High-temperature-resistant oil-outlet TPE (Thermoplastic Elastomer) material, product prepared from same and application of product

Abstract

The invention provides an oil locking stabilizer for a TPE (Thermoplastic Elastomer) material. The oil locking stabilizer comprises a cross-linking agent, a cross-linked network surface modifier and optional heat-resistant resin. The invention also provides a high-temperature-resistant oil-outlet TPE material. The material comprises a rubber elastomer, extending oil, polyolefin resin, the oil locking stabilizer, inorganic filler and optional auxiliaries. The invention also provides a product prepared from the high-temperature-resistant oil-outlet TPE material, especially a switch button of an electrical product. A product prepared from the TPE material resistant to high-temperature oil outlet has the advantages of high temperature resistance, oil outlet resistance, good material processing performance and the like.

Description

Technical Field

[0001] The present disclosure relates to an oil-locking stabilizer for TPE materials, a high-temperature resistant oil-discharging TPE material comprising the oil-locking stabilizer, and products and applications prepared therefrom. The high-temperature resistant oil-discharging TPE material disclosed herein has the advantages of high temperature resistance, oil-discharging resistance, and good material processing performance, and is suitable for electrical products, such as switch buttons of household appliances and charging gun products. Background Art

[0002] Thermoplastic elastomer (TPE) materials have the advantages of soft touch and high elasticity of rubber and easy molding and processing of plastic. They are currently widely used in many fields such as automobiles, electrical appliances, stationery, sports equipment and daily necessities. Due to its good skin-friendly and soft touch, TPE materials are increasingly used in household appliances, new energy vehicle charging guns and other product fields, especially for parts that are in direct contact with the human body, such as switches and buttons of electrical products.

[0003] Compared with thermoplastic vulcanizate TPV materials, TPE materials do not require vulcanization, are more environmentally friendly, and have simpler production processes. Since the rubber component in the TPE material formula has a high viscosity and is difficult to process directly, it is necessary to add an appropriate amount of filler oil to improve its processing performance. However, the rubber component and filler oil in the TPE material system are only blended through physical action. Due to the lack of rubber vulcanization and cross-linking to restrain the filler oil, and the general heat resistance of TPE materials, when the external ambient temperature is high, the molecular chain movement is accelerated, and the filler oil will penetrate into the surface of the material, causing oil and stickiness on the surface of the product, affecting the normal use of the product. Outdoor application scenarios and the heating of electrical products during power-on operation may cause the TPE material to produce oil after being heated. Generally, the lower the hardness of the TPE material, the higher the content of rubber and filler oil in the formula, and the greater the risk of oil discharge in a high temperature environment.

[0004] Therefore, there is an urgent need in the art to solve the problem of oil release in high temperature environments when TPE materials are used in electrical products. Summary of the invention

[0005] The first aspect of the present disclosure provides an oil-locking stabilizer for TPE materials, the oil-locking stabilizer comprising a cross-linking agent, a cross-linked network surface modifier and an optional heat-resistant resin, wherein the weight ratio of the cross-linking agent, the cross-linked network surface modifier and the heat-resistant resin is (0.5-5):(1-15):(0-10).

[0006] A second aspect of the present disclosure provides a high temperature resistant oil-discharging TPE material, the material comprising a rubber elastomer, a filler oil, a polyolefin resin, the oil lock stabilizer described in the present disclosure, an inorganic filler and optional auxiliary agents.

[0007] The third aspect of the present disclosure provides a method for preparing a high-temperature resistant oil-discharging TPE material, the method comprising mixing and extruding a rubber elastomer, an extension oil, a polyolefin resin, a crosslinking agent, a crosslinking network surface modifier, a heat-resistant resin, an inorganic filler and optional additives.

[0008] The fourth aspect of the present disclosure provides a product made from the high temperature resistant oil-releasing TPE material described in the present disclosure, preferably the product is a switch button of an electrical product.

[0009] A fifth aspect of the present disclosure provides use of the oil-locking stabilizer described in the present disclosure in improving the high-temperature oil release resistance of a TPE material. DETAILED DESCRIPTION

[0010] The inventor of the present disclosure has conducted in-depth research on the high-temperature oil release principle of TPE materials and found that the high-temperature oil release problem of current TPE materials when used in electrical products can be solved by modifying the TPE materials with an oil-locking stabilizer including a cross-linking agent, a cross-linking network surface modifier, and an optional heat-resistant resin, through chemical cross-linking oil lock, cross-linking network surface modification, and / or improving heat resistance. On this basis, the present disclosure was completed.

[0011] The oil-locking stabilizer for TPE materials disclosed herein comprises a crosslinking agent, a crosslinked network surface modifier and an optional heat-resistant resin, wherein the weight ratio of the crosslinking agent, the crosslinked network surface modifier and the heat-resistant resin is (0.5-5):(1-15):(0-10).

[0012] The components of the oil-locking stabilizer for TPE materials disclosed in the present invention are described in detail below:

[0013] Crosslinking agent

[0014] Cross-linking agents can produce chemical bonds between linear molecules, connecting the linear molecules together. The polymer segments that undergo cross-linking reactions form a three-dimensional cross-linked network structure to improve material performance.

[0015] The crosslinking agent used in the present disclosure includes at least one crosslinking agent selected from the following group: dicumyl peroxide (DCP), di-tert-butyl dicumyl peroxide (BIPB), dibenzoyl peroxide (BPO) and trimethylolpropane triacrylate (TMPTA). Preferably, the crosslinking agent includes dicumyl peroxide (DCP) as a main crosslinking agent, and trimethylolpropane triacrylate (TMPTA) as an auxiliary crosslinking agent, wherein the weight ratio of dicumyl peroxide (DCP) to trimethylolpropane triacrylate (TMPTA) is (1-10):1, preferably (2-6):1. Dicumyl peroxide (DCP) as a main crosslinking agent initiates free radical polymerization in rubber elastomer and polyolefin resin, and trimethylolpropane triacrylate (TMPTA) as an auxiliary crosslinking agent synergistically improves the crosslinking reaction efficiency and crosslinking density, so that the heat resistance, solvent resistance, weather resistance, corrosion resistance and oil lock performance of the material are greatly improved.

[0016] Based on the total weight of the oil-locking stabilizer, the amount of the crosslinking agent is 5-50% by weight, preferably 10-40% by weight, and more preferably 12-20% by weight.

[0017] Cross-linked network surface modifier

[0018] In the present disclosure, the cross-linked network surface modifier can perform sealing modification on the cross-linked network surface, greatly improving the high-temperature oil locking ability of the cross-linked rubber elastomer. The cross-linked network surface modifier has special molecular structures such as ester bonds, ether bonds, carboxyl groups, hydroxymethyl groups, and phenolic hydroxyl groups, and is easy to form a hydrogen bond network structure with the rubber elastomer, and is entangled with the cross-linked network structure. It can be used as a thickener and sealant to perform sealing modification on the cross-linked network surface.

[0019] In the present disclosure, the cross-linked network surface modifier includes at least one resin selected from the group consisting of hydrogenated terpene resin, poly-α-methylstyrene resin and hydrogenated rosin pentaerythritol ester. Preferably, the cross-linked network surface modifier includes hydrogenated terpene resin. The hydrogenated terpene resin obtained by hydrogenation of ordinary terpene resin has excellent properties such as good heat resistance, acid and alkali resistance, light aging resistance and oxidation resistance. After being blended with rubber elastomer, especially SEPS, the heat resistance and high temperature oil lock performance of the material can be significantly improved.

[0020] Based on the total weight of the oil-locking stabilizer, the amount of the cross-linked network surface modifier is 20-75% by weight, preferably 30-70% by weight, and more preferably 33-50% by weight.

[0021] Heat resistant resin

[0022] In the present disclosure, the molecular main chain of the heat-resistant resin contains a complex ring structure, preferably a ladder polymer with two main chains on the macromolecular chain, especially a ladder polymer containing benzothiazole or benzimidazole repeating units in the molecular main chain. Due to the particularity of its molecular structure, the molecular chains of the twisted structure are arranged in a high-density spiral, and there is a strong π-π stacking and conjugation effect between molecules, so that the polymer molecules are tightly bound, the structure is stable, and more external energy is required for the molecular chain to break. Therefore, this heterocyclic polymer is more excellent in mechanical properties and high temperature resistance compared with ordinary heat-resistant polymer resins.

[0023] In the present disclosure, the heat-resistant resin includes at least one polymer selected from the following group: polystyrene, styrene-acrylonitrile copolymer, polyphenylene ether, polybutylene terephthalate, poly-1,3,4-oxadiazole, polyphenylquinoxaline, polybenzoxazole, polybenzothiazole, sulfonated polyaryletherketone copolymer, polybenzimidazole; preferably, the heat-resistant resin includes at least one polymer selected from the following group: poly-1,3,4-oxadiazole, polyphenylquinoxaline, polybenzoxazole, polybenzothiazole, sulfonated polyaryletherketone copolymer, polybenzimidazole; more preferably, the heat-resistant resin includes at least one polymer selected from the following group: sulfonated polyaryletherketone copolymer, polybenzimidazole.

[0024] The sulfonated polyaryletherketone copolymer is a ladder polymer containing a benzothiazole group, which can be obtained by reacting raw materials such as bisphenol A monomer, 2,6-dichlorobenzothiazole, 4,4'-difluorobenzophenone and 3,3'-sodium disulfonate-4,4'-difluorobenzophenone according to a molar ratio of (7-10): (2-6): (1-3): (2-6).

[0025] Based on the total weight of the oil-locking stabilizer, the amount of the heat-resistant resin is 0-60% by weight, preferably 15-55% by weight, and more preferably 30-50% by weight.

[0026] In the oil-locking stabilizer, the weight ratio of the crosslinking agent, the crosslinking network surface modifier and the heat-resistant resin is preferably (1-3): (3-10): (3-8), and most preferably 2:5:5.

[0027] The high temperature resistant oil-discharging TPE material disclosed in the present invention comprises a rubber elastomer, a filler oil, a polyolefin resin, the oil-locking stabilizer as described above, an inorganic filler and optional auxiliary agents.

[0028] The components of the high temperature resistant oil-discharging TPE material disclosed in the present invention are described in detail below:

[0029] Rubber elastic body

[0030] In the present disclosure, the rubber elastomer includes at least one elastomer selected from the group consisting of SBS, SEBS, SIS, SEPS, SIBS, SEEPS, EPDM, POE and TPU. Preferably, the rubber elastic includes SEBS and SEPS. SEBS is a linear triblock copolymer with polystyrene as the terminal segment and ethylene-butylene copolymer obtained by hydrogenating polybutadiene as the middle elastic block. SEPS is a hydrogenated styrene-isoprene thermoplastic elastomer obtained by selectively hydrogenating the conjugated unsaturated double bonds in styrene-isoprene-styrene block copolymer (SIS). Both SEBS and SEPS are hydrogenated styrene elastomers with no unsaturated double bonds in the molecular chain, and have better heat resistance, weather resistance and oil absorption properties than conventional styrene elastomers. Compared with SEBS, the soft block of SEPS is more randomized, the EP block is softer than the EB block, and has a lower degree of crystallinity, better elasticity and higher elongation. Blending SEBS and SEPS can not only ensure good oil absorption capacity, but also utilize the synergistic effect of SEPS and cross-linked network surface modifiers to improve the sealing of the cross-linked network structure as well as the tear resistance and high temperature resistance of the material.

[0031] In a preferred embodiment, the rubber elastomer comprises a mixture of SEBS and SEPS in a weight ratio of (1-5):1.

[0032] Based on the total weight of the high temperature resistant oil-discharging TPE material, the amount of the rubber elastic body is 10-60% by weight, preferably 20-50% by weight, and more preferably 30-35% by weight.

[0033] Filling oil

[0034] Since the rubber component in the TPE material formula has a high viscosity and is difficult to process directly, an appropriate amount of filler oil needs to be added to improve its processing performance. There is no specific limitation on the filler oil added to the high temperature resistant oil-discharging TPE material disclosed in the present invention, and various commercially available filler oils can be used as long as they do not limit the purpose of the invention disclosed in the present invention.

[0035] In a specific embodiment, the filler oil includes at least one oil selected from the group consisting of naphthenic oil, paraffin oil and aromatic oil. Preferably, the filler oil includes paraffin oil. The linear molecular structure of paraffin oil is more flexible, has good compatibility with SEBS and SEPS, and can improve the fluidity, flex resistance and light stability of rubber elastomers.

[0036] Based on the total weight of the high temperature resistant oil-discharging TPE material, the amount of the filler oil is 10-60% by weight, preferably 20-50% by weight, and more preferably 35-40% by weight.

[0037] In a preferred embodiment of the present disclosure, the weight ratio of the rubber elastomer to the filler oil is 2:1-1:2, preferably 1:1-1:2.

[0038] Polyolefin resin

[0039] In the present disclosure, the polyolefin resin includes polypropylene and / or polyethylene. Polyolefin resin is cheap and abundant in source, and can reduce the melt viscosity of rubber elastomer, improve processing performance and reduce cost.

[0040] Suitable polyolefin resins include homopolypropylene (PPH), block copolymer polypropylene (PPB), random copolymer polypropylene (PPR), high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE) and ultra high molecular weight polyethylene (UHMWPE).

[0041] PP as a plastic phase itself does not absorb oil, and after crystallization, PP will produce phase separation of crystalline and amorphous regions. Therefore, it is preferred to use PPR resin with lower crystallinity and add LLDPE at the same time, using their own crystallization characteristics to interfere with each other's crystallization, reduce the crystallinity of the plastic phase, and thus improve the oil absorption effect. In a preferred embodiment, the polyolefin resin includes PPR and LLDPE, wherein the weight ratio of PPR to LLDPE is (1-10):1, preferably (2-5):1.

[0042] Based on the total weight of the high temperature resistant oil-discharging TPE material, the amount of the polyolefin resin is 1-50% by weight, preferably 5-30% by weight, and more preferably 8-15% by weight.

[0043] Oil lock stabilizer

[0044] The use of the oil-locking stabilizer disclosed in the present invention can greatly reduce the high-temperature oiling phenomenon of TPE materials. When the amount of the oil-locking stabilizer added reaches a certain level, the effect of improving the high-temperature oiling resistance of the TPE material tends to be saturated. If the amount of addition is further increased, the hardness of the material will increase and the processing performance of the material may be affected. Therefore, based on the total weight of the high-temperature oiling resistant TPE material, the amount of the oil-locking stabilizer is 1-25% by weight, preferably 3-20% by weight, and more preferably 10-15% by weight.

[0045] In a preferred embodiment of the present disclosure, the weight ratio of the polyolefin resin to the oil-locking stabilizer is 5:1-1:5, preferably 2:1-1:2.

[0046] Inorganic fillers

[0047] In the present disclosure, inorganic fillers are used to adjust the hardness of the material and reduce the formulation cost. There is no specific limitation on the inorganic fillers added to the high temperature resistant oil-discharging TPE material of the present disclosure, and various commercially available fillers can be used as long as they do not limit the purpose of the invention of the present disclosure.

[0048] In a specific embodiment, the inorganic filler includes at least one filler selected from the group consisting of talc, wollastonite, calcium carbonate, barium sulfate, magnesium sulfate and calcium sulfate. Preferably, the inorganic mineral includes calcium carbonate. Calcium carbonate has the advantages of wide sources and low price.

[0049] Based on the total weight of the high temperature resistant oil-discharging TPE material, the amount of the inorganic filler is 1-20% by weight, preferably 2-15% by weight, and more preferably 4-10% by weight.

[0050] Optional additives

[0051] The additives include but are not limited to compatibilizers, ultraviolet absorbers, antioxidants, lubricants, masterbatches, surfactants, etc., which are used to improve the thermal oxidation aging resistance, weather resistance, and processability of the TPE material. There is no specific limitation on the additives added to the high temperature resistant oil-discharging TPE material disclosed in the present invention, and various commercially available additives can be used as long as they do not limit the purpose of the invention disclosed in the present invention.

[0052] In a specific embodiment of the present disclosure, the auxiliary agent includes an antioxidant, an ultraviolet absorber, a lubricant and a masterbatch. The ultraviolet absorber is added to improve the outdoor weather resistance of the material. The role of the lubricant is to reduce the friction between the internal molecules of the plastic, improve the processing performance of the plastic, and improve production efficiency. The role of the antioxidant is to extend the service life of the material.

[0053] In one embodiment of the present disclosure, the antioxidant includes at least one of a hindered phenolic primary antioxidant and a phosphite secondary antioxidant. In a specific example of the present disclosure, the antioxidant consists of a hindered phenolic primary antioxidant and a phosphite secondary antioxidant, wherein the weight ratio of the hindered phenolic primary antioxidant to the phosphite secondary antioxidant is 1:2. In one embodiment of the present disclosure, the ultraviolet absorber includes a benzotriazole ultraviolet absorber. In one embodiment of the present disclosure, the lubricant includes a silicone masterbatch. In one embodiment of the present disclosure, the masterbatch includes a black masterbatch with PE as a carrier and carbon black as a colorant.

[0054] Based on the total weight of the high temperature resistant oil-discharging TPE material, the amount of the auxiliary agent is 0-5% by weight, preferably 0.1%-3% by weight, and more preferably 0.5-2% by weight.

[0055] In a specific embodiment of the present disclosure, the weight ratio of the rubber elastomer, the filler oil, the polyolefin resin and the oil-locking stabilizer is (10-60): (10-60): (5-50): (2-25), preferably (20-50): (20-50): (8-30): (5-20), and more preferably (30-40): (30-40): (9-20): (7-15).

[0056] In a preferred embodiment of the present disclosure, the high temperature resistant oil-discharging TPE material comprises:

[0057]

[0058]

[0059] The method for preparing a high temperature resistant oil-discharging TPE material disclosed in the present invention comprises mixing and extruding a rubber elastomer, an extension oil, a polyolefin resin, a crosslinking agent, a crosslinking network surface modifier, a heat resistant resin, an inorganic filler and optional auxiliary agents.

[0060] In a preferred embodiment, the method comprises mixing the rubber elastomer and the filler oil at a high speed in a ratio of (10-60): (10-60), preferably (20-50): (20-50), and more preferably (30-40): (30-40), and standing to allow the rubber elastomer to fully absorb the oil; and fully mixing the oil-filled rubber elastomer with a polyolefin resin, an oil-locking stabilizer, an inorganic filler and an additive in a ratio of (5-50): (2-25): (1-20): (0.5-5), preferably (8-30): (5-20): (1-10): (0.5-2), and then extruding for high-temperature melt granulation.

[0061] Various products can be prepared using the high temperature resistant oil-discharging TPE material disclosed in the present disclosure. The products can be prepared by extruding the high temperature resistant oil-discharging TPE material disclosed in the present disclosure.

[0062] Extrusion molding can be carried out using methods and equipment known in the art, for example, the extrusion step can be carried out using a twin-screw extruder, preferably a conical twin-screw extruder. Those skilled in the art can adjust the reaction conditions and equipment parameters used according to their common technical knowledge, as long as the purpose of the present disclosure can be achieved.

[0063] The product can be a car sealing strip, a cable protective cover, a mobile phone case, a plastic toy, etc., especially a switch button of a household appliance, a car charging gun, etc.

[0064] The beneficial effects of the present disclosure are:

[0065] The present invention introduces hydrogenated terpene resin as a cross-linked network surface modifier on the basis of TPE chemical cross-linking. The synergistic effect of SEPS and hydrogenated terpene resin improves the sealing and high temperature resistance of the chemical cross-linked network. In addition, by introducing a ladder polymer resin with excellent heat resistance, the high temperature resistance of the TPE material is further improved, so that a TPE material with good high temperature resistant oil discharge performance is finally obtained. The present invention greatly improves the oil discharge problem of the TPE material in a high temperature environment through chemical cross-linking modification, three-dimensional cross-linked network surface sealing modification and introduction of a ladder polymer heat-resistant resin, and improves the application range and service life of the TPE material in a high temperature environment. The modified and optimized TPE material has both good soft touch and high temperature resistant oil discharge performance.

[0066] In the present disclosure, the term "containing" or "including" or "using" indicates that various components can be used together in the mixture or composition of the present disclosure. Therefore, the terms "mainly composed of..." and "consisting of..." are included in the terms "containing" or "including" or "using". It should be understood that the degree of "high", "low", etc. used in the present disclosure is well known in the art. For example, for "heat-resistant", those skilled in the art can judge whether a certain material is a heat-resistant material in combination with existing materials.

[0067] Unless otherwise specified, various raw materials disclosed herein can be obtained commercially; or prepared according to conventional methods in the art. Unless otherwise defined or specified, all professional and scientific terms used herein have the same meanings as those familiar to those skilled in the art. In addition, any methods and materials similar or equivalent to those described herein can be applied to the methods disclosed herein. Other aspects of the disclosure are obvious to those skilled in the art due to the disclosure herein.

[0068] The present disclosure will be further described below in conjunction with specific examples. It should be understood that these examples are only used to illustrate the present disclosure and are not intended to limit the scope of the present disclosure. The experimental methods for which specific conditions are not specified in the following examples are usually measured in accordance with national standards. If there is no corresponding national standard, then it is carried out in accordance with general international standards, conventional conditions, or according to the conditions recommended by the manufacturer. Unless otherwise stated, all parts are parts by weight, all percentages are percentages by weight, and the polymer molecular weight is the number average molecular weight.

[0069] Raw material source and preparation:

[0070] The rubber elastomer is a mixture of SEBS:SEPS=1:1, wherein the styrene content of SEBS is 32%, the product brand is 6151, purchased from Taiwan Rubber Corporation; the styrene content of SEPS is 21%, the product brand is G1730, purchased from Kraton Corporation of the United States.

[0071] The filling oil is paraffin oil, viscosity 32mm 2 / s (100°C), flash point 292°C, product brand KP6030, purchased from PetroChina Karamay Petrochemical Co., Ltd.;

[0072] The polyolefin resin is a mixture of PPR:LLDPE=3:1, the melt mass flow rate of PPR resin at 230°C / 2.16KG is 15g / 10min, the product brand is 5090T, and it is purchased from Formosa Plastics Group; the melt mass flow rate of LLDPE at 190°C / 2.16KG is 2g / 10min, the product brand is 7042, and it is purchased from Zhenhai Refining and Chemical Company of China Petrochemical Corporation.

[0073] Crosslinking agent:

[0074] A mixture of diisopropylbenzene peroxide (DCP): trimethylolpropane triacrylate (TMPTA) in a ratio of 4:1; a mixture of diisopropylbenzene ditert-butylperoxide (BIPB): trimethylolpropane triacrylate (TMPTA) in a ratio of 4:1. The diisopropylbenzene peroxide (DCP) product brand BC-FF was purchased from Akzo Nobel; the trimethylolpropane triacrylate (TMPTA) product brand EM231-TF was purchased from Changxing Chemical Industry Co., Ltd.; and the diisopropylbenzene ditert-butylperoxide (BIPB) product brand Perkadox 14-40B-PD was purchased from Akzo Nobel.

[0075] The cross-linked network surface modifier is hydrogenated terpene resin, product brand HTAF110, purchased from Guangdong Nuochi New Materials Co., Ltd.

[0076] Heat-resistant resin:

[0077] The sulfonated polyaryletherketone copolymer is prepared by reacting bisphenol A monomer, 2,6-dichlorobenzothiazole, 4,4'-difluorobenzophenone and 3,3'-sodium disulfonate-4,4'-difluorobenzophenone in a molar ratio of 10:3:3:4.

[0078] Polybenzimidazole, product brand U-60, was purchased from PBI (Pressure BioSciences Inc), USA.

[0079] The inorganic mineral is calcium carbonate, mesh size 3000 mesh, product brand CMS-888, purchased from Heshan Chemical (Liaoning) Co., Ltd.

[0080] The additives include antioxidants, ultraviolet absorbers, lubricants and masterbatches, wherein the antioxidant is composed of a hindered phenol main antioxidant and a phosphite auxiliary antioxidant in a ratio of 1:2, the antioxidant accounts for 30% by weight of the additives, and the antioxidant is purchased from BASF SE; the ultraviolet absorber is a benzotriazole ultraviolet absorber, accounting for 30% by weight of the additives, and the ultraviolet absorber is purchased from Anhui Xinxiu Chemical Co., Ltd.; the lubricant is a silicone masterbatch, accounting for 20% by weight of the additives, and purchased from Dow Chemical Company; the masterbatch is a black masterbatch with PE as a carrier and carbon black as a coloring body, accounting for 20% by weight of the additives, and purchased from Cabot Corporation.

[0081] Product performance test:

[0082] (1) Shore hardness: The hardness of the product is tested according to the method described in GB / T 2411.

[0083] (2) High temperature resistance and oil release: According to the GB / T 2099.1 test standard, the samples were placed in a (70±2)℃ heating box, a (90±2)℃ heating box, and a (110±2)℃ heating box for 168h. After the test, the oil release on the sample surface was observed. Specific embodiments

[0085] Example 1

[0086] The high temperature resistant oil-discharging TPE material is prepared by the following steps:

[0087] 1): 40 parts of rubber elastic body and 30 parts of filling oil are mixed continuously for 15-30 minutes by a high-speed mixer. The oil filling temperature is (40-60)℃. After the oil filling is completed, it is allowed to stand at room temperature for more than 24 hours to allow the rubber elastic body to fully absorb the oil;

[0088] 2): Weigh 17 parts of polyolefin resin, 1 part of cross-linking agent, 3 parts of cross-linking network surface modifier, 3 parts of heat-resistant resin, 5 parts of inorganic filler and 1 part of auxiliary agent, then fully mix the rubber elastomer after oil filling in step 1) with the above components in a low-speed mixer for about 15 minutes, and finally use a twin-screw extruder for high-temperature melt granulation to obtain a modified high-temperature resistant oil-discharging TPE material, wherein the granulation temperature range of the twin-screw extruder is (180-230) ° C, and the temperature increases from the feeding section to the homogenization section.

[0089] Example 2

[0090] Example 2 is carried out according to the method described in Example 1. The difference from Example 1 is that on the basis of Example 1, the rubber elastomer content is reduced to 30 parts, the filler oil content is increased to 40 parts, and the types and contents of other raw materials in the formula remain consistent with those in Example 1.

[0091] Example 3

[0092] Example 3 is carried out according to the method described in Example 1. The difference from Example 1 is that on the basis of Example 1, the rubber elastomer content is reduced to 35 parts, the filler oil content is increased to 35 parts, and the types and contents of other raw materials in the formula remain consistent with those in Example 1.

[0093] Example 4

[0094] Example 4 is carried out according to the method described in Example 3. The difference from Example 3 is that on the basis of Example 3, the content of the cross-linking agent is increased to 2 parts, the content of the polyolefin resin is reduced to 16 parts, and the types and contents of other raw materials in the formula remain consistent with those in Example 3.

[0095] Example 5

[0096] Example 5 is carried out according to the method described in Example 3. The difference from Example 3 is that on the basis of Example 3, the cross-linking agent content is increased to 3 parts, the polyolefin resin content is reduced to 15 parts, and the types and contents of other raw materials in the formula remain consistent with Example 3.

[0097] Example 6

[0098] Example 6 is carried out according to the method described in Example 4. The difference from Example 4 is that on the basis of Example 4, the content of the cross-linked network surface modifier is increased to 5 parts, and the content of the polyolefin resin is reduced to 14 parts. The types and contents of other raw materials in the formula remain consistent with those in Example 4.

[0099] Example 7

[0100] Example 7 is carried out according to the method described in Example 4. The difference from Example 1 is that on the basis of Example 4, the content of the cross-linked network surface modifier is increased to 10 parts, and the content of the polyolefin resin is reduced to 9 parts. The types and contents of other raw materials in the formula remain consistent with those in Example 4.

[0101] Example 8

[0102] Example 8 is carried out according to the method described in Example 6. The difference from Example 6 is that on the basis of Example 6, the content of heat-resistant resin is increased to 5 parts, and the content of polyolefin resin is reduced to 12 parts. The types and contents of other raw materials in the formula remain consistent with those in Example 6.

[0103] Example 9

[0104] Example 9 was carried out according to the method described in Example 8. The difference from Example 8 was that on the basis of Example 8, the cross-linking agent diisopropylbenzene peroxide (DCP): trimethylolpropane triacrylate (TMPTA) = 4:1 mixture was replaced with an equal amount of di-tert-butyl peroxide diisopropylbenzene (BIPB): trimethylolpropane triacrylate (TMPTA) = 4:1 mixture, and the types and contents of other raw materials in the formula remained consistent with Example 8.

[0105] Example 10

[0106] Example 10 is carried out according to the method described in Example 8. The difference from Example 8 is that on the basis of Example 8, the heat-resistant resin sulfonated polyaryletherketone copolymer is replaced with polybenzimidazole in equal amounts, and the types and contents of other raw materials in the formula remain consistent with those in Example 8.

[0107] Embodiment 11

[0108] Example 11 is carried out according to the method described in Example 6. The difference from Example 6 is that on the basis of Example 6, the content of heat-resistant resin is increased to 8 parts, and the content of polyolefin resin is reduced to 9 parts. The types and contents of other raw materials in the formula remain consistent with those in Example 6.

[0109] Comparative Example 1

[0110] Comparative Example 1 was carried out according to the method described in Example 8. The difference from Example 8 was that the cross-linking agent content was reduced to 0 parts, the polyolefin resin content was increased to 14 parts, and the types and contents of other raw materials in the formula remained consistent with those in Example 8.

[0111] Comparative Example 2

[0112] Comparative Example 2 was carried out according to the method described in Example 8. The difference from Example 8 was that on the basis of Example 8, the content of the cross-linked network surface modifier was reduced to 0 parts, the content of the polyolefin resin was increased to 17 parts, and the types and contents of other raw materials in the formula remained consistent with those in Example 8.

[0113] Comparative Example 3

[0114] Comparative Example 3 was carried out according to the method described in Example 8. The difference from Example 8 is that on the basis of Example 8, the content of heat-resistant resin was reduced to 0 parts, and the content of polyolefin resin was increased to 17 parts. The types and contents of other raw materials in the formula remained consistent with those in Example 8.

[0115] Comparative Example 4

[0116] Comparative Example 4 is carried out according to the method described in Example 8. The difference from Example 8 is that on the basis of Example 8, the content of the cross-linking agent, the cross-linking network surface modifier, and the heat-resistant resin is reduced to 0 parts, and the content of the polyolefin resin is increased to 24 parts. The types and contents of other raw materials in the formula remain consistent with those in Example 8.

[0117] The formulation compositions and weights of the components of Examples 1-11 and Comparative Examples 1-4 are listed in Table 1 below:

[0118] Table 1 Composition ratio

[0119]

[0120]

[0121] The materials prepared in Examples 1-11 and Comparative Examples 1-4 were respectively injection molded to prepare samples, and then the material properties were tested and evaluated. The test results are shown in Table 2.

[0122] Table 2 Test results

[0123]

[0124]

[0125] From the above test results in Table 2, it can be seen that the TPE material of Example 4, which has not undergone chemical crosslinking and heat-resistant optimization treatment, has poor high-temperature oil-release performance and obvious oil release. When the crosslinking agent, crosslinked network surface modifier and heat-resistant resin are added separately, they have a certain positive effect on improving the high-temperature oil release phenomenon of the TPE material. Example 3, in which the crosslinking agent and the crosslinked network surface modifier are used in combination, can reduce the aging oil release phenomenon at 70°C, and the effect is better than that of Examples 1 and 2. When the crosslinking agent, the crosslinked network surface modifier and the heat-resistant resin are used in combination, the high-temperature oil release phenomenon of the TPE material can be greatly reduced. The materials prepared in Examples 8-10 have extremely low oil release and achieved the best improvement effect. When the amount of crosslinking agent, crosslinked network surface modifier and heat-resistant resin added reaches a certain level, the effect of improving the high-temperature oil release of the TPE material tends to be saturated. At this time, continuing to increase the amount added will cause the material hardness to increase, and may affect the material processing performance and affect the soft touch. In order to reduce the amount of oil and avoid affecting the hardness, the weight ratio of the rubber elastomer to the filler oil is preferably 1: 1-1: 2, and the weight ratio of the polyolefin to the oil-locking stabilizer is preferably greater than 2: 1. Similar other peroxide crosslinking agents and other types of ladder polymers can also be used in the present disclosure, which can achieve a considerable level of improvement.

[0126] The above description is only a preferred embodiment of the present disclosure and is not intended to limit the scope of the substantial technical content of the present disclosure. The substantial technical content of the present disclosure is broadly defined in the scope of the claims of the application. Any technical entity or method completed by others, if it is exactly the same as that defined in the scope of the claims of the application or an equivalent variation, will be deemed to be included in the scope of the claims.

[0127] All documents mentioned in this disclosure are cited as references in this application, just as each document is cited as reference individually. In addition, it should be understood that after reading the above content of this disclosure, those skilled in the art may make various changes or modifications to this disclosure, and these equivalent forms also fall within the scope defined by the claims attached to this application.

Claims

1. An oil-locking stabilizer for TPE materials, characterized in that: The oil-locking stabilizer comprises a crosslinking agent, a crosslinking network surface modifier and an optional heat-resistant resin, wherein the weight ratio of the crosslinking agent, the crosslinking network surface modifier and the heat-resistant resin is (0.5-5):(1-15):(0-10).

2. The oil-locking stabilizer according to claim 1, characterized in that: The oil-locking stabilizer comprises a crosslinking agent, a crosslinking network surface modifier and a heat-resistant resin, and the weight ratio of the crosslinking agent, the crosslinking network surface modifier and the heat-resistant resin is (1-3): (3-10): (3-8).

3. The oil-locking stabilizer according to claim 1 or 2, characterized in that: The crosslinking agent comprises at least one crosslinking agent selected from the group consisting of dicumyl peroxide (DCP), di-tert-butyl dicumyl peroxide (BIPB), dibenzoyl peroxide (BPO) and trimethylolpropane triacrylate (TMPTA); and / or The cross-linked network surface modifier comprises at least one resin selected from the group consisting of hydrogenated terpene resin, poly-α-methylstyrene resin and hydrogenated rosin pentaerythritol ester; and / or The heat-resistant resin includes at least one polymer selected from the group consisting of polystyrene, styrene-acrylonitrile copolymer, polyphenylene ether, polybutylene terephthalate, poly-1,3,4-oxadiazole, polyphenylquinoxaline, polybenzoxazole, polybenzothiazole, sulfonated polyaryletherketone copolymer, and polybenzimidazole.

4. A high temperature resistant oil-discharging TPE material, comprising a rubber elastomer, a filler oil, a polyolefin resin, an oil-locking stabilizer as claimed in claim 1 or 2, an inorganic filler and optional additives.

5. The high temperature resistant oil-discharging TPE material according to claim 4, characterized in that: The rubber elastomer comprises at least one elastomer selected from the group consisting of SBS, SEBS, SIS, SEPS, SIBS, SEEPS, EPDM, POE and TPU; and / or The extender oil comprises at least one oil selected from the group consisting of naphthenic oil, paraffinic oil and aromatic oil; and / or The polyolefin resin comprises polypropylene and / or polyethylene; and / or The inorganic filler comprises at least one filler selected from the group consisting of talc, wollastonite, calcium carbonate, barium sulfate, magnesium sulfate and calcium sulfate; and / or The auxiliary agent includes an antioxidant, an ultraviolet absorber, a lubricant and / or a masterbatch.

6. The high temperature resistant oil-discharging TPE material according to claim 4, characterized in that: The weight ratio of the rubber elastic body to the filler oil is 2:1-1:2, preferably 1:1-1:2; and / or The weight ratio of the polyolefin resin to the oil-locking stabilizer is 5:1-1:5, preferably 2:1-1:

2.

7. The high temperature resistant oil-discharging TPE material according to claim 4, characterized in that: The rubber elastic body comprises SEBS and SEPS, wherein the weight ratio of SEBS to SEPS is (1-5):1; and / or The extender oil comprises paraffin oil; and / or The polyolefin resin comprises PPR and LLDPE, wherein the weight ratio of PPR to LLDPE is (1-10):1; and / or The crosslinking agent comprises dicumyl peroxide (DCP) and trimethylolpropane triacrylate (TMPTA), wherein the weight ratio of dicumyl peroxide (DCP) to trimethylolpropane triacrylate (TMPTA) is (1-10):1; and / or The cross-linked network surface modifier comprises a hydrogenated terpene resin; and / or The heat-resistant resin comprises a sulfonated polyaryletherketone copolymer; and / or The inorganic filler includes calcium carbonate.

8. The high temperature resistant oil-discharging TPE material according to claim 4, comprising:

9. A method for preparing a high temperature resistant oil-discharging TPE material, the method comprising blending and extruding a rubber elastomer, a filler oil, a polyolefin resin, a crosslinking agent, a crosslinking network surface modifier, a heat resistant resin, an inorganic filler and an optional auxiliary agent to form a granule.

10. A product prepared using the high temperature resistant oil-discharging TPE material according to any one of claims 4 to 8.

11. Use of the oil-locking stabilizer according to claim 1 in improving the high-temperature oil release resistance of TPE materials.

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