Alkenoic acid modified filler, silicone rubber material and preparation method thereof

Abstract

The invention discloses an olefine acid modified filler, a silicone rubber material and a preparation method thereof, and relates to the technical field of high polymer materials. And reacting carboxylic acid functional groups in the olefine acid with the filler to prepare the olefine acid modified filler. The olefine acid contains one or more vinyl and carboxyl functional groups, the filler is metal oxide, metal hydroxide or carbonate solid particles, and the modification method comprises a dry method and a wet method. The invention further discloses a silicone rubber material prepared from the olefine acid modified filler and a preparation method of the silicone rubber material. The silicone rubber is filled with the olefine acid modified filler, the material performance is improved, and the heat conductivity coefficient, the tensile strength and the Shore OO hardness of the obtained material are higher than those of a silicone rubber material prepared from an unmodified filler.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, and in particular to an olefinic acid modified filler, a silicone rubber material and a preparation method thereof. Background Art

[0002] Silicone rubber refers to a rubber whose backbone consists of alternating silicon and oxygen atoms, with two organic groups typically attached to the silicon atoms. Ordinary silicone rubber primarily consists of silicon-oxygen chains containing methyl groups and a small amount of vinyl groups. Silicone rubber exhibits excellent heat and cold resistance, as well as electrical insulation properties. It is commonly used as a sealing and adhesive material, making it a highly versatile polymer material with excellent performance. However, the mechanical and thermal conductivity properties of silicone rubber require the addition of fillers to significantly improve their overall performance.

[0003] Currently, the traditional method for modifying fillers used in silicone rubber preparation is to use silane coupling agents to physically modify the fillers, thereby improving the compatibility of the fillers in the silicone rubber and, in turn, the performance of the silicone rubber material. However, the silane coupling agents used in traditional methods are costly, complex, and have limited effectiveness in improving silicone rubber performance. Summary of the Invention

[0004] The present invention provides an olefinic acid-modified filler, a silicone rubber material, and a preparation method thereof, aiming to address the aforementioned problems in the background art. The present invention employs a chemical method to introduce reactive vinyl groups onto the filler surface by reacting the reactive carboxyl groups in the olefinic acid with the filler. During the vulcanization process, these reactive vinyl groups undergo addition reactions with double bonds in the silicone rubber, becoming incorporated into the silicone rubber backbone and thereby enhancing various properties of the silicone rubber.

[0005] In order to achieve the above technical objectives, the present invention mainly adopts the following technical solutions:

[0006] The invention discloses an olefinic acid modified filler. The olefinic acid is an olefinic acid having single or multiple vinyl and carboxyl functional groups. The filler is modified by reacting the carboxylic acid functional group in the olefinic acid with the filler to obtain the olefinic acid modified filler.

[0007] In a preferred embodiment of the present invention, the olefinic acid includes one or more of acrylic acid, methacrylic acid, butenoic acid, methylbutenoic acid, pentenoic acid, 2-allyl-4-pentenoic acid, undecenoic acid, oleic acid, linoleic acid, linolenic acid, and octadecenedioic acid.

[0008] In a preferred embodiment of the present invention, the filler is solid particles selected from one or more of metal oxides, metal hydroxides or carbonates.

[0009] Preferably, the metal oxide includes one or more of aluminum oxide, magnesium oxide, copper oxide, and zinc oxide; the metal hydroxide includes one or more of aluminum hydroxide and magnesium hydroxide; and the carbonate includes one or more of calcium carbonate, magnesium carbonate, and barium carbonate.

[0010] The present invention also discloses a method for preparing the olefinic acid modified filler as described above, wherein the olefinic acid modified filler is prepared by dry modification or wet modification.

[0011] In a preferred embodiment of the present invention, when dry modification is adopted, the following steps are included:

[0012] (1) Weigh the filler and place it into an eggplant-shaped bottle;

[0013] (2) adding olefinic acid according to the mass ratio of filler;

[0014] (3) Place the eggplant-shaped bottle on a rotary evaporator, adjust the temperature of the water bath, rotate and mix the reaction under normal pressure, take out and seal for storage, and the modified filler is obtained.

[0015] In a preferred embodiment of the present invention, when wet modification is adopted, the following steps are included:

[0016] (1) Weigh the filler and place it into an eggplant-shaped bottle;

[0017] (2) adding alcohol and olefinic acid according to the mass ratio of filler;

[0018] (3) Adjust the temperature and stir the reaction;

[0019] (4) Filter the reactants, vacuum dry them, take them out and seal them for storage to obtain the modified filler.

[0020] The invention also discloses an application of the above-mentioned olefinic acid modified filler in filling silicone rubber to prepare silicone rubber material.

[0021] The present invention also discloses a silicone rubber material, comprising the following raw materials in parts by weight:

[0022]

[0023] Wherein, the filler is the olefinic acid modified filler as described above.

[0024] The present invention also discloses a method for preparing the silicone rubber material as described above, comprising the following steps: weighing silicone rubber, silicone oil, vulcanizing agent, reactive diluent, and filler in proportion, mixing them evenly, placing them in a vulcanizing apparatus, adjusting the temperature, and performing a vulcanization reaction to obtain the silicone rubber material.

[0025] Compared with the prior art, the present invention has the following beneficial effects:

[0026] The present invention utilizes an olefinic acid modified filler, which is filled into silicone rubber to improve the performance of the material. The thermal conductivity, tensile strength and Shore OO hardness of the silicone rubber material are higher than those of the silicone rubber material prepared with unmodified filler. DETAILED DESCRIPTION

[0027] In order to better understand the present invention, the contents of the present invention are further illustrated in conjunction with the following examples. However, in order to enable ordinary technicians in this field to fully understand the technical solutions and beneficial effects of the present invention, the present invention is further illustrated in conjunction with specific examples below. The examples are merely simple examples of the present invention and do not represent or limit the scope of protection of the present invention. The scope of protection of the present invention shall be subject to the claims.

[0028] Example 1

[0029] S1: Preparation of modified alumina as filler by dry process:

[0030] (1) Weigh 300.0 g of aluminum oxide and place it in an eggplant-shaped bottle;

[0031] (2) adding 15.0 g of acrylic acid;

[0032] (3) Place the eggplant-shaped bottle on a rotary evaporator, adjust the water bath to 30°C, rotate and mix at 30 rpm under normal pressure for 16 hours, take out and seal for storage.

[0033] S2: Preparation of silicone rubber material:

[0034]

[0035] Weigh the aforementioned parts by weight of di-tert-butyl cumene peroxide, tetramethyltetravinylcyclotetrasiloxane, vinyl silicone oil, the alumina modified in step S1, and methyl vinyl silicone rubber, mix thoroughly, and then repeatedly roll and knead the mixture on a two-roll mill at room temperature for 30 minutes. Place the mixture in a vulcanizer at 200°C and vulcanize for 1 hour to obtain a silicone rubber material.

[0036] Example 2

[0037] S1: Preparation of modified alumina filler by wet process:

[0038] (1) Weigh 300.0 g of aluminum oxide and place it in an eggplant-shaped bottle;

[0039] (2) adding 300.0 g of ethanol and 15.0 g of acrylic acid;

[0040] (3) Adjust to 30°C and stir for 16 hours;

[0041] (4) Filter, vacuum dry, remove and seal for storage.

[0042] S2: Preparation of silicone rubber material:

[0043]

[0044] Weigh the above-mentioned parts by weight of di-tert-butyl peroxide isopropyl benzene, tetramethyltetravinylcyclotetrasiloxane, vinyl silicone oil, modified alumina, and methyl vinyl silicone rubber, mix thoroughly, and then repeatedly roll and knead the mixture on a two-roll mill at room temperature for 30 minutes. Place the mixture in a vulcanizer at 200°C and vulcanize for 1 hour to obtain a silicone rubber material.

[0045] Example 3

[0046] S1: Preparation of modified alumina as filler by dry process:

[0047] (1) Weigh 300.0 g of aluminum oxide and place it in an eggplant-shaped bottle;

[0048] (2) adding 15.0 g of methacrylic acid;

[0049] (3) Place the eggplant-shaped bottle on a rotary evaporator, adjust the water bath to 60°C, rotate and mix at 30 rpm under normal pressure for 6 hours, take out and seal for storage.

[0050] S2: Preparation of silicone rubber material:

[0051]

[0052] Weigh the above-mentioned parts by weight of di-tert-butyl peroxide isopropyl benzene, tetramethyltetravinylcyclotetrasiloxane, vinyl silicone oil, modified alumina, and methyl vinyl silicone rubber, mix thoroughly, and then repeatedly roll and knead the mixture on a two-roll mill at room temperature for 30 minutes. Place the mixture in a vulcanizer at 200°C and vulcanize for 1 hour to obtain a silicone rubber material.

[0053] Example 4

[0054] S1: Preparation of modified magnesium oxide as filler by dry process:

[0055] (1) Weigh 300.0 g of magnesium oxide and place it in an eggplant-shaped bottle;

[0056] (2) adding 15.0 g of acrylic acid;

[0057] (3) Place the eggplant-shaped bottle on a rotary evaporator, adjust the water bath to 30°C, rotate and mix at 30 rpm under normal pressure for 16 hours, take out and seal for storage.

[0058] S2: Preparation of silicone rubber material:

[0059]

[0060] Weigh the above-mentioned parts by weight of di-tert-butyl peroxide isopropyl benzene, tetramethyltetravinylcyclotetrasiloxane, vinyl silicone oil, modified magnesium oxide, and methyl vinyl silicone rubber, mix thoroughly, and then repeatedly roll and knead the mixture on a two-roll mill at room temperature for 30 minutes. Place the mixture in a vulcanizer at 200°C and vulcanize for 1 hour to obtain a silicone rubber material.

[0061] Example 5

[0062] S1: Preparation of modified calcium carbonate filler by wet process:

[0063] (1) Weigh 300.0 g of calcium carbonate and place it in an eggplant-shaped bottle;

[0064] (2) adding 300.0 g of ethanol and 6.0 g of acrylic acid;

[0065] (3) Adjust to 30°C and stir for 16 hours;

[0066] (4) Filter, vacuum dry, remove and seal for storage.

[0067] S2: Preparation of silicone rubber material:

[0068]

[0069] Weigh the above-mentioned parts by weight of di-tert-butyl peroxide isopropyl benzene, tetramethyltetravinylcyclotetrasiloxane, vinyl silicone oil, modified calcium carbonate, and methyl vinyl silicone rubber, mix thoroughly, and then repeatedly roll and knead the mixture on a two-roll mill at room temperature for 30 minutes. Place the mixture in a vulcanizer at 200°C and vulcanize for 1 hour to obtain a silicone rubber material.

[0070] Example 6

[0071] S1: Preparation of modified alumina as filler by dry process:

[0072] (1) Weigh 300.0 g of aluminum oxide and place it in an eggplant-shaped bottle;

[0073] (2) adding 15.0 g of acrylic acid;

[0074] (3) Place the eggplant-shaped bottle on a rotary evaporator, adjust the water bath to 30°C, rotate and mix at 30 rpm under normal pressure for 16 hours, take out and seal for storage.

[0075] S2: Preparation of silicone rubber material:

[0076]

[0077] The above-mentioned parts by weight of vinyl silicone oil, hydrogenated silicone oil, platinum (0)-1,3-diethene-1,1,3,3-tetramethyldisiloxane, ethynylcyclohexanol and modified alumina were weighed, mixed evenly, vacuum degassed, placed in a vulcanizing apparatus, adjusted to a temperature of 200° C., and vulcanized for 1 hour to obtain a silicone rubber material.

[0078] Comparative Example 1

[0079] Preparation of silicone rubber material:

[0080]

[0081] Weigh the above-mentioned parts by weight of di-tert-butyl cumene peroxide, tetramethyltetravinylcyclotetrasiloxane, vinyl silicone oil, unmodified alumina, and methyl vinyl silicone rubber, mix thoroughly, and then repeatedly roll and knead the mixture on a two-roll mill at room temperature for 30 minutes. Place the mixture in a vulcanizer at 200°C and vulcanize for 1 hour to obtain a silicone rubber material.

[0082] Comparative Example 2

[0083] Preparation of silicone rubber material:

[0084]

[0085] Weigh the above-mentioned parts by weight of di-tert-butyl cumene peroxide, tetramethyltetravinylcyclotetrasiloxane, vinyl silicone oil, unmodified magnesium oxide, and methyl vinyl silicone rubber, mix thoroughly, and then repeatedly roll and knead the mixture on a two-roll mill at room temperature for 30 minutes. Place the mixture in a vulcanizer at 200°C and vulcanize for 1 hour to obtain a silicone rubber material.

[0086] Comparative Example 3

[0087] Preparation of silicone rubber material:

[0088]

[0089] Weigh the above-mentioned parts by weight of di-tert-butyl cumene peroxide, tetramethyltetravinylcyclotetrasiloxane, vinyl silicone oil, unmodified calcium carbonate, and methyl vinyl silicone rubber, mix thoroughly, and then repeatedly roll and knead the mixture on a two-roll mill at room temperature for 30 minutes. Place the mixture in a vulcanizer at 200°C and vulcanize for 1 hour to obtain a silicone rubber material.

[0090] Comparative Example 4

[0091] Preparation of silicone rubber material:

[0092]

[0093] The above-mentioned parts by weight of vinyl silicone oil, hydrogenated silicone oil, platinum (0)-1,3-diethene-1,1,3,3-tetramethyldisiloxane, ethynylcyclohexanol and unmodified alumina were weighed and mixed evenly. After vacuum degassing, the mixture was placed in a vulcanization apparatus, the temperature was adjusted to 200° C., and vulcanization was performed for 1 hour to obtain a silicone rubber material.

[0094] The silicone rubber materials prepared in Examples 1-6 and Comparative Examples 1-4 were subjected to performance testing. Thermal conductivity was measured using a DRE-III multifunctional rapid thermal conductivity tester; tensile strength was measured using a universal tensile testing machine with a Type 2 dumbbell tester as specified in GB / T528-2009; and Shore OO hardness was measured using a Shore A durometer in accordance with the national standard GB / T531.1-2008 for the thermal interface hardness of the silicone rubber. The results are shown in Table 1 below.

[0095] Table 1 Performance comparison of silicone rubber materials

[0096]

[0097] According to the data in Table 1, the thermal conductivity, tensile strength and Shore OO hardness of the silicone rubber material prepared by the modified filler are higher than those of the silicone rubber material prepared by the unmodified filler, and the comparison between Examples 1, 2, 3 and Comparative Example 1, Example 4 and Comparative Example 2, Example 5 and Comparative Example 3, and Example 6 and Comparative Example 4 are analyzed, which proves that the modification method has a beneficial effect on improving the silicone rubber material.

[0098] Those skilled in the art will understand that the embodiments described above are exemplary and can be improved by those skilled in the art. The methods described in various embodiments can be freely combined without any conflict in principle, thereby achieving the preparation of silicone rubber materials with higher performance on the basis of solving the technical problems of the present invention.

[0099] The specific embodiments of the present invention described above do not limit the scope of protection of the present invention. Any other corresponding changes and modifications made based on the technical concept of the present invention should be included in the scope of protection of the claims of the present invention.

Claims

1. An olefinic acid modified filler, characterized in that: The olefinic acid is an olefinic acid having single or multiple vinyl and carboxyl functional groups. The filler is modified by reacting the carboxylic acid functional group in the olefinic acid with the filler to obtain the olefinic acid-modified filler.

2. The olefinic acid modified filler according to claim 1, characterized in that: The olefinic acid includes one or more of acrylic acid, methacrylic acid, butenoic acid, methylbutenoic acid, pentenoic acid, 2-allyl-4-pentenoic acid, undecenoic acid, oleic acid, linoleic acid, linolenic acid, and octadecenedioic acid.

3. The olefinic acid modified filler according to claim 1, characterized in that: The filler is solid particles, selected from one or more of metal oxides, metal hydroxides or carbonates.

4. The olefinic acid modified filler according to claim 3, characterized in that: The metal oxide includes one or more of aluminum oxide, magnesium oxide, copper oxide, and zinc oxide; the metal hydroxide includes one or more of aluminum hydroxide and magnesium hydroxide; and the carbonate includes one or more of calcium carbonate, magnesium carbonate, and barium carbonate.

5. The method for preparing the olefinic acid modified filler according to any one of claims 1 to 4, wherein: The olefinic acid modified filler is prepared by dry modification or wet modification.

6. The method for preparing an olefinic acid modified filler according to claim 5, wherein: When dry modification is used, the following steps are included: (1) Weigh the filler and place it into an eggplant-shaped bottle; (2) adding olefinic acid according to the mass ratio of filler; (3) Place the eggplant-shaped bottle on a rotary evaporator, adjust the temperature of the water bath, rotate and mix the reaction under normal pressure, take out and seal for storage, and the modified filler is obtained.

7. The method for preparing an olefinic acid modified filler according to claim 5, wherein: When wet modification is adopted, the following steps are included: (1) Weigh the filler and place it into an eggplant-shaped bottle; (2) adding alcohol and olefinic acid according to the mass ratio of filler; (3) Adjust the temperature and stir the reaction; (4) Filter the reactants, vacuum dry them, take them out and seal them for storage to obtain the modified filler.

8. Use of the olefinic acid modified filler according to any one of claims 1 to 4 in filling silicone rubber to prepare silicone rubber materials.

9. A silicone rubber material, characterized in that: The invention comprises the following raw materials in parts by weight: Wherein, the filler is the olefinic acid modified filler according to any one of claims 1 to 4.

10. The method for preparing a silicone rubber material according to claim 9, wherein: The method comprises the following steps: weighing silicone rubber, silicone oil, vulcanizing agent, active diluent and filler in proportion, mixing them evenly, placing them in a vulcanizing apparatus, adjusting the temperature and performing vulcanization reaction to obtain silicone rubber material.

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