CN116285194B - Waterproof flame-retardant optical cable sheath material master batch and preparation method thereof - Google Patents
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Abstract
The application relates to the technical field of cable materials, and particularly discloses a waterproof flame-retardant optical cable sheath material master batch and a preparation method thereof. The raw materials comprise: polyethylene resin, eighty-seventh fluorine decyl cage-shaped polysilsesquioxane powder, carbon black, polyether-ether-ketone composite material and lubricant. The preparation method comprises the following steps: s1, preparing a polyether-ether-ketone composite material; s2, mixing; s3, granulating. The cable prepared by the application can be applied to various places such as high temperature, high humidity and the like, has low smoke and zero halogen, has good waterproof and flame retardant properties, is not easy to damage under natural conditions of high strength of the cable outer coating material, has self-repairing capability when the outer coating material is damaged by external force, can achieve the aim of maintaining good integrity for a long time, and can maintain good waterproof and flame retardant properties for a long time.
Description
Technical Field
The application relates to the technical field of cable materials, in particular to a waterproof flame-retardant optical cable sheath material master batch and a preparation method thereof.
Background
The cable sheath material needs to meet special application requirements of cables in different scenes, such as resistance to damp and heat, corrosion, water, fatigue, halogen-free flame retardance and the like, and the service life needs to be more than twenty years, so that the cable sheath material needs to have good durability. At present, the cable mostly adopts a double-layer structure, the outer sheath material needs to ensure the performances of corrosion resistance, weather resistance, wear resistance, water resistance and the like, the outer electric sheath material has high probability of directly contacting with environments of high temperature, humidity and the like, the performances of heat resistance, corrosion resistance, wear resistance, flexibility and the like are not ideal, especially, after the sheath material is damaged by external force, the damaged part cannot be self-repaired, the phenomenon that an internal lead is exposed occurs, the water resistance and flame retardance are reduced, and the service life of the cable is further shortened, so the improvement of the unilaterally-improved sheath material is obviously limited, and the sheath material master batch with stable performance and stronger durability is researched again to solve the problems of reduced water resistance and flame retardance and shortened service life of the cable due to various conditions.
Disclosure of Invention
The application provides a waterproof flame-retardant optical cable sheath material master batch and a preparation method thereof, aiming at solving the problems that an outer coating material of a cable is easy to damage and the service life of the cable is shortened.
The application provides a waterproof flame-retardant optical cable sheath material master batch and a preparation method thereof, which adopts the following technical scheme: the waterproof flame-retardant optical cable sheath material master batch comprises the following raw materials in parts by weight: 150-180 parts of polyethylene resin, 100-120 parts of eighty-seven-fluoro-decyl cage-shaped polysilsesquioxane powder, 20-30 parts of carbon black, 100-140 parts of polyether-ether-ketone composite material and 15-20 parts of lubricant.
By adopting the technical scheme, the super-hydrophobic eighty-seventy-seven-fluorodecyl cage-shaped polysilsesquioxane powder with a self-repairing function is adopted, and the eighty-seven-fluorodecyl with reactivity is grafted and polymerized with other organic polymers in the raw materials, so that the chemical bond interaction between the polymers is generated, the problems of aggregation of inorganic particles and weak bonding force of two-phase interfaces are avoided, uniform dispersion on a molecular layer is realized, and the polymer is easy to compound with other polymer matrixes, so that the sheath material master batch prepared by the method has good stability, and further has the characteristics of low smoke, zero halogen and difficult damage; the polyether-ether-ketone composite material has good self-lubricating property and fatigue resistance, so that the prepared optical cable sheath material is bending-resistant, stronger and wear-resistant, the dosage of the lubricant can be greatly reduced due to the good self-lubricating effect, the sheath material has excellent mechanical property, and the service life of the optical cable prepared from the sheath material master batch can be effectively prolonged.
Preferably, the polyether-ether-ketone composite material is a composite material formed by 10 (0.6-1.4) of polyether-ether-ketone and graphite in a weight ratio.
By adopting the technical scheme, the sheath material master batch can be ensured to have excellent self-lubricating performance due to the adoption of the polyether-ether-ketone and graphite composite material with the proportion in a fixed range, and the serious surface abrasion phenomenon is effectively prevented.
Preferably, the polyethylene resin is further modified by vinyl silane crosslinking.
By adopting the technical scheme, free radicals generated by the decomposition of vinyl silane and unsaturated sites in PE form reactive centers, the vinyl silane containing double bonds reacts with a molten polymer to form bonds under the action of an initiator, vinyl and alkoxy polyfunctional silane is grafted on a PE main chain, and then is hydrolyzed and condensed into Si-O-Si-crosslinking bonds under the action of water and silanol condensation catalysts, so that a reticular oxyalkane chain crosslinking structure is formed. The silane crosslinking technology has the advantages of simple equipment, easily controlled process, less investment, high crosslinking degree of finished products and good quality, thereby greatly promoting the production and application of crosslinked polyethylene resin. The polyethylene resin is subjected to crosslinking modification, so that the polyethylene resin has good mechanical properties, and meanwhile, the silane end has good affinity with other silicon-containing raw materials, so that the internal structure of the sheath material master batch is more stable, the high temperature resistance and the mechanical properties are further improved, and adverse phenomena such as smoking and the like are avoided.
Preferably, the eighty-seventh fluoro decyl polyhedral oligomeric silsesquioxane powder in the filler component is sieved through a 100-120 mesh sieve.
Preferably, the lubricant is ethylene bis-oleamide.
Preferably, the carbon black has a particle size of 10-20nm and a particle size of 30-50nm, and the ratio of the particle size to the particle size is (5-7): 2.
By adopting the technical scheme, the wear resistance of the material is enhanced, the two nano carbon blacks balance the whole lubrication degree of the material, the sheath material is endowed with various performances of maintaining the wear resistance, the water resistance and the flame retardance of the cable, and the service life of the cable is prolonged.
In a second aspect, the application provides a preparation method of waterproof flame-retardant optical cable sheath material master batch, which adopts the following technical scheme:
a preparation method of waterproof flame-retardant optical cable sheath material master batch comprises the following steps:
s1, preparing a polyether-ether-ketone composite material: mixing polyether-ether-ketone and graphite, and stirring uniformly to obtain the product;
s2, mixing, namely heating and mixing the lubricant and the carbon black, then adding the polyethylene resin, the polyether-ether-ketone composite material and the eighty-seventh fluorine decyl cage-shaped polysilsesquioxane powder, continuously stirring and mixing uniformly, starting banburying, carrying out melt processing on the mixed material after banburying, extruding a material strip, and cooling to obtain the modified polyurethane foam;
and S3, granulating, namely extruding the material strips, cutting the material strips into granules, and drying to obtain the finished product.
By adopting the technical scheme, the lubricant is firstly used for dispersing the carbon black, so that the aggregation of the carbon black can be avoided, the carbon black is uniformly distributed, and the wear resistance is better improved.
The step S1 also comprises the step of carrying out silane crosslinking modification on the polyethylene resin, wherein the modification method comprises the following steps: mixing vinyl trimethoxy silane, polyethylene resin, a catalyst, an initiator and an antioxidant, heating and melting, reacting for 2-4h, and finishing the reaction to obtain the modified polyvinyl alcohol.
In summary, the application has the following beneficial effects:
1. according to the application, the water-repellent sheath material component octaseventy-7 fluorodecyl cage-shaped polysilsesquioxane with a self-repairing function is adopted to be matched with the polyether-ether-ketone composite material with excellent flame retardant property, so that the waterproof flame retardant property of the sheath material is greatly improved, the master batch has excellent mechanical property, the polyether-ether-ketone and the graphite are compounded according to a proportion, so that the sheath material can obtain excellent self-lubricating property, the sheath material is difficult to abrade and crack under the combined action of the raw materials, fine scars can be repaired by self, the sheath material has low smoke, no halogen, fatigue resistance and excellent mechanical property, the phenomenon that the conductive component is exposed after the cable outer coating material is damaged is avoided, the sheath material master batch prepared by the application has the advantages of waterproof flame retardance, abrasion resistance and stable performance, and the service life of the optical cable prepared by the master batch is prolonged.
2. Because the polyethylene resin is crosslinked and modified in the application, the polyethylene resin has good mechanical properties, and meanwhile, the silane end has good affinity with other silicon-containing raw materials, so that the internal structure of the sheath material master batch is more stable, the high temperature resistance and the mechanical properties are further improved, and adverse phenomena such as smoke emission and the like can not occur.
Detailed Description
The application is further described in detail below with reference to the following examples, which are specifically described: the following examples, in which no specific conditions are noted, are conducted under conventional conditions or conditions recommended by the manufacturer, and the raw materials used in the following examples are commercially available from ordinary sources except for the specific descriptions.
The vinyl trimethoxy silane is produced by Nanjing Netherlands New Material technology Co., ltd, and the model is SCA-V71M; the polyethylene resin is produced by the company Cheng Xiangsu of Laizhou city;
the catalyst is 3, 5-trimethylhexyl ester with the mass ratio of 3.5-4.5:1, zinc oxide;
the initiator is benzoyl peroxide produced by Jinan Jinbang environmental protection technology Co., ltd;
the antioxidant is produced by Tianjin Li Anlong new material stock company, and the model is antioxidant DLTP;
the ethylene bis-oleamide is produced by Shandong Neurospora Biotechnology Co.
Examples
Example 1
A preparation method of waterproof flame-retardant optical cable sheath material master batch comprises the following steps:
s1, preparing a polyether-ether-ketone composite material: mixing 92.7kg of polyether-ether-ketone and 5.7kg of graphite, and uniformly stirring to obtain the modified graphite;
s2, mixing, namely heating and mixing 15kg of ethylene bis-oleamide and 20kg of carbon black, then adding 150kg of polyethylene resin, 100kg of polyether-ether-ketone composite material and 100kg of octaseventy-seven-fluorodecyl cage-shaped polysilsesquioxane powder, continuously stirring and mixing uniformly, starting banburying, adding the banburying mixture into a double-screw extruder for melt processing, and putting a material strip extruded from a nozzle of the extruder into a water tank for cooling;
s3, granulating, namely pouring the granules into a screw extruder for extruding, and then granulating the strips by a granulator, and drying to obtain the finished product;
wherein the addition ratio of the carbon black with the particle size of 10nm and 30nm in 20kg of carbon black is 5:2.
Example 2
A preparation method of waterproof flame-retardant optical cable sheath material master batch comprises the following steps:
s1, preparing a polyether-ether-ketone composite material: mixing 109kg of polyether-ether-ketone and 11kg of graphite, and uniformly stirring to obtain the catalyst;
s2, mixing, namely heating and mixing 17.5kg of ethylene bis-oleamide and 25kg of carbon black, then adding 165kg of polyethylene resin, 120kg of polyether-ether-ketone composite material and 110kg of octaseventy-seven-fluorodecyl cage-shaped polysilsesquioxane powder, continuously stirring and mixing uniformly, starting banburying, adding the banburying mixture into a double-screw extruder for melt processing, and putting a material strip extruded from a nozzle of the extruder into a water tank for cooling;
s3, granulating, namely pouring the granules into a screw extruder for extruding, and then granulating the strips by a granulator, and drying to obtain the finished product;
wherein, the adding ratio of the carbon black with the particle size of 15nm and the carbon black with the particle size of 40nm is 3:1.
Example 3
A preparation method of waterproof flame-retardant optical cable sheath material master batch comprises the following steps:
s1, preparing a polyether-ether-ketone composite material: 127.7kg of polyether-ether-ketone and 12.3kg of graphite are mixed and stirred uniformly to obtain the composite material;
s2, mixing, namely heating and mixing 20kg of ethylene bis-oleamide and 30kg of carbon black, then adding 180kg of polyethylene resin, 140kg of polyether-ether-ketone composite material and 120kg of octaseventeen fluorine decyl cage-shaped polysilsesquioxane powder, continuously stirring and mixing uniformly, starting banburying, adding the mixed material after banburying into a double-screw extruder for melt processing, and putting a material strip extruded from a nozzle of the extruder into a water tank for cooling;
s3, granulating, namely pouring the granules into a screw extruder for extruding, and then granulating the strips by a granulator, and drying to obtain the finished product;
wherein, the addition ratio of the carbon black with the particle size of 20nm and the carbon black with the particle size of 50nm is 7:2.
Example 4
The method of example 1 is performed, except that the step S1 further includes silane crosslinking modification of the polyethylene resin, where the modification method is as follows: 50kg of vinyl trimethoxy silane, 150kg of polyethylene resin, 1kg of catalyst, 2kg of initiator and 8kg of antioxidant are prepared into a mixed material, the mixed material is heated to 190 ℃ until the mixed material is molten, and then the mixed material is stirred by regulating the rotating speed to 800rpm and reacts for 3 hours to obtain the vinyl trimethoxy silane.
Example 5
The procedure of example 1 was followed except that ethylene bis-oleamide was replaced with calcium stearate in equal amounts.
Example 6
The procedure of example 1 was followed except that the carbon black having a particle diameter of 10nm was replaced with an equivalent of 30nm.
Example 7
The procedure of example 1 was followed, except that carbon blacks having particle diameters of 10nm and 30nm were added at an addition ratio of 3:2.
Example 8
The process of example 1 was followed, except that the polyetheretherketone composite was a polyetheretherketone-graphite composite with a weight addition ratio of 10:3.
Example 9
The process of example 1 was followed, except that the polyetheretherketone composite was a composite of polyetheretherketone and graphite in a weight ratio of 10:0.2.
Example 10
The procedure of example 1 was followed, except that carbon blacks having particle diameters of 10nm and 30nm were added at an addition ratio of 4:1.
Comparative example
Comparative example 1
The procedure of example 1 was followed except that the polyetheretherketone composite in the outer envelope material was replaced with polyetheretherketone in equal amounts.
Comparative example 2
The procedure of example 1 was followed except that no carbon black was added to the outer coating material.
Comparative example 3
The procedure of example 1 was followed except that the fill composition was single and the octaheptadecafluorodecyl cage polysilsesquioxane was replaced equally with polyethylene resin.
Performance test
1. Basic parameters
2. Self-healing performance test
Detection method
1. Basic parameters: each index detection is carried out according to the cables prepared in the examples and the comparative examples, and the detection results are shown in tables 1 and 2;
2. self-repairing performance test: the sheath material master batches prepared in the examples and the comparative examples are processed to prepare sheath material test pieces with the size of 100mm and the thickness of 100mm, each test piece is subjected to steel wire brush and other force abrasion treatment, a weight of 10kg is applied to the upper part of the steel wire brush, the lower sheath material test pieces are abraded by utilizing gravity, and scratches formed by abrasion are specifically divided into: a. slight scratch: visible only to the naked eye when viewed under careful light; b. moderate scratch: the scratch is visible under natural light, and the damage of the surface layer of the sheath material is less than 1mm; c. severe scratches: the scratch damages the surface layer of the sheath material test piece to be more than 1mm; and the repair effect after 28d was recorded, and the detection results are shown in Table 3.
TABLE 1
TABLE 2
| Detecting items | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Tensile Strength/Mpa | 10 | 9 | 10 |
| Heat aged tensile strength change rate/% | 16 | 22 | 26 |
| Elongation at break/% | 150 | 148 | 144 |
| 5h 105 ℃ Heat distortion/% | 5 | 5 | 10 |
| Halogen acid gas content mg/g | ≤1 | ≤1 | ≤1 |
| Smoke density | ≤5 | ≤5 | ≤10 |
| Thermal cracking resistance | No cracking | No cracking | No cracking |
TABLE 3 Table 3
| Scratch rating at formation | Scratch rating after repair | Number of scratches formed | |
| Example 1 | a | No scratch | 6 |
| Example 2 | a | No scratch | 5 |
| Example 3 | a | No scratch | 5 |
| Example 4 | a | No scratch | 1 |
| Example 5 | b | a | 9 |
| Example 6 | b | a | 11 |
| Example 7 | b | a | 10 |
| Example 8 | a | a | 7 |
| Example 9 | b | a | 8 |
| Example 10 | b | a | 3 |
| Comparative example 1 | c | b | 14 |
| Comparative example 2 | c | b | 8 |
| Comparative example 3 | c | c | 11 |
As can be seen from the performance detection results of the embodiment 1 and the embodiment 4, the crosslinked polyethylene resin has better fusion property and more firm combination degree between sheath materials, and the prepared sheath material has better mechanical properties, and simultaneously improves the stability, oxidation resistance and flame retardance of the polyethylene resin at high temperature.
As can be seen from the performance test results of examples 1 and 5, the carbon black can be well dispersed by using the calcium stearate lubricant, but the fatigue resistance and self-lubricity of the prepared sheath material are slightly reduced, and the service life of the optical cable prepared from the sheath material master batch of the application can not be remarkably prolonged according to the abrasion degree.
As can be seen from the performance test results of examples 1 and 6, when the carbon black is replaced by carbon black with a particle size of 30nm, the fatigue resistance is reduced, the self-lubricating performance is reduced, the abrasion probability is increased, and the service life of the optical cable is possibly shortened; as can be seen from the performance test results of examples 1 and 7, increasing the proportion of 30nm in the carbon black also results in a decrease in fatigue resistance and self-lubricating properties, and an increase in wear probability, thereby possibly shortening the service life of the optical cable; as can be seen from the results of performance tests in examples 1 and 10, when the amount of carbon black added having a particle diameter of 10nm was increased, the probability of occurrence of scratches was decreased, and the number of scratches was small, but the abrasion resistance was also decreased as reflected in the depth of scratches.
As can be seen from the performance test results of examples 1 and 8, the graphite still has good self-lubricating performance after the addition amount of graphite is increased, but the progress is not great, and the mechanical performance and the high temperature resistance are reduced; in combination with the performance test results of examples 1 and 9, the self-lubricating performance was insufficient when the amount of graphite added was reduced, and the optical cable sheath was also easily worn.
As can be seen from the performance test results of example 1 and comparative example 1, the fatigue resistance and the self-lubricating wear resistance of the outer coating material are significantly reduced after the polyetheretherketone compound is replaced with polyetheretherketone in equal amount.
As can be seen from the performance test results of example 1 and comparative example 3, the equivalent replacement of the seventy-seven-fluorodecyl polyhedral oligomeric silsesquioxane with the polyethylene resin has reduced mechanical properties, significantly reduced fatigue resistance due to insufficient flexibility, and no obvious self-repairing capability.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.
Claims (7)
1. The waterproof flame-retardant optical cable sheath material master batch is characterized by comprising the following raw materials in parts by weight: 150-180 parts of polyethylene resin, 100-120 parts of octa-heptadecafluorodecyl cage-shaped polysilsesquioxane powder, 20-30 parts of carbon black, 100-140 parts of polyether-ether-ketone composite material and 15-20 parts of lubricant; the polyether-ether-ketone composite material is composed of 10 (0.6-1.4) of polyether-ether-ketone and graphite in a weight ratio.
2. The waterproof flame-retardant optical cable sheath material master batch according to claim 1, wherein: the polyethylene resin also needs to be modified by vinyl silane crosslinking.
3. The waterproof flame-retardant optical cable sheath material master batch according to claim 1, wherein: the octa-heptadecafluorodecyl polyhedral oligomeric silsesquioxane powder needs to be sieved by a 100-120 mesh sieve.
4. The waterproof flame-retardant optical cable sheath material master batch according to claim 1, wherein: the lubricant is ethylene bis-oleamide.
5. The waterproof flame-retardant optical cable sheath material master batch according to claim 1, wherein: the carbon black has a particle size of 10-20nm and a particle size of 30-50nm, and the adding ratio of the two particle sizes is (5-7): 2.
6. The method for preparing the waterproof flame-retardant optical cable sheath material master batch according to any one of claims 1 to 5, comprising the following steps:
s1, preparing a polyether-ether-ketone composite material: mixing polyether-ether-ketone and graphite, and stirring uniformly to obtain the product;
s2, mixing, namely heating and mixing the lubricant and the carbon black, then adding the polyethylene resin, the polyether-ether-ketone composite material and the octa-heptadecafluorodecyl cage-shaped polysilsesquioxane powder, continuously stirring and uniformly mixing, starting banburying, carrying out melt processing on the mixed material after banburying, extruding a material strip, and cooling to obtain the modified polyurethane foam;
and S3, granulating, namely extruding the material strips, cutting the material strips into granules, and drying to obtain the finished product.
7. The method for preparing waterproof and flame-retardant optical cable sheath material master batch according to claim 6, wherein the step S1 further comprises silane crosslinking modification of polyethylene resin, and the modification method comprises the following steps: mixing vinyl trimethoxy silane, polyethylene resin, a catalyst, an initiator and an antioxidant, heating and melting, reacting for 2-4h, and finishing the reaction to obtain the modified polyvinyl alcohol.
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| CN106062079A (en) * | 2014-03-07 | 2016-10-26 | 株式会社东进世美肯 | Thermoplastic resin composition comprising silsesquioxane composite polymer |
| CN104277182A (en) * | 2014-05-12 | 2015-01-14 | 浙江大学 | Preparation method of crosslinked low density polyethylene (LDPE) |
| CN110066447A (en) * | 2019-05-10 | 2019-07-30 | 江阴市江泰高分子新材料有限公司 | A kind of high wet and heat ageing resistant and the PE film of anti-corrosive properties and preparation method thereof |
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