Organosilicone elastomer material and preparation method thereof

Abstract

The invention provides an organic silicon elastomer material, the organic silicon elastomer material comprises grafted VMQ polysiloxane, the grafted VMQ polysiloxane is alpha, omega-divinyl polydimethylvinyl siloxane, methyl thioglycolate is grafted, and the grafting ratio is gt; and (CH2 = CH) (CH3) 2SiO1 / 2 is linked and terminated, and the invention also provides a preparation method of the organic silicon elastomer material. The organic silicon elastomer material has the advantages of low swelling degree, high mechanical property retention rate and the like.

Description

Technical Field

[0001] The present invention belongs to the field of polymer materials, and more specifically, relates to an organic silicon elastomer material and a preparation method thereof. Background Art

[0002] Thermoplastic silicone elastomer (TPSIV material) is a high-performance material that combines the advantages of silicone and thermoplastic materials. TPSIV material is ideal for outdoor applications due to its adjustable color and dirt resistance, as well as excellent UV resistance. In addition, TPSIV material has a simple processing process and supports a variety of secondary processing technologies, which can meet the market's demand for product diversification.

[0003] In terms of physical properties, TPSIV material exhibits excellent high strength and high elasticity, as well as good wear resistance, hydrolysis resistance and excellent chemical resistance. These characteristics make TPSIV material also have advantages in green environmental protection, because it can be recycled and reused, reducing the impact on the environment. The wide application of TPSIV material covers many fields such as consumer electronics, medical, and automobiles. In the field of consumer electronics, TPSIV material can be used to manufacture high-performance components for devices such as smart watches; in the medical field, it is suitable for the production of various medical devices; and in the automotive field, TPSIV material can be used to manufacture various automotive parts. In addition, the unique human aesthetic touch of TPSIV material also makes it an ideal material for daily consumer products such as baby products and sports equipment.

[0004] Although TPSIV materials excel in versatility and high performance, they are limited in oil and solvent resistance. The structural characteristics of TPSIV materials make them less resistant to certain oils and solvents. Long-term contact with these substances may cause the material to swell or degrade in performance, making it unable to meet the use requirements of certain products. Therefore, there is an urgent need to develop a new type of oil-resistant and solvent-resistant thermoplastic silicone elastomer material in the market to overcome this limitation of existing TPSIV materials and meet the needs of a wider range of industrial applications.

[0005] Patent No. 201580060822.1 discloses a thermoplastic silicone elastomer blend and its preparation method. The patent uses thermoplastic polyolefin organic polymer, silicone base material, plasticizer, catalyst, coupling agent, etc. to prepare a thermoplastic silicone elastomer vulcanization composition, which has high mechanical properties, wear resistance, scratch resistance and chemical stability, and is suitable for automotive interiors, medical devices, sports devices, etc. However, the patent does not evaluate its oil resistance, solvent resistance and other properties.

[0006] Patent application number 202210324334.9 discloses an oil-resistant and solvent-resistant rubber composite material, its preparation method and application in cables. In the patent, the present invention controls the chlorine content in the ternary copolymerized chloroether rubber, so that the rubber composite material has oil-resistant and solvent-resistant properties while also having good processing properties. However, the invented material contains halogens, has poor environmental protection, and cannot be used in high-end application fields such as daily cosmetics. At the same time, the invented material is a thermosetting material. Summary of the invention

[0007] In order to solve the above problems, the present invention provides an organic silicone elastomer material and a preparation method thereof, which has the advantages of low swelling degree and high mechanical property retention rate.

[0008] In order to better solve the above problems, the present invention adopts the following technical solutions:

[0009] A silicone elastomer material, the silicone elastomer comprises a grafted VMQ polysiloxane, the grafted VMQ polysiloxane is α,ω-divinyl polydimethylvinylsiloxane, methyl thioglycolate grafted, the grafting rate is>70%, (CH2=CH)(CH3)2SiO 1 / 2 Link capping.

[0010] As a preferred technical solution, the molar mass fraction of (CH3)2SiO linkage in the grafted VMQ polysiloxane is greater than 90%, the molar mass fraction of (CH2=CH)(CH3)SiO linkage is 0.5-10%, and the molar mass fraction of (CH2=CH)(CH3)2SiO 1 / 2 The chain is capped and the degree of polymerization is 2000-10000.

[0011] As a preferred technical solution, the material comprises the following components by weight:

[0012] Grafted VMQ polysiloxane 20-70 parts, VMQ silicone resin 8-20 parts, hydroxy silicone oil 1-10 parts, polyolefin resin 20-50 parts, filler 1-20 parts, vulcanizer 0.1-1 parts, antioxidant 0.1-1 parts.

[0013] As a preferred technical solution, the VMQ silicone resin is a vinyl MQ silicone resin, with an M / Q value of 0.1-0.9, a vinyl mass fraction of 0.1-3.0%, and a solid content of more than 50%.

[0014] As a preferred technical solution, the hydroxy silicone oil is a hydroxyl-terminated methyl vinyl silicone oil, the hydroxyl content of which is greater than 3%, and the vinyl content of which is greater than 3%.

[0015] As a preferred technical solution, the polyolefin resin is polyethylene and ethylene-α-olefin copolymer.

[0016] As a preferred technical solution, the filler is one or more of precipitated silica, fumed silica, diatomaceous earth, calcium carbonate, quartz powder, calcium silicate, zirconium silicate, titanium dioxide, zinc oxide, iron oxide, kaolin or nano clay.

[0017] As a preferred technical solution, the vulcanizing agent is a peroxide vulcanizing agent or a hydrosilylation vulcanizing agent.

[0018] In order to better solve the above technical problems, the present invention also discloses the following technical solutions:

[0019] A method for preparing the silicone elastomer material as described above, comprising the following steps:

[0020] Add VMQ polysiloxane to a glass kettle to fully dissolve it in a solvent; stir the solution for 5-8 hours to prepare a uniform glue solution; add a certain amount of methyl thioglycolate to the glue solution so that the molar ratio of C=C and HS groups reaches 1:1.5; continue stirring for 30-60 minutes; add initiator DMPA to the glass kettle; irradiate the mixture with ultraviolet light for 1-3 hours to complete the grafting reaction; and separate to obtain the grafted VMQ polysiloxane.

[0021] As a preferred technical solution, the preparation method further comprises the following steps:

[0022] The obtained grafted VMQ polysiloxane and VMQ silicone resin, hydroxy silicone oil, polyolefin resin, filler, vulcanizer and antioxidant are kneaded in an internal mixer at 180-220° C. for 8-15 minutes, and the silicone elastomer material is obtained by granulation.

[0023] The beneficial effects of the present invention are as follows: the oil-resistant and solvent-resistant thermoplastic silicone elastomer material provided by the present invention utilizes the click chemistry reaction between a thiol group (-SH) and an olefin group (such as a vinyl group) to carry out functional modification of VMQ polysiloxane, thereby realizing modification of the polysiloxane molecular chain under mild conditions, introducing polar groups into the polysiloxane molecular chain, improving the compatibility of the components in the formula, and giving the prepared thermoplastic silicone elastomer material excellent oil and solvent resistance. DETAILED DESCRIPTION

[0024] In order to make the technical problems, technical solutions and beneficial effects to be solved by the present invention more clearly understood, the present invention is further described in detail below in combination with specific descriptions and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0025] Although TPSIV materials perform well in many aspects, they have certain limitations in oil resistance and solvent resistance. Its structural characteristics lead to weak resistance to some oils and solvents. Long-term contact may cause swelling or performance degradation, and cannot meet the product use requirements. To solve this problem, the present application provides a silicone elastomer material, the silicone elastomer comprises a grafted VMQ polysiloxane, the grafted VMQ polysiloxane is α, ω-divinyl polydimethylvinylsiloxane, methyl thioglycolate grafted, the grafting rate is> 70%, (CH2=CH)(CH3)2SiO 1 / 2 Link capping.

[0026] Specifically, in one embodiment, the molar mass fraction of (CH3)2SiO linkage in the grafted VMQ polysiloxane is greater than 90%, the molar mass fraction of (CH2=CH)(CH3)SiO linkage is 0.5-10%, and the molar mass fraction of (CH2=CH)(CH3)2SiO 1 / 2 Linked end-capping, degree of polymerization is 2000-10000, and grafting rate is >70%.

[0027] In one embodiment, the material comprises the following components by weight:

[0028] Grafted VMQ polysiloxane 20-70 parts, VMQ silicone resin 8-20 parts, hydroxy silicone oil 1-10 parts, polyolefin resin 20-50 parts, filler 1-20 parts, vulcanizer 0.1-1 parts, antioxidant 0.1-1 parts.

[0029] In one embodiment, the VMQ silicone resin is a vinyl MQ silicone resin, with an M / Q value of 0.1-0.9, a vinyl mass fraction of 0.1-3.0%, and a solid content of >50%.

[0030] In one embodiment, the hydroxy silicone oil is a hydroxyl-terminated methyl vinyl silicone oil, wherein the hydroxyl content thereof is greater than 3%, and the vinyl content thereof is greater than 3%.

[0031] In one embodiment, the polyolefin resin is polyethylene and ethylene-α-olefin copolymer. For example, the polyolefin resin can be one or more of ethylene-vinyl acetate copolymer, ethylene-acrylic acid or acrylic acid ester copolymer, polypropylene and propylene-α-olefin copolymer, poly-1-butene, poly-4-methyl-1-pentene, and cycloolefin polymer.

[0032] In one embodiment, the filler is one or more of precipitated silica, fumed silica, diatomaceous earth, calcium carbonate, quartz powder, calcium silicate, zirconium silicate, titanium dioxide, zinc oxide, iron oxide, kaolin or nano clay. For example, the filler is spherical precipitated silica, and its sphericity is greater than 96%.

[0033] In one embodiment, the vulcanizing agent is a peroxide vulcanizing agent or a hydrosilylation vulcanizing agent.

[0034] In one embodiment, the antioxidant is one or more of a phenolic antioxidant, a phosphorus antioxidant, a sulfur antioxidant, and a polymeric phenolic antioxidant.

[0035] In order to better solve the above technical problems, the present invention also discloses the following technical solutions:

[0036] A method for preparing the silicone elastomer material as described above, comprising the following steps:

[0037] Add VMQ polysiloxane to a glass kettle to fully dissolve it in a solvent; stir the solution for 5-8 hours to prepare a uniform glue solution; add a certain amount of methyl thioglycolate to the glue solution so that the molar ratio of C=C and HS groups reaches 1:1.5; continue stirring for 30-60 minutes; add initiator DMPA to the glass kettle; irradiate the mixture with ultraviolet light for 1-3 hours to complete the grafting reaction; and separate to obtain the grafted VMQ polysiloxane.

[0038] As a preferred technical solution, the preparation method further comprises the following steps:

[0039] The obtained grafted VMQ polysiloxane and VMQ silicone resin, hydroxy silicone oil, polyolefin resin, filler, vulcanizer and antioxidant are kneaded in an internal mixer at 180-220° C. for 8-15 minutes, and the silicone elastomer material is obtained by granulation.

[0040] In one embodiment, a method for preparing an organosilicon elastomer material comprises the following steps:

[0041] (1) Preparation of grafted VMQ polysiloxane: VMQ polysiloxane was added to a 500 L glass kettle and fully dissolved in THF, stirred for 5 h to prepare a uniform glue solution, and then a certain amount of methyl thioglycolate was added to make the molar ratio of C=C and HS groups 1:1.5; after stirring for another 30 minutes, the initiator DMPA was added, and ultraviolet light was irradiated for 1 h. After the grafting reaction was completed, the glue solution was precipitated with ethanol solution and then dried to obtain the grafted VMQ polysiloxane.

[0042] (2) The grafted VMQ polysiloxane in step 1 is kneaded with other components in an internal mixer at 180° C. for 8 min, and granulated by a single screw extruder at a granulation temperature of 170-180° C. to obtain an oil-resistant and solvent-resistant thermoplastic silicone elastomer material.

[0043] The technical solution of the present application is further described below in conjunction with the embodiments:

[0044] Unless otherwise specified, the raw materials in the following examples and comparative examples were purchased from commercial sources.

[0045] Preparation of grafted VMQ polysiloxane:

[0046] Grafted VMQ polysiloxane A: Add 100 parts of VMQ polysiloxane a (α, ω-divinyl polydimethylvinylsiloxane, wherein the molar mass fraction of (CH3)2SiO linkage is greater than 90%, the molar mass fraction of (CH2=CH)(CH3)SiO linkage is 3.2%, (CH2=CH)(CH3)2SiO1 / 2 linkage is end-capped, and the degree of polymerization is 3500) into a 500L glass kettle, fully dissolve it in THF, stir for 5 hours to form a uniform glue solution, and then add a certain amount of methyl thioglycolate to make the molar ratio of C=C and HS group be 1:1.5; after stirring for another 30 minutes, add initiator DMPA, irradiate with ultraviolet light for 1 hour, and after the grafting reaction is completed, precipitate the glue solution with ethanol solution and dry it to obtain a grafted VMQ polysiloxane with a grafting rate of 85%.

[0047] Grafted VMQ polysiloxane B: Add 100 parts of VMQ polysiloxane b (α, ω-divinyl polydimethylvinylsiloxane, wherein the molar mass fraction of (CH3)2SiO linkage is greater than 90%, the molar mass fraction of (CH2=CH)(CH3)SiO linkage is 6.0%, (CH2=CH)(CH3)2SiO1 / 2 linkage is end-capped, and the degree of polymerization is 5000) into a 500L glass kettle, fully dissolve it in THF, stir for 5 hours to form a uniform glue solution, and then add a certain amount of methyl thioglycolate to make the molar ratio of C=C and HS group be 1:1.5; after stirring for another 30 minutes, add initiator DMPA, irradiate with ultraviolet light for 1 hour, and after the grafting reaction is completed, precipitate the glue solution with ethanol solution and dry it to obtain a grafted VMQ polysiloxane with a grafting rate of 85%.

[0048] Grafted VMQ polysiloxane C: Add 100 parts of VMQ polysiloxane c (α, ω-divinyl polydimethylvinylsiloxane, wherein the molar mass fraction of (CH3)2SiO linkage is greater than 90%, the molar mass fraction of (CH2=CH)(CH3)SiO linkage is 8.5%, (CH2=CH)(CH3)2SiO1 / 2 linkage is end-capped, and the degree of polymerization is 5000) into a 500L glass kettle, fully dissolve it in THF, stir for 5 hours to form a uniform glue solution, and then add a certain amount of methyl thioglycolate to make the molar ratio of C=C and HS group be 1:1.5; after stirring for another 30 minutes, add initiator DMPA, irradiate with ultraviolet light for 1 hour, and after the grafting reaction is completed, precipitate the glue solution with ethanol solution and dry it to obtain a grafted VMQ polysiloxane with a grafting rate of 85%.

[0049] Grafted VMQ polysiloxane D: Add 100 parts of VMQ polysiloxane b (α, ω-divinyl polydimethylvinylsiloxane, wherein the molar mass fraction of (CH3)2SiO linkage is greater than 90%, the molar mass fraction of (CH2=CH)(CH3)SiO linkage is 6.0%, (CH2=CH)(CH3)2SiO1 / 2 linkage is end-capped, and the degree of polymerization is 5000) into a 500L glass kettle, fully dissolve it in THF, stir for 5 hours to form a uniform glue solution, and then add a certain amount of methyl thioglycolate to make the molar ratio of C=C and HS group be 1:1.5; after stirring for another 30 minutes, add initiator DMPA, irradiate with ultraviolet light for 1 hour, and after the grafting reaction is completed, precipitate the glue solution with ethanol solution and dry it to obtain a grafted VMQ polysiloxane with a grafting rate of 91%.

[0050] The preparation methods of the materials in Examples 1-5 and Comparative Example 1 are as follows:

[0051] The grafted VMQ polysiloxane was kneaded with other components in a 180°C internal mixer for 8 minutes according to the formula components, and granulated by a single screw at a granulation temperature of 170-180°C to obtain an oil-resistant and solvent-resistant thermoplastic silicone elastomer material.

[0052] Table 1

[0053]

[0054]

[0055] The performance of the material obtained above was tested, and the test results are shown in Table 2.

[0056] Table 2

[0057]

[0058] It can be found from the examples and comparative examples that Examples 1 to 5 have excellent oil and solvent resistance.

[0059] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A silicone elastomer material, characterized in that: The organic silicone elastomer comprises a grafted VMQ polysiloxane, wherein the grafted VMQ polysiloxane is α,ω-divinyl polydimethylvinylsiloxane, grafted with methyl thioglycolate, with a grafting rate of >70%, (CH2=CH)(CH3)2SiO 1 / 2 Link capping.

2. The organic silicon elastomer material according to claim 1, characterized in that: The molar mass fraction of (CH3)2SiO linkage in the grafted VMQ polysiloxane is greater than 90%, the molar mass fraction of (CH2=CH)(CH3)SiO linkage is 0.5-10%, and the molar mass fraction of (CH2=CH)(CH3)2SiO 1 / 2 The chain is capped and the degree of polymerization is 2000-10000.

3. The organic silicon elastomer material according to claim 1, characterized in that: The materials include the following components by weight: Grafted VMQ polysiloxane 20-70 parts, VMQ silicone resin 8-20 parts, hydroxy silicone oil 1-10 parts, polyolefin resin 20-50 parts, filler 1-20 parts, vulcanizer 0.1-1 parts, antioxidant 0.1-1 parts.

4. The organic silicon elastomer material according to claim 3, characterized in that: The VMQ organic silicone resin is a vinyl MQ silicone resin, with an M / Q value of 0.1-0.9, a vinyl mass fraction of 0.1-3.0%, and a solid content of more than 50%.

5. The organic silicon elastomer material according to claim 3, characterized in that: The hydroxy silicone oil is a hydroxyl-terminated methyl vinyl silicone oil, the hydroxyl content of which is greater than 3%, and the vinyl content of which is greater than 3%.

6. The organic silicon elastomer material according to claim 3, characterized in that: The polyolefin resin is polyethylene and ethylene-α-olefin copolymer.

7. The organic silicon elastomer material according to claim 3, characterized in that: The filler is one or more of precipitated silica, fumed silica, diatomaceous earth, calcium carbonate, quartz powder, calcium silicate, zirconium silicate, titanium dioxide, zinc oxide, iron oxide, kaolin or nano clay.

8. The organic silicon elastomer material according to claim 3, characterized in that: The vulcanizing agent is a peroxide vulcanizing agent or a hydrosilylation vulcanizing agent.

9. A method for preparing the organic silicon elastomer material according to any one of claims 1 to 8, characterized in that: The following steps are involved: Add VMQ polysiloxane to a glass kettle to fully dissolve it in a solvent; stir the solution for 5-8 hours to prepare a uniform glue solution; add a certain amount of methyl thioglycolate to the glue solution so that the molar ratio of C=C and HS groups reaches 1:1.5; continue stirring for 30-60 minutes; add initiator DMPA to the glass kettle; irradiate the mixture with ultraviolet light for 1-3 hours to complete the grafting reaction; and separate to obtain the grafted VMQ polysiloxane.

10. The method for preparing an organosilicon elastomer material according to claim 9, characterized in that: The following steps are also included: The obtained grafted VMQ polysiloxane and VMQ silicone resin, hydroxy silicone oil, polyolefin resin, filler, vulcanizer and antioxidant are kneaded in an internal mixer at 180-220° C. for 8-15 minutes, and the silicone elastomer material is obtained by granulation.

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