Elastomeric putty and preparation method and applications thereof

Abstract

This invention relates to an elastic putty, its preparation method, and its application. The elastic putty comprises the following components by weight: 60-80 parts of methylvinylsiloxane, 15-25 parts of phenylsiloxane, 2-8 parts of reinforcing agent, and 5-15 parts of antioxidant. The elastic putty provided by this invention overcomes the problems of abnormally high viscosity and decreased fluidity during use of traditional putties, and improves the damping durability of the putty through formulation design.

Description

1. Description of an Elastic Putty, its Preparation Method, and Application Technical Field This invention relates to the field of putty technology, and more particularly to an elastic putty, its preparation method, and its application. Background Art Elastic putty, as a high-quality medium for dampers and buffers, possesses excellent elasticity and damping characteristics. However, during use, it has been found that ordinary putty exhibits a problem of increased viscosity, failing to meet the high durability requirements of dampers. CN104830070A discloses a sealing putty and its processing method, which includes the following raw material components and proportions: 100 parts of polysiloxane, 26-40 parts of filler one, 35-62 parts of filler two, 96-138 parts of filler three, 0.85-1.2 parts of filler four, 2.8-6.5 parts of additive one, and 0.45-1.3 parts of additive two. Among them, filler one is a carbon black reinforcing agent, filler two is an oxide filler reinforcing agent, filler three is a hydroxide flame retardant, filler four is a stearate internal release agent, additive one is a liquid additive, and additive two is a solid additive. The sealing putty prepared by this invention has good waterproofness, flexibility, plasticity, and thermal conductivity, but it does not mention how to maintain the appropriate viscosity and fluidity of the putty. CN109554158A discloses a putty, its preparation method, and its application. The putty comprises the following components by weight: 80-120 parts phenylsiloxane, 1-10 parts reinforcing agent, 10-20 parts rare earth tungstate, 5-15 parts rare earth molybdate, 20-30 parts boron-containing glass microspheres, and 1-10 parts viscosity modifier, wherein the boron content in the boron-containing glass microspheres is 60-80%. The prepared putty exhibits good damping performance and can reduce the volume expansion coefficient and internal pressure of the putty. However, it does not address how to maintain suitable viscosity and flowability of the putty in damper applications. Therefore, it is necessary to provide an elastic putty with suitable viscosity and flowability to improve damping durability. To solve the above technical problems, this invention provides an elastic putty, its preparation method, and its application. The elastic putty provided by this invention overcomes the problems of abnormal viscosity increase and decreased flowability during use of traditional putties, and improves the damping durability of the putty through formulation design. To achieve this objective, the present invention adopts the following technical solution: In a first aspect, the present invention provides an elastic putty, wherein the elastic putty comprises the following components by mass parts: 60-80 parts of methyl vinyl siloxane HK 20138789 A 15-25 parts of 2-phenyl siloxane, 2-8 parts of reinforcing agent, and 5-15 parts of antioxidant.In this invention, the methyl vinyl siloxane can be, for example, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, etc.; the phenyl siloxane can be, for example, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, etc.; the reinforcing agent can be, for example, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, etc.; and the antioxidant can be, for example, 5 parts, 8 parts, 10 parts, 12 parts, 15 parts, etc. In this invention, methyl vinyl siloxane is used as the base material. The introduction of phenyl siloxane improves high-temperature stability (temperature resistance up to 250℃) and reduces heat-induced crosslinking; the addition of antioxidants inhibits crosslinking caused by thermo-oxidative aging; and the addition of reinforcing agents, with the components working together, results in an elastic putty that maintains suitable viscosity (ensuring damping force) and fluidity (avoiding curing failure), exhibiting high damping durability. Preferably, the methyl group in the methyl vinyl siloxane has a mass content greater than 95% (e.g., 95.5%, 96%, 96.5%, 97%, 97.5%, etc.), and the vinyl group has a mass content of 0.1-1% (e.g., 0.1%, 0.2%, 0.5%, 0.8%, 1%, etc.). Preferably, the phenyl group in the phenyl siloxane has a mass content of 7-15% (e.g., 7%, 8%, 10%, 12%, 14%, 15%, etc.). Preferably, the reinforcing agent includes any one or a combination of at least two of silica, calcium carbonate, or cerium oxide. Preferably, the reinforcing agent includes a combination of silica and cerium oxide. Preferably, the mass ratio of silica to cerium oxide is 1:(0.2-0.8) (e.g., 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, etc.). In this invention, when the reinforcing agent is a combination of silica and cerium oxide, the two have a synergistic effect, which can jointly improve the damping durability of the elastic putty. Preferably, the antioxidant includes hindered phenolic antioxidants and / or amine antioxidants. Preferably, the hindered phenolic antioxidant includes any one or a combination of at least two of tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] pentaerythritol (antioxidant 1010), octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (antioxidant 1076), or butylated hydroxyanisole. Preferably, the amine antioxidant includes any one or a combination of at least two of bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate (hindered amine 770), N-phenyl-1-naphthylamine (antioxidant A), or N-isopropyl-N'-phenyl-p-phenylenediamine (antioxidant 4010NA). Preferably, the antioxidant comprises a combination of hindered phenolic antioxidants and amine antioxidants.Preferably, the mass ratio of the hindered phenolic antioxidant to the amine antioxidant is 1:(0.8-1.2) (e.g., HK 20138789 A 3, such as 1:0.8, 1:0.9, 1:1, 1:1.1, 1:1.2, etc.). In this invention, the damping durability of the elastic putty is better when hindered phenolic antioxidants and amine antioxidants are used simultaneously. Preferably, the elastic putty further includes 5-15 parts by mass of a viscosity modifier (e.g., 5 parts, 8 parts, 10 parts, 12 parts, 15 parts, etc.). Preferably, the viscosity modifier includes methyl silicone oil. Preferably, the viscosity of the methyl silicone oil is 50-100 cst (e.g., 50 cst, 60 cst, 70 cst, 80 cst, 90 cst, 100 cst, etc.). Preferably, the elastic putty further comprises 2-8 parts by weight of plasticizer (e.g., 2, 3, 4, 5, 6, 7, 8, etc.). Preferably, the plasticizer comprises aromatic hydrocarbon oil. Aromatic hydrocarbon oil, also known as aromatic hydrocarbon or aromatic hydrocarbon, refers to hydrocarbons containing a benzene ring structure in their molecules. It is one of the basic products and raw materials of petrochemicals, mainly including benzene, toluene, xylene, ethylbenzene, etc. Adding aromatic hydrocarbon oil can improve the plasticity of the putty and reduce its viscosity. In this invention, adding viscosity modifier and plasticizer can dilute the system and delay the increase in viscosity. The effect is better when both are used simultaneously. In a second aspect, this invention provides a method for preparing the elastic putty according to the first aspect, the method comprising: mixing the components of the elastic putty to obtain the elastic putty. Preferably, the mixing temperature is 90-120℃ (e.g., 90℃, 100℃, 110℃, 120℃, etc.), and the time is 1-5h (e.g., 1h, 2h, 3h, 4h, 5h, etc.). In a third aspect, the present invention provides an application of the elastic putty described in the first aspect in a damper or buffer. Compared with the prior art, the present invention has at least the following beneficial effects: The components in the elastic putty formulation provided by the present invention have a synergistic effect, wherein phenylsiloxane can improve high-temperature stability and reduce thermally induced crosslinking, and the antioxidant inhibits crosslinking caused by thermo-oxidative aging. The resulting elastic putty can maintain suitable viscosity (ensuring damping force) and fluidity (avoiding curing failure), and has high damping durability. Specific embodiments are provided below for ease of understanding of the present invention. Those skilled in the art should understand that the embodiments are merely helpful in understanding the present invention and should not be considered as specific limitations of the present invention.The materials used in the following examples are sourced from the following sources: Methyl vinyl siloxane has a methyl content of 96% and a vinyl content of 0.1% by mass; HK 20138789 A 4, grade CAS67762-96-0.1, manufactured by Zibo Hangyu Biotechnology Co., Ltd.; Phenyl siloxane has a phenyl content of 12%; grade DB-255-12, manufactured by Dongguan Dibo Silicone Factory (customized); Methyl silicone oil has a viscosity of 50 cst; grade 201-50, manufactured by Shenzhen Jipeng Silicon Fluorine Materials Co., Ltd.; Aromatic hydrocarbon oil has a grade DG-40#-1, manufactured by Guangdong Dongheng Petrochemical Co., Ltd.; Silica is manufactured by Shandong Xinxing Silica Co., Ltd.; Cerium oxide has a particle size of 50 nm, manufactured by Ningbo Yutian Materials Technology Co., Ltd.; Antioxidant 1010 is pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]; Antioxidant 1076 The product is β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate octadecyl ester; hindered amine 770 is bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacic acid ester; antioxidant A is N-phenyl-1-naphthylamine. Example 1 This example provides an elastic putty, which comprises the following components by mass parts: 70 parts methyl vinylsiloxane, 20 parts phenylsiloxane, 10 parts methyl silicone oil, 5 parts aromatic hydrocarbon oil, 2 parts silica, 1 part cerium oxide, 5 parts antioxidant 1010, and 5 parts hindered amine 770; The preparation method of the elastic putty includes: mixing and stirring each component at 110°C for 3 hours to obtain the product. Example 2 This example provides an elastic putty, which comprises the following components by weight: 60 parts methyl vinyl siloxane, 25 parts phenyl siloxane, 6 parts methyl silicone oil, 8 parts aromatic hydrocarbon oil, 6 parts silica, 0.2 parts cerium oxide, 3 parts antioxidant 1076, 5 parts HK 20138789 A, and 2.5 parts anti-aging agent A. The preparation method of the elastic putty includes mixing and stirring the components at 90°C for 5 hours. Example 3 This example provides an elastic putty, which comprises the following components by weight: 80 parts methyl vinyl siloxane, 15 parts phenyl siloxane, 14 parts methyl silicone oil, 3 parts aromatic hydrocarbon oil, 1.5 parts silica, 1.2 parts cerium oxide, 6 parts antioxidant 1010, and 7 parts hindered amine 770. The preparation method of the elastic putty includes mixing and stirring the components at 120°C for 1 hour. Example 4 This example provides an elastic putty, which differs from Example 1 only in that it does not contain silica, and its mass fraction is allocated to cerium oxide, while other aspects are the same as in Example 1.Example 5: This example provides an elastic putty, differing from Example 1 only in that it does not contain cerium oxide, and its mass fraction is allocated to silica; otherwise, it is the same as in Example 1. Example 6: This example provides an elastic putty, differing from Example 1 only in that it does not contain antioxidant 1010, and its mass fraction is allocated to hindered amine 770; otherwise, it is the same as in Example 1. Example 7: This example provides an elastic putty, differing from Example 1 only in that it does not contain hindered amine 770, and its mass fraction is allocated to antioxidant 1010; otherwise, it is the same as in Example 1. Example 8: This example provides an elastic putty, differing from Example 1 only in that it does not contain methyl silicone oil, and its mass fraction is allocated to aromatic hydrocarbon oil; otherwise, it is the same as in Example 1. Example 9: This example provides an elastic putty, differing from Example 1 only in that it does not contain aromatic hydrocarbon oil, and its mass fraction is allocated to methyl silicone oil; otherwise, it is the same as in Example 1. Example 10 HK 20138789 A 6 This example provides an elastic putty, which differs from Example 1 only in that it does not contain aromatic hydrocarbon oil and methyl silicone oil; otherwise, it is the same as Example 1. Comparative Example 1 This comparative example provides an elastic putty, which differs from Example 1 only in that it does not contain phenylsiloxane, but its mass fraction is allocated to methyl vinylsiloxane; otherwise, it is the same as Example 1. Comparative Example 2 This comparative example provides an elastic putty, which differs from Example 1 only in that it does not contain antioxidant 1010 and hindered amine 770; otherwise, it is the same as Example 1. Test Example Viscosity Test The initial viscosity and the viscosity after tensile compression test of the elastic putty were tested respectively. The viscosity test method was as follows: the viscosity of the putty was measured with a rotational viscometer at 25°C, and a suitable rotor was selected according to the viscosity range. The specific operation of the tensile and compression test is as follows: The damper is subjected to a tensile and compression test on a dynamic testing machine. The damper is continuously stretched and compressed dynamically. The maximum test speed is 150 mm / s, the maximum damping force is 12 KN ± 10%, the tensile and compression stroke is 40-80 mm, and the test is conducted at room temperature with air cooling. The product surface temperature is controlled to not exceed 95℃ by controlling the test frequency. The test time is 60-150 hours, and the viscosity of the putty is then tested after disassembly. The elastic putty provided in Examples 1-10 and Comparative Examples 1-2 were tested respectively, and the results are shown in Table 1.Table 1. Initial Viscosity of Samples (MPa·s) Test Time (h) Viscosity After Test (MPa·s) Viscosity Difference (MPa·s) Example 1 2.1×10⁵ 150 2.3×10⁵ 0.2×10⁵ Example 2 2.2×10⁵ 150 2.5×10⁵ 0.3×10⁵ Example 3 2.0×10⁵ 150 2.4×10⁵ 0.4×10⁵ Example 4 2.0×10⁵ 150 3.0×10⁵ 1.0×10⁵ Example 5 1.9×10⁵ 150 3.1×10⁵ 1.2×10⁵ Example 6 2.0×10⁵ 150 3.5×10⁵ 1.5×10⁵ Example 7 2.1×10⁵ 150 3.7×10⁵ 1.6×10⁵ HK 20138789 A 7 Example 8 2.3×10⁵ 150 4.2×10⁵ 1.9×10⁵ Example 9 2.2×10⁵ 150 4.0×10⁵ 1.8×10⁵ Example 10 2.5×10⁵ 150 4.5×10⁵ 2.0×10⁵ Comparative Example 1 2.3×10⁵ 60 2.2×10⁶ 1.97×10⁶ Comparative Example 2 1.9×10⁵ 60 1.5×10⁶ 1.31×10⁶ The test results show that: (1) Through Examples 1 to 10 It can be seen that the present invention, through reasonable compounding of the components in the elastic putty, produces putty with appropriate viscosity and fluidity. In the preferred scheme, the viscosity before and after testing is (1.8-2.5)×105 mpa·s, which meets the performance requirements. (2) By comparing Example 1 and Examples 4-7, it can be seen that the reinforcing agents, such as silica and cerium oxide, and the antioxidants, such as hindered phenolic antioxidants and amine antioxidants, have synergistic effects, which help maintain a suitable initial viscosity and improve the durability of the putty. By comparing Example 1 and Examples 8-10, it can be seen that the viscosity modifier and plasticizer have synergistic effects, which help maintain a suitable viscosity and fluidity of the putty. (3) By comparing Example 1 and Comparative Examples 1-2, it can be seen that the damping force increases after 60 hours of testing, exceeding the acceptable range of damping force. This indicates that phenylsiloxane and antioxidants are indispensable in the formulation of the present invention. The interaction of the components makes the elastic putty have a suitable viscosity and fluidity, providing the damping durability of the elastic putty. The applicant declares that the above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention fall within the protection and disclosure scope of the present invention.HK 20138789 A 1. Claim 1. An elastic putty, characterized in that the elastic putty comprises the following components by mass parts: 60-80 parts of methyl vinylsiloxane, 15-25 parts of phenylsiloxane, 2-8 parts of reinforcing agent, and 5-15 parts of antioxidant. 2. The elastic putty according to claim 1, characterized in that the methyl content in the methyl vinylsiloxane is greater than 95%, and the vinyl content is 0.1-1%; preferably, the phenyl content in the phenylsiloxane is 7-15%. 3. The elastic putty according to claim 1 or 2, characterized in that the reinforcing agent comprises any one or a combination of at least two of silica, calcium carbonate, or cerium oxide. 4. The elastic putty according to any one of claims 1-3, characterized in that the reinforcing agent comprises a combination of silica and cerium oxide; preferably, the mass ratio of silica to cerium oxide is 1:(0.2-0.8). 5. The elastic putty according to any one of claims 1-4, characterized in that the antioxidant comprises hindered phenolic antioxidants and / or amine antioxidants; preferably, the hindered phenolic antioxidant comprises any one or a combination of at least two of tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] pentaerythritol, octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, or butyl hydroxyanisole; preferably, the amine antioxidant comprises any one or a combination of at least two of bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, N-phenyl-1-naphthylamine, or N-isopropyl-N'-phenyl-p-phenylenediamine; preferably, the antioxidant comprises a combination of hindered phenolic antioxidants and amine antioxidants; preferably, the mass ratio of the hindered phenolic antioxidant to the amine antioxidant is 1:(0.8-1.2). 6. The elastic putty according to any one of claims 1-5, characterized in that the elastic putty further comprises 5-15 parts by weight of a viscosity modifier; preferably, the viscosity modifier comprises methyl silicone oil; preferably, the viscosity of the methyl silicone oil is 50-100 cst. 7. The elastic putty according to any one of claims 1-6, characterized in that the elastic putty further comprises 2-8 parts by weight of a plasticizer; preferably, the plasticizer comprises aromatic hydrocarbon oil. HK 20138789 A 2 8. A method for preparing the elastic putty according to any one of claims 1-7, characterized in that the preparation method comprises: mixing the components of the elastic putty to obtain the elastic putty. 9. The preparation method according to claim 8, characterized in that the mixing temperature is 90-120℃ and the time is 1-5h.10. The application of an elastic putty according to any one of claims 1-7 in a damper or buffer. HK 20138789 A.