Waterproof and fireproof protective sleeve material for optical cable and preparation method of waterproof and fireproof protective sleeve material

Abstract

The invention belongs to the field of optical cable sheaths, and particularly relates to a waterproof and fireproof protective sleeve material for an optical cable and a preparation method thereof. The waterproof and fireproof protective sleeve material for the optical cable comprises the following components in parts by weight: 100-120 parts of polyethylene resin, 15-20 parts of modified polyether polyol, 10-15 parts of a plasticizer, 3-5 parts of a stabilizer, 0.5-1 part of an antioxidant and 1-2 parts of a silane coupling agent, the preparation method of the modified polyether polyol comprises the following steps: taking polyether polyol, inorganic alkali carbonate and (+ / -)-BOC-A-phosphonoglycine trimethyl ester, heating to react, and treating to obtain the modified polyether polyol. The preparation process of the stabilizer comprises the following steps: taking epoxidized soybean oil, lithium bromide and magnesium perchlorate to react at normal temperature, and treating to obtain the stabilizer. According to the technical scheme, the mechanical property is greatly improved while the waterproof and fireproof performance is improved.

Description

Technical Field

[0001] The present invention belongs to the field of optical cable sheaths, and in particular, to a waterproof and fireproof protective sleeve material for optical cables and a preparation method thereof. Background Art

[0002] In contemporary society, optical cables are widely used in the communication field, such as data transmission, long-distance communication, telecommunication networks, and video transmission. It supports the high-speed transmission of the Internet, meets the needs of big data and cloud computing, becomes the first choice for cross-sea communication, improves communication quality, and ensures clear and stable signals. At the same time, optical cables also play an important role in fields such as radio and television, transportation, military defense, and industrial automation, such as supporting traffic communication, military command, and industrial equipment communication. The normal operation of optical cables is easily affected by various factors, so the use of protective sleeves is particularly important.

[0003] CN108919453A discloses a waterproof and flame-retardant communication optical cable, including a cable core and a sheath. The outer surface of the cable core is coated with a first refractory layer, the outer surface of the first refractory layer is coated with a water-blocking layer, the outer surface of the water-blocking layer is coated with an insulating layer, the outer surface of the insulating layer is coated with a steel wire mesh layer, the outer surface of the steel wire mesh layer is coated with a wear-resistant layer, the outer surface of the wear-resistant layer is coated with an oxygen barrier layer, the outer surface of the oxygen barrier layer is coated with an elastic layer, the outer surface of the elastic layer is coated with a second refractory layer, the outer surface of the second refractory layer is coated with an armor layer, and the outer surface of the armor layer is coated with a sheath; this technical solution achieves the purpose of waterproofing and flame-retardant of the optical cable by superimposing protective layers, which will significantly limit the application range of the optical cable due to its heavy volume.

[0004] CN108359171A discloses a low-friction, low-smoke, halogen-free flame-retardant optical cable sheath material, including the following raw materials: EVA (ethylene-vinyl acetate copolymer) resin, metallocene PE, PE grafting material, main flame retardant aluminum hydroxide, inorganic filler calcium carbonate, auxiliary flame retardant red phosphorus masterbatch, low-friction lubricant, carbon black, coupling agent, antioxidant; this technical solution mainly improves the flame retardancy of the optical cable sheath material by adding inorganic flame retardants. However, it does not further study its application in waterproofing and fireproofing.

[0005] Therefore, it is urgent to develop an optical cable protective sleeve material with excellent waterproof and fireproof performance, which realizes the functions of traditional multi-layer protection with a single-layer structure, so as to break through the bottleneck of the limited application scenarios of current optical cable sheath materials. Summary of the Invention

[0006] The present invention provides a waterproof and fireproof protective sleeve material for optical cables, which has excellent waterproof and fireproof performance.

[0007] To achieve the above object, the technical solutions adopted by the present invention are as follows: A waterproof and fireproof protective sleeve material for optical cables, by weight, comprises the following components: 100 - 120 parts of polyethylene resin, 15 - 20 parts of modified polyether polyol, 10 - 15 parts of plasticizer, 3 - 5 parts of stabilizer, 0.5 - 1 part of antioxidant, and 1 - 2 parts of silane coupling agent; the preparation of the modified polyether polyol comprises the following steps: taking polyether polyol, inorganic carbonate base, (±)-BOC-A-phosphonylglycine trimethyl ester, heating and reacting, and then obtaining the modified polyether polyol through treatment; the preparation process of the stabilizer comprises the following steps: taking epoxidized soybean oil, lithium bromide, magnesium perchlorate, reacting at room temperature, and then obtaining the stabilizer through treatment.

[0008] Preferably, the dosage ratio of the polyether polyol, inorganic carbonate base, and (±)-BOC-A-phosphonylglycine trimethyl ester is 30:(6 - 10):(30 - 32).

[0009] Preferably, the temperature of the heating reaction is 80 - 100 °C, and the time of the heating reaction is 3 - 5 h.

[0010] Preferably, the molar dosage ratio of the epoxidized soybean oil, lithium bromide, and magnesium perchlorate is 1:(6 - 10):(6 - 10).

[0011] Preferably, the time of the room temperature reaction is 10 - 12 h.

[0012] Preferably, the plasticizer is one or two of dioctyl phthalate and dioctyl terephthalate.

[0013] Preferably, the antioxidant is one or two of antioxidant 1010 and antioxidant 168.

[0014] Preferably, the silane coupling agent is coupling agent KH-550.

[0015] Preferably, the polyethylene resin is one or two of ethylene-octene copolymer elastomer and high-density polyethylene.

[0016] Preferably, the polyether polyol is polytetrahydrofuran diol.

[0017] Preferably, the inorganic carbonate base is one of sodium carbonate, cesium carbonate, and potassium carbonate.

[0018] According to the above preparation method of the waterproof and fireproof protective sleeve material for optical cables, it includes the following steps: Step 1: Weigh polyethylene resin, modified polyether polyol, plasticizer, antioxidant, stabilizer, and silane coupling agent, vacuum dry them at 60 - 80 °C for 10 - 16 h and then mix evenly to obtain the prepared material for standby; Step 2: Put the prepared material for standby into an internal mixer and knead at 140 - 160 °C for 15 - 30 min, transfer the kneaded material to a twin-screw extruder, extrude at 150 - 155 °C, and granulate to obtain the waterproof and fireproof protective sleeve material for optical cables.

[0019] Compared with the prior art, the present invention has the following beneficial effects: In the present invention, modified polyether polyol is prepared by modifying polyether polyol with (±)-BOC-A-phosphonoglycine trimethyl ester, and thus is scientifically proportioned with polyethylene resin, plasticizer, antioxidant, stabilizer, and silane coupling agent, and then the waterproof and fireproof protective sleeve material for optical cables is prepared. While improving its waterproof and fireproof performance, its mechanical properties are also greatly improved, thereby expanding its application range.

[0020] The modified polyether polyol of the present invention itself still has hydroxyl groups, which belong to hydrophilic groups. When combined with other raw materials of the present invention, the flame-retardant effect cannot be achieved. And in principle, the hydrophilic groups will affect the hydrophilicity of substances. Therefore, in the present invention, the active hydroxyl groups in polyether polyol are modified by reacting with (±)-BOC-A-phosphonoglycine trimethyl ester. On the one hand, the flame-retardant performance of polyether polyol is improved, and on the other hand, the negative impact of the hydrophilic groups on the waterproof property during long-term use is also reduced.

[0021] In the present invention, stabilizer is prepared by modifying epoxidized soybean oil. After modification, bromine atoms and hydroxyl groups are introduced into the stabilizer; the hydroxyl groups form hydrogen bonds with other components, significantly improving the interfacial adhesion strength and increasing the tear strength and peel strength; partial bromination and hydroxylation can combine the advantages of both. For example, bromine enhances polarity and hydroxyl groups provide reaction activity, further cooperating with other fillers to achieve improved stable cross-linking of the materials in rubber. Specific Embodiments

[0022] In order to enable those skilled in the art to better understand and implement the technical solution of the present invention, the present invention will be further described below in conjunction with specific embodiments. In the description of the present invention, unless otherwise specified, the reagents used are commercially available, and the methods used are conventional techniques in the art. Example 1

[0023] A waterproof and fireproof protective sheath material for optical cables comprises the following components by weight: 110 parts of ethylene-octene copolymer elastomer, 18 parts of modified polyether polyol, 12 parts of dioctyl phthalate, 5 parts of stabilizer, 0.8 parts of antioxidant 1010 and 1.3 parts of coupling agent KH-550.

[0024] The preparation of the modified polyether polyol comprises the following steps: taking 30 parts of polytetrahydrofuran diol, 8 parts of sodium carbonate, and 30 parts of (±)-BOC-A-phosphonylglycine trimethyl ester and reacting them at 90°C for 2.5 hours, cooling the reaction system to room temperature, adding water to the reaction system, separating the solid and the water phase after ultrasonic treatment at room temperature for 20 minutes, and drying the solid in an oven to obtain the modified polyether polyol.

[0025] The preparation process of the stabilizer includes the following steps, and the materials are calculated by molar proportion: 10 parts of polyepoxidized soybean oil, 100 parts of lithium bromide, and 100 parts of magnesium perchlorate are reacted at room temperature for 12 hours, water is added to the reaction system, and the solid and the water phase are separated after ultrasonic treatment at room temperature for 20 minutes, and the solid is dried in an oven to obtain the stabilizer.

[0026] A waterproof and fireproof protective cover material for optical cables, the preparation process of which comprises the following steps: step 1: weighing ethylene-octene copolymer elastomer, modified polyether polyol, dioctyl phthalate, antioxidant 1010, coupling agent KH-550, vacuum drying at 70°C for 14 hours and then mixing them evenly to obtain a prepared material; step 2: putting the prepared material into an internal mixer and internally mixing at 150°C for 20 minutes, transferring the internally mixed material to a twin-screw extruder, extruding at 150°C, and granulating to obtain the waterproof and fireproof protective cover material for optical cables. Example 2

[0027] A waterproof and fireproof protective sheath material for optical cables comprises the following components by weight: 100 parts of high-density polyethylene, 20 parts of modified polyether polyol, 10 parts of dioctyl terephthalate, 0.5 parts of antioxidant 168, and 1.0 parts of coupling agent KH-550.

[0028] The preparation of the modified polyether polyol comprises the following steps: taking 30 parts of polytetrahydrofuran diol, 6 parts of potassium carbonate, and 31 parts of (±)-BOC-A-phosphonylglycine trimethyl ester and reacting them at 100° C. for 4 hours, cooling the reaction system to room temperature, adding water to the reaction system, ultrasonically separating the solid and the water phase at room temperature for 20 minutes, and drying the solid in an oven to obtain the modified polyether polyol.

[0029] The preparation process of the stabilizer includes the following steps, with the materials calculated by mole parts: Take 10 parts of polyepoxy soybean oil, 80 parts of lithium bromide, and 80 parts of magnesium perchlorate and react at room temperature for 12 h. Add water to the reaction system, ultrasonicate for 20 min at room temperature, then separate the solid and the aqueous phase. Dry the solid in an oven to obtain the stabilizer.

[0030] A waterproof and fireproof protective sheath material for optical cables, and its preparation process includes the following steps: Step 1: Weigh high-density polyethylene, modified polyether polyol, dioctyl terephthalate, antioxidant 168, and coupling agent KH-550. After vacuum drying at 60 °C for 16 h, mix them evenly to obtain the prepared material for standby; Step 2: Put the prepared material for standby into an internal mixer and knead at 160 °C for 15 min. Transfer the kneaded material to a twin-screw extruder and extrude at 155 °C to granulate, obtaining the waterproof and fireproof protective sheath material for optical cables. Example 3

[0031] A waterproof and fireproof protective sheath material for optical cables, calculated by weight parts, includes the following components: 60 parts of ethylene-octene copolymer elastomer, 60 parts of high-density polyethylene, 20 parts of modified polyether polyol, 15 parts of dioctyl phthalate, 4 parts of stabilizer, 1.0 part of antioxidant 1010, and 2.0 parts of coupling agent KH-550.

[0032] The preparation of the modified polyether polyol includes the following steps: Take 30 parts of polytetrahydrofuran diol, 10 parts of cesium carbonate, and 32 parts of (±)-BOC-A-phosphonoglycine trimethyl ester and react at 80 °C for 5 h. After cooling the reaction system to room temperature, add water to the reaction system, ultrasonicate for 20 min at room temperature, then separate the solid and the aqueous phase. Dry the solid in an oven to obtain the modified polyether polyol.

[0033] The preparation process of the stabilizer includes the following steps, with the materials calculated by mole parts: Take 10 parts of polyepoxy soybean oil, 60 parts of lithium bromide, and 60 parts of magnesium perchlorate and react at room temperature for 10 h. Add water to the reaction system, ultrasonicate for 20 min at room temperature, then separate the solid and the aqueous phase. Dry the solid in an oven to obtain the stabilizer.

[0034] A waterproof and fireproof protective sheath material for optical cables, and its preparation process includes the following steps: Step 1: Weigh ethylene-octene copolymer elastomer, high-density polyethylene, modified polyether polyol, dioctyl phthalate, antioxidant 1010, and coupling agent KH-550. After vacuum drying at 80 °C for 16 h, mix them evenly to obtain the prepared material for standby; Step 2: Put the prepared material for standby into an internal mixer and knead at 140 °C for 30 min. Transfer the kneaded material to a twin-screw extruder and extrude at 150 °C to granulate, obtaining the waterproof and fireproof protective sheath material for optical cables.

[0035] Comparative Example 1 A waterproof and fireproof protective sleeve material for optical cables, by weight, comprises the following components: 60 parts of ethylene-octene copolymer elastomer, 60 parts of high-density polyethylene, 20 parts of modified polyether polyol, 15 parts of dioctyl phthalate, 3 parts of epoxidized soybean oil, 0.5 part of antioxidant 1010, 0.5 part of antioxidant 168, and 2.0 parts of coupling agent KH-550.

[0036] The preparation of the modified polyether polyol comprises the following steps: Take 30 parts of polytetrahydrofuran diol, 10 parts of cesium carbonate, and 32 parts of (±)-BOC-A-phosphonylglycine trimethyl ester, react at 80 °C for 5 h. After cooling the reaction system to room temperature, add water to the reaction system, ultrasonicate for 20 min at room temperature, then separate the solid and the aqueous phase, and dry the solid in an oven to obtain the modified polyether polyol.

[0037] A waterproof and fireproof protective sleeve material for optical cables, the preparation process comprises the following steps: Step 1: Weigh and mix ethylene-octene copolymer elastomer, high-density polyethylene, modified polyether polyol, dioctyl phthalate, antioxidant 1010 / 168, and coupling agent KH-550, vacuum dry at 80 °C for 16 h and then mix evenly to obtain the prepared stock; Step 2: Put the prepared stock into an internal mixer, knead at 140 °C for 30 min, transfer the kneaded material to a twin-screw extruder, extrude at 150 °C, and pelletize to obtain the waterproof and fireproof protective sleeve material for optical cables.

[0038] Comparative Example 2 A waterproof and fireproof protective sleeve material for optical cables, by weight, comprises the following components: 110 parts of ethylene-octene copolymer elastomer, 12 parts of dioctyl phthalate, 0.8 part of antioxidant 1010, and 1.3 parts of coupling agent KH-550.

[0039] A waterproof and fireproof protective sleeve material for optical cables, the preparation process comprises the following steps: Step 1: Weigh and mix ethylene-octene copolymer elastomer, dioctyl phthalate, antioxidant 1010, and coupling agent KH-550, vacuum dry at 70 °C for 14 h and then mix evenly to obtain the prepared stock; Step 2: Put the prepared stock into an internal mixer, knead at 150 °C for 20 min, transfer the kneaded material to a twin-screw extruder, extrude at 150 °C, and pelletize to obtain the waterproof and fireproof protective sleeve material for optical cables.

[0040] Comparative Example 3 A waterproof and fireproof protective sleeve material for optical cables, by weight, comprises the following components: 110 parts of ethylene-octene copolymer elastomer, 18 parts of polyether polyol, 12 parts of dioctyl phthalate, 0.8 part of antioxidant 1010, and 1.3 parts of coupling agent KH-550.

[0041] A waterproof and fireproof protective sleeve material for optical cables, the preparation process includes the following steps: Step 1: Weigh ethylene-octene copolymer elastomer, modified polyether polyol, dioctyl phthalate, antioxidant 1010, and coupling agent KH-550, vacuum dry them at 70°C for 14h, and then mix them evenly to obtain the prepared material for standby; Step 2: Put the prepared material for standby into an internal mixer, knead it at 150°C for 20min, transfer the kneaded material to a twin-screw extruder, extrude it at 150°C, and granulate it to obtain the waterproof and fireproof protective sleeve material for optical cables.

[0042] Performance Test Perform performance tests on Examples 1 to 3 and Comparative Examples 1 to 3. Conduct tensile strength and elongation at break tests according to the test methods provided in "GB / T1040.3-2006"; conduct oxygen index tests according to the test methods provided in "GBT 2406.2-2009"; for the immersed water voltage test, the sample is 20m long, immersed in water at (20±5)°C for 3h, and then subjected to a 5min voltage test (DC 130kV) without breakdown, as specifically described in Table 1.

[0043] Table 1 Performance Test

[0044] As can be seen from Table 1, compared with Examples 1 to 3, the fireproof performance of Comparative Examples 1 to 3 is poor, which indicates that unmodified polyether polyol does not have good fireproof performance. In Comparative Example 2, the modified polyether polyol is replaced with an equal amount of polyether polyol, and its fireproof performance is slightly better than that of Comparative Example 1 where the modified polyether polyol is omitted, which shows that the combination of polyether polyol and polyethylene resin can improve the limited fireproof performance, but still cannot reach the high flame retardancy performance mentioned in the industry; when conducting the immersed water voltage test on Examples 1 to 3 and Comparative Examples 1 to 2, no breakdown occurs, which indicates that their waterproof performance can meet the industry requirements. The mechanical properties of Comparative Examples 1 to 3 are weaker than those of Examples 1 to 3, indicating that partial bromination and hydroxylation can combine the advantages of both. For example, bromine enhances polarity, and hydroxyl provides reaction activity, and further cooperate with other fillers to achieve improved stable crosslinking of the materials in the rubber. In short, the hydrophilic group of polyether polyol will affect the hydrophilicity of the substance. Therefore, in the present invention, the active hydroxyl group in polyether polyol is reacted with (±)-BOC-A-phosphonoglycine trimethyl ester for modification, which on the one hand improves the flame retardancy of polyether polyol, and on the other hand also reduces the negative impact of the hydrophilic group on polyether polyol on the waterproof property during long-term use.

[0045] Obviously, those skilled in the art can make several modifications and refinements to the present invention without departing from the protection scope of the present invention. Thus, if these modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalent technologies, the present invention also intends to include these modifications and variations.

Claims

1. A waterproof and fireproof protective sheath material for optical cables, characterized in that: The invention comprises the following components by weight: 100-120 parts of polyethylene resin, 15-20 parts of modified polyether polyol, 10-15 parts of plasticizer, 3-5 parts of stabilizer, 0.5-1 parts of antioxidant and 1-2 parts of silane coupling agent; the preparation of the modified polyether polyol comprises the following steps: Taking polyether polyol, inorganic carbonate and (±)-BOC-A-phosphonylglycine trimethyl ester and heating them for reaction, and then treating them to obtain modified polyether polyol; The preparation process of the stabilizer comprises the following steps: taking epoxy soybean oil, lithium bromide and magnesium perchlorate to react at room temperature and then treating to obtain the stabilizer.

2. The waterproof and fireproof protective sheath material for optical cable according to claim 1, characterized in that: The mass ratio of the polyether polyol, inorganic carbonate base and (±)-BOC-A-phosphonylglycine trimethyl ester is 30:(6-10):(30-32).

3. The waterproof and fireproof protective sheath material for optical cable according to claim 1, characterized in that: The temperature of the heating reaction is 80-100°C, and the time of the heating reaction is 3-5h.

4. The waterproof and fireproof protective sheath material for optical cable according to claim 1, characterized in that: The molar ratio of the epoxidized soybean oil, lithium bromide and magnesium perchlorate is 1:(6-10):(6-10).

5. The waterproof and fireproof protective sheath material for optical cable according to claim 1, characterized in that: The reaction time at room temperature is 10 to 12 hours.

6. The waterproof and fireproof protective sheath material for optical cable according to claim 1, characterized in that: The plasticizer is one or both of dioctyl phthalate and dioctyl terephthalate; the antioxidant is one or both of antioxidant 1010 and antioxidant 168; and the silane coupling agent is coupling agent KH-550.

7. The waterproof and fireproof protective sheath material for optical cable according to claim 1, characterized in that: The polyethylene resin is one or both of ethylene-octene copolymer elastomer and high-density polyethylene; the polyether polyol is polytetramethylene glycol.

8. The waterproof and fireproof protective sheath material for optical cable according to claim 2, characterized in that: The inorganic carbonate alkali is one of sodium carbonate, cesium carbonate and potassium carbonate.

9. The method for preparing the waterproof and fireproof protective sheath material for optical cable according to any one of claims 1 to 8, characterized in that: The method comprises the following steps: step 1: weighing polyethylene resin, modified polyether polyol, plasticizer, antioxidant, stabilizer and silane coupling agent, vacuum drying them at 60-80°C for 10-16h and then mixing them evenly to obtain a prepared material; step 2: putting the prepared material into an internal mixer and internally mixing them at 140-160°C for 15-30min, transferring the internally mixed material to a twin-screw extruder, extruding at 150-155°C, and granulating to obtain a waterproof and fireproof protective cover material for an optical cable.

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