High-temperature-resistant oiling TPE material, product prepared therefrom and application thereof

Abstract

The present disclosure provides a locking oil stabilizer for TPE material, which comprises a crosslinking agent, a crosslinking network surface modifier and an optional heat-resistant resin. A high-temperature resistant and oil-bleeding TPE material is also provided, which comprises a rubber elastomer, a filling oil, a polyolefin resin, the locking oil stabilizer, an inorganic filler and an optional auxiliary agent. The present disclosure further provides an article prepared from the high-temperature resistant and oil-bleeding TPE material, in particular, a switch key of an electrical product. The article prepared from the high-temperature resistant and oil-bleeding TPE material has the advantages of high-temperature resistance, oil-bleeding resistance and good material processing performance.

Description

TECHNICAL FIELD

[0001] The present disclosure relates to a locking oil stabilizer for TPE materials, a high-temperature resistant and oil-bleeding TPE material comprising the locking oil stabilizer, and an article prepared therefrom and applications thereof. The high-temperature resistant and oil-bleeding TPE material of the present disclosure has the advantages of high-temperature resistance, oil-bleeding resistance, and good material processing performance, and is suitable for use in electrical products, such as household appliances, switch keys of charging gun products, and the like. BACKGROUND

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

[0003] Compared with thermoplastic vulcanized rubber (TPV) materials, TPE materials do not need to be vulcanized, are more environmentally friendly, and have simpler production processes. However, due to the high viscosity of the rubber component in the TPE material formula, it is difficult to be directly processed, and therefore a suitable amount of filling oil needs to be added to improve its processing performance. However, the rubber component and the filling oil in the TPE material system are only physically blended, and due to the lack of binding of the filling oil by rubber vulcanization crosslinking, combined with the general heat resistance of TPE materials, when the external environment temperature is high, the molecular chain movement accelerates, and the filling oil penetrates to the surface of the material, resulting in the phenomenon of oil bleeding and stickiness on the surface of the product, which affects the normal use of the product. The heating phenomenon of outdoor application scenarios and electrical products during power-on operation can all cause the TPE material to produce oil bleeding after being heated. Generally, the lower the hardness of the TPE material, the higher the content of rubber and filling oil in the formula, and the greater the risk of oil bleeding in a high-temperature environment.

[0004] Therefore, there is an urgent need in the art to solve the problem of oil bleeding of TPE materials in a high-temperature environment when applied to electrical products. SUMMARY

[0005] The first aspect of the present disclosure provides a locking oil stabilizer for TPE materials, the locking oil stabilizer comprising a crosslinking agent, a crosslinked network surface modifier, and optionally a heat-resistant resin, and 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).

[0006] The second aspect of the present disclosure provides a high-temperature resistant and oil-bleeding TPE material, the material comprising a rubber elastomer, a filling oil, a polyolefin resin, the locking oil stabilizer of the present disclosure, an inorganic filler, and optionally an auxiliary agent.

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

[0008] The fourth aspect of the present disclosure provides an article prepared from the high-temperature oiling-resistant TPE material described in the present disclosure, preferably the article is a switch key of an electrical product.

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

[0010] The present inventors have conducted in-depth research on the high-temperature oiling principle of TPE materials and found that the high-temperature oiling problem of TPE materials in the application of electrical products can be solved by modifying the TPE materials with an oil-locking stabilizer comprising a crosslinking agent, a crosslinking network surface modifier, and optionally a heat-resistant resin, through chemical crosslinking of oil, crosslinking network surface modification, and / or improvement of heat resistance. On this basis, the present disclosure is completed.

[0011] The oil-locking stabilizer for TPE materials of the present disclosure comprises a crosslinking agent, a crosslinking network surface modifier, and optionally a heat-resistant resin, and 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).

[0012] The components of the oil-locking stabilizer for TPE materials of the present disclosure are described in detail as follows:

[0013] Crosslinker

[0014] The crosslinking agent can form chemical bonds between linear molecules, so that the linear molecules are connected together, and the polymer chain segments after the crosslinking reaction form a three-dimensional crosslinking network structure to improve the material performance.

[0015] The crosslinking agent used in the present disclosure includes at least one selected from the group consisting of dicumyl peroxide (DCP), bis-tert-butyl peroxide diisopropylbenzene (BIPB), dibenzoyl peroxide (BPO) and trimethylolpropane triacrylate (TMPTA). Preferably, the crosslinking agent includes dicumyl peroxide (DCP) as the main crosslinking agent and trimethylolpropane triacrylate (TMPTA) as the 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 the main crosslinking agent initiates free radical polymerization in the rubber elastomer and the polyolefin resin, and trimethylolpropane triacrylate (TMPTA) as the auxiliary crosslinking agent cooperatively improves the crosslinking reaction efficiency and the crosslinking density, so that the heat resistance, solvent resistance, weather resistance, corrosion resistance and oil locking performance of the material are greatly improved.

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

[0017] Crosslinking network surface modifier

[0018] In the present disclosure, the crosslinking network surface modifier can seal and modify the surface of the crosslinking network, greatly improving the high-temperature oil locking capacity of the crosslinking rubber elastomer. The crosslinking network surface modifier has special molecular structures such as ester bond, ether bond, carboxyl group, hydroxymethyl group and phenolic hydroxyl group, is easy to form a hydrogen bond network structure with the rubber elastomer, and is intertwined with the crosslinking network structure, so as to be used as a thickening agent and a sealing agent to seal and modify the surface of the crosslinking network.

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

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

[0021] Heat-resistant resin

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

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

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

[0025] The amount of the heat-resistant resin in the oil-lock stabilizer is 0-60 wt%, preferably 15-55 wt%, and more preferably 30-50 wt%, based on the total weight of the oil-lock stabilizer.

[0026] In the oil-lock 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-out TPE material of the present disclosure comprises a rubber elastomer, an oil filler, a polyolefin resin, an oil-lock stabilizer as described above, an inorganic filler, and optionally an auxiliary agent.

[0028] The components of the high-temperature resistant oil-out TPE material of the present disclosure are described in detail as follows:

[0029] Rubber elastomer

[0030] In the present disclosure, the rubber elastomer comprises at least one elastomer selected from the group consisting of SBS, SEBS, SIS, SEPS, SIBS, SEEPS, EPDM, POE and TPU. Preferably, the rubber elastomer comprises SEBS and SEPS. SEBS is a linear tri-block copolymer with polystyrene as end block and ethylene-butene copolymer obtained by hydrogenation of polybutadiene as middle elastic block. SEPS is a hydrogenated styrene-isoprene thermoplastic elastomer obtained by selective hydrogenation of conjugated unsaturated double bonds in styrene-isoprene-styrene block copolymer (SIS). Both SEBS and SEPS are hydrogenated styrene elastomers, without unsaturated double bonds in the molecular chain, and have more excellent heat resistance, weather resistance and oil absorption performance compared with conventional styrene elastomers. Compared with SEBS, the soft block of SEPS is more random, the EP block is softer than the EB block, and has lower crystallinity, better elasticity and higher elongation. By blending SEBS and SEPS, both good oil absorption capacity and the synergistic effect of SEPS and crosslinked network surface modifier on improving the sealing property of crosslinked network structure and the tear resistance and high temperature resistance of the material can be achieved.

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

[0032] The amount of the rubber elastomer is 10-60 wt%, preferably 20-50 wt%, and more preferably 30-35 wt% based on the total weight of the high temperature resistant oil-bleeding TPE material.

[0033] Extending oil

[0034] Since the rubber component in the TPE material formula has a large viscosity and is difficult to be directly processed, an appropriate amount of filling oil is needed to improve its processing performance. The filling oil added in the high temperature resistant oil-bleeding TPE material of the present disclosure is not specifically limited, and various commercially available filling oils can be used as long as they do not limit the purpose of the present disclosure.

[0035] In a specific embodiment, the filling oil comprises at least one oil selected from the group consisting of naphthenic oil, paraffin oil and aromatic oil. Preferably, the filling oil comprises paraffin oil. The linear molecular structure of paraffin oil is more flexible, and has better compatibility with SEBS and SEPS, which can improve the flowability, flex resistance and light stability of the rubber elastomer.

[0036] The amount of the filling oil is 10-60 wt%, preferably 20-50 wt%, and more preferably 35-40 wt% based on the total weight of the high temperature resistant oil-bleeding TPE material.

[0037] In one preferred embodiment of the present disclosure, the weight ratio of the rubber elastomer and the filling 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 inexpensive and abundant in source, can reduce the melt viscosity of the rubber elastomer, improve the processing performance, and reduce the cost.

[0040] Suitable polyolefin resins that can be listed include homopolymer polypropylene (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 produces phase separation of crystalline regions and amorphous regions, so it is preferred to use PPR resin with lower crystallinity, and at the same time, LLDPE is added, and the crystallization characteristics of the two are used to interfere with each other to reduce the crystallinity of the plastic phase, thereby improving the oil absorption effect. In one preferred embodiment, the polyolefin resin includes PPR and LLDPE, and the weight ratio of PPR and LLDPE is (1-10):1, preferably (2-5):1.

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

[0043] Lock oil stabilizer

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

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

[0046] Inorganic filler

[0047] In the present disclosure, inorganic fillers are used to adjust the hardness of the material and reduce the cost of the formulation. There is no specific limitation on the inorganic fillers added to the high-temperature resistant oiling 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 present disclosure.

[0048] In one 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] The amount of the inorganic filler is 1-20 wt%, preferably 2-15 wt%, and more preferably 4-10 wt%, based on the total weight of the high-temperature resistant oiling TPE material.

[0050] Optional adjuvant

[0051] The auxiliary agents include, but are not limited to, compatibilizers, ultraviolet absorbers, antioxidants, lubricants, color master batches, surfactants, etc., and are used to improve the properties of the TPE material such as thermal-oxidative aging resistance, weather resistance, and processability. There is no specific limitation on the auxiliary agents added to the high-temperature resistant oiling TPE material of the present disclosure, and various commercially available auxiliary agents can be used as long as they do not limit the purpose of the present disclosure.

[0052] In one specific embodiment of the present disclosure, the auxiliary agents include antioxidants, ultraviolet absorbers, lubricants, and color master batches. The ultraviolet absorber is added to improve the outdoor weather resistance of the material. The lubricant functions to reduce the friction between the molecules in the plastic, improve the processability of the plastic, and increase the production efficiency. The antioxidant functions 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 one specific example of the present disclosure, the antioxidant consists of a hindered phenolic primary antioxidant and a phosphite secondary antioxidant, and 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 master batch. In one embodiment of the present disclosure, the color master batch includes a black master batch with PE as the carrier and carbon black as the coloring body.

[0054] The amount of the auxiliary agent is 0-5 wt%, preferably 0.1-3 wt%, and more preferably 0.5-2 wt%, based on the total weight of the high-temperature resistant oiling TPE material.

[0055] In one embodiment of the present disclosure, the weight ratio of the rubber elastomer, the filling 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), more preferably (30-40):(30-40):(9-20):(7-15).

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

[0057]

[0058]

[0059] The method for preparing the high-temperature resistant oil-bleeding TPE material of the present disclosure comprises mixing and extruding the rubber elastomer, the filling oil, the polyolefin resin, the crosslinking agent, the crosslinking network surface modifier, the heat-resistant resin, the inorganic filler and the optional auxiliary agent.

[0060] In one preferred embodiment, the method comprises high-speed mixing the rubber elastomer and the filling oil at a ratio of (10-60):(10-60), preferably (20-50):(20-50), more preferably (30-40):(30-40), and allowing the rubber elastomer to fully absorb the oil; fully mixing the oil-bleeding rubber elastomer with the polyolefin resin, the oil-locking stabilizer, the inorganic filler and the auxiliary agent at 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 to perform high-temperature melt granulation.

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

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

[0063] The products can be automobile sealing strips, cable protection sleeves, mobile phone cases, plastic toys, etc., in particular, switches and keys of household appliances, automobile charging guns, etc.

[0064] The present disclosure has the following beneficial effects:

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

[0066] In the present disclosure, the term "containing" or "including" or "using" means that various components can be applied together in the mixture or composition of the present disclosure. Therefore, the terms "mainly consisting of" and "consisting of" are included in the term "containing" or "including" or "using". It should be understood that the degree of "high", "low" and the like used in the present disclosure is well known in the art. For example, for "heat-resistant", a person 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 of the present disclosure can be obtained by market or prepared according to conventional methods in the art. Unless otherwise defined or specified, all professional and scientific terms used herein have the same meaning as familiar to those skilled in the art. In addition, any method and material similar or equivalent to the described content can be applied to the method of the present disclosure. Other aspects of the present disclosure are obvious to those skilled in the art from the disclosure herein.

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

[0069] Raw material source and preparation:

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

[0071] The filling oil is paraffin oil, viscosity 32 mm 2 / s (100℃), flash point 292℃, product grade 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 is 15 g / 10 min at 230℃ / 2.16KG, product grade 5090T, purchased from Formosa Plastics Corporation; the melt mass flow rate of LLDPE is 2 g / 10 min at 190℃ / 2.16KG, product grade 7042, purchased from Zhenhai Refining and Chemical Co., Ltd.

[0073] The crosslinking agent is:

[0074] The dicumyl peroxide (DCP) is a mixture of trimethylolpropane triacrylate (TMPTA) = 4:1; the bis-tert-butyl peroxydicumyl (BIPB) is a mixture of trimethylolpropane triacrylate (TMPTA) = 4:1. The dicumyl peroxide (DCP) product grade BC-FF, purchased from AkzoNobel; trimethylolpropane triacrylate (TMPTA) product grade EM231-TF, purchased from Changxing Chemical Industry Co., Ltd.; bis-tert-butyl peroxydicumyl (BIPB) product grade Perkadox 14-40B-PD, purchased from AkzoNobel.

[0075] The crosslinking network surface modifier is hydrogenated terpene resin, product grade HTAF110, purchased from Guangdong Nuochi New Material Co., Ltd.

[0076] The heat-resistant resin is:

[0077] The sulfonated polyaryletherketone copolymer is self-made from raw materials such as bisphenol A monomer, 2,6-dichlorobenzothiazole, 4,4'-difluorobenzophenone and 3,3'-disulfonic acid sodium-4,4'-difluorobenzophenone, according to the molar ratio of 10:3:3:4.

[0078] The polybenzimidazole is product grade U-60, purchased from Pressure BioSciences Inc.

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

[0080] The auxiliary agents include antioxidants, ultraviolet absorbers, lubricants, and color master batches, wherein the antioxidants are composed of a hindered phenol main antioxidant: phosphite auxiliary antioxidant = 1:2, the antioxidants account for 30% by weight of the auxiliary agents, the antioxidants are purchased from BASF SE; the ultraviolet absorbers are benzotriazole ultraviolet absorbers, accounting for 30% by weight of the auxiliary agents, the ultraviolet absorbers are purchased from Anhui Xiuji Chemical Co., Ltd.; the lubricants are silicone master batches, accounting for 20% by weight of the auxiliary agents, and are purchased from Dow; the color master batch is a black color master batch with PE as a carrier and carbon black as a coloring body, accounting for 20% by weight of the auxiliary agents, and is 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 oil resistance: according to the test standard GB / T 2099.1, the sample plates are respectively placed in a (70±2) ℃ heating box, a (90±2) ℃ heating box, and a (110±2) ℃ heating box for 168 h, and the oiling condition on the surface of the sample is observed after the test. Specific embodiments

[0085] Example 1

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

[0087] 1) : 40 parts of rubber elastomer and 30 parts of filling oil are continuously mixed by a high-speed mixer for 15-30 min, the oiling temperature is (40-60) ℃, and after the oiling is completed, the rubber elastomer is allowed to stand at room temperature for more than 24 h to allow the rubber elastomer to fully absorb oil;

[0088] 2) : 17 parts of polyolefin resin, 1 part of crosslinking agent, 3 parts of crosslinking network surface modifier, 3 parts of heat-resistant resin, 5 parts of inorganic filler, and 1 part of auxiliary agent are weighed, and then the oil-filled rubber elastomer of step 1) is mixed with the above components in a low-speed mixer for about 15 min, and finally a double-screw extruder is used for high-temperature melt granulation to obtain a modified high-temperature oil-resistant TPE material, wherein the double-screw extruder granulation temperature range is (180-230) ℃, and the temperature increases from the feeding section to the homogenizing section.

[0089] Example 2

[0090] Example 2 is prepared according to the method described in Example 1, and the difference from Example 1 is that the rubber elastomer content is reduced to 30 parts and the filling oil content is increased to 40 parts on the basis of Example 1, and the types and contents of other raw materials in the formula remain the same as in Example 1.

[0091] Example 3

[0092] Example 3 was conducted according to the method of Example 1, except that the rubber elastomer content was reduced to 35 parts, the extender oil content was increased to 35 parts, and the other ingredients were the same as in Example 1.

[0093] Example 4

[0094] Example 4 was conducted according to the method of Example 3, except that the crosslinking agent content was increased to 2 parts, the polyolefin resin content was reduced to 16 parts, and the other ingredients were the same as in Example 3.

[0095] Example 5

[0096] Example 5 was conducted according to the method of Example 3, except that the crosslinking agent content was increased to 3 parts, the polyolefin resin content was reduced to 15 parts, and the other ingredients were the same as in Example 3.

[0097] Example 6

[0098] Example 6 was conducted according to the method of Example 4, except that the crosslinking network surface modifier content was increased to 5 parts, the polyolefin resin content was reduced to 14 parts, and the other ingredients were the same as in Example 4.

[0099] Example 7

[0100] Example 7 was conducted according to the method of Example 4, except that the crosslinking network surface modifier content was increased to 10 parts, the polyolefin resin content was reduced to 9 parts, and the other ingredients were the same as in Example 4.

[0101] Example 8

[0102] Example 8 was conducted according to the method of Example 6, except that the heat resistant resin content was increased to 5 parts, the polyolefin resin content was reduced to 12 parts, and the other ingredients were the same as in Example 6.

[0103] Example 9

[0104] Example 9 was conducted according to the method described in Example 8, except that on the basis of Example 8, the crosslinking agent mixture of dicumyl peroxide (DCP) : trimethylolpropane triacrylate (TMPTA) = 4: 1 was replaced by an equal amount of mixture of bis (tert-butyl) peroxide dicumyl (BIPB) : trimethylolpropane triacrylate (TMPTA) = 4: 1, and the other raw material types and contents in the formula remained the same as in Example 8.

[0105] Example 10

[0106] Example 10 was conducted according to the method described in Example 8, except that on the basis of Example 8, the heat-resistant resin sulfonated polyaryletherketone copolymer was replaced by an equal amount of polybenzimidazole, and the other raw material types and contents in the formula remained the same as in Example 8.

[0107] Example 11

[0108] Example 11 was conducted according to the method described in Example 6, except that on the basis of Example 6, the heat-resistant resin content was increased to 8 parts, and the polyolefin resin content was reduced to 9 parts, and the other raw material types and contents in the formula remained the same as in Example 6.

[0109] Comparative Example 1

[0110] Comparative Example 1 was conducted according to the method described in Example 8, except that on the basis of Example 8, the crosslinking agent content was reduced to 0 parts, and the polyolefin resin content was increased to 14 parts, and the other raw material types and contents in the formula remained the same as in Example 8.

[0111] Comparative Example 2

[0112] Comparative Example 2 was conducted according to the method described in Example 8, except that on the basis of Example 8, the crosslinking network surface modifier content was reduced to 0 parts, and the polyolefin resin content was increased to 17 parts, and the other raw material types and contents in the formula remained the same as in Example 8.

[0113] Comparative Example 3

[0114] Comparative Example 3 was conducted according to the method described in Example 8, except that on the basis of Example 8, the heat-resistant resin content was reduced to 0 parts, and the polyolefin resin content was increased to 17 parts, and the other raw material types and contents in the formula remained the same as in Example 8.

[0115] Comparative Example 4

[0116] Comparative Example 4 was prepared according to the method described in Example 8, except that the crosslinking agent, crosslinking network surface modifier, and heat-resistant resin were reduced to 0 parts, and the polyolefin resin was increased to 24 parts, based on Example 8. The other ingredients in the formulation were the same as in Example 8.

[0117] The formulation compositions and the weight of each component 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 injection molded into samples, and then the material performance tests and evaluations were performed. The test results are shown in Table 2.

[0122] Table 2 Test Results

[0123]

[0124]

[0125] As can be seen from the above test results in Table 2, the TPE material of Comparative Example 4, which was not subjected to chemical crosslinking and heat-resistant optimization treatment, had poor high-temperature oil bleeding resistance, and the oil bleeding was obvious. The addition of the crosslinking agent, crosslinking network surface modifier, and heat-resistant resin alone had a certain positive effect on improving the high-temperature oil bleeding of the TPE material. The combination of the crosslinking agent and crosslinking network surface modifier in Comparative Example 3 could reduce the oil bleeding during aging at 70°C, and the effect was better than that of Comparative Examples 1 and 2. The combination of the crosslinking agent, crosslinking network surface modifier, and heat-resistant resin could greatly reduce the high-temperature oil bleeding of the TPE material. The materials prepared in Examples 8-10 had very low oil bleeding, and the best improvement effect was achieved. When the addition amounts of the crosslinking agent, crosslinking network surface modifier, and heat-resistant resin reached a certain level, the effect of improving the high-temperature oil bleeding of the TPE material tended to be saturated, and at this time, increasing the addition amount would result in an increase in the hardness of the material, and might affect the processing performance and soft touch of the material. From the perspective of reducing the oil bleeding and avoiding affecting the hardness, the weight ratio of the rubber elastomer to the filling 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. Similarly, other peroxide crosslinking agents and other types of ladder polymers can also be used in the present disclosure, and can achieve a comparable improvement effect.

[0126] The above description is only the preferred embodiment of the present disclosure, not to limit the scope of the technical content of the present disclosure, the technical content of the present disclosure is broadly defined in the scope of the claims of the application, any other technical entity or method, if it is exactly the same as the scope defined by the claims of the application, or an equivalent change, will be regarded as covered in the scope of the claims.

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

Claims

1. A high-temperature resistant oil-bleeding TPE material, the material comprising a rubber elastomer, a filling oil, a polyolefin resin, an oil-bleeding stabilizer, and optionally an auxiliary agent, wherein the oil-bleeding stabilizer comprises a crosslinking agent, a crosslinking network surface modifier, and optionally a heat-resistant resin, the weight ratio of the crosslinking agent, the crosslinking network surface modifier, and the heat-resistant resin being (0.5-5) : (1-15) : (0-10); the crosslinking agent comprises dicumyl peroxide (DCP) and trimethylolpropane triacrylate (TMPTA), di-tert-butyl peroxide (BIPB) and trimethylolpropane triacrylate (TMPTA), or dibenzoyl peroxide (BPO) and trimethylolpropane triacrylate (TMPTA); the crosslinking network surface modifier comprises a hydrogenated terpene resin; and the rubber elastomer comprises SEBS and SEPS.

2. The high temperature resistant, oil-extended TPE material of claim 1, wherein, The oil-bleeding stabilizer comprises a crosslinking agent, a crosslinking network surface modifier, and a heat-resistant resin, the weight ratio of the crosslinking agent, the crosslinking network surface modifier, and the heat-resistant resin being (1-3) : (3-10) : (3-8).

3. The high temperature resistant, oil-extended TPE material according to claim 1 or 2, characterized in that, The heat-resistant resin comprises at least one polymer selected from the group consisting of polystyrene, styrene-acrylonitrile copolymer, polyphenylene ether, polybutylene terephthalate, poly-1, 3, 4-oxadiazole, polyphenyl quinoxaline, polybenzoxazole, polybenzothiazole, sulfonated polyaryletherketone copolymer, and polybenzimidazole.

4. The high temperature resistant, oil-extended TPE material according to claim 1 or 2, characterized in that, The filling oil comprises at least one oil selected from the group consisting of naphthenic oil, paraffinic oil, and aromatic oil.

5. The high-temperature resistant oil-bleeding TPE material of claim 1 or 2, wherein The polyolefin resin comprises polypropylene and / or polyethylene.

6. The high temperature oil resistant TPE material according to claim 1 or 2, wherein, 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.

7. The high temperature oil resistant TPE material according to claim 1 or 2, wherein The auxiliary agent comprises an antioxidant, an ultraviolet absorber, a lubricant, and / or a color master batch.

8. The high temperature oil resistant TPE material according to claim 1 or 2, wherein, The weight ratio of the rubber elastomer and the filling oil is 2: 1-1:

2.

9. The high temperature oil resistant TPE material according to claim 1 or 2, wherein, The weight ratio of the rubber elastomer and the filling oil is 1: 1-1:

2.

10. The high temperature oil resistant TPE material according to claim 1 or 2, wherein, The weight ratio of the polyolefin resin and the oil-bleeding stabilizer is 5: 1-1:

5.

11. The high temperature oil resistant TPE material according to claim 1 or 2, wherein The weight ratio of the polyolefin resin and the oil-bleeding stabilizer is 2: 1-1:

2.

12. The high temperature oil resistant TPE material according to claim 1 or 2, wherein, The weight ratio of SEBS and SEPS in the rubber elastomer is (1-5) :

1.

13. The high temperature oil resistant TPE material according to claim 1 or 2, wherein The filling oil comprises paraffinic oil.

14. The high temperature oil resistant TPE material according to claim 1 or 2, wherein The polyolefin resin comprises PPR and LLDPE, and the weight ratio of PPR and LLDPE is (1-10) :

1.

15. The high temperature oil resistant TPE material according to claim 1 or 2, wherein The crosslinking agent comprises dicumyl peroxide (DCP) and trimethylolpropane triacrylate (TMPTA), and the weight ratio of dicumyl peroxide (DCP) and trimethylolpropane triacrylate (TMPTA) is (1-10) :

1.

16. The high temperature oil resistant TPE material according to claim 1 or 2, wherein The heat-resistant resin comprises sulfonated polyaryletherketone copolymer.

17. The high temperature oil resistant TPE material according to claim 1 or 2, wherein The inorganic filler comprises calcium carbonate.

18. The high-temperature resistant oil-bleeding TPE material of claim 1, the material comprising:

19. A method for preparing the high-temperature oil-resistant TPE material of claim 1, the method comprising blending extruding granulating a rubber elastomer, a filling oil, a polyolefin resin, a crosslinking agent, a crosslinked network surface modifier, a heat-resistant resin, an inorganic filler, and optionally an auxiliary, wherein the oil-lock stabilizer comprises the crosslinking agent, the crosslinked network surface modifier, and the optional heat-resistant resin, the weight ratio of the crosslinking agent, the crosslinked network surface modifier, and the heat-resistant resin being (0.5-5) : (1-15) : (0-10); the crosslinking agent comprises dicumyl peroxide (DCP) and trimethylolpropane triacrylate (TMPTA), bis-tert-butyl peroxide diisopropyl benzene (BIPB) and trimethylolpropane triacrylate (TMPTA), or dibenzoyl peroxide (BPO) and trimethylolpropane triacrylate (TMPTA); the crosslinked network surface modifier comprises a hydrogenated terpene resin; and the rubber elastomer comprises SEBS and SEPS.

20. An article prepared using the high-temperature oil-resistant TPE material of any one of claims 1-18.

21. Use of an oil-lock stabilizer in improving the high-temperature oil resistance of a TPE material, wherein the TPE material comprises a rubber elastomer, a filling oil, a polyolefin resin, an oil-lock stabilizer, an inorganic filler, and optionally an auxiliary, the oil-lock stabilizer comprises a crosslinking agent, a crosslinked network surface modifier, and an optional heat-resistant resin, the weight ratio of the crosslinking agent, the crosslinked network surface modifier, and the heat-resistant resin being (0.5-5) : (1-15) : (0-10); the crosslinking agent comprises dicumyl peroxide (DCP) and trimethylolpropane triacrylate (TMPTA), bis-tert-butyl peroxide diisopropyl benzene (BIPB) and trimethylolpropane triacrylate (TMPTA), or dibenzoyl peroxide (BPO) and trimethylolpropane triacrylate (TMPTA); the crosslinked network surface modifier comprises a hydrogenated terpene resin; and the rubber elastomer comprises SEBS and SEPS.

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