CN110713719A - Silicon rubber composition and preparation method thereof - Google Patents
Silicon rubber composition and preparation method thereof Download PDFInfo
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- CN110713719A CN110713719A CN201810771637.9A CN201810771637A CN110713719A CN 110713719 A CN110713719 A CN 110713719A CN 201810771637 A CN201810771637 A CN 201810771637A CN 110713719 A CN110713719 A CN 110713719A
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- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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Abstract
The invention discloses a silicone rubber composition and a preparation method thereof, the composition comprises composite insulator silicone rubber powder and room temperature curing silicone rubber, wherein the composite insulator silicone rubber powder is obtained by treating retired composite insulator silicone rubber, preferably, the composite insulator silicone rubber powder is retired composite insulator silicone rubber powder modified by a coupling agent, and the composition has good mechanical properties. The invention also provides a preparation method of the silicon rubber composition, the preparation method has the advantages of easily available raw materials, simple process, mild conditions and easy realization, and realizes the cyclic utilization of the silicon rubber of the retired composite insulator, thereby reducing the material cost, saving resources and protecting the environment.
Description
Technical Field
The invention belongs to the technical field of composite insulators, relates to a recycling method of a silicon rubber product of a retired composite insulator, and particularly relates to a silicon rubber composition and a preparation method thereof.
Background
With the progress of society, electric power has been rapidly developed as a main energy source. The transmission lines all over the region can be seen everywhere, wherein, in alternating current operation lines of various voltage classes and newly-built line engineering, the composite insulator can be used in large quantities even in all lines, and the silicon rubber composite insulator with excellent performance can be widely applied.
However, with the mass production and consumption of the silicone rubber composite insulators, a large amount of production waste, processing waste, leftover materials and the like of the composite insulators are correspondingly generated. In addition, along with the decommissioning of the composite insulators, a large number of decommissioned composite insulators occupy a large number of plants, and are abandoned due to the fact that no better treatment method is available, so that environmental pollution and resource waste are caused.
The silicon rubber in the silicon rubber composite insulator has excellent performance, such as the characteristics of high thermal stability, high hydrophobicity and the like, and has higher recycling value, so that the recycling of the retired composite insulator and the leftover materials thereof has important practical significance for reducing environmental pollution and improving the economic benefit of products.
The recycling of the retired composite insulator is mainly faced with the problem of recycling of silicon rubber therein. The silicon rubber in the composite insulator has the performances of corrosion resistance, oxidation resistance, ultraviolet resistance and the like, and is difficult to degrade in a natural environment. At present, the treatment method of the silicon rubber in the retired composite insulator mainly realizes the recycling of the organic siloxane compound by a chemical cracking or thermal cracking method, but the content of D4 in a cracking product of the chemical cracking method is high, a large amount of waste liquid is generated, and secondary pollution is easily caused; the thermal cracking method needs high temperature, more side reactions and low yield. The composite insulator silicon rubber is made of rubber materials in special environment, is treated by special processes such as high-temperature vulcanization, radiation crosslinking and the like, and is not suitable by adopting a conventional treatment method, so other simple and feasible methods for treating the composite insulator silicon rubber need to be found.
The use of silicone rubber composite insulator rubber powder as EPDM filler is reported in China, but the performance of the obtained product is reduced, and the practical use value is lacking [ Sunjin, Cao-hong Wei, Dulin Juan, and the like.
In China, waste insulator silicon rubber is modified by adopting treatment modes such as acidification, hydrosilation and the like, and is compounded with ammonium polyphosphate to be applied to flame-retardant polylactic acid (PLA), and the modified decommissioned composite insulator rubber powder is added to have a better flame-retardant effect on the PLA, so that the waste insulator silicon rubber modification and application in the flame-retardant polylactic acid [ J ] polymer material science and engineering, 2017,33(11):119-124 ] have a great significance on recycling of the decommissioned composite insulator silicon rubber powder.
Therefore, a method for treating the ex-service composite insulator silicone rubber is sought, and the ex-service composite insulator silicone rubber powder is used as a filler to carry out filling modification on a proper matrix, so that the method is a simple and easy scheme for realizing recycling of the silicone rubber insulator, and is also an important development direction in the field of composite insulators.
Disclosure of Invention
In order to overcome the above problems, the present inventors have conducted intensive studies and, as a result, found that: the ex-service composite insulator silicone rubber is treated, and the obtained ex-service composite insulator silicone rubber powder and room temperature curing silicone rubber are mixed and cured to prepare the silicone rubber composition, so that the mechanical property of the silicone rubber composition is further improved, the recycling of the ex-service composite insulator silicone rubber is realized, the material cost is reduced, the resources are saved, and the environment is protected, thereby completing the invention.
The invention aims to provide a silicone rubber composition which comprises room-temperature cured silicone rubber and composite insulator silicone rubber powder, wherein the composite insulator silicone rubber powder is obtained by treating retired composite insulator silicone rubber.
Another object of the present invention is to provide a method for preparing a silicone rubber composition, wherein the method comprises the steps of:
step 1, recycling the ex-service composite insulator silicone rubber, and treating to obtain ex-service composite insulator silicone rubber powder;
step 2, mixing the decommissioned composite insulator silicone rubber powder with room-temperature cured silicone rubber;
and 3, pouring the mixture obtained in the step 2 into a mold, and curing.
The invention has the following beneficial effects:
(1) in the invention, the ex-service composite insulator silicone rubber powder/room temperature curing silicone rubber composition is obtained by adding the ex-service composite insulator silicone rubber powder into the room temperature curing silicone rubber, so that the mechanical property of the silicone rubber composition is improved.
(2) According to the invention, the modified decommissioned composite insulator silicone rubber powder is added into the room temperature curing silicone rubber as a filler to prepare the silicone rubber composition, a chemical bond is formed between the modified decommissioned composite insulator silicone rubber powder and the room temperature curing silicone rubber, so that the modified decommissioned composite insulator silicone rubber powder and the room temperature curing silicone rubber have good interface bonding force and compatibility, the mechanical property of the silicone rubber composition is further improved, and the silicone rubber powder in the silicone rubber composition is uniform in distribution, good in thermal stability and high in energy storage modulus (for example, when 30g of YDH-151 modified rubber powder is added, the Young modulus of the silicone rubber composition is improved by more than 85% compared with the room temperature curing silicone rubber without.
(3) The preparation method of the room temperature curing silicone rubber/retired composite insulator silicone rubber powder composition provided by the invention has the advantages of easily available raw materials, simple process, mild conditions, easiness in realization, energy conservation and environmental friendliness;
(4) the invention realizes the recycling of the silicon rubber of the retired composite insulator, recycles the waste, reduces the material cost, saves the resources, protects the environment and meets the requirement of green development.
Drawings
FIG. 1 shows an SEM image of the final product obtained in comparative example 1 of the present invention;
FIG. 2 shows an SEM picture of the final product obtained in example 9 of the present invention;
FIG. 3 shows an SEM image of the final product obtained in example 10 of the present invention;
FIG. 4 shows an SEM photograph of the final product obtained in example 11 of the present invention;
FIG. 5 shows an SEM picture of the final product obtained in example 5 of the present invention;
FIG. 6 shows an SEM photograph of the final product obtained in example 12 of the present invention;
Detailed Description
The invention is explained in more detail below with reference to the drawings and preferred embodiments. The features and advantages of the present invention will become more apparent from the description.
The invention provides a silicon rubber composition which comprises room temperature curing silicon rubber and composite insulator silicon rubber powder, wherein the composite insulator silicon rubber powder is obtained by treating retired composite insulator silicon rubber.
According to the invention, the content of the composite insulator silicone rubber powder in the silicone rubber composition is 5-40%, preferably 5-35%, more preferably 5-10%, wherein the weight of the room temperature curing silicone rubber is 100%.
In the invention, the composite insulator silicon rubber powder is a silicon rubber composition obtained by adding the composite insulator silicon rubber powder as a filler into a matrix material room temperature curing silicon rubber.
Room temperature cured silicone Rubber (RTV) refers to a type of silicone rubber in which active functional groups at both ends of a molecular chain undergo a crosslinking reaction under the action of water molecules or a certain catalyst to form a three-dimensional network structure at room temperature. The strength of the room temperature curing silicone rubber is low, and the mechanical property of the room temperature curing silicone rubber needs to be further improved.
According to the invention, the room temperature curing silicone rubber is adopted as a matrix material, and the curing can be completed under the room temperature condition to obtain the silicone rubber composition, so that the raw materials and the products are convenient and easy to obtain, and the silicone rubber composition is energy-saving and environment-friendly.
The ex-service composite insulator silicone rubber comprises production waste, processing waste and leftover materials in the process of producing the composite insulator silicone rubber and the silicone rubber in the ex-service composite insulator.
According to the invention, the treatment method of the retired composite insulator silicone rubber comprises the following steps: and recycling the decommissioned composite insulator silicone rubber, and cleaning and crushing to obtain the decommissioned composite insulator silicone rubber powder.
In the invention, the ex-service composite insulator silicone rubber is waste composite insulator silicone rubber, the ex-service composite insulator silicone rubber is recycled and is added into a matrix material as a filler to prepare the composition, and the ex-service composite insulator silicone rubber needs to be treated to obtain ex-service composite insulator silicone rubber powder which is better mixed with the matrix material.
In the invention, the reclaimed retired composite insulator silicon rubber has a plurality of impurities on the surface, and the reclaimed retired composite insulator silicon rubber needs to be cleaned to remove surface impurities.
According to the invention, the medium for cleaning the retired composite insulator silicon rubber is water or an organic solvent.
According to the present invention, the organic solvent is selected from one or more of methanol, ethanol, acetone, tetrahydrofuran, acetates and glycol derivatives, preferably one or more of methanol, ethanol, acetone and tetrahydrofuran, more preferably methanol or ethanol, such as ethanol. The low-boiling-point organic solvent can dry the cleaned product in a shorter time and at a lower temperature, so that the aim of saving energy is fulfilled.
According to the invention, the cleaning mode can adopt an ultrasonic cleaning mode and/or a mechanical oscillation cleaning mode. The cleaning time is selected as required.
In the invention, after being cleaned, the decommissioned composite insulator silicone rubber needs to be crushed to obtain the decommissioned composite insulator silicone rubber powder so as to realize the recycling of the decommissioned composite insulator silicone rubber, and the obtained silicone rubber powder is used as a rubber powder filler and added into a matrix material to prepare the composition.
According to the invention, the decommissioned composite insulator silicone rubber is crushed, firstly, the cleaned silicone rubber is pretreated on a slicer and/or a granulator to prepare a prefabricated product, and then, the prefabricated product is crushed in a rubber crusher and/or a crusher to obtain the decommissioned composite insulator silicone rubber powder.
The inventor finds that the ex-service composite insulator silicone rubber powder can be added into a matrix material as a filler to prepare a composition, so that the ex-service composite insulator silicone rubber can be recycled, but in the process of preparing the composition, for some matrix materials, after the ex-service composite insulator silicone rubber powder is added into the matrix material as the filler, the rubber powder and the matrix material cannot be well compatible, and an obvious interface exists between the rubber powder and the matrix material, so that the obtained composition has poor mechanical properties, and the ex-service composite insulator silicone rubber powder can be subjected to surface modification treatment for improving the interface compatibility and the bonding force of the rubber powder and the matrix material.
The inventor finds that the surface treatment is carried out on the silicon rubber powder of the retired composite insulator, and the silicon rubber powder is bonded with the matrix material, so that the compatibility of the silicon rubber powder and the matrix is enhanced, the interface bonding force between the silicon rubber powder and the matrix is enhanced, and the performance of the composition is improved.
According to the invention, the treatment step of the decommissioned composite insulator silicone rubber further comprises the following steps: and carrying out surface modification on the obtained ex-service composite insulator silicone rubber powder.
According to the invention, the surface modification treatment is carried out on the silicone rubber powder of the retired composite insulator by adopting a coupling agent, and a group on the coupling agent is bonded with the retired composite insulator.
In the invention, the surface modification treatment is carried out on the retired composite insulator silicone rubber powder by adopting the coupling agent, and the coupling agent enables the rubber powder and the interface of the matrix material to form a chemical bond, thereby enhancing the interface bonding strength between the rubber powder and the matrix material and improving the performance of the composition.
According to the invention, the coupling agent is chosen from silane coupling agents or titanate coupling agents.
According to the invention, the silane coupling agent is selected from one or more of gamma-aminopropyltriethoxysilane (KH-550), gamma-methacryloxypropyltrimethoxysilane (KH-570), vinyltriethoxysilane (YDH-151) and gamma- (2, 3-epoxypropoxy) propyltriethoxysilane (KH-560), preferably from one or more of KH-550, KH-570 and YDH-151, and more preferably from YDH-151; and/or
The titanate coupling agent is one or two selected from tetraisopropyl titanate, tetra-n-butyl titanate, isopropyl tri (isostearyl) titanate (KR-TTS), isopropyl tri (dioctyl pyrophosphoryl) titanate (KR-38S) and isopropyl di (methacryloyl) isostearyl titanate (KR-7).
According to the invention, the specific process for treating the silicone rubber powder of the retired composite insulator by using the coupling agent comprises the following steps: preparing a coupling agent and an alcohol organic solvent into a solution, facilitating the dispersion of the coupling agent on the surface of rubber powder, then spraying the solution into the decommissioned composite insulator silicone rubber powder one to many times, stirring for 5-30 min, preferably 10-25 min, filtering and drying after the reaction is finished, and obtaining the modified decommissioned composite insulator silicone rubber powder.
According to the invention, the addition amount of the coupling agent is 0.5-1.2%, preferably 0.8-1.0%, for example 1% of the mass of the rubber powder of the ex-service composite insulator silicone rubber powder to be subjected to surface treatment, wherein the weight of the ex-service composite insulator silicone rubber powder is 100%.
In another aspect, the present invention provides a method for preparing a silicone rubber composition, preferably a method for preparing a silicone rubber composition according to the first aspect of the present invention, comprising the steps of:
step 1, recycling the ex-service composite insulator silicone rubber, and treating to obtain ex-service composite insulator silicone rubber powder;
according to the invention, in the step 1, the ex-service composite insulator silicone rubber is waste composite insulator silicone rubber, the ex-service composite insulator silicone rubber is recycled and is added into a matrix material as a filler to prepare the composition, and the ex-service composite insulator silicone rubber needs to be treated to obtain ex-service composite insulator silicone rubber powder which is better mixed with the matrix material.
In the invention, a lot of impurities exist on the surface of the silicon rubber of the retired composite insulator, and the impurities on the surface need to be removed during application so as to be better mixed with a matrix material.
According to the invention, in step 1, the treatment of the decommissioned composite insulator silicone rubber comprises cleaning the decommissioned composite insulator silicone rubber.
According to the invention, in the step 1, the medium for cleaning the retired composite insulator silicone rubber is water or an organic solvent, and impurities on the surface layer of the silicone rubber are removed.
According to the present invention, in step 1, the organic solvent is selected from one or more of methanol, ethanol, acetone, tetrahydrofuran, acetates, and glycol derivatives, preferably methanol, ethanol, acetone, or tetrahydrofuran, more preferably methanol or ethanol, such as ethanol. The low-boiling-point organic solvent can dry the cleaned product in a shorter time and at a lower temperature, so that the aim of saving energy is fulfilled.
According to the invention, the cleaning mode can adopt an ultrasonic cleaning mode and/or a mechanical oscillation cleaning mode.
In the invention, after the retired composite insulator silicon rubber is cleaned, the silicon rubber powder is obtained by crushing treatment so as to realize the recycling of the silicon rubber, and the obtained silicon rubber powder is used as rubber powder filler to be added into a matrix material to prepare the composition.
According to the invention, the decommissioned composite insulator silicone rubber is crushed, firstly, the cleaned silicone rubber is pretreated on a slicer and/or a granulator to prepare a prefabricated product, and then, the prefabricated product is crushed in a rubber crusher and/or a crusher to obtain the decommissioned composite insulator silicone rubber powder.
According to the invention, the grain diameter or mesh number of the obtained decommissioned composite insulator silicone rubber powder is 50-300 meshes, preferably 200-300 meshes. The rubber powder with the mesh number of more than 300 greatly increases the manufacturing cost.
The inventor finds that the ex-service composite insulator silicone rubber powder can be added into a matrix material as a filler to prepare a composition, so that the ex-service composite insulator silicone rubber can be recycled, but in the process of preparing the composition, for some matrix materials, after the ex-service composite insulator silicone rubber powder is added into the matrix material as the filler, the rubber powder and the matrix material cannot be well compatible, and an obvious interface exists between the rubber powder and the matrix material, so that the obtained composition has poor mechanical properties, and the ex-service composite insulator silicone rubber powder can be subjected to surface modification treatment for improving the interface compatibility and the bonding force of the rubber powder and the matrix material.
The inventor finds that the surface treatment is carried out on the silicon rubber powder of the retired composite insulator, and the silicon rubber powder is bonded with the matrix material, so that the compatibility of the silicon rubber powder and the matrix is enhanced, the interface bonding force between the silicon rubber powder and the matrix is enhanced, and the performance of the composition is improved.
According to the invention, in the step 1, the treatment of the ex-service composite insulator silicone rubber further comprises surface modification treatment, preferably, coupling agent is adopted to carry out surface modification treatment on the ex-service composite insulator silicone rubber powder, and a group on the coupling agent is bonded with the ex-service composite insulator.
According to the invention, the coupling agent is chosen from silane coupling agents or titanate coupling agents.
In the invention, the surface modification treatment is carried out on the retired composite insulator silicone rubber powder by adopting the coupling agent, and the coupling agent enables the rubber powder and the interface of the matrix material to form a chemical bond, thereby enhancing the interface bonding strength between the rubber powder and the matrix material and improving the performance of the composition.
According to the invention, the silane coupling agent is selected from one or more of gamma-aminopropyl triethoxysilane (KH-550), gamma-methacryloxypropyl trimethoxysilane (KH-570), vinyl triethoxysilane (YDH-151) and gamma- (2, 3-epoxypropoxy) propyl triethoxysilane (KH-560); and/or
According to the invention, the titanate coupling agent is selected from one or two of tetraisopropyl titanate, tetra-n-butyl titanate, isopropyltris (isostearoyl) titanate (KR-TTS), isopropyltris (dioctylphosphato) titanate (KR-38S), isopropylbis (methacryloyl) isostearoyl titanate (KR-7).
According to the invention, the specific process for treating the silicone rubber powder of the retired composite insulator by using the coupling agent comprises the following steps: preparing a coupling agent and an alcohol organic solvent into a solution, facilitating the dispersion of the coupling agent on the surface of rubber powder, then spraying the solution into the decommissioned composite insulator silicone rubber powder one to many times, stirring for 5-30 min, preferably 10-25 min, filtering and drying after the reaction is finished, and obtaining the modified decommissioned composite insulator silicone rubber powder.
According to the invention, the addition amount of the coupling agent is 0.5-1.2%, preferably 0.8-1.0%, for example 1% of the mass of the rubber powder of the ex-service composite insulator silicone rubber powder to be subjected to surface treatment, wherein the weight of the ex-service composite insulator silicone rubber powder is 100%.
Step 2, mixing the decommissioned composite insulator silicone rubber powder with room-temperature cured silicone rubber;
in the invention, in the step 2, the rubber powder of the retired composite insulator silicon rubber is treated by a coupling agent or is not treated by the coupling agent.
In the invention, room temperature curing silicone Rubber (RTV) refers to a silicone rubber of which active functional groups at two ends of a molecular chain generate a cross-linking reaction under the action of water molecules or a certain catalyst to generate a three-dimensional network structure. The curing agent can be used as a matrix material of the rubber powder filler, can complete the curing process at room temperature, does not need to be heated, and achieves the purpose of energy conservation. The strength of the room temperature curing silicone rubber is low, the mechanical property of the room temperature curing silicone rubber needs to be further improved, and the composite insulator silicone rubber powder is added into the room temperature curing silicone rubber as a filler, so that the mechanical property of the room temperature curing silicone rubber is hopeful to be improved.
In the present invention, the source of the room temperature curing silicone rubber is not particularly limited, and it may be a self-made or commercially available silicone rubber, preferably a commercially available room temperature curing silicone rubber RTV-668 available from Silicones technology.
The inventor finds that the ex-service composite insulator silicone rubber powder is added into room temperature curing silicone rubber as a filler and is cured to obtain the ex-service composite insulator silicone rubber powder/room temperature curing silicone rubber composition, when the addition amount of the ex-service composite insulator silicone rubber powder is within a certain range, the mechanical property of the composition can be improved, the addition amount of the rubber powder is too large, and the mechanical property of the obtained composition is poor because the rubber powder particles have large specific surface area and can be agglomerated and cannot be uniformly dispersed in the room temperature curing silicone rubber.
According to the invention, the addition amount of the decommissioned composite insulator silicone rubber powder is 5-40%, more preferably 5-35%, and more preferably 5-10%, wherein the weight of the room-temperature cured silicone rubber is 100%.
According to the invention, in order to ensure that the room temperature curing silicone rubber and the decommissioned composite insulator silicone rubber powder are uniformly mixed, the decommissioned composite insulator silicone rubber powder and the room temperature curing silicone rubber are firstly premixed, and then added into a mixing device for high-speed mixing after uniform premixing, and are stirred uniformly to obtain a mixture.
According to the invention, the mixing device is selected from a high-speed stirrer and/or a two-roll mixer.
According to the invention, the stirring temperature of the high-speed stirrer is 20-30 ℃, preferably room temperature is 25 ℃, the rotating speed is 3000-.
According to the invention, the mixing temperature of the double-roller mixing mill is 20-30 ℃, preferably the room temperature is 25 ℃, the rotating speed is 100-.
And 3, pouring the mixture obtained in the step 2 into a mold, and curing.
In the present invention, step 3 comprises pouring the mixture obtained in step 2 into a mold and curing.
According to the invention, in step 3, the curing temperature is 15-30 ℃, the humidity is 40-60%, preferably the curing temperature is 20-25 ℃, the humidity is 45-55%, for example, the room temperature is 25 ℃, and the humidity is 50%.
According to the invention, in step 3, the mixture is poured into a mold and cured in the mold, wherein the curing time is 12-48 hours, preferably 12-36 hours, more preferably 12-24 hours, for example 24 hours.
According to the invention, step 3 further comprises: and demolding the cured product in the mold, and continuously curing to obtain the silicone rubber composition.
According to the invention, the time for curing is 2 to 10 days, preferably 2 to 8 days, for example 7 days, after demoulding.
Examples
The present invention is further described below by way of specific examples. However, these examples are only illustrative and do not set any limit to the scope of the present invention.
Example 1
Recycling the silicon rubber of the retired composite insulator, cleaning the silicon rubber with ethanol, slicing and crushing the silicon rubber to obtain the silicon rubber powder of the retired composite insulator;
weighing 10g of ex-service composite insulator silicone rubber powder, adding the 10g of ex-service composite insulator silicone rubber powder into 100g of room-temperature curing silicone rubber, preliminarily mixing, adding the mixture into a high-speed stirrer, stirring at the temperature of 25 ℃, at the rotating speed of 27000r/min for 10min, and uniformly stirring and mixing to obtain a mixture;
pouring the mixture into a mold, and curing for 24 hours at 25 ℃ in an environment with humidity of 50% to obtain a cured intermediate product;
the cured intermediate was demolded and left to stand at 25 ℃ under 50% humidity for 7 days.
Example 2
The preparation process of example 1 was repeated except that 20g of the decommissioned composite insulator silicone rubber powder was weighed, and the rest was the same as in example 1.
Example 3
The preparation process of example 1 was repeated except that 30g of the decommissioned composite insulator silicone rubber powder was weighed, and the rest was the same as in example 1.
Example 4
The preparation process of example 1 was repeated except that 40g of the decommissioned composite insulator silicone rubber powder was weighed, and the rest was the same as example 1.
Example 5
Recycling the retired composite insulator silicon rubber, cleaning with ethanol, slicing and crushing to obtain retired composite insulator silicon rubber powder, adding 1g of silane coupling agent YDH-151 into 9g of absolute ethanol to prepare a solution, spraying the solution into 100g of composite insulator silicon rubber powder by 5 times, and stirring for 10min to obtain the retired composite insulator silicon rubber powder modified by the silane coupling agent YDH-151;
weighing 30g of silane coupling agent YDH-151 modified ex-service composite insulator silicone rubber powder, adding the powder into 100g of room-temperature curing silicone rubber, premixing, adding the mixture into a high-speed stirrer, stirring at the stirring temperature of 25 ℃, the rotation speed of 27000r/min and the stirring time of 10min, and uniformly mixing to obtain a mixture;
pouring the mixture into a mold, and curing for 24 hours at 25 ℃ in an environment with humidity of 50% to obtain a cured intermediate product;
the cured intermediate was demolded and left to stand at 25 ℃ under 50% humidity for 7 days.
Example 6
The procedure in example 5 was repeated except that the silane coupling agent KH-550 was used as the coupling agent, and the procedure was otherwise the same as in example 5.
Example 7
The procedure of example 5 was repeated except that the silane coupling agent KH-570 was used as the coupling agent, and the procedure was otherwise the same as in example 5.
Example 8
The procedure of example 5 was repeated except that tetraisopropyl titanate was used as the coupling agent, and the procedure was otherwise the same as in example 5.
Example 9
The preparation process of example 5 was repeated except that 5g of silane coupling agent YDH-151 modified ex-service composite insulator silicone rubber powder was added, and the rest was the same as example 5.
Example 10
The preparation process of example 5 was repeated except that 10g of silane coupling agent YDH-151 modified ex-service composite insulator silicone rubber powder was added, and the rest was the same as in example 5.
Example 11
The preparation process of example 5 was repeated except that 20g of silane coupling agent YDH-151 modified ex-service composite insulator silicone rubber powder was added, and the rest was the same as example 5.
Example 12
The preparation process of example 5 was repeated except that 35g of silane coupling agent YDH-151 modified ex-service composite insulator silicone rubber powder was added, and the rest was the same as example 5.
Example 13
The preparation process of example 5 was repeated except that 40g of silane coupling agent YDH-151 modified ex-service composite insulator silicone rubber powder was added, and the rest was the same as example 5.
Example 14
The preparation process of example 5 was repeated, except that 20g of silane coupling agent YDH-151 modified rubber powder of the retired composite insulator silicone rubber was added, pre-mixed and mixed in a two-roll mixer at 25 ℃, 1000r/min and 30min, and the rest was the same as example 5.
Example 15
The preparation process of example 5 was repeated, except that 30g of silane coupling agent YDH-151 modified rubber powder of the retired composite insulator silicone rubber was added, pre-mixed and mixed in a two-roll mixer at 25 ℃, 1000r/min and 30min, and the rest was the same as example 5.
Comparative example
Comparative example 1
Pouring 100g of room temperature curing silicone rubber into a mold, and curing for 24 hours at 25 ℃ in an environment with humidity of 50% to obtain a curing intermediate product;
the cured intermediate was demolded and left to stand at 25 ℃ under 50% humidity for 7 days.
Examples of the experiments
Experimental example 1
The final products obtained in examples 1-4 and comparative example 1 were subjected to mechanical property tests according to GB/T13477-2017 at a tensile rate of 500mm/min, and the test results are shown in Table 1.
TABLE 1
As can be seen from Table 1, the tensile strength of the room temperature curing silicone rubber composition with the addition of the rubber powder is higher than that of the room temperature curing silicone rubber without the addition of the rubber powder, and when the addition amount of the rubber powder is 10g, namely the addition amount of the rubber powder is 10 percent of that of the room temperature curing silicone rubber, the tensile strength of the final product is improved by 15.4 percent compared with the room temperature curing silicone rubber without the addition of the rubber powder. The added retired composite insulator composite silicone rubber powder plays a role in reinforcement.
Experimental example 2
The final products obtained in example 3, examples 5 to 8 and comparative example 1 were subjected to mechanical property tests, and the test results are shown in table 2.
TABLE 2
As can be seen from Table 2, the tensile strength of the composition to which the coupling agent-modified rubber powder of the retired composite insulator was added was higher than that of the composition to which the unmodified rubber powder was added. The result shows that after the modification of the coupling agent, the retired composite insulator silicone rubber powder and the room temperature curing silicone rubber have strong interface binding force, and further the mechanical property of the composition is improved. It can also be seen that the tensile strength of the composition with the gum powder treated with tetraisopropyl titanate and YDH-151 is greater than that of the room temperature silicone rubber without the gum powder added.
Experimental example 3
The final products of example 5, examples 9-13 and comparative example 1 were subjected to mechanical property tests, and the test results are shown in table 3.
TABLE 3
As can be seen from Table 3, when the addition amount of the YDH-151 modified ex-service composite insulator silicone rubber powder is 5-35%, the tensile strength of the composition is greater than that of the room-temperature silicone rubber without the addition of the rubber powder, and when the addition amount of the rubber powder is more than 35%, the tensile strength of the composition is reduced. It can also be seen that the tensile stress Se (100) and hardness of the composition added with the YDH-151 modified and retired composite insulator silicon rubber powder are both higher than those of the composition without the rubber powder.
Experimental example 4
The final products obtained in examples 5, 11, 14, 15 and comparative example 1 were subjected to mechanical property tests, and the test results are shown in table 4.
TABLE 4
As can be seen from Table 4, when the retired composite silicone rubber powder subjected to YDH-151 modification treatment and room temperature curing silicone rubber are used for preparing a composition, the tensile strength of the composition obtained by mixing the compound with a high-speed stirrer is greater than that of the composition mixed by a two-roll mixing mill.
Experimental example 5
The final products obtained in examples 5, 9-12 and comparative example 1 were subjected to thermogravimetric analysis (TGA) tests, the results of which are shown in table 5.
TABLE 5
As can be seen from Table 5, the temperatures of 5% and 10% weight loss of the cured specimens of the silicone rubber with various amounts of YDH-151 modified rubber powder were lower than the temperatures of 5% and 10% weight loss of the cured specimens of the silicone rubber without addition of rubber powder. The maximum degradation rate temperature of the cured sample strips added with 10g, 20g, 30g and 35g of YDH-151 modified rubber powder is higher than that of the cured sample strips without the rubber powder.
Experimental example 6
The final products obtained in example 5, examples 9 to 11 and comparative example 1 were subjected to Dynamic Mechanical Thermal Analysis (DMTA) tests, the results of which are shown in Table 6.
TABLE 6
As can be seen from Table 6, the storage modulus E' at 30 ℃ of the composition added with the YDH-151 treated retired composite insulator rubber powder is greater than that of the room-temperature silicone rubber without added retired composite insulator rubber powder.
Experimental example 7
The final products obtained in examples 5, 9 to 12 and comparative example 1 were subjected to Scanning Electron Microscope (SEM) tests, and the results are shown in fig. 1 to 6.
As can be seen from the graphs in FIGS. 1-6, the fracture surface of the cured sample strip of the rubber powder added with YDH-151 modification treatment is smoother than that of the cured sample strip without the rubber powder, and after the rubber powder is added, rubber powder particles can be observed on the fracture surface, and as can be seen from the graphs in FIGS. 2-6, the small bright spots are the rubber powder particles, and the rubber powder particles are dispersed more uniformly.
The invention has been described in detail with reference to the preferred embodiments and illustrative examples. It should be noted, however, that these specific embodiments are only illustrative of the present invention and do not limit the scope of the present invention in any way. Various modifications, equivalent substitutions and alterations can be made to the technical content and embodiments of the present invention without departing from the spirit and scope of the present invention, and these are within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (10)
1. The silicone rubber composition is characterized by comprising room-temperature cured silicone rubber and composite insulator silicone rubber powder, wherein the composite insulator silicone rubber powder is obtained by treating retired composite insulator silicone rubber.
2. The silicone rubber composition according to claim 1, wherein the composite insulator silicone rubber powder is present in the silicone rubber composition in an amount of 5% to 40%, preferably 5% to 35%, based on 100% by weight of the room-temperature-curing silicone rubber.
3. The silicone rubber composition according to claim 1 or 2, characterized in that the treatment method comprises: and recycling the decommissioned composite insulator silicone rubber, and cleaning and crushing to obtain the decommissioned composite insulator silicone rubber powder.
4. Silicone rubber composition according to claim 3, characterised in that the cleaning medium is water or an organic solvent, preferably an organic solvent,
the organic solvent is selected from one or more of methanol, ethanol, acetone, tetrahydrofuran, acetate and glycol derivatives, and preferably one or more of methanol, ethanol, acetone and tetrahydrofuran.
5. The silicone rubber composition according to claim 3 or 4, characterized in that the treatment method further comprises: and carrying out surface modification on the obtained ex-service composite insulator silicone rubber powder.
6. The silicone rubber composition according to claim 5, wherein the surface modification is a modification of the rubber powder of the ex-service composite insulator silicone rubber by using a coupling agent, and the amount of the coupling agent is 0.5-1.2%, preferably 0.8-1.0%, wherein the amount of the coupling agent is 100% by weight of the rubber powder of the ex-service composite insulator silicone rubber.
7. The silicone rubber composition according to claim 6,
the coupling agent comprises a silane coupling agent and a titanate coupling agent,
the silane coupling agent is selected from one or more of gamma-aminopropyl triethoxysilane, gamma-methacryloxypropyl trimethoxysilane, vinyl triethoxysilane and gamma- (2, 3-epoxypropoxy) propyl triethoxysilane; and/or
The titanate coupling agent is one or two of tetraisopropyl titanate, tetra-n-butyl titanate, isopropyl tri (isostearyl) titanate, isopropyl tri (dioctyl pyrophosphoryl) titanate and isopropyl di (methacryloyl) isostearyl titanate.
8. A method for preparing a silicone rubber composition, characterized in that the method comprises the steps of:
step 1, recycling the ex-service composite insulator silicone rubber, and treating to obtain ex-service composite insulator silicone rubber powder;
step 2, mixing the decommissioned composite insulator silicone rubber powder with room-temperature cured silicone rubber;
and 3, pouring the mixture obtained in the step 2 into a mold, and curing.
9. The method according to claim 7, wherein in step 1, the treatment process comprises washing and crushing, the washing medium is water or an organic solvent, preferably an organic solvent,
the organic solvent is selected from one or more of methanol, ethanol, acetone, tetrahydrofuran, acetates and glycol derivatives;
the crushing specific process is that the cleaned decommissioned composite insulator silicon rubber is pretreated on a slicer and/or a granulator and then crushed in a rubber crusher and/or a crusher.
10. The method of claim 9, wherein in the step 1, the treatment further comprises modification treatment, preferably modification treatment by a coupling agent, of the ex-service composite insulator silicone rubber powder,
the coupling agent is selected from silane coupling agent or titanate coupling agent,
the silane coupling agent is selected from one or more of gamma-aminopropyl triethoxysilane, gamma-methacryloxypropyl trimethoxysilane, vinyl triethoxysilane and gamma- (2, 3-epoxypropoxy) propyl triethoxysilane; and/or
The titanate coupling agent is selected from tetraisopropyl titanate, tetra-n-butyl titanate, isopropyl tri (isostearoyl) titanate, isopropyl tri (dioctyl pyrophosphoryl) titanate and isopropyl di (methacryloyl) isostearoyl titanate.
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