CN111675850A - Low-shrinkage high-flame-retardant polyolefin cable material and preparation method thereof - Google Patents
Low-shrinkage high-flame-retardant polyolefin cable material and preparation method thereof Download PDFInfo
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Abstract
The application relates to the technical field of wires and cables, and particularly discloses a low-shrinkage high-flame-retardant polyolefin cable material and a preparation method thereof. The technical key points are as follows: the low-shrinkage high-flame-retardant polyolefin cable material comprises the following components in parts by weight: linear low density polyethylene: 100 parts of (A); ethylene-vinyl acetate copolymer: 5-15 parts; ethylene-propylene copolymer: 5-10 parts; ethylene-octene copolymer: 1-5 parts; maleic anhydride grafted ethylene-vinyl acetate copolymer: 20-50 parts; tert-butyl peroxide: 0.01-0.1 part; inorganic flame retardant: 80-100 parts of a binder; antioxidant: 0.5-1 part; silicone oil: 2-5 parts. The polyolefin cable material prepared by the method has the advantages of low shrinkage and high flame retardance.
Description
Technical Field
The application relates to the technical field of wires and cables, in particular to a low-shrinkage high-flame-retardant polyolefin cable material and a preparation method thereof.
Background
According to the national plans of the main application fields of the electric wire and the electric cable, such as electric power, rail transit, aerospace, ocean engineering and the like, the electric wire and the electric cable industry in China has good prospect in the future, the upgrading trend of industrial products is obvious, and the scale of the industry demand is expected to exceed 1.9 trillion yuan in 2024 years. The requirements of high-end cables, especially cables used for 5G communication, are more strict, and the variation of the shrinkage rate of cable products directly affects the accuracy of the products and the stability of the performance.
The high-voltage cable of 35KV and below is composed of a cable core and a sheath, the sheath is mainly made of polyolefin materials at present, the polyolefin material sheath can shrink greatly when the environmental temperature is higher, the shrinkage rate of the existing cable materials on the market is about 4.3%, the high-temperature resistance is poor or even exceeds 7%, and the national standard requirement on the thermal shrinkage rate of the cable materials is 5%, so that the thermal shrinkage performance of the cable materials in the industry is still to be improved, the cable sheath can shrink in a low-temperature mode due to the influence of cable heating and the heat dissipation condition of the environment, the larger the thermal shrinkage value of the sheath is, the easier the sheath is separated from the cable core, and the poorer the cable protection effect is. Therefore, a new solution is needed to solve the above problems.
Disclosure of Invention
Aiming at the problem of high shrinkage rate of the existing cable material in the related art, the present application aims to provide a low-shrinkage high-flame-retardant polyolefin cable material which has the advantages of low shrinkage rate and high flame retardancy.
The second purpose of the application is to provide a preparation method of the low-shrinkage high-flame-retardant polyolefin cable material, which has the advantages of simple operation and suitability for industrial production.
In order to achieve the first purpose, the application provides the following technical scheme:
a low-shrinkage high-flame-retardant polyolefin cable material comprises the following components in parts by weight:
linear low density polyethylene: 100 parts of (A);
ethylene-vinyl acetate copolymer: 5-15 parts;
ethylene-propylene copolymer: 5-10 parts;
ethylene-octene copolymer: 1-5 parts;
maleic anhydride grafted ethylene-vinyl acetate copolymer: 20-50 parts;
tert-butyl peroxide: 0.01-0.1 part;
inorganic flame retardant: 80-100 parts of a binder;
antioxidant: 0.5-1 part;
silicone oil: 2-5 parts.
By adopting the technical scheme, compared with conventional polyolefin base materials such as polyethylene and the like, linear low-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-propylene copolymer and ethylene-octene copolymer are preferably adopted as matrix resin in the cable material, the crystallinity of the obtained matrix resin is greatly reduced by utilizing the difference of glass transition temperature among the polymers, and the cable material prepared from the matrix resin has lower shrinkage.
The preferable compatilizer is maleic anhydride grafted ethylene-vinyl acetate copolymer, and can improve the compatibility among different resins and indirectly increase the macroscopic properties of the cable material, such as mechanics and the like. The addition of the inorganic flame retardant can endow the cable material with better flame retardance. In addition, tert-butyl peroxide is added as a catalyst and is matched with the maleic anhydride grafted ethylene-vinyl acetate copolymer for use, so that the crystallization speed of the resin can be greatly reduced, the crystallinity of the resin is reduced, and the obtained polyolefin cable material has low shrinkage.
Further preferably, the low-shrinkage high-flame-retardant polyolefin cable material comprises the following components in parts by weight:
linear low density polyethylene: 100 parts of (A);
ethylene-vinyl acetate copolymer: 10 parts of (A);
ethylene-propylene copolymer: 7 parts;
ethylene-octene copolymer: 2 parts of (1);
maleic anhydride grafted ethylene-vinyl acetate copolymer: 35 parts of (B);
tert-butyl peroxide: 0.05 part;
inorganic flame retardant: 90 parts of a mixture;
antioxidant: 0.7 part;
silicone oil: 4 parts.
By adopting the technical scheme, the raw material components with the above dosage are preferably selected, and the obtained polyolefin cable material has low shrinkage and high flame retardance.
More preferably, the linear low density polyethylene has a density of 0.9230-0.9235g/m3The melt index is 5-10g/10 min.
By adopting the technical scheme, the linear low-density polyethylene with the density and the melt index is selected, the compatibility between the linear low-density polyethylene and other resins is good, and the obtained cable material has good heat resistance and low corresponding shrinkage rate.
More preferably, the ethylene-vinyl acetate copolymer has a monomer content of 20-30wt% and a melt index of 5-10g/10 min.
By adopting the technical scheme, the ethylene-vinyl acetate copolymer with the monomer content and the melt index is preferably selected, the compatibility between the ethylene-vinyl acetate copolymer and other resins is good, the obtained cable material has good heat resistance and high mechanical property, and the cracking phenomenon is not easy to occur in the using process.
More preferably, the ethylene-propylene copolymer has a melt index of 3 to 6g/10min, and the ethylene-octene copolymer has a melt index of 5 to 8g/10 min.
By adopting the technical scheme, the ethylene-propylene copolymer and the ethylene-octene copolymer with the melt index are preferably selected, the compatibility between the ethylene-propylene copolymer and other resins is good, and the obtained cable material has good heat resistance and relatively low shrinkage.
More preferably, the inorganic flame retardant is selected from one or two of magnesium hydroxide and aluminum hydroxide.
By adopting the technical scheme, when the cable material is burnt, the magnesium hydroxide and the aluminum hydroxide release crystal water and absorb a large amount of heat to reduce the surface temperature of the synthetic material filled in the cable material in flame, and the cable material has the effects of inhibiting the decomposition of the cable material and cooling the generated combustible gas.
More preferably, the inorganic flame retardant is further subjected to modification treatment, and the specific modification steps are as follows: adding the inorganic flame retardant into the silane coupling agent, filtering, drying and crushing to obtain the silane coupling agent modified inorganic flame retardant powder.
By adopting the technical scheme, the silane coupling agent is adopted to modify the surface of the inorganic flame retardant, so that the inorganic flame retardant has good affinity with polyolefin, the dispersion of inorganic particles in a matrix is solved under the condition of ensuring the flame retardant performance, the interface effect between the inorganic flame retardant and the matrix is enhanced, and the mechanical property of the cable material is improved.
More preferably, the particle size of the magnesium hydroxide is 50-80nm, and the particle size of the aluminum hydroxide is 80-100 nm.
By adopting the technical scheme, the smaller the particle size of magnesium hydroxide and aluminum hydroxide is, the better the flame retardant property is, but the poorer the dispersibility is, so that the mechanical property of the polymer cable material is poorer.
In order to achieve the second purpose, the application provides the following technical scheme:
a preparation method of a low-shrinkage high-flame-retardant polyolefin cable material comprises the following steps:
s1, uniformly mixing the linear low-density polyethylene, the ethylene-vinyl acetate copolymer, the ethylene-propylene copolymer, the ethylene-octene copolymer, the maleic anhydride grafted ethylene-vinyl acetate copolymer and the inorganic flame retardant at the rotating speed of 300-500rpm for 5-10min to obtain a mixture A;
s2, adding tert-butyl peroxide, an antioxidant and silicone oil into the mixture A, and continuously mixing for 5-10min at the rotating speed of 300-500rpm to obtain a mixture B;
s3, putting the mixture B into an internal mixer, and internally mixing for 15-25min at the temperature of 60-75 ℃;
s4, putting the banburied materials into a twin-screw extruder with the working temperature of 120-130 ℃ for extrusion granulation, cooling and grain cutting, and obtaining the low-shrinkage high-flame-retardant polyolefin cable material.
In summary, compared with the prior art, the application has the following beneficial effects:
(1) the linear low-density polyethylene, the ethylene-vinyl acetate copolymer, the ethylene-propylene copolymer and the ethylene-octene copolymer are preferably adopted as matrix resins, the crystallinity of the obtained matrix resins is greatly reduced by utilizing the difference of glass transition temperatures among the polymers, and the cable material prepared from the matrix resins has lower shrinkage;
(2) the preferable compatilizer is maleic anhydride grafted ethylene-vinyl acetate copolymer, so that the compatibility among different resins can be improved, and the mechanical and other macroscopic properties of the cable material can be indirectly improved; the tert-butyl peroxide and the maleic anhydride grafted ethylene-vinyl acetate copolymer are matched for use, so that the crystallization rate of the resin can be greatly reduced, the crystallinity of the resin is reduced, and the obtained polyolefin cable material has low shrinkage
(3) The self-made modified inorganic flame retardant is added, so that the dispersibility of the inorganic flame retardant is improved, and the compatibility between the inorganic flame retardant and resin is improved, so that the flame retardance of the cable material is improved, and the shrinkage rate of the cable material is reduced.
Drawings
Fig. 1 is a flow chart of a preparation process of the low-shrinkage high-flame-retardant polyolefin cable material of the present application.
Detailed Description
The present application will be described in detail below with reference to the drawings and examples.
The antioxidants in the examples in this application are all oxygen agents 1010, available from Shanghai Ciba Gaobao chemical Co.
Maleic anhydride grafted ethylene-vinyl acetate copolymer was purchased from Nanjing plastitai polymer science and technology, Inc.
Other raw material components are all purchased from common markets.
Example 1: the low-shrinkage high-flame-retardant polyolefin cable material is prepared by the following steps, wherein the components and the corresponding parts by weight are shown in table 1, and the components are shown in figure 1:
s1, uniformly mixing linear low-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-propylene copolymer, ethylene-octene copolymer, maleic anhydride grafted ethylene-vinyl acetate copolymer and inorganic flame retardant at the rotating speed of 300rpm for 10min to obtain a mixture A;
s2, adding tert-butyl peroxide, an antioxidant and silicone oil into the mixture A, and continuously mixing for 10min at the rotating speed of 300rpm to obtain a mixture B;
s3, putting the mixture B into an internal mixer, and internally mixing for 25min at the temperature of 60 ℃;
s4, putting the banburied materials into a five-section double-screw extruder with the temperature controlled at 120 ℃, 120 ℃, 125 ℃, 125 ℃ and 130 ℃ for extrusion granulation, cooling by cold water at 20 ℃, and pelletizing to obtain the low-shrinkage high-flame-retardant polyolefin cable material.
In this example, the linear low density polyethylene had a density of 0.9230g/m3The melt index was 5g/10 min.
The ethylene-vinyl acetate copolymer has a monomer content of 20 wt% and a melt index of 5g/10 min.
The melt index of the ethylene-propylene copolymer was 3g/10min, and the melt index of the ethylene-octene copolymer was 5g/10 min.
The inorganic flame retardant adopts modified magnesium hydroxide with the average particle size of 60nm, and the modification steps are as follows: adding 100mg of magnesium hydroxide into 1000mL of silane coupling agent KH570, soaking for 2h, filtering, drying in an oven at 40 ℃, and crushing to obtain the magnesium hydroxide of example 2-6: a low-shrinkage high-flame-retardant polyolefin cable material is different from example 1 in that the components and the corresponding parts by weight are shown in Table 1.
TABLE 1 Components and parts by weight of examples 1-6
Example 7: a low-shrinkage high-flame-retardant polyolefin cable material, which is different from the material prepared in the example 1 in that the cable material is prepared by the following steps:
s1, uniformly mixing linear low-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-propylene copolymer, ethylene-octene copolymer, maleic anhydride grafted ethylene-vinyl acetate copolymer and inorganic flame retardant at the rotating speed of 500rpm for 5min to obtain a mixture A;
s2, adding tert-butyl peroxide, an antioxidant and silicone oil into the mixture A, and continuously mixing for 5min at the rotating speed of 500rpm to obtain a mixture B;
s3, putting the mixture B into an internal mixer, and internally mixing for 15min at the temperature of 75 ℃;
s4, putting the banburied materials into a five-section double-screw extruder with the temperature controlled at 120 ℃, 120 ℃, 125 ℃, 125 ℃ and 130 ℃ for extrusion granulation, and then cooling by cold water at 25 ℃ and dicing to obtain the low-shrinkage high-flame-retardant polyolefin cable material.
In this example, the linear low density polyethylene had a density of 0.9235g/m3The melt index was 10g/10 min.
The ethylene-vinyl acetate copolymer had a monomer content of 30wt% and a melt index of 10g/10 min.
The melt index of the ethylene-propylene copolymer was 6g/10min, and the melt index of the ethylene-octene copolymer was 8g/10 min.
The inorganic flame retardant adopts modified aluminum hydroxide with the average particle size of 90nm, and the modification steps are as follows: adding 100mg of aluminum hydroxide into 1000mL of silane coupling agent KH570, soaking for 2h, filtering, drying in an oven at 40 ℃, and crushing to obtain the following components in the following proportion of 1: a polyolefin cable material, which is different from that of example 1 in that no ethylene-vinyl acetate copolymer is added.
Comparative example 2: a polyolefin cable material, which differs from example 1 in that no ethylene-propylene copolymer and no ethylene-octene copolymer were added.
Comparative example 3: a polyolefin cable material, which differs from example 1 in that no linear low density polyethylene was added.
Comparative example 4: a polyolefin cable material, which is different from example 1 in that maleic anhydride grafted polyethylene is used instead of the maleic anhydride grafted ethylene-vinyl acetate copolymer of example 1.
Comparative example 5: a polyolefin cable material, which differs from example 1 in that t-butyl peroxide is not added.
Comparative example 6: a polyolefin cable material is different from the polyolefin cable material in example 1 in that unmodified magnesium hydroxide is used as an antioxidant.
Performance testing
The polyolefin cable materials obtained in examples 1 to 7 and comparative examples 1 to 6 were subjected to performance tests, and the test results are shown in the following table 2.
Wherein the tensile strength is carried out according to the GB/T1040.3-2006 standard;
the limiting oxygen index is carried out according to the GB/T2406-2009 standard;
the shrinkage was carried out according to GB/T15585-1995 at 130 ℃ for 1 h.
As can be seen from the test data in table 2, compared to comparative examples 1 to 5, examples 1 to 7 using the composite resin as the matrix resin and adding the maleic anhydride-grafted ethylene-vinyl acetate copolymer and t-butyl peroxide resulted in cable materials with lower shrinkage, which can be as low as 1.9%. Compared with the comparative example 6, the cable materials obtained by adopting the modified inorganic flame retardant and strictly controlling the particle size in the examples 1-7 have higher flame retardance, and the maximum limit oxygen index can reach 42%. In addition, the polyolefin cable material prepared by the method has good mechanical property, and the tensile strength reaches more than 17.6 MPa.
Table 2 results of performance testing
The above description is only a preferred embodiment of the present application, and the protection scope of the present application is not limited to the above embodiments, and all technical solutions belonging to the idea of the present application belong to the protection scope of the present application. It should be noted that several improvements and modifications to the present application without departing from the principles of the present application will occur to those skilled in the art, and such improvements and modifications should also be considered within the scope of the present application.
Claims (9)
1. The low-shrinkage high-flame-retardant polyolefin cable material is characterized by comprising the following components in parts by weight:
linear low density polyethylene: 100 parts of (A);
ethylene-vinyl acetate copolymer: 5-15 parts;
ethylene-propylene copolymer: 5-10 parts;
ethylene-octene copolymer: 1-5 parts;
maleic anhydride grafted ethylene-vinyl acetate copolymer: 20-50 parts;
tert-butyl peroxide: 0.01-0.1 part;
inorganic flame retardant: 80-100 parts of a binder;
antioxidant: 0.5-1 part;
silicone oil: 2-5 parts.
2. The low-shrinkage high-flame-retardant polyolefin cable material as claimed in claim 1, which comprises the following components in parts by weight:
linear low density polyethylene: 100 parts of (A);
ethylene-vinyl acetate copolymer: 10 parts of (A);
ethylene-propylene copolymer: 7 parts;
ethylene-octene copolymer: 2 parts of (1);
maleic anhydride grafted ethylene-vinyl acetate copolymer: 35 parts of (B);
tert-butyl peroxide: 0.05 part;
inorganic flame retardant: 90 parts of a mixture;
antioxidant: 0.7 part;
silicone oil: 4 parts.
3. The low shrinkage high flame retardant polyolefin cable material of claim 1, wherein the linear low density polyethylene has a density of 0.9230-0.9235g/m3The melt index is 5-10g/10 min.
4. The low-shrinkage high-flame-retardant polyolefin cable material according to claim 1, wherein the ethylene-vinyl acetate copolymer has a monomer content of 20-30wt% and a melt index of 5-10g/10 min.
5. The low shrinkage high flame retardant polyolefin cable material according to claim 1, wherein the ethylene-propylene copolymer has a melt index of 3 to 6g/10min and the ethylene-octene copolymer has a melt index of 5 to 8g/10 min.
6. The low-shrinkage high-flame-retardant polyolefin cable material according to claim 1, wherein the inorganic flame retardant is one or two selected from magnesium hydroxide and aluminum hydroxide.
7. The low-shrinkage high-flame-retardant polyolefin cable material as claimed in claim 6, wherein the inorganic flame retardant is further modified by the following specific modification steps: adding the inorganic flame retardant into the silane coupling agent, filtering, drying and crushing to obtain the silane coupling agent modified inorganic flame retardant powder.
8. The low-shrinkage high-flame-retardant polyolefin cable material according to claim 7, wherein the particle size of the magnesium hydroxide is 50-80nm, and the particle size of the aluminum hydroxide is 80-100 nm.
9. The method for preparing a low-shrinkage high-flame-retardant polyolefin cable material according to any one of claims 1 to 8, comprising the steps of:
s1, uniformly mixing the linear low-density polyethylene, the ethylene-vinyl acetate copolymer, the ethylene-propylene copolymer, the ethylene-octene copolymer, the maleic anhydride grafted ethylene-vinyl acetate copolymer and the inorganic flame retardant at the rotating speed of 300-500rpm for 5-10min to obtain a mixture A;
s2, adding tert-butyl peroxide, an antioxidant and silicone oil into the mixture A, and continuously mixing for 5-10min at the rotating speed of 300-500rpm to obtain a mixture B;
s3, putting the mixture B into an internal mixer, and internally mixing for 15-25min at the temperature of 60-75 ℃;
s4, putting the banburied materials into a twin-screw extruder with the working temperature of 120-130 ℃ for extrusion granulation, cooling and grain cutting, and obtaining the low-shrinkage high-flame-retardant polyolefin cable material.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114316418A (en) * | 2021-12-09 | 2022-04-12 | 成都金发科技新材料有限公司 | Low-shrinkage flame-retardant polyethylene composition, and preparation method and application thereof |
| CN114316418B (en) * | 2021-12-09 | 2023-08-04 | 成都金发科技新材料有限公司 | Low-shrinkage flame-retardant polyethylene composition, and preparation method and application thereof |
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