Thermoplastic copolymer block polyamide silicone elastomers

Abstract

A thermoplastic elastomer composition comprising a blend of: (A) a thermoplastic organic polyether block amide copolymer, (B) a silicone composition comprising: (B1) a silicone base comprising: (B1a) a diorganopolysiloxane polymer having a viscosity of at least 1,000,000 mPa·s at 25°C and an average of at least 2 alkenyl groups per molecule, and (B1b) a reinforcing filler in an amount of 1 to 50% by weight based on the weight of (B1a), (B2) an organohydrogenated silicone compound containing an average of at least 2 hydrogen groups bonded to silicon per molecule, (C) a hydrogenated silanization catalyst, and optionally: one or more additive components (D), wherein the weight ratio of the thermoplastic organic polyether block amide copolymer (A) to the silicone composition (B) is from 50:50 to 95:5, and wherein components (B2) and (C) are sufficient to cure the silicone composition (B1). The quantity exists.

Description

[0001] This application is a divisional application of application No. 201880008670.4 entitled “Thermoplastic copolymer block polyamide silicone elastomer”, filed on January 30, 2018.

[0002] This invention relates to thermoplastic elastomers (TPEs), particularly high-value-added engineering polymers used in various fields such as electronics, automobiles, or sports, thermoplastic elastomer compositions for manufacturing them, and a method for forming vulcanized thermoplastic elastomer compositions.

[0003] Thermoplastic elastomers (TPEs) are polymeric materials that combine plasticity and rubber-like properties. Although TPEs possess elastomeric mechanical properties, unlike conventional thermosetting rubbers, they can be further processed at elevated temperatures.

[0004] This reprocessing capability is a major advantage of TPE over chemically cross-linked rubber, as it allows the manufactured parts to be recycled and results in a significant reduction in waste.

[0005] Generally, two main types of thermoplastic elastomers are known: block copolymers (TPE) and simple blends (TPE) (physical blends).

[0006] Block copolymer TPE contains: (i) Blocks or segments referred to as hard or rigid (i.e., exhibiting thermoplastic behavior), typically having a melting point or glass transition temperature above ambient temperature; and (ii) Referred to as soft blocks or segments, which are soft or flexible (i.e., exhibiting elastomeric behavior) and typically have a low glass transition temperature (T0) significantly below room temperature. g (or melting point)

[0007] The phrase "low glass transition temperature" should be understood as referring to the glass transition temperature T. g Below 15°C, preferably below 0°C, advantageously below -15°C, more advantageously below -30°C, possibly below -50°C.

[0008] In block copolymer thermoplastic elastomers, hard segments aggregate to form distinct microphases and act as physical crosslinkers of the soft phases, thereby imparting rubber-like properties at room temperature. At elevated temperatures, the hard segments melt or soften, allowing the copolymer to flow and be processed. Hard blocks are typically based on polyamides, polyurethanes, polyesters, or mixtures thereof. Soft blocks are typically based on polyethers (PEs), polyesters, and their copolymers or blends. An example of such copolymers containing both hard and soft blocks is a copolymer containing both polyamide and polyether blocks (polyether-block-amide is often abbreviated as PEBA).

[0009] PEBA is typically a plasticizer-free thermoplastic elastomer, considered an engineered polymer. In a single polymer, it is possible to combine unparalleled mechanical properties with very good heat or UV aging resistance, and low density. Therefore, they make it possible to produce lightweight parts. In particular, at equal hardness, they dissipate less energy than other materials, providing them with very good resistance to dynamic stresses when bent or stretched, and they exhibit exceptional elastic rebound. However, it is difficult to produce soft PEBA-type materials with low Shore A hardness (i.e., <100) without sacrificing many of the aforementioned benefits. Typically, PEBA is approximately a 1:1 combination of hard and soft blocks, and any significant increase in the proportion of soft blocks can lead to manufacturing problems.

[0010] By uniformly mixing the elastomer component with a thermoplastic resin, a TPE known as a simple blend or physical blend can be obtained. When the elastomer component is also crosslinked during mixing, a thermoplastic elastomer, known in the art as a thermoplastic vulcanizate (TPV), is produced. Because the crosslinked elastomer phase of TPV is insoluble and non-flowable at elevated temperatures, TPV typically exhibits improved oil and solvent resistance and reduced compression set compared to simple blends.

[0011] Typically, TPVs are formed by a method called dynamic vulcanization, in which an elastomer and a thermoplastic matrix are mixed, and the elastomer is cured during the mixing process by means of a crosslinking agent and / or catalyst. Many such TPVs are known in the art, including some TPVs in which the crosslinked elastomer component can be a silicone polymer, while the thermoplastic component is an organic non-silicone polymer (i.e., thermoplastic silicone vulcanization or TPSiV).

[0012] US Patent 6,281,286 describes a high-impact-strength composition made of polyamide homopolymer and silicone resin.

[0013] US Patent 6,362,288 describes a method for obtaining a thermoplastic silicone elastomer from a compatibilized polyamide resin, a silicone resin, a filler, and a compatibilizer (coupling agent, organofunctional diorganopolysilane or siloxane copolymer).

[0014] The present invention seeks to obtain thermoplastics containing PEBA in the thermoplastic phase, which have low hardness, i.e., a Shore A hardness value below 90, alternatively, a Shore A hardness value below 85, and as another alternative, a Shore A hardness value below 80. In each of the above, the hardness value is obtained in the absence of plasticizers and / or compatibilizers.

[0015] This article provides a thermoplastic elastomer composition comprising a blend of the following: (A) Thermoplastic organic polyether block amide copolymer, (B) An organosilicon composition comprising: (B1) Organosilicon-based materials, comprising: (B1a) A diorganopolysiloxane polymer having a viscosity of at least 1,000,000 mPa·s at 25°C and an average of at least 2 alkenyl groups per molecule, and (B1b) Reinforcing filler, in an amount of 1 to 50% by weight based on (B1a). (B2) Organohydrogenated organosilicon compounds, each molecule of which contains an average of at least two hydrogen groups bonded to silicon. (C) Hydrosilylation catalyst, and optionally: One or more additive components (D) The thermoplastic organic polyether block amide copolymer (A) is present in a weight ratio of 50:50 to 95:5 of the silicone composition (B), and components (B2) and (C) are present in an amount sufficient to cure the silicone composition B1.

[0016] It has been determined that the cured product obtained by curing the above-mentioned substances provides a material with low hardness, i.e., a Shore A hardness value below 90, alternatively, a Shore A hardness value below 85, and as another alternative, a Shore A hardness value below 80. Furthermore, as can be seen from the above composition, these values ​​can be obtained in the absence of plasticizers and / or compatibilizers.

[0017] It has been observed that the product of the above-described composition according to the present invention unexpectedly maintains substantially the impact resistance or shock resistance of component (A), which would have been expected in the absence of component (B).

[0018] Advantageously, plasticizers and / or compatibilizers are not required to obtain the thermoplastic-based silicone block copolymer amide elastomer of the present invention.

[0019] To avoid ambiguity, silanes and siloxanes are silicon-containing compounds.

[0020] • Silanes are compounds derived from SiH4. Silanes typically contain at least one Si-C bond. Silanes typically contain only one Si atom.

[0021] • Siloxanes are compounds containing at least one Si-O bond.

[0022] Polysiloxanes contain several Si-O-Si- bonds that form polymer chains, with the repeating unit being -(Si-O)-. Organopolysiloxanes are sometimes called organosilicones. Organopolysiloxanes contain repeating -(Si-O)- units, where at least one Si atom carries at least one organic group. "Organic" means containing at least one carbon atom. An organic group is a chemical group containing at least one carbon atom.

[0023] Polysiloxanes contain end groups and side groups. End groups are chemical groups located on Si atoms at the ends of the polymer chain. Side groups are groups located on Si atoms that are not at the ends of the polymer chain.

[0024] A polymer is a compound containing repeating units, which typically form at least one polymer chain. Polymers can be homopolymers or copolymers. Homopolymers are polymers formed from only one type of monomer. Copolymers are polymers formed from at least two different monomers. When the repeating units contain carbon atoms, the polymer is called an organic polymer.

[0025] Some polymers are thermosetting: once cooled and hardened, these polymers retain their shape and cannot return to their original form. Other polymers are thermoplastics: they can soften and return to their original form when heated.

[0026] A crosslinking reaction is a reaction in which two or more molecules (at least one of which is a polymer) are linked together to harden or cure the polymer. A crosslinking agent is a compound that can produce a crosslinking reaction in a polymer.

[0027] The viscosity value (e.g., ≥ 1,000,000 MPa.s) of the high-viscosity diorganopolysiloxane polymers required as in (B1a) can be measured using an AR2000 rheometer from TA Instruments, Newcastle, Delaware, USA, or a suitable Brinell viscometer with the most appropriate rotor for viscosity measurement. However, (B1a) can be a silicone resin, which is a high molecular weight polymer with very high viscosity. The resin will typically have a viscosity of at least 2,000,000 mPa.s at 25°C, but often significantly higher. Therefore, given that viscosity becomes very difficult to measure, the resin is typically characterized by its Williams plasticity value according to ASTM D-926-08.

[0028] This article also provides a method for forming a vulcanized thermoplastic elastomer from the above composition, the method comprising contacting a thermoplastic material (A) with an organosilicon composition (B).

[0029] The weight ratio of (A) to (B) is 50:50 to 95:5.

[0030] Additional components (D) may be added to the composition, and when necessary, to produce the necessary properties according to the requirements of the end-use application.

[0031] Thermoplastic organic polyether block amide copolymer (A) Thermoplastic organic polyether block amide copolymer (hereinafter referred to as PEBA) (A) contains hard blocks and soft blocks. The hard blocks are based on polyamide (abbreviated as PA) blocks and may contain homopolymers or copolymers.

[0032] In PEBA, the weight percentage of the at least one rigid polyamide block is 5% to 95%, preferably 15% to 95%, relative to the total weight of the copolymer, and the weight percentage of the at least one flexible block is 5% to 95%, preferably 5% to 85%.

[0033] Preferably, based on the polystyrene equivalent using the method described in ASTM D6474-12, the number-average molar mass Mn of the polyamide block comprises 400 to 20,000 g / mol, preferably 500 to 10,000 g / mol, and more preferably 500 to 3,000 g / mol, and even more preferably 500 to 2,000 g / mol.

[0034] In block copolymers, PA blocks may contain carboxylic acid end groups, and are thus referred to as diacid PA, or alternatively they may contain amine end groups, and are referred to as diamine PA. Therefore, the bond between the PA block and the soft block (SB) can be an ester bond or an amide bond. Polyamide blocks containing dicarboxylic acid end groups originate from, for example, the condensation of a polyamide precursor in the presence of a chain-restricted dicarboxylic acid.

[0035] Three types of polyamides can be part of the composition of these PA blocks.

[0036] i) A condensation product of at least one (aliphatic, alicyclic or aromatic) dicarboxylic acid (e.g., those having 4 to 36 carbon atoms, or alternatively 6 to 18 carbon atoms) and one or more aliphatic, alicyclic or aromatic diamines (particularly selected from those having 2 to 36 carbon atoms, preferably those having 6 to 12 carbon atoms).

[0037] ii) A condensation product of one or more α,ω-aminocarboxylic acids and / or one or more lactams having 6 to 12 carbon atoms in the presence of a dicarboxylic acid or diamine having 4 to 36 carbon atoms. Advantageously, the second type of polyamide block is polyamide 11, polyamide 12 or polyamide 6.

[0038] iii) Polycondensation of at least one α,ω-aminocarboxylic acid (or a lactam) with at least one diamine and one dicarboxylic acid. In this case, the PA block is prepared by polycondensation of the following in the presence of a chain restrictor selected from dicarboxylic acids or diamines, or in excess of a diacid or diamine used as a structural unit: one or more aliphatic, alicyclic, or aromatic diamines having X carbon atoms; one or more dicarboxylic acids having Y carbon atoms; and One or more comonomers {Z} selected from lactams and α,ω-aminocarboxylic acids having Z carbon atoms; advantageously, a dicarboxylic acid having Y carbon atoms is used as a chain limiting agent, said dicarboxylic acid being introduced in stoichiometric excess relative to one or more diamines.

[0039] iv) At least two different α,ω-aminocarboxylic acids or at least two different lactams having 6 to 12 carbon atoms, or a condensation product of a lactam and an aminocarboxylic acid having different numbers of carbon atoms, optionally in the presence of a chain restrictor.

[0040] Examples of aliphatic diacids include, for example, succinic acid, adipic acid, octanoic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, myristic acid, tetradecanedicarboxylic acid, hexadecanedicarboxylic acid, octadecanedicarboxylic acid, and dimer fatty acids. An example of an alicyclic diacid is 1,4-cyclohexyldicarboxylic acid. Examples of aromatic diacids may include sodium, potassium, or lithium salts of terephthalic acid (T), isophthalic acid (I), and 5-sulfoisophthalic acid.

[0041] Examples of aliphatic diamines include tetramethylenediamine, hexamethylenediamine, 1,10-decamethylenediamine, dodecamethylenediamine, and trimethylhexamethylenediamine. Examples of alicyclic diamines may include isomers of bis(4-aminocyclohexyl)methane (BACM or PACM), bis(3-methyl-4-aminocyclohexyl)methane (BMACM or MACM), 2,2-bis(3-methyl-4-aminocyclohexyl)propane (BMACP), isophorone diamine (IPDA), 2,6-bis(amino-methyl)norbornene (BAMN), and piperazine (Pip).

[0042] Examples of α,ω-aminocarboxylic acids include aminohexanoic acid, 7-aminoheptanoic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid. Examples of lactams include caprolactam, heptanolactam, and laurolactam.

[0043] The product of (i) above may include at least one based on PA 4.4, PA 4.6, PA 4.9, PA 4.10, PA 4.12, PA 4.13, PA 4.14, PA 4.16, PA 4.18, PA 4.36, PA 6.4, PA 6.6, PA 6.9, PA 6.10, PA 6.12, PA 6.13, PA 6.14, PA 6.16, PA 6.18, PA 6.36, PA 9.4, PA 9.6, PA 9.10, PA 9.12, PA 9.13, PA 9.14, PA 9.16, PA 9.18, PA 9.36, PA 10.4, PA 10.6, PA 10.9, PA 10.10, PA 10.12, PA 10.13, PA 10.14, PA 10.16, PA 10.18, PA 10.36, PA 10.T, PA 10.1, PABMACM.4, PA BMACM.6, PA BMACM.9, PA BMACM.10, PA BMACM.12, PA BMACM.13, PABMACM.14, PA BMACM.16, PA BMACM.18, PA BMACM.36, PA PACM.4, PA PACM.6, PA PACM.9, PAPACM.10, PA PACM.12, PA PACM.13, PA PACM.14, PA PACM.16, PA PACM.18, PA PACM.36, PAPip.4, PA Pip.6, PA Pip.9, PA Pip.10, PA Pip.12, PA Pip.13,PA Pip.14,PA PA blocks of Pip.16, PAPip.18 and / or PA Pip.36 and their copolymers.

[0044] Alternatively, the polyamide block can be made from the following polyamides (copolyamides): PA 6 / 12, where 6 represents caprolactam and 12 represents laurolactam; PA 11 / 12, where 11 represents 11-aminoundecanoic acid and 12 represents laurolactam; PA 6 / 11, where 6 represents caprolactam and 11 represents 11-aminoundecanoic acid; PA 6 / 6.6, where 6 represents caprolactam and 6.6 represents a monomer obtained by condensation of hexamethylenediamine with adipic acid. Examples include PA 10.10 / 11, PA 6.10 / 11, PA 10.12 / 11, PA 10.10 / 11 / 12, PA 6.10 / 10.10 / 11, PA 6.10 / 6.12 / 11, PA 6.10 / 6.12 / 10.10, PA 11 / 6.36, PA 11 / 10.36, and PA 10.10 / 10.36.

[0045] Examples of polyamide blocks include those comprising at least one of the following molecules: PA-12, PA-11, PA-10, 10, PA-6, 10, PA-6, PA-6 / 12; and copolyamides comprising at least one of the following monomers: 11, 5, 4, 5, 9, 5, 10, 5, 12, 5, 13, 5, 14, 5, 16, 5, 18, 5, 36, 6, 4, 6, 9, 6, 10, 6 ,12、6、13、6、14、6、16、6、18、6、36、10、4、10、9、10、10、10、12、10、13、10、14、10、16、10、18、10、36、10、T、12、4、12、9、12、10、12、12、12、13、12、14、12、16、12、18、12、36、12、T and their blends or copolymers.

[0046] The polyamide block copolymer (A) also comprises soft or flexible blocks, which can be contemplated in the copolymer according to the invention, and should be particularly understood to be those selected from polyether blocks. By way of example, the polyether blocks are selected from poly(ethylene glycol) (PEG), poly(1,2-propanediol) (PPG), poly(1,3-propanediol) (PO3G), poly(tetramethylene glycol) (PTMG), and copolymers or blends thereof. Preferably, the number-average molecular weight M of the soft block according to the invention is based on the polystyrene equivalent using the method described in ASTM D6474-12. n Within the range of 250 extending to 5000 g / mol, alternatively 250 extending to 3000 g / mol, and alternatively 500 extending to 2000 g / mol.

[0047] According to a preferred embodiment, the PA block of the copolymer used in the present invention comprises an equimolar combination of at least one alicyclic diamine and at least one aliphatic (preferably linear) dicarboxylic acid having 12 to 18 carbon atoms, at a concentration greater than 70 mol%, preferably greater than 80 mol%, preferably greater than 90 mol%, preferably 100 mol%.

[0048] Any suitable PEBA may be used herein as PEBA (A), for example, said PEBA (A) may contain PA-12 / PEG, PA-6 / PEG, PA-6 / 12 / PEG, PA-11 / PEG, PA-12 / PTMG, PA-6 / PTMG, PA-6 / 12 / PTMG, PA-11 / PTMG, PA-12 / PEG / PPG, PA-6 / PEG / PPG, PA-6 / 12 / PEG / PPG, PA-11 / PEG / PPG, PA-11 / PO3G, PA-6,10 / PO3G and / or PA-10,10 / PO3G.

[0049] PEBA copolymers are commercially available, such as those sold by Arkema under the PEBAX® trademark or by Evonik under the Vestamid® trademark.

[0050] Organosilicon composition B Organosilicon-based materials (B1) Two organopolysiloxane polymers (B1a) The diorganopolysiloxane polymer (B1a) may have a predominantly linear molecular structure. The diorganopolysiloxane polymer (B1a) may, for example, comprise α,ω-vinyldimethylsiloxane, α,ω-vinyldimethylsiloxane copolymers comprising α,ω-vinyldimethylsiloxane and dimethylsiloxane units, and / or α,ω-trimethylsiloxane copolymers comprising methylvinylsiloxane and dimethylsiloxane units. The diorganopolysiloxane polymer (B1a) has a viscosity of at least 1,000,000 mPa·s at 25°C, which is measured using an AR 2000 rheometer from TA Instruments, Newcastle, Delaware, USA, or a suitable Brookfield viscometer with the most appropriate rotor for viscosity measurement. If desired, the diorganopolysiloxane polymer (B1a) may be a resin characterized by a Vickers plasticity value as measured by a Vickers parallel plate plasticizer according to ASTM D-926-08, which becomes very difficult to determine accurately given such high viscosity values. If desired, the diorganopolysiloxane polymer (B1a) can be modified with a small amount of non-reactive organosilicon such as trimethylsilyl-terminated polydimethylsiloxane. Alternatively, the diorganopolysiloxane polymer (B1a) is a resin.

[0051] The alkenyl group in the diorganopolysiloxane (B1a) can be exemplified by vinyl, hexenyl, allyl, butenyl, pentenyl, and heptenyl. The silicon-bonded organic groups in the diorganopolysiloxane polymer (B1a), other than alkenyl, can be exemplified by methyl, ethyl, propyl, butyl, pentyl, hexyl, or similar alkyl groups; or phenyl, tolyl, xylyl, or similar aryl groups.

[0052] Reinforcing filler (B1b) The reinforcing filler (B1b) can be, for example, silica. Silica can be, for example, fumed (pyrolytic) silica, such as that sold by Cabot under the trademark Cab-O-Sil MS-75D, or it can be precipitated silica. The particle size of the silica is, for example, 0.5 µm to 20 µm, or alternatively 1 µm to 10 µm. The silica can be treated silica, for example, produced by treating silica with a silane or polysiloxane. The silane or polysiloxane used to treat silica typically contains hydrophilic groups and aliphatic unsaturated hydrocarbons or hydroxyl groups bonded to the silica surface and / or hydrogen atoms bonded to Si.

[0053] Silica can be treated, for example, with alkoxysilanes, such as silanes containing at least one alkoxy group bonded to Si and at least one alkenyl group bonded to Si or at least one hydrogen atom bonded to Si. Alkoxysilanes can be monoalkoxysilanes, dialkoxysilanes, or trimekoxysilanes containing at least one aliphatic unsaturated hydrocarbon group, such as vinylalkoxysilanes, for example vinyltrimethoxysilane, vinyltriethoxysilane, or vinylmethyldimethoxysilane. The Si-bonded alkoxy group can readily hydrolyze into a silanol group bonded to the surface of silica.

[0054] Alternatively, silica can be treated with polysiloxanes, such as oligomeric organopolysiloxanes containing alkenyl and silanol end groups bonded to Si.

[0055] Silica can be treated, for example, with 2% to 60% by weight (based on silica) of an alkenyl-containing alkoxysilane or an alkenyl-containing oligomeric organopolysiloxane.

[0056] Organohydrogenated organosilicon compounds (B2) The organohydrogenated organosilicon compound (B2), having at least two hydrogen atoms bonded to Si per molecule, can be, for example, a low molecular weight organosilicon resin or a short-chain or long-chain organosiloxane polymer, which can be linear or cyclic. The organohydrogenated organosilicon compound (B2) preferably has at least three hydrogen atoms bonded to silicon per molecule, and is capable of reacting with the alkenyl or other aliphatic unsaturated groups of the diorganopolysiloxane polymer (B1a). The organohydrogenated organosilicon compound (B2) can, for example, have the following general formula. R 3 R 4 2SiO(R 4 2SiO) p (R 4 HSiO) q SiR 4 2R 3 or Where R 4 It indicates an alkyl or aryl group having up to 10 carbon atoms, and R 3 Represents group R 4 Or hydrogen atoms, p has a value of 0 to 20 and q has a value of 1 to 70, and each molecule contains at least 2 or 3 hydrogen atoms bonded to silicon. R 4It can be, for example, a lower alkyl group having 1 to 3 carbon atoms, such as methyl. The organohydrogenated organosilicon compound (B2) can, for example, have a viscosity of 1 to 150 mPa·s at 25°C, or alternatively 2 to 100 mPa·s or 5 to 60 mPa·s at 25°C. The average degree of polymerization of the organopolysiloxane (B2) can, for example, be 30 to 400 siloxane units per molecule. Examples of suitable organohydrogenated organosilicon compounds (B2) include trimethylsiloxane-terminated polymethylhydrosiloxanes, dimethylhydrosiloxane-terminated methylhydrosiloxanes, dimethylsiloxane-methylhydrosiloxane copolymers, and tetramethylcyclotetrasiloxanes. The organohydrogenated organosilicon compound (B2) can include mixtures of more than one of these materials.

[0057] The molar ratio of Si-H groups in the organohydrogenated organosilicon compound (B2) to aliphatic unsaturated groups in the diorganopolysiloxane polymer (B1a) is preferably at least 1:1, and can be up to 8:1 or 10:1. For example, the molar ratio of Si-H groups to aliphatic unsaturated groups is from 1.5:1 to 5:1.

[0058] Hydrosilylation catalyst (C) is preferably a platinum group metal (Group VIII of the periodic table) or a compound thereof. Platinum and / or platinum compounds are preferred, such as finely powdered platinum; chloroplatinic acid or an alcoholic solution of chloroplatinic acid; olefinic complexes of chloroplatinic acid; complexes of chloroplatinic acid and alkenylsiloxanes; platinum-diketone complexes; metallic platinum on silica, alumina, carbon, or similar supports; or thermoplastic resin powders containing platinum compounds. Catalysts based on other platinum group metals can be exemplified by rhodium, ruthenium, iridium, or palladium compounds. For example, these catalysts can be represented by the following formulas: RhCl(PPh3)3, RhCl(CO)(PPh3)2, Ru3(CO). 12 IrCl(CO)(PPh3)2 and Pd(PPh3)4 (where Ph represents phenyl).

[0059] Based on the polyorganosiloxane composition (B), the catalyst (C) is preferably used in an amount of platinum group metals from 0.5 to 100 parts per million, more preferably from 1 to 50 parts per million, by weight. The hydrosilylation catalyst (C) catalyzes the reaction of the alkenyl group of the diorganopolysiloxane polymer (B1a) with the Si-H group of the organohydrosilicon compound (B2).

[0060] Additive - Component D Component (D) is present in the thermoplastic elastomer composition of the present invention to obtain the desired processing or performance properties of the thermoplastic elastomer.

[0061] Such additives may include, for example, softening mineral oils, plasticizers, other mineral fillers (i.e., excluding (B1b) reinforcing fillers), viscosity modifiers, stabilizers, lubricants, polydimethylsiloxane (PDMS), thermoplastic elastomers and refractory additives, colorants such as pigments and / or dyes; effect pigments such as diffractive pigments; interference pigments such as pearlescent agents; reflective pigments and mixtures thereof and mixtures of any of the above pigments; UV stabilizers, anti-aging agents, antioxidants, fluidizing agents, anti-wear agents, release agents, stabilizers, plasticizers, impact modifiers, surfactants, whitening agents, fillers, fibers, waxes, and mixtures thereof, and / or any other additives well known in the polymer field.

[0062] This component should be used alone or in combination. The addition level of component (D) should be up to 30% by weight of the total composition. Preferably, if one or more components (D) are present, the total cumulative amount of the additive is typically 0.01% to 20%, preferably 0.01% to 10%, preferably 0.01% to 5%, by weight of the total weight of the composition.

[0063] Mineral oil is usually C 15 To C 40 The range includes petroleum distillates such as white oil, liquid paraffin, or naphthenic oil. If used, the mineral oil may be premixed, for example, with a thermoplastic organic polyether block amide copolymer. Based on the thermoplastic organic polyether block amide copolymer, the mineral oil may be present, for example, in an amount of 0.5 to 20% by weight.

[0064] Plasticizers can be present in combination with or as a substitute for mineral oil. Examples of suitable plasticizers include phosphate plasticizers, such as isopropylated triaryl phosphate, resorcinol bis-(diphenyl phosphate), or phosphate esters marketed by Great Lakes Chemical Corporation under the trademark Reofos® RDP. Such plasticizers can be used, for example, from 0.5% to 15%.

[0065] Examples of other mineral fillers include talc or calcium carbonate. The filler can be treated to make its surface hydrophobic. If present, such fillers are preferably present at lower levels than reinforcing fillers (B1b) such as silica. The filler can be premixed with thermoplastic organic polyether block amide copolymers or silicone-based materials (B1).

[0066] Examples of pigments include carbon black and titanium dioxide. Pigments can be premixed, for example, with thermoplastic organic polyether block amide copolymers.

[0067] Stabilizers can be, for example, antioxidants, such as hindered phenolic antioxidants, like tetra(methylene(3,5-di-tert-butyl-4-hydroxy-hydrogenated cinnamate)methane sold by BASF under the trademark 'Irganox 1010'. Such antioxidants can be used, for example, at 0.05 to 0.5% by weight of the thermoplastic elastomer composition.

[0068] Lubricants can be, for example, surface lubricating additives that improve the processability of thermoplastic elastomers during molding operations. An example of a surface lubricating additive is ethyl butyl stearamide, marketed by CRODA under the trademark 'Crodamide-EBS'. The lubricant can be used, for example, at 0.1 to 2% by weight of the thermoplastic elastomer composition.

[0069] Within the scope of this invention, the use of flame-retardant additives is also contemplated to provide flame retardancy to the compositions of this invention. Conventional flame retardants may be used herein and may be selected from the group consisting of: halogenated species, such as polydibromostyrene, copolymers of dibromostyrene, polybromostyrene, brominated polystyrene, tetrabromophthalates, tetrabromophthalic acid glycol, tetrabromophthalic anhydride, tetrabromobenzoates, hexabromocyclododecane, tetrabromobisphenol A, tetrabromobisphenol A bis(2,3-dibromopropyl ether), tetrabromobisphenol A bis(allyl ether), phenoxy-terminated carbonate oligomers of tetrabromobisphenol A, decabromodiphenyl ethane, decabromodiphenyl ether, bis-(tribromophenoxy)ethane, ethane-1,2-bis(pentabromophenyl), tetradecylbromodiphenoxybenzene, ethylene bis(tetrabromophthalimide), ammonium bromide, polypentabromobenzyl acrylate, brominated epoxy polymers, brominated epoxy oligomers, and brominated epoxy resins. Other non-halogenated types can be selected from materials such as isopropyltriaryl phosphate, toluene diphenyl phosphate, tricresyl phosphate, trimethylbenzyl phosphate, triphenyl phosphate, butylated triaryl phosphate, resorcinol bis-(diphenyl phosphate), bisphenol A bis(diphenyl phosphate), melamine phosphate, melamine pyrophosphate, melamine polyphosphate, bis(melamine) phosphate, melamine, melamine cyanurate, magnesium hydroxide, antimony trioxide, red phosphorus, zinc borate, and zinc stannate. The amount of flame retardant that can be added to produce the desired effect is known to those skilled in the art. Those amounts are also useful herein.

[0070] As described above, this article also provides a method for forming a vulcanized thermoplastic elastomer from the above-described thermoplastic elastomer composition. This is achieved by contacting a thermoplastic organic polyether block amide copolymer (A) with an organosilicon composition (B).

[0071] The weight ratio of (A) to (B) is 50:50 to 95:5.

[0072] Additional components (D) can be added to the composition to further manage the inventive properties according to the specific needs of the end application.

[0073] Thermoplastic elastomers are produced by contacting the following: a thermoplastic organic polyether block amide copolymer (A) (which may be premixed with an additive (D) (when present), i.e., = (A) + (D) (if (D) is present)) with an organosilicon composition B, said organosilicon composition comprising (B1) an organosilicon base, said organosilicon base comprising: (B1a) A diorganopolysiloxane polymer (preferably a resin) having an average of at least 2 alkenyl groups per molecule. (B1b) Based on a diorganopolysiloxane polymer (B1a), 1 to 50% by weight of reinforcing filler, and (B2) Organohydrogenated organosilicon compounds, each molecule of which contains an average of at least two hydrogen groups bonded to silicon. (C) Hydrosilylation catalyst.

[0074] The above components are typically contacted at elevated temperatures, such as 100°C to 250°C. Temperatures of 160°C to 240°C, or alternatively 180°C to 220°C, can be conveniently used. The reaction of the alkenyl group of the organopolysiloxane polymer (B1a) with the Si-H group of the organohydrogenated organosilicon compound (B2) is carried out simultaneously with a premixture of the mixed organosilicon composition (B) and (A) or (A) + (D) (if (D) is present), resulting in the production of a vulcanized thermoplastic elastomer composition.

[0075] The components are mixed in any apparatus capable of uniformly dispersing the silicone component in the thermoplastic organic polyether block amide copolymer. The premixture of (A) or (A) + (D) (if (D) is present) and the silicone composition (B) can be blended, for example, in an extruder. The extruder can be a single-screw extruder, a twin-screw extruder, or a multi-screw extruder. A twin-screw extruder, particularly one with a length / diameter (L / D) ratio exceeding 40, is generally suitable. The screw speed can be, for example, 150 to 300 rpm. The residence time of the premixture of (A) or (A) + (D) (if (D) is present) and the silicone base material (B1) in the extruder can be, for example, 30 to 240 seconds.

[0076] The silicone base material (B1) can be prepared by premixing a diorganopolysiloxane polymer (preferably a resin) (B1a) and reinforcing filler (B1b) before feeding the silicone base material (B1) into an extruder or other mixing unit, or the diorganopolysiloxane polymer (B1a) and reinforcing filler (B1b) can be fed into the mixing unit separately. The silicone base material (B1) can be mixed with a premixture of (A) or (A) + (D) (if (D) is present) in the initial processing section of the extruder. The premixture of (A) or (A) + (D) (if (D) is present) can be introduced, for example, into the main feed of a co-rotating twin-screw extruder operating at a temperature sufficiently high to melt the thermoplastic organic polymer. The silicone base material (B1) can be added to the molten olefin polymer phase using, for example, a gear pump. To maintain the quality of the working environment and avoid side reactions, inert gas flushing or degassing using single-stage or multi-stage ventilation can be used.

[0077] The organohydrosilane compound (B2) and the hydrosilaneization catalyst (C) can be added in a later stage of the extruder. When both the organohydrosilane compound (B2) and the hydrosilaneization catalyst (C) have been added to the composition, dynamic curing or vulcanization of the diorganopolysiloxane typically occurs within the extruder during the mixing stage. The order of addition of the organohydrosilane compound (B2) and the hydrosilaneization catalyst (C) is not critical. However, whichever of these components is added first should be well dispersed in the mixture before adding another component to initiate dynamic vulcanization. For example, after a premixture of (A) or (A) + (D) (if (D) is present) and the silicone base material (B1) has been mixed, the organohydrosilane compound (B2) can be added to the composition, and the hydrosilaneization catalyst (C) can be added subsequently to initiate dynamic vulcanization while mixing continues. Alternatively, the organohydrogenated organosilicon compound (B2) can be added to the composition together with the organosilicon base material (B1). In another alternative, after a premixture of (A) or (A) + (D) (if (D) is present) and the organosilicon base material (B1) has been mixed, a hydrogenated silylation catalyst (C) can be added to the composition, and the organohydrogenated organosilicon compound (B2) can be subsequently added to initiate dynamic sulfidation while mixing continues.

[0078] Alternative plastic mixing equipment can be used, such as batch internal mixers, Z-blade mixers, or Banbury mixers. The components can be mixed in the order described above, allowing sufficient time for the silicone base material (B1) and the organohydrosilicone compound (B2) to be well dispersed in the thermoplastic polyurethane polymer before adding the hydrogenated silanization catalyst to initiate dynamic vulcanization.

[0079] The weight ratio of the two components (A) : (B) is always the individual amounts of (A) and (B), where the total amount of (A) + (B) is 100.

[0080] If (D) is present, the weight ratio of the premixture of (A) + (D) to the silicone composition (B) is typically 50:50 to 95:5. Within this range, the level of silica in the silicone composition (B), the weight ratio of the premixture of (A) + (D) to the silicone composition (B) if (D) is present, and the crosslinking density of the silicone can be varied to produce a desired balance of soft touch, mechanical properties, moisture resistance, chemical resistance to cosmetics, and scratch resistance. The crosslinking density of the silicone can be varied by changing the diorganopolysiloxane polymer (B1a) used, particularly regarding the length of the siloxane chain between the alkenyl groups. Long-chain diorganopolysiloxane polymer resins (B1a) with only two terminal alkenyl groups will form softer thermoplastic elastomers; diorganopolysiloxane polymer resins (B1a) with more alkenyl groups or shorter chain lengths will form harder thermoplastic elastomers.

[0081] use The elastomer obtained by curing the above thermoplastic elastomer composition combines high mechanical properties, scratch resistance, and improved durability with a desirable soft touch, and can be used in a wide range of applications, such as: Thermoplastic elastomers can be used, for example, to manufacture parts or components for automotive applications, such as gear knobs, seat belt connectors, inner pads, airbag covers, and molded covers for dashboards and armrests; functional automotive parts, such as pipes like air ducts, cable insulation, oil hoses and fuel tank airbag covers, steering wheel covers, gear knobs, grab handles, armrests, inner pads, car mats (such as cup holders, trash cans, glove box mats), small knobs, switches, and large automotive parts (large means with a surface area greater than 20 cm²). 2 Examples include glove box panels, dashboards, and door panels.

[0082] Thermoplastic elastomers can also be used to manufacture parts or components for electronic products and appliances, such as belts, bracelets, soft foot covers, protective covers and wearable electronics; hoses, boots, bellows, gaskets, soft-feel covers, keyboard palm rests, laptop and tablet devices.

[0083] Thermoplastic elastomers can also be used to manufacture sports application components for the soles of footwear used in sprinting, football, rugby, tennis, basketball, running, alpine or Nordic skiing, as well as parts or components in golf balls and many other sporting goods; Thermoplastic elastomers can also be used to manufacture parts or components for electronic devices used in portable electronics, electrical appliances, communications, and appliances; Thermoplastic elastomers can also be used to manufacture parts or components for medical device applications, notably as catheters, angioplasty balloons, and peristaltic strips; Thermoplastic elastomers can also be used to manufacture wearable items or their parts or components, such as watch-style bracelets, GPS bracelets, temple covers and nose pads for sunglasses and reading glasses. Such wearable items retain their properties when in prolonged contact with human skin and various cosmetic chemicals on the skin (such as perfumes, moisturizers and creams) as well as skin exudates such as sweat.

[0084] Thermoplastic elastomers are also used in general rubber applications where durable aesthetics, tactile and ergonomic properties are required, along with stability and low staining upon exposure to the most common chemicals, as well as high mechanical properties, abrasion resistance, and scratch resistance (conveyor belts, as breathable raincoats). Due to its inherent elastomeric properties, it can also be used for climate insulation, such as mirror seals, internal and external seals. Due to the combination of scratch resistance, durability, and elastomeric properties, it can be used in footwear applications.

[0085] Thermoplastic elastomers can also be used to manufacture other applications such as protective shields; liquid piping components and air ducts (non-automotive); building seals; bottle caps; furniture parts; durable and soft-feel handles for handheld devices; packaging components such as seals, bottles, cans, and cups; medical and health devices; and cookware parts and accessories. Thermoplastic elastomers can be extruded, co-extruded, extruded-laminated, calendered, extruded-calendered, or laminated to form thermoplastic films, thermoplastic sheets, and synthetic leather with granular or non-granular surfaces. For example, it can be applied to textiles to create laminates that form synthetic leather products. Co-extrusion or post-processing with compatible materials, thermoplastic, synthetic woven or nonwoven textiles, can be achieved to form composite laminates. Co-extrusion or post-processing with incompatible materials, thermoplastic, synthetic or natural woven or nonwoven textiles, can be achieved to form composite laminates using sufficient primer or interface materials.

[0086] Examples of such applications are: - Synthetic leather for automotive applications, such as seats, door panels, gear knobs, armrests, steering wheels, and wheel covers. - Synthetic leather for electronic applications, such as electronic devices like laptops or tablets, to provide a soft touch. - Synthetic leather for sporting goods and footwear applications - The strap or belt of the fitness tracker - 2K or two-shot injection molded parts based on parts overmolded, co-extruded, or backed-up molded using the thermoplastic elastomer composition and compatible materials of the present invention. - 2K or double-shot injection molded parts based on the thermoplastic elastomer composition of the present invention and incompatible materials, plus the use of sufficient adhesion promoters or techniques to bond these overmolded, co-extruded or backing molded parts.

[0087] The weight ratio of the two components (A) : (B) is always the individual amounts of (A) and (B), where the total amount of (A) + (B) is 100.

[0088] The weight ratio of thermoplastic organoether block amide copolymer to silicone composition (B) is typically from 50:50 to 95:5. Within this range, the level of silica in silicone composition (B), the weight ratio of thermoplastic organoether block amide copolymer to silicone composition (B), and the crosslinking density of silicone can be varied to achieve a desired balance of soft touch, mechanical properties, moisture resistance, chemical resistance to cosmetics, and scratch resistance. The crosslinking density of silicone can be varied by changing the diorganopolysiloxane polymer (B1a) used (e.g., the resin used), particularly regarding the length of the siloxane chain between the alkenyl groups. Long-chain diorganopolysiloxane resins (B1a) with only two terminal alkenyl groups will form softer thermoplastic elastomers; diorganopolysiloxane resins (B1a) with more alkenyl groups or shorter chain lengths will form harder thermoplastic elastomers.

[0089] Example The present invention is illustrated by the following examples, wherein, unless otherwise stated, parts and percentages are by weight.

[0090] The materials used in the example are: • Si-Rubber 1: An uncatalyzed silicone rubber base material comprising vinyl-terminated diorganopolysiloxane resin and silica. The base material has a plasticity value of 360 mm / 100, measured using a Vickers parallel plate plasticity tester according to ASTM D-926-08. Si-Rubber 1 is intended to have a Shore A hardness of 70 upon curing.

[0091] • Si-Rubber 2: An uncatalyzed silicone rubber base material comprising vinyl-terminated diorganopolysiloxane resin and silica. The base material has a plasticity value of 169 mm / 100, measured using a Vickers parallel plate plasticity tester according to ASTM D-926-08. Si-Rubber 2 is intended to have a Shore A hardness of 40 upon curing.

[0092] • An organosilicon-based catalyst solution containing a sufficient catalyst concentration to cure the aforementioned Si rubber base material. • An organosilicon-based crosslinking agent solution containing a sufficient catalyst concentration to cure the Si rubbers listed above. Four alternative PEBA samples with different physical properties were used and are referred to as follows: • PEBA 1:41 Shore D thermoplastic organic polyether block amide copolymer • PEBA 2:35 Shore D thermoplastic organic polyether block amide copolymer • PEBA 3:25 Shore D thermoplastic organic polyether block amide copolymer • PEBA 4:22 Shore D thermoplastic organic polyether block amide copolymer Thermoplastic elastomers are prepared by the method of the present invention. The components are mixed and vulcanized using a twin-screw extruder. The processing section is heated to 160°C to 240°C, with a screw speed of 150 to 400 rpm. In the first section of the extruder, Si-rubber 1 or 2 is added to the organic thermoplastic preblister, followed by the addition of a crosslinking agent and a catalyst solution, which initiates the vulcanization of the organosilicon composition within the thermoplastic matrix. The proportions of the materials used are shown in the table below.

[0093] Test specimens for mechanical and scratch resistance testing were prepared by injection molding. The injection molding heating temperature was set to 180°C to 220°C, and the mold temperature was set to 40°C. Mechanical properties were tested according to international standards listed in Tables 1, 2, 3, and 4.

[0094] Gloss measurement Gloss is determined by projecting a beam of light onto the surface of the base material at a fixed intensity and angle (in the case of 60°) and measuring the amount of reflected light at equal but opposite angles.

[0095] When evaluating the results in Tables 1, 2, and 3, it becomes clear that the choice of PEBA strongly influences the final hardness of the materials in this invention: PEBA, such as PEBA 3, allows for high hardness variations (-16 Shore A), while harder PEBA (e.g., PEBA 1), when mixed with silicone materials as described above (even for high silicone ratios), has a smaller effect on softness (-8 Shore A). Table 3 shows that silicone-free elastomers exhibit hardness limited to 74 Shore A (PEBA 4), while the silicone-based elastomers of this invention exhibit hardness below 65 Shore A.

[0096] Furthermore, as can be seen from the results in Table 4, different examples of the present invention obtained flexural modulus similar to PEBA4 measured at room temperature, and even had different hardness values.

[0097] Another benefit of this invention is a significant reduction in surface gloss, especially for materials with high silicone content.

[0098] Dynamic elastic shear modulus values ​​were determined to illustrate the viscoelastic behavior of some example compositions and compared with PEBA. A Haak Mars III apparatus was used at a frequency of 1 Hz, a strain of 0.01%, and a temperature variation of 2 °C / min.

[0099] Table 5: Dynamic elastic shear modulus values ​​(Pa)

[0100] The advantage of this invention is that it uses hard PEBA and limits the soft block content to obtain a material with low hardness. This thus maintains the benefits of high hard block content, such as heat resistance, as shown in Table 5 above, despite the relatively low hardness. It can be seen that the examples have a dynamic elastic shear modulus at 30°C similar to that of pure PEBA. However, when compared with the results for comparative PEBA, the loss of dynamic elastic shear modulus with increasing temperature is less significant for the materials described herein, especially at temperatures above 110°C.

Claims

1. A thermoplastic elastomer composition comprising a blend of the following: (A) Thermoplastic organic polyether block amide copolymer, (B) An organosilicon composition comprising: (B1) Organosilicon-based materials, comprising: (B1a) A diorganopolysiloxane polymer having a viscosity of at least 1,000,000 mPa·s at 25°C and an average of at least 2 alkenyl groups per molecule, and (B1b) Reinforcing filler, in an amount of 1 to 50% by weight based on (B1a). (B2) Organohydrogenated organosilicon compounds, each molecule of which contains an average of at least two hydrogen groups bonded to silicon. (C) Hydrosilylation catalyst, and optionally: One or more additive components (D), wherein the weight ratio of the thermoplastic organic polyether block amide copolymer (A) to the silicone composition (B) is 50:50 to 95:5, and wherein components (B2) and (C) are present in an amount sufficient to cure the silicone composition B1.

2. The thermoplastic elastomer composition according to claim 1, wherein, The organopolysiloxane polymer (B1a) is an organopolysiloxane resin.

3. The thermoplastic elastomer composition according to claim 1, wherein, The reinforcing filler (B1b) is silicon dioxide.

4. The thermoplastic elastomer composition according to claim 3, wherein, Based on the two organopolysiloxane polymers (B1a), the silica-reinforcing filler (B1b) is present in an amount of 2 to 10% by weight.

5. The thermoplastic elastomer composition according to claim 3, wherein, Based on the organopolysiloxane polymer (B1a), the silica-reinforcing filler (B1b) is present in an amount of 6 to 20% by weight.

6. The thermoplastic elastomer composition according to claim 1, wherein, The weight ratio of the thermoplastic copolymer (A) to the organosilicon composition (B) is from 50:50 to 95:

5.

7. A method for forming a thermoplastic elastomer, comprising: The following items are brought into contact: (A) a thermoplastic organic polyether block amide copolymer, (B1) a silicone base material comprising: (B1a) a diorganopolysiloxane having a viscosity of at least 1,000,000 mPa·s at 25°C and an average of at least 2 alkenyl groups per molecule, and (B1b) 1 to 50% by weight of reinforcing filler based on the diorganopolysiloxane (B1a), (B2) an organohydrogenated silicone compound containing an average of at least 2 silicon-bonded hydrogen groups per molecule, and (C) a hydrogenation silanization catalyst, wherein the weight ratio of the thermoplastic organic polyether block amide copolymer to the total weight of the silicone base material (B1) and the organohydrogenated silicone compound (B2) is from 50:50 to 95:

5.

8. The method according to claim 7, wherein, The thermoplastic organic polyether block amide copolymer (A), the organosilicon base material (B1), the organohydrogenated organosilicon compound (B2), and the hydrogenated silanization catalyst (C) are brought into contact at a temperature of 100°C to 250°C.

9. The method according to claim 7, wherein, The thermoplastic organic copolymer (A), the organosilicon base material (B1), the organohydrogenated organosilicon compound (B2) and the hydrogenated silanization catalyst (C) are blended in an extruder.

10. The method according to claim 7, wherein, After the thermoplastic elastomer is formed, it is extruded, co-extruded, laminated, calendered, and / or extruded-calendered to form a thermoplastic film or thermoplastic sheet.

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