CN112375302A - Modified insulating rubber for alternating-current cable accessories and preparation method thereof - Google Patents
Modified insulating rubber for alternating-current cable accessories and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 claims abstract description 27
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- 230000003712 anti-aging effect Effects 0.000 claims description 12
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- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims description 10
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 10
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- 239000013543 active substance Substances 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 9
- -1 methyl phenyl methoxy Chemical group 0.000 claims description 7
- 238000004513 sizing Methods 0.000 claims description 7
- 235000021355 Stearic acid Nutrition 0.000 claims description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 6
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 6
- 229920002545 silicone oil Polymers 0.000 claims description 6
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- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- 239000011787 zinc oxide Substances 0.000 claims description 6
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 5
- 239000003921 oil Substances 0.000 claims description 5
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 claims description 5
- 239000005864 Sulphur Substances 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
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- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/28—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances natural or synthetic rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention provides an insulating rubber for modified alternating current cable accessories and a preparation method thereof. The electrical property and the mechanical property of the ethylene propylene diene monomer are regulated and controlled by adding a proper amount of white carbon black into the ethylene propylene diene monomer material; the adhesive property of the rubber is improved by adding a proper amount of adhesive; the ethylene propylene diene monomer material has changed properties through the optimization of the formula, and the conductivity can be controlled in a reasonable range in the process of ultrahigh voltage alternating current transmission, so that the safety and reliability of ultrahigh voltage alternating current transmission lines and cable accessories thereof are ensured.
Description
Technical Field
The invention belongs to the technical field of insulating rubber preparation, and particularly relates to insulating rubber for a modified alternating current cable accessory and a preparation method thereof.
Background
Power cable accessories are products for connecting cables to transmission and distribution lines and related distribution equipment, generally referring to the intermediate and terminal connections of the various cables in the cable lines, which together with the cables form the power transmission network. The cable accessories are mainly based on the characteristics of the cable structure, not only can the performance of the cable be recovered, but also the extension of the cable length and the connection of the terminal can be ensured. At present, cable manufacturers in China have maturely researched low-voltage and medium-voltage cable accessory insulating materials. In the research and development field of high-voltage (10 kV-220 kV) and ultrahigh-voltage (330 kV-750 kV) insulating materials, related documents are less reported.
At present, the silicon rubber and the ethylene propylene diene monomer are suitable for serving as insulating material base materials of cable accessories in the ultrahigh voltage field. Both the two rubbers have the performances of high and low temperature resistance, excellent electrical insulation performance, ozone resistance, high voltage resistance, weather resistance and the like. The silicon atoms of the silicon rubber are connected with methyl groups, the molecular flexibility is large, the interaction force among molecular chains is weak, so that the mechanical properties such as tensile strength, tear strength and the like of the vulcanized silicon rubber are poor, and the price of the vulcanized silicon rubber is higher than that of ethylene propylene diene monomer. Ethylene-propylene-diene rubber is a terpolymer of ethylene, propylene and a non-conjugated diene. The non-conjugated diene has the characteristics that the main chain is completely saturated, and only a small amount of unsaturated double bonds exist in the side chain, so that the ethylene propylene diene rubber has excellent weather resistance, heat resistance, acid and alkali resistance, excellent electric insulating property and corona resistance, and is more suitable for being used as the base material of the insulating material of high-voltage and ultrahigh-voltage alternating-current cable accessories. But the ethylene propylene diene monomer also has the problems of large dielectric loss, poor mechanical and adhesive properties and the like. The dielectric loss of the material in the ultrahigh-voltage alternating-current electric field generates heat, consumes energy and may cause thermal breakdown of the dielectric, so that a plurality of potential safety hazards exist. In addition, along with the improvement of the voltage-resistant grade, the requirements on the performances of the insulating material such as electrical property, mechanical property, aging property, forming property and the like are higher.
Therefore, in the research and development field of the insulation material of the AC cable accessory, an insulation material which has excellent performance and can be used for the extra-high voltage AC cable accessory is developed, and compared with a medium-low voltage insulation material, the insulation material has important significance for improving the core competitiveness of enterprises and developing the market.
Disclosure of Invention
The first technical problem to be solved by the invention is as follows: provided is an insulating rubber which has high adhesion and can be used for extra-high voltage AC cable accessories.
The second technical problem to be solved by the invention is: provides a preparation method of high-adhesiveness insulating rubber for extra-high voltage alternating current cable accessories.
The modified insulating rubber for the AC cable accessories according to the embodiment of the first aspect of the invention comprises the following preparation raw materials: ethylene propylene diene monomer, adhesive, reinforcing agent, vulcanizing agent, auxiliary crosslinking agent and auxiliary agent; the adhesive comprises xylene formaldehyde resin, the vulcanizing agent comprises at least one organic peroxide, and the reinforcing agent is white carbon black.
According to some embodiments of the invention, the adjuvant comprises the following preparation starting materials: the adhesive comprises an active agent, an anti-aging agent, a plasticizer, a structure control agent and a silane coupling agent.
According to some embodiments of the present invention, the modified insulating rubber for ac cable accessories is prepared from the following raw materials in parts by weight:
ethylene propylene diene monomer: 100 parts of (A); adhesive: 2-4 parts; vulcanizing agent: 3-5 parts; auxiliary crosslinking agent: 1-2 parts; active agent(s): 5-8 parts; an anti-aging agent: 1-2 parts; plasticizer: 6-10 parts of a solvent; reinforcing agent: 20-40 parts of a solvent; a structure control agent: 2-4 parts; silane coupling agent: 2-4 parts.
In the prior art, in order to obtain technical indexes meeting high electrical and mechanical properties, in addition to selecting ethylene propylene diene monomer with high ethylene content and low mooney viscosity as a base material, white carbon black with low impurity content, obvious reinforcing effect and excellent insulativity is selected as a filler in the formula design, and a binder is selected to improve the adhesive property of a rubber material.
According to some embodiments of the invention, the raw material for preparing the ethylene propylene diene monomer comprises a third monomer, wherein the third monomer is ENB; preferably, the content of the ENB is 2-10 wt%.
According to some embodiments of the invention, the raw materials for the production of the ethylene-propylene-diene monomer rubber comprise ethylene; preferably, the content of ethylene is 55 to 75 wt%.
According to some embodiments of the invention, the ethylene propylene diene monomer has a Mooney viscosity value of 20 to 30, the Mooney viscosity value being measured under the following conditions: ML 1+4, 125 ℃.
In the selection of the vulcanization system, a peroxide rubber system is selected. Carbon-carbon bonds generated by peroxide vulcanization can improve the electrical stability and the aging resistance of the rubber in a high-temperature environment.
According to some embodiments of the invention, the vulcanizing agent is at least one of dicumyl peroxide and 2, 5-dimethyl-2, 5-di-tert-butylperoxyhexane; preferably, the auxiliary crosslinking agent is at least one of triallyl isocyanurate, 2-mercaptobenzothiazole and sulfur.
According to some embodiments of the invention, the sulphur is preferably insoluble sulphur.
The assistant crosslinking agent in the vulcanization system can accelerate the vulcanization speed and improve the vulcanization efficiency.
According to some embodiments of the invention, the active agents are zinc oxide and stearic acid.
According to some embodiments of the invention, the white carbon black is a white carbon black prepared by a gas phase method.
The white carbon black prepared by the gas phase method has higher purity which can reach more than 99.8 percent, large specific surface area and better reinforcing effect.
The structure control agent is used for improving the structuring effect of the white carbon black filler and the rubber, preventing the viscosity from increasing in storage and facilitating industrial mass production.
According to some embodiments of the invention, the structure-controlling agent is methyl phenyl methoxy silicone oil.
The silane coupling agent has the functions of improving the compatibility and the dispersibility of the white carbon black filler in rubber and improving the reinforcing effect of the filler.
According to some embodiments of the invention, the silane coupling agent is at least one of bis- (γ -triethoxysilylpropyl) tetrasulfide and vinyltris (β -methoxyethoxy) silane.
The anti-aging agent is used for improving the thermo-oxidative aging resistance of the rubber material.
According to some embodiments of the invention, the antioxidant is antioxidant RD.
The plasticizer not only meets the plasticizing requirement, but also can improve aging shrinkage, improve poor bubble appearance of the sizing material and the like, improve the processing and forming performance, and reduce the cost.
According to some embodiments of the invention, the plasticizer is at least one of a paraffinic oil and a naphthenic oil.
In order to solve the second technical problem, the invention provides a method for preparing the modified insulating rubber for the AC cable accessories, which comprises the following steps:
s1: taking ethylene propylene diene monomer, an active agent, an anti-aging agent, a plasticizer, a reinforcing agent, a structure control agent, a silane coupling agent, a binder, a vulcanizing agent and an auxiliary crosslinking agent;
s2: plasticating and breaking the ethylene propylene diene monomer;
s3: adding an active agent, an anti-aging agent and a structure control agent into the ethylene propylene diene monomer treated in the step S2, and mixing for the first time;
s4: adding the binder, the silane coupling agent, part of the reinforcing agent and part of the plasticizer into the rubber mixed in the step S3, uniformly mixing, and then adding the rest reinforcing agent and the plasticizer to perform secondary mixing;
s5: after the rubber material mixed in the step S4 is milled, taking out and standing;
s6: and (4) after the sizing material treated in the step S5 is subjected to thin passing on an open mill, adding a vulcanizing agent and an auxiliary crosslinking agent into the sizing material, and performing vulcanization treatment after thin passing again to obtain the modified insulating rubber for the alternating current cable accessories.
In step S2, mastication and rubber breaking are performed in a pressurized internal mixer. The time for plastication and rubber breaking is 5-10 min.
In step S3, the time for the first mixing is 2-4 min.
In step S4, the mass ratio of the reinforcing agent added first to the remaining reinforcing agent added later is 1: 1. And (3) adding the silane coupling agent, part of the reinforcing agent and part of the plasticizer into the rubber mixed in the step S3, and uniformly mixing for 3-5 min. And adding the rest reinforcing agent and the plasticizer for secondary mixing for 3-5 min.
In the step S5, the taking-out and standing time is 16-24 h, and the taking-out and standing temperature is 23 +/-2 ℃.
According to some embodiments of the present invention, the temperature of the vulcanization treatment in the step S5 is 160-175 ℃, the time of the vulcanization treatment is 25-35 min, and the pressure of the vulcanization treatment is 10-14 MPa.
In the prior art, medium and low voltage cable accessory insulating materials are well researched, are applied to the field of ultrahigh voltage, and have higher requirements on electrical, mechanical, aging and forming performances. Although the ethylene propylene diene monomer base material has good heat resistance, acid and alkali resistance and excellent electrical insulation performance, if the ethylene propylene diene monomer base material is applied to the application field of extra-high voltage cable accessory materials, the defects of high dielectric loss, low breakdown strength, poor adhesion, poor mechanical performance and the like exist.
When the insulating material is in a high electric field intensity or high frequency, the dielectric loss value is too high, so that the material is seriously heated, the energy consumption is increased, and the risk of voltage breakdown exists.
The key points of the invention are as follows: and modifying ethylene propylene diene monomer. Aiming at the problems of large dielectric loss, poor mechanical and adhesive properties and the like of the ethylene propylene diene monomer, the ethylene propylene diene monomer is modified to meet the technical index requirements in the field of ultrahigh-voltage alternating-current cable accessories.
The modified insulating rubber for the AC cable accessories according to the embodiment of the invention has at least the following technical effects: the invention selects the ethylene propylene diene monomer as the base material, and realizes high electrical and mechanical properties by regulating and controlling the ethylene content and the Mooney viscosity value of the ethylene propylene diene monomer. The reinforcing agents such as white carbon black are selected, and the excellent insulating property and the efficient reinforcing effect of the reinforcing agents such as white carbon black are utilized, so that the electrical and mechanical properties are effectively improved. The adhesive property of the rubber is improved by adjusting the content of the adhesive. And the proper auxiliary crosslinking agent is selected, so that the crosslinking density is increased, the free ion content is reduced, and the electrical performance is further improved. In addition, the xylene formaldehyde resin is acidic, has certain influence on a peroxide curing system, can consume part of a curing agent, and enables the components to play the maximum synergistic effect by adjusting the dosage of the components in the formula. The insulating rubber provided by the invention has various properties, and can be used in the field of insulating materials for extra-high voltage alternating current cable accessories.
Detailed Description
The following are specific examples of the present invention, and the technical solutions of the present invention will be further described with reference to the examples, but the present invention is not limited to the examples.
Example one
The first embodiment of the invention is as follows: the modified insulating rubber for the AC cable accessories comprises the following chemical components in parts by weight: ethylene-propylene-diene monomer rubber having korean brocade lake designation KEP510 (ethylene content 71%, mooney viscosity value 23(ML 1+4, 125 ℃), third monomer ENB content 5.7%): 100 parts, zinc oxide: 5 parts, stearic acid: 1 part of an antioxidant RD: 1 part, paraffin oil: 8 parts of white carbon black: 32 parts, methyl phenyl methoxy silicone oil: 2.5 parts of bis- (gamma-triethoxysilylpropyl) tetrasulfide: 3 parts of xylene formaldehyde resin: 2 parts, dicumyl peroxide: 3 parts, insoluble sulfur: 0.5 part, 2-mercaptobenzothiazole: 0.5 part, triallyl isocyanurate: 1 part.
The preparation method of the insulating rubber comprises the following steps:
s1: putting the ethylene propylene diene monomer rubber with the formula amount into a pressurized internal mixer for plastifying for 8min and breaking;
s2: adding zinc oxide, stearic acid, an anti-aging agent RD, xylene formaldehyde resin and methyl phenyl methoxy silicone oil according to the formula ratio into a pressure type internal mixer for mixing for 3 min;
s3: adding 1/2 white carbon black, 1/2 paraffin oil and all bis- (gamma-triethoxysilylpropyl) tetrasulfide according to the formula ratio, and mixing for 3 min; adding the remaining 1/2 white carbon black and 1/2 naphthenic oil according to the formula amount, and mixing for 4 min;
s4: performing heat treatment after discharging: placing the rubber discharged from the internal mixer into an open mill, carrying out heat treatment at 190 ℃ for 10min, cooling to room temperature, and standing for 24 h;
s5: and (3) placing the material which is taken out and stands into an open mill for thinly passing for 2 times, then adding dicumyl peroxide, triallyl isocyanurate and insoluble sulfur into the open mill according to the formula amount, thinly passing for 10 times, and then vulcanizing and flaking to obtain the rubber. In this example, the temperature of the vulcanization treatment was 160 ℃, the time of the vulcanization treatment was 35min, and the pressure of the vulcanization treatment was 14 MPa.
Example two
The second embodiment of the invention adopts the same preparation method as the first embodiment to prepare the modified insulating rubber for the AC cable accessories, and the modified insulating rubber comprises the following chemical components in parts by weight: ethylene propylene diene monomer with Korea Jinhu brand of KEP 510: 100 parts, zinc oxide: 6 parts, stearic acid: 2 parts of an anti-aging agent RD: 1 part, paraffin oil: 5 parts, naphthenic oil: 5 parts of white carbon black: 20 parts of methyl phenyl methoxy silicone oil: 2.5 parts of bis- (gamma-triethoxysilylpropyl) tetrasulfide: 2 parts of xylene formaldehyde resin: 4 parts of 2, 5-dimethyl-2, 5-di-tert-butylperoxyhexane: 4 parts, 2-mercaptobenzothiazole: 0.3 part, triallyl isocyanurate: 1 part.
EXAMPLE III
The third embodiment of the invention adopts the same preparation method as the first embodiment to prepare the modified insulating rubber for the AC cable accessories, and the modified insulating rubber comprises the following chemical components in parts by weight: ethylene propylene diene monomer with Korea Jinhu brand of KEP 510: 100 parts, zinc oxide: 6 parts, stearic acid: 2 parts of an anti-aging agent RD: 1 part, paraffin oil: 4 parts, naphthenic oil: 4 parts of white carbon black: 30 parts of methyl phenyl methoxy silicone oil: 2.5 parts of vinyltris (. beta. -methoxyethoxy) silane: 3 parts of xylene formaldehyde resin: 4 parts, dicumyl peroxide: 4 parts, 2-mercaptobenzothiazole: 1 part, insoluble sulfur: 0.5 part.
Comparative example 1
The first comparative example of the present invention prepared an insulating rubber for cable accessories by the same preparation method as the first example, and the specific preparation raw materials were different from the first example in that ethylene propylene diene monomer was used as KEP7141, the rubber characteristics were ethylene content 51%, mooney viscosity 27(ML 1+4, 125 ℃), and the ENB content of the third monomer was 4.5%.
Comparative example No. two
The second preparation method is the same as the first preparation method, and the cable accessory insulating rubber is prepared, wherein the specific preparation raw materials are different from the first preparation method in that 2.5 parts of dicumyl peroxide serving as a vulcanizing agent is adopted.
Comparative example No. three
The third comparative example of the invention adopts the same preparation method as the first example to prepare the cable accessory insulating rubber, and the difference between the specific preparation raw material and the first example is that 4.5 parts of dicumyl peroxide is taken as a vulcanizing agent.
Comparative example No. four
The fourth comparative example of the invention adopts the same preparation method as the first example to prepare the cable accessory insulating rubber, and the specific preparation raw materials are different from the first example in that no auxiliary crosslinking agent is added.
Comparative example five
The fifth comparative example of the invention adopts the same preparation method as the first example to prepare the cable accessory insulating rubber, and the difference between the specific preparation raw materials and the first example is that 15 parts of white carbon black is added.
Comparative example six
Sixth comparative example of the present invention, a cable accessory insulating rubber was prepared by the same preparation method as in first example, and the difference between the specific preparation raw materials and the first example is that the paraffin oil was added in an amount of 12 parts.
Comparative example seven
The seventh preparation method of the invention is the same as the first preparation method of the first embodiment, and the cable accessory insulating rubber is prepared by using the specific preparation raw materials which are different from the first preparation method of the first embodiment and do not contain xylene formaldehyde resin.
Example of detection
The insulation rubbers for extra-high voltage cable accessories prepared in the first to third examples and the first to seventh comparative examples were measured for their respective molding properties such as hardness, tear strength, tensile strength, elongation at break, adhesive strength, volume resistivity, dielectric loss tangent, ac breakdown strength, aging properties, mooney viscosity. The method for testing the hardness is GB/T531.1-2008, the method for testing the tear resistance is GB/T5292008, the method for testing the tensile strength is GB/T5282009, the method for testing the elongation at break is GB/T5282009, the method for testing the bonding strength is GB/T5282009, the method for testing the volume resistivity is GB/T1692-2008, the method for testing the dielectric loss tangent is GB/T16932007, the method for testing the alternating current breakdown strength is GB/T16952005, the method for testing the aging performance is GB/T5282009, the method for testing the Mooney viscosity value is GB/T1232.12016, and the test results are shown in tables 1 and 2.
TABLE 1 results of measurements of properties of rubbers prepared in examples one to three
TABLE 2 results of measurements of properties of rubbers prepared in comparative examples one to seven
As can be seen from the results of the measurements in tables 1 and 2, the results of the performance test of the formulation of example one are the best in the combination of electrical, mechanical, aging, molding, etc. In the second and third embodiments, on the basis of the formula of the first embodiment, the selection and the dosage of the compounding ingredients are properly adjusted within the scope of the claims, the comprehensive performance is reduced, and the reasonable dosage in the formula can ensure that the components can play the maximum synergistic effect.
The difference between the formula of the first comparative example and the formula of the first example is that the ethylene propylene diene monomer base material is selected. The ethylene-propylene-diene monomer rubber of KEP510 (ethylene content 71%, Mooney viscosity value 23(ML 1+4, 125 ℃), third monomer ENB content 5.7%) was replaced by KEP7141 (ethylene content 51%, Mooney viscosity 27(ML 1+4, 125 ℃), third monomer ENB content 4.5%). The main changes in substrate properties are: the ethylene content in the ethylene propylene diene monomer is reduced from 71 percent to 51 percent, the Mooney viscosity is increased from 23 to 27, and the content of the ENB in the third monomer is close. The results of comparative example 1 show that the ethylene content is reduced, the electrical and mechanical properties are greatly reduced, the Mooney viscosity is large, and the aging performance is unchanged. The ethylene propylene diene monomer with high ethylene content and low Mooney is used as a base material, which is more favorable for realizing the technical index requirement.
Comparative example two compared to the formulation of example one, the vulcanizing agent dicumyl peroxide was reduced from 3.5 parts to 2.5 parts. As a result, it was found that the electrical, mechanical, and aging properties were deteriorated except for the increase in elongation at break. Indicating that the optimum amount of sulfiding agent is present. The amount of the vulcanizing agent is reduced, the crosslinking density is reduced, and the mechanical properties are weakened except for the fact that the elongation at break is increased (the crosslinking density is low, the molecular chain movement capability is enhanced). In addition, the crosslinking density of the rubber system decreases, and the "binding" effect on free ions in the system becomes weak, which may cause a decrease in electrical properties.
Compared with the formula of the first example, the vulcanizing agent dicumyl peroxide is increased from 3.5 parts to 4.5 parts, and the excessive crosslinking density has almost no influence on the electrical property, but can cause the reduction of elongation at break (the crosslinking density is high, the movement of molecular chains is limited) and the hardness is larger.
Compared with the formula of the first embodiment, the vulcanizing agent in the vulcanizing system is dicumyl peroxide, and an auxiliary crosslinking agent is not added, so that the mechanical, electrical and aging properties are obviously reduced. The assistant crosslinking agent can accelerate the vulcanization speed and improve the crosslinking efficiency, and meanwhile, short bonds in a rubber material system also participate in crosslinking reaction to generate a more compact crosslinking network structure. By adopting the peroxide vulcanizing agent, carbon-carbon bonds with poor movement performance exist in a network structure of a rubber system, the bond has poor movement performance and is difficult to slide under the action of external force (shown as low tear strength and low hardness). A small amount of vulcanization accelerator, such as sulfur, is added to participate in the generated monosulfur bond or polysulfide bond, so that the rubber has better flexibility, can regenerate after being fractured, can uniformly disperse concentrated stress and delay the damage, and thus the performances of machinery, aging and the like are enhanced.
Compared with the first embodiment, the fifth embodiment reduces the white carbon black dosage from 32 parts to 15 parts. The white carbon black has a good reinforcing effect, and can effectively improve the electrical and mechanical properties of the rubber base material by using a proper amount. The consumption of white carbon black is reduced, and the electrical and mechanical properties of the rubber are reduced to different degrees.
Comparative example six compared to example one, the amount of paraffin oil was increased from 8 parts to 12 parts. The paraffin oil has low molecular weight, can increase the rubber molecular distance, weaken the intermolecular force, enable the molecular chain to slide easily, macroscopically reduce the Mooney viscosity of the sizing material, increase the fluidity of the sizing material and facilitate the molding. However, the amount of paraffin oil is in an optimum range, and the amount is too much, which means that the formula is diluted, and the effect of each formula auxiliary agent is weakened, so that the mechanical property is reduced. In addition, paraffin oil has a low volume resistivity (about 1X 10)14Ω · cm), too large a quantity will degrade the electrical properties of the rubber.
Comparative example seven compared to example one, no xylene formaldehyde resin was added to the formulation. In the components of the cable accessories, the insulating material and the semi-conductive material are formed in a bonding mode, and if the bonding force of the insulating material and the semi-conductive material is insufficient, the insulating material and the semi-conductive material cannot be applied. The xylene formaldehyde resin is acidic, has a certain influence on a peroxide curing system, and can consume part of the curing agent. Therefore, in comparative example No xylene formaldehyde resin was added, which corresponds to an increase in the amount of vulcanizing agent, resulting in a slight increase in mechanical properties such as tensile strength and a decrease in elongation at break.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all equivalent modifications made by the present invention in the specification or directly or indirectly applied to the related technical field are included in the scope of the present invention.
Claims (10)
1. The utility model provides a modified is insulating rubber for AC cable annex which characterized in that: the method comprises the following preparation raw materials: ethylene propylene diene monomer, adhesive, reinforcing agent, vulcanizing agent, auxiliary crosslinking agent and auxiliary agent; the adhesive comprises xylene formaldehyde resin, the vulcanizing agent comprises at least one organic peroxide, and the reinforcing agent is white carbon black.
2. The modified insulating rubber for AC cable accessories as claimed in claim 1, wherein: the auxiliary agent comprises the following preparation raw materials: the adhesive comprises an active agent, an anti-aging agent, a plasticizer, a structure control agent and a silane coupling agent.
3. The modified insulating rubber for AC cable accessories as claimed in claim 2, wherein: the composition is prepared from the following raw materials in parts by weight:
ethylene propylene diene monomer: 100 parts of (A); adhesive: 2-4 parts; vulcanizing agent: 3-5 parts; auxiliary crosslinking agent: 1-2 parts; active agent(s): 5-8 parts; an anti-aging agent: 1-2 parts; plasticizer: 6-10 parts of a solvent; reinforcing agent: 20-40 parts of a solvent; a structure control agent: 2-4 parts; silane coupling agent: 2-4 parts.
4. The modified insulating rubber for AC cable accessories as claimed in any one of claims 1 to 3, wherein: the preparation raw material of the ethylene propylene diene monomer comprises a third monomer, wherein the third monomer is ENB; preferably, the content of the ENB is 2-10 wt%.
5. The modified insulating rubber for AC cable accessories as claimed in any one of claims 1 to 3, wherein: the raw material for preparing the ethylene propylene diene monomer comprises ethylene; preferably, the content of ethylene is 55 to 75 wt%.
6. The modified insulating rubber for AC cable accessories as claimed in any one of claims 1 to 3, wherein: the Mooney viscosity value of the ethylene propylene diene monomer is 20-30, and the Mooney viscosity value is measured under the following conditions: ML 1+4, 125 ℃.
7. The modified insulating rubber for AC cable accessories as claimed in any one of claims 1 to 3, wherein: the vulcanizing agent is at least one of dicumyl peroxide and 2, 5-dimethyl-2, 5-di-tert-butyl peroxy hexane; preferably, the auxiliary crosslinking agent is at least one of triallyl isocyanurate, 2-mercaptobenzothiazole and sulfur; preferably, the sulphur is insoluble sulphur.
8. The modified insulating rubber for AC cable accessories as claimed in claim 2 or 3, wherein: the plasticizer is at least one of paraffin oil and naphthenic oil; preferably, the active agents are zinc oxide and stearic acid; preferably, the structure control agent is methyl phenyl methoxy silicone oil; preferably, the silane coupling agent is at least one of bis- (gamma-triethoxysilylpropyl) tetrasulfide and vinyltris (beta-methoxyethoxy) silane.
9. A method for preparing insulating rubber for modified AC cable accessories is characterized by comprising the following steps: the method comprises the following steps:
s1: taking ethylene propylene diene monomer, an active agent, an anti-aging agent, a plasticizer, a reinforcing agent, a structure control agent, a silane coupling agent, a binder, a vulcanizing agent and an auxiliary crosslinking agent;
s2: plasticating and breaking the ethylene propylene diene monomer;
s3: adding an active agent, an anti-aging agent and a structure control agent into the ethylene propylene diene monomer treated in the step S2, and mixing for the first time;
s4: adding the binder, the silane coupling agent, part of the reinforcing agent and part of the plasticizer into the rubber mixed in the step S3, uniformly mixing, and then adding the rest reinforcing agent and the plasticizer to perform secondary mixing;
s5: after the rubber material mixed in the step S4 is milled, taking out and standing;
s6: and (4) after the sizing material treated in the step S5 is subjected to thin passing on an open mill, adding a vulcanizing agent and an auxiliary crosslinking agent into the sizing material, and performing vulcanization treatment after thin passing again to obtain the modified insulating rubber for the alternating current cable accessories.
10. The process for preparing a modified insulating rubber for AC cable accessories according to claim 9, wherein: the temperature of the vulcanization treatment is 160-175 ℃, the time of the vulcanization treatment is 25-35 min, and the pressure of the vulcanization treatment is 10-14 MPa.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114516990A (en) * | 2022-03-16 | 2022-05-20 | 重庆泰山电缆有限公司 | Ethylene propylene diene monomer insulating material with high mechanical property and preparation method thereof |
| CN115181368A (en) * | 2022-07-29 | 2022-10-14 | 江苏亨通高压海缆有限公司 | Preparation method and application of EPDM (ethylene-propylene-diene monomer) insulating rubber |
| CN115286874A (en) * | 2022-08-23 | 2022-11-04 | 江苏亨通叁原电工科技有限公司 | Rubber cable accessory material and preparation method thereof |
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| CN115286874A (en) * | 2022-08-23 | 2022-11-04 | 江苏亨通叁原电工科技有限公司 | Rubber cable accessory material and preparation method thereof |
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Application publication date: 20210219 |