Polyolefin-vinyl silicone rubber thermoplastic elastomer as well as preparation method and application thereof

Abstract

The invention provides a polyolefin-vinyl silicone rubber thermoplastic elastomer as well as a preparation method and application thereof, and belongs to the technical field of functional materials. The polyolefin-vinyl silicone rubber thermoplastic elastomer provided by the invention is prepared from the following preparation raw materials in parts by mass: 100-400 parts of polyolefin resin; 20 to 80 parts of vinyl silicone rubber; 0.1 to 5 parts of vulcanizing agent; 5-50 parts of an inorganic filler; 1-8 parts of a structure control agent; the polyolefin resin is polypropylene, an ethylene-octylene copolymer and an olefin block copolymer. Polyolefin resin and vinyl silicone rubber are adopted as base materials, the polyolefin resin is polypropylene, an ethylene-octene copolymer and an olefin block copolymer which are compounded for use, and under the action of a vulcanizing agent, an inorganic filler and a structure control agent, the mechanical property of the composite material is improved, and the mechanical property of the composite material is improved. The polyolefin-vinyl silicone rubber thermoplastic elastomer has the advantages of excellent comprehensive mechanical properties, high tensile strength and high elongation at break.

Description

Technical Field

[0001] The invention relates to the technical field of functional materials, and in particular to a polyolefin-vinyl silicone rubber thermoplastic elastomer and a preparation method and application thereof. Background Art

[0002] Silicone rubber has excellent high and low temperature resistance and aging resistance, but its mechanical properties and oil resistance are poor. Polypropylene has high crystallinity, 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 composite materials are prepared by using polypropylene and silicone rubber to complement the properties of the two. For example, the thermoplastic elastomer composite material has 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 the present invention is to provide a polyolefin-vinyl silicone rubber thermoplastic elastomer and a preparation method and application thereof. The polyolefin-vinyl silicone rubber thermoplastic elastomer provided by the present invention has excellent comprehensive mechanical properties, and has high tensile strength and elongation at break.

[0005] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0006] The present invention provides a polyolefin-vinyl silicone rubber thermoplastic elastomer, which is prepared from the following raw materials in parts by weight:

[0007] 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; 1-8 parts of structure control agent;

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

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

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

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

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

[0013] Preferably, the vulcanizing agent is an organic peroxide; and 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; and the inorganic filler includes one or more of white carbon black, calcium carbonate and talc.

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

[0016] The vinyl silicone rubber, the inorganic filler and the structure control agent are mixed to obtain a mixed material;

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

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

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

[0020] The present invention provides the use 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] The present invention provides a polyolefin-vinyl silicone rubber thermoplastic elastomer, which is prepared from the following raw materials in parts by mass: 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; 1-8 parts of structure control agent; the polyolefin resin is polypropylene, ethylene octene copolymer and olefin block copolymer. The present invention adopts polyolefin resin and vinyl silicone rubber as matrix materials, wherein the polyolefin resin is polypropylene, ethylene octene copolymer and olefin block copolymer, and the three are used in combination. Under the action of vulcanizing agent, inorganic filler and structure control agent, the polyolefin-vinyl silicone rubber thermoplastic elastomer has excellent comprehensive mechanical properties, and has high tensile strength and elongation at break. DETAILED DESCRIPTION

[0022] The present invention provides a polyolefin-vinyl silicone rubber thermoplastic elastomer, which is prepared from the following raw materials in parts by weight:

[0023] 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; 1-8 parts of structure control agent;

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

[0025] The present invention adopts polyolefin resin and vinyl silicone rubber as matrix materials, wherein the polyolefin resin is polypropylene, ethylene octene copolymer and olefin block copolymer, wherein polypropylene has high crystallinity, regular structure, excellent mechanical properties, good chemical stability and electrical insulation properties; ethylene octene copolymer has excellent mechanical properties (such as strength, toughness, elasticity and wear resistance), and has good chemical stability, and can resist the erosion of various chemical substances and environmental factors such as acid, alkali, oxidant, ultraviolet light; olefin block copolymer has high thermal stability, and can resist the influence of environmental factors such as high temperature, oxidation, ultraviolet light; the three are used in combination, under the action of vulcanizing agent, inorganic filler and structure control agent, the polyolefin-vinyl silicone rubber thermoplastic elastomer has excellent comprehensive mechanical properties, tensile strength and elongation at break are high. The polyolefin-vinyl silicone rubber thermoplastic elastomer of the present invention is described in detail below.

[0026] In the present invention, unless otherwise specified, the raw materials used are commercially available products well known to those skilled in the art.

[0027] In terms of mass fractions, the raw materials for preparing the polyolefin-vinyl silicone rubber thermoplastic elastomer of the present invention include 100 to 400 parts of polyolefin resin, and further can be 110 to 250 parts, and specifically can be 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 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 to 90:30 to 105, and specifically can be 30:30:60, 30:30:90, 30:60:90, 30:75:105 or 30:90:30. In the embodiment of the present invention, the polypropylene is purchased from SK General Chemical Co., Ltd. of South Korea, model BX3920; the ethylene octene copolymer is purchased from The Dow Chemical Company of the United States, model ENGAGE8402; the olefin block copolymer is purchased from The Dow Chemical Company of the United States, model INFUSE9817.

[0028] The present invention adopts polypropylene, ethylene octene copolymer and olefin block copolymer for compound use, and controls the total amount thereof within the above range, which can enhance the mechanical properties of the product, such as tensile strength and elongation at break; in the embodiment of the present invention, the mass ratio of polypropylene, ethylene octene copolymer and olefin block copolymer is controlled within the above range, which can improve the processing performance, is conducive to maintaining good toughness and elongation, and reduces the apparent viscosity of the melt during processing.

[0029] Based on the mass fraction of the polyolefin resin, the raw material for preparing the polyolefin-vinyl silicone rubber thermoplastic elastomer of the present invention includes 20 to 80 parts of vinyl silicone rubber, specifically 20 parts, 30 parts, 40 parts, 50 parts, 60 parts, 65 parts, 70 parts, 75 parts 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 above-mentioned types of vinyl silicone rubber used in the embodiments of the present invention can maintain good elasticity and weather resistance, which is conducive to improving the overall weather resistance and service life of the product.

[0030] Based on the mass fraction of the polyolefin resin, the raw material for preparing the polyolefin-vinyl silicone rubber thermoplastic elastomer of the present invention includes 0.1 to 5 parts of a vulcanizing agent, specifically 0.1 parts, 0.5 parts, 0.8 parts, 1 parts, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, 2 parts, 2.2 parts, 2.4 parts, 2.6 parts, 2.8 parts, 3 parts, 4 parts or 5 parts. As an embodiment of the present invention, the vulcanizing agent may be an organic peroxide, and the organic peroxide 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 the embodiment of the present invention, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane is used as a vulcanizing agent and its amount is controlled within the above range, which can significantly improve the tensile strength and hardness of the product while reducing its elongation and compression deformation, which is conducive to making the product have 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 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts or 50 parts. As an embodiment of the present invention, the filler may be an inorganic filler; the inorganic filler may include one or more of white carbon black, calcium carbonate and talcum powder, specifically white carbon black; the white carbon black may include precipitated white carbon black and / or fumed white carbon black, specifically fumed white carbon black. As an embodiment of the present invention, the index parameters of the fumed white carbon black include: specific surface area of ​​180 to 200 m 2 / g; particle size is 10-20nm; SiO2 content is not less than 99.8wt%. In the embodiment of the present invention, fumed silica is used as 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 material for preparing the polyolefin-vinyl silicone rubber thermoplastic elastomer of the present invention includes 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 hydroxy silicone oil and / or methyltriethoxysilane, specifically hydroxy silicone oil. In the embodiment of the present invention, hydroxy silicone oil is used as a structure control agent, which can reduce the mutual adsorption between vinyl silicone rubber molecules, which is beneficial to improve plasticity and processability.

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

[0034] The vinyl silicone rubber, the inorganic filler and the structure control agent are mixed to obtain a mixed material;

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

[0036] The present invention mixes vinyl silicone rubber, inorganic filler and structure control agent to obtain a mixed material. In the present invention, the mixing conditions include: the temperature can be 60-170°C, further can be 100-140°C, specifically can be 100°C, 110°C, 115°C, 120°C, 125°C, 130°C or 140°C; the time can be 1-4h, specifically can be 1h, 1.5h, 2h, 3h or 4h; the speed can be 15-50rpm, specifically can be 15rpm, 20rpm, 30rpm, 40rpm or 50rpm. In an embodiment of the present invention, the mixing can be specifically carried out in an internal mixer.

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

[0038] As an embodiment of the present invention, the dynamic vulcanization reaction further includes sequentially performing extrusion and granulation. The present invention has no special limitation on the extrusion and granulation, and processes well known to those skilled in the art may be used.

[0039] In the embodiment of the present invention, the dynamic vulcanization technology is used to prepare the polyolefin-vinyl silicone rubber thermoplastic elastomer. Under the shear force and heating of the twin-screw extruder, the vulcanizer (such as organic peroxide) and the vinyl silicone rubber are cross-linked and dispersed into micron-sized vulcanized rubber particles in the molten polyolefin resin continuous phase. The obtained polyolefin-vinyl silicone rubber thermoplastic elastomer has excellent mechanical properties and good weather resistance, chemical resistance, heat resistance and friction resistance, and can be widely used in electronic appliances, food, medical and other fields. In addition, the present invention adopts a thermoplastic plastic processing method, which is simple to operate, has low production cost, and can be repeatedly processed and utilized.

[0040] The present invention provides the use 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. As an embodiment of the present invention, the medical device may specifically include a seal, a catheter or an artificial joint; the electronic product accessories may specifically include a mobile phone case or an earphone cable. The present invention does not specifically limit the application method of the polyolefin-vinyl silicone rubber thermoplastic elastomer, and the method familiar to those skilled in the art can be used.

[0041] The technical solutions in the present invention will be described clearly and completely below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0042] Examples 1 to 6

[0043] Methyl vinyl silicone rubber (vinyl molar content of 0.2%), filler (fumed silica, specific surface area of ​​180-200m 2 / g, a particle size of 10 to 20 nm, and an SiO2 content of not less than 99.8 wt %) and a structure control agent (hydroxy silicone oil) are added into an internal mixer, and the mixture is mixed at a temperature of 120° C. and a rotation speed of 40 rpm for 1.5 h to obtain a mixed vinyl silicone rubber;

[0044] The mixed vinyl silicone rubber, polyolefin resin (SKBX3920, Dow ENGAGE8402 and Dow INFUSE9817) and vulcanizing agent (2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane) are added to a twin-screw extruder, and a dynamic vulcanization reaction is carried out for 1.5 minutes at a temperature of 170° C. and a screw speed of 180 rpm; after the dynamic vulcanization reaction, the mixture is extruded and granulated to obtain a polyolefin-vinyl silicone rubber thermoplastic elastomer.

[0045] Comparative Examples 1 to 3

[0046] A polyolefin-vinyl silicone rubber thermoplastic elastomer was prepared by referring to the method of Example 1, except that the raw materials for preparing the polyolefin-vinyl silicone rubber thermoplastic elastomer were different.

[0047] The amounts of raw materials used in preparing the polyolefin-vinyl silicone rubber thermoplastic elastomer in Examples 1 to 6 and Comparative Examples 1 to 3 are specifically shown in Table 1, where the amounts of each raw material used in Table 1 are in parts by mass.

[0048] Table 1 Amount of raw materials used in the preparation of polyolefin-vinyl silicone rubber thermoplastic elastomer in the examples and comparative examples

[0049]

[0050] Test Example 1

[0051] The polyolefin-vinyl silicone rubber thermoplastic elastomer prepared in the embodiment and the comparative example was subjected to performance tests, and the test results are shown in Table 2, wherein the hardness test method is GB / T6031-2017 (room temperature LS-A rubber Shore A hardness meter); the tensile strength test method is GB / T 1040 (room temperature electronic tensile testing machine tensile rate is 500 mm / min); the elongation at break test method is GB / T 1040; the tear strength test method is GB / T529-2008 (room temperature electronic tensile testing machine tensile rate is 500 mm / min); and the compression permanent deformation test method is GB / T 7759.1-2015.

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

[0053]

[0054] As can be seen from Table 2, the polyolefin-vinyl silicone rubber thermoplastic elastomers prepared in Examples 1 to 6 have excellent comprehensive properties. The results of Examples 1 to 4 show that the greater 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 as the amount of ENGAGE8402 added increases and the amount of INFUSE9817 added decreases, the tensile strength of the polyolefin-vinyl silicone rubber thermoplastic elastomer increases and the elongation at break decreases. The results of Examples 2 and 6 show that as the amount of vulcanizing agent used increases, the tensile strength of the polyolefin-vinyl silicone rubber thermoplastic elastomer increases and the elongation decreases.

[0055] In addition, it can be seen from Table 2 that, compared with Example 2, in Comparative Example 1, no vulcanizer was added, and various properties of the polyolefin-vinyl silicone rubber thermoplastic elastomer were reduced; in Comparative Example 2, no INFUSE9817 was added, and the tensile strength of the polyolefin-vinyl silicone rubber thermoplastic elastomer was increased, and the elongation at break was decreased; in Comparative Example 3, no ENGAGE8402 was added, and the tensile strength of the polyolefin-vinyl silicone rubber thermoplastic elastomer was decreased, and the elongation at break was increased.

[0056] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A polyolefin-vinyl silicone rubber thermoplastic elastomer 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; 1-8 parts of structure control agent; The polyolefin resin is polypropylene, ethylene octene copolymer and olefin block copolymer.

2. The polyolefin-vinyl silicone rubber thermoplastic elastomer according to claim 1, characterized in that: The mass ratio of the polypropylene, ethylene octene copolymer and olefin block copolymer is 30:30-90:30-105.

3. The polyolefin-vinyl silicone rubber thermoplastic elastomer according to claim 1 or 2, characterized in that: The model of the polypropylene is BX3920, the model of the ethylene octene copolymer is ENGAGE8402, and the model of the olefin block copolymer is INFUSE9817.

4. The polyolefin-vinyl silicone rubber thermoplastic elastomer according to claim 1, characterized in that: The vinyl silicone rubber includes methyl vinyl silicone rubber and / or methyl phenyl vinyl silicone rubber; the vinyl molar content of the vinyl silicone rubber is 0.04-1%.

5. The polyolefin-vinyl silicone rubber thermoplastic elastomer according to claim 1, characterized in that: The structure control agent includes hydroxy silicone oil and / or methyltriethoxysilane.

6. The polyolefin-vinyl silicone rubber thermoplastic elastomer according to claim 1, characterized in that: The vulcanizing agent is an organic peroxide; and the filler is an inorganic filler.

7. The polyolefin-vinyl silicone rubber thermoplastic elastomer according to claim 6, characterized in that: 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 white carbon black, calcium carbonate and talc.

8. The method for preparing the polyolefin-vinyl silicone rubber thermoplastic elastomer according to any one of claims 1 to 7, comprising the following steps: The vinyl silicone rubber, the inorganic filler and the structure control agent are mixed to obtain a mixed material; The mixed material, polyolefin resin and vulcanizing agent are subjected to dynamic vulcanization reaction to obtain the polyolefin-vinyl silicone rubber thermoplastic elastomer.

9. The preparation method according to claim 8, characterized in that: The mixing conditions include: temperature of 60-170°C, time of 1-4h, and rotation speed of 15-50rpm; The conditions of the dynamic vulcanization reaction include: temperature of 160-170° C., time of 1-3 min, and rotation speed of 100-300 rpm.

10. Use of the polyolefin-vinyl silicone rubber thermoplastic elastomer according to any one of claims 1 to 7 or the polyolefin-vinyl silicone rubber thermoplastic elastomer prepared by the preparation method according to claim 8 or 9 in the preparation of medical devices or electronic product accessories.

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