Polymer blend

Abstract

A polymer blend comprising a copolyether-ester copolymer and a reaction product of a polyacrylate copolymer and an aminosilane. Also provided herein are methods of making the polymer blend and articles comprising the polymer blend.

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims priority to U.S. Provisional Patent Application No. 62 / 956,070, filed on 31 December 2019 pursuant to Section 365 of the U.S. Patent Act, and to U.S. Provisional Patent Application No. 63 / 024,510, filed on 13 May 2020, the entirety of each of said application is incorporated herein by reference.

[0002] The present invention relates to polymer blends comprising a polyether-polyester block copolymer and a reaction product of a polyacrylate copolymer and an aminosilane; a method for producing polymer blends; and articles comprising polymer blends. [Background technology]

[0003] Several patents, patent applications, and publications are incorporated herein by reference to better illustrate the current state of the art to which the present invention pertains. The entire disclosures of each of these patents, patent applications, and publications are incorporated herein by reference.

[0004] Polymer blends are essential materials for the manufacture of a wide range of consumer products and industrial equipment. Therefore, improving the properties, synthesis, processing, cost-effectiveness, and appearance of polymer blends remains a constant and important area of ​​interest.

[0005] One well-known method for improving polymer compositions is to blend two or more polymers. By combining polymers, it is possible to provide the advantages of one or more of the individual components. For example, by combining a relatively expensive material with desirable physical properties with a less expensive material, a polymer blend with a more favorable balance of cost and performance can be produced.

[0006] Elastomers are an important type of polymer with desirable properties and are widely applicable to many industries, and various types of elastomer blends are known. Elastomer blends may contain two or more elastomers, or one or more elastomers and one or more non-elastomerous polymers. Elastomer blends can be alloys or solid solutions, for example, if the elastomers and other polymers are miscible. If the blend contains two or more immiscible polymers, it may take other forms such as dispersions or co-continuous blends.

[0007] One type of blend that can contain elastomers is a thermoplastic vulcanized material ("TPV") which contains a thermoplastic phase and a "vulcanized" or crosslinked elastomer phase. TPVs combine many desirable characteristics of crosslinked or vulcanized materials with certain characteristics of thermoplastic resins. For example, TPVs can be melt-processed using thermoplastic resin processing equipment such as extruders. TPVs, in particular copolyether-ester TPVs, such as those described in the international patent application brochure International Publication No. 2004 / 029155, are used in a wide range of applications, including the manufacture of articles for use in automobiles, wires and cables, fluid power, electrical and electronic applications, hoses and pipes, and home appliances, due to their excellent tear strength, tensile strength, flex life, chemical resistance, and broad end-use temperature range.

[0008] In this regard, U.S. Patent No. 6,448,343, issued to Schombourg et al., describes a TPV comprising two polymers, in which one polymer is grafted or copolymerized with a carboxylic acid anhydride, and then this grafted polymer is reacted with an aminosilane that reacts with the acid anhydride, and then this one polymer is crosslinked.

[0009] Furthermore, U.S. Patent No. 7,074,857, issued to Bendler et al., describes a curable thermoplastic elastomer blend comprising a combination of a polyalkylene phthalate polyester polymer or copolymer and polyacrylate or polyethylene / acrylate rubber with an effective amount of peroxide free radical initiator and organic diene crosslinking aid.

[0010] However, thermoplastic vulcanized materials and other elastomer blends can be difficult to process. If the selection of starting materials, reagents, and processing conditions is not optimal, it can lead to undesirable properties or results, including, for example, hazardous reagents such as peroxides; hazardous conditions such as crosslinking by irradiation; slow reaction rates; polymer degradation, e.g., due to exposure to radiation or free radicals; undesirable stickiness resulting from insufficient crosslinking or polymer degradation; formation of gel defects, black spots, and other foreign matter due to gel formation; instability of the extrusion die, manifested as surface roughness of extruded parts or lumps in blow-molded parts; and processing difficulties due to excessive crosslinking, e.g., rubber scorching. [Overview of the Initiative] [Problems that the invention aims to solve]

[0011] Therefore, there remains a desire to manufacture novel polymer blends with properties tailored for use under demanding conditions. There also remains a desire to improve the processes for manufacturing such polymer blends to enhance their safety and efficiency, as well as improve their aesthetic quality. [Means for solving the problem]

[0012] Accordingly, this specification provides polymer blends comprising a polyester-polyether block copolymer and a reaction product of a polyacrylate copolymer and an aminosilane. The polyester-polyether block copolymer comprises copolymer residues of polybutylene terephthalate and polyetherdiol, and the polyacrylate copolymer comprises copolymer residues of acid anhydride cure site comonomers.

[0013] Furthermore, a process for producing this polymer blend is also provided. In the first process, the polyacrylate copolymer and aminosilane are combined, the polyester-polyether block copolymer is added, and in the second step, the mixture is melt-kneaded. In the second process, the polyester-polyether block copolymer, polyacrylate copolymer and aminosilane are combined in a molten mixture.

[0014] Furthermore, the company also provides articles containing polymer blends, such as household appliances (power cord sheathing and strain relief); consumer goods, such as footwear outsoles and midsoles; soft-touch overmoldings, straps or bands for power tools and other handheld instruments; sealing applications such as automotive intake manifold gaskets; wire and cable applications such as sheathing; oil and gas flat packs for the oil and gas industry; automotive boots such as inboard and outboard constant velocity joint (CVJ) boots, propeller shaft boots and diaphragm boots; and air ducts for use in transport vehicles such as automobiles. These articles can be manufactured using methods common to manufacturing thermoplastic or thermosetting polymers. [Modes for carrying out the invention]

[0015] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art to which the present invention pertains. Similar or equivalent methods and materials may be used in the implementation or testing of these embodiments, but preferred methods and materials are described below. The materials, methods, and examples described herein are illustrative and not intended to be limiting.

[0016] The terms “comprises,” “comprising,” “includes,” “including,” “has,” “having,” “contains,” and “containing,” as used herein, or any other variation thereof, mean non-exclusive inclusion. For example, a process, method, article, or apparatus that includes a list of components may include, but is not limited to, other components not expressly enumerated or specific to such process, method, article, or apparatus.

[0017] The transitional phrase "consisting essentially of" limits the scope of the claim to what is not substantially affected by the specified materials or steps and the essential and novel features of the claimed invention. "'Consisting essentially of' claims occupy an intermediate position between closed claims written in the 'consisting of' form and fully open claims drafted in the 'including' form." When an invention or part thereof is described using non-restrictive terms such as "comprising," unless specifically stated in the context, this description should be understood to also include descriptions of the invention using the terms "consisting of" and "consisting essentially of."

[0018] As used herein, the term "consisting essentially of" when used with respect to a polymer, phase or composition means a phase or composition that contains the stated component in an amount greater than 95% or greater than 99% by weight based on the total weight of the polymer, phase or composition. Thus, a polymer, phase or composition to which this term applies may include one or more other comonomers, components or additives such as those described hereinafter, including any carrier that may be introduced together with other components or additives. At such levels, the other comonomers, components, additives and their carriers do not change the basic and novel characteristics of the phases or compositions described herein.

[0019] Furthermore, unless the contrary is explicitly stated, "or" means inclusive "or" and not exclusive "or". For example, the condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or absent), A is false (or absent) and B is true (or present), and both A and B are true (or present).

[0020] Similarly, the indefinite articles "a" or "an" are also used to describe the elements and components of the present invention. This is done merely for convenience and to indicate the general sense of the present invention. This description should be construed to include one or at least one, and the singular form also includes the plural form unless expressly stated otherwise in limited circumstances.

[0021] As used herein, the term "about" means that the amounts, sizes, formulations, parameters and other quantities and characteristics are not exact and need not be exact, but reflect allowable values, conversion factors, rounding, measurement errors, etc., and other factors known to those skilled in the art, and may be approximate and / or larger or smaller as desired. Generally, an amount, size, formulation, parameter or other quantity or characteristic is "about" or "approximately" whether or not so stated.

[0022] In addition, the ranges set forth herein include their endpoints unless specifically stated otherwise in limited circumstances. Further, when a quantity, concentration, or other value or parameter is given as a range, a list of one or more preferred ranges, or preferred upper and lower values, this is to be understood as specifically disclosing all ranges formed from any pair of any range upper limit or preferred upper value and any range lower limit or preferred lower value, whether or not such pairs are separately disclosed.

[0023] Moreover, when numerical ranges are recited herein, unless otherwise specified in specific circumstances, these ranges are intended to include their endpoints as well as all integers, fractions, and real numbers within the ranges. The scope of the present invention is not intended to be limited to the specific values recited when defining the ranges. Finally, when the term "about" is used to represent a value or the endpoint of a range, this disclosure is to be understood as including the specific value or endpoint being referred to.

[0024] As used herein, the term “copolymer” means a polymer containing copolymer units resulting from the copolymerization of two or more comonomers. In this context, copolymers may be described herein by reference to their constituent comonomers, or by reference to the amount of those constituent comonomers, for example, “a copolymer containing ethylene and 15% by weight of acrylic acid” or similar expressions. Such expressions may be considered informal in that they do not refer to comonomers as copolymer units; they do not include conventional nomenclature for copolymers, such as the International Union of Pure and Applied Chemistry (IUPAC) nomenclature; they do not use product-by-process expression; or for other reasons. However, as used herein, a description of a copolymer by reference to its constituent comonomers or the amount of those constituent comonomers means that the copolymer contains copolymer units of the specified comonomers (in the specified amounts, if specified). The terms “unit” and “residue” herein are synonymous and interchangeable with respect to the constituent comonomers of a copolymer. As a natural consequence, a copolymer is not the product of a reaction mixture containing a given comonomer in a given amount, unless explicitly stated in specific circumstances.

[0025] In this specification, the term "(meth)acrylic," used alone or in combination with "(meth)acrylate," means acrylic or methacrylic, for example, "acrylic acid or methacrylic acid" or "alkyl acrylate or alkyl methacrylate."

[0026] The terms “copolyether-ester polymer,” “polyether-polyester block copolymer,” and “polyester-polyether block copolymer” are synonymous and interchangeable in this specification. Some, though not all, polyester-polyether block copolymers exhibit elastomeric properties.

[0027] As used herein, the term “thermoplastic vulcanized material” (“TPV”) refers to a polymer material in which a crosslinked rubber phase is dispersed in a continuous thermoplastic phase.

[0028] As used herein, the term "polymer blend" refers to a melt-processable polymer material having a crosslinked rubber phase and a thermoplastic phase.

[0029] This specification provides polymer blends comprising a copolyether-ester polymer and a reaction product of a polyacrylate copolymer and an aminosilane.

[0030] Advantageously, aminosilanes are relatively safe and highly efficient crosslinking agents. They do not have the drawbacks associated with peroxide or free radical crosslinking by irradiation. Furthermore, aminosilanes are less reactive than many peroxides, making them safer to store and handle. For example, crosslinking with aminosilanes does not have the inhibition problem common to free radical reactions due to the presence of antioxidants. Moreover, polymer components in polymer compositions crosslinked with aminosilanes do not decompose by reacting with free radicals, and there is no formation of black spots or other foreign matter that can result from uncontrolled oxidation.

[0031] Aminosilanes offer several advantages compared to crosslinking with polyamines. While the ester bonds in copolyether-ester polymers can be degraded by amines, aminosilanes have a lower amine content compared to polyamines, minimizing such undesirable side reactions. Furthermore, when using polyamine curing agents to graft polyacrylate copolymers, suspended amine functional groups may remain, which persist reactivity in subsequent processing and negatively impact the extrusion quality of the polymer blend. In contrast, the silane functional groups of aminosilanes are readily hydrolyzed and condensed even at room temperature. Therefore, any remaining reactivity disappears during storage. Finally, aminosilanes offer a wide range of choices regarding the reactivity of the two parts, reducing the technical effort required to balance crosslinking for various polymer blends, TPV compositions, and processing options.

[0032] A suitable polyester-polyether block copolymer is described in the international patent application publication, International Publication No. 2020 / 047406 by Publn. Szekely et al. However, to put it simply, a suitable polyester-polyether block copolymer has a large number of repeats of long-chain and short-chain ester units linked head-to-tail via ester bonds, wherein the long-chain ester units are of formula (A):

[0033] [ka]

[0034] It is represented by the formula (B):

[0035] [ka]

[0036] (In the formula, G is a divalent group obtained by removing the terminal hydroxyl group from a poly(alkylene oxide) glycol having a number average molecular weight of about 400 to about 6000 g / mol, preferably about 400 to about 3000 g / mol. R is a divalent group obtained by removing the carboxyl group from a dicarboxylic acid having a molecular weight of less than approximately 300 g / mol. D is represented as a divalent group obtained by removing a hydroxyl group from a diol with a molecular weight of less than approximately 250 g / mol.

[0037] The weight percentages of copolymer units of formula (A) and formula (B) in the copolyether-ester copolymer are complementary. That is, the sum of the weight percentages of copolymer units of formula (A) and formula (B) is 100% by weight. Similarly, the molar percentages of R groups in copolymer units of formula (A) and formula (B) in the copolyether-ester copolymer are complementary. That is, the sum of the molar percentages of R groups in copolymer units of formula (A) and formula (B) is 100 mol%.

[0038] In the present invention, the term “long-chain ester unit” applied to a unit in a polymer chain refers to the reaction product of a long-chain glycol and a dicarboxylic acid. Preferred long-chain glycols are poly(alkylene oxide) glycols having hydroxyl groups at the terminal (or as close to the terminal as possible) and a number-average molecular weight of about 400 to about 6000 g / mol, preferably about 600 to about 3000 g / mol. Preferred poly(alkylene oxide) glycols include poly(tetramethylene oxide) glycol, poly(trimethylene oxide) glycol, poly(propylene oxide) glycol, poly(ethylene oxide) glycol, copolymer glycols of these alkylene oxides, and block copolymers such as ethylene oxide-terminated poly(propylene oxide) glycol. Mixtures of two or more of these glycols can be used. The long-chain ester unit of formula (A) can also be referred to as a “soft segment” of the copolyether-ester polymer.

[0039] In the present invention, the term "short-chain ester unit" applied to units in the polymer chain of a copolyether ester means a low molecular weight compound or polymer chain unit having a molecular weight of less than approximately 550 g / mol. These are produced by reacting a low molecular weight (molecular weight less than approximately 250 g / mol) diol or a mixture of diols with a dicarboxylic acid to form the ester unit represented by formula (B) above. The short-chain ester unit of formula (B) may also be referred to as the "hard segment" of the copolyether-ester polymer.

[0040] Preferred low molecular weight diols that form short-chain ester units in the reaction are aliphatic diols containing 2 to 8 carbon atoms, with a more preferred diol being 1,4-butanediol. In the present invention, the term "diol" includes equivalent ester-forming derivatives, such as those mentioned. For example, ethylene oxide or ethylene carbonate can be used instead of ethylene glycol. Molecular weight refers to the molecular weight of the diol, not the molecular weight of the ester-forming derivative.

[0041] The dicarboxylic acids that can react with the long-chain glycols and low-molecular-weight diols described above to produce copolyether esters are aliphatic, alicyclic, or aromatic dicarboxylic acids having a low molecular weight, i.e., a molecular weight of less than approximately 300 g / mol. As used herein, the term “dicarboxylic acid” includes functional equivalents of dicarboxylic acids having two carboxyl functional groups that function substantially similarly to dicarboxylic acids in their reaction with glycols and diols to form copolyether ester polymers. These equivalents include esters and ester-forming derivatives such as acid halides and acid anhydrides. This molecular weight requirement pertains to the acid, and not to its equivalent ester or ester-forming derivative.

[0042] Aromatic dicarboxylic acids are preferred. As used herein, the term "aromatic dicarboxylic acid" means a dicarboxylic acid having two carboxyl groups bonded to carbon atoms in a carbocyclic aromatic ring structure. Both functional carboxyl groups do not need to be bonded to the same aromatic ring; if more than one ring is present, these may be bonded by divalent aliphatic or aromatic groups or divalent groups such as -O- or -SO2-.

[0043] Suitable aromatic dicarboxylic acids include phthalic acid, terephthalic acid and isophthalic acid; other benzoic dicarboxylic acids; substituted dicarboxy compounds with two benzene rings, such as bis(p-carboxyphenyl)methane; p-oxy-1,5-naphthalenedicarboxylic acid; 2,6-naphthalenedicarboxylic acid; 2,7-naphthalenedicarboxylic acid; 4,4'-sulfonyldibenzoic acid; and their C1-C 12 Alkyl and ring-substituted derivatives, such as halo, alkoxy, and aryl derivatives, are also used. If aromatic dicarboxylic acids are also used, hydroxy acids such as p-(beta-hydroxyethoxy)benzoic acid can also be used. Aromatic acids having 8 to 16 carbon atoms are preferred, and terephthalic acid, isophthalic acid, and mixtures of phthalic acid and isophthalic acid are more preferred.

[0044] The copolyether-ester polymer preferably contains 15 or about 15 to 99 or about 99% by weight of copolymerized short-chain ester units corresponding to formula (B) based on the total weight of the copolyether-ester, and the remainder of the weight of the copolyether-ester consists of copolymerized long-chain ester units corresponding to formula (A) described above. More preferably, the copolyether-ester polymer contains 20 or about 20 to 95 or about 95% by weight of copolymerized short-chain ester units, even more preferably 30 or about 30 to 90 or about 90% by weight or 50 or about 50 to 90 or about 90% by weight, and similarly, the remainder of the weight of the copolyether-ester consists of copolymerized long-chain ester units.

[0045] More preferably, at least about 70 mol% of the divalent group represented by R in formulas (A) and (B) above is a 1,4-phenylene divalent group, and at least about 70 mol% of the group represented by D in formula (B) above is a 1,4-butylene group. In this more preferred copolyether ester, the sum of the mole percentages of the R group other than the 1,4-phenylene divalent group and the D group other than the 1,4-butylene group does not exceed 30 in dimensionless terms.

[0046] When a mixture of two or more dicarboxylic acids is used in the preparation of the copolyether-ester, the preferred second dicarboxylic acid is isophthalic acid. A mixture of isophthalic acid and terephthalic acid is more preferred. For example, in a preferred mixture, the amount of copolymerized isophthalic acid ester residues in the copolyether-ester is preferably less than 35 mol% or less than 30 mol%, more preferably less than 25 mol%, based on the total number of moles of copolymerized dicarboxylic acid residues -(-C(O)RC(O)-)- in the copolyether-ester, and the remainder, at least 70 mol%, of phenylene divalent groups is derived from terephthalic acid. In some preferred embodiments, the copolymerized isophthalic acid ester residues in the copolyether-ester are less than 35% by weight, more preferably less than 25% by weight, based on the total weight of copolymerized dicarboxylic acid residues -(-C(O)RC(O)-)- in the copolyether-ester. Similarly, in a preferred mixture, for example, the remainder of the phenylene divalent groups is derived from terephthalic acid, based on the total weight of the copolymerized dicarboxylic acid residues -(-C(O)RC(O)-)- in the copolyether-ester.

[0047] Preferred polymer blends include copolyether-ester polymers prepared from monomers comprising: (1) glycols (EO / PO glycols) containing poly(tetramethylene glycol) or poly(trimethylene glycol), poly(propylene glycol), poly(ethylene glycol), propylene oxide, and ethylene oxide residues, and mixtures of two or more thereof; (2) dicarboxylic acids selected from the group consisting of isophthalic acid, terephthalic acid, and mixtures of two or more thereof; and (3) diols selected from the group consisting of 1,4-butanediol, 1,3-propanediol, and mixtures of two or more thereof. Furthermore, the copolyether-ester polymers in the preferred polymer blends are thermoplastic, i.e., they are melt-workable and exhibit a melt peak temperature.

[0048] Particularly preferred are copolyether esters having a hard segment composed of polybutylene terephthalate and a soft segment composed of a reaction product of polyether glycol and aromatic diacid, in an amount of approximately 5 or 10% to about 70 or 80% by weight, preferably about 10 or 20% to about 60% by weight. The polyether block is derived from polytetramethylene glycol and has a molecular weight of approximately 1000 g / mol to 2000 g / mol. Complementarily, the proportion of the hard segment is approximately 20 or 30% to 90 or 95% by weight, preferably about 40 to about 80 or 90% by weight.

[0049] Suitable polyether-polyester copolymers are commercially available under the trademark Hytrel® from DuPont Specialty Products USA, LLC in Wilmington, DE.

[0050] The polymer blends described herein also include reaction products of one or more polyacrylate copolymers with aminosilanes. Suitable polyacrylate copolymers are described in U.S. Patent No. 8,779,044 issued to Steven R. Oriani. However, to put it simply, suitable acrylate copolymers are amorphous, a) At least 45% by weight or at least 50% by weight, based on the total weight of the amorphous acrylate copolymer, of the structure:

[0051] [Chemical formula]

[0052] (wherein R 1 is H or C1-C 10 alkyl, and R 2 is C1-C 12 alkyl, C1-C 20 alkoxyalkyl, C1-C 12 cyanoalkyl or C1-C 12 fluoroalkyl) of at least one kind of monomer copolymerized units; b) Copolymerized units of one or more crosslinking point comonomers selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides and contains.

[0053] The polyacrylate copolymer is preferably amorphous. As used herein, the term "amorphous" when representing a polyacrylate copolymer refers to a copolymer that shows little or no crystalline structure under stress-free conditions at room temperature. Alternatively, an amorphous material has a heat of fusion of less than 4 J / g measured in accordance with ASTM D3418-08.

[0054] Preferred polyacrylate copolymers contain copolymerized units of a) at least one alkyl ester or alkoxyalkyl ester of propenoic acid and b) a crosslinking point monomer. Suitable alkyl and alkoxyalkyl esters of propenoic acid include, for example, alkyl acrylates and alkoxyalkyl acrylates, in addition to where the propenoic acid is C1-C 10Examples of such species include alkyl methacrylates, alkyl ethylacrylates, alkyl propacrylates and alkyl hexacrylates, alkoxyalkyl methacrylates, alkoxyalkyl ethylacrylates, alkoxyalkyl propacrylates and alkoxyalkyl hexacrylates. Polyacrylate copolymers may also contain one or more alkyl ester or alkoxyalkyl ester species, for example, two alkyl acrylate copolymer units, or α-olefins such as propene, 1-butene, and 1-hexene.

[0055] The alkyl and alkoxyalkyl esters of propenoic acid and substituted propenoic acid are preferably C1-C of acrylic or methacrylic acid. 12 C1-C of alkyl esters, acrylics, or methacrylic acids 20 These are alkoxyalkyl esters. Preferred esters include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-(n-propoxy)ethyl acrylate, 2-(n-butoxy)ethyl acrylate, 3-methoxypropyl acrylate, and 3-ethoxypropyl acrylate. More preferably, the ester group contains a branched or unbranched C1-C8 alkyl group. Even more preferably, the ester group is an unbranched C1-C4 alkyl group. Even more preferred alkyl(meth)acrylate esters include methyl acrylate, methyl methacrylate, ethyl acrylate, and butyl acrylate.

[0056] The amount of propenoic acid ester comonomer in the polyacrylate copolymer is at least 45% by weight or at least 50% by weight, based on the total weight of the polyacrylate copolymer. Preferably, this concentration is at least 55% by weight, more preferably at least 60% by weight. If the propenoic acid ester concentration is less than 45% or 50% by weight, it is likely that some degree of crystallinity will be present in the polyethylene / acrylate rubber, for example, as described below. Crystallinity of the polyacrylate copolymer or polyethylene / acrylate rubber may reduce the elasticity of the reaction product between the polyacrylate copolymer or polyethylene / acrylate rubber and aminosilane, or it may reduce the elasticity of the polymer blend.

[0057] Polyacrylate copolymers useful for carrying out the present invention further comprise copolymer units of crosslinking monomers selected from the group consisting of unsaturated carboxylic acids, anhydrides of unsaturated carboxylic acids, unsaturated epoxides, and mixtures of two or more thereof. These crosslinking monomer units contain functional groups that can react with amines or other nitrogen-containing chemical species, such as carbamates.

[0058] Suitable unsaturated carboxylic acids include, but are not limited to, acrylic acid and methacrylic acid, 1,4-butenioic acid, citraconic acid, and monoalkyl esters of 1,4-butenioic acid. The 1,4-butenioic acid before polymerization may be present as a cis- or trans isomer or both, for example, a mixture of maleic acid or fumaric acid. Suitable crosslinking comonomers also include anhydrides of unsaturated carboxylic acids, such as maleic anhydride, citraconic anhydride, and itaconic anhydride. Preferred crosslinking monomers include maleic acid and any of its acid half-esters (monoesters) or diesters, particularly methyl or ethyl acid half-esters (e.g., monoethyl maleate); fumaric acid and any of its acid half-esters or diesters, particularly methyl, ethyl, or butyl acid half-esters; and monoalkyl and monoarylalkyl esters of itaconic acid. A preferred polyacrylate copolymer contains 0.3 or 0.5 to 10% by weight, or 1.0 or 1.5 to 8% by weight, or 1.7 or 2 to 5% by weight, copolymer residues derived from one or more crosslinking point comonomers.

[0059] Preferred polyacrylate copolymers consist of or are essentially composed of copolymer units of propenoic acid esters and crosslinking point comonomers.

[0060] Suitable acrylate copolymers are manufactured by Zeon Chemicals LP in Louisville, KY and marketed under the trade name HyTemp® elastomers, and Noxtite® ACM acrylic rubber is available from Unimatec Chemicals America, Inc. in Novi, MI.

[0061] Polyethylene / acrylate rubber is a preferred type of polyacrylate copolymer. A suitable polyethylene / acrylate rubber contains the acrylic acid ester and crosslinking point comonomers mentioned above in the amounts mentioned above, in addition to copolymer units derived from ethylene, in an amount of 85 mol% or less or 82 mol% or less based on the total number of moles of copolymerized comonomer units in the polyethylene / acrylate rubber.

[0062] A preferred polyethylene / acrylate rubber contains copolymer residues derived from one or more alkyl acrylates in an amount of 45% or more by weight or 50% or more by weight, based on the total weight of the polyethylene / acrylate rubber, and copolymer residues derived from one or more crosslinking comonomers in an amount of at least 0.1 mol%, 0.3 mol%, or 0.5 mol%. More preferably, the polyethylene / acrylate rubber contains copolymer residues derived from one or more alkyl acrylates in an amount of 45-80% by weight, 50-70% by weight, or 50-65% by weight. Branched or unbranched alkyl groups containing 1-6 carbon atoms are preferred, and unbranched alkyl groups containing 1-4 carbon atoms are more preferred. Furthermore, a preferred polyethylene / acrylate rubber contains copolymer residues derived from one or more crosslinking comonomers in an amount of 0.3 or 0.5-10% by weight, 1.0 or 1.5-8% by weight, or 1.7 or 2-5% by weight. The remainder of polyethylene / acrylate rubber consists of or is based on ethylene copolymer units.

[0063] Suitable polyethylene / acrylate rubber is commercially available under the Vamac® trademark from DuPont Specialty Products USA, LLC in Wilmington, DE.

[0064] A suitable aminosilane has at least one hydrolyzable group suspended from a silicon atom, such as an alkoxy, acetoxy, or halo, preferably an alkoxy. Preferably, there are at least two such hydrolyzable groups capable of crosslinking condensation. The amine moiety must react sufficiently with the crosslinking comonomer. Generally, tertiary amines react slowly with the preferred crosslinking comonomers and are therefore less preferred. A mixture of two or more different aminosilanes can also be used.

[0065] Aminosilane is given by the formula YNHBSi(OR) a (X) 3-a The formula can be represented as (wherein a=1 to 3, preferably 2 or 3; Y is hydrogen, alkyl, alkenyl, hydroxyalkyl, alkaryl, alkylsilyl, alkylamine, C(=O)OR or C(=O)NR; R is an acyl, alkyl, aryl or alkaryl group; X may be R or a halogen atom; B is a divalent crosslinking group, preferably an alkylene group). Suitable alkylene groups for B are unbranched, branched (e.g., neohexylene) or cyclic (e.g., cyclohexylene). B may include heteroatom crosslinking, e.g., ether linkages. Preferably, B is a propylene moiety (-C3H6-). Preferably, R is a methyl or ethyl group. Preferably, Y is an aminoalkyl, hydrogen or alkyl group. More preferably, Y is hydrogen or a primary aminoalkyl group (e.g., aminoethyl). Preferably, X is a chlorine atom or a methyl group, more preferably a methyl group.

[0066] Preferred aminosilanes for reaction with polyacrylate copolymers include, but are not limited to, (3-aminopropyl)trimethoxysilane, (3-aminopropyl)triethoxysilane, N-β-(aminoethyl)-γ-aminopropyl-trimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, vinylbenzylaminoethylaminopropyltrimethoxysilane, bis(trimethoxysilylpropyl)amine, and mixtures of two or more of these. Preferred aminosilanes are commercially available from Dow Chemical Company in Midland, MI; from MilliporeSigma in St. Louis, MO; and from Momentive Performance Materials, Inc. in Waterford, NY under the trade name SILQUEST®.

[0067] While we do not wish to be bound by theory, it can be hypothesized that the amine group of aminosilane reacts with a dicarboxylic acid group or derivative to form imide groups along the main chain of the polyacrylate copolymer. The silane group of aminosilane is suspended from the nitrogen of the imide, which is also derived from the aminosilane reagent. Furthermore, it can be hypothesized that two or more suspended silane groups react to form a silane-oxygen-silane conjugated bond by the elimination of one or more XH or RH molecules, such as alkanols, aryl alkanols, carboxylic acids, or haloacid molecules, thus enabling the crosslinking of the polyacrylate copolymer. This crosslinking can be formed by a single -[-Si-O-Si-]- moiety, or by reacting multiple alkoxysilane groups to form a siloxane network containing three or more silicon atoms. This type of reaction is described, for example, by Xiangke Shi et al., Silicon (2012) 4:109-119.

[0068] The molar ratio of aminosilane to dicarboxylic acid crosslinking points of the polyacrylate copolymer in the reaction mixture is preferably in the range of 0.2 to 1.5, more preferably in the range of 0.2 to 1.0, and even more preferably in the range of 0.25 to 0.8. Importantly, adding an excess amount of aminosilane to the mixture can lead to premature crosslinking and insufficient dispersion of the polyacrylate copolymer in the polymer blend, potentially degrading the surface appearance of the molded or extruded articles. Equally important, insufficient amounts of aminosilane added to the reaction mixture can result in a sticky polymer blend, which, if possible, will inevitably be difficult to process.

[0069] The reaction products of the copolyether-ester polymer and the polyacrylate copolymer and aminosilane can be combined in any relative amounts depending on the desired properties of the polymer blend. Preferably, the weight ratio of the copolyether-ester polymer to the weight ratio of the reaction product of the polyacrylate copolymer and aminosilane is between 0.5:1 and 19:1, more preferably between 0.66:1 and 19:1, most preferably between 1:1 and 4:1, or between 1.5:1 and 4:1. Alternatively, the copolyester-ether is preferably present in the polymer blend at about 30% to 95% by weight, more preferably 40% to 95% by weight, and even more preferably 50% to 80% by weight, based on the total weight of the copolyether-ester, polyacrylate copolymer, and aminosilane.

[0070] When calculating the weight percentage of the reaction product between a polyacrylate copolymer and an aminosilane, the weight of the reaction product is assumed to be equal to the weight of the starting materials added during the production of the polymer blend, i.e., the polymer and the aminosilane, and small amounts of molecules, typically alcohol and water that inevitably arise from the condensation of silane groups and the reaction between the amine and the carboxylic acid crosslinking sites of the polyacrylate copolymer, are ignored. Depending on the degree of liquefaction during the production of the polymer blend, these molecules may be removed or incorporated into the blend by transesterification.

[0071] The blend of the copolyether-ester polymer and the reaction product of the polyacrylate copolymer and aminosilane may further contain one or more other components of any kind or amount necessary to satisfy technical requirements, such as additives, fillers, processing aids, plasticizers, stabilizers, viscosity modifiers, colorants, and pigments. In durable consumer goods applications, antioxidants, specifically phenolic, phosphite, and amine-containing antioxidants, are particularly useful. These other components may be added at any stage of blend production or in subsequent processing steps in amounts commonly used in the art. The reaction of aminosilane and polyacrylate copolymer can be carried out in the mixing process, for example, in a two-roll rubber mixer, or using a closed mixer suitable for compounding gum rubber compositions, such as a Banbury® closed mixer, Haake Rheocord® mixer, Brabender Plastograph® mixer, Farrel® continuous mixer, Buss® kneader, or single-screw and twin-screw extruders. A twin-screw extruder is preferred. Preferably, one or more polyacrylate copolymers are supplied to the extruder after one or more aminosilanes have been injected into the polymer.

[0072] The extruder barrel temperature before injecting the aminosilane is preferably 150°C or lower, while the barrel temperature downstream of the injection point is preferably 150°C or higher. Injecting the aminosilane at an extruder temperature of 150°C or lower ensures that the aminosilane is reliably mixed with the polyacrylate copolymer before silane condensation occurs, which in turn improves the efficiency of aminosilane crosslinking and reduces the amount of aminosilane required to achieve a given cured state. At temperatures of 150°C or higher, the aminosilane grafts onto the polyacrylate copolymer via the reaction between the amine and the crosslinking sites, and the silane rapidly condenses to form crosslinks. The copolyester-ether polymer can be added at any point before being discharged from the extruder. Preferably, the copolyester-ether polymer is added when the barrel temperature is 150°C or lower, so that silane condensation occurs substantially simultaneously with the melting and kneading of the copolyester-ether polymer.

[0073] The aminosilane can be optionally diluted with one or more nonreactive solvents or carriers as needed. Suitable solvents and carriers include, but are not limited to, anhydrous toluene, anhydrous ethanol, and acetone. The concentration of aminosilane in the solvent or carrier can be in the range of about 10% to about 95% by weight, based on the total weight of aminosilane and solvent or carrier.

[0074] The extruder screw should be designed to ensure uniform mixing of the liquid aminosilane with the polymer at the injection point and downstream thereof. In the portion of the extruder screw where polyacrylate crosslinking occurs, a high-work element, such as a kneading block, is preferably used to ensure the crosslinked elastomer is dispersed within the copolyether-ester polymer. Other screw elements, such as reverse feed elements, gear mixers, forward feed elements, and blister rings, are well known to those skilled in the art of reactive extrusion, for controlling the degree of kneading, temperature, and residence time of the polymer reaction mixture, reaction product, or blend within the extruder. Preferably, the extruder has at least one vacuum defoliation port for removing volatile substances generated by the curing reaction. The extruder screw speed can be varied over a wide range, typically between 200 and 600 RPM, more preferably between 250 and 400 RPM. Preferably, the barrel temperature is set between 100°C and 240°C.

[0075] Catalysts to accelerate reactions occurring during the production of polymer blends can also be added at any point in the process. For example, a catalyst suitable for accelerating the reaction between an amine and the crosslinking sites of a polyacrylate copolymer is preferably added before, simultaneously with, or essentially simultaneously with, the addition of the aminosilane, so that the aminosilane reacts with the crosslinking sites of the polyacrylate copolymer before the silane condenses to form siloxane bonds. Suitable catalysts are well known in the art as accelerators for polyamine curing of polyacrylate copolymers. Several suitable catalysts are described, for example, in U.S. Patent No. 3,883,472. Tertiary amines are a preferred type of catalyst for accelerating the grafting of aminosilanes into polyacrylate copolymers. A particularly preferred catalyst is 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). Preferably, the polymer blend contains at least an effective amount of catalyst to accelerate the reaction between the amine and the crosslinking sites of the polyacrylate copolymer. The catalyst can be present in an amount of 1 part by weight (pbw) to 50 pbw based on the weight of the aminosilane. More preferably, the catalyst is present in an amount of 1 pbw per 5 pbw of aminosilane.

[0076] Catalysts to promote the formation of siloxane bonds can also be added at any point during the polymer blend production. Suitable catalysts are well known in the art, as described in S. Levigoureux, P. Garcia, M. Ficquenet and I. Denizet, “Catalyst alternatives to replace DBTDL and crosslink speed improvement of a low voltage cable insulation”, 9th International Conference on Insulated Power Cables, Versailles, France, June 2015. Such catalysts include sulfonic acids and carboxylic acids, metal hydroxides, and organotin compounds. However, catalysts for siloxane formation are preferably not present in the polymer blend. At least part of the reason for this is that they can catalyze undesirable hydrolysis or alkalisis of the copolyester-ether polymer as water and alcohols are generated by silane condensation and the reaction of amines with crosslinking sites of the elastomer.

[0077] The process conditions and amounts of aminosilane used in the production of the polymer blends described herein can be modified to achieve various technical objectives. If the crosslinking of the polyacrylate copolymer is insufficient, the blend may become too sticky to be pelletized, or even if pelletized, the blend pellets may mass or clump together. Such problems can be addressed by increasing the aminosilane content, by including a catalyst that increases the reaction rate between the amine and the elastomer crosslinking sites, or by changing the conditions for adding aminosilane to ensure that the aminosilane is completely mixed with the polyacrylate copolymer before silane condensation is induced. In principle, the tensile strength and extensibility of the blend are optimized by using an amount of aminosilane slightly greater than the minimum amount required to produce non-aggregating pellets. If the amount of aminosilane is greater than this, the elastic modulus of the blend tends to increase, while the extensibility tends to decrease.

[0078] Skilled scientists and technicians in the field of reactive extrusion technology can apply conventional principles regarding the operation of the extruder, screw design, and method of supplying raw materials to the extruder so as to achieve acceptable operating parameters to satisfy the technical requirements for the production of polymer blends described herein. For example, the design of the aminosilane injection mechanism is preferably such that it is less prone to clogging and provides a continuously stable flow. The extruder screw preferably incorporates elements such as a kneading block for rapid and uniform mixing of the aminosilane with the polymer. To ensure that the aminosilane and elastomer are grafted, a reverse feed element and a geared mixer can be used to increase the residence time in this section. The screw section involved in the melting and kneading of the copolyether-ester copolymer, polyacrylate copolymer, and aminosilane should incorporate a kneading block, a reverse feed element, or other high-performance elements to ensure that the elastomer is well dispersed in the copolyether-ester copolymer. As is well known to those skilled in the art, the extruder feed rate, extrusion rate, screw RPM, and melting temperature also affect the residence time and kneading. The screw speed of a typical extruder can be in the range of 100 to 500 RPM, more typically in the range of 200 to 400 RPM. The polymer temperature at the extruder outlet is typically in the range of 240°C to 315°C, 240°C to 300°C, preferably 250°C to 290°C.

[0079] Furthermore, the resulting polymer blend can be post-treated to increase its viscosity by solid-phase polymerization. In this technique, the polymer blend is exposed to a temperature approximately 10°C to 40°C lower than the melt peak temperature of the copolyether-ester polymer for a sufficient time to promote the esterification of any remaining hydroxyl and carboxylic acid residues, thereby increasing the viscosity of the polymer blend.

[0080] Polymer blends can be characterized by a wide range of forms, from discontinuous crosslinked elastomer particles dispersed within a copolyester-ether polymer matrix to cocontinuous phases containing lightly crosslinked elastomers and copolyester-ethers, and mixtures of these forms. Some of these forms may not be suitable for use in the articles described herein. This is because they may be difficult to further compound, or they may have poor elasticity, such as having a tensile elongation to break of less than 100%, or they may have poor aging behavior, or they may be unstable, i.e., the polymer blend may become coarse if held at a temperature above the melt peak temperature of the copolyester-ether copolymer. Most preferably, the reaction products of aminosilane and polyacrylate copolymers exist as discontinuous particles in the polyester-ether block copolymer. This form of polymer blend is a thermoplastic vulcanized product, i.e., a TPV.

[0081] Generally, the distribution and dispersion of reaction products in a copolyether-polyester block copolymer can be evaluated by forming tensile test specimens and measuring the tensile strength of the polymer blend. The mechanical properties of the polymer blend can be evaluated using injection-molded 5A specimens in accordance with ISO-527-1(2019) and a tensile speed of 20 mm / min via a load frame such as an Instron tensile testing machine. Poor dispersion of the reaction products between aminosilane and polyacrylate copolymer reduces the tensile strength of the blend. The tensile strength also depends on the type and amount of copolyester-ether polymer in the blend, but those skilled in the art can apply these principles and techniques to optimize the properties of the blend.

[0082] A preferred polymer blend exhibits a stable morphology even when held at a temperature exceeding the melt peak temperature of the copolyester-ether copolymer. Unstable morphologies of the blend will exhibit significant roughening, lumping, or other distortion of the extruded product under such conditions. The stability of the blend morphology can be evaluated using a single-screw extruder fitted with a tape die. The blend composition to be tested is extruded at a constant speed, and a sheet or tape sample is collected. The extruder screw is then stopped, during which the temperature of the blend is maintained, and a second sample is collected immediately after restarting the extruder. Most preferably, both extruded products are smooth in appearance and show no change after the holding period. Less preferable is when the initial sample is smooth, while the second sample is rough, lumpy, or distorted. Most unpredictable is when both samples are rough, lumpy, or distorted.

[0083] By changing the types and weight ratios of copolyether-ester copolymers and polyacrylate copolymers, the polymer blends described herein can be varied in many ways, from soft (Shore A approximately 60) highly elastic thermoplastic elastomers to more rigid (Shore D approximately 70) flexible plastics. Generally, as the content of the elastomeric reaction product between the polyacrylate copolymer and aminosilane increases, the strength and rigidity of the polymer blend decrease, while resistance to degradation by hot air and hot water improves. The polymer blends of the present invention described herein exhibit superior resistance to degradation by hot air and hot water compared to pure copolyester-ether polymers having the same hardness.

[0084] The polymer blends described herein can be used in a wide range of industrial applications, such as insulation for electric wires and cables; household appliances; consumer goods such as footwear; flat packs for the oil and gas industry; air ducts used in transport vehicles such as automobiles, and boots such as inboard and outboard constant velocity joint (CVJ) boots, diaphragm boots, and propeller shaft boots; soft-touch materials, fittings, and sealing applications; fluids and air ducts used in transport vehicles such as automobiles; and in the manufacture of other articles used in automobiles, fluid power (such as fluid power transmission lines), electrical and electronic applications, hoses and pipes, and articles in the field of home appliances.

[0085] These articles can be manufactured using conventional methods for producing articles from thermoplastic polymer materials, such as injection molding, blow molding, extrusion, compression molding, press blow molding (Ossberger molding), accumulator blow molding, extrusion blow molding, or injection blow molding.

[0086] The following are examples to illustrate the present invention in more detail. These examples show preferred embodiments currently available for carrying out the present invention, but they are intended to illustrate the invention and not to limit it. [Examples]

[0087] material Copolyester ether A contains copolymer residues of 2000 g / mol PTMEG (72.5 wt%), terephthalic acid (18.4 wt%), and 1,4-butanediol (9.1 wt%). This polymer contains approximately 22.6 wt% short-chain ester units (hard segments) and 77.4 wt% long-chain ester units (soft segments), and has a melt peak temperature of 177°C.

[0088] Copolyester-ether B contains copolymer residues of 1000 g / mol PTMEG (7.8 wt%), terephthalic acid (55.8 wt%), and 1,4-butanediol (36.4 wt%). This polymer contains approximately 91 wt% short-chain ester units and 9 wt% long-chain ester units, and has a melt peak temperature of 221°C.

[0089] Copolyester-ether C contains copolymer residues of 2000 g / mol PTMEG (50.6 wt%), terephthalic acid (31 wt%), and 1,4-butanediol (18.4 wt%). This polymer contains approximately 46 wt% short-chain ester units and 54 wt% long-chain ester units and is subjected to solid-phase polymerization to increase its molecular weight. The melt peak temperature of this polymer is 198°C.

[0090] Polyethylene / acrylate rubber A contains 55% by weight of methyl acrylate copolymer units, 3.1% by weight of crosslinking point monomers having carboxylic acid functional groups, and the remainder being ethylene copolymer units. This polymer is amorphous and does not exhibit a melt peak temperature.

[0091] Polyethylene / acrylate rubber B contains 23% by weight of copolymer units derived from methyl acrylate, 41% by weight of copolymer units derived from butyl acrylate, and 3.2% by weight of copolymer units derived from crosslinked comonomers having carboxylic acid functional groups, with the remainder being copolymer units of ethylene. This polymer is amorphous and does not exhibit a melt peak temperature.

[0092] Polyacrylate copolymer A contains 54% by weight of ethyl acrylate, 44% by weight of butyl acrylate, and 2% by weight of a crosslinking monomer having a carboxylic acid functional group. This polymer is amorphous and does not exhibit a melt peak temperature.

[0093] PBT is polybutylene terephthalate available as Crastin® 6129 from DuPont de Nemours, Inc. in Wilmington, Delaware.

[0094] Aminosilane A is 3-aminopropyltriethoxysilane, available from Sigma-Aldrich Corporation.

[0095] Aminosilane B is 3-aminopropyltrimethoxysilane, available from Sigma-Aldrich Corporation.

[0096] The diamine is 2,2,4(2,4,4)-trimethyl-1,6-hexanediamine, available from Sigma-Aldrich Corporation.

[0097] DBU is 1,8-diazabicyclo[5.4.0]undec-7-ene, a tertiary amine catalyst available from Sigma-Aldrich Corporation.

[0098] Test method Before injection molding, the pellets were dried overnight or in a vacuum oven at at least 80°C to 90°C for 4 or 6 hours. The material was injection molded using an Arburg 1.5 oz machine. The barrel temperature was set to a temperature exceeding the melt peak temperature of the copolyether-ester polymer as measured by ASTM D3418-15.

[0099] The tensile properties (tensile strength and elongation at break) of the polymer blend were measured using an Instron® tensile testing machine in accordance with ISO-527-1 (2019), using injection-molded 5A specimens at a tensile speed of 20 mm / min. The flexibility of the polymer blend was evaluated using an Instron® bending testing machine in accordance with ISO-178 (2019), using injection-molded 4 mm multipurpose specimens at a test speed of 1.270 mm / min. The hardness (Shore A and Shore D) of the polymer blend was evaluated using the standard conditions described in ISO-868 (2003). A change was made to report peak (initial) hardness instead of hardness after 15 seconds, using injection-molded 4 mm multipurpose or 5A specimens. All samples were conditioned in accordance with their respective ISO standards.

[0100] The extrusion quality and stability of the polymer blend are evaluated using a 19.1 mm diameter single-screw extruder fitted with a 25.4 mm × 0.8 mm tape die. The extruder barrel has three heating zones, and the die has a single heating zone. The temperature is set as described in the examples, typically increasing from the feed zone towards the die, so that the final extruder temperature and die temperature are approximately 20°C higher than the melt peak temperature of the copolyether-ester copolymer in the blend being tested. Two air-cooled extruded tapes are collected and their extrusion quality is evaluated: Tape 1 was recovered while the extruder was operated at a steady state of 25 rpm. After retrieving Tape 2 and Tape 1, the screw rotation is stopped for 5 minutes, then restarted at 25 rpm. The extruded material retrieved immediately after restarting is designated as Tape 2.

[0101] Visually inspect the tape according to the following instructions: Smooth: The surface has a glossy appearance and is free from ridges, bumps, undulations, or other defects. Matte finish: The surface appears dull, but no other defects are visible. Rough: The surface has ridges, bumps, undulations, or other continuous or discontinuous defects.

[0102] Example 1 Examples E1, E2, and E3 in Table I demonstrate that using a copolyester-ether copolymer with a high soft segment content yields thermoplastic elastomers with low hardness and good physical properties and extrusion quality. These examples further demonstrate the advantages of using a catalyst in combination with aminosilane. The polymer blends in Table I were produced using a 30 mm co-rotating twin-screw extruder with 12 barrel zones, operated at 300 rpm and a discharge rate of 10.9 kg / hr. The copolyester-ether copolymer was supplied to barrel zone 1, polyethylene / acrylate rubber to barrel zone 4, and aminosilane or diamine crosslinking agent to barrel zone 5. The temperature set for barrel zones 1-7 was 100°C, while zones 8-12 were set to 220°C. The polymer blend was extruded through a strand die set to 220°C, and the resulting strands were cooled in a water bath and pelletized. When a catalyst was used, aminosilane or diamine was pre-mixed.

[0103] The extrusion quality of the polymer blends in Table I was evaluated using a single-screw extruder with temperature settings of 170°C, 180°C, and 190°C (from the feed zone to the discharge), and the tape die temperature set to 190°C. The polymer blends of Examples E1, E2, and E3 were extruded smoothly both before and after a 5-minute pause in the extruder (tapes 1 and 2), but tape 2 of Comparative Example CE1 was rough and of inferior quality.

[0104] In Examples E1 and E3, the combined use of a DBU catalyst and aminosilane yielded polymer blends with superior tensile strength compared to blends containing aminosilane alone (E2) or a DBU catalyst and diamine (CE1). The use of the DBU catalyst also reduced the amount of aminosilane required to produce non-stick, free-flowing pellets. In Examples E1, E2, and E3, aminosilane was used in the minimum amount necessary to produce free-flowing pellets. In E2, where no catalyst was present, the required primary amine equivalent was more than 20% more than the aminosilane required in E1 or E3.

[0105] [Table 1]

[0106] Example 2 The polymer blends in Table II were prepared according to the process conditions described in Example 1, except that the temperature of barrel zones 8-12 of the twin-screw extruder was increased from 220°C to 240°C. To accommodate the higher melt peak temperature of copolyester-ether B, the temperature profiles used for tape extrusion were set to 220°C, 230°C, and 240°C (from the feed zone to the discharge), and the tape die temperature was set to 240°C.

[0107] Examples E4 and E5 in Table II demonstrate the use of copolyester-ether copolymers with low soft segment content, with or without a DBU catalyst. The combined use of a DBU catalyst and aminosilane allows for increased tensile strength and elongation of the polymer blend while reducing the amount of aminosilane used, which is consistent with the results of Example 1. E4 and E5 exhibit excellent tape extrusion quality, and no roughening is observed even after a 5-minute rest (extruded tape 2).

[0108] Comparative Example CE2 uses a conventional diamine curing agent, and the extrusion quality of extruded tape 2 is inferior. Comparative Example CE3 replaces the copolyester-ether copolymer of E4 with polybutylene terephthalate homopolymer (PBT). Surprisingly, even though the only compositional difference between copolyester-ether B and PBT is the presence of 7.8 wt% PTMEG, CE3 is far less flexible and extensible than E4. The present invention aims to provide a solution for adjusting polymer blends to meet stringent requirements, and using copolyester-ether copolymers offers far greater formulation flexibility than using homopolymer polyesters.

[0109] [Table 2]

[0110] Example 3 The polymer blends in Table III demonstrate the use of blending solid-phase polymerized copolyester-ether copolymers with polyacrylate copolymers to increase molecular weight. Examples E6 and E7 were prepared according to the process of Example 1. Temperature profiles of 200°C, 210°C, and 220°C (from the feed zone to the ejection zone) were used for tape extrusion, and the tape die temperature was set to 220°C.

[0111] The results in Table III show that E6, using polyethylene / acrylate rubber, has higher strength and extensibility than E7, which is based on polyacrylate copolymer. Both E6 and E7 exhibit good tape extrusion characteristics, and no degradation of surface finish is observed between tapes 1 and 2. However, E6 has a smooth finish, while E7 has a matte finish. Both are acceptable, but in certain applications, one or the other may be preferred.

[0112] [Table 3]

[0113] While certain preferred embodiments of the present invention have been described and illustrated above, the invention is not intended to be limited to such embodiments. Various modifications can be made without departing from the scope and spirit of the invention, as shown in the following claims.

Claims

1. It is a polymer blend: (a) a copolyether-ester copolymer comprising copolymer residues of polyalkylene terephthalate and copolymer residues of polyetherdiol; (b) a reaction product of a polyacrylate copolymer and an aminosilane; i) The polyacrylate copolymer contains at least 0.3% by weight of copolymerized residues of the crosslinking point comonomer, and the sum of the weight percentages of copolymerized residues in the polyacrylate copolymer is 100% by weight; and ii) The polymer blend is a polymer blend comprising 5 to 70% by weight of the reaction product of the polyacrylate copolymer and the aminosilane, based on the total weight of the polymer blend.

2. The polymer blend according to claim 1, wherein the copolyether-ester copolymer comprises a copolymerization unit of polybutylene phthalate.

3. The polymer blend according to claim 1 or claim 2, wherein the copolyether-ester copolymer contains copolymer residues of one or more polyetherdiols in an amount of about 5 to about 80% by weight, based on the total weight of the copolyether-ester copolymer.

4. The polymer blend according to claim 1 or claim 2, wherein the copolyether-ester copolymer further comprises copolymer residues of polyalkylene isophthalate.

5. The polymer blend according to claim 1, wherein the copolyether-ester copolymer comprises a copolymerization unit of polybutylene isophthalate.

6. The polymer blend according to any one of claims 1 to 5, wherein the polyacrylate copolymer further comprises an ethylene copolymer residue.

7. The polymer blend according to any one of claims 1 to 6, wherein the polyacrylate copolymer comprises, based on the total weight of the polyacrylate copolymer, 0.3 to 10% by weight of copolymer residues derived from one or more crosslinking point comonomers; 45 to 80% by weight of copolymer residues derived from one or more alkyl acrylates; and 10 to 55% by weight of copolymer residues derived from ethylene, and the sum of the weight percentages of all copolymer residues in the polyacrylate copolymer is 100% by weight.

8. The aforementioned aminosilane is given by formula YNHBSi(OR) ａ (X) ３－ａ A polymer blend according to any one of claims 1 to 7, represented by the formula (wherein a is an integer of 1, 2, or 3; Y is a hydrogen atom or an alkyl, alkenyl, hydroxyalkyl, alkaryl, alkylsilyl, alkylamine, C(=O)OR, or C(=O)NR group; R is an acyl, alkyl, aryl, or alkaryl group; X is R or a halogen atom; B is a divalent crosslinking group).

9. The polymer blend according to any one of claims 1 to 8, wherein the aminosilane comprises one or more compounds selected from the group consisting of (3-aminopropyl)trimethoxysilane, (3-aminopropyl)triethoxysilane, N-β-(aminoethyl)-γ-aminopropyl-trimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, vinylbenzylaminoethylaminopropyltrimethoxysilane, and bis(trimethoxysilylpropyl)amine.

10. The polymer blend according to any one of claims 1 to 9, wherein the aminosilane is 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, or a combination of 3-aminopropyltriethoxysilane and 3-aminopropyl-trimethoxysilane.

11. The polymer blend according to any one of claims 1 to 10, further comprising one or more other components selected from the group consisting of additives, fillers, processing aids, plasticizers, stabilizers, viscosity modifiers, colorants, pigments, and antioxidants.

12. The polymer blend according to claim 11, wherein the antioxidant is selected from the group consisting of phenolic, phosphite, and amine-containing antioxidants.

13. A polymer blend according to any one of claims 1 to 12, comprising a thermoplastic vulcanized product.

14. The polymer blend according to any one of claims 1 to 13, comprising at least an effective amount of catalyst for promoting the reaction between the amine and the crosslinking sites of the polyacrylate copolymer.

15. The polymer blend according to claim 14, wherein the catalyst is a tertiary amine.

16. The polymer blend according to claim 14, wherein the catalyst is 1,8-diazabicyclo[5.4.0]undeca-7-ene (DBU).

17. A process for producing a polymer blend according to any one of claims 1 to 16: a) A step of producing a composition by kneading one or more types of polyacrylate copolymers with aminosilane; b) A process comprising the step of melt-kneading one or more types of copolyether-ester copolymers with the composition.

18. The process according to claim 17, wherein step (a) is carried out at a temperature of less than 150°C.

19. Step (b) is the process according to claim 17, wherein step (b) is carried out at a temperature of 150°C or higher.

20. The process according to claim 17, wherein steps (a) and (b) are performed sequentially in a twin-screw extruder.

21. A process for producing a polymer blend according to any one of claims 1 to 16: a) The step of melt-kneading one or more types of polyacrylate copolymers with one or more types of copolyether-ester copolymers; b) A process comprising the step of melt-kneading the composition of part (a) with an aminosilane.

22. A process for producing a polymer blend according to any one of claims 1 to 16, comprising mixing the polyacrylate copolymer with the aminosilane and the copolyether-ester copolymer in a molten state to produce a molten state containing the copolyether-ester copolymer and the reaction product of the polyacrylate copolymer and the aminosilane, wherein the molten state is cooled to produce the polymer blend.

23. Articles comprising a polymer blend as described in any one of claims 1 to 16, selected from the group consisting of: household appliances including power cord sheathing and strain relief; consumer goods including outsoles and midsoles for footwear; soft-touch overmoldings for power tools and other handheld devices; applications for fasteners such as laces or belts; sealing applications such as intake manifold gaskets for automobiles; applications for wires and cables such as sheathing; flat packs for the oil and gas industry; boots for use in transport vehicles such as automobiles, including inboard and outboard constant velocity joint (CVJ) boots, propeller shaft boots and diaphragm boots; fluid ducts and air ducts for use in transport vehicles such as automobiles; and other articles for use in the fields of transport, automobiles, fluid power (including fluid power transmission lines), electrical, electronic, hoses and pipes and household appliances.

24. The article according to claim 23, manufactured by a method selected from the group consisting of injection molding, blow molding, extrusion, compression molding, press blow molding, accumulator blow molding, extrusion blow molding, injection blow molding, and additive manufacturing.

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