CN110591212A - High-strength tear-resistant sheath material and preparation method thereof - Google Patents
High-strength tear-resistant sheath material and preparation method thereof Download PDFInfo
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- CN110591212A CN110591212A CN201910860817.9A CN201910860817A CN110591212A CN 110591212 A CN110591212 A CN 110591212A CN 201910860817 A CN201910860817 A CN 201910860817A CN 110591212 A CN110591212 A CN 110591212A
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- 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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
Abstract
The invention discloses a high-strength tear-resistant sheath material and a preparation method thereof, and belongs to the technical field of high polymer materials. The product developed by the invention comprises EVA resin, linear low-density polyethylene, organic layered silicate, an anti-aging agent, an antioxidant and a lubricant, and in the preparation process, the components are weighed according to the composition of raw materials; mixing EVA resin, linear low-density polyethylene, organic layered silicate, an anti-aging agent and an antioxidant, kneading, adding a lubricant, continuously kneading, extruding, granulating, performing injection molding, and continuously stretching for 100-200 s under the tension of 3-5 MPa to obtain the high-strength tear-resistant sheath. The product obtained by the invention has good tear resistance.
Description
Technical Field
The invention discloses a high-strength tear-resistant sheath material and a preparation method thereof, and belongs to the technical field of high polymer materials.
Background
Because the using environment of the sheath material used for the cable needs to resist the influence of various factors such as heat, water, oxygen, ultraviolet rays and the like, and in the long-term using process, along with the acting of external force, the cable sheath also needs to meet good mechanical properties, especially tear resistance. In the national standard GB 12972-91 mining rubber flexible cable, the tear strength of the chloroprene sheath rubber of the flexible cable for coal mining machines and mobile cables of 0.66/1.14kV and below is required to be more than 7.5N/mm (according to the test of GB 2951.34-83).
The tear strength of the chloroprene rubber pure vulcanized rubber is only about 5.0N/mm generally. Therefore, the improvement of the tear resistance of the chloroprene rubber sheath depends on the selection of raw materials and the matching technology of the formula to a great extent. In addition, factors such as the vulcanization degree of the rubber and the test conditions are sensitive to the influence of the tear resistance of the chloroprene rubber.
In the prior art, for reinforcing chloroprene rubber, a technical means of adding a reinforcing agent such as carbon black is adopted more frequently. The influence of the added carbon black on the tear resistance of the chloroprene rubber is complex, the filling amount, the particle size and the number of active groups on the surface of the carbon black can cause different influences on the tear resistance of the chloroprene rubber, and although the tear strength of the chloroprene rubber can be obviously improved by adopting the proper type of carbon black, the tear strength is still higher than 7.5N/mm, and the influence is difficult to realize in actual production; the white carbon black is used as a reinforcing agent, has a very outstanding effect on improving the tear strength, but has the defect of high quality. Namely, the viscosity of the rubber material is increased along with the increase of the using amount of the rubber material, the temperature rise is accelerated in the mixing and extrusion processing processes, the scorching time is shortened, and the processing safety and the processing technological property are poor.
Therefore, how to maintain good processability and obviously improve the mechanical properties of the chloroprene rubber sheath product, especially the tear resistance, in the preparation process of the chloroprene rubber sheath product is one of the problems to be solved by the technical personnel in the field.
Disclosure of Invention
Aiming at the defects that the processing performance of the traditional sheath material is not enough and the tear resistance of the product cannot be further improved, the high-strength tear-resistant sheath material and the preparation method thereof are provided.
In order to solve the technical problems, the invention adopts the technical scheme that:
the high-strength tear-resistant sheath material comprises the following raw materials in parts by weight:
the preparation process of the organic layered silicate comprises the following steps:
taking 40-50 parts of layered silicate, 100-150 parts of strong acid solution, 100-130 parts of rare earth salt solution, 40-50 parts of gelatin solution with the mass fraction of 1-5% and 8-10 parts of ethyl orthosilicate in sequence according to parts by weight;
pouring the layered silicate and the strong acid solution into a hydrothermal kettle, carrying out hydrothermal reaction for 3-5 h, filtering, washing and drying to obtain dry pretreated silicate;
heating the dried pretreated silicate and the rare earth salt solution for ultrasonic reaction for 3-5 h, then adding a gelatin solution and tetraethoxysilane, continuing stirring for reaction, then concentrating, drying, roasting at a low temperature of 180 ℃ in an air atmosphere, heating to 600-680 ℃ under the protection of inert gas, preserving heat, carbonizing, cooling, and discharging to obtain the organic layered silicate.
The layered silicate is any one or more of hydrotalcite, muscovite, montmorillonite and sepiolite.
The strong acid solution is 3-5% by mass; the strong acid is any one of hydrochloric acid, sulfuric acid or nitric acid.
The rare earth salt solution is a rare earth salt solution with the mass fraction of 1-5%; the rare earth salt is any one or more of cerium nitrate, cerium chloride and lanthanum nitrate.
The anti-aging agent is any one of anti-aging agent 4020, anti-aging agent RD or anti-aging agent NBC.
The antioxidant is any one of antioxidant 1010, antioxidant 1076 or antioxidant 168.
The lubricant is any one of magnesium stearate, calcium stearate or zinc stearate.
A high-strength tear-resistant sheath material is prepared by the following steps:
(1) weighing the components according to the composition of the raw materials;
(2) mixing EVA resin, linear low-density polyethylene, organic layered silicate, an anti-aging agent and an antioxidant, kneading, adding a lubricant, continuously kneading, extruding, granulating, performing injection molding, and continuously stretching for 100-200 s under the tension of 3-5 MPa to obtain the high-strength tear-resistant sheath material.
Has the advantages that:
according to the technical scheme, the organic layered silicate is added into a resin system, the lubricant is added later, and in the kneading process, firstly, a high-viscosity kneading process is performed, in the process, the organic layered silicate can be uniformly inserted into molecular chains of EVA resin and polyethylene resin matrixes, and the organic layered silicate is more beneficial to inserting linear molecular chains of the EVA resin and the polyethylene resin into an organic silicate lamellar structure, so that lamellar gaps are enlarged, and a certain intercalation structure is formed; then, matching with a stretching effect with certain strength, before stretching, in the bonding process, the linear molecular chain of the matrix resin is randomly wound into an amorphous state, under the stretching strength, the linear molecular chain can be straightened, further oriented under the constraint of the organic phyllosilicate and stress induction, and under the stress induction, stretching crystallization is generated, so that the matrix resin generates a reinforcing effect per se, and the tear resistance of the product is obviously improved;
according to the technical scheme, the layered silicate is treated by using a strong acid solution, the porosity of an interlayer channel of the layered silicate is improved, the rare earth salt is used for doping modification, an internal channel is further replaced, tetraethoxysilane is introduced in the preparation process of the organized layered silicate, a hydrolysate of tetraethoxysilane is adsorbed by the silicate in the reaction process, and after adsorption and fixation, in the subsequent organizing process, the hydrolysate, namely silica, is effectively fixed on the surface and the pores of a layered structure through an organic carbon chain, the organic molecular chain can be mutually drawn with matrix resin in a system, the layered silicate and the silica are respectively arranged at two ends of the organic molecular chain, and the existence of the two can generate a strong limiting effect, so that the tear resistance of the product is further improved.
Detailed Description
The following is a detailed description of embodiments of the invention, but the invention can be implemented in many different ways, as defined and covered by the claims.
Example 1
Detailed Description
Organic layered silicate:
according to parts by weight, 40 parts of hydrotalcite, 100 parts of nitric acid solution with the mass fraction of 3%, 100 parts of cerium nitrate solution with the mass fraction of 1%, 40 parts of gelatin solution with the mass fraction of 1% and 8 parts of silicate ester are taken in sequence; pouring hydrotalcite and a nitric acid solution into a hydrothermal kettle, carrying out hydrothermal stirring reaction for 3 hours at the temperature of 160 ℃, the pressure of 2.1MPa and the stirring speed of 300r/min, discharging, filtering, collecting a filter cake, washing the filter cake with deionized water until a washing solution is neutral, and drying the washed filter cake for 3 hours at the temperature of 85 ℃ to obtain dried pretreated hydrotalcite; mixing the dried pretreated silicate and a cerium nitrate solution, heating and carrying out ultrasonic reaction for 3h under the conditions that the temperature is 75 ℃ and the ultrasonic frequency is 45kHz, then adding a gelatin solution and tetraethoxysilane, continuing the ultrasonic reaction for 45min, then carrying out reduced pressure concentration for 45min under the conditions that the temperature is 75 ℃ and the pressure is 400mmHg to obtain a concentrate, drying the concentrate to constant weight under the condition that the temperature is 105 ℃ to obtain a dried concentrate, then heating the dried concentrate to 180 ℃ in an air atmosphere, carrying out heat preservation roasting for 45min, transferring the dried concentrate into a carbonization furnace, heating to 600 ℃ at the rate of 3 ℃/min under the protection of argon, carrying out heat preservation carbonization for 3h, cooling to room temperature along with the furnace, and discharging to obtain the organic layered silicate;
high-strength tear-resistant sheath material:
according to the weight parts, 100 parts of EVA260 resin, 20 parts of linear low-density polyethylene FV149M, 20 parts of organic layered silicate, 1 part of antioxidant RD, 1 part of antioxidant 1010 and 1 part of calcium stearate are taken in sequence, the EVA resin, the linear low-density polyethylene, the organic layered silicate, the antioxidant and the antioxidant are mixed, then the lubricant is added after kneading, after continuing kneading, extrusion granulation and injection molding are carried out, and then the high-strength tear-resistant sheath material is obtained after continuous stretching for 100s under the tension of 3 MPa.
And (3) performance testing:
testing the tensile strength according to a GB1040-92 mechanical property testing method, wherein the tensile strength of the product is 52.3 MPa;
the notch impact strength is tested by referring to the test method of GB/T1043-93 impact strength, and the measured notch impact strength is 46.2kJ/m2；
The product tear strength test is carried out according to GB2951.34-83, and the product tear strength is 9.2N/mm.
Example 2
Detailed Description
Organic layered silicate:
according to the weight parts, 45 parts of hydrotalcite, 120 parts of nitric acid solution with the mass fraction of 4%, 120 parts of cerous nitrate solution with the mass fraction of 2%, 45 parts of gelatin solution with the mass fraction of 4% and 9 silicate are taken in sequence; pouring hydrotalcite and a nitric acid solution into a hydrothermal kettle, carrying out hydrothermal stirring reaction for 4 hours at the temperature of 170 ℃, the pressure of 2.5MPa and the stirring speed of 400r/min, discharging, filtering, collecting a filter cake, washing the filter cake with deionized water until a washing liquid is neutral, and drying the washed filter cake for 4 hours at the temperature of 90 ℃ to obtain dry pretreated hydrotalcite; mixing the dried pretreated silicate and a cerium nitrate solution, heating and carrying out ultrasonic reaction for 4 hours at the temperature of 80 ℃ and the ultrasonic frequency of 60kHz, then adding a gelatin solution and tetraethoxysilane, continuing the ultrasonic reaction for 50 minutes, then carrying out reduced pressure concentration for 50 minutes at the temperature of 80 ℃ and the pressure of 450mmHg to obtain a concentrate, drying the concentrate to constant weight at the temperature of 108 ℃ to obtain a dried concentrate, then heating the dried concentrate to 180 ℃ in an air atmosphere, carrying out heat preservation roasting for 50 minutes, transferring the dried concentrate into a carbonization furnace, heating to 650 ℃ at the speed of 4 ℃/min under the protection of argon, carrying out heat preservation carbonization for 4 hours, cooling to room temperature along with the furnace, and discharging to obtain the organic layered silicate;
high-strength tear-resistant sheath material:
according to the weight parts, 120 parts of EVA260 resin, 25 parts of linear low-density polyethylene FV149M, 25 parts of organic layered silicate, 1.5 parts of antioxidant RD, 1.5 parts of antioxidant 1010 and 1.5 parts of calcium stearate are taken in sequence, the EVA resin, the linear low-density polyethylene, the organic layered silicate, the antioxidant and antioxidant raw materials are mixed, then a lubricant is added after kneading, after continuous kneading, extrusion granulation and injection molding are carried out, and continuous stretching is carried out for 150s under the tension of 4MPa, so that the high-strength tear-resistant sheath material is obtained.
And (3) performance testing:
testing the tensile strength according to a GB1040-92 mechanical property testing method, wherein the tensile strength of the product is 54.2 MPa;
the notch impact strength is tested by referring to a GB/T1043-93 impact strength test method, and the measured notch impact strength is 48.6kJ/m2；
The product tear strength test is carried out according to GB2951.34-83, and the product tear strength is 9.6N/mm.
Example 3
Detailed Description
Organic layered silicate:
according to parts by weight, 50 parts of hydrotalcite, 150 parts of nitric acid solution with the mass fraction of 5%, 130 parts of cerium nitrate solution with the mass fraction of 5%, 50 parts of gelatin solution with the mass fraction of 5% and 10 parts of silicate ester are taken in sequence; pouring hydrotalcite and a nitric acid solution into a hydrothermal kettle, carrying out hydrothermal stirring reaction for 5 hours at the temperature of 180 ℃, the pressure of 2.8MPa and the stirring speed of 500r/min, discharging, filtering, collecting a filter cake, washing the filter cake with deionized water until the washing liquid is neutral, and drying the washed filter cake for 5 hours at the temperature of 95 ℃ to obtain dry pretreated hydrotalcite; mixing the dried pretreated silicate and a cerous nitrate solution, heating and carrying out ultrasonic reaction for 5h under the conditions that the temperature is 85 ℃ and the ultrasonic frequency is 80kHz, then adding a gelatin solution and tetraethoxysilane, continuing the ultrasonic reaction for 60min, then carrying out reduced pressure concentration for 60min under the conditions that the temperature is 85 ℃ and the pressure is 500mmHg to obtain a concentrate, drying the concentrate to constant weight under the condition that the temperature is 110 ℃ to obtain a dried concentrate, then heating the dried concentrate to 180 ℃ in an air atmosphere, carrying out heat preservation roasting for 60min, transferring the dried concentrate into a carbonization furnace, heating to 680 ℃ at the speed of 5 ℃/min under the protection of argon, carrying out heat preservation carbonization for 5h, cooling to room temperature along with the furnace, and discharging to obtain the organic layered silicate;
high-strength tear-resistant sheath material:
according to the weight parts, 150 parts of EVA260 resin, 30 parts of linear low-density polyethylene FV149M, 30 parts of organic layered silicate, 2 parts of antioxidant RD, 2 parts of antioxidant 1010 and 2 parts of calcium stearate are taken in sequence, the EVA resin, the linear low-density polyethylene, the organic layered silicate, the antioxidant and the antioxidant are mixed, then the lubricant is added after kneading, after continuing kneading, extrusion granulation and injection molding are carried out, and the high-strength tear-resistant sheath material is obtained after continuous stretching for 200s under the tension of 5 MPa.
And (3) performance testing:
testing the tensile strength according to a GB1040-92 mechanical property testing method, and testing to obtain a product with the tensile strength of 56.3 MPa;
the notched impact strength is tested by referring to a GB/T1043-93 impact strength test method, and the notched impact strength is measured to be 49.2kJ/m2；
The product tear strength test is carried out according to GB2951.34-83, and the product tear strength is 10.1N/mm.
Example 4
Compared with the embodiment 1, the hydrotalcite is changed into the fumed silica, and the rest conditions are unchanged;
and (3) performance testing:
the tensile strength is tested according to a GB1040-92 mechanical property test method, and the tensile strength of the product is 34.2 MPa;
the notch impact strength is tested by referring to a GB/T1043-93 impact strength test method, and the measured notch impact strength is 28.2kJ/m2；
The product tear strength test is carried out according to GB2951.34-83, and the product tear strength is 5.6N/mm.
Example 5
The difference between this example and example 1 is:
high-strength tear-resistant sheath material:
according to the weight parts, 100 parts of EVA260 resin, 20 parts of linear low-density polyethylene FV149M, 20 parts of hydrotalcite, 1 part of antioxidant RD, 1 part of antioxidant 1010 and 1 part of calcium stearate are taken in sequence, EVA resin, linear low-density polyethylene, organic layered silicate, the antioxidant and antioxidant raw materials are mixed, then a lubricant is added after kneading, after continuing kneading, extrusion granulation and injection molding are carried out, and then the high-strength tear-resistant sheath material is obtained after continuous stretching for 100s under the tension of 3 MPa.
And (3) performance testing:
testing the tensile strength according to a GB1040-92 mechanical property testing method, wherein the tensile strength of the product is 22.5 MPa;
the notch impact strength is tested by referring to the GB/T1043-93 impact strength test method, and the measured notch impact strength is 26.2kJ/m2；
The product tear strength test was carried out with reference to GB2951.34-83 and found to be 4.2N/mm.
Example 6
The difference between this example and example 1 is:
high-strength tear-resistant sheath material:
according to the weight parts, 120 parts of EVA260 resin, 25 parts of linear low-density polyethylene FV149M, 25 parts of organic layered silicate, 1.5 parts of antioxidant RD, 1.5 parts of antioxidant 1010 and 1.5 parts of calcium stearate are taken in sequence, the EVA resin, the linear low-density polyethylene, the organic layered silicate, the antioxidant and antioxidant raw materials are mixed, then a lubricant is added after kneading, extrusion granulation and injection molding are carried out after kneading is continued, and the high-strength tear-resistant sheath material is obtained.
And (3) performance testing:
testing the tensile strength according to a GB1040-92 mechanical property testing method, wherein the tensile strength of the product is 45.2 MPa;
the notch impact strength is tested by referring to a GB/T1043-93 impact strength test method, and the measured notch impact strength is 44.6kJ/m2；
The product tear strength test is carried out according to GB2951.34-83, and the product tear strength is measured to be 8.6N/mm.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, but rather as the subject matter of the invention is to be construed in all aspects and as broadly as possible, and all changes, equivalents and modifications that fall within the true spirit and scope of the invention are therefore intended to be embraced therein.
Claims (9)
1. The high-strength tear-resistant sheath is characterized by comprising the following raw materials in parts by weight:
2. a high strength tear resistant sheath according to claim 1 wherein said organized layered silicate is prepared by:
taking 40-50 parts of layered silicate, 100-150 parts of strong acid solution, 100-130 parts of rare earth salt solution, 40-50 parts of gelatin solution with the mass fraction of 1-5% and 8-10 parts of ethyl orthosilicate in sequence according to parts by weight;
pouring the layered silicate and the strong acid solution into a hydrothermal kettle, carrying out hydrothermal reaction for 3-5 h, filtering, washing and drying to obtain dry pretreated silicate;
heating the dried pretreated silicate and the rare earth salt solution for ultrasonic reaction for 3-5 h, then adding a gelatin solution and tetraethoxysilane, continuing stirring for reaction, then concentrating, drying, roasting at a low temperature of 180 ℃ in an air atmosphere, heating to 600-680 ℃ under the protection of inert gas, preserving heat, carbonizing, cooling, and discharging to obtain the organic layered silicate.
3. The high-strength tear-resistant sheath according to claim 2, wherein the layered silicate is any one or more of hydrotalcite, muscovite, montmorillonite and sepiolite.
4. The high-strength tear-resistant sheath according to claim 2, wherein the strong acid solution is 3-5% by weight; the strong acid is any one of hydrochloric acid, sulfuric acid or nitric acid.
5. The high-strength tear-resistant sheath according to claim 2, wherein the rare earth salt solution is 1-5% by mass; the rare earth salt is any one or more of cerium nitrate, cerium chloride and lanthanum nitrate.
6. The high strength tear resistant sheath according to claim 1, wherein the antioxidant is any one of antioxidant 4020, antioxidant RD, or antioxidant NBC.
7. A high strength tear resistant sheath according to claim 1 wherein: the antioxidant is any one of antioxidant 1010, antioxidant 1076 or antioxidant 168.
8. A high strength tear resistant sheath according to claim 1 wherein: the lubricant is any one of magnesium stearate, calcium stearate or zinc stearate.
9. A flame retardant sheath material for extra-high voltage cables as claimed in any one of claims 1 to 8, wherein: the preparation steps of the high-strength tear-resistant sheath are as follows:
(1) weighing the components according to the composition of the raw materials;
(2) mixing EVA resin, linear low-density polyethylene, organic layered silicate, an anti-aging agent and an antioxidant, kneading, adding a lubricant, continuously kneading, extruding, granulating, performing injection molding, and continuously stretching for 100-200 s under the tension of 3-5 MPa to obtain the high-strength tear-resistant sheath.
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| EP1717264A1 (en) * | 2005-04-29 | 2006-11-02 | Campine | Process for producing a polyamide and/or polyester composition comprising nanoclay |
| CN1891726A (en) * | 2005-07-07 | 2007-01-10 | 张发饶 | Method for preparing lamella silicate modified ethylene-vinyl acetate copolymer |
| CN102020804A (en) * | 2009-09-15 | 2011-04-20 | 山东安澜高分子材料有限公司 | Thermoplastic crack resistant type low smoke zero halogen flame-retardant polyolefin cable sheath material and preparation method thereof |
| US20130224463A1 (en) * | 2011-09-23 | 2013-08-29 | Exxonmobil Chemical Patents Inc. | Modified Polyethylene Compositions for Blown Film |
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2019
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1717264A1 (en) * | 2005-04-29 | 2006-11-02 | Campine | Process for producing a polyamide and/or polyester composition comprising nanoclay |
| CN1891726A (en) * | 2005-07-07 | 2007-01-10 | 张发饶 | Method for preparing lamella silicate modified ethylene-vinyl acetate copolymer |
| CN102020804A (en) * | 2009-09-15 | 2011-04-20 | 山东安澜高分子材料有限公司 | Thermoplastic crack resistant type low smoke zero halogen flame-retardant polyolefin cable sheath material and preparation method thereof |
| US20130224463A1 (en) * | 2011-09-23 | 2013-08-29 | Exxonmobil Chemical Patents Inc. | Modified Polyethylene Compositions for Blown Film |
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Application publication date: 20191220 |