CN115838505A - Polyethylene sheath material with thermal stability and application thereof in optical fiber cable - Google Patents
Polyethylene sheath material with thermal stability and application thereof in optical fiber cable Download PDFInfo
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- CN115838505A CN115838505A CN202211555908.XA CN202211555908A CN115838505A CN 115838505 A CN115838505 A CN 115838505A CN 202211555908 A CN202211555908 A CN 202211555908A CN 115838505 A CN115838505 A CN 115838505A
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Abstract
The invention relates to the technical field of optical fiber cables and discloses a polyethylene sheath material with thermal stability. The obtained nano titanium dioxide grafted polyethylene and high-density polyethylene are blended and modified to obtain a polyethylene sheath material, after polyethylene molecular chains are grafted, the compatibility of the nano titanium dioxide in the high-density polyethylene is excellent, the interface strength of the nano titanium dioxide and the high-density polyethylene is high, and the nano titanium dioxide forms a physical cross-linking network in a high-density polyethylene matrix, so that the molecular chain movement of the polyethylene is blocked, the thermal decomposition of the molecular chain is delayed, the thermal decomposition temperature of the polyethylene sheath material is increased, and the polyethylene sheath material has better thermal stability.
Description
Technical Field
The invention relates to the technical field of optical fiber cables, in particular to a polyethylene sheath material with thermal stability and application thereof in optical fiber cables.
Background
The polyethylene sheath material has excellent insulation property, good mechanical property and low cost, is widely applied to optical fiber cables, has higher and higher performance requirements on the polyethylene sheath material along with the rapid development of the optical fiber cable industry, and has important significance for improving the performances of polyethylene such as thermal stability and the like, for example, chinese patent document CN201920953062.2, namely a cable insulating material containing nano magnesium oxide/low-density polyethylene/modified bentonite and application thereof, discloses that the polyethylene is filled and modified by adopting modified bentonite, magnesium oxide, glass fiber and the like, so that the heat resistance and the strength of the polyethylene insulating cable material are improved.
The nano titanium dioxide has good mechanical property and strong ultraviolet shielding property, has good application in high polymer materials such as polyethylene, polyvinyl chloride and the like, and is a research hotspot for modifying the surface of the nano titanium dioxide and enhancing the compatibility with polymer groups, such as modified TiO 2 Research on dispersion behavior in PVC matrix reports that the polymethyl methacrylate is adopted to modify the surface of the nano titanium dioxide, so that the nano titanium dioxide has good dispersibility in the polyvinyl chloride and the mechanical property of the polyvinyl chloride is improved.
Disclosure of Invention
Technical problem to be solved
The invention provides a polyethylene sheath material with thermal stability, which is applied to the field of optical fiber cables.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: a polyethylene sheath material with thermal stability comprises 100 parts by weight of high-density polyethylene, 10-18 parts by weight of toughening agent EVA resin and 0.1-0.6 part by weight of antioxidant, and the preparation method of the polyethylene sheath material with thermal stability comprises the following steps:
(1) Dispersing 100 parts by weight of benzoic acid modified nano titanium dioxide into a reaction solvent, then adding 400-1500 parts by weight of glycidyl acrylate grafted polyethylene, uniformly stirring, dropwise adding a catalyst triphenylphosphine, stirring for reaction, adding ethanol for precipitation after reaction, filtering the solvent, and washing with deionized water and ethanol in sequence to obtain the nano titanium dioxide grafted polyethylene.
(2) Extruding and granulating the high-density polyethylene, the nano titanium dioxide grafted polyethylene, the EVA resin and the antioxidant in a double-screw extruder, and then performing injection molding to obtain the polyethylene sheath material with thermal stability.
Preferably, the solvent in (1) comprises N, N-dimethylformamide, N-dimethylacetamide and xylene.
Preferably, the amount of the catalyst triphenylphosphine in the step (1) is 0.3-0.8% of the total mass of the reactants.
Preferably, the reaction in the step (1) is carried out at 80-100 ℃ for 18-48 h.
Preferably, the amount of the nano titanium dioxide grafted polyethylene in the step (1) is 1 to 6 percent of the mass of the high-density polyethylene.
Preferably, the preparation method of the benzoic acid modified nano titanium dioxide in the step (1) comprises the following steps: dispersing the nano titanium dioxide into an ethanol solvent, then dropwise adding 3, 4-dihydroxybenzoic acid, reacting at room temperature in a dark place for 12-24 h, filtering the solvent after the reaction, and washing with ethanol to obtain the benzoic acid modified nano titanium dioxide.
Preferably, the using amount of the 3, 4-dihydroxy benzoic acid is 20-50% of the mass of the nano titanium dioxide.
(III) advantageous technical effects
The catechol structure of 3, 4-dihydroxy benzoic acid and the surface of nano titanium dioxide are utilized to form a coordinate bond, so that the 3, 4-dihydroxy benzoic acid is chemically bonded to the surface of the nano titanium dioxide to obtain benzoic acid modified nano titanium dioxide, then, the aryl carboxyl and the epoxy group of glycidyl acrylate grafted polyethylene are subjected to ring-opening esterification reaction under the catalysis of triphenylphosphine to obtain nano titanium dioxide grafted polyethylene, and a polyethylene molecular chain is grafted on the surface of the nano titanium dioxide, so that the surface modification of the nano titanium dioxide is realized. The obtained nano titanium dioxide grafted polyethylene and high-density polyethylene are blended and modified to obtain a polyethylene sheath material, after polyethylene molecular chains are grafted, the compatibility of the nano titanium dioxide in the high-density polyethylene is excellent, the interface strength of the nano titanium dioxide and the high-density polyethylene is high, and the nano titanium dioxide forms a physical cross-linking network in a high-density polyethylene matrix, so that the molecular chain movement of the polyethylene is blocked, the thermal decomposition of the molecular chain is delayed, the thermal decomposition temperature of the polyethylene sheath material is increased, and the polyethylene sheath material has better thermal stability.
Detailed Description
Example 1
(1) Dispersing 100 parts by weight of nano titanium dioxide into an ethanol solvent, then dropwise adding 20 parts by weight of 3, 4-dihydroxybenzoic acid, reacting at room temperature in a dark place for 12 hours, filtering the solvent after the reaction, and washing with ethanol to obtain the benzoic acid modified nano titanium dioxide.
(2) Dispersing 100 parts by weight of benzoic acid modified nano titanium dioxide into N, N-dimethylformamide, then adding 400 parts by weight of glycidyl acrylate grafted polyethylene, uniformly stirring, dropwise adding 1.5 parts by weight of catalyst triphenylphosphine, stirring at 90 ℃ to react for 48 hours, adding ethanol to precipitate after the reaction, filtering the solvent, and washing with deionized water and ethanol in sequence to obtain the nano titanium dioxide grafted polyethylene.
(2) 100 parts by weight of high-density polyethylene, 15 parts by weight of toughening agent EVA resin, 0.1 part by weight of antioxidant 1076 and 1 part by weight of nano titanium dioxide grafted polyethylene are extruded and granulated in a double-screw extruder, and then injection molding is carried out to obtain the polyethylene sheath material with thermal stability.
Example 2
(1) Dispersing 100 parts by weight of nano titanium dioxide into an ethanol solvent, then dropwise adding 20 parts by weight of 3, 4-dihydroxybenzoic acid, reacting at room temperature in a dark place for 24 hours, filtering the solvent after the reaction, and washing with ethanol to obtain the benzoic acid modified nano titanium dioxide.
(2) Dispersing 100 parts by weight of benzoic acid modified nano titanium dioxide into xylene, then adding 700 parts by weight of glycidyl acrylate grafted polyethylene, uniformly stirring, dropwise adding 4 catalyst triphenylphosphine, stirring at 90 ℃ for reacting for 18 hours, adding ethanol for precipitation after reaction, filtering a solvent, and washing with deionized water and ethanol in sequence to obtain the nano titanium dioxide grafted polyethylene.
(2) 100 parts by weight of high-density polyethylene, 18 parts by weight of toughening agent EVA resin, 0.5 part by weight of antioxidant 168 and 2 parts by weight of nano titanium dioxide grafted polyethylene are extruded and granulated in a double-screw extruder, and then injection molding is carried out to obtain the polyethylene sheath material with thermal stability.
Example 3
(1) Dispersing 100 parts by weight of nano titanium dioxide into an ethanol solvent, then dropwise adding 40 parts by weight of 3, 4-dihydroxybenzoic acid, reacting at room temperature in a dark place for 24 hours, filtering the solvent after the reaction, and washing with ethanol to obtain the benzoic acid modified nano titanium dioxide.
(2) Dispersing 100 parts by weight of benzoic acid modified nano titanium dioxide into N, N-dimethylformamide, then adding 1000 parts by weight of glycidyl acrylate grafted polyethylene, uniformly stirring, dropwise adding 6.5 parts by weight of catalyst triphenylphosphine, stirring at 100 ℃ to react for 18 hours, adding ethanol to precipitate after the reaction, filtering the solvent, and washing with deionized water and ethanol in sequence to obtain the nano titanium dioxide grafted polyethylene.
(2) 100 parts by weight of high-density polyethylene, 8 parts by weight of toughening agent EVA resin, 0.1 part by weight of antioxidant 168 and 3 parts by weight of nano titanium dioxide grafted polyethylene are extruded and granulated in a double-screw extruder, and then injection molding is carried out to obtain the polyethylene sheath material with thermal stability.
Example 4
(1) Dispersing 100 parts by weight of nano titanium dioxide into an ethanol solvent, then dropwise adding 50 parts by weight of 3, 4-dihydroxybenzoic acid, reacting at room temperature in a dark place for 24 hours, filtering the solvent after the reaction, and washing with ethanol to obtain the benzoic acid modified nano titanium dioxide.
(2) Dispersing 100 parts by weight of benzoic acid modified nano titanium dioxide into N, N-dimethylacetamide, then adding 1200 parts by weight of glycidyl acrylate grafted polyethylene, uniformly stirring, dropwise adding 6.5 parts by weight of catalyst triphenylphosphine, stirring at 80 ℃ for reacting for 36 hours, adding ethanol for precipitation after reaction, filtering a solvent, and washing with deionized water and ethanol in sequence to obtain the nano titanium dioxide grafted polyethylene.
(2) 100 parts by weight of high-density polyethylene, 18 parts by weight of toughening agent EVA resin, 0.4 part by weight of antioxidant 1076 and 5 parts by weight of nano titanium dioxide grafted polyethylene are extruded and granulated in a double-screw extruder, and then injection molding is carried out to obtain the polyethylene sheath material with thermal stability.
Example 5
(1) Dispersing 100 parts by weight of nano titanium dioxide into an ethanol solvent, then dropwise adding 40 parts by weight of 3, 4-dihydroxybenzoic acid, reacting at room temperature in a dark place for 24 hours, filtering the solvent after the reaction, and washing with ethanol to obtain the benzoic acid modified nano titanium dioxide.
(2) Dispersing 100 parts by weight of benzoic acid modified nano titanium dioxide into N, N-dimethylformamide, then adding 1500 parts by weight of glycidyl acrylate grafted polyethylene, uniformly stirring, dropwise adding 12.8 parts by weight of catalyst triphenylphosphine, stirring at 100 ℃ to react for 48 hours, adding ethanol to precipitate after the reaction, filtering the solvent, and washing with deionized water and ethanol in sequence to obtain the nano titanium dioxide grafted polyethylene.
(2) 100 parts by weight of high-density polyethylene, 14 parts by weight of toughening agent EVA resin, 0.6 part by weight of antioxidant 168 and 6 parts by weight of nano titanium dioxide grafted polyethylene are extruded and granulated in a double-screw extruder, and then injection molding is carried out to obtain the polyethylene sheath material with thermal stability.
Comparative example 1
(1) Extruding and granulating 100 parts by weight of high-density polyethylene, 10 parts by weight of toughening agent EVA resin, 0.5 part by weight of antioxidant 1076 and 1 part by weight of nano titanium dioxide in a double-screw extruder, and then carrying out injection molding to obtain the polyethylene sheath material.
Comparative example 2
(1) Dispersing 100 parts by weight of nano titanium dioxide into an ethanol solvent, then dropwise adding 40 parts by weight of 3, 4-dihydroxybenzoic acid, reacting at room temperature in a dark place for 24 hours, filtering the solvent after the reaction, and washing with ethanol to obtain the benzoic acid modified nano titanium dioxide.
(2) 100 parts by weight of high-density polyethylene, 10 parts by weight of toughening agent EVA resin, 0.4 part by weight of antioxidant 1076 and 1 part by weight of benzoic acid modified nano titanium dioxide are extruded and granulated in a double-screw extruder, and then injection molding is carried out to obtain the polyethylene sheath material.
Carrying out thermogravimetric performance test on the polyethylene sheath material in a thermogravimetric analyzer under the nitrogen atmosphere, wherein the heating rate is 10 ℃/min, and the temperature range is 25-800 ℃.
| T 5 % | T 50 % | Weight（%） | |
| Example 1 | 372.4 | 450.0 | 8.1 |
| Example 2 | 379.0 | 453.1 | 9.6 |
| Example 3 | 384.7 | 459.2 | 11.7 |
| Example 4 | 385.4 | 456.2 | 14.0 |
| Example 5 | 376.0 | 449.7 | 17.2 |
| Comparative example 1 | 360.2 | 456.4 | 6.9 |
| Comparative example 2 | 370.9 | 443.7 | 7.3 |
T 5 % is the temperature at 5% mass loss rate. T is a unit of 50 % is the temperature at 50% mass loss and Weight is the Weight remaining.
Claims (7)
1. A polyethylene sheath material with thermal stability comprises 100 parts by weight of high-density polyethylene, 10-18 parts by weight of toughening agent EVA resin and 0.1-0.6 part by weight of antioxidant, and is characterized in that: the preparation method of the polyethylene sheath material with the thermal stability comprises the following steps:
(1) Dispersing 100 parts by weight of benzoic acid modified nano titanium dioxide into a reaction solvent, then adding 400-1500 parts by weight of glycidyl acrylate grafted polyethylene, uniformly stirring, dropwise adding a catalyst triphenylphosphine, and stirring for reaction to obtain nano titanium dioxide grafted polyethylene;
(2) Extruding and granulating the high-density polyethylene, the nano titanium dioxide grafted polyethylene, the EVA resin and the antioxidant in a double-screw extruder, and then performing injection molding to obtain the polyethylene sheath material with thermal stability.
2. The thermally stable polyethylene sheathing compound according to claim 1, wherein: the solvent in the step (1) comprises N, N-dimethylformamide, N-dimethylacetamide and xylene.
3. The thermally stable polyethylene sheathing compound according to claim 1, wherein: the dosage of the catalyst triphenylphosphine in the step (1) is 0.3-0.8% of the total mass of reactants.
4. The thermally stable polyethylene sheathing compound according to claim 1, wherein: the reaction in the step (1) is carried out at 80-100 ℃ for 18-48 h.
5. The thermally stable polyethylene sheathing compound according to claim 1, wherein: the dosage of the nano titanium dioxide grafted polyethylene in the step (1) is 1-6% of the mass of the high-density polyethylene.
6. The thermally stable polyethylene sheathing compound according to claim 1, wherein: the preparation method of the benzoic acid modified nano titanium dioxide in the step (1) comprises the following steps: dispersing the nano titanium dioxide into an ethanol solvent, then dropwise adding 3, 4-dihydroxy benzoic acid, and reacting at room temperature in a dark place for 12-24 h to obtain the benzoic acid modified nano titanium dioxide.
7. The thermally stable polyethylene sheathing compound according to claim 6, wherein: the dosage of the 3, 4-dihydroxy benzoic acid is 20-50% of the mass of the nano titanium dioxide.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211555908.XA CN115838505A (en) | 2022-12-06 | 2022-12-06 | Polyethylene sheath material with thermal stability and application thereof in optical fiber cable |
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| CN202211555908.XA CN115838505A (en) | 2022-12-06 | 2022-12-06 | Polyethylene sheath material with thermal stability and application thereof in optical fiber cable |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1322773A (en) * | 2001-05-24 | 2001-11-21 | 宁波信高塑化有限公司 | Inorganic nanometer particle modified optical cable protecting casing material and its prepn |
| CN102086309A (en) * | 2010-04-03 | 2011-06-08 | 兰州交通大学 | Preparation method of modified inorganic nanoparticle grafted by polymers through esterification at room temperature |
| CN105968533A (en) * | 2016-07-04 | 2016-09-28 | 苏州云舒新材料科技有限公司 | PE sheath and preparation method thereof |
| CN108912457A (en) * | 2018-07-18 | 2018-11-30 | 合肥安力电力工程有限公司 | A kind of cracking resistance anti-corrosion cable material and preparation method thereof |
| CN114539691A (en) * | 2022-04-01 | 2022-05-27 | 昆山淼挺管业有限公司 | Polyvinyl chloride compound for industrial pipeline and preparation method thereof |
| CN114940732A (en) * | 2022-06-15 | 2022-08-26 | 扬州实嘉电缆材料有限公司 | Anti-ultraviolet titanium dioxide modified polyvinyl chloride plastic and preparation method thereof |
-
2022
- 2022-12-06 CN CN202211555908.XA patent/CN115838505A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1322773A (en) * | 2001-05-24 | 2001-11-21 | 宁波信高塑化有限公司 | Inorganic nanometer particle modified optical cable protecting casing material and its prepn |
| CN102086309A (en) * | 2010-04-03 | 2011-06-08 | 兰州交通大学 | Preparation method of modified inorganic nanoparticle grafted by polymers through esterification at room temperature |
| CN105968533A (en) * | 2016-07-04 | 2016-09-28 | 苏州云舒新材料科技有限公司 | PE sheath and preparation method thereof |
| CN108912457A (en) * | 2018-07-18 | 2018-11-30 | 合肥安力电力工程有限公司 | A kind of cracking resistance anti-corrosion cable material and preparation method thereof |
| CN114539691A (en) * | 2022-04-01 | 2022-05-27 | 昆山淼挺管业有限公司 | Polyvinyl chloride compound for industrial pipeline and preparation method thereof |
| CN114940732A (en) * | 2022-06-15 | 2022-08-26 | 扬州实嘉电缆材料有限公司 | Anti-ultraviolet titanium dioxide modified polyvinyl chloride plastic and preparation method thereof |
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