylate silane terpolymer and mixtures thereof. In some preferred embodiments, the monomers include, for example, methyl acrylate, ethyl acrylate, n-butyl acrylate, i-butyl acrylate, 2-ethylhexyl acrylate, and mixtures thereof.

[0050] In some embodiments, when component (A) of the elastomeric polymer composition is at least one ethylene-alkyl (meth)acrylate-silane terpolymer and the olefin monomer portion of the terpolymer is ethyl (meth)acrylate, the olefin monomer portion content of the terpolymer, i.e., the ethyl (meth)acrylate content, can be from 1% to 50% by weight in one broad embodiment, from 5% to 40% by weight in another embodiment, and from 10% to 30% by weight in yet another embodiment. The ethyl (meth)acrylate content of the terpolymer can be determined by proton nuclear magnetic resonance spectroscopy ( 1 H NMR) can be used to determine the molecular weight of ethyl (meth)acrylate. 1 It can be determined by 1 H NMR spectroscopy or other analytical techniques known to those skilled in the art, such as those described in Analytical Chemistry, Vol. 35, No. 12, pages 1948-1950, 1963.

[0051] In some embodiments, the ethylene-olefin monomer-silane terpolymer may have a silane moiety content of 0.1 wt % to 2.5 wt % in one broad embodiment, 0.5 wt % to 2.0 wt % in another embodiment, and 0.8 wt % to 1.5 wt % in yet another embodiment. The silane content of the terpolymer may be determined by nuclear magnetic resonance (NMR) or neutron activation analysis (NAA).

[0052] In some embodiments, the ethylene-olefin monomer-silane terpolymer of the elastomeric polymer composition used in the present invention, component (A), has a melt index of 0.1 g / 10 min to 10.0 g / 10 min in one broad embodiment, 0.5 g / 10 min to 5 g / 10 min in another embodiment, and 1.0 g / 10 min to 2.5 g / 10 min in yet another embodiment. The melt index (MI) of the terpolymer can be determined as described in ASTM D1238. The MI measurement of the ethylene-olefin monomer-silane polymer used in the present invention provides an indication of the processability and physical properties of the compound, and in one broad preferred embodiment, the melt index of the terpolymer is in the range of 0.1 g / 10 min to 10.0 g / 10 min.

[0053] In some embodiments, the ethylene-olefin monomer-silane terpolymer of the elastomeric polymer composition used in the present invention, component (A), has a melting enthalpy of less than 85 J / g in one broad embodiment, from 0.1 J / g to 70 J / g in another embodiment, from 1.0 J / g to 60 J / g in yet another embodiment, and from 1.0 J / g to 50 J / g in yet another embodiment. The melting enthalpy of the terpolymer can be determined by the method described in ASTM D3418. The melting enthalpy measurement of the ethylene-olefin monomer-silane polymer used in the present invention provides a measure of the crystallinity of the polymer. Maintaining the melting enthalpy range of the terpolymer below 85 J / g ensures that the polymer has a sufficiently low crystallinity, which in turn provides a sufficiently low compression set for the desired sealing performance of the polymer.

[0054] In one broad embodiment, the concentration of the ethylene-olefin monomer-silane terpolymer, component (A), useful in preparing the elastomeric polymer composition, can range from 20% to 99% by weight, from 35% to 95% by weight in another embodiment, and from 50% to 90% by weight in yet another embodiment, based on the total weight of all components in the composition.

[0055] Component (B) of the elastomeric polymer composition is at least one curing catalyst that promotes moisture curing and / or thermal curing of the elastomeric polymer composition. For example, the catalyst can be selected from acids such as Lewis acids, Bronsted acids, and mixtures thereof. Bases may also be used as catalysts. In a preferred embodiment, component (B) can include, for example, dibutyltin dilaurate, sulfonic acids, and mixtures thereof. Examples of Lewis acids that can be used in the practice of the present invention include, but are not limited to, dibutyltin dilaurate, dimethylhydroxytin oleate, dioctyltin maleate, di-n-butyltin maleate, dibutyltin diacetate, dibutyltin dioctoate, stannous carboxylates such as stannous acetate, stannous octoate, and various other organometallic compounds such as various titanates, lead naphthenate, zinc caprylate, and cobalt naphthenate, and mixtures thereof.

[0056] Examples of suitable Bronsted acid catalysts useful in the present invention include, but are not limited to, monosulfonic acids and disulfonic acids; and mixtures thereof. Sulfonic acids are organic acids having one or more sulfonic acid (i.e., -SO3) groups and the general formula RS(=O)2-OH, where R is an organic alkyl or aryl or substituted aryl group, and the S(=O)2-OH group is a sulfonyl hydroxide. Sulfonic acids may be aliphatic or aromatic and may have significantly different melting points. Examples of aromatic sulfonic acids are benzenesulfonic acid, alkylbenzenesulfonic acid, alkylethylbenzenesulfonic acid, alkyltoluenesulfonic acid, dodecylbenzenesulfonic acid, 4-methylbenzenesulfonic acid (also known as p-toluenesulfonic acid), alkylxylenesulfonic acid, naphthalenesulfonic acid, alkylnaphthalenesulfonic acid, and blocked sulfonic acids; and mixtures thereof. Sulfonic acids include, for example, the silanol condensation catalysts disclosed in US Pat. No. 8,460,770 (B2).

[0057] In other embodiments, the silanol condensation catalyst can be a blocked sulfonic acid. The blocked sulfonic acid can be amine blocked (which is an ionic, charged species) or covalently blocked (through reaction with an alcohol, epoxy, or functional polymer). The blocked sulfonic acid dissociates at high temperatures by hydrolysis, alcoholysis, or decomposition reactions to produce the free acid. Further information on blocked sulfonic acids is provided in "Coatings Materials and Surface Coatings" (CRC Press, Nov. 7, 2006; edited by Arthur A. Tracton) and "Handbook of Coating Additives" (CRC Press, May 26, 2004; edited by John J. Florio, Daniel J. Miller). The NACURE™ materials (all King Industries products) disclosed in US Patent Application Publication No. 2011 / 0171570 are examples of blocked sulfonic acids with various dissociation temperatures. Examples of commercially available blocked sulfonic acids include NACURE™ 1419 (a King Industries product), which is a 30% solution of covalently blocked dinonylnaphthalene sulfonic acid in xylene / 4-methyl-2-pentanone, and NACURE™ 5414 (a King Industries product), which is a 25% solution of covalently blocked dodecylbenzene sulfonic acid in xylene.

[0058] In various embodiments of the present invention, a combination of two or more acidic silanol condensation catalysts may be employed. In one or more embodiments, the acidic silanol condensation catalyst may be selected from the group consisting of alkylaromatic sulfonic acids, hydrolyzable precursors of alkylaromatic sulfonic acids, organic phosphonic acids, hydrolyzable precursors of organic phosphonic acids, halogen acids, and mixtures of two or more thereof. In other embodiments, the acidic silanol condensation catalyst comprises an alkylaromatic sulfonic acid. Examples of commercially available alkylaromatic sulfonic acids include NACURE™ CD-2180 and NACURE™ B201 (available from King Industries, Norwalk, CT, USA), and ARISTONIC™ Acid 9900 (available from Pilot Chemical Company, Cincinnati, OH, USA). In another preferred embodiment, component (B) of the elastomeric polymer composition useful in the present invention comprises, consists essentially of, or consists of, for example, a dibutyltin dilaurate masterbatch, or a sulfonic acid masterbatch and mixtures thereof.

[0059] The concentration of the cure catalyst, component (B), useful in preparing the elastomeric polymer composition can be from 0.1% to 10% by weight in one broad embodiment, from 0.25% to 5% by weight in another embodiment, and from 0.5% to 2.5% by weight in yet another embodiment, based on the total weight of all components in the composition.

[0060] The combination of components (A) and (B) that form the resulting elastomeric polymer composition useful in the present invention provides an elastomeric polymer composition that can be cured using moisture and / or using heat. Without being limited to any one particular theory, the silane functional groups of the elastomeric polymer composition useful for producing the profiles or articles of the present invention are cured using moisture and / or using heat.

[0061] Optionally, the elastomeric polymer composition may be formulated with a wide variety of additives to perform specific functions while maintaining the superior benefits / properties of the elastomeric polymer composition. For example, the optional additives useful in the elastomeric polymer composition, component (C), may be selected from the group consisting of colorants, carbon black, inorganic fillers, processing oils, flame retardants, blowing agents, processing aids, antioxidants, UV light stabilizers, scorch retarding additives, and mixtures thereof.

[0062] In other embodiments, the optional additives added to the elastomeric polymer composition may include one or more polymeric components of polypropylene, polyethylene, thermoplastic vulcanizates, ethylene propylene diene monomer, ethyl vinyl acetate, and mixtures thereof.

[0063] The optional compounds, when used in making the elastomeric polymer composition, can be present in an amount ranging from about 0% to 50% by weight in one embodiment, from 0.01% to 40% by weight in another embodiment, and from 0.1% to 30% by weight in yet another embodiment.

[0064] In another broad embodiment, a method for making a profile or article using a moisture curable and / or heat curable elastomeric polymer composition or formulation includes mixing, admixing, or blending (A) at least one ethylene-olefin monomer-silane polymer having (i) an olefin monomer content of 1 wt.% to 50 wt.%, (ii) a silane content of 0.1 wt.% to 2.5 wt.%, and (iii) a melt index of 0.1 g / 10 min to 10.0 g / 10 min, and (B) at least one silanol condensation catalyst. Optionally, one or more additional optional components, component (C), may be added to the elastomeric polymer composition. Optionally, optional additive component (C) may be mixed with either one of components (A) and (B) or with both components (A) and (B). The order of mixing the components is not important, and two or more components may be mixed together before the remaining components are added. The ingredients of the formulation can be mixed together by any conventional mixing process and equipment known to those skilled in the art of mixing.

[0065] In another embodiment, a method for making a profile or article using a moisture curable or thermosetting elastomeric polymer composition comprises the steps of: (I) weighing the following components: (A) at least one ethylene-olefin monomer-silane polymer; and (B) a curing catalyst to provide appropriate amounts of components (A) and (B); (II) mixing or blending the components of step (I) to form a curable reactive mixture elastomeric polymer composition that can be cured by moisture or by heat / temperature; (III) forming the moisture curable and / or thermosetting elastomeric polymer composition resulting from step (II) into the shape of an uncured final part or article; (IV) curing the shaped, uncured final part or article from step (III) by exposing the formed / uncured part or article to moisture and / or heat to form a cured final part or article.

[0066] In some embodiments, the at least one ethylene-olefin monomer-silane polymer, component (A), useful in the above process has an olefin monomer content of from 5% to 50% by weight and a silane content of from 0.1% to 2.5% by weight, the at least one ethylene-olefin monomer-silane polymer having a melt index of from 0.1 g / 10 min to 10.0 g / 10 min.

[0067] In some embodiments, the curing catalyst, component (B), useful in the above process, can be at least one silanol condensation catalyst to form the reactive mixture elastomeric polymer composition.

[0068] The moisture-curable and / or thermosetting elastomeric polymer compositions produced by the above-mentioned methods have several advantageous properties and / or benefits compared to known elastomeric polymer compositions. For example, some of the properties / benefits exhibited by the elastomeric polymer compositions useful for making the profiles or articles of the present invention include, for example: (1) the elastomeric polymer compositions can be cured by moisture at ambient conditions or at elevated temperatures in a moisture-controlled environment such as a hot water bath or sauna, (2) the moisture-cured elastomeric polymer compositions have a much lower density relative to EPDM compounds, and (3) the moisture-cured elastomeric polymer compositions have better long-term heat resistance, better weatherability, better compression set, and improved NVH than conventional elastomeric polymer compositions.

[0069] The elastomeric polymer compositions useful in the present invention can be used, for example, in automotive applications to manufacture various automotive profiles, parts or articles including, for example, weather seals, flexible hoses (e.g., fabric reinforced hoses), coextruded multi-layer tubes, belts, or profile products.

[0070] Automotive weather seals generally consist of low density sponge profiles co-extruded onto high density profiles with metal carriers for attachment to doors and car bodies. These automotive weather seals (door-mounted seals and body-mounted seals) contribute to the comfort inside the car by providing insulation from water, vibration, and aerodynamic noise. To improve the overall sealing performance, the geometry of the sponge profiles has become more and more complex over the years. A typical manufacturing process for automotive weather seals includes the following steps: formulation and mixing, profile extrusion, curing and foaming, surface coating if necessary, cutting and forming, connecting the final assembly, followed by finishing, packaging and shipping.

[0071] A typical construction of a flexible hose consists of an inner tube layer, a reinforcing layer, and an outer jacket layer. The first layer is the inner tube that carries the material to be transported. The thickness of the inner tube varies depending on the intended application. The next layer is called the reinforcing layer, which consists of metal (mesh or wire), synthetic polymer, and / or woven jacket (or a combination of these materials) and allows the hose to withstand internal and external pressures and abuse. Commonly used reinforcing fabrics (fabrics) include cotton, fiberglass, aramid fibers (such as Kevlar® and Nomex® brands), nylon, polyester, and rayon. The outer jacket layer protects the reinforcing material from damage caused by environmental exposure, fluid contamination, and physical abuse. Flexible hoses need to be flexible to accommodate misalignment, ease of routing and installation, movement, portability, thermal expansion, and vibration.

[0072] In one broad embodiment, a method for making a weatherseal, hose (e.g., a fabric reinforced hose), coextruded multi-layer tube, belt, or profile product includes: (I) mixing or blending (A) at least one ethylene-olefin monomer-silane terpolymer having a composition by weight of 5% to 50% olefin monomer and 0.1% to 2.5% silane content and having a melt index of 0.1 g / 10 min to 10.0 g / 10 min, and (B) at least one silanol condensation catalyst to form a reactive blend composition; and (II) forming the reactive blend composition from step (I) into the shape of a final part or article. (III) curing the final part or article from step (II) by exposing the manufactured part or article from step (II) to moisture and / or heat to form a cured final part or article.

[0073] The conditions for mixing or blending the components of the composition, step (I), include, for example, those that allow mixing to occur at a temperature between 85° C. and 225° C. using conventional mixing or blending equipment, such as a roll mill, an internal mixer, a single screw extruder, or a twin screw compounding extruder.

[0074] Process conditions for carrying out step (II) of the above method, i.e., for forming the reactive blend composition from step (I) into the shape of a final part or article, include, for example, conducting step (II) at temperatures between 85° C. and 225° C. using conventional polymer manufacturing equipment, such as single screw extruders, twin screw extruders, coextrusion lines, injection molding machines, and calendar molding machines.

[0075] In the above method, steps (I) and (II) can be combined into one step to accomplish both mixing of components (A) at least one ethylene-olefin monomer-silane terpolymer and (B) at least one silanol condensation catalyst, and forming the reactive mixture composition from step (I) into the shape of a final part or article.

[0076] In carrying out the curing step, which is step (III) of the above method, the conditions for curing the uncured part or article formed from step (II) include conditions for moisture curing (including, for example, the use of a water bath) at ambient temperature and ambient moisture content / humidity level, or at elevated temperature and / or humidity. For example, moisture curing can be carried out at a temperature of 0° C. to 100° C. in one broad embodiment, at a temperature of 15° C. to 90° C. in another embodiment, and at a temperature of 25° C. to 40° C. in yet another embodiment. The moisture content / humidity level during curing is 0% to 100% in one broad embodiment, 20% to 80% in another embodiment, and 40% to 80% in yet another embodiment. EXAMPLES

[0077] The following Inventive Examples (Inv. Ex.) and Comparative Examples (Comp. Ex.) (collectively "Examples") are presented herein to further illustrate the features of the present invention, but are not intended to be construed, either explicitly or implicitly, as limiting the scope of the claims. Inventive Examples are identified by Arabic numerals, and Comparative Examples are represented by alphabetical letters. The following experiments analyze the performance of embodiments of the compositions described herein. Unless otherwise indicated, all parts and percentages are by weight based on total weight.

[0078] Abbreviation Some of the names and abbreviations used for some of the materials and items used in the examples are as follows: "VTMS" stands for vinyltrimethoxysilane. "E / EA / VTMS" stands for ethylene / ethyl acrylate / vinyltrimethoxysilane terpolymer. "E / VTMS" stands for ethylene / vinyltrimethoxysilane copolymer. "DPTT" stands for dipentamethylene thiuram tetrasulfide. "TMTD" stands for tetramethylthiuram disulfide. "ZDBC" stands for zinc dibutyldithiocarbamate. "MBT" means mercaptobenzothiazole. "MBTS" stands for mercaptobenzothiazole disulfide.

[0079] With respect to plasticizer oil, the term "bleed oil" as used in the tables described in the Examples refers to an excess amount of plasticizer oil that migrates to the surface of a fully formulated part formed from the moisture and / or thermoset elastomeric polymer composition described above after a storage period of several days.

[0080] Raw materials (ingredients) The relevant raw materials (products or ingredients) used in the examples are listed in Table I. The catalyst used in the examples and listed in the tables below is a masterbatch of a concentrate of 1.5 wt. % aromatic sulfonic acid and 5 wt. % antioxidant in polyethylene (available from The Dow Chemical Company). [Table 1]

[0081] polymer The polymers used in the examples are EPDM rubber, polyolefin elastomer, E / VTMS copolymer and E / EA / VTMS terpolymer. The properties of these polymers are summarized in Tables II and III. Furthermore, the E / VTMS copolymer used in the examples has a density of 0.922 g / cc and a melt index of 1.5 g / 10 min (2.16 kg / cm, 190° C.). [Table 2] [Table 3] *The measured enthalpy of fusion (J / g) is the integrated value from -40°C to the end temperature of the DSC heating curve (approximately 150°C).

[0082] Measurement of enthalpy of fusion versus compression set The curable polymer formulation is prepared by mixing the polymer, carbon black, paraffin oil, and peroxide curing agent. The mixtures, recipes, and tests used to measure the above formulations are shown in Table 2 of the NORDEL™ EPDM Product Selection Guide published by The Dow Chemical Company in October 2018. The enthalpy of fusion of the polymers used in the formulations is measured independently. After the polymer formulation is cured, the compression set of the cured polymer formulation is measured. The results of the measurements are listed in Table IV. [Table 4] *The measured enthalpy of fusion (J / g) is the integrated value from -40°C to the end temperature of the DSC heating curve (approximately 150°C).

[0083] E / EA / VTMS or E / BA / VTMS terpolymer manufacturing / polymerization procedure The solution used to prepare the acrylate / VTMS terpolymer was the peroxide initiator tert-butyl peroctoate (TBPO, 1 wt% solution in odorless mineral spirits). The vessel (reactor) used in preparing the polymerization procedure was sparged with nitrogen for 5 minutes prior to use and kept under a nitrogen pad during operation. Typical polymerization conditions used in the preparation method and exact details of each experiment are listed in Table V below. The reactor used was a 545 mL high pressure continuous stirred tank reactor (CSTR) equipped with an external heating jacket to minimize CSTR heat loss to the environment.

[0084] An ethylene stream was injected into the CSTR stirred at 2200 rpm under the following reactor conditions: Ethyl acrylate, VTMS, and propylene, which served as a chain transfer agent (CTA), were added separately to the ethylene stream at a pressure of 62 bar, with the propylene CTA controlled at a rate to produce a range of end products. A TBPO initiator solution was added directly to the CSTR through the side wall at a pressure of 1,930 bar at a rate that controlled the internal temperature of the CSTR at 220°C. [Table 5] *"Temperature" = "Temperature"

[0085] Quantitation of ethyl acrylate using nuclear magnetic resonance 1 1 H NMR. 1 H NMR samples were prepared by dissolving 0.1–0.2 g of sample in a Norell 1001-7 10 mm NMR tube with 0.001 M Cr(AcAc) 3 and about 75 ppm butylated hydroxytoluene (BHT). The sample was purged by bubbling N2 through the solvent via a pipette inserted into the tube for approximately 3 minutes to remove oxygen, capped, sealed with Teflon tape, and heated and vortexed at 115°C to dissolve and ensure homogeneity.

[0086] A Bruker AVANCE 600MHz spectrometer equipped with a Bruker high-temperature CryoProbe was used at a sample temperature of 120°C. 1 H NMR was performed. The spectrum was acquired with a ZG pulse and a 2 second AQ16 scan with a relaxation delay of 20 seconds.

[0087] Formulation Formulations containing example moisture curable and / or thermosetting elastomeric polymer compositions are set forth in Table VI (comparative examples) and Table VII (inventive examples). The catalyst used in the examples and set forth in the tables below is a masterbatch of a concentrate of 1.5 wt. % aromatic sulfonic acid and 5 wt. % antioxidant in polyethylene (available from The Dow Chemical Company). [Table 6] [Table 7]

[0088] General Process for Mixing Compounds The compounds were mixed in a Brabender or Banbury internal mixer using a standard "upside down" mixing procedure, with the carbon black and oil added first, followed by the polymer (EPDM rubber or E / EA / VTMS terpolymer) last. The mixing conditions were as follows: the fill factor, which is the ratio of the volume of the mixed material to the volume of the mixing chamber, was set at 75%, the rotor speed was kept constant at 50 RPM during the mixing cycle, and the mixer body temperature was set at 60°C. The samples were removed from the mixer when the temperature of the mix reached 115°C.

[0089] Compression molded plaque and moisture cured Specimens were cut from the above thoroughly mixed uncured compound mixtures and then molded in a compression molding machine at 130° C. to produce test specimens. Each molded specimen was a 15.24 cm wide by 15.24 cm long plaque with a thickness of 2 mm.

[0090] To vulcanize the plaque samples made with the terpolymer, the molded plaque samples were placed in a water bath and held in the bath at 60° C. for 24 hours.

[0091] To vulcanize the plaque samples made of EPDM rubber, the molded plaque samples were placed in a hot press at 180° C. for 15 minutes.

[0092] Test Method Tensile strength and elongation tests The physical properties of the vulcanized samples were measured according to the procedures described in ASTM D412.

[0093] Compression set Compression set of all vulcanized samples was measured at 23° C. for 22 hours according to the procedure described in ASTM D395 (25% deflection method B).

[0094] hardness Shore A type hardness was measured using three-ply laminated vulcanized sample plaques according to the procedure described in ASTM D2240.

[0095] result The results of testing vulcanized plaque samples using the above test methods are set forth in Table VIII (comparative examples) and Table IX (inventive examples). [Table 8] *BO stands for "bleed oil" [Table 9] *BO stands for "bleed oil"

[0096] Other embodiments In one embodiment, in the process of the present invention, the olefin monomer content of the ethylene-olefin monomer-silane polymer is from 5 weight percent to 50 weight percent, and the silane content of the ethylene-olefin monomer-silane polymer is from 0.1 weight percent to 2.5 weight percent.

[0097] In another embodiment, in the method of the present invention, step (II) of forming the reactive mixture composition comprises extruding at least one ethylene-olefin monomer-silane polymer from step (I) and a silanol condensation catalyst into the shape of a final part or article.

[0098] In another embodiment, in the method of the present invention, the mixing or compounding step is carried out using a mixing or compounding device selected from the group consisting of a roll mill, an internal mixer, a single screw extruder, a twin screw compounding extruder, and combinations thereof.

[0099] In another embodiment, in the method of the present invention, the reactive mixture composition of step (II) is formed into the shape of a final part or article selected from the group consisting of a weather seal, a hose, a belt, and a profiled article.

[0100] In another embodiment, the method of the present invention, the final part or article is an automotive weatherseal, an automotive weather seal, an automotive hose, an automotive belt, or an automotive profile article.

[0101] In another embodiment, in the article of the present invention, the olefin monomer content of the ethylene-olefin monomer-silane polymer is from 5 weight percent to 50 weight percent, and the silane content of the ethylene-olefin monomer-silane polymer is from 0.1 weight percent to 2.5 weight percent.

Claims

1. 1. A profile or article formed from a moisture curable and / or thermosetting elastomeric polymer composition, comprising: (A) at least one ethylene-olefin monomer-silane polymer having a melt index of 0.1 grams / 10 minutes to 10.0 grams / 10 minutes and an enthalpy of fusion of less than 85 J / g; (B) at least one silanol condensation catalyst.

2. The article of claim 1 , wherein the formed article is at least one of a weatherseal, a hose, or a belt.

3. The article of claim 1, wherein the at least one ethylene-olefin monomer-silane polymer is a terpolymer or a tetrapolymer.

4. The article of claim 3, wherein the at least one ethylene-olefin monomer-silane polymer is an ethylene-olefin monomer-silane terpolymer.

5. 5. The article of claim 4, wherein the olefin monomer content of the ethylene-olefin monomer-silane terpolymer is from 5 weight percent to 50 weight percent and the silane content of the ethylene-olefin monomer-silane terpolymer is from 0.1 weight percent to 2.5 weight percent.

6. 6. The article of claim 5, wherein the concentration of the at least one ethylene-olefin monomer-silane terpolymer is from 20 weight percent to 99 weight percent, based on the total weight of all components in the composition, and the concentration of the at least one silanol condensation catalyst is from 0.1 weight percent to 10 weight percent, based on the total weight of all components in the composition.

7. The article of claim 4, wherein said at least one ethylene-olefin monomer-silane terpolymer is at least one ethylene-alkyl (meth)acrylate-silane terpolymer.

8. 7. The article of claim 6, wherein the at least one ethylene-alkyl (meth)acrylate-silane terpolymer is selected from the group consisting of at least one ethylene-ethyl acrylate-silane terpolymer, at least one ethylene-butyl acrylate-silane terpolymer, and mixtures thereof.

9. 10. The article of claim 1, further comprising one or more additives selected from the group consisting of colorants, inorganic fillers, processing oils, flame retardants, blowing agents, processing aids, antioxidants, and mixtures thereof.

10. 10. The article of claim 1, further comprising one or more polymeric components of polypropylene, polyethylene, thermoplastic vulcanizates, ethylene propylene diene monomer, ethyl vinyl acetate, and mixtures thereof.

11. 1. A method for making a weatherseal, hose, or belt product, comprising: (I) (A) at least one ethylene-olefin monomer-silane polymer having a melt index of 0.1 grams / 10 minutes to 10.0 grams / 10 minutes and an enthalpy of fusion of less than 85 J / g; (B) mixing or blending at least one silanol condensation catalyst; (II) forming the reactive blend composition from step (I) into the shape of a final part or article; (III) curing the final part or article from step (II) by exposing the final part or article from step (II) to moisture and / or heat to form a cured final part or article.

12. 1. An article, including a weather seal, a hose, a belt, or a profile article, prepared using the moisture and / or heat curable elastomeric polymer composition, (A) at least one ethylene-olefin monomer-silane polymer having a melt index of 0.1 grams / 10 minutes to 10.0 grams / 10 minutes, the terpolymer having an enthalpy of fusion of less than 85 J / g; (B) at least one silanol condensation catalyst.

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