CN117624750A - Thermoplastic dynamic cross-linked elastomer and preparation method thereof - Google Patents

Abstract

A thermoplastic dynamically crosslinked elastomer comprising the following components: about 100 parts by weight of (A) a styrene copolymer rubber, (B) about 40 to 90 parts by weight of a thermoplastic elastomer, (C) about 5 to 15 parts by weight of an interface compatible resin, and (D) about 0.2 to 3 parts by weight of a crosslinking agent and a crosslinking auxiliary agent, wherein the content of the component (A) is greater than the content of the component (B). The component (A) is dispersed in the component (B) in a particle size of about 0.5 to 10. Mu.m.

Description

Thermoplastic dynamic cross-linked elastomer and preparation method thereof

Technical Field

The present disclosure relates to an elastomer, a method for preparing the same, and an application thereof, and more particularly, to a thermoplastic dynamic cross-linked elastomer and a method for preparing the same.

Background

The thermoplastic dynamically crosslinked elastomer (thermoplastic vulcanizates, TPV) has thermoplastic, easy processability, elastic, and compressibility properties. The thermoplastic dynamic cross-linked elastomer can be processed for a plurality of times, and has the characteristic of being recyclable compared with the traditional thermosetting rubber, so that the thermoplastic dynamic cross-linked elastomer can be used for replacing the thermosetting rubber. The traditional thermoplastic dynamic cross-linked elastic system is mainly composed of polypropylene/ethylene propylene diene monomer (PP/EPDM). However, conventional thermoplastic dynamic cross-linked elastomers have poor wear and slip resistance properties and low polarity of the material surface.

Conventional athletic shoe constructions include an upper member, a midsole member, an outsole member, and an adhesive member that connects the upper member, midsole member, and outsole member together. Conventional midsole components are made from ethylene/vinyl acetate copolymer (EVA). Ethylene/vinyl acetate copolymers are polar materials. The outsole component comprising the conventional thermoplastic dynamically crosslinked elastomer and the midsole component comprising the ethylene/vinyl acetate copolymer may not firmly conform together due to the polarity difference between the conventional thermoplastic dynamically crosslinked elastomer and the ethylene/vinyl acetate copolymer.

Disclosure of Invention

The present disclosure provides a novel thermoplastic dynamic cross-linked elastomer and a method of making the same.

According to an embodiment of the present disclosure, there is provided a thermoplastic dynamic cross-linked elastomer comprising the following components: about 100 parts by weight of (A) a styrene copolymer rubber, (B) about 40 to 90 parts by weight of a thermoplastic elastomer, (C) about 5 to 15 parts by weight of an interface compatible resin, and (D) about 0.2 to 3 parts by weight of a crosslinking agent and a crosslinking auxiliary agent, wherein the content of the component (A) is greater than the content of the component (B). The component (A) is uniformly dispersed in the component (B) in a particle size of about 0.5 to 10. Mu.m.

According to another embodiment of the present disclosure, there is provided a method for preparing a thermoplastic dynamic cross-linked elastomer, comprising the steps of: preparing a first mixture, wherein the first mixture comprises rubber, a cross-linking agent and a cross-linking auxiliary agent; performing an extrusion granulation process to form first mixture particles from the first mixture; mixing the thermoplastic elastomer, the interface compatible resin, and the first mixture particles to form a second mixture, wherein the content of rubber in the first mixture particles is greater than the content of the thermoplastic elastomer in parts by weight; and performing a dynamic cross-linking process to form a thermoplastic dynamic cross-linked elastomer from the second mixture, wherein the dynamic cross-linking process uses a process temperature of about 170 ℃ to 200 ℃ and a rotational speed of about 150 to 300 rpm.

Drawings

The foregoing and other objects, features and advantages of the disclosure will be more apparent from the following description of embodiments of the disclosure with reference to the accompanying drawings, in which:

FIG. 1 is a flow chart of a method of preparing a thermoplastic dynamically crosslinked elastomer according to an embodiment of the present disclosure.

FIG. 2 is an SEM image of thermoplastic dynamically crosslinked elastomer particles according to one embodiment of the disclosure.

Reference numerals illustrate:

10: the preparation method; s101, S103, S105, S107: step (a)

Detailed Description

For the purposes of promoting an understanding of the principles and advantages of the disclosure, reference will now be made to the embodiments illustrated in the drawings and specific language will be used to describe the same.

As used in this disclosure, "about" is meant to include the values as well as values in a range of acceptable deviation that would occur to one having ordinary skill in the art in view of measurement problems and measurement errors (i.e., limitations of the measurement system). For example, "about" may represent a value that is within one or more standard deviations of the value or within ±30%, 20%, 10%, 5% of the value. The amounts given herein are about amounts, i.e., where "about", "substantially" are not specifically recited, the meaning of "about", "substantially" may be implied. In the present disclosure, the expression "a to b" means that a value equal to or greater than a and a value equal to or less than b are included.

Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and the present disclosure and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.

Some embodiments of the present disclosure are described below, and additional steps may be provided before, during, and/or after the various stages described in these embodiments. Some of the stages may be replaced or eliminated in different embodiments. Although some of the embodiments discussed are performed in a specific order of steps, these steps may be performed in another logical order.

The present disclosure provides a thermoplastic dynamic cross-linked elastomer comprising the following components: about 100 parts by weight of (A) a styrene copolymer rubber, (B) about 40 to 90 parts by weight of a thermoplastic elastomer, (C) about 5 to 15 parts by weight of an interface compatible resin, and (D) about 0.2 to 3 parts by weight of a crosslinking agent and a crosslinking auxiliary agent, wherein the content of the component (A) is greater than the content of the component (B). In some embodiments, the thermoplastic dynamically crosslinked elastomer may further include about 5 to 50 parts by weight of an additive as component (E). In some embodiments, the thermoplastic dynamically crosslinked elastomer may further include about 0 to 20 parts by weight of a non-aromatic rubber as component (F). In some embodiments, the weight ratio of component (A) to component (F) in the thermoplastic dynamically crosslinked elastomer is about 8-10:0-2. In some embodiments, the weight ratio of component (A) to component (F) is about 9:1.

In some embodiments, the thermoplastic dynamically crosslinked elastomer may include about 40 to 90 parts by weight, about 50 to 85 parts by weight, about 60 to 84 parts by weight, about 70 to 83.5 parts by weight, about 75 parts by weight, or about 90 parts by weight of component (B) based on 100 parts by weight of component (a). In some embodiments, the thermoplastic dynamically crosslinked elastomer may include about 5 to 15 parts by weight, about 8 to 12 parts by weight, about 9 to 11 parts by weight, or about 9.0 to 10.5 parts by weight, 10.2 parts by weight, or about 9.2 parts by weight of component (C) based on 100 parts by weight of component (A). In some embodiments, the thermoplastic dynamically crosslinked elastomer may include about 0.2 to 2.9 parts by weight, about 0.25 to 2.85 parts by weight, about 0.30 to 2.75 parts by weight, about 0.40 to 2.70 parts by weight, about 0.45 parts by weight, about 2.45 parts by weight, or about 2.675 parts by weight of component (D) based on 100 parts by weight of component (a). In some embodiments, the thermoplastic dynamically crosslinked elastomer may include about 5.5 to 50 parts by weight, about 10 to 50 parts by weight, about 6.0 to 49.5 parts by weight, about 16.0 to 49.0 parts by weight, about 6.45 parts by weight, about 7.16 parts by weight, about 16.45 parts by weight, or about 48.95 parts by weight of component (E) based on 100 parts by weight of component (A). In some embodiments, the thermoplastic dynamically crosslinked elastomer may include about 0 to 20 parts by weight, about 5 to 15 parts by weight, about 10 to 12 parts by weight, or about 11.4 parts by weight of component (F) based on 100 parts by weight of component (A).

In one embodiment, component (B) may be a continuous phase and component (a) may be a dispersed phase dispersed in component (B). The above features can be observed by scanning electron microscopy (Scanning Electron Microscope, SEM). Specifically, after obtaining an SEM image of the thermoplastic dynamic crosslinked elastomer of the present disclosure using a scanning electron microscope, it can be seen from an observation of the obtained SEM image that the thermoplastic dynamic crosslinked elastomer of the present disclosure has a continuous phase and a dispersed phase, and the dispersed phase is dispersed in the continuous phase in the form of a plurality of particles. In one embodiment, component (A) is spherical particles having a particle size of about 0.5 to 10 μm. In some embodiments, component (A) is spherical particles having a particle size of about 0.5 to 5 μm. The particle diameter of the particles of the dispersed phase described in the present disclosure is obtained by performing calculation of the average particle diameter of spherical particles using image processing software, based on the obtained SEM image.

The thermoplastic dynamic crosslinked elastomers of the present disclosure including the above features may have a Shore A hardness of about 45-80, an abrasion loss of about 50-250 mg according to DIN 53516, and a wet skid resistance coefficient of about 0.25-0.45 according to F1677. In some embodiments, the thermoplastic dynamically crosslinked elastomers of the present disclosure have a shore a hardness of about 50 to 75, about 50 to 70, or about 55 to 65. In some embodiments, the thermoplastic dynamically crosslinked elastomers of the present disclosure have an abrasion loss of about 80 to 250mg, about 90 to 250mg, or about 100 to 250 mg. In some embodiments, the thermoplastic dynamically crosslinked elastomers of the present disclosure have a wet skid coefficient of from about 0.28 to 0.45, from about 0.30 to 0.43, or from about 0.33 to 0.40.

In summary, the thermoplastic dynamic cross-linked elastomer of the present disclosure has better abrasion resistance and better wet skid resistance. The thermoplastic dynamic cross-linked elastomers of the present disclosure are therefore applicable to any field having high abrasion resistance and high wet skid resistance requirements. In some embodiments, the thermoplastic dynamically crosslinked elastomers of the present disclosure are suitable for use in soles, sporting goods, construction materials, and industrial materials, but the present disclosure is not limited thereto.

The components (a) to (F) in the thermoplastic dynamically crosslinked elastomer of the present disclosure are further described below.

(A) Styrene copolymer rubber

The styrene copolymer rubber in the thermoplastic dynamically crosslinked elastomer of the present disclosure may be any copolymer including styrene groups therein. In some embodiments, the styrene copolymer rubber comprises a crosslinked styrene copolymer having high slip resistance characteristics. Examples of the styrene copolymer rubber may include one of or any combination of a soluble polystyrene-butadiene rubber (SSBR), a dairy polystyrene-butadiene rubber (ESBR), a styrene-ethylene-butylene-styrene (SEBS) rubber, a styrene-ethylene-propylene-styrene (SEPS) rubber, a styrene-butadiene (SB) rubber, a styrene-isoprene-styrene (SIS) rubber, a styrene-butadiene-Styrene (SBs) rubber, but the present disclosure is not limited thereto.

SSB rubber has the characteristics of good abrasion resistance, good color, good wet skid resistance and the like. The ESB rubber has the characteristics of good abrasion resistance, low production cost, good wet skid resistance and the like. The SEBS rubber has the characteristics of high strength, ozone and ultraviolet resistance, good thermal stability, heat resistance, good toughness and the like. The styrene-ethylene-propylene-styrene SEPS rubber has the characteristics of good heat resistance, good oxidation resistance and the like. SB rubber has the characteristics of good ageing resistance, good heat resistance, good wear resistance and the like. SIS rubber has the characteristics of good softness and high elasticity. SBS rubber has the characteristics of high strength, high transparency, good tensile strength and the like. The kind, proportion and content of the styrene copolymer rubber can be selected by a person having ordinary skill in the relevant art according to the need.

For example, if it is desired to obtain a thermoplastic dynamic crosslinked elastomer having better abrasion resistance, the styrene copolymer rubber may use one of SB rubber, SSB rubber, ESB rubber, or any combination thereof, or increase the content of one of SB rubber, SSB rubber, ESB rubber, or any combination thereof. If it is desired to obtain a thermoplastic dynamically crosslinked elastomer having higher strength, the styrene copolymer rubber may be used as the SEBS rubber, or the content of the SEBS rubber may be increased. If it is desired to obtain a thermoplastic dynamic crosslinked elastomer having higher strength, the styrene copolymer rubber may be used only with the SEBS rubber, or the content of the SEBS rubber may be increased, but the present disclosure is not limited thereto.

In some embodiments, the styrene copolymer rubber may include one of SSB rubber, ESB rubber, SB rubber, SEBS rubber, SEPS rubber, SIS rubber, or any combination thereof, but the disclosure is not limited thereto. In some embodiments, the styrene copolymer rubber may include one of SSB rubber, ESB rubber, SB rubber, SEBS rubber, or any combination thereof, but the disclosure is not limited thereto.

(B) Thermoplastic elastomer

The thermoplastic elastomer in the thermoplastic dynamically crosslinked elastomer of the present disclosure may include any thermoplastic elastomer having a high polarity. In some embodiments, the thermoplastic elastomer may include one or a combination of a thermoplastic polyamide elastomer (TPEE) and a thermoplastic polyetherester elastomer (TPEE). In some embodiments, the thermoplastic elastomer may comprise one or any combination of thermoplastic polyamide elastomer, polyether polyester elastomer, polyester elastomer.

In some embodiments, the thermoplastic elastomer may include one or any combination of a thermoplastic polyamide elastomer, a polyether polyester elastomer, a polyester elastomer having a shore D hardness of about 25-50. In some embodiments, the thermoplastic elastomer may include a polyether polyester elastomer and/or a polyester elastomer having a Shore D hardness of about 25-50. When the Shore D hardness is less than about 25, the elastomer is too soft, possibly resulting in insufficient strength of the subsequently formed thermoplastic dynamically crosslinked elastomer. When the Shore D hardness is higher than about 50, the elastomer is too hard, which may result in poor slip resistance of the subsequently formed thermoplastic dynamically crosslinked elastomer.

The thermoplastic polyamide elastomer refers to a block copolymer composed of a hard segment including an amide and a soft segment including a polyether or a polyester. Examples of amides in the hard segment in the thermoplastic polyamide elastomer may include, but are not limited to, polycaprolactam (Nylon 6), polyamide 66 (PA 66), polydodecyl (PA 12), aromatic polyamide (aromatic polyamide). Examples of polyesters in the soft segment in the thermoplastic polyamide elastomer may include, but are not limited to, polyglycolide (PGA), polylactide (PLA), polycaprolactone (polycaprolactone diol). Examples of polyethers in the soft segment in the thermoplastic polyamide elastomer may include, but are not limited to (polytetramethylene etherglycol, PTMEG), polyethylene glycol ethers (polyethylene glycol ethers), polypropylene glycol ethers (poly (propyleneglycol) diglycidylether).

The thermoplastic polyetherester elastomer refers to a block copolymer composed of a hard segment comprising polybutylene terephthalate (PBT) and a soft segment comprising polyether or polyester. Thermoplastic polyetherester elastomers can be classified into polyether polyester elastomers and polyester elastomers according to the composition in the soft segment. Examples of soft segments in the polyether polyester elastomer may include, but are not limited to, polytetramethylene ether glycol, polyethylene glycol ether, polypropylene glycol ether. Examples of soft segments in the polyester elastomer may include, but are not limited to, polyglycolides, polylactides, polycaprolactone.

(C) Interfacial compatible resin

The interfacial compatible resin in the thermoplastic dynamic cross-linked elastomer of the present disclosure may include any resin that can make (a) a styrene copolymer rubber compatible with (B) a thermoplastic elastomer. In some embodiments, the interface compatible resin may include a maleic anhydride graft polymer (maleic anhydride grafted polymer), but the disclosure is not limited thereto.

Examples of the maleic anhydride graft polymer may include, but are not limited to, maleic anhydride grafted polyethylene (PE-MAH), maleic anhydride grafted ethylene-vinyl acetate copolymer (EVA-MAH), maleic anhydride grafted polyolefin elastomer (POE-MAH), maleic anhydride grafted ethylene propylene diene monomer (EPDM-MAH), maleic anhydride grafted styrene-ethylene-butylene-styrene rubber (SEBS-MAH), and Styrene Maleic Anhydride (SMA), but the present disclosure is not limited thereto.

In some embodiments, the maleic anhydride-grafted polymer has a grafting ratio of about 0.3 to 2.0%. When the grafting ratio of the maleic anhydride graft polymer is less than about 0.3%, the thermoplastic elastomer (B) cannot smoothly perform the complete grafting reaction and the compatibility with the styrene copolymer rubber (A) is improved, so that the compatibility of the two is too low to be well compatible. When the grafting ratio of the maleic anhydride-grafted polymer is higher than about 2.0%, the (A) styrene copolymer rubber and the (B) thermoplastic elastomer may be excessively compatible, affecting the subsequent dynamic crosslinking phase inversion behavior.

(D) Crosslinking agent and crosslinking aid

The crosslinking agent and the crosslinking aid in the thermoplastic dynamically crosslinked elastomer of the present disclosure include any formulation that can dynamically crosslink (A) the styrene copolymer rubber with (B) the thermoplastic elastomer. In some embodiments, the crosslinking agent and the crosslinking aid may include a crosslinking agent and a crosslinking aid, but the disclosure is not limited thereto.

Examples of the above-mentioned crosslinking agent may include one or any combination of 2, 5-dimethyl-2, 5-di (tert-butyl peroxy) hexane (2, 5-bis) -2, 5-dimethylhexane), dicumyl peroxide (DCP), benzoyl peroxide (benzoyl peroxide), di (tert-butyl) peroxide (di-tert-butyl peroxide), but the present disclosure is not limited thereto. Examples of the above-mentioned crosslinking aid may include one of trimethylolpropane trimethacrylate (TMPTMA), triallylisocyanurate (TAIC), trimethylolpropane triacrylate (TMPTA), triallylmethacrylate (TAC), triallylphosphonate (TAP), and Triallylbororate (TAB) or any combination thereof, but the present disclosure is not limited thereto.

(E) Additive agent

Additives in the thermoplastic dynamically crosslinked elastomers of the present disclosure may include additives to reinforce the thermoplastic dynamically crosslinked elastomer or to provide desired functional characteristics of the thermoplastic dynamically crosslinked elastomer. The additive may be any additive that does not adversely affect the dynamic crosslinking reaction of component (a) and component (B) in the thermoplastic dynamic crosslinked elastomer. In some embodiments, examples of additives may include one or any combination of reinforcing additives, antioxidants, plasticizers, and silane coupling agents, but the present disclosure is not limited thereto.

The reinforcing additive is any compound that enhances the mechanical properties and/or chemical resistance of the thermoplastic dynamically crosslinked elastomer. In some embodiments, the reinforcing additive may include a carbonaceous material, such as one or any combination of carbon black, white carbon black, graphene materials, but the disclosure is not limited thereto.

Antioxidants can prevent and/or reduce degradation of thermoplastic dynamically crosslinked elastomers due to light, heat, mechanical shear forces, etc., during processing and in the environment. In some embodiments, the antioxidant may include one or any combination of a phenolic antioxidant and a phosphorous antioxidant, but the disclosure is not limited thereto. Examples of the phenolic antioxidants may include, but are not limited to, 2,6-di-tert-butylphenol (2, 6-di-tert-butylphenol), 2, 6-di-tert-4-ethylphenol (2, 6-di-tert-butyl-4-ethylphenol), 2,6-di-tert-butyl-4-methylphenol (2, 6-di-tert-butyl-4-methylphenol), 4-hydroxymethyl-2,6-di-tert-butylphenol (4-hydroxymethyl-2, 6-di-tert-butylphenol), 2,4-dimethyl-6-tert-butylphenol (2, 4-dimethyl-6-tert-butylphenol). Examples of phosphorus-based antioxidants may include, but are not limited to, tris (2, 4-di-tert-butylphenyl) phosphite and trisnonylphenyl phosphite (tris (nonylphenyl) phosphinate).

Plasticizers can increase the softness of the thermoplastic dynamically crosslinked elastomer. In some embodiments, the plasticizer may include one or a combination of petroleum type plasticizers and non-petroleum type plasticizers. Examples of petroleum type plasticizers include, but are not limited to, paraffinic, naphthenic, or aromatic oils. Examples of non-petroleum plasticizers include, but are not limited to, glutarate (glutarate), adipate (adipates).

The silane coupling agent can improve the mechanical property, heat resistance, water resistance, weather resistance and the like of the thermoplastic dynamic cross-linked elastomer. In some embodiments, the silane coupling agent may include, but is not limited to, vinyltrichlorosilane (VTC), vinyltriethoxysilane (vinyltrietoxirane), 3-chloropropyltrimethoxysilane (3-chloropropyl) and 3-chloropropyltriethoxysilane (3-chloropropyl) but the disclosure is not limited thereto.

(F) Non-aromatic rubber

The non-aromatic rubber in the thermoplastic dynamically crosslinked elastomer of the present disclosure is a rubber in which an aromatic group is not included. Examples of the non-aromatic rubber may include one of Butadiene Rubber (BR), butyl rubber (IIR), brominated butyl rubber (BIIR), natural Rubber (NR), or any combination thereof, but the disclosure is not limited thereto. In some embodiments, the non-aromatic rubber comprises one of butadiene rubber, butyl rubber, or a combination thereof. The non-aromatic rubber can further improve the abrasion resistance, weather resistance and compression set resistance.

The present disclosure further provides a method of preparing a thermoplastic dynamically crosslinked elastomer. FIG. 1 is a flow chart of a method 10 of preparing a thermoplastic dynamically crosslinked elastomer according to an embodiment of the present disclosure. As shown in fig. 1, the preparation method 10 includes a step S101 of preparing a first mixture; a step 103 of performing an extrusion granulation process to form first mixture particles from the first mixture; a step S105 of mixing the thermoplastic elastomer, the interface compatible resin, and the first mixture particles to form a second mixture; and a step S107 of performing a dynamic crosslinking process to form a thermoplastic dynamic crosslinked elastomer from the second mixture. Steps S101 to S107 are further described below.

The step S101 of preparing the first mixture includes adding the rubber and the crosslinking agent and the crosslinking aid to an internal mixer to form the first mixture including the rubber and the crosslinking agent and the crosslinking aid, but the disclosure is not limited thereto. In an embodiment, the rubber may include the styrene copolymer rubber described in the above component (a) and the non-aromatic rubber described in the above component (F), and the crosslinking agent and the crosslinking assistant may include the crosslinking agent and the crosslinking assistant described in the above component (D), so that the description thereof will be omitted. In one embodiment, the weight ratio of the styrene copolymer rubber described in component (A) to the non-aromatic rubber described in component (F) is about 8-10:0-2. In some embodiments, the weight ratio of the styrene copolymer rubber described in component (A) above to the non-aromatic rubber described in component (F) above is 9:1.

In one embodiment, about 100 to 120 parts by weight of rubber and about 0.2 to 3 parts by weight of crosslinking agent and crosslinking aid may be added to the internal mixer in step S101. In one embodiment, the rubber comprises about 100 parts by weight of a styrene copolymer rubber and about 0 to 20 parts by weight of a non-aromatic rubber. About 0.2 to 2.9 parts by weight, about 0.25 to 2.85 parts by weight, about 0.30 to 2.75 parts by weight, about 0.40 to 2.70 parts by weight, about 0.45 parts by weight, about 2.45 parts by weight, or about 2.675 parts by weight of a crosslinking agent and a crosslinking assistant may be added to the internal mixer in step S101 based on about 100 parts by weight of the styrene copolymer rubber.

In an embodiment, the step S101 of preparing the first mixture may further comprise adding additives to the internal mixer. In one embodiment, the additive may include the additive described in the above component (E), and thus will not be described herein. In this embodiment, about 5 to 50 parts by weight, about 5.5 to 50 parts by weight, about 10 to 50 parts by weight, about 6.0 to 49.5 parts by weight, about 16.0 to 49.0 parts by weight, about 6.45 parts by weight, about 7.16 parts by weight, about 16.45 parts by weight, or about 48.95 parts by weight of the additive may be added to the internal mixer in step S101 based on 100 parts by weight of the styrene copolymer rubber.

The step 103 of performing an extrusion granulation process to form first mixture particles from the first mixture includes the steps of adding the first mixture to an extruder, kneading the first mixture at a screw speed of about 50 to 100rpm, and extruding the granulated product. In some embodiments, the extrusion granulation process of step S103 may include an extrusion temperature of about 60-80 ℃. In some embodiments, the extruder is a rubber extruder. In some embodiments, examples of extruders may include, but are not limited to, kneaders, ten-thousand horsepower machines, single-shaft extruders, or twin-shaft extruders. In one embodiment, the extruder is a twin-shaft extruder.

The step S105 of mixing the thermoplastic elastomer, the interface compatible resin, and the first mixture particles to form a second mixture includes a step of adding the thermoplastic elastomer, the interface compatible resin, and the first mixture particles obtained from the step S103 to an extruder. In some embodiments, step 105 further comprises a pretreatment step of drying the thermoplastic elastomer at a temperature of about 60-100 ℃ for about 2-5 hours prior to mixing the thermoplastic elastomer, the interface compatible resin, and the first mixture particles. In some embodiments, examples of extruders may include, but are not limited to, kneaders, ten-thousand horsepower machines, single-shaft extruders, or twin-shaft extruders. In one embodiment, the extruder is a twin-shaft extruder. In an embodiment, the thermoplastic elastomer may include the thermoplastic elastomer as described in the above component (B), and the interfacial compatible resin may include the interfacial compatible resin as described in the above component (C), so that the description thereof is omitted.

In step S105, the amount of thermoplastic elastomer added to the extruder is less than the content of rubber in the first mixture particles in parts by weight. In one embodiment, the thermoplastic elastomer and the interface compatible resin added to the extruder may be about 40 to 90 parts by weight and about 5 to 15 parts by weight, respectively, based on 100 parts by weight of the styrene copolymer rubber in the first mixture particles. That is, in embodiments where the first mixture particles do not include additives, the thermoplastic elastomer, the interface compatible resin, and the first mixture particles may be mixed in a ratio of about 40 to 90 parts by weight of the thermoplastic elastomer, about 5 to 15 parts by weight of the interface compatible resin, and about 100.2 to 123 parts by weight of the first mixture particles. In embodiments where the first mixture particles include additives, the thermoplastic elastomer, the interface compatible resin, and the first mixture particles may be mixed in a ratio of about 40 to 90 parts by weight of the thermoplastic elastomer, about 5 to 15 parts by weight of the interface compatible resin, and about 105.2 to 173 parts by weight of the first mixture particles.

The step S107 of performing the dynamic crosslinking process to form the thermoplastic dynamic crosslinked elastomer from the second mixture includes performing the dynamic crosslinking process at a screw speed of about 150 to 300rpm and a reaction temperature of about 170 to 200 ℃. In one embodiment, the dynamic crosslinking process is performed in the extruder described in step S105 after the second mixture is obtained in step S105. In some embodiments, step S107 further comprises the step of performing an extrusion granulation process to form thermoplastic dynamically crosslinked elastomer particles from the thermoplastic dynamically crosslinked elastomer. In some embodiments, the extrusion granulation process may include an extrusion temperature of 160-200 ℃. In some embodiments, step 107 further comprises a drying step of drying the thermoplastic dynamically crosslinked elastomer particles at a temperature of about 80 to 120 ℃ for about 6 to 10 hours.

The thermoplastic dynamic cross-linked elastomer prepared by the above preparation method may have a Shore A hardness of about 45 to 80, an abrasion amount of about 50 to 250mg according to DIN 53516, and a wet skid resistance coefficient of about 0.25 to 0.45 according to F1677. In some embodiments, the thermoplastic dynamically crosslinked elastomer prepared via the above-described preparation method may have a Shore A hardness of about 50 to 75, about 50 to 70, or about 55 to 65. In some embodiments, the thermoplastic dynamically crosslinked elastomer prepared via the above-described preparation method may have an abrasion loss of about 80 to 250mg, about 90 to 250mg, or about 100 to 250 mg. In some embodiments, the thermoplastic dynamically crosslinked elastomer prepared via the above-described preparation method may have a wet skid coefficient of about 0.28 to 0.45, about 0.30 to 0.43, or about 0.33 to 0.40. The present disclosure further provides a thermoplastic dynamically crosslinked elastomer prepared via the above-described preparation method.

In summary, the thermoplastic dynamically crosslinked elastomer prepared by the preparation method can have better abrasion resistance and better wet skid resistance. The thermoplastic dynamically crosslinked elastomers prepared according to the preparation methods of the present disclosure are therefore applicable to any field having high abrasion resistance and high wet skid resistance requirements. In some embodiments, the thermoplastic dynamically crosslinked elastomers of the present disclosure are suitable for use in soles, sporting goods, construction materials, and industrial materials, but the present disclosure is not limited thereto.

The following specific examples of the disclosure are provided to further illustrate the advantages of the disclosure over the prior art, but the advantages of the disclosure are not limited thereto.

The materials and equipment used in the specific examples of the present disclosure are shown below.

Rubber material

SSBR: polystyrene-butadiene-soluble (SSB) rubber, available from table rubber inc, model TAIPOL 1453.

SEBS: styrene-ethylene-butylene-styrene rubber, available from Taiwan rubber Inc., model TAIPOL 6014.

BR: butadiene rubber, available from Taiwan rubber Inc., model TAIPOL 0150.

IIR: BUTYL rubber, model number BUTYL 065, available from Futai trade (stock).

Crosslinking agent and crosslinking aid

TAIC: triallyl isocyanurate, a type GY-TAIC70, available from Hao Yuan real Co., ltd, was used as a crosslinking aid.

TMPTMA: the trimethylolpropane trimethacrylate, used as a crosslinking aid, is available from double bond chemical Co., ltd., model DOUBLEMER TMPTMA.

DCP: dicumyl peroxide, which is used as a crosslinking agent, is available from Hao Yuan Utility Co., ltd.

Additive agent

AO1050: antioxidants, available from the Anonet industries, inc.

Silica: reinforcing additives, available from Pelin corporation under the model Hi-Sil 255.

Si69: silane coupling agents, available from Haoyuan industries, inc.

Paraffin oil: purchased from Di Yi chemical industry, model EP paraffin oil.

Thermoplastic elastomer

TPEE: polyester-based polyester elastomer, available from Dissman DSM, model EL150.

Interfacial compatible resin

SMA: styrene maleic anhydride, available from Yuan hong Co., ltd., model SMA1000.

SEBS-MAH: maleic anhydride grafted styrene-ethylene-butylene-styrene rubber, available from co-source trade company, model ANP-7131.

Banbury mixer: available from Shanxiang machinery Co., ltd., model SKM-20L.

A first extruder: a twin-screw extruder, model ZSK25, was purchased from coperion gmbh. The ratio (L/D) of the effective length of the screw to the screw diameter was 40 and the helix angle ψ was 25.

A second extruder: a twin-screw extruder, model ZSK26, was purchased from coperion gmbh. The ratio (L/D) of the effective length of the screw to the screw diameter was 60 and the helix angle ψ was 26.

The preparation methods of comparative examples 1 to 4 and examples 1 to 11 are as follows:

the rubber, the crosslinking agent, the crosslinking auxiliary agent, and the additives described above were charged into an internal mixer in the parts by weight shown in the following tables 1 and 2 to obtain a first mixture.

The first mixture is fed into a first extruder and kneaded and forced pelletized at an extrusion temperature of about 60 to 80 ℃ and a screw speed of about 50 to 100rpm to form first mixture particles.

The thermoplastic elastomer particles are dried at about 80 c for about 3 to 4 hours. The dried thermoplastic elastomer particles, the first mixture particles, and the interface compatible resin were fed into a second extruder in the parts by weight shown in tables 1 and 2 below based on 100 parts by weight of the styrene copolymer rubber in the first mixture particles to form a second mixture. The dynamic crosslinking reaction is then carried out at a screw speed of about 150 to 300rpm and a reaction temperature of about 170 to 200 ℃ to form a thermoplastic dynamic crosslinked elastomer from the second mixture. Extrusion granulation is performed at an extrusion temperature of 160-200 ℃ to crosslink the elastomer in an automatic state to form thermoplastic dynamic crosslinked elastomer particles. Finally, the obtained thermoplastic dynamically crosslinked elastomer particles were dried at about 80 to 100℃for about 6 to 8 hours to complete the preparation of the thermoplastic dynamically crosslinked elastomer particles of comparative examples 1 to 4 and examples 1 to 11.

TABLE 1

TABLE 2

SEM images of the thermoplastic dynamically crosslinked elastomer particles of examples 1 to 11 were obtained using a scanning electron microscope (manufacturer FEI (Thermo Fisher Scientific), model Talos F200XG 2). Fig. 2 is an SEM image of thermoplastic dynamically crosslinked elastomer particles according to example 8 of the present disclosure. Taking the SEM image of fig. 2 as an example, it can be seen that the rubber system is homogeneously dispersed in the thermoplastic polyetherester elastomer in the form of spherical particles. Then, the spherical grain boundaries were treated with image processing software, and the average grain size from the SEM images of examples 1 to 1l was analyzed to obtain grains having a grain size of about 0.5 to 10. Mu.m.

The Shore A hardness of the thermoplastic dynamically crosslinked elastomer particles of comparative examples 1 to 4 and examples 1 to 11 was measured using a Shore A durometer (manufacturer Teclock, model Shore A). The tensile strength of the thermoplastic dynamically crosslinked elastomer particles of comparative examples 1 to 4 and examples 1 to 11 was measured by a universal tensile tester (manufacturer Quan Hua precision, model EJA Vantage). The elongation of the thermoplastic dynamically crosslinked elastomer particles of comparative examples 1 to 4 and examples 1 to 11 was measured by a universal tensile tester (manufacturer Quan Hua precision, model EJA Vantage). The abrasion amounts of the thermoplastic dynamically crosslinked elastomer particles of comparative examples 1 to 4 and examples 1 to 11 were measured according to DIN 53516 using a DIN abrasion tester (manufactured by Ware instruments Co., ltd., model QC-618A). The dry slip resistance of the thermoplastic dynamically crosslinked elastomer particles of comparative examples 1-4 and examples 1-11 were measured using a hand-held toggle slip resistance tester (model TNL108MARK-2, nami instruments, st. Co., ltd.). The wet skid coefficients of the thermoplastic dynamically crosslinked elastomer particles of comparative examples 1-4 and examples 1-11 were measured using a hand-held toggle slip test machine (model TNL108MARK-2, manufactured by Nami instruments Inc., suzhou, co., ltd.) according to the F1677 standard. The measurement results are shown in the following tables 3 and 4.

TABLE 3 Table 3

TABLE 4 Table 4

From the measurement results of table 3 and table 4 above, it can be seen that the thermoplastic dynamically crosslinked elastomers of comparative examples 1 to 4 have an abrasion loss of about 300mg or more and a wet skid resistance of about 0.25 or less. The thermoplastic dynamic cross-linked elastomers of examples 1 to 11 of the present disclosure have an abrasion loss of about 250mg or less and a wet skid coefficient of about 0.35 or more. The thermoplastic dynamically crosslinked elastomers of examples 8 to 11 had an abrasion loss of about 150mg or less. The thermoplastic dynamically crosslinked elastomers of examples 9 to 11 comprising the addition of the reinforcing additive may further have an abrasion loss of about 120mg or less.

The above measurement results show that the thermoplastic dynamic crosslinked elastomer of the present disclosure has better abrasion resistance and better wet skid resistance than the thermoplastic dynamic crosslinked elastomer of the comparative example. The thermoplastic dynamic cross-linked elastomers of the present disclosure are therefore applicable to any field having high abrasion resistance and high wet skid resistance requirements. In some embodiments, the thermoplastic dynamically crosslinked elastomers of the present disclosure are suitable for use in soles, sporting goods, construction materials, and industrial materials, but the present disclosure is not limited thereto.

While the foregoing embodiments have been described in some detail for purposes of clarity of understanding, it will be understood that the foregoing embodiments are merely illustrative of the invention and are not intended to limit the invention, and that any modifications, equivalents, improvements, etc. that fall within the spirit and principles of the present disclosure are intended to be included within the scope of the present disclosure.

Claims (12)

1. A thermoplastic dynamically crosslinked elastomer comprising the following components:

(A) 100 parts by weight of styrene copolymer rubber;

(B) 40-90 parts by weight of a thermoplastic elastomer;

(C) 5-15 parts by weight of interfacial compatible resin; and

(D) 0.2 to 3 parts by weight of a cross-linking agent and a cross-linking auxiliary agent;

wherein the content of the component (A) is larger than the content of the component (B), and the component (A) is dispersed in the component (B) in the form of spherical particles having a particle diameter of 0.5 to 10. Mu.m.

2. The thermoplastic dynamic crosslinked elastomer according to claim 1, wherein the component (A) is dispersed in the component (B) in a particle size of 0.5 to 5. Mu.m.

3. The thermoplastic dynamic cross-linked elastomer according to claim 1, wherein the component (a) comprises one of or any combination of a polystyrene-butadiene rubber, a milk polystyrene-butadiene rubber, a styrene-ethylene-butylene-styrene rubber, a styrene-ethylene-propylene-styrene rubber, a styrene-butadiene rubber, a styrene-isoprene-styrene rubber, a styrene-butadiene-styrene rubber.

4. The thermoplastic dynamic cross-linked elastomer according to claim 1, wherein the component (B) comprises one of a thermoplastic polyamide elastomer, a thermoplastic polyetherester elastomer, or a combination thereof.

5. The thermoplastic dynamically crosslinked elastomer according to claim 1, wherein the component (C) comprises a maleic anhydride graft polymer.

6. The thermoplastic dynamic cross-linked elastomer of claim 1, wherein the cross-linking agent comprises one or any combination of 2, 5-dimethyl-2, 5-di (tertiary butyl peroxy) hexane, dicumyl peroxide, benzoyl peroxide, di (tertiary butyl) peroxide.

7. The thermoplastic dynamic cross-linked elastomer of claim 1, wherein the cross-linking aid comprises one or any combination of trimethylolpropane trimethacrylate, triallyl isocyanurate, trimethylolpropane triacrylate, triallyl isocyanurate, triallyl phosphite and triallyl borate.

8. The thermoplastic dynamically crosslinked elastomer according to claim 1, further comprising component (E): comprises 5 to 50 parts by weight of one or any combination of a reinforcing additive, an antioxidant, a plasticizer and a silane coupling agent.

9. The thermoplastic dynamically crosslinked elastomer according to claim 1, further comprising component (F): 0 to 20 parts by weight of non-aromatic rubber.

10. The thermoplastic dynamic cross-linked elastomer according to claim 9, wherein the component (F) comprises one of butadiene rubber, butyl rubber, brominated butyl rubber, natural rubber, or any combination thereof.

11. A method for preparing a thermoplastic dynamic cross-linked elastomer, which is characterized by comprising the following steps:

preparing a first mixture, wherein the first mixture comprises a rubber, a cross-linking agent and a cross-linking auxiliary agent;

performing an extrusion granulation process to form a first mixture particle from the first mixture;

mixing a thermoplastic elastomer, an interface compatible resin, and the first mixture particles to form a second mixture, wherein the rubber content of the first mixture particles is greater than the thermoplastic elastomer content in parts by weight; and

performing a dynamic cross-linking process to form a thermoplastic dynamic cross-linked elastomer from the second mixture,

wherein the dynamic crosslinking process uses a process temperature of 170 ℃ to 200 ℃ and a rotational speed of 150 rpm to 300 rpm.

12. The production method according to claim 11, wherein the second mixture comprises 100.2 to 123 parts by weight of the first mixture particles, 40 to 90 parts by weight of the thermoplastic elastomer, and 5 to 15 parts by weight of the interface compatible resin.