A highly wear-resistant communication optical cable waterproof material and preparation method thereof

Abstract

The invention discloses a highly wear-resistant communication optical cable waterproof material, wherein the raw materials include hydroxy acrylic resin, filler particles, vinyl triethoxysilane, initiator BPO, propylene glycol diacrylate, styrene, acrylic acid, HDI curing agent and xylene. The waterproof material prepared by the method of the invention has good hydrophobicity and surface hardness, and can achieve good waterproof effect when sprayed on the surface of the optical cable, and has good wear resistance, has strong protective effect on the surface of the optical cable, and prevents the surface of the optical cable from being worn.

Description

Technical Field

[0001] The invention relates to the technical field of wire and cable materials, and in particular to a highly wear-resistant communication optical cable waterproof material and a preparation method thereof. Background Art

[0002] With the rapid development of the information technology industry, optical fiber communication technology has made great achievements. Optical fiber has been widely used in the communication industry due to its performance advantages, accelerating the pace of copper's retreat. At present, the most mainstream communication medium is communication optical cable. Since the use environment of communication optical cable is often harsh, the performance requirements of optical cable are also high, especially waterproof and wear resistance. Good waterproof and wear resistance can ensure the long-term use of communication optical cable, reduce the number of repairs, and reduce maintenance costs. Summary of the invention

[0003] To this end, the present invention provides a highly wear-resistant communication optical cable waterproof material, the raw materials of which include hydroxy acrylic resin, filler particles, vinyl triethoxy silane, initiator BPO, propylene glycol diacrylate, styrene, acrylic acid, HDI curing agent and xylene; the preparation method of the filler particles is:

[0004] (1) preparing an ethanol solution of tetraethyl orthosilicate and preparing a mixed aqueous solution of ammonia water, deionized water and ethanol; stirring the mixed aqueous solution of ammonia water, deionized water and ethanol, and then adding hexadecyltrimethylammonium bromide to the solution under stirring, continuing to stir the solution for more than 20 minutes after the addition is completed, and then dropwise adding the ethanol solution of tetraethyl orthosilicate to the solution under stirring, continuing to stir for 1 to 2 minutes after the addition is completed, standing for more than 2 hours, and then separating the solid and the liquid, washing the solid phase with deionized water for more than 3 times, drying at 60° C. for 30 to 40 minutes, and then calcining at 550° C. for 5 to 6 hours to obtain nano silicon dioxide particles;

[0005] (2) preparing a mixture of bis(dioctyloxypyrophosphate)ethylene titanate coupling agent and ethanol, heating the mixture of the bis(dioctyloxypyrophosphate)ethylene titanate coupling agent and ethanol in a water bath to 60±5° C., then adding the nano-silica particles to the solution under the heat preservation state, and stirring the solution at 60±5° C. for 100 to 120 minutes after the addition is completed, condensing and reflux during the heat preservation process, and then air cooling to room temperature, solid-liquid separation, and solid phase drying at 60° C. for more than 5 hours to obtain a modified powder;

[0006] (3) preparing an ethanol solution of polyethyleneimine, adding the modified powder to the ethanol solution of polyethyleneimine, stirring for more than 20 minutes after the addition is completed, and then adding Span80 and polyethylene glycol to the solution under stirring, continuing to stir the solution for more than 1 hour after the addition is completed, and then separating the solid and liquid, washing the solid phase with ethanol for more than 3 times, and drying at 60° C. for more than 30 minutes to obtain a modified powder;

[0007] (4) adding the modified powder and dopamine hydrochloride into a Tris-HCl buffer solution, then heating the mixture in a water bath to 40±2° C. and stirring the mixture for more than 20 h, separating the solid from the liquid, washing the solid phase with deionized water for more than 3 times, and drying the mixture at 60° C. for more than 30 min to obtain the filler particles.

[0008] Furthermore, the raw materials are calculated by weight as follows: 50-60 parts of hydroxy acrylic resin, 5-6 parts of filler particles, 5-10 parts of vinyl triethoxy silane, 0.7-0.8 parts of initiator BPO, 2-3 parts of propylene glycol diacrylate, 4-6 parts of styrene, 1-3 parts of acrylic acid, 15-16 parts of HDI curing agent, and 100 parts of xylene.

[0009] Furthermore, in the step (1), the mass percentage of tetraethyl orthosilicate in the ethanol solution of tetraethyl orthosilicate is 8%; the mixed volume ratio of ammonia water, deionized water and ethanol is ammonia water: deionized water: ethanol = 0.2-0.3:10:1; the mass percentage of the solute in the ammonia water is 20%; the amount of hexadecyltrimethylammonium bromide and the ethanol solution of tetraethyl orthosilicate added to the mixed aqueous solution of ammonia water, deionized water and ethanol is hexadecyltrimethylammonium bromide: ethanol solution of tetraethyl orthosilicate: mixed aqueous solution of ammonia water, deionized water and ethanol = 0.6-0.8g: 1-2mL: 10mL.

[0010] Furthermore, in the step (2), in the mixed solution of bis(dioctyl pyrophosphate)ethylene titanate coupling agent and ethanol, the mass ratio of bis(dioctyl pyrophosphate)ethylene titanate coupling agent to ethanol is bis(dioctyl pyrophosphate)ethylene titanate coupling agent:ethanol=2-3:100; and the nano-silica particles are added to the solution in a mass ratio of nano-silica:solution=1:50.

[0011] Furthermore, in the step (3), in the ethanol solution of polyethyleneimine, the mass percentage of polyethyleneimine is 5%, and the solvent is ethanol; the mass ratio of the modified powder added to the ethanol solution of polyethyleneimine is modified powder: ethanol solution of polyethyleneimine = 1:80; the mass ratio of the added mass of Span80 and polyethylene glycol to the mass ratio of the modified powder in the solution is Span80: polyethylene glycol: modified powder = 0.5~0.8:1.2~1.6:1.

[0012] Furthermore, in the step (4), the modified powder and dopamine hydrochloride are added to the Tris-HCl buffer in a ratio of modified powder: dopamine hydrochloride: Tris-HCl buffer = 0.4-0.5 g: 0.2-0.3 g: 100 mL, and the concentration of tris(hydroxymethyl)aminomethane in the Tris-HCl buffer is 0.01 mol / L, and the pH is 8.5.

[0013] The present invention also discloses a method for preparing the waterproof material: weighing each raw material according to the weight proportion, then uniformly mixing the raw materials in a nitrogen atmosphere, spraying the raw materials on the surface of the optical cable, and then heating to 110° C. under nitrogen protection, keeping the temperature for 2 hours, and cooling to room temperature to obtain the waterproof material.

[0014] The beneficial effects of the present invention are as follows: the waterproof material prepared by the method of the present invention has good hydrophobicity and surface hardness. When sprayed on the surface of an optical cable, it can achieve a good waterproof effect and has good wear resistance. It has a strong protective effect on the surface of the optical cable and prevents the surface of the optical cable from being worn. DETAILED DESCRIPTION

[0015] The present invention will be further described below in conjunction with the embodiments.

[0016] Example 1

[0017] A highly wear-resistant communication optical cable waterproof material, the raw materials include hydroxy acrylic resin, filler particles, vinyl triethoxysilane, initiator BPO, propylene glycol diacrylate, styrene, acrylic acid, HDI curing agent and xylene; each of the raw materials is calculated by weight: 50 parts of hydroxy acrylic resin, 5 parts of filler particles, 5 parts of vinyl triethoxysilane, 0.7 parts of initiator BPO, 2 parts of propylene glycol diacrylate, 4 parts of styrene, 1 part of acrylic acid, 15 parts of HDI curing agent, and 100 parts of xylene. The preparation method of the filler particles is:

[0018] (1) preparing an ethanol solution of tetraethyl orthosilicate, wherein the mass percentage of tetraethyl orthosilicate in the ethanol solution of tetraethyl orthosilicate is 8%; preparing a mixed aqueous solution of ammonia water, deionized water and ethanol; the mixed volume ratio of ammonia water, deionized water and ethanol is ammonia water: deionized water: ethanol = 0.2:10:1; wherein the mass percentage of the solute in the ammonia water is 20%; stirring the mixed aqueous solution of ammonia water, deionized water and ethanol, and then adding hexadecyltrimethylammonium bromide to the solution under stirring, continuing to stir the solution for 20 minutes after the addition is completed, and then stirring under stirring The ethanol solution of tetraethyl orthosilicate is added dropwise to the solution, and the amount of hexadecyltrimethylammonium bromide, the ethanol solution of tetraethyl orthosilicate and the mixed aqueous solution of ammonia water, deionized water and ethanol is in the ratio of hexadecyltrimethylammonium bromide: ethanol solution of tetraethyl orthosilicate: mixed aqueous solution of ammonia water, deionized water and ethanol = 0.6 g: 1 mL: 10 mL; after the addition is completed, stirring is continued for 1 min, standing for 2 h, and then solid-liquid separation is performed, the solid phase is washed with deionized water 3 times, dried at 60° C. for 30 min, and then calcined at 550° C. for 5 h to obtain nano silicon dioxide particles;

[0019] (2) preparing a mixture of bis(dioctyl pyrophosphate)ethylene titanate coupling agent and ethanol, wherein the mass ratio of bis(dioctyl pyrophosphate)ethylene titanate coupling agent to ethanol is bis(dioctyl pyrophosphate)ethylene titanate coupling agent:ethanol=2:100; heating the mixture of bis(dioctyl pyrophosphate)ethylene titanate coupling agent and ethanol in a water bath to 60±5° C. and then adding the nano-silica particles to the solution under the heat preservation state, wherein the mass ratio of the nano-silica particles to the solution is nano-silica:solution=1:50; after the addition is completed, the solution is kept at 60±5° C. and stirred for 100 minutes, condensed and refluxed during the heat preservation process, and then air-cooled to room temperature, solid-liquid separation is performed, and the solid phase is dried at 60° C. for 5 hours to obtain a modified powder;

[0020] (3) preparing an ethanol solution of polyethyleneimine, wherein the mass percentage of polyethyleneimine in the ethanol solution of polyethyleneimine is 5% and the solvent is ethanol; adding the modified powder to the ethanol solution of polyethyleneimine, wherein the mass ratio of the modified powder to the ethanol solution of polyethyleneimine is modified powder: ethanol solution of polyethyleneimine = 1:80; stirring for 20 minutes after the addition is completed, and then adding Span80 and polyethylene glycol (PEG1000) to the solution under stirring, wherein the mass ratio of the added Span80 and polyethylene glycol to the mass of the modified powder in the solution is Span80: polyethylene glycol: modified powder = 0.5:1.2:1; after the addition is completed, the solution is stirred for 1 hour, and then the solid-liquid separation is performed, the solid phase is washed with ethanol 3 times, and dried at 60°C for 30 minutes to obtain a modified powder;

[0021] (4) adding the modified powder and dopamine hydrochloride to a Tris-HCl buffer solution, wherein the modified powder and dopamine hydrochloride are added to the Tris-HCl buffer solution in a ratio of modified powder: dopamine hydrochloride: Tris-HCl buffer solution = 0.4 g: 0.2 g: 100 mL, wherein the concentration of tris(hydroxymethyl)aminomethane in the Tris-HCl buffer solution is 0.01 mol / L, and the pH value is 8.5; then heating the mixture in a water bath to 40±2° C. and stirring for 20 h, separating the solid from the liquid, washing the solid phase with deionized water for 3 times, and drying the mixture at 60° C. for 30 min to obtain the filler particles.

[0022] Weigh each raw material according to the above weight proportions, then mix the raw materials evenly in a nitrogen atmosphere, spray them on the surface of the test sample, and then heat to 110° C. under nitrogen protection, keep warm for 2 hours, and cool to room temperature to obtain the waterproof material.

[0023] Example 2

[0024] A highly wear-resistant communication optical cable waterproof material, the raw materials include hydroxy acrylic resin, filler particles, vinyl triethoxysilane, initiator BPO, propylene glycol diacrylate, styrene, acrylic acid, HDI curing agent and xylene; each of the raw materials is calculated by weight: 50 parts of hydroxy acrylic resin, 5 parts of filler particles, 7 parts of vinyl triethoxysilane, 0.7 parts of initiator BPO, 2 parts of propylene glycol diacrylate, 5 parts of styrene, 2 parts of acrylic acid, 15 parts of HDI curing agent, and 100 parts of xylene. The preparation method of the filler particles is:

[0025] (1) preparing an ethanol solution of tetraethyl orthosilicate, wherein the mass percentage of tetraethyl orthosilicate in the ethanol solution of tetraethyl orthosilicate is 8%; preparing a mixed aqueous solution of ammonia water, deionized water and ethanol; the mixed volume ratio of ammonia water, deionized water and ethanol is ammonia water: deionized water: ethanol = 0.2:10:1; wherein the mass percentage of the solute in the ammonia water is 20%; stirring the mixed aqueous solution of ammonia water, deionized water and ethanol, and then adding hexadecyltrimethylammonium bromide to the solution under stirring, continuing to stir the solution for 20 minutes after the addition is completed, and then stirring under stirring The ethanol solution of tetraethyl orthosilicate is added dropwise to the solution, and the amount of hexadecyltrimethylammonium bromide, the ethanol solution of tetraethyl orthosilicate and the mixed aqueous solution of ammonia water, deionized water and ethanol is in the ratio of hexadecyltrimethylammonium bromide: ethanol solution of tetraethyl orthosilicate: mixed aqueous solution of ammonia water, deionized water and ethanol = 0.7 g: 1 mL: 10 mL; after the addition is completed, stirring is continued for 1 min, standing for 2 h, and then solid-liquid separation is performed, the solid phase is washed with deionized water 3 times, dried at 60° C. for 30 min, and then calcined at 550° C. for 5 h to obtain nano silicon dioxide particles;

[0026] (2) preparing a mixture of bis(dioctyl pyrophosphate)ethylene titanate coupling agent and ethanol, wherein the mass ratio of bis(dioctyl pyrophosphate)ethylene titanate coupling agent to ethanol is bis(dioctyl pyrophosphate)ethylene titanate coupling agent:ethanol=2:100; heating the mixture of bis(dioctyl pyrophosphate)ethylene titanate coupling agent and ethanol in a water bath to 60±5° C. and then adding the nano-silica particles to the solution under the heat preservation state, wherein the mass ratio of the nano-silica particles to the solution is nano-silica:solution=1:50; after the addition is completed, the solution is kept at 60±5° C. and stirred for 100 minutes, condensed and refluxed during the heat preservation process, and then air-cooled to room temperature, solid-liquid separation is performed, and the solid phase is dried at 60° C. for 5 hours to obtain a modified powder;

[0027] (3) preparing an ethanol solution of polyethyleneimine, wherein the mass percentage of polyethyleneimine in the ethanol solution of polyethyleneimine is 5% and the solvent is ethanol; adding the modified powder to the ethanol solution of polyethyleneimine, wherein the mass ratio of the modified powder to the ethanol solution of polyethyleneimine is modified powder: ethanol solution of polyethyleneimine = 1:80; stirring for 20 minutes after the addition is completed, and then adding Span80 and polyethylene glycol (PEG1000) to the solution under stirring, wherein the mass ratio of the added Span80 and polyethylene glycol to the mass ratio of the modified powder in the solution is Span80: polyethylene glycol: modified powder = 0.6:1.4:1; after the addition is completed, the solution is stirred for 1 hour, and then the solid-liquid separation is performed, the solid phase is washed with ethanol 3 times, and dried at 60°C for 30 minutes to obtain a modified powder;

[0028] (4) adding the modified powder and dopamine hydrochloride to a Tris-HCl buffer solution, wherein the modified powder and dopamine hydrochloride are added to the Tris-HCl buffer solution in a ratio of modified powder: dopamine hydrochloride: Tris-HCl buffer solution = 0.4 g: 0.2 g: 100 mL, wherein the concentration of tris(hydroxymethyl)aminomethane in the Tris-HCl buffer solution is 0.01 mol / L, and the pH value is 8.5; then heating the mixture in a water bath to 40±2° C. and stirring for 20 h, separating the solid from the liquid, washing the solid phase with deionized water for 3 times, and drying the mixture at 60° C. for 30 min to obtain the filler particles.

[0029] Weigh each raw material according to the above weight proportions, then mix the raw materials evenly in a nitrogen atmosphere, spray them on the surface of the test sample, and then heat to 110° C. under nitrogen protection, keep warm for 2 hours, and cool to room temperature to obtain the waterproof material.

[0030] Example 3

[0031] A highly wear-resistant communication optical cable waterproof material, the raw materials include hydroxy acrylic resin, filler particles, vinyl triethoxysilane, initiator BPO, propylene glycol diacrylate, styrene, acrylic acid, HDI curing agent and xylene; each of the raw materials is calculated by weight: 60 parts of hydroxy acrylic resin, 6 parts of filler particles, 8 parts of vinyl triethoxysilane, 0.8 parts of initiator BPO, 3 parts of propylene glycol diacrylate, 5 parts of styrene, 2 parts of acrylic acid, 16 parts of HDI curing agent, and 100 parts of xylene. The preparation method of the filler particles is:

[0032] (1) preparing an ethanol solution of tetraethyl orthosilicate, wherein the mass percentage of tetraethyl orthosilicate in the ethanol solution of tetraethyl orthosilicate is 8%; preparing a mixed aqueous solution of ammonia water, deionized water and ethanol; the mixed volume ratio of ammonia water, deionized water and ethanol is ammonia water: deionized water: ethanol = 0.3:10:1; wherein the mass percentage of the solute in the ammonia water is 20%; stirring the mixed aqueous solution of ammonia water, deionized water and ethanol, and then adding hexadecyltrimethylammonium bromide to the solution under stirring, continuing to stir the solution for 20 minutes after the addition is completed, and then stirring under stirring The ethanol solution of tetraethyl orthosilicate is added dropwise to the solution, and the amount of hexadecyltrimethylammonium bromide, the ethanol solution of tetraethyl orthosilicate and the mixed aqueous solution of ammonia water, deionized water and ethanol is in the ratio of hexadecyltrimethylammonium bromide: ethanol solution of tetraethyl orthosilicate: mixed aqueous solution of ammonia water, deionized water and ethanol = 0.7 g: 2 mL: 10 mL; after the addition is completed, stirring is continued for 1 min, standing for 2 h, and then solid-liquid separation is performed, the solid phase is washed with deionized water 3 times, dried at 60° C. for 30 min, and then calcined at 550° C. for 5 h to obtain nano silicon dioxide particles;

[0033] (2) preparing a mixture of bis(dioctyl pyrophosphate)ethylene titanate coupling agent and ethanol, wherein the mass ratio of bis(dioctyl pyrophosphate)ethylene titanate coupling agent to ethanol is bis(dioctyl pyrophosphate)ethylene titanate coupling agent:ethanol=3:100; heating the mixture of bis(dioctyl pyrophosphate)ethylene titanate coupling agent and ethanol in a water bath to 60±5° C. and then adding the nano-silica particles to the solution under the heat preservation state, wherein the mass ratio of the nano-silica particles to the solution is nano-silica:solution=1:50; after the addition is completed, the solution is kept at 60±5° C. and stirred for 100 minutes, condensed and refluxed during the heat preservation process, and then air-cooled to room temperature, solid-liquid separation is performed, and the solid phase is dried at 60° C. for 5 hours to obtain a modified powder;

[0034] (3) preparing an ethanol solution of polyethyleneimine, wherein the mass percentage of polyethyleneimine in the ethanol solution of polyethyleneimine is 5% and the solvent is ethanol; adding the modified powder to the ethanol solution of polyethyleneimine, wherein the mass ratio of the modified powder to the ethanol solution of polyethyleneimine is modified powder: ethanol solution of polyethyleneimine = 1:80; stirring for 20 minutes after the addition is completed, and then adding Span80 and polyethylene glycol (PEG1000) to the solution under stirring, wherein the mass ratio of the added Span80 and polyethylene glycol to the mass ratio of the modified powder in the solution is Span80: polyethylene glycol: modified powder = 0.7:1.4:1; after the addition is completed, the solution is stirred for 1 hour, and then the solid-liquid separation is performed, the solid phase is washed with ethanol 3 times, and dried at 60°C for 30 minutes to obtain a modified powder;

[0035] (4) Adding the modified powder and dopamine hydrochloride to Tris-HCl buffer, the ratio of modified powder to dopamine hydrochloride added to Tris-HCl buffer is modified powder: dopamine hydrochloride: Tris-HCl buffer = 0.5 g: 0.3 g: 100 mL, the concentration of tris(hydroxymethyl)aminomethane in the Tris-HCl buffer is 0.01 mol / L, and the pH is 8.5; then heating in a water bath to 40±2° C. and stirring for 20 h, separating the solid and the liquid, washing the solid phase with deionized water for 3 times, and drying at 60° C. for 30 min to obtain the filler particles.

[0036] Weigh each raw material according to the above weight proportions, then mix the raw materials evenly in a nitrogen atmosphere, spray them on the surface of the test sample, and then heat to 110° C. under nitrogen protection, keep warm for 2 hours, and cool to room temperature to obtain the waterproof material.

[0037] Example 4

[0038] A highly wear-resistant communication optical cable waterproof material, the raw materials include hydroxy acrylic resin, filler particles, vinyl triethoxysilane, initiator BPO, propylene glycol diacrylate, styrene, acrylic acid, HDI curing agent and xylene; each of the raw materials is calculated by weight: 60 parts of hydroxy acrylic resin, 6 parts of filler particles, 10 parts of vinyl triethoxysilane, 0.8 parts of initiator BPO, 3 parts of propylene glycol diacrylate, 6 parts of styrene, 3 parts of acrylic acid, 16 parts of HDI curing agent, and 100 parts of xylene. The preparation method of the filler particles is:

[0039] (1) preparing an ethanol solution of tetraethyl orthosilicate, wherein the mass percentage of tetraethyl orthosilicate in the ethanol solution of tetraethyl orthosilicate is 8%; preparing a mixed aqueous solution of ammonia water, deionized water and ethanol; the mixed volume ratio of ammonia water, deionized water and ethanol is ammonia water: deionized water: ethanol = 0.3:10:1; wherein the mass percentage of the solute in the ammonia water is 20%; stirring the mixed aqueous solution of ammonia water, deionized water and ethanol, and then adding hexadecyltrimethylammonium bromide to the solution under stirring, continuing to stir the solution for 20 minutes after the addition is completed, and then stirring under stirring The ethanol solution of tetraethyl orthosilicate is added dropwise to the solution, and the amount of hexadecyltrimethylammonium bromide, the ethanol solution of tetraethyl orthosilicate and the mixed aqueous solution of ammonia water, deionized water and ethanol is in the ratio of hexadecyltrimethylammonium bromide: ethanol solution of tetraethyl orthosilicate: mixed aqueous solution of ammonia water, deionized water and ethanol = 0.8 g: 2 mL: 10 mL; after the addition is completed, stirring is continued for 1 min, standing for 2 h, and then solid-liquid separation is performed, the solid phase is washed with deionized water 3 times, dried at 60° C. for 30 min, and then calcined at 550° C. for 5 h to obtain nano silicon dioxide particles;

[0040] (2) preparing a mixture of bis(dioctyl pyrophosphate)ethylene titanate coupling agent and ethanol, wherein the mass ratio of bis(dioctyl pyrophosphate)ethylene titanate coupling agent to ethanol is bis(dioctyl pyrophosphate)ethylene titanate coupling agent:ethanol=3:100; heating the mixture of bis(dioctyl pyrophosphate)ethylene titanate coupling agent and ethanol in a water bath to 60±5° C. and then adding the nano-silica particles to the solution under the heat preservation state, wherein the mass ratio of the nano-silica particles to the solution is nano-silica:solution=1:50; after the addition is completed, the solution is kept at 60±5° C. and stirred for 100 minutes, condensed and refluxed during the heat preservation process, and then air-cooled to room temperature, solid-liquid separation is performed, and the solid phase is dried at 60° C. for 5 hours to obtain a modified powder;

[0041] (3) preparing an ethanol solution of polyethyleneimine, wherein the mass percentage of polyethyleneimine in the ethanol solution of polyethyleneimine is 5% and the solvent is ethanol; adding the modified powder to the ethanol solution of polyethyleneimine, wherein the mass ratio of the modified powder to the ethanol solution of polyethyleneimine is modified powder: ethanol solution of polyethyleneimine = 1:80; stirring for 20 minutes after the addition is completed, and then adding Span80 and polyethylene glycol (PEG1000) to the solution under stirring, wherein the mass ratio of the added Span80 and polyethylene glycol to the mass of the modified powder in the solution is Span80: polyethylene glycol: modified powder = 0.8:1.6:1; after the addition is completed, the solution is stirred for 1 hour, and then the solid-liquid separation is performed, the solid phase is washed with ethanol 3 times, and dried at 60°C for 30 minutes to obtain a modified powder;

[0042] (4) Adding the modified powder and dopamine hydrochloride to Tris-HCl buffer, the ratio of modified powder to dopamine hydrochloride added to Tris-HCl buffer is modified powder: dopamine hydrochloride: Tris-HCl buffer = 0.5 g: 0.3 g: 100 mL, the concentration of tris(hydroxymethyl)aminomethane in the Tris-HCl buffer is 0.01 mol / L, and the pH is 8.5; then heating in a water bath to 40±2° C. and stirring for 20 h, separating the solid and the liquid, washing the solid phase with deionized water for 3 times, and drying at 60° C. for 30 min to obtain the filler particles.

[0043] Weigh each raw material according to the above weight proportions, then mix the raw materials evenly in a nitrogen atmosphere, spray them on the surface of the test sample, and then heat to 110° C. under nitrogen protection, keep warm for 2 hours, and cool to room temperature to obtain the waterproof material.

[0044] Comparative Example 1

[0045] A waterproof material for comparison, the raw materials include hydroxy acrylic resin, filler particles, vinyl triethoxysilane, initiator BPO, propylene glycol diacrylate, styrene, acrylic acid, HDI curing agent and xylene; each of the raw materials is calculated by weight: 60 parts of hydroxy acrylic resin, 6 parts of filler particles, 8 parts of vinyl triethoxysilane, 0.8 parts of initiator BPO, 3 parts of propylene glycol diacrylate, 5 parts of styrene, 2 parts of acrylic acid, 16 parts of HDI curing agent, 100 parts of xylene. The preparation method of the filler particles is:

[0046] (1) preparing an ethanol solution of tetraethyl orthosilicate, wherein the mass percentage of tetraethyl orthosilicate in the ethanol solution of tetraethyl orthosilicate is 8%; preparing a mixed aqueous solution of ammonia water, deionized water and ethanol; the mixed volume ratio of ammonia water, deionized water and ethanol is ammonia water: deionized water: ethanol = 0.3:10:1; wherein the mass percentage of the solute in the ammonia water is 20%; stirring the mixed aqueous solution of ammonia water, deionized water and ethanol, and then adding hexadecyltrimethylammonium bromide to the solution under stirring, continuing to stir the solution for 20 minutes after the addition is completed, and then stirring under stirring The ethanol solution of tetraethyl orthosilicate is added dropwise to the solution, and the amount of hexadecyltrimethylammonium bromide, the ethanol solution of tetraethyl orthosilicate and the mixed aqueous solution of ammonia water, deionized water and ethanol is in the ratio of hexadecyltrimethylammonium bromide: ethanol solution of tetraethyl orthosilicate: mixed aqueous solution of ammonia water, deionized water and ethanol = 0.7 g: 2 mL: 10 mL; after the addition is completed, stirring is continued for 1 min, standing for 2 h, and then solid-liquid separation is performed, the solid phase is washed with deionized water 3 times, dried at 60° C. for 30 min, and then calcined at 550° C. for 5 h to obtain nano silicon dioxide particles;

[0047] (2) preparing an ethanol solution of polyethyleneimine, wherein the mass percentage of polyethyleneimine in the ethanol solution of polyethyleneimine is 5% and the solvent is ethanol; adding the nano-silica particles to the ethanol solution of polyethyleneimine, wherein the mass ratio of the nano-silica particles to the ethanol solution of polyethyleneimine is nano-silica particles: ethanol solution of polyethyleneimine = 1:80; stirring for 20 minutes after the addition is completed, and then adding Span80 and polyethylene glycol (PEG1000) to the solution under stirring, wherein the mass ratio of the added Span80 and polyethylene glycol to the mass ratio of the nano-silica particles in the solution is Span80: polyethylene glycol: nano-silica particles = 0.7:1.4:1; after the addition is completed, the solution is stirred for 1 hour, and then the solid-liquid separation is performed, the solid phase is washed with ethanol 3 times, and dried at 60° C. for 30 minutes to obtain the modified powder of this comparative example;

[0048] (3) Adding the modified powder and dopamine hydrochloride to Tris-HCl buffer, the ratio of modified powder to dopamine hydrochloride added to Tris-HCl buffer is modified powder: dopamine hydrochloride: Tris-HCl buffer = 0.5 g: 0.3 g: 100 mL, the concentration of tris(hydroxymethyl)aminomethane in the Tris-HCl buffer is 0.01 mol / L, and the pH is 8.5; then heating in a water bath to 40±2° C. and stirring for 20 h, separating the solid and the liquid, washing the solid phase with deionized water for 3 times, and drying at 60° C. for 30 min to obtain the filler particles.

[0049] Weigh each raw material according to the above-mentioned weight proportions, then mix the raw materials evenly in a nitrogen atmosphere, spray them on the surface of the test sample, and then heat to 110° C. under nitrogen protection, keep warm for 2 hours, and cool to room temperature to obtain the waterproof material described in this comparative example.

[0050] Comparative Example 2

[0051] A waterproof material for comparison, the raw materials include hydroxy acrylic resin, filler particles, vinyl triethoxysilane, initiator BPO, propylene glycol diacrylate, styrene, acrylic acid, HDI curing agent and xylene; each of the raw materials is calculated by weight: 60 parts of hydroxy acrylic resin, 6 parts of filler particles, 8 parts of vinyl triethoxysilane, 0.8 parts of initiator BPO, 3 parts of propylene glycol diacrylate, 5 parts of styrene, 2 parts of acrylic acid, 16 parts of HDI curing agent, 100 parts of xylene. The preparation method of the filler particles is:

[0052] (1) preparing an ethanol solution of tetraethyl orthosilicate, wherein the mass percentage of tetraethyl orthosilicate in the ethanol solution of tetraethyl orthosilicate is 8%; preparing a mixed aqueous solution of ammonia water, deionized water and ethanol; the mixed volume ratio of ammonia water, deionized water and ethanol is ammonia water: deionized water: ethanol = 0.3:10:1; wherein the mass percentage of the solute in the ammonia water is 20%; stirring the mixed aqueous solution of ammonia water, deionized water and ethanol, and then adding hexadecyltrimethylammonium bromide to the solution under stirring, continuing to stir the solution for 20 minutes after the addition is completed, and then stirring under stirring The ethanol solution of tetraethyl orthosilicate is added dropwise to the solution, and the amount of hexadecyltrimethylammonium bromide, the ethanol solution of tetraethyl orthosilicate and the mixed aqueous solution of ammonia water, deionized water and ethanol is in the ratio of hexadecyltrimethylammonium bromide: ethanol solution of tetraethyl orthosilicate: mixed aqueous solution of ammonia water, deionized water and ethanol = 0.7 g: 2 mL: 10 mL; after the addition is completed, stirring is continued for 1 min, standing for 2 h, and then solid-liquid separation is performed, the solid phase is washed with deionized water 3 times, dried at 60° C. for 30 min, and then calcined at 550° C. for 5 h to obtain nano silicon dioxide particles;

[0053] (2) preparing a mixture of bis(dioctyl pyrophosphate)ethylene titanate coupling agent and ethanol, wherein the mass ratio of bis(dioctyl pyrophosphate)ethylene titanate coupling agent to ethanol is bis(dioctyl pyrophosphate)ethylene titanate coupling agent:ethanol=3:100; heating the mixture of bis(dioctyl pyrophosphate)ethylene titanate coupling agent and ethanol in a water bath to 60±5° C. and then adding the nano-silica particles to the solution under the heat preservation state, wherein the mass ratio of the nano-silica particles to the solution is nano-silica:solution=1:50; after the addition is completed, the solution is kept at 60±5° C. and stirred for 100 minutes, condensed and refluxed during the heat preservation process, and then air-cooled to room temperature, solid-liquid separation is performed, and the solid phase is dried at 60° C. for 5 hours to obtain a modified powder;

[0054] (3) Add the modified powder and dopamine hydrochloride to Tris-HCl buffer, the amount ratio of modified powder and dopamine hydrochloride added to Tris-HCl buffer is modified powder: dopamine hydrochloride: Tris-HCl buffer = 0.5 g: 0.3 g: 100 mL, the concentration of tris(hydroxymethyl)aminomethane in the Tris-HCl buffer is 0.01 mol / L, and the pH is 8.5; then heat in a water bath to 40±2° C. and keep stirring for 20 hours, separate the solid and liquid, wash the solid phase with deionized water 3 times, and dry at 60° C. for 30 minutes to obtain the filler particles of this comparative example.

[0055] Weigh each raw material according to the above-mentioned weight proportions, then mix the raw materials evenly in a nitrogen atmosphere, spray them on the surface of the test sample, and then heat to 110° C. under nitrogen protection, keep warm for 2 hours, and cool to room temperature to obtain the waterproof material described in this comparative example.

[0056] Comparative Example 3

[0057] A waterproof material for comparison, the raw materials include hydroxy acrylic resin, filler particles, vinyl triethoxysilane, initiator BPO, propylene glycol diacrylate, styrene, acrylic acid, HDI curing agent and xylene; each of the raw materials is calculated by weight: 60 parts of hydroxy acrylic resin, 6 parts of filler particles, 8 parts of vinyl triethoxysilane, 0.8 parts of initiator BPO, 3 parts of propylene glycol diacrylate, 5 parts of styrene, 2 parts of acrylic acid, 16 parts of HDI curing agent, 100 parts of xylene. The preparation method of the filler particles is:

[0058] (1) preparing an ethanol solution of tetraethyl orthosilicate, wherein the mass percentage of tetraethyl orthosilicate in the ethanol solution of tetraethyl orthosilicate is 8%; preparing a mixed aqueous solution of ammonia water, deionized water and ethanol; the mixed volume ratio of ammonia water, deionized water and ethanol is ammonia water: deionized water: ethanol = 0.3:10:1; wherein the mass percentage of the solute in the ammonia water is 20%; stirring the mixed aqueous solution of ammonia water, deionized water and ethanol, and then adding hexadecyltrimethylammonium bromide to the solution under stirring, continuing to stir the solution for 20 minutes after the addition is completed, and then stirring under stirring The ethanol solution of tetraethyl orthosilicate is added dropwise to the solution, and the amount of hexadecyltrimethylammonium bromide, the ethanol solution of tetraethyl orthosilicate and the mixed aqueous solution of ammonia water, deionized water and ethanol is in the ratio of hexadecyltrimethylammonium bromide: ethanol solution of tetraethyl orthosilicate: mixed aqueous solution of ammonia water, deionized water and ethanol = 0.7 g: 2 mL: 10 mL; after the addition is completed, stirring is continued for 1 min, standing for 2 h, and then solid-liquid separation is performed, the solid phase is washed with deionized water 3 times, dried at 60° C. for 30 min, and then calcined at 550° C. for 5 h to obtain nano silicon dioxide particles;

[0059] (2) preparing a mixture of bis(dioctyl pyrophosphate)ethylene titanate coupling agent and ethanol, wherein the mass ratio of bis(dioctyl pyrophosphate)ethylene titanate coupling agent to ethanol is bis(dioctyl pyrophosphate)ethylene titanate coupling agent:ethanol=3:100; heating the mixture of bis(dioctyl pyrophosphate)ethylene titanate coupling agent and ethanol in a water bath to 60±5° C. and then adding the nano-silica particles to the solution under the heat preservation state, wherein the mass ratio of the nano-silica particles to the solution is nano-silica:solution=1:50; after the addition is completed, the solution is kept at 60±5° C. and stirred for 100 minutes, condensed and refluxed during the heat preservation process, and then air-cooled to room temperature, solid-liquid separation is performed, and the solid phase is dried at 60° C. for 5 hours to obtain a modified powder;

[0060] (3) preparing an ethanol solution of polyethyleneimine, wherein the mass percentage of polyethyleneimine in the ethanol solution of polyethyleneimine is 5% and the solvent is ethanol; adding the modified powder to the ethanol solution of polyethyleneimine, wherein the mass ratio of the modified powder to the ethanol solution of polyethyleneimine is modified powder: ethanol solution of polyethyleneimine = 1:80; stirring for 20 minutes after the addition is completed, and then adding Span80 and polyethylene glycol (PEG1000) to the solution under stirring, wherein the mass ratio of the added Span80 and polyethylene glycol to the mass ratio of the modified powder in the solution is Span80: polyethylene glycol: modified powder = 0.7:1.4:1; after the addition is completed, the solution is stirred for 1 hour, and then the solid-liquid separation is performed, the solid phase is washed with ethanol 3 times, and dried at 60°C for 30 minutes to obtain the filler particles of this comparative example.

[0061] Weigh each raw material according to the above-mentioned weight proportions, then mix the raw materials evenly in a nitrogen atmosphere, spray them on the surface of the test sample, and then heat to 110° C. under nitrogen protection, keep warm for 2 hours, and cool to room temperature to obtain the waterproof material described in this comparative example.

[0062] Example 5

[0063] The water contact angles of the waterproof materials prepared by the methods described in the above embodiments and comparative examples were tested, and the surface hardness of the waterproof materials prepared by the methods described in the above embodiments and comparative examples were tested according to the requirements of standard GB / T6739-2006. The results are shown in Table 1.

[0064] As shown in Table 1, the waterproof material prepared by the method of the present invention has good hydrophobicity and surface hardness, and it is sprayed on the surface of the optical cable, which can play a good waterproof effect, and the wear resistance is good, and the optical cable surface has a strong protective effect to prevent the optical cable surface from being worn. Introducing filler particles in the resin substrate can play a second phase strengthening effect, improve the mechanical properties of the resin, but also bring the problem that the two-phase interface is not combined sufficiently, and microcrack holes are easily produced, and the filler particles are generally finer, and agglomeration is likely to occur, causing uneven distribution in the material, and stress concentration is prone to defects when stressed. Therefore, the application processes filler so that the filler surface forms macromolecular functional groups, improves the bonding force of filler and resin, reduces interphase defects, improves the density of waterproof material, makes water difficult to penetrate, and the surface energy of the modified surface after the filler treatment is relatively low, on the one hand, the agglomeration of filler can be well prevented, so that the filler distribution is more uniform, and on the other hand, the adhesion of water can also be reduced, and a good hydrophobic effect is played.

[0065] Table 1

[0066] Experimental Group Water contact angle (°) hardness Example 1 157.8 6H Example 2 159.2 6H Example 3 160.1 6H Example 4 159.7 6H Comparative Example 1 127.5 5H Comparative Example 2 132.4 5H Comparative Example 3 130.9 5H

[0067] The technical solution provided by the present invention is introduced in detail above. For those skilled in the art, according to the concept of the embodiments of the present invention, there may be changes in the specific implementation method and application scope. In summary, the content of this specification should not be understood as limiting the present invention.

Claims

1. A highly wear-resistant communication optical cable waterproof material, characterized in that: The raw materials include hydroxy acrylic resin, filler particles, vinyl triethoxysilane, initiator BPO, propylene glycol diacrylate, styrene, acrylic acid, HDI curing agent and xylene; the preparation method of the filler particles is: (1) preparing an ethanol solution of tetraethyl orthosilicate and preparing a mixed aqueous solution of ammonia water, deionized water and ethanol; stirring the mixed aqueous solution of ammonia water, deionized water and ethanol, and then adding hexadecyltrimethylammonium bromide to the solution under stirring, continuing to stir the solution for more than 20 minutes after the addition is completed, and then dropwise adding the ethanol solution of tetraethyl orthosilicate to the solution under stirring, continuing to stir for 1 to 2 minutes after the addition is completed, standing for more than 2 hours, and then separating the solid and the liquid, washing the solid phase with deionized water for more than 3 times, drying at 60° C. for 30 to 40 minutes, and then calcining at 550° C. for 5 to 6 hours to obtain nano silicon dioxide particles; (2) preparing a mixture of bis(dioctyloxypyrophosphate)ethylene titanate coupling agent and ethanol, heating the mixture of the bis(dioctyloxypyrophosphate)ethylene titanate coupling agent and ethanol in a water bath to 60±5° C., then adding the nano-silica particles to the solution under the heat preservation state, and stirring the solution at 60±5° C. for 100 to 120 minutes after the addition is completed, condensing and reflux during the heat preservation process, and then air cooling to room temperature, solid-liquid separation, and solid phase drying at 60° C. for more than 5 hours to obtain a modified powder; (3) preparing an ethanol solution of polyethyleneimine, adding the modified powder to the ethanol solution of polyethyleneimine, stirring for more than 20 minutes after the addition is completed, and then adding Span80 and polyethylene glycol to the solution under stirring, continuing to stir the solution for more than 1 hour after the addition is completed, and then separating the solid and liquid, washing the solid phase with ethanol for more than 3 times, and drying at 60° C. for more than 30 minutes to obtain a modified powder; (4) adding the modified powder and dopamine hydrochloride into a Tris-HCl buffer solution, then heating the mixture in a water bath to 40±2° C. and stirring the mixture for more than 20 h, separating the solid from the liquid, washing the solid phase with deionized water for more than 3 times, and drying the mixture at 60° C. for more than 30 min to obtain the filler particles.

2. A highly wear-resistant communication optical cable waterproof material according to claim 1, characterized in that: The raw materials are calculated in parts by weight as follows: 50-60 parts of hydroxy acrylic resin, 5-6 parts of filler particles, 5-10 parts of vinyl triethoxy silane, 0.7-0.8 parts of initiator BPO, 2-3 parts of propylene glycol diacrylate, 4-6 parts of styrene, 1-3 parts of acrylic acid, 15-16 parts of HDI curing agent, and 100 parts of xylene.

3. The highly wear-resistant communication optical cable waterproof material according to claim 1, characterized in that: In the step (1), the mass percentage of tetraethyl orthosilicate in the ethanol solution of tetraethyl orthosilicate is 8%; the mixed volume ratio of ammonia water, deionized water and ethanol is ammonia water: deionized water: ethanol = 0.2-0.3:10:1; The mass percentage of the solute in the ammonia water is 20%; the amount of hexadecyltrimethylammonium bromide and the ethanol solution of tetraethyl orthosilicate added to the mixed aqueous solution of ammonia water, deionized water and ethanol is hexadecyltrimethylammonium bromide: ethanol solution of tetraethyl orthosilicate: mixed aqueous solution of ammonia water, deionized water and ethanol = 0.6-0.8g: 1-2mL: 10mL.

4. The highly wear-resistant communication optical cable waterproof material according to claim 1, characterized in that: In the step (2), in the mixed solution of bis(dioctyloxypyrophosphate)ethylene titanate coupling agent and ethanol, the mass ratio of bis(dioctyloxypyrophosphate)ethylene titanate coupling agent to ethanol is bis(dioctyloxypyrophosphate)ethylene titanate coupling agent:ethanol=2-3:100; the nano-silica particles are added to the solution in a mass ratio of nano-silica:solution=1:

50.

5. The highly wear-resistant communication optical cable waterproof material according to claim 1, characterized in that: In the step (3), in the ethanol solution of polyethyleneimine, the mass percentage of polyethyleneimine is 5%, and the solvent is ethanol; the mass ratio of the modified powder added to the ethanol solution of polyethyleneimine is modified powder: ethanol solution of polyethyleneimine = 1:80; the mass ratio of the added mass of Span80 and polyethylene glycol to the mass ratio of the modified powder in the solution is Span80: polyethylene glycol: modified powder = 0.5~0.8:1.2~1.6:

1.

6. The highly wear-resistant communication optical cable waterproof material according to claim 1, characterized in that: In the step (4), the modified powder and dopamine hydrochloride are added to the Tris-HCl buffer in a ratio of modified powder: dopamine hydrochloride: Tris-HCl buffer = 0.4-0.5 g: 0.2-0.3 g: 100 mL, the concentration of tris(hydroxymethyl)aminomethane in the Tris-HCl buffer is 0.01 mol / L, and the pH is 8.5.