Method for improving peel strength between metal belts in optical cable sheath

Abstract

The invention discloses a method for improving the peel strength between metal belts in an optical cable sheath, the sheath and the metal belts are bonded through a hot melt adhesive, and the preparation method of the hot melt adhesive comprises the following steps: (1) preparing modified particles; (2) preparing filler particles; (3) heating the amorphous alpha-olefin copolymer to a molten state, adding dicumyl peroxide, stirring, and adding (3-aminopropyl) triethoxysilane to obtain a molten mixture; and (4) adding the filler particles, the PP wax and the C5 petroleum resin, stirring, cooling, and adding the antioxidant 1010 to obtain the hot melt adhesive. The hot melt adhesive prepared by adopting the method disclosed by the invention has good bonding performance and relatively high peel strength, and the durability of the optical cable is improved.

Description

Technical Field

[0001] The invention relates to the technical field of hot melt adhesive materials, and in particular to a method for improving the peeling strength between metal tapes in an optical cable sheath. Background Art

[0002] The metal tape layer commonly found in optical cables not only ensures the cable's ability to prevent moisture penetration, but also improves the cable's ability to resist lateral pressure, protecting the optical fiber in the cable core sleeve from external pressure. The metal tape layer and the sheath material need to be well bonded to fully exert their functions, otherwise it will lead to the degradation of the cable's performance such as water seepage and stretching. Peel strength is an important indicator to measure the bonding between the metal tape layer and the sheath material, which directly affects the performance of the optical cable, so it is crucial to choose an adhesive with better performance. Summary of the invention

[0003] To this end, the present invention provides a method for improving the peel strength between metal tapes in an optical cable sheath, wherein the sheath and the metal tape are bonded by hot melt adhesive, and the preparation steps of the hot melt adhesive include:

[0004] (1) adding 1,3-bis[3-(dimethylamino)propyl]urea to an acetone solution of monobromododecane to obtain a mixture, heating the mixture to 60±5° C. in a water bath, and stirring the mixture at a constant temperature for more than 12 hours to obtain a modifier; mixing graphite carbon nitride and ammonia water in a reactor, stirring the mixture for more than 30 minutes, and then sealing the reactor, heating to 140±5° C. and keeping the temperature for more than 10 hours, cooling to room temperature after the end of the heat preservation, opening the reactor, separating the solid and the liquid, washing the solid phase with deionized water for more than 3 times, and drying to obtain Ammoniated particles; adding the ammoniated particles to an aqueous solution of sodium xanthate, heating in a water bath to 35±3°C, stirring at a constant temperature for more than 2 hours, separating the solid and the liquid after the constant temperature stirring, washing the solid phase with deionized water for more than 3 times, adding the solid phase to deionized water after washing and stirring for more than 30 minutes to obtain a water suspension, and then adding the modifier to the water suspension under stirring, heating in a water bath to 60±5°C after adding, stirring at a constant temperature for more than 4 hours, then separating the solid and the liquid, washing the solid phase with deionized water for more than 3 times, and drying to obtain modified particles;

[0005] (2) preparing a composite tetrahydrofuran solution of polytetramethylene ether glycol and dibutyltin dilaurate, heating the composite tetrahydrofuran solution of polytetramethylene ether glycol and dibutyltin dilaurate to 35±3° C. in a nitrogen atmosphere, stirring at a constant temperature for more than 20 minutes after reaching the temperature, and then adding toluene 2,4-diisocyanate under stirring. After the addition is completed, stirring at a constant temperature of 35±3° C. in a nitrogen atmosphere for more than 40 minutes, and then adding the modified particles, stirring at a constant temperature of 35±3° C. in a nitrogen atmosphere for more than 30 minutes, separating the solid and the liquid, washing the solid phase with ethanol for more than 3 times, and drying to obtain filler particles;

[0006] (3) heating the amorphous α-olefin copolymer to 155±5° C. to form a molten state, then adding dicumyl peroxide under stirring, and continuing to stir the mixture for 5 to 10 minutes after the addition is completed, and then adding (3-aminopropyl) triethoxysilane under stirring, and continuing to stir the mixture at a constant temperature of 155±5° C. for 20 to 30 minutes after the addition is completed to obtain a molten mixture;

[0007] (4) Add the filler particles, PP wax and C5 petroleum resin to the molten mixture kept at 155±5°C, keep the mixture at 155±5°C and stir for 30-40 minutes, cool the mixture to 120±5°C, add an antioxidant, keep the mixture at 120±5°C and stir for 20-30 minutes to obtain the hot melt adhesive.

[0008] Furthermore, in the step (1), the mass ratio of 1,3-bis[3-(dimethylamino)propyl]urea added to the acetone solution of monobromododecane is 1,3-bis[3-(dimethylamino)propyl]urea: acetone solution of monobromododecane = 1 to 2:20; the mass percentage of monobromododecane in the acetone solution of monobromododecane is 8% to 10%; the mass ratio of the graphite phase carbon nitride and ammonia water is graphite phase carbon nitride: ammonia water = 1:50 to 100, wherein the mass percentage of the solute in the ammonia water is 10% to 20%; the mass ratio of the aminated particles added to the aqueous solution of sodium xanthate is aminated particles: aqueous solution of sodium xanthate = 1:50 to 100, wherein the concentration of sodium xanthate in the aqueous solution of sodium xanthate is 22 to 26 g / L; the mass ratio of the modifier added to the aqueous suspension is aqueous suspension: modifier = 5 to 6:1.

[0009] Furthermore, in the step (2), in the composite tetrahydrofuran solution of polytetramethylene ether glycol and dibutyltin dilaurate, the concentration of polytetramethylene ether glycol is 16-20 g / 100 mL, the concentration of dibutyltin dilaurate is 0.8-1 g / 100 mL, and the solvent is tetrahydrofuran; the amount ratio of the added mass of the toluene 2,4-diisocyanate and the modified particles to the composite tetrahydrofuran solution of polytetramethylene ether glycol and dibutyltin dilaurate is toluene 2,4-diisocyanate: modified particles: composite tetrahydrofuran solution of polytetramethylene ether glycol and dibutyltin dilaurate = 1.2-1.4 g: 0.5-0.8 g: 20 mL.

[0010] Furthermore, in the step (3), the mass ratio of the amorphous α-olefin copolymer, dicumyl peroxide and (3-aminopropyl)triethoxysilane is amorphous α-olefin copolymer: dicumyl peroxide: (3-aminopropyl)triethoxysilane = 100: 0.8-1: 7-10.

[0011] Furthermore, in the step (4), the mass ratio of the added mass of the filler particles, PP wax, C5 petroleum resin, and antioxidant to the mass ratio of the amorphous α-olefin copolymer used to prepare the molten mixture is amorphous α-olefin copolymer: filler particles: PP wax: C5 petroleum resin: antioxidant = 100: 4-6: 3-4: 10-15: 0.1-0.2.

[0012] The beneficial effect of the present invention is that the hot melt adhesive prepared by the method of the present invention has good bonding performance and high peel strength, thereby improving the durability of the optical cable. By adding the filler particles of the present invention, the bonding property of the hot melt adhesive can be significantly improved, which is manifested in a significant increase in peel strength. This is mainly because: the present invention first uses ammonia water hydrothermal treatment method to form a large number of amino groups on the surface of graphite phase carbon nitride to obtain aminated particles, then uses sodium xanthate to graft part of the amino groups to form disulfide functional groups, and then uses 1,3-bis[3-(dimethylamino)propyl]urea and monobromododecane to react with quaternary ammonium salts to form a surfactant modifier, and exchanges the sodium cations on the surface of the grafted particles to obtain modified particles. In this way, on the one hand, a macromolecular structure can be introduced on the surface of the particles to improve the dispersibility of the particles and the bonding force between the particles and the amorphous α-olefin copolymer matrix; on the other hand, a diamide bond-containing group can be introduced into the hot melt adhesive; subsequently, the urea carbamate structure is introduced through the step (2), and a macromolecular network structure with filler particles as nodes is formed through chemical crosslinking, which shows that the bonding strength of the hot melt adhesive is significantly improved on a macro scale, and the introduced urea carbamate groups and the above-mentioned diamide bond-containing groups are both strong polar groups, so that strong hydrogen bonds are formed between the hot melt adhesive and the surface of the adherend, thereby improving the adhesion. DETAILED DESCRIPTION

[0013] The present invention will be further described below in conjunction with the embodiments.

[0014] Example 1

[0015] A method for improving the peel strength between metal tapes in an optical cable sheath, wherein the sheath and the metal tape are bonded by hot melt adhesive, and the preparation steps of the hot melt adhesive include:

[0016] (1) adding 1,3-bis[3-(dimethylamino)propyl]urea to an acetone solution of monobromododecane to obtain a mixture, wherein the mass ratio of 1,3-bis[3-(dimethylamino)propyl]urea to the acetone solution of monobromododecane is 1:20; the mass percentage of monobromododecane in the acetone solution of monobromododecane is 8%; mixing The mixture was heated to 60°C in a water bath and stirred at a constant temperature for 12 hours to obtain a modifier; graphite phase carbon nitride (sieved powder passing through a 2000 mesh sieve) and ammonia water were mixed in a reactor, wherein the mixing mass ratio of the graphite phase carbon nitride and ammonia water was graphite phase carbon nitride: ammonia water = 1:50, wherein the mass percentage of the solute in the ammonia water was 10%; the mixture was stirred for 30 minutes, and then the reactor was closed and heated to 140°C for 10 hours, and after the insulation was completed, the reactor was emptied. Cool to room temperature, open the reactor, separate the solid and liquid, wash the solid phase with deionized water for 3 times, and dry at 60°C for 3h to obtain aminated particles; add the aminated particles to an aqueous solution of sodium xanthate, the mass ratio of the aminated particles added to the aqueous solution of sodium xanthate is aminated particles: aqueous solution of sodium xanthate = 1:50, wherein the concentration of sodium xanthate in the aqueous solution of sodium xanthate is 22g / L; heat in a water bath to 35°C, stir at a constant temperature for 2h, separate the solid and liquid after constant temperature stirring, wash the solid phase with deionized water for 3 times, add it to deionized water after washing and stir for 30min to obtain a water suspension, then add the modifier to the water suspension under stirring, the mass ratio of the modifier added to the water suspension is water suspension: modifier = 5:1; heat in a water bath to 60°C after adding, stir at a constant temperature for 4h, then separate the solid and liquid, wash the solid phase with deionized water for 3 times, and dry at 60°C for 3h to obtain modified particles;

[0017] (2) preparing a composite tetrahydrofuran solution of polytetramethylene ether glycol (PTMEG-1000) and dibutyltin dilaurate, wherein the concentration of polytetramethylene ether glycol in the composite tetrahydrofuran solution of polytetramethylene ether glycol and dibutyltin dilaurate is 16 g / 100 mL, the concentration of dibutyltin dilaurate is 0.8 g / 100 mL, and the solvent is tetrahydrofuran; heating the composite tetrahydrofuran solution of polytetramethylene ether glycol and dibutyltin dilaurate to 35° C. in a water bath in a nitrogen atmosphere, stirring at a constant temperature for 20 min after reaching the temperature, and then adding toluene 2,4-dihydrogen sulfide under stirring; isocyanate, after the addition is completed, continue to stir at a constant temperature of 35°C for 40 minutes in a nitrogen atmosphere, then add the modified particles, the added mass ratio of the toluene 2,4-diisocyanate and the modified particles to the composite tetrahydrofuran solution of polytetramethylene ether glycol and dibutyltin dilaurate is toluene 2,4-diisocyanate: modified particles: composite tetrahydrofuran solution of polytetramethylene ether glycol and dibutyltin dilaurate = 1.2g: 0.5g: 20mL; stir at a constant temperature of 35°C for 30 minutes in a nitrogen atmosphere, separate the solid and liquid, wash the solid phase with ethanol 3 times, and dry at 60°C for 3h to obtain filler particles;

[0018] (3) heating an amorphous α-olefin copolymer (APAO-750) to 155° C. to form a molten state, then adding diisopropylbenzene peroxide under stirring, and continuing to stir the mixture for 5 minutes after the addition is completed, and then adding (3-aminopropyl) triethoxysilane under stirring, wherein the mass ratio of the amorphous α-olefin copolymer, diisopropylbenzene peroxide and (3-aminopropyl) triethoxysilane used is amorphous α-olefin copolymer: diisopropylbenzene peroxide: (3-aminopropyl) triethoxysilane = 100:0.8:7; after the addition is completed, continuing to stir the mixture at a constant temperature of 155° C. for 20 minutes to obtain a molten mixture;

[0019] (4) Add the filler particles, PP wax and C5 petroleum resin to the molten mixture kept at 155° C., keep the mixture at 155° C. and stir for 30 minutes after adding the materials, cool the mixture to 120° C., add antioxidant 1010, and the mass ratio of the added filler particles, PP wax, C5 petroleum resin and antioxidant 1010 to the mass ratio of the amorphous α-olefin copolymer used to prepare the molten mixture is amorphous α-olefin copolymer: filler particles: PP wax: C5 petroleum resin: antioxidant 1010 = 100:4:3:10:0.1; keep the mixture at 120° C. and stir for 20 minutes after adding the materials to obtain the hot melt adhesive.

[0020] Example 2

[0021] A method for improving the peel strength between metal tapes in an optical cable sheath, wherein the sheath and the metal tape are bonded by hot melt adhesive, and the preparation steps of the hot melt adhesive include:

[0022] (1) adding 1,3-bis[3-(dimethylamino)propyl]urea to an acetone solution of monobromododecane to obtain a mixture, wherein the mass ratio of 1,3-bis[3-(dimethylamino)propyl]urea to the acetone solution of monobromododecane is 1:20; the mass percentage of monobromododecane in the acetone solution of monobromododecane is 9%; and the mixture is heated in a water bath until 60°C, constant temperature stirring for 12h to obtain a modifier; mixing graphite phase carbon nitride (sieved powder passing through a 2000 mesh sieve) and ammonia water in a reactor, the mixing mass ratio of the graphite phase carbon nitride and ammonia water is graphite phase carbon nitride: ammonia water = 1:50, wherein the mass percentage of the solute in the ammonia water is 10%; stirring the mixture for 30min, then sealing the reactor, heating to 140°C and keeping the temperature for 10h, air cooling to room temperature after the end of the heat preservation, opening the reactor,

[0023] Solid-liquid separation, the solid phase is washed with deionized water for 3 times, and dried at 60°C for 3h to obtain aminated particles; the aminated particles are added to an aqueous solution of sodium xanthate, and the mass ratio of the aminated particles added to the aqueous solution of sodium xanthate is aminated particles: aqueous solution of sodium xanthate = 1:50, wherein the concentration of sodium xanthate in the aqueous solution of sodium xanthate is 24g / L; water bath heating to 35°C, constant temperature stirring for 2h, solid-liquid separation after constant temperature stirring, the solid phase is washed with deionized water for 3 times, and after washing, it is added to deionized water and stirred for 30min to obtain a water suspension, and then the modifier is added to the water suspension under stirring, and the mass ratio of the modifier added to the water suspension is water suspension: modifier = 5:1; after adding, water bath heating to 60°C, constant temperature stirring for 4h, and then solid-liquid separation, the solid phase is washed with deionized water for 3 times, and dried at 60°C for 3h to obtain modified particles;

[0024] (2) preparing a composite tetrahydrofuran solution of polytetramethylene ether glycol (PTMEG-1000) and dibutyltin dilaurate, wherein the concentration of polytetramethylene ether glycol in the composite tetrahydrofuran solution of polytetramethylene ether glycol and dibutyltin dilaurate is 18 g / 100 mL, the concentration of dibutyltin dilaurate is 0.9 g / 100 mL, and the solvent is tetrahydrofuran; heating the composite tetrahydrofuran solution of polytetramethylene ether glycol and dibutyltin dilaurate to 35° C. in a water bath in a nitrogen atmosphere, stirring at a constant temperature for 20 min after reaching the temperature, and then adding toluene 2,4-dihydrogen sulfide under stirring; isocyanate, after the addition is completed, continue to stir at a constant temperature of 35°C for 40 minutes in a nitrogen atmosphere, then add the modified particles, the amount ratio of the added mass of the toluene 2,4-diisocyanate and the modified particles to the composite tetrahydrofuran solution of polytetramethylene ether glycol and dibutyltin dilaurate is toluene 2,4-diisocyanate: modified particles: composite tetrahydrofuran solution of polytetramethylene ether glycol and dibutyltin dilaurate = 1.3g: 0.6g: 20mL; stir at a constant temperature of 35°C for 30 minutes in a nitrogen atmosphere, separate the solid and liquid, wash the solid phase with ethanol 3 times, and dry at 60°C for 3h to obtain filler particles;

[0025] (3) heating the amorphous α-olefin copolymer (APAO-750) to 155° C. to form a molten state, then adding diisopropylbenzene peroxide under stirring, continuing to stir the mixture for 5 minutes after the addition is completed, and then adding (3-aminopropyl) triethoxysilane under stirring, the mass ratio of the amorphous α-olefin copolymer, diisopropylbenzene peroxide and (3-aminopropyl) triethoxysilane used is amorphous α-olefin copolymer: diisopropylbenzene peroxide: (3-aminopropyl) triethoxysilane = 100:0.9:8; after the addition is completed, continue to stir the mixture at a constant temperature of 155° C. for 20 minutes to obtain a molten mixture;

[0026] (4) Add the filler particles, PP wax and C5 petroleum resin to the molten mixture kept at 155° C., keep the mixture at 155° C. and stir for 30 minutes after adding the materials, cool the mixture to 120° C., add antioxidant 1010, and the mass ratio of the added filler particles, PP wax, C5 petroleum resin and antioxidant 1010 to the mass ratio of the amorphous α-olefin copolymer used to prepare the molten mixture is amorphous α-olefin copolymer: filler particles: PP wax: C5 petroleum resin: antioxidant 1010 = 100:5:3:12:0.1; keep the mixture at 120° C. and stir for 20 minutes after adding the materials to obtain the hot melt adhesive.

[0027] Example 3

[0028] A method for improving the peel strength between metal tapes in an optical cable sheath, wherein the sheath and the metal tape are bonded by hot melt adhesive, and the preparation steps of the hot melt adhesive include:

[0029] (1) adding 1,3-bis[3-(dimethylamino)propyl]urea to an acetone solution of monobromododecane to obtain a mixture, wherein the mass ratio of 1,3-bis[3-(dimethylamino)propyl]urea to the acetone solution of monobromododecane is 1,3-bis[3-(dimethylamino)propyl]urea:acetone solution of monobromododecane=2:20; the mass percentage of monobromododecane in the acetone solution of monobromododecane is 9%; and the mixture is heated in a water bath until 60°C, constant temperature stirring for 12h to obtain a modifier; mixing graphite phase carbon nitride (sieved powder passing through a 2000 mesh sieve) and ammonia water in a reactor, the mixing mass ratio of the graphite phase carbon nitride and ammonia water is graphite phase carbon nitride: ammonia water = 1:50, wherein the mass percentage of the solute in the ammonia water is 20%; stirring the mixture for 30min, then sealing the reactor, heating to 140°C and keeping the temperature for 10h, air cooling to room temperature after the end of the heat preservation, opening the reactor,

[0030] Solid-liquid separation, the solid phase is washed with deionized water for 3 times, and dried at 60°C for 3h to obtain aminated particles; the aminated particles are added to an aqueous solution of sodium xanthate, and the mass ratio of the aminated particles added to the aqueous solution of sodium xanthate is aminated particles: aqueous solution of sodium xanthate = 1:50, wherein the concentration of sodium xanthate in the aqueous solution of sodium xanthate is 24g / L; water bath heating to 35°C, constant temperature stirring for 2h, solid-liquid separation after constant temperature stirring, the solid phase is washed with deionized water for 3 times, and after washing, it is added to deionized water and stirred for 30min to obtain a water suspension, and then the modifier is added to the water suspension under stirring, and the mass ratio of the modifier added to the water suspension is water suspension: modifier = 6:1; after adding, water bath heating to 60°C, constant temperature stirring for 4h, and then solid-liquid separation, the solid phase is washed with deionized water for 3 times, and dried at 60°C for 3h to obtain modified particles;

[0031] (2) preparing a composite tetrahydrofuran solution of polytetramethylene ether glycol (PTMEG-1000) and dibutyltin dilaurate, wherein the concentration of polytetramethylene ether glycol in the composite tetrahydrofuran solution of polytetramethylene ether glycol and dibutyltin dilaurate is 18 g / 100 mL, the concentration of dibutyltin dilaurate is 0.9 g / 100 mL, and the solvent is tetrahydrofuran; heating the composite tetrahydrofuran solution of polytetramethylene ether glycol and dibutyltin dilaurate to 35° C. in a water bath in a nitrogen atmosphere, stirring at a constant temperature for 20 min after reaching the temperature, and then adding toluene 2,4-dihydrogen sulfide under stirring; isocyanate, after the addition is completed, continue to stir at a constant temperature of 35°C for 40 minutes in a nitrogen atmosphere, then add the modified particles, the added mass ratio of the toluene 2,4-diisocyanate and the modified particles to the composite tetrahydrofuran solution of polytetramethylene ether glycol and dibutyltin dilaurate is toluene 2,4-diisocyanate: modified particles: composite tetrahydrofuran solution of polytetramethylene ether glycol and dibutyltin dilaurate = 1.3g: 0.7g: 20mL; stir at a constant temperature of 35°C for 30 minutes in a nitrogen atmosphere, separate the solid and liquid, wash the solid phase with ethanol 3 times, and dry at 60°C for 3h to obtain filler particles;

[0032] (3) heating an amorphous α-olefin copolymer (APAO-750) to 155° C. to form a molten state, then adding diisopropylbenzene peroxide under stirring, continuing to stir and mix for 5 minutes after the addition is completed, and then adding (3-aminopropyl) triethoxysilane under stirring, wherein the mass ratio of the amorphous α-olefin copolymer, diisopropylbenzene peroxide and (3-aminopropyl) triethoxysilane used is amorphous α-olefin copolymer: diisopropylbenzene peroxide: (3-aminopropyl) triethoxysilane = 100:0.9:9; after the addition is completed, continuing to stir the mixture at a constant temperature of 155° C. for 20 minutes to obtain a molten mixture;

[0033] (4) Add the filler particles, PP wax and C5 petroleum resin to the molten mixture kept at 155° C., keep the mixture at 155° C. and stir for 30 minutes after adding the materials, cool the mixture to 120° C., add antioxidant 1010, and the mass ratio of the added filler particles, PP wax, C5 petroleum resin and antioxidant 1010 to the mass ratio of the amorphous α-olefin copolymer used to prepare the molten mixture is amorphous α-olefin copolymer: filler particles: PP wax: C5 petroleum resin: antioxidant 1010 = 100:5:4:14:0.2; keep the mixture at 120° C. and stir for 20 minutes after adding the materials to obtain the hot melt adhesive.

[0034] Example 4

[0035] A method for improving the peel strength between metal tapes in an optical cable sheath, wherein the sheath and the metal tape are bonded by hot melt adhesive, and the preparation steps of the hot melt adhesive include:

[0036] (1) adding 1,3-bis[3-(dimethylamino)propyl]urea to an acetone solution of monobromododecane to obtain a mixture, wherein the mass ratio of 1,3-bis[3-(dimethylamino)propyl]urea to the acetone solution of monobromododecane is 1,3-bis[3-(dimethylamino)propyl]urea:acetone solution of monobromododecane=2:20; the mass percentage of monobromododecane in the acetone solution of monobromododecane is 10%; and the mixture is stirred for 1 h. The mixture was heated to 60°C in a water bath and stirred at a constant temperature for 12 hours to obtain a modifier; graphite phase carbon nitride (sieved powder passing through a 2000 mesh sieve) and ammonia water were mixed in a reactor, wherein the mixing mass ratio of the graphite phase carbon nitride and ammonia water was graphite phase carbon nitride: ammonia water = 1:50, wherein the mass percentage of the solute in the ammonia water was 20%; the mixture was stirred for 30 minutes, and then the reactor was closed and heated to 140°C for 10 hours. After the insulation was completed, Air-cool to room temperature, open the reactor, separate the solid and liquid, wash the solid phase with deionized water for 3 times, and dry at 60°C for 3h to obtain aminated particles; add the aminated particles to an aqueous solution of sodium xanthate, the mass ratio of the aminated particles added to the aqueous solution of sodium xanthate is aminated particles: aqueous solution of sodium xanthate = 1:50, wherein the concentration of sodium xanthate in the aqueous solution of sodium xanthate is 26g / L; heat in a water bath to 35°C, stir at a constant temperature for 2h, separate the solid and liquid after constant temperature stirring, wash the solid phase with deionized water for 3 times, add it to deionized water after washing and stir for 30min to obtain a water suspension, then add the modifier to the water suspension under stirring, the mass ratio of the modifier added to the water suspension is water suspension: modifier = 6:1; heat in a water bath to 60°C after adding, stir at a constant temperature for 4h, then separate the solid and liquid, wash the solid phase with deionized water for 3 times, and dry at 60°C for 3h to obtain modified particles;

[0037] (2) preparing a composite tetrahydrofuran solution of polytetramethylene ether glycol (PTMEG-1000) and dibutyltin dilaurate, wherein the concentration of polytetramethylene ether glycol in the composite tetrahydrofuran solution of polytetramethylene ether glycol and dibutyltin dilaurate is 20 g / 100 mL, the concentration of dibutyltin dilaurate is 1 g / 100 mL, and the solvent is tetrahydrofuran; heating the composite tetrahydrofuran solution of polytetramethylene ether glycol and dibutyltin dilaurate to 35° C. in a water bath in a nitrogen atmosphere, stirring at a constant temperature for 20 min after reaching the temperature, and then adding toluene 2,4-diisopropylamine under stirring; Cyanate, after the addition is completed, continue to stir at a constant temperature of 35°C for 40 minutes in a nitrogen atmosphere, then add the modified particles, the added mass ratio of the toluene 2,4-diisocyanate and the modified particles to the composite tetrahydrofuran solution of polytetramethylene ether glycol and dibutyltin dilaurate is toluene 2,4-diisocyanate: modified particles: composite tetrahydrofuran solution of polytetramethylene ether glycol and dibutyltin dilaurate = 1.4g: 0.8g: 20mL; stir at a constant temperature of 35°C for 30 minutes in a nitrogen atmosphere, separate the solid and liquid, wash the solid phase with ethanol 3 times, and dry at 60°C for 3h to obtain filler particles;

[0038] (3) heating an amorphous α-olefin copolymer (APAO-750) to 155° C. to form a molten state, then adding diisopropylbenzene peroxide under stirring, and continuing to stir the mixture for 5 minutes after the addition is completed, and then adding (3-aminopropyl) triethoxysilane under stirring, wherein the mass ratio of the amorphous α-olefin copolymer, diisopropylbenzene peroxide and (3-aminopropyl) triethoxysilane used is amorphous α-olefin copolymer: diisopropylbenzene peroxide: (3-aminopropyl) triethoxysilane = 100:1:10; after the addition is completed, continuing to stir the mixture at a constant temperature of 155° C. for 20 minutes to obtain a molten mixture;

[0039] (4) Add the filler particles, PP wax and C5 petroleum resin to the molten mixture kept at 155° C., keep the mixture at 155° C. and stir for 30 minutes after adding the materials, cool the mixture to 120° C., add antioxidant 1010, and the mass ratio of the added filler particles, PP wax, C5 petroleum resin and antioxidant 1010 to the mass ratio of the amorphous α-olefin copolymer used to prepare the molten mixture is amorphous α-olefin copolymer: filler particles: PP wax: C5 petroleum resin: antioxidant 1010 = 100:6:4:15:0.2; keep the mixture at 120° C. and stir for 20 minutes after adding the materials to obtain the hot melt adhesive.

[0040] Comparative Example 1

[0041] A hot melt adhesive for comparison, the preparation steps of the hot melt adhesive include:

[0042] (1) Mixing graphite phase carbon nitride (sieved powder passing through a 2000 mesh sieve) and ammonia water in a reactor, wherein the mixing mass ratio of graphite phase carbon nitride and ammonia water is graphite phase carbon nitride: ammonia water = 1:50, wherein the mass percentage of the solute in the ammonia water is 10%; stirring the mixture for 30 minutes, then sealing the reactor, heating to 140° C. and keeping the temperature for 10 hours, cooling to room temperature after the end of the heat preservation, opening the reactor, separating the solid and the liquid, washing the solid phase with deionized water for 3 times, and 60 ℃ drying for 3h to obtain aminated particles; adding the aminated particles to an aqueous solution of sodium xanthate, the mass ratio of the aminated particles to the aqueous solution of sodium xanthate is aminated particles: aqueous solution of sodium xanthate = 1:50, wherein the concentration of sodium xanthate in the aqueous solution of sodium xanthate is 24g / L; heating to 35℃ in a water bath, stirring at constant temperature for 2h, separating the solid and the liquid after the constant temperature stirring is completed, washing the solid phase with deionized water 3 times, and drying at 60℃ for 3h to obtain the modified particles of this comparative example;

[0043] (2) preparing a composite tetrahydrofuran solution of polytetramethylene ether glycol (PTMEG-1000) and dibutyltin dilaurate, wherein the concentration of polytetramethylene ether glycol in the composite tetrahydrofuran solution of polytetramethylene ether glycol and dibutyltin dilaurate is 18 g / 100 mL, the concentration of dibutyltin dilaurate is 0.9 g / 100 mL, and the solvent is tetrahydrofuran; heating the composite tetrahydrofuran solution of polytetramethylene ether glycol and dibutyltin dilaurate to 35° C. in a water bath in a nitrogen atmosphere, stirring at a constant temperature for 20 min after reaching the temperature, and then adding toluene 2,4-dihydrogen sulfide under stirring; isocyanate, after the addition is completed, continue to stir at a constant temperature of 35°C for 40 minutes in a nitrogen atmosphere, then add the modified particles, the amount ratio of the added mass of the toluene 2,4-diisocyanate and the modified particles to the composite tetrahydrofuran solution of polytetramethylene ether glycol and dibutyltin dilaurate is toluene 2,4-diisocyanate: modified particles: composite tetrahydrofuran solution of polytetramethylene ether glycol and dibutyltin dilaurate = 1.3g: 0.6g: 20mL; stir at a constant temperature of 35°C for 30 minutes in a nitrogen atmosphere, separate the solid and liquid, wash the solid phase with ethanol 3 times, and dry at 60°C for 3h to obtain filler particles;

[0044] (3) heating the amorphous α-olefin copolymer (APAO-750) to 155° C. to form a molten state, then adding diisopropylbenzene peroxide under stirring, continuing to stir the mixture for 5 minutes after the addition is completed, and then adding (3-aminopropyl) triethoxysilane under stirring, the mass ratio of the amorphous α-olefin copolymer, diisopropylbenzene peroxide and (3-aminopropyl) triethoxysilane used is amorphous α-olefin copolymer: diisopropylbenzene peroxide: (3-aminopropyl) triethoxysilane = 100:0.9:8; after the addition is completed, continue to stir the mixture at a constant temperature of 155° C. for 20 minutes to obtain a molten mixture;

[0045] (4) Add the filler particles, PP wax and C5 petroleum resin to the molten mixture kept at 155° C., keep the mixture at 155° C. and stir for 30 minutes after adding the materials, cool the mixture to 120° C., add antioxidant 1010, and the mass ratio of the filler particles, PP wax, C5 petroleum resin and antioxidant 1010 to the mass ratio of the amorphous α-olefin copolymer used to prepare the molten mixture is amorphous α-olefin copolymer: filler particles: PP wax: C5 petroleum resin: antioxidant 1010 = 100:5:3:12:0.1; keep the mixture at 120° C. and stir for 20 minutes after adding the materials to obtain the hot melt adhesive described in this comparative example.

[0046] Comparative Example 2

[0047] A hot melt adhesive for comparison, the preparation steps of the hot melt adhesive include:

[0048] (1) adding 1,3-bis[3-(dimethylamino)propyl]urea to an acetone solution of monobromododecane to obtain a mixture, wherein the mass ratio of 1,3-bis[3-(dimethylamino)propyl]urea to the acetone solution of monobromododecane is 1:20; the mass percentage of monobromododecane in the acetone solution of monobromododecane is 9%; and the mixture is added to the acetone solution of monobromododecane in an amount of 1:20. The water bath was heated to 60°C and stirred at a constant temperature for 12 hours to obtain a modifier; graphite phase carbon nitride (sieved powder passing through a 2000 mesh sieve) and ammonia water were mixed in a reactor, wherein the mixing mass ratio of the graphite phase carbon nitride and ammonia water was graphite phase carbon nitride: ammonia water = 1:50, wherein the mass percentage of the solute in the ammonia water was 10%; the mixture was stirred for 30 minutes, and then the reactor was closed and heated to 140°C for 10 hours, and after the insulation was completed, air-cooled to At room temperature, open the reactor, separate the solid and liquid, wash the solid phase with deionized water for 3 times, and dry it at 60°C for 3h to obtain aminated particles; add the aminated particles to an aqueous solution of sodium xanthate, and the mass ratio of the aminated particles added to the aqueous solution of sodium xanthate is aminated particles: aqueous solution of sodium xanthate = 1:50, wherein the concentration of sodium xanthate in the aqueous solution of sodium xanthate is 24g / L; heat in a water bath to 35°C, stir at a constant temperature for 2h, separate the solid and liquid after constant temperature stirring, wash the solid phase with deionized water for 3 times, add it to deionized water after washing and stir for 30min to obtain a water suspension, and then add the modifier to the water suspension under stirring, and the mass ratio of the modifier added to the water suspension is water suspension: modifier = 5:1; heat in a water bath to 60°C after adding, stir at a constant temperature for 4h, then separate the solid and liquid, wash the solid phase with deionized water for 3 times, and dry it at 60°C for 3h to obtain the filler particles of this comparative example;

[0049] (2) heating an amorphous α-olefin copolymer (APAO-750) to 155° C. to form a molten state, then adding diisopropylbenzene peroxide under stirring, continuing to stir and mix for 5 minutes after the addition is completed, and then adding (3-aminopropyl)triethoxysilane under stirring, wherein the mass ratio of the amorphous α-olefin copolymer, diisopropylbenzene peroxide and (3-aminopropyl)triethoxysilane used is amorphous α-olefin copolymer: diisopropylbenzene peroxide: (3-aminopropyl)triethoxysilane = 100:0.9:8; after the addition is completed, continuing to stir the mixture at a constant temperature of 155° C. for 20 minutes to obtain a molten mixture;

[0050] (3) Add the filler particles, PP wax and C5 petroleum resin to the molten mixture kept at 155° C., keep the mixture at 155° C. and stir for 30 minutes after adding the materials, cool the mixture to 120° C., add antioxidant 1010, and the mass ratio of the filler particles, PP wax, C5 petroleum resin and antioxidant 1010 to the mass ratio of the amorphous α-olefin copolymer used to prepare the molten mixture is amorphous α-olefin copolymer: filler particles: PP wax: C5 petroleum resin: antioxidant 1010 = 100:5:3:12:0.1; keep the mixture at 120° C. and stir for 20 minutes after adding the materials to obtain the hot melt adhesive described in this comparative example.

[0051] Example 5

[0052] According to the requirements of GB / T 2790-1995, the 180° peel strength of the hot melt adhesive prepared by the methods described in the above embodiments and comparative examples was tested. The bonded material was PP material; the coating thickness was 0.4 mm. After bonding, a molding machine was used to maintain the pressure at 1 MPa and 140°C for 5 minutes to obtain a peeling specimen, which was then placed at room temperature for 5 days and then tested for peel strength; 3 specimens were tested in each group and the average value was taken as the peel strength value of the group. The results are shown in Table 1.

[0053] As can be seen from Table 1, the hot melt adhesive prepared by the method of the present invention has good bonding properties, a relatively high peel strength, and improves the durability of the optical cable. Comparing Example 2 of the present invention with each comparative example, it can be seen that by adding the filler particles of the present invention, the adhesiveness of the hot melt adhesive can be significantly improved, manifested as a significant increase in the peel strength. This is mainly because: the present invention first uses the method of hydrothermal treatment with ammonia water to form a large number of amino groups on the surface of graphitic carbon nitride to obtain ammoniated particles, then grafts part of the amino groups with sodium xanthate to form dithiocarbonate functional groups, and then uses 1,3-bis[3-(dimethylamino)propyl]urea and 1-bromododecane to carry out a quaternization reaction to form a surfactant modifier, and exchanges the sodium cations on the surface of the grafted particles to obtain modified particles. In this way, on the one hand, a macromolecular structure can be introduced on the particle surface to improve the dispersibility of the particles and the binding force between the particles and the amorphous α-olefin copolymer matrix; on the other hand, a group containing a bisamide bond can be introduced into the hot melt adhesive; subsequently, a urethane group is introduced through the above step (2), and a macromolecular network structure with filler particles as nodes is formed through chemical cross-linking. Macroscopically, the bonding strength of the hot melt adhesive is significantly improved, and the introduced urethane group and the above-mentioned group containing a bisamide bond are both strongly polar groups, so that strong hydrogen bonds are formed between the hot melt adhesive and the surface of the adhered object, thereby improving the adhesiveness.

[0054] Table 1

[0055] Experimental Group Peel strength (N / cm) Example 1 3.59 Example 2 3.68 Example 3 3.66 Example 4 3.62 Comparative Example 1 2.51 Comparative Example 2 2.75

[0056] The above has introduced the technical solution provided by the present invention in detail. For those of ordinary skill in the art, according to the idea of the embodiments of the present invention, there will be changes in the specific implementation manners and application scopes. In summary, the content of this specification should not be construed as a limitation to the present invention.

Claims

1. A method for improving the peel strength between metal tapes in an optical cable sheath, wherein the sheath and the metal tape are bonded by hot melt adhesive, characterized in that: The preparation steps of the hot melt adhesive include: (1) adding 1,3-bis[3-(dimethylamino)propyl]urea to an acetone solution of monobromododecane to obtain a mixture, heating the mixture to 60±5° C. in a water bath, and stirring the mixture at a constant temperature for more than 12 hours to obtain a modifier; mixing graphite carbon nitride and ammonia water in a reactor, stirring the mixture for more than 30 minutes, and then sealing the reactor, heating to 140±5° C. and keeping the temperature for more than 10 hours, cooling to room temperature after the end of the heat preservation, opening the reactor, separating the solid and the liquid, washing the solid phase with deionized water for more than 3 times, and drying to obtain Ammoniated particles; adding the ammoniated particles to an aqueous solution of sodium xanthate, heating in a water bath to 35±3°C, stirring at a constant temperature for more than 2 hours, separating the solid and the liquid after the constant temperature stirring, washing the solid phase with deionized water for more than 3 times, adding the solid phase to deionized water after washing and stirring for more than 30 minutes to obtain a water suspension, and then adding the modifier to the water suspension under stirring, heating in a water bath to 60±5°C after adding, stirring at a constant temperature for more than 4 hours, then separating the solid and the liquid, washing the solid phase with deionized water for more than 3 times, and drying to obtain modified particles; (2) preparing a composite tetrahydrofuran solution of polytetramethylene ether glycol and dibutyltin dilaurate, heating the composite tetrahydrofuran solution of polytetramethylene ether glycol and dibutyltin dilaurate to 35±3° C. in a nitrogen atmosphere, stirring at a constant temperature for more than 20 minutes after reaching the temperature, and then adding toluene 2,4-diisocyanate under stirring. After the addition is completed, stirring at a constant temperature of 35±3° C. in a nitrogen atmosphere for more than 40 minutes, and then adding the modified particles, stirring at a constant temperature of 35±3° C. in a nitrogen atmosphere for more than 30 minutes, separating the solid and the liquid, washing the solid phase with ethanol for more than 3 times, and drying to obtain filler particles; (3) heating the amorphous α-olefin copolymer to 155±5° C. to form a molten state, then adding dicumyl peroxide under stirring, and continuing to stir the mixture for 5 to 10 minutes after the addition is completed, and then adding (3-aminopropyl) triethoxysilane under stirring, and continuing to stir the mixture at a constant temperature of 155±5° C. for 20 to 30 minutes after the addition is completed to obtain a molten mixture; (4) Add the filler particles, PP wax and C5 petroleum resin to the molten mixture kept at 155±5°C, keep the mixture at 155±5°C and stir for 30-40 minutes, cool the mixture to 120±5°C, add an antioxidant, keep the mixture at 120±5°C and stir for 20-30 minutes to obtain the hot melt adhesive.

2. A method for improving the peel strength between metal tapes in an optical cable sheath according to claim 1, characterized in that: In the step (1), the mass ratio of 1,3-bis[3-(dimethylamino)propyl]urea added to the acetone solution of monobromododecane is 1,3-bis[3-(dimethylamino)propyl]urea: acetone solution of monobromododecane = 1-2:20; the mass percentage of monobromododecane in the acetone solution of monobromododecane is 8%-10%; the mass ratio of the graphite phase carbon nitride and ammonia water is graphite phase carbon nitride: ammonia water = 1:50-100, wherein the mass percentage of the solute in the ammonia water is 10%-20%; the mass ratio of the aminated particles added to the aqueous solution of sodium xanthate is aminated particles: aqueous solution of sodium xanthate = 1:50-100, wherein the concentration of sodium xanthate in the aqueous solution of sodium xanthate is 22-26 g / L; the mass ratio of the modifier added to the aqueous suspension is aqueous suspension: modifier = 5-6:

1.

3. A method for improving the peel strength between metal tapes in an optical cable sheath according to claim 1, characterized in that: In the step (2), in the composite tetrahydrofuran solution of polytetramethylene ether glycol and dibutyltin dilaurate, the concentration of polytetramethylene ether glycol is 16-20 g / 100 mL, the concentration of dibutyltin dilaurate is 0.8-1 g / 100 mL, and the solvent is tetrahydrofuran; the amount ratio of the added mass of the toluene 2,4-diisocyanate and the modified particles to the composite tetrahydrofuran solution of polytetramethylene ether glycol and dibutyltin dilaurate is toluene 2,4-diisocyanate: modified particles: composite tetrahydrofuran solution of polytetramethylene ether glycol and dibutyltin dilaurate = 1.2-1.4 g: 0.5-0.8 g: 20 mL.

4. A method for improving the peel strength between metal tapes in an optical cable sheath according to claim 1, characterized in that: In the step (3), the mass ratio of the amorphous α-olefin copolymer, dicumyl peroxide and (3-aminopropyl)triethoxysilane is amorphous α-olefin copolymer: dicumyl peroxide: (3-aminopropyl)triethoxysilane = 100: 0.8-1: 7-10.

5. A method for improving the peel strength between metal tapes in an optical cable sheath according to claim 1, characterized in that: In the step (4), the mass ratio of the added mass of the filler particles, PP wax, C5 petroleum resin, and antioxidant to the mass ratio of the amorphous α-olefin copolymer used to prepare the molten mixture is amorphous α-olefin copolymer: filler particles: PP wax: C5 petroleum resin: antioxidant = 100: 4-6: 3-4: 10-15: 0.1-0.2.