CN114400112A

CN114400112A - Cold-resistant flexible mobile cable

Info

Publication number: CN114400112A
Application number: CN202210067737.XA
Authority: CN
Inventors: 石学军; 朱卫保; 李远清
Original assignee: Anhui Honghai Cable Co ltd
Current assignee: Anhui Honghai Cable Co ltd
Priority date: 2022-01-20
Filing date: 2022-01-20
Publication date: 2022-04-26
Anticipated expiration: 2042-01-20
Also published as: CN114400112B

Abstract

The invention relates to a cold-resistant flexible mobile cable, and belongs to the technical field of special cables. The cable comprises a plurality of groups of composite wire cores inside and a cold-resistant rubber sleeve outside, wherein the composite wire cores are made by extruding and coating insulating silicon rubber on stranded copper wire cores, and the cold-resistant rubber sleeve is made by taking a copolymer of modified acrylate and vinyl trimethoxy silane as a matrix; fluorine-containing groups are introduced to the modified acrylate, so that the tolerance performance is improved, and the side chain length is increased by adopting oligomeric fluorine-containing glycol ether, so that the chain layer spacing is increased, and the problem of flexibility reduction caused by the introduction of branched chains is solved; vinyl trimethoxy silane is introduced into the modified rubber sleeve for block copolymerization, siloxane is introduced on a side chain, and the siloxane is crosslinked to form an interconnected network structure, so that the strength of the modified rubber sleeve is improved. The prepared cold-resistant rubber sleeve has the elongation at break of 72% under the environment of-40 ℃, and the prepared cable has the bending times of 85 times under the bending test of-40 ℃ and 90 degrees and has excellent cold resistance.

Description

Cold-resistant flexible mobile cable

Technical Field

The invention belongs to the technical field of special cables, and particularly relates to a cold-resistant flexible mobile cable.

Background

The cold-resistant cable is used for mechanical power supply and line control in alpine regions, and the cable is required to keep good elasticity and flexibility even under the action of external force under the ultralow temperature working condition.

In the prior art, the method for realizing the cold resistance of the cable is always the following methods:

1. the composite structure adopts the method that a plurality of protective layers are sleeved outside the wire core, such as a method of coating a polyimide film layer and the like, and the cable has complex manufacturing process and low production efficiency;

2. adding a low-temperature-resistant plasticizer, and adding a large amount of plasticizer into a sheath material of the outer layer of the cable to improve low-temperature flexibility, but the addition of the plasticizer reduces the mechanical property of the sheath and is easy to damage when being impacted by external force;

3. the acrylate rubber is adopted as a sheath material, has excellent cold resistance, but has poor solvent resistance and low mechanical strength, and can only be used on partial control lines.

Disclosure of Invention

In order to solve the technical problems mentioned in the background technology, the invention provides a cold-resistant flexible mobile cable.

The purpose of the invention can be realized by the following technical scheme:

a cold-resistant flexible mobile cable comprises a plurality of groups of composite wire cores inside and a cold-resistant rubber sleeve outside, wherein the composite wire cores are made by extruding, coating and stranding copper wire cores by insulating silicon rubber, and the cold-resistant rubber sleeve is made by taking a copolymer of modified acrylate and vinyl trimethoxy silane as a matrix;

specifically, the cold-resistant rubber sleeve comprises 55-70 parts by weight of modified acrylate, 32-37 parts by weight of vinyl trimethoxy silane, 0.6-0.8 part by weight of plasticizer, 1.5-3 parts by weight of vulcanizing agent and 3-6 parts by weight of composite auxiliary agent;

the cold-resistant rubber sleeve is prepared by the following steps:

step S1: taking modified acrylate, vinyl trimethoxy silane and tetrahydrofuran, stirring and mixing, then adding ammonium persulfate and deionized water, heating to 60 ℃, keeping the temperature, stirring and reacting for 27-33min, stirring and washing with deionized water after the reaction is finished, standing, and taking down-layer gel to obtain a copolymerization rubber material;

step S2: adding the copolymerization rubber material, the plasticizer and the composite auxiliary agent into an internal mixer, internally mixing for 2-3h at 135 +/-10 ℃, then adding a vulcanizing agent for mixing, controlling the mixing time to be not more than 15min, and immediately extruding into circulating cooling water after mixing to obtain a raw rubber sleeve;

step S3: and putting the raw rubber sleeve into a vulcanizing kettle for vulcanization molding to obtain the cold-resistant rubber sleeve.

Further, the plasticizer is any one of dilauryl phthalate and dioctyl sebacate.

Further, the vulcanizing agent is TMTD.

Further, the compound auxiliary agent comprises one or more of an anti-aging agent TK100, carbon black and an anti-scorching agent E80 which are mixed according to any proportion.

The modified acrylate was prepared by the following steps:

step A1: taking tetrafluorobutanediol, stirring and dissolving the tetrafluorobutanediol in dimethyl sulfoxide, then dispersing the composite catalytic powder in a dissolving solution, adding propylene oxide under a stirring state, carrying out ultrasonic oscillation reaction for 35-45min in ice water bath, carrying out suction filtration on the reaction solution to remove the composite catalytic powder, heating the filtrate to 60 ℃, stirring for 20-30min, removing the propylene oxide in the filtrate, heating to 130 +/-3 ℃, distilling, and taking fractions to obtain oligomeric fluorine-containing glycol ether;

step A2: mixing and dissolving acrylic acid and absolute ethyl alcohol, heating to 40-50 ℃, slowly dripping thionyl chloride under the stirring state, keeping the temperature and stirring for 20-25min after dripping is finished, then heating to 70 +/-2 ℃, stirring at high speed, volatilizing the absolute ethyl alcohol, and decomposing the thionyl chloride to obtain a vinyl acyl chloride monomer;

step A3: stirring and dissolving oligomeric fluorine-containing glycol ether in tetrahydrofuran, adding triethylamine, mixing to form a reaction system, placing the reaction system in a constant-temperature water bath at 0-5 ℃, slowly dropwise adding vinyl acyl chloride monomer into the reaction system, stirring, continuously keeping the temperature and stirring for reaction for 40-50min after dropwise adding is finished, washing the reaction solution for multiple times by using deionized water, and finally standing, layering, taking lower-layer oily liquid and drying to obtain the modified acrylate.

Further, the composite catalytic powder comprises zirconium oxide and zinc oxide, wherein the mass ratio of the zirconium oxide to the zinc oxide is 3: 1.

Further, the using ratio of tetrafluorobutanediol to propylene oxide is 1.1-1.2 mol: 1 mol.

Further, the amount ratio of acrylic acid to thionyl chloride is 1 mol: 1.3-1.4 mol.

Further, the dosage ratio of the oligomeric fluorine-containing glycol ether to the vinyl chloride monomer is 100 g: 15-22 mL.

The invention has the beneficial effects that:

the cold-resistant rubber sleeve of the cable is an acrylate rubber material, has good durability, has elongation at break of 72 percent at the temperature of-40 ℃, has the bending times of 85 times under the bending test of-40 ℃ and 90 degrees, and has excellent cold resistance.

The excellent cold-resistant and fracture-resistant mechanism mainly comes from the following two points:

1. the modified acrylate is prepared by reacting oligomeric fluorine-containing glycol ether and acyl chlorinated acrylic acid, and a fluorine-containing group is introduced into a polymerized monomer, so that on one hand, fluorine on a polymerized side chain protects a main chain and improves the tolerance performance of acrylate rubber, and on the other hand, the oligomeric fluorine-containing glycol ether is prepared by oligomerization of tetrafluorobutanediol and propylene oxide, and the length of the side chain is increased, so that the distance between chain layers is increased, the problem of flexibility reduction caused by introduction of a branched chain is solved, and the finally prepared modified rubber sleeve has good flexibility;

2. vinyl trimethoxy silane is introduced into the modified rubber sleeve for block copolymerization, siloxane is introduced on a side chain, and the siloxane is crosslinked to form an interconnected network structure, so that the strength of the cold-resistant rubber sleeve is improved.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.

Fig. 1 is a schematic sectional structure view of a cold-resistant flexible mobile cable according to the present invention.

In the figure:

10. a cold-resistant rubber sleeve; 20. and (4) a composite wire core.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

The modified acrylate prepared in this example was specifically prepared as follows:

step A1: 1.78kg of tetrafluorobutanediol is taken to be stirred and dissolved in 2.8L of dimethyl sulfoxide, 35g of zirconium oxide and 7g of zinc oxide are taken to be mixed, crushed and completely screened by a sieve with 80 meshes to obtain composite catalytic powder, then the composite catalytic powder is dispersed in a dissolving solution, 580g of propylene oxide is added at the stirring speed of 360rmp, ultrasonic oscillation reaction is carried out for 35min in ice water bath, 120 meshes of suction filtration are adopted for removing the composite catalytic powder in the reaction solution, the filtrate is firstly heated to 60 ℃ and stirred for 20min, the propylene oxide in the filtrate is removed, then the temperature is heated to 130 +/-3 ℃ for distillation, and the fraction is taken to obtain oligomeric fluorine-containing glycol ether;

step A2: taking 720g of acrylic acid and 1.5L of absolute ethyl alcohol, stirring, mixing, heating to 40 ℃, slowly dripping 1.15kg of thionyl chloride in a stirring state, keeping the temperature and stirring for 20min after dripping is finished, then heating to 70 +/-2 ℃, stirring at a high speed, volatilizing the absolute ethyl alcohol, and decomposing the thionyl chloride to obtain a vinyl acyl chloride monomer;

step A3: 1kg of oligomeric fluorine-containing glycol ether is taken, stirred, mixed and dissolved in 700mL of tetrahydrofuran, then 12mL of triethylamine is added, mixed to form a reaction system, the reaction system is placed in a constant-temperature water bath at 0 ℃, 150mL of vinyl chloride monomer is slowly dripped into the reaction system and stirred, the dripping is completed, the heat preservation and stirring reaction is continuously carried out for 50min, the reaction liquid is repeatedly washed for 3 times by deionized water, and finally, the mixture is stood for layering, the lower-layer oily liquid is taken and dried by a drying filter column, and the modified acrylate is obtained.

Example 2

step A1: 1.95kg of tetrafluorobutanediol is taken to be stirred and dissolved in 3.2L of dimethyl sulfoxide, 40g of zirconium oxide and 8g of zinc oxide are taken to be mixed, crushed and completely screened by a sieve with 80 meshes to obtain composite catalytic powder, then the composite catalytic powder is dispersed in a dissolving solution, 580g of propylene oxide is added at the stirring speed of 360rmp, ultrasonic oscillation reaction is carried out for 45min in ice water bath, 120 meshes of suction filtration are adopted for removing the composite catalytic powder from the reaction solution, the filtrate is firstly heated to 60 ℃ and stirred for 30min, the propylene oxide in the filtrate is removed, then the temperature is heated to 130 +/-3 ℃ for distillation, and the fraction is taken to obtain oligomeric fluorine-containing glycol ether;

step A2: taking 720g of acrylic acid and 2L of absolute ethyl alcohol, stirring, mixing, heating to 50 ℃, slowly dripping 1.66kg of thionyl chloride in a stirring state, keeping the temperature and stirring for 25min after dripping is finished, then heating to 70 +/-2 ℃, stirring at a high speed, volatilizing the absolute ethyl alcohol, and decomposing the thionyl chloride to obtain a vinyl acyl chloride monomer;

step A3: 1kg of oligomeric fluorine-containing glycol ether is taken, stirred, mixed and dissolved in 700mL of tetrahydrofuran, then 12mL of triethylamine is added, mixed to form a reaction system, the reaction system is placed in a constant-temperature water bath at 0-5 ℃, 220mL of vinyl chloride monomer is slowly dripped into the reaction system and stirred, the dripping is completed, heat preservation and stirring reaction is continuously carried out for 50min, the reaction liquid is repeatedly washed for 3 times by deionized water, and finally, the mixture is stood, layered, taken out of lower-layer oily liquid and dried by a drying filter column, so that the modified acrylate is obtained.

Example 3

In this embodiment, the cold-resistant rubber sleeve 10 is prepared by the following specific implementation process;

step S1: taking 550g of the modified acrylate prepared in the example 1, 320g of vinyl trimethoxy silane and 650mL of tetrahydrofuran, stirring and mixing, then taking 13g of ammonium persulfate and 100mL of deionized water, adding into the mixed solution, heating to 60 ℃, keeping the temperature, stirring and reacting for 27min, stirring and washing for 2 times by using deionized water after the reaction is finished, standing, and taking out the lower-layer gel to obtain a copolymerization rubber material;

step S2: mixing 10g of an anti-aging agent TK100 and 20g of carbon black to obtain a composite auxiliary agent, adding a copolymerization rubber material, 6g of dilauryl phthalate and the composite auxiliary agent into an internal mixer, internally mixing at 135 +/-10 ℃ for 2h, adding 15g of a vulcanizing agent TMTD, mixing for 15min, and extruding into circulating cooling water by using an extruder to obtain a raw rubber sleeve;

step S3: and (3) putting the raw rubber sleeve into a vulcanizing kettle, controlling the vulcanizing temperature to be 95 ℃, and vulcanizing for 5 hours to obtain the cold-resistant rubber sleeve 10.

Example 4

step S1: taking 700g of the modified acrylate prepared in the embodiment 2, 370g of vinyl trimethoxy silane and 750mL of tetrahydrofuran, stirring and mixing, then taking 18g of ammonium persulfate and 120mL of deionized water, adding into the mixed solution, heating to 60 ℃, keeping the temperature, stirring and reacting for 33min, stirring and washing for 2 times by using deionized water after the reaction is finished, standing, and taking out the lower-layer gel to obtain a copolymerization rubber material;

step S2: mixing 20g of age resister TK100, 20g of carbon black and 20g of scorch retarder E80 to form a composite auxiliary agent, adding a copolymerization rubber material, 8g of dioctyl sebacate and the composite auxiliary agent into an internal mixer, internally mixing at 135 +/-10 ℃ for 3h, adding 15g of vulcanizing agent TMTD, mixing for 15min, and extruding into circulating cooling water by an extruder after mixing to obtain a raw rubber sleeve;

Example 5

In this embodiment, a cold-resistant flexible mobile cable is prepared, as shown in fig. 1, and the specific implementation process is as follows:

step Z1: taking 4 groups of 5-core stranded copper wire cores, and coating 1mm of insulating silicon rubber (provided by Mitsui electric Co., Ltd., Wenzhou) on the surfaces of the stranded copper wire cores through an extruder to obtain a composite wire core 20;

step Z2: the composite wire core 20 was inserted into the cold-resistant rubber sleeve 10 prepared in example 3, and then softened with hot air and extrusion-compounded by an extruder to remove the inner gap, to obtain a cold-resistant flexible mobile cable.

Example 6

This example was carried out in the same manner as in example 5, and referring to fig. 1, the cold-resistant rubber sleeve 10 prepared in example 3 was replaced with the cold-resistant rubber sleeve 10 prepared in example 4.

The cold-resistant rubber sleeve 10 prepared in example 3 and example 4 is subjected to a cold-resistant elongation test, and the specific test method is as follows: 3 pieces of the samples of example 3 and example 4 were taken, cut to a length of 5cm, frozen at-40 ℃ and-60 ℃ for 5 hours, respectively, and then subjected to a tensile test to calculate the elongation at break, the specific data being shown in Table 1:

TABLE 1

	Elongation at break (-40 ℃ C. 5 h)/%)	Elongation at break (-60 ℃ C. 5 h)/%)
			Example 3	72	54
Example 4	69	52

As shown in the data in Table 1, the cold-resistant rubber sleeve 10 prepared in example 3 has an elongation at break of 72% at-40 ℃ and good toughness, and can maintain an elongation at break of 54% at-60 ℃ and have good low-temperature toughness.

The cables prepared in example 5 and example 6 were used to simulate low temperature bending resistance, and the test method was: the cables prepared in the embodiment 5 and the embodiment 6 are respectively taken to be 10cm, are frozen for 5 hours at the temperature of minus 40 ℃, are subjected to bending test by a bending machine, the bending angle is 90 degrees (the horizontal direction is 0 degree), the bending directions are consistent, whether cracks are visible at the bending part is observed after each 5 times of bending, the time interval of each time of bending is 3min, the number of times of bending of the cracks is recorded, and the specific data are shown in table 2:

TABLE 2

	Number of bending (-40 ℃ 90 ℃) per turn
		Example 5	85
Example 6	80

As can be seen from the data in Table 2, the cable prepared in example 5 has good low-temperature folding resistance, and cracks are visible only on the surface of the cold-resistant rubber sleeve 10 after being continuously bent for 85 times at-40 ℃.

In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.

Claims

1. A cold-resistant flexible mobile cable comprises a plurality of groups of composite wire cores (20) inside and a cold-resistant rubber sleeve (10) sleeved outside, and is characterized in that the cold-resistant rubber sleeve (10) is made of a copolymer of modified acrylate and vinyl trimethoxy silane as a matrix;

the preparation method of the modified acrylate comprises the following steps: stirring and dissolving oligomeric fluorine-containing glycol ether in tetrahydrofuran, adding triethylamine, mixing to form a reaction system, placing the reaction system in a constant-temperature water bath at 0-5 ℃, dropwise adding vinyl acyl chloride monomer into the reaction system, stirring, continuously keeping the temperature and stirring for reacting for 40-50min after dropwise adding, washing the reaction solution, standing, layering, and taking a lower layer to obtain the modified acrylate.

2. The cold-resistant flexible mobile cable according to claim 1, wherein the preparation method of the oligomeric fluorinated glycol ether comprises: and (2) taking tetrafluorobutanediol, stirring and dissolving the tetrafluorobutanediol into dimethyl sulfoxide, dispersing the composite catalytic powder into a dissolving solution, adding propylene oxide under a stirring state, carrying out ultrasonic oscillation reaction for 35-45min in an ice water bath, carrying out suction filtration on the reaction solution to remove the catalytic powder, heating the filtrate to 60 ℃, stirring for 20-30min, heating to 130 +/-3 ℃, distilling, and taking a fraction to obtain the oligomeric fluorine-containing glycol ether.

3. The cold-resistant flexible mobile cable according to claim 1, wherein the preparation method of the vinyl chloride monomer comprises the following steps: mixing and dissolving acrylic acid and absolute ethyl alcohol, heating to 40-50 ℃, dropwise adding thionyl chloride under the stirring state, keeping the temperature and stirring for 20-25min after dropwise adding is finished, and then heating to 70 +/-2 ℃ and stirring for reaction to obtain the vinyl acyl chloride monomer.

4. The cold-resistant flexible mobile cable as claimed in claim 2, wherein the composite catalytic powder comprises zirconium oxide and zinc oxide, and the mass ratio of the zirconium oxide to the zinc oxide is 3: 1.

5. The cold-resistant flexible mobile cable as claimed in claim 2, wherein the ratio of the amount of tetrafluorobutanediol to the amount of propylene oxide is 1.1-1.2 mol: 1 mol.

6. The cold-resistant flexible mobile cable as claimed in claim 3, wherein the ratio of the amount of acrylic acid to thionyl chloride is 1 mol: 1.3-1.4 mol.

7. The cold-resistant flexible mobile cable according to claim 1, wherein the ratio of the oligomeric fluorinated glycol ether to the vinyl chloride monomer is 100 g: 15-22 mL.