CN111978729A - Preparation method of silicone rubber composite material with reversible sacrificial bonds - Google Patents

Preparation method of silicone rubber composite material with reversible sacrificial bonds Download PDF

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CN111978729A
CN111978729A CN201910449590.9A CN201910449590A CN111978729A CN 111978729 A CN111978729 A CN 111978729A CN 201910449590 A CN201910449590 A CN 201910449590A CN 111978729 A CN111978729 A CN 111978729A
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cnt
dopa
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silicone rubber
composite material
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杨琨
李岱原
谢旺强
李�昊
于鑫然
杨晓
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Tianjin University of Science and Technology
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K2201/011—Nanostructured additives

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  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
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Abstract

The invention belongs to the technical field of high polymer materials, and discloses a preparation method of a silicone rubber composite material with reversible sacrificial bonds. Modifying CNT by utilizing DOPA, wherein the vulcanized rubber consists of the following components in parts by weight based on coordination of the DOPA and Fe3 +: 100 parts of silicon rubber, 5 parts of modified CNT and 1.5 parts of dipentane. And putting the mixture into mixing equipment for mixing, and vulcanizing at the vulcanization temperature of 170 ℃ and the pressure of 10MPa according to the vulcanization time measured by a vulcanizer to prepare the silicone rubber composite material with the reversible sacrificial bonds.

Description

Preparation method of silicone rubber composite material with reversible sacrificial bonds
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a preparation method of a silicone rubber composite material with reversible sacrificial bonds
Background
Natural materials such as spider silk, mussels and bone are known for their excellent strength and toughness. Experimental and theoretical studies have shown that molecules that cause attractive propertiesThe mechanism is due to the presence of sacrificial bonds in these natural materials, such as domains in proteins and Ca in bone2+Unfolding of the mediated bond. The sacrificial bonds may bear loads during initial deformation, but break before covalent bonds in the polymer backbone, thereby consuming a significant amount of mechanical energy and allowing the integrity of the overall material to survive. Inspired by nature, many intelligent approaches including the introduction of double networks, double cross-linked structures and biomimetic modular domains have been explored to transfer the sacrificial bond principle into artificial polymers with the goal of achieving biomimetic strength and toughness.
Ducrot and colleagues utilize sequential free radical polymerization to create an isotropic pre-stretched network within the elastomer by swelling and then polymerizing with a second monomer. The pre-stretched chains act as sacrificial bonds, preferentially breaking and dissipating energy to toughen the elastomer. However, the rupture of the sacrificial covalent bond can lead to permanent damage to the material. To achieve a recoverable energy dissipation mechanism, reversible bonds such as hydrogen bonds, metal-ligand and ionic interactions have been highly introduced as sacrificial bonds into the polymer matrix. In addition, reversible bonds can respond to external stimuli such as heat, light, and solvents, which can be used to access a macro-responsive material that adapts and responds to the environment.
Rubbers having high elasticity are considered to be a strategically important material because of their indispensable applications in tires, seals and shock absorbers. Most of the neat rubbers have poor mechanical properties, which seriously hampers their practical use. To address this problem, rubbers are widely reinforced and toughened by the addition of various nanofillers. However, the composite rubber and the nano filler pose significant limitations in terms of nano filler dispersion/aggregation, interface adjustment and processing difficulty. In this regard, great efforts have been made to introduce efficient energy consuming mechanisms to improve the mechanical properties of unfilled rubbers, such as sliding elastomers and heterogeneous rubbers. In addition to reinforcing rubber, expanding the rubber application gallery is another important issue in material science and engineering. Recently, rubber has been explored as electronic skin, overheating materials and actuators for advanced applications.
Under external loading, the metal-ligand bonds act as sacrificial bonds that preferentially break before the covalent network, dissipating energy and promoting rubber chain orientation. Based on the functional mechanism, the modulus, tensile strength and toughness of the sample are simultaneously improved without sacrificing elongation, and these properties can be conveniently adjusted by changing the structural parameters of the covalent cross-linking network and the metal-ligand bond.
Disclosure of Invention
According to the invention, through the modification of CNT by DOPA, a metal-ligand bond is formed by utilizing the coordination reaction between DOPA and metal ions, and the silicon rubber composite material with reversible sacrificial bonds is prepared.
The purpose of the invention can be realized by the following scheme:
100 parts of silicon rubber
1-5 parts of modified CNT
Vulcanizing agent 1.5 parts
Preferably, the vulcanizing agent is 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane, abbreviated as dipentaerythritol
Preferably, the modified CNT is a Dopamine (DOPA) modified CNT. Dispersing CNT in deionized water, performing ultrasonic treatment for 1h, adding tris (hydroxymethyl) aminomethane into the suspension, adjusting pH to about 8.5 with hydrochloric acid (HCl), adding DOPA into the suspension, and magnetically stirring for 24 h. And carrying out suction filtration to obtain the product DOPA-CNT. Redispersing DOPA-CNT in deionized water, adding FeCl 3(molDOPA∶molFe3: 1), adjusting the pH value to the required value by NaOH, and filtering the obtained Fe [ DOPA ] by suction]3-CNT
Preferably, the CNT is modified with DOPA such that DOPA and CNT are 0.5: 1, 1: 1, 1.5: 1, 2: 1, 3: 1
Preferably, 100 parts of silicone rubber, 5 parts of modified CNT and 1.5 parts of Bierwu are mixed in an open mill, the temperature of a mixing roller is controlled to be 40 ℃ at once, and the temperature of a front roller is 5-10 ℃ lower than that of a rear roller so as to wrap the front roller. The rubber compound is vulcanized and prepared on a plate vulcanizing machine, the pressure during vulcanization is 10MPa, the vulcanization temperature is 170 ℃, and the vulcanization time is t90+1min, after vulcanization, placing the vulcanized rubber according to the specification (more than 16 h) to obtain the silicon rubber composite material with reversible sacrificial bonds
Meanwhile, the inventor discovers that the formed metal coordination network has different strength and the dosage of DOPA is increased by changing the proportion of DOPA and CNT through research, thereby being beneficial to improving the formation of a cross-linked network
The invention has the following advantages and beneficial effects:
the sacrificial bonds may bear loads during initial deformation, but break before covalent bonds in the polymer backbone, thereby consuming a significant amount of mechanical energy and allowing the integrity of the overall material to survive. A metal-ligand bond is introduced into the silicone rubber structure. The metal-ligand bond is capable of reversible cleavage and reformation, i.e., acts as a sacrificial bond under external load to dissipate energy and promote rubber chain orientation, thereby greatly enhancing mechanical properties. In addition, modification with CNTs is more easily dispersed in the silicone rubber matrix, forming a conductive composite.
The specific implementation mode is as follows:
the invention is further described with reference to the following examples:
preparation of DOPA-modified CNTs: dispersing CNT in 500mL deionized water, performing ultrasonic treatment for 1h, adding tris (hydroxymethyl) aminomethane into the suspension, adjusting pH to about 8.5 with hydrochloric acid (HCl), adding DOPA into the suspension, and magnetically stirring for 24 h. And carrying out suction filtration to obtain the product DOPA-CNT. Redispersing DOPA-CNT in deionized water, adding FeCl3(molDOPA∶molFe3: 1), adjusting the pH value to the required value by NaOH, and filtering the obtained Fe [ DOPA ] by suction]3-CNT
Example 1
The preparation method of the silicone rubber composite material with reversible sacrificial bonds comprises the following steps: 100 parts of silicon rubber, 5 parts of modified CNT (DOPA: CNT is 0.5: 1) and 1.5 parts of dipentane, and the silicon rubber is mixed in an open mill, the temperature of a mixing roller is controlled to be 40 ℃ at one time, and the temperature of a front roller is 5-10 ℃ lower than that of a rear roller so as to be wrapped on the front roller. The rubber compound is vulcanized and prepared on a plate vulcanizing machine, the pressure during vulcanization is 10MPa, the vulcanization temperature is 170 ℃, and the vulcanization time is t90And+ 1min, after vulcanization, placing the vulcanized rubber according to the specification (more than 16 h) to obtain the silicone rubber composite material with reversible sacrificial bonds. Test itThe properties are shown in Table 1.
Example 2
The preparation method of the silicone rubber composite material with reversible sacrificial bonds comprises the following steps: 100 parts of silicon rubber, 5 parts of modified CNT (DOPA: CNT is 1: 1) and 1.5 parts of dipentane, and the silicon rubber is mixed in an open mill, the temperature of a mixing roller is controlled to be 40 ℃ at one time, and the temperature of a front roller is 5-10 ℃ lower than that of a rear roller so as to be wrapped on the front roller. The rubber compound is vulcanized and prepared on a plate vulcanizing machine, the pressure during vulcanization is 10MPa, the vulcanization temperature is 170 ℃, and the vulcanization time is t90And+ 1min, after vulcanization, placing the vulcanized rubber according to the specification (more than 16 h) to obtain the silicone rubber composite material with reversible sacrificial bonds. The properties thereof were measured and shown in Table 1.
Example 3
The preparation method of the silicone rubber composite material with reversible sacrificial bonds comprises the following steps: 100 parts of silicon rubber, 5 parts of modified CNT (DOPA: CNT is 1.5: 1) and 1.5 parts of dipentane, and the silicon rubber is mixed in an open mill, the temperature of a mixing roller is controlled to be 40 ℃ at one time, and the temperature of a front roller is 5-10 ℃ lower than that of a rear roller so as to be wrapped on the front roller. The rubber compound is vulcanized and prepared on a plate vulcanizing machine, the pressure during vulcanization is 10MPa, the vulcanization temperature is 170 ℃, and the vulcanization time is t90And+ 1min, after vulcanization, placing the vulcanized rubber according to the specification (more than 16 h) to obtain the silicone rubber composite material with reversible sacrificial bonds. The properties thereof were measured and shown in Table 1.
Example 4
The preparation method of the silicone rubber composite material with reversible sacrificial bonds comprises the following steps: 100 parts of silicon rubber, 5 parts of modified CNT (DOPA: CNT is 2: 1) and 1.5 parts of dipentane, and the silicon rubber is mixed in an open mill, the temperature of a mixing roller is controlled to be 40 ℃ at one time, and the temperature of a front roller is 5-10 ℃ lower than that of a rear roller so as to be wrapped on the front roller. The rubber compound is vulcanized and prepared on a plate vulcanizing machine, the pressure during vulcanization is 10MPa, the vulcanization temperature is 170 ℃, and the vulcanization time is t90And+ 1min, after vulcanization, placing the vulcanized rubber according to the specification (more than 16 h) to obtain the silicone rubber composite material with reversible sacrificial bonds. The properties thereof were measured and shown in Table 1.
Example 5
The preparation method of the silicone rubber composite material with reversible sacrificial bonds comprises the following steps: 100 parts of silicon rubber, 5 parts of modified CNT (DOPA: CNT is 3: 1) and 1.5 parts of dipentane, and the silicon rubber is mixed in an open mill, the temperature of a mixing roller is controlled to be 40 ℃ at one time, and the temperature of a front roller is 5-10 ℃ lower than that of a rear roller so as to be wrapped on the front roller. The rubber compound is vulcanized and prepared on a plate vulcanizing machine, the pressure during vulcanization is 10MPa, the vulcanization temperature is 170 ℃, and the vulcanization time is t90And+ 1min, after vulcanization, placing the vulcanized rubber according to the specification (more than 16 h) to obtain the silicone rubber composite material with reversible sacrificial bonds. The properties thereof were measured and shown in Table 1.
Table 1 shows the test results of the silicone rubber composite material with reversible sacrificial bonds
Figure BSA0000183762270000041

Claims (6)

1. A preparation method of a silicone rubber composite material with reversible sacrifice bonds comprises the following specific steps:
100 parts of silicon rubber
1-5 parts of modified CNT
1.5 parts of a vulcanizing agent.
2. The silicone rubber composite material with reversible sacrificial bonds of claim 1, wherein: the vulcanizing agent is 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane, which is abbreviated as dipenta.
3. The silicone rubber composite material with reversible sacrificial bonds of claim 1, wherein: the modified CNT is modified by Dopamine (DOPA) to CNT. Dispersing CNT in deionized water, performing ultrasonic treatment for 1h, adding tris (hydroxymethyl) aminomethane into the suspension, adjusting pH to about 8.5 with hydrochloric acid (HCl), adding DOPA into the suspension, and magnetically stirring for 24 h. And carrying out suction filtration to obtain the product DOPA-CNT. Redispersing DOPA-CNT in deionized water, adding FeCl3(molDOPA∶molFe3: 1), adjusting the pH value to the required value by NaOH, and filtering the obtained Fe [ DOPA ] by suction]3-CNT。
4. The DOPA-modified CNT of claim 3, characterized in that: the CNT is modified by DOPA, and the ratio of DOPA to CNT is 0.5: 1, 1: 1, 1.5: 1, 2: 1 and 3: 1.
5. The silicone rubber composite material with reversible sacrificial bonds of claim 1, wherein: 100 parts of silicon rubber, 5 parts of modified CNT, and 1.5 parts of dipentane and dipentane are mixed in an open mill, the temperature of a mixing roller is controlled to be 40 ℃, and the temperature of a front roller is 5-10 ℃ lower than that of a rear roller so as to wrap the front roller. The rubber compound is vulcanized and prepared on a plate vulcanizing machine, the pressure during vulcanization is 10MPa, the vulcanization temperature is 170 ℃, and the vulcanization time is t90And+ 1min, after vulcanization, placing the vulcanized rubber according to the specification (more than 16 h) to obtain the silicone rubber composite material with reversible sacrificial bonds.
6. Use of a silicone rubber composite prepared according to claim 5 to form reversible sacrificial bonds.
CN201910449590.9A 2019-05-22 2019-05-22 Preparation method of silicone rubber composite material with reversible sacrificial bonds Pending CN111978729A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116426074A (en) * 2023-05-29 2023-07-14 江苏海洋大学 Preparation method of double-crosslinked-network-enhanced stabilized ethylene propylene diene monomer rubber

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116426074A (en) * 2023-05-29 2023-07-14 江苏海洋大学 Preparation method of double-crosslinked-network-enhanced stabilized ethylene propylene diene monomer rubber
CN116426074B (en) * 2023-05-29 2024-04-26 江苏海洋大学 Preparation method of double-crosslinked-network-enhanced stabilized ethylene propylene diene monomer rubber

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Application publication date: 20201124