A polyolefin-vinyl silicone rubber thermoplastic elastomer, its preparation method and application

Abstract

This invention provides a polyolefin-vinyl silicone rubber thermoplastic elastomer, its preparation method, and its applications, belonging to the field of functional materials technology. The polyolefin-vinyl silicone rubber thermoplastic elastomer provided by this invention is prepared from the following raw materials in parts by weight: 100-400 parts of polyolefin resin; 20-80 parts of vinyl silicone rubber; 0.1-5 parts of vulcanizing agent; 5-50 parts of inorganic filler; and 1-8 parts of structure control agent. The polyolefin resin is a polypropylene, ethylene-octene copolymer, and olefin block copolymer. This invention uses polyolefin resin and vinyl silicone rubber as matrix materials, wherein the polyolefin resin is a polypropylene, ethylene-octene copolymer, and olefin block copolymer. The three are used in combination, and under the action of the vulcanizing agent, inorganic filler, and structure control agent, the polyolefin-vinyl silicone rubber thermoplastic elastomer possesses excellent comprehensive mechanical properties, with high tensile strength and elongation at break.

Description

Technical Field

[0001] This invention relates to the field of functional materials technology, and in particular to a polyolefin-vinyl silicone rubber thermoplastic elastomer, its preparation method, and its application. Background Technology

[0002] Silicone rubber has excellent resistance to high and low temperatures and aging, but its mechanical properties and oil resistance are relatively poor. Polypropylene has high crystallinity and regular structure, good chemical stability and electrical insulation properties, as well as excellent mechanical properties and oil resistance, but its heat resistance is insufficient.

[0003] Thermoplastic elastomer composites are prepared by using polypropylene and silicone rubber to achieve complementary properties. For example, the thermoplastic elastomer composites have good high temperature resistance and oil resistance, but the comprehensive mechanical properties such as tensile strength and elongation at break still need to be improved. Summary of the Invention

[0004] The purpose of this invention is to provide a polyolefin-vinyl silicone rubber thermoplastic elastomer, its preparation method and application. The polyolefin-vinyl silicone rubber thermoplastic elastomer provided by this invention has excellent comprehensive mechanical properties, with high tensile strength and elongation at break.

[0005] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0006] This invention provides a polyolefin-vinyl silicone rubber thermoplastic elastomer, prepared from raw materials comprising the following parts by weight:

[0007] Polyolefin resin 100-400 parts; vinyl silicone rubber 20-80 parts; vulcanizing agent 0.1-5 parts; inorganic filler 5-50 parts; structure control agent 1-8 parts;

[0008] The polyolefin resin is a copolymer of polypropylene, ethylene octene, and olefin block copolymer.

[0009] Preferably, the mass ratio of the polypropylene, ethylene octene copolymer and olefin block copolymer is 30:30 to 90:30 to 105.

[0010] Preferably, the polypropylene is of type BX3920, the ethylene octene copolymer is of type ENGAGE8402, and the olefin block copolymer is of type INFUSE9817.

[0011] Preferably, the vinyl silicone rubber comprises methyl vinyl silicone rubber and / or methyl phenyl vinyl silicone rubber; the vinyl molar content in the vinyl silicone rubber is 0.04-1%.

[0012] Preferably, the structure control agent includes hydroxyl silicone oil and / or methyltriethoxysilane.

[0013] Preferably, the vulcanizing agent is an organic peroxide; the filler is an inorganic filler.

[0014] Preferably, the organic peroxide includes one or more of 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane and / or 1,1-di-tert-butylperoxy-3,3,5-trimethylcyclohexane; the inorganic filler includes one or more of silica, calcium carbonate and talc.

[0015] This invention provides a method for preparing the polyolefin-vinyl silicone rubber thermoplastic elastomer described in the above technical solution, comprising the following steps:

[0016] Vinyl silicone rubber, inorganic fillers and structure control agents are mixed to obtain a compound material;

[0017] The compounded materials, polyolefin resin, and vulcanizing agent are subjected to a dynamic vulcanization reaction to obtain the polyolefin-vinyl silicone rubber thermoplastic elastomer.

[0018] Preferably, the mixing conditions include: a temperature of 60–170°C, a time of 1–4 hours, and a rotation speed of 15–50 rpm;

[0019] The conditions for the dynamic vulcanization reaction include: a temperature of 160–170°C, a time of 1–3 min, and a rotation speed of 100–300 rpm.

[0020] This invention provides the application of the polyolefin-vinyl silicone rubber thermoplastic elastomer described in the above technical solution or the polyolefin-vinyl silicone rubber thermoplastic elastomer prepared by the preparation method described in the above technical solution in the preparation of medical devices or electronic product accessories.

[0021] This invention provides a polyolefin-vinyl silicone rubber thermoplastic elastomer, prepared from the following raw materials in parts by weight: 100-400 parts polyolefin resin; 20-80 parts vinyl silicone rubber; 0.1-5 parts vulcanizing agent; 5-50 parts inorganic filler; and 1-8 parts structure control agent. The polyolefin resin is a polypropylene, ethylene-octene copolymer, and olefin block copolymer. This invention uses polyolefin resin and vinyl silicone rubber as the matrix materials, wherein the polyolefin resin is a polypropylene, ethylene-octene copolymer, and olefin block copolymer. The three are used in combination, and under the action of the vulcanizing agent, inorganic filler, and structure control agent, the polyolefin-vinyl silicone rubber thermoplastic elastomer possesses excellent comprehensive mechanical properties, with high tensile strength and elongation at break. Detailed Implementation

[0022] This invention provides a polyolefin-vinyl silicone rubber thermoplastic elastomer, prepared from raw materials comprising the following parts by weight:

[0023] Polyolefin resin 100-400 parts; vinyl silicone rubber 20-80 parts; vulcanizing agent 0.1-5 parts; inorganic filler 5-50 parts; structure control agent 1-8 parts;

[0024] The polyolefin resin is a copolymer of polypropylene, ethylene octene, and olefin block copolymer.

[0025] This invention uses polyolefin resin and vinyl silicone rubber as matrix materials. The polyolefin resin is a polypropylene, ethylene octene copolymer, and olefin block copolymer. Polypropylene has high crystallinity, a regular structure, excellent mechanical properties, good chemical stability, and electrical insulation properties. The ethylene octene copolymer has excellent mechanical properties (such as strength, toughness, elasticity, and abrasion resistance) and good chemical stability, resisting the erosion of various chemicals and environmental factors such as acids, alkalis, oxidants, and ultraviolet radiation. The olefin block copolymer has high thermal stability, resisting the effects of high temperature, oxidation, and ultraviolet radiation. The combination of these three materials, along with the action of vulcanizing agents, inorganic fillers, and structure control agents, gives the polyolefin-vinyl silicone rubber thermoplastic elastomer excellent comprehensive mechanical properties, with high tensile strength and elongation at break. The polyolefin-vinyl silicone rubber thermoplastic elastomer of this invention will be described in detail below.

[0026] Unless otherwise specified, all raw materials used in this invention are commercially available products well known to those skilled in the art.

[0027] The raw materials for preparing the polyolefin-vinyl silicone rubber thermoplastic elastomer of the present invention, by weight, include 100-400 parts of polyolefin resin, more preferably 110-250 parts, specifically 110 parts, 120 parts, 130 parts, 140 parts, 150 parts, 160 parts, 170 parts, 180 parts, 190 parts, 200 parts, 210 parts, 220 parts, 230 parts, 240 parts, or 250 parts. In the present invention, the polyolefin resin is a polypropylene, ethylene octene copolymer, and olefin block copolymer; as an embodiment of the present invention, the mass ratio of the polypropylene, ethylene octene copolymer, and olefin block copolymer can be 30:30-90:30-105, specifically 30:30:60, 30:30:90, 30:60:90, 30:75:105, or 30:90:30. In this embodiment of the invention, the polypropylene was purchased from SK Chemicals, Inc. of South Korea, model BX3920; the ethylene octene copolymer was purchased from Dow Chemical Company of the United States, model ENGAGE8402; and the olefin block copolymer was purchased from Dow Chemical Company of the United States, model INFUSE9817.

[0028] This invention uses a compound of polypropylene, ethylene octene copolymer and olefin block copolymer, and controls their total amount within the above range, which can enhance the mechanical properties of the product, such as tensile strength and elongation at break. In the embodiments of this invention, the mass ratio of polypropylene, ethylene octene copolymer and olefin block copolymer is controlled within the above range, which can improve processing performance, help maintain good toughness and extensibility, and reduce the apparent viscosity of the melt during processing.

[0029] Based on the mass fraction of the polyolefin resin, the raw materials for preparing the polyolefin-vinyl silicone rubber thermoplastic elastomer of the present invention include 20 to 80 parts of vinyl silicone rubber, specifically 20, 30, 40, 50, 60, 65, 70, 75, or 80 parts. As an embodiment of the present invention, the vinyl silicone rubber may include methyl vinyl silicone rubber and / or methylphenyl vinyl silicone rubber, specifically methyl vinyl silicone rubber; the vinyl molar content in the vinyl silicone rubber may be 0.04 to 1%, specifically 0.04%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 1%, 1.5%, or 2%. The use of the above-mentioned types of vinyl silicone rubber in the embodiments of the present invention can maintain good elasticity and weather resistance, which is beneficial to improving the overall weather resistance and service life of the product.

[0030] Based on the mass fraction of the polyolefin resin, the raw materials for preparing the polyolefin-vinyl silicone rubber thermoplastic elastomer of the present invention include 0.1 to 5 parts of vulcanizing agent, specifically 0.1, 0.5, 0.8, 1, 1.2, 1.4, 1.6, 1.8, 2, 2.2, 2.4, 2.6, 2.8, 3, 4, or 5 parts. As an embodiment of the present invention, the vulcanizing agent can be an organic peroxide, which may include 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane and / or 1,1-di-tert-butylperoxy-3,3,5-trimethylcyclohexane, specifically 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane. In this embodiment of the invention, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane is used as a vulcanizing agent and its dosage is controlled within the above range. This can significantly improve the tensile strength and hardness of the product, while reducing its elongation and compression deformation, which is beneficial to giving the product better physical properties.

[0031] Based on the mass fraction of the polyolefin resin, the raw materials for preparing the polyolefin-vinyl silicone rubber thermoplastic elastomer of the present invention include 5 to 50 parts of inorganic filler, specifically 5, 10, 15, 20, 25, 30, 35, 40, 45, or 50 parts. As an embodiment of the present invention, the filler can be an inorganic filler; the inorganic filler may include one or more of silica, calcium carbonate, and talc, specifically silica; the silica may include precipitated silica and / or fumed silica, specifically fumed silica. As an embodiment of the present invention, the index parameters of the fumed silica include: a specific surface area of ​​180 to 200 m² / g. 2 / g; particle size 10-20nm; SiO2 content not less than 99.8wt%. In this embodiment of the invention, fumed silica is used as a filler, which can play a reinforcing role and is beneficial to improving the tensile strength, tear resistance and wear resistance of the product.

[0032] Based on the mass fraction of the polyolefin resin, the raw materials for preparing the polyolefin-vinyl silicone rubber thermoplastic elastomer of the present invention include 1 to 8 parts of a structure control agent, specifically 1 part, 2 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 6 parts, 7 parts, or 8 parts. As an embodiment of the present invention, the structure control agent may include hydroxyl silicone oil and / or methyltriethoxysilane, specifically hydroxyl silicone oil. The use of hydroxyl silicone oil as a structure control agent in this embodiment of the present invention can reduce the mutual adsorption between vinyl silicone rubber molecules, which is beneficial to improving plasticity and processability.

[0033] This invention provides a method for preparing the polyolefin-vinyl silicone rubber thermoplastic elastomer described in the above technical solution, comprising the following steps:

[0034] Vinyl silicone rubber, inorganic fillers and structure control agents are mixed to obtain a compound material;

[0035] The compounded materials, polyolefin resin, and vulcanizing agent are subjected to a dynamic vulcanization reaction to obtain the polyolefin-vinyl silicone rubber thermoplastic elastomer.

[0036] This invention involves mixing vinyl silicone rubber, inorganic fillers, and structure control agents to obtain a compound material. In this invention, the mixing conditions include: a temperature of 60–170°C, more specifically 100–140°C, and more specifically 100°C, 110°C, 115°C, 120°C, 125°C, 130°C, or 140°C; a time of 1–4 hours, specifically 1 hour, 1.5 hours, 2 hours, 3 hours, or 4 hours; and a rotational speed of 15–50 rpm, specifically 15 rpm, 20 rpm, 30 rpm, 40 rpm, or 50 rpm. In embodiments of this invention, the mixing can be carried out in an internal mixer.

[0037] After obtaining the compounded material, the present invention performs a dynamic vulcanization reaction on the compounded material, polyolefin resin, and vulcanizing agent to obtain the polyolefin-vinyl silicone rubber thermoplastic elastomer. In the present invention, the conditions for the dynamic vulcanization reaction include: a temperature of 160–170°C, specifically 160°C, 163°C, 165°C, 168°C, or 170°C; a time of 1–3 min, specifically 1 min, 1.5 min, 2 min, 2.5 min, or 3 min; and a rotational speed of 100–300 rpm, specifically 120 rpm, 160 rpm, 180 rpm, 200 rpm, 260 rpm, or 300 rpm. In an embodiment of the present invention, the dynamic vulcanization reaction can be carried out in a twin-screw extruder, and the rotational speed of the dynamic vulcanization reaction specifically refers to the screw speed in the twin-screw extruder.

[0038] As one embodiment of the present invention, the dynamic vulcanization reaction is followed by extrusion and granulation in sequence; the present invention does not have any special limitations on the extrusion and granulation, and any process known to those skilled in the art can be used.

[0039] This invention employs dynamic vulcanization technology to prepare polyolefin-vinyl silicone rubber thermoplastic elastomers. Under the shear force and heating of a twin-screw extruder, the vulcanizing agent (such as an organic peroxide) crosslinks with the vinyl silicone rubber and disperses into micron-sized vulcanized rubber particles in the continuous phase of the molten polyolefin resin. The resulting polyolefin-vinyl silicone rubber thermoplastic elastomer exhibits excellent mechanical properties, as well as good weather resistance, chemical resistance, heat resistance, and abrasion resistance, making it widely applicable in electronics, food, and medical fields. Furthermore, this invention utilizes a thermoplastic processing method, which is simple to operate, has low production costs, and allows for repeated processing and reuse.

[0040] This invention provides the application of the polyolefin-vinyl silicone rubber thermoplastic elastomer described in the above-described technical solutions, or the polyolefin-vinyl silicone rubber thermoplastic elastomer prepared by the preparation method described in the above-described technical solutions, in the manufacture of medical devices or electronic product accessories. As one embodiment of this invention, the medical device may specifically include a seal, a catheter, or an artificial joint; the electronic product accessory may specifically include a mobile phone case or an earphone cable. This invention does not specifically limit the application of the polyolefin-vinyl silicone rubber thermoplastic elastomer; any method well known to those skilled in the art can be used.

[0041] The technical solutions of this invention will be clearly and completely described below with reference to the embodiments thereof. Obviously, the described embodiments are only a part of the embodiments of this invention, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.

[0042] Examples 1-6

[0043] Methyl vinyl silicone rubber (vinyl content 0.2%) and filler (fumed silica, specific surface area 180-200 m²) were used. 2 / g, with a particle size of 10-20nm and a SiO2 content of not less than 99.8wt%, and a structure control agent (hydroxyl silicone oil) are added to a mixer and mixed at 120℃ and 40rpm for 1.5h to obtain a compounded vinyl silicone rubber.

[0044] The compounded vinyl silicone rubber, polyolefin resin (SKBX3920, Dow ENGAGE8402 and Dow INFUSE9817) and vulcanizing agent (2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane) were added to a twin-screw extruder and subjected to dynamic vulcanization reaction for 1.5 min at a temperature of 170°C and a screw speed of 180 rpm. After dynamic vulcanization reaction, the mixture was extruded and granulated to obtain polyolefin-vinyl silicone rubber thermoplastic elastomer.

[0045] Comparative Examples 1-3

[0046] Polyolefin-vinyl silicone rubber thermoplastic elastomers were prepared according to the method of Example 1, except that the raw materials used to prepare the polyolefin-vinyl silicone rubber thermoplastic elastomers were different.

[0047] The specific amounts of raw materials used in the preparation of polyolefin-vinyl silicone rubber thermoplastic elastomers in Examples 1-6 and Comparative Examples 1-3 are shown in Table 1. The amounts of each raw material used in Table 1 are expressed in parts by mass.

[0048] Table 1. Raw material amounts used in the preparation of polyolefin-vinyl silicone rubber thermoplastic elastomers in the examples and comparative examples.

[0049]

[0050] Test Example 1

[0051] The polyolefin-vinyl silicone rubber thermoplastic elastomers prepared in the examples and comparative examples were subjected to performance tests. The test results are shown in Table 2. The hardness test method was GB / T6031-2017 (room temperature LS-A rubber Shore A hardness tester); the tensile strength test method was GB / T 1040 (room temperature electronic tensile testing machine with a tensile rate of 500 mm / min); the elongation at break test method was GB / T 1040; the tear strength test method was GB / T529-2008 (room temperature electronic tensile testing machine with a tensile rate of 500 mm / min); and the compression set test method was GB / T 7759.1-2015.

[0052] Table 2. Performance test results of polyolefin-vinyl silicone rubber thermoplastic elastomers in the examples and comparative examples.

[0053]

[0054] Table 2 shows that the polyolefin-vinyl silicone rubber thermoplastic elastomers prepared in Examples 1-6 exhibit excellent overall performance. Specifically, the results of Examples 1-4 indicate that the higher the amount of polyolefin resin added, the higher the tensile strength and elongation at break of the polyolefin-vinyl silicone rubber thermoplastic elastomer. The results of Examples 2 and 5 show that increasing the amount of ENGAGE8402 and decreasing the amount of INFUSE9817 increases the tensile strength and decreases the elongation at break of the polyolefin-vinyl silicone rubber thermoplastic elastomer. The results of Examples 2 and 6 show that increasing the amount of vulcanizing agent increases the tensile strength and decreases the elongation at break of the polyolefin-vinyl silicone rubber thermoplastic elastomer.

[0055] Furthermore, as shown in Table 2, compared with Example 2, in Comparative Example 1, without the addition of a vulcanizing agent, all aspects of the properties of the polyolefin-vinyl silicone rubber thermoplastic elastomer were reduced; in Comparative Example 2, without the addition of INFUSE9817, the tensile strength of the polyolefin-vinyl silicone rubber thermoplastic elastomer increased and the elongation at break decreased; in Comparative Example 3, without the addition of ENGAGE8402, the tensile strength of the polyolefin-vinyl silicone rubber thermoplastic elastomer decreased and the elongation at break increased.

[0056] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1.A polyolefin-vinyl silicone rubber thermoplastic elastomer, prepared from raw materials comprising the following mass fractions: polyolefin resin 210 parts; vinyl silicone rubber 70 parts; vulcanizing agent 1.2 parts; inorganic filler 30 parts; structure control agent 4 parts; wherein the polyolefin resin is polypropylene, ethylene octene copolymer and olefin block copolymer, and the mass ratio of the polypropylene, ethylene octene copolymer and olefin block copolymer is 30:75:105; the polypropylene is BX3920, the ethylene octene copolymer is ENGAGE8402, and the olefin block copolymer is INFUSE9817; the inorganic filler is fumed white carbon black; and the structure control agent is hydroxyl silicone oil. 2.A method for preparing the polyolefin-vinyl silicone rubber thermoplastic elastomer of claim 1, comprising the following steps: mixing the vinyl silicone rubber, inorganic filler and structure control agent to obtain a mixed material; wherein the mixing conditions include a temperature of 60-120℃, a time of 1-1.5h, and a rotation speed of 15-50rpm; and dynamically vulcanizing the mixed material, polyolefin resin and vulcanizing agent to obtain the polyolefin-vinyl silicone rubber thermoplastic elastomer; wherein the dynamic vulcanization conditions include a temperature of 160-170℃, a time of 1.5min, and a rotation speed of 100-300rpm. 3.The method for preparing the polyolefin-vinyl silicone rubber thermoplastic elastomer of claim 1 or 2, comprising the following steps: mixing the vinyl silicone rubber, inorganic filler and structure control agent to obtain a mixed material; wherein the mixing conditions include a temperature of 60-120℃, a time of 1-1.5h, and a rotation speed of 15-50rpm; and dynamically vulcanizing the mixed material, polyolefin resin and vulcanizing agent to obtain the polyolefin-vinyl silicone rubber thermoplastic elastomer; wherein the dynamic vulcanization conditions include a temperature of 160-170℃, a time of 1.5min, and a rotation speed of 100-300rpm. 4.Use of the polyolefin-vinyl silicone rubber thermoplastic elastomer of claim 1 or 2 or the polyolefin-vinyl silicone rubber thermoplastic elastomer prepared by the method of claim 3 in the preparation of medical devices or electronic product accessories. ​ ​ ​ ​ 2. The polyolefin-vinyl silicone rubber thermoplastic elastomer according to claim 1, characterized in that, ​ ​ ​ ​ ​

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