阅读说明：本技术 一种防蚁鼠线缆及其制备方法 (Anti-termite and anti-mouse cable and preparation method thereof ) 是由 姜梦 黄晓鹏 寿荣 于 2020-11-24 设计创作，主要内容包括：本发明提出了一种防蚁鼠线缆,包括缆芯和包裹在缆芯外的护套,所述护套由以下原料按重量份制备而成：多孔二氧化硅/羧基化聚苯乙烯双层中空球10-20份、正-壬酸香草酰胺2-7份、聚乙烯100-200份、复合阻燃剂2-5份、增韧剂1-2份、抗氧剂0.5-1.5份、分散剂0.1-1份、微晶纤维素2-5份。本发明制备了一种表面有大量介孔的多孔二氧化硅/羧基化聚苯乙烯双层中空球,内层为含有羧基结构的壁层,正-壬酸香草酰胺中的氨基与内层壁层的羧基进行缩合,起到缓释的效果,对鼠蚁长效的驱避效果,表面吸附复合阻燃剂、增韧剂、以及其他改性料,有效改善聚乙烯材料的综合性能,具有广阔的应用前景。(The invention provides an ant and mouse prevention cable which comprises a cable core and a sheath wrapped outside the cable core, wherein the sheath is prepared from the following raw materials in parts by weight: 10-20 parts of porous silicon dioxide/carboxylated polystyrene double-layer hollow spheres, 2-7 parts of n-nonanoic acid vanilloyl amide, 100 parts of polyethylene, 2-5 parts of composite flame retardant, 1-2 parts of toughening agent, 0.5-1.5 parts of antioxidant, 0.1-1 part of dispersing agent and 2-5 parts of microcrystalline cellulose. The invention prepares a porous silicon dioxide/carboxylated polystyrene double-layer hollow sphere with a large number of mesopores on the surface, the inner layer is a wall layer containing a carboxyl structure, amino in n-nonanoic vanilloylamine is condensed with carboxyl on the wall layer of the inner layer, a slow release effect is achieved, a long-acting repellent effect on rats and ants is achieved, a composite flame retardant, a toughening agent and other modifying materials are adsorbed on the surface, the comprehensive performance of a polyethylene material is effectively improved, and the porous silicon dioxide/carboxylated polystyrene double-layer hollow sphere has a wide application prospect.)

1. The ant and mouse prevention cable is characterized by comprising a cable core and a sheath wrapped outside the cable core, wherein the sheath is prepared from the following raw materials in parts by weight: 10-20 parts of porous silicon dioxide/carboxylated polystyrene double-layer hollow spheres, 2-7 parts of n-nonanoic acid vanilloyl amide, 100 parts of polyethylene, 2-5 parts of composite flame retardant, 1-2 parts of toughening agent, 0.5-1.5 parts of antioxidant, 0.1-1 part of dispersing agent and 2-5 parts of microcrystalline cellulose.

2. The ant-rat proof cable according to claim 1, wherein the sheath is prepared from the following raw materials in parts by weight: 12-17 parts of porous silicon dioxide/carboxylated polystyrene double-layer hollow spheres, 3-6 parts of n-nonanoic acid vanilloyl amide, 180 parts of polyethylene 120-one, 3-4 parts of composite flame retardant, 1.2-1.8 parts of toughening agent, 0.7-1.2 parts of antioxidant, 0.2-0.8 part of dispersant and 3-4 parts of microcrystalline cellulose.

3. The ant-rat resistant cable according to claim 1, wherein the porous silica/carboxylated polystyrene bilayer hollow sphere is prepared by:

s1, mixing water, alcohol and styrene, heating the system to 70-80 ℃ under the protection of nitrogen, adding a first initiator, reacting for 2-5 hours, stopping the reaction to obtain polystyrene seed microspheres, centrifuging for many times, washing and collecting for later use;

s2, uniformly mixing water, a first surfactant, alcohol and DMSO, heating to 60-70 ℃ while stirring, adding the polystyrene seed microspheres obtained in the step S1 and a mixed solution of p-divinylbenzene and methacrylic acid dissolved with a second initiator, heating to 75-80 ℃ for polymerization, reacting for 1-3h, swelling the coated core-shell structure microspheres with anhydrous ether to remove cores, and obtaining carboxymethylated polystyrene hollow microspheres;

s3, dispersing the carboxymethylated polystyrene hollow microspheres in an organic solvent, adding an amino-containing silane coupling agent, and uniformly stirring to obtain a first oil phase; dissolving tetraethoxysilane in an organic solvent, and uniformly stirring and mixing to obtain a second oil phase; dissolving a second surfactant and a pore-forming agent in water to obtain a water phase; and adding the first oil phase into the water phase, mixing, performing ultrasonic dispersion uniformly, continuously adding a second oil phase, performing homogeneous emulsification to obtain an emulsion, adjusting the pH value of the solution to 7.5-8.5, reacting for 2-4h to obtain porous silicon dioxide/carboxylated polystyrene double-layer hollow sphere emulsion, performing suction filtration, and drying to obtain the porous silicon dioxide/carboxylated polystyrene double-layer hollow sphere.

4. The ant-rat proof cable according to claim 3, wherein the alcohol is selected from one or more of methanol, ethanol, propanol, propylene glycol, glycerol, n-butanol, n-pentanol, n-hexanol; the first initiator is selected from one or a mixture of sodium persulfate, ammonium persulfate and potassium persulfate; the second initiator is selected from one or a mixture of more of benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxypivalate, methyl ethyl ketone peroxide, cyclohexanone peroxide, diisopropyl peroxydicarbonate and dicyclohexyl peroxydicarbonate; the first surfactant is selected from one or a mixture of sodium dodecyl benzene sulfonate, sodium dodecyl sulfonate and sodium dodecyl sulfate; the second surfactant is selected from one of sodium dodecyl benzene sulfonate, sodium dodecyl sulfonate, sodium stearate, calcium stearate and potassium stearate; the organic solvent is one or a mixture of DMSO, THF, dichloromethane, chloroform, methyl acetate, ethyl acetate and petroleum ether; the silane coupling agent containing amino is selected from one of KH550, KH602 and KH 792.

5. The ant-rat prevention cable according to claim 3, wherein the pore-foaming agent is prepared from a macroporous pore-foaming agent and a mesoporous pore-foaming agent according to a mass ratio of 1: (1-3) mixing to obtain the macroporous pore-foaming agent, wherein the macroporous pore-foaming agent is selected from one of polyoxyethylene sorbitan fatty acid ester, polyethylene glycol octyl phenyl ether and sorbitan fatty acid ester; the mesoporous pore-forming agent is selected from one of an oxyethylene-oxypropylene triblock copolymer P123 and an oxyethylene-oxypropylene triblock copolymer F127.

6. The ant-rat proof cable according to claim 3, wherein the mass ratio of the water, the alcohol, the styrene and the first initiator in the step S1 is 100: (10-30): (22-37): 1; in the step S2, the mass ratio of the water, the first surfactant, the alcohol, the DMSO, the polystyrene seed microspheres, the second initiator, the p-divinylbenzene, and the methacrylic acid is 70: (1-3): (10-30): (100-120): (12-20): (0.5-1.5): (27-45): (22-30); the mass ratio of the carboxymethylated polystyrene hollow microspheres, the amino-containing silane coupling agent, the ethyl orthosilicate, the second surfactant and the pore-forming agent in the step S3 is (25-40): (1-4): (35-50): (2-5): (3-7); the method for adjusting the pH value of the solution is to drip an alkali solution, the mass concentration of the alkali solution is 1-3mol/L, and the alkali is NaOH or KOH.

7. The ant-rat proof cable according to claim 1, wherein the composite flame retardant is a mixture of expanded graphite and chlorinated paraffin in a mass ratio of (2-5): 1.

8. the ant-proof rat cable according to claim 1, wherein the toughening agent is selected from one or more of carboxyl group liquid nitrile rubber, carboxyl group-terminated liquid nitrile rubber, polysulfide rubber, liquid silicone rubber, polyether, polysulfone and polyimide, the antioxidant is selected from one or more of diphenylamine, p-phenylenediamine, 2, 6-tertiary butyl-4-methylphenol, bis (3, 5-tertiary butyl-4-hydroxyphenyl) sulfide, pentaerythrityl tetrakis [ beta- (3, 5-tertiary butyl-4-hydroxyphenyl) propionate ], dihydroquinoline, didodecanol ester, dimyristyl alcohol ester, dioctadecyl alcohol ester, trioctyl ester, tridecyl ester, tridodecyl alcohol ester and trihexadecyl alcohol ester, and the dispersant is selected from one or more of calcium stearate, potassium stearate, polyimide, and mixtures thereof, One or more of magnesium stearate, zinc stearate and barium stearate.

9. A method of making an ant-proof rat cable according to any one of claims 1 to 8, comprising the steps of:

s1, dissolving n-nonanoic vanillylamide in DMSO, adding a porous silica/carboxylated polystyrene double-layer hollow sphere, performing ultrasonic dispersion uniformly, heating to 45-65 ℃, reacting for 1-2h, centrifuging, washing the solid with water and DMSO, and obtaining the n-nonanoic vanillylamide-coated porous silica/carboxylated polystyrene double-layer sphere;

s2, adding polyethylene, a composite flame retardant, a toughening agent, an antioxidant, a dispersing agent, microcrystalline cellulose and porous silicon dioxide/carboxylated polystyrene double-layer balls wrapping n-nonanoic vanillylamide into a double-screw extruder to be extruded into a molten state, extruding the mixture into an injection molding machine after the mixture is completely molten, and performing extrusion molding to obtain the ant and mouse prevention cable sheath material;

and S3, extruding the sheath material of the termite and rat proof cable outside the cable core to obtain the termite and rat proof cable.

10. The method as claimed in claim 9, wherein the injection temperature is 200-220 ℃.

Technical Field

The invention relates to the field of cables, in particular to an ant and mouse prevention cable and a preparation method thereof.

Background

The electric cable and the optical cable are collectively called as a cable. Most of the existing cable sheath materials are prepared from polyethylene materials, and the materials are very easy to be bitten by ants and mice, so that the development of ant-proof and mouse-proof sheath materials is necessary. At present, ant-proof and rat-proof sheathing materials are generally treated by adopting trace toxin additives, are fatal to ants or rats and the like, do not have great influence on human bodies, such as pungent agents and the like, but have the defects of short persistence, volatilization after being used outdoors for about 3 months after being made into cables, no long-time effect, and pungent odor generated in the sheathing process.

Disclosure of Invention

The invention aims to provide an ant and mouse prevention cable and a preparation method thereof, wherein a porous silica/carboxylated polystyrene double-layer hollow ball with a large number of mesopores on the surface is prepared, the inner layer is a wall layer with a carboxyl structure, amino in n-nonanoic acid vanilloylamine is condensed with carboxyl on the wall layer of the inner layer, so that a slow-release effect is achieved, a long-acting repellent effect on rats and ants is achieved, a composite flame retardant, a toughening agent and other modifying materials are adsorbed on the surface, the comprehensive performance of a polyethylene material is effectively improved, and the ant and mouse prevention cable has a wide application prospect.

The technical scheme of the invention is realized as follows:

the invention provides an ant and mouse prevention cable which comprises a cable core and a sheath wrapped outside the cable core, wherein the sheath is prepared from the following raw materials in parts by weight: 10-20 parts of porous silicon dioxide/carboxylated polystyrene double-layer hollow spheres, 2-7 parts of n-nonanoic acid vanilloyl amide, 100 parts of polyethylene, 2-5 parts of composite flame retardant, 1-2 parts of toughening agent, 0.5-1.5 parts of antioxidant, 0.1-1 part of dispersing agent and 2-5 parts of microcrystalline cellulose.

As a further improvement of the invention, the sheath is prepared from the following raw materials in parts by weight: 12-17 parts of porous silicon dioxide/carboxylated polystyrene double-layer hollow spheres, 3-6 parts of n-nonanoic acid vanilloyl amide, 180 parts of polyethylene 120-one, 3-4 parts of composite flame retardant, 1.2-1.8 parts of toughening agent, 0.7-1.2 parts of antioxidant, 0.2-0.8 part of dispersant and 3-4 parts of microcrystalline cellulose.

As a further improvement of the invention, the preparation of the porous silica/carboxylated polystyrene double-layer hollow sphere:

s1, mixing water, alcohol and styrene, heating the system to 70-80 ℃ under the protection of nitrogen, adding a first initiator, reacting for 2-5 hours, stopping the reaction to obtain polystyrene seed microspheres, centrifuging for many times, washing and collecting for later use;

s2, uniformly mixing water, a first surfactant, alcohol and DMSO, heating to 60-70 ℃ while stirring, adding the polystyrene seed microspheres obtained in the step S1 and a mixed solution of p-divinylbenzene and methacrylic acid dissolved with a second initiator, heating to 75-80 ℃ for polymerization, reacting for 1-3h, swelling the coated core-shell structure microspheres with anhydrous ether to remove cores, and obtaining carboxymethylated polystyrene hollow microspheres;

s3, dispersing the carboxymethylated polystyrene hollow microspheres in an organic solvent, adding an amino-containing silane coupling agent, and uniformly stirring to obtain a first oil phase; dissolving tetraethoxysilane in an organic solvent, and uniformly stirring and mixing to obtain a second oil phase; dissolving a second surfactant and a pore-forming agent in water to obtain a water phase; and adding the first oil phase into the water phase, mixing, performing ultrasonic dispersion uniformly, continuously adding a second oil phase, performing homogeneous emulsification to obtain an emulsion, adjusting the pH value of the solution to 7.5-8.5, reacting for 2-4h to obtain porous silicon dioxide/carboxylated polystyrene double-layer hollow sphere emulsion, performing suction filtration, and drying to obtain the porous silicon dioxide/carboxylated polystyrene double-layer hollow sphere.

As a further improvement of the invention, the alcohol is selected from one or a mixture of several of methanol, ethanol, propanol, propylene glycol, glycerol, n-butanol, n-pentanol and n-hexanol; the first initiator is selected from one or a mixture of sodium persulfate, ammonium persulfate and potassium persulfate; the second initiator is selected from one or a mixture of more of benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxypivalate, methyl ethyl ketone peroxide, cyclohexanone peroxide, diisopropyl peroxydicarbonate and dicyclohexyl peroxydicarbonate; the first surfactant is selected from one or a mixture of sodium dodecyl benzene sulfonate, sodium dodecyl sulfonate and sodium dodecyl sulfate; the second surfactant is selected from one of sodium dodecyl benzene sulfonate, sodium dodecyl sulfonate, sodium stearate, calcium stearate and potassium stearate; the organic solvent is one or a mixture of DMSO, THF, dichloromethane, chloroform, methyl acetate, ethyl acetate and petroleum ether; the silane coupling agent containing amino is selected from one of KH550, KH602 and KH 792.

As a further improvement of the invention, the pore-foaming agent is prepared from a macroporous pore-foaming agent and a mesoporous pore-foaming agent according to the mass ratio of 1: (1-3) mixing to obtain the macroporous pore-foaming agent, wherein the macroporous pore-foaming agent is selected from one of polyoxyethylene sorbitan fatty acid ester, polyethylene glycol octyl phenyl ether and sorbitan fatty acid ester; the mesoporous pore-forming agent is selected from one of an oxyethylene-oxypropylene triblock copolymer P123 and an oxyethylene-oxypropylene triblock copolymer F127.

As a further improvement of the present invention, in step S1, the mass ratio of the water, the alcohol, the styrene, and the first initiator is 100: (10-30): (22-37): 1; in the step S2, the mass ratio of the water, the first surfactant, the alcohol, the DMSO, the polystyrene seed microspheres, the second initiator, the p-divinylbenzene, and the methacrylic acid is 70: (1-3): (10-30): (100-120): (12-20): (0.5-1.5): (27-45): (22-30); the mass ratio of the carboxymethylated polystyrene hollow microspheres, the amino-containing silane coupling agent, the ethyl orthosilicate, the second surfactant and the pore-forming agent in the step S3 is (25-40): (1-4): (35-50): (2-5): (3-7); the method for adjusting the pH value of the solution is to drip an alkali solution, the mass concentration of the alkali solution is 1-3mol/L, and the alkali is NaOH or KOH.

As a further improvement of the invention, the composite flame retardant is a mixture of expanded graphite and chlorinated paraffin, and the mass ratio of the expanded graphite to the chlorinated paraffin is (2-5): 1.

as a further improvement of the invention, the toughening agent is selected from one or a mixture of more of carboxyl liquid nitrile rubber, carboxyl-terminated liquid nitrile rubber, polysulfide rubber, liquid silicone rubber, polyether, polysulfone and polyimide, the antioxidant is selected from one or a mixture of more of diphenylamine, p-phenylenediamine, 2, 6-tertiary butyl-4-methylphenol, bis (3, 5-tertiary butyl-4-hydroxyphenyl) thioether, pentaerythritol tetrakis- [ beta- (3, 5-tertiary butyl-4-hydroxyphenyl) propionate ], dihydroquinoline, didodecanol ester, ditetradecanol ester, dioctadecyl ester, trioctyl ester, tridecanol ester, tridodecanol ester and trihexadecanol ester, and the dispersant is selected from one or a mixture of more of calcium stearate, potassium stearate, magnesium stearate, zinc stearate, One or more of barium stearate.

The invention further protects a preparation method of the ant and mouse prevention cable, which comprises the following steps:

s1, dissolving n-nonanoic vanillylamide in DMSO, adding a porous silica/carboxylated polystyrene double-layer hollow sphere, performing ultrasonic dispersion uniformly, heating to 45-65 ℃, reacting for 1-2h, centrifuging, washing the solid with water and DMSO, and obtaining the n-nonanoic vanillylamide-coated porous silica/carboxylated polystyrene double-layer sphere;

s2, adding polyethylene, a composite flame retardant, a toughening agent, an antioxidant, a dispersing agent, microcrystalline cellulose and the porous silicon dioxide/carboxylated polystyrene double-layer ball coated with n-nonanoic vanillylamide into a double-screw extruder, extruding the mixture into a molten state, extruding the mixture into an injection molding machine after the mixture is completely molten, and performing extrusion molding to obtain the ant and mouse prevention cable.

As a further improvement of the invention, the injection molding temperature is 200-220 ℃.

The invention has the following beneficial effects: the invention adopts a sol-gel method and a template method to prepare a porous silica/carboxylated polystyrene double-layer hollow sphere with a large number of mesopores on the surface, the inner layer is a wall layer containing a carboxyl structure, amino in n-nonanoic acid vanilloylamine is condensed with carboxyl on the wall layer of the inner layer, and most spicy n-nonanoic acid vanilloylamine in capsaicin is wrapped in the hollow sphere and fixed in the hollow sphere, thereby playing a slow-release effect and having a long-acting repellent effect on rat and ant; the silicon dioxide hollow spheres form a large number of mesopores and macropores on the surface through the pore-forming agent, the macropores have the function of enabling a polyethylene molecular chain to pass through the microspheres so as not to break, and the mechanical property of the polyethylene resin is prevented from being influenced, and the mesopores have the function of adsorbing modifiers such as a flame retardant, an antioxidant, a toughening agent and the like, so that the mechanical property of the resin is prevented from being changed due to different phases of the modifiers and matrix resin.

The composite flame retardant additionally added in the invention comprises expanded graphite and chlorinated paraffin, so that the flame retardant property of the sheathing material can be obviously improved, and the situation that fire is caused by possible short circuit of the sheathing material after the sheathing material is gnawed by rats and ants is avoided, thus improving the safety performance of the sheathing material, improving the high and low temperature resistance of the sheathing material and having the synergistic effect;

the porous silicon dioxide double-layer hollow spheres added in the polyethylene material have large specific surface area, and can adsorb composite flame retardant, toughening agent and other modified materials, so that the compatibility and the dispersibility of the additives in the polyethylene material are improved, and the comprehensive performance of the polyethylene material can be effectively improved.

The invention prepares a porous silicon dioxide/carboxylated polystyrene double-layer hollow sphere with a large number of mesopores on the surface, the inner layer is a wall layer containing a carboxyl structure, amino in n-nonanoic vanilloylamine is condensed with carboxyl on the wall layer of the inner layer, a slow release effect is achieved, a long-acting repellent effect on rats and ants is achieved, a composite flame retardant, a toughening agent and other modifying materials are adsorbed on the surface, the comprehensive performance of a polyethylene material is effectively improved, and the porous silicon dioxide/carboxylated polystyrene double-layer hollow sphere has a wide application prospect.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.

FIG. 1 is an SEM photograph of a porous silica/carboxylated polystyrene double-layer hollow sphere prepared in preparation example 1;

FIG. 2 is a TEM image of the porous silica/carboxylated polystyrene bilayer hollow spheres obtained in preparation example 2.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Preparation example 1 preparation of porous silica/carboxylated polystyrene double-layer hollow sphere

The preparation method comprises the following steps:

s1, mixing 100g of water, 10g of methanol and 22g of styrene, heating the system to 70 ℃ under the protection of nitrogen, adding 1g of sodium persulfate, reacting for 2 hours, stopping the reaction to obtain polystyrene seed microspheres, centrifuging for many times, washing and collecting for later use;

s2, uniformly mixing 70g of water, 1g of sodium dodecyl sulfate, 10g of methanol and 100g of DMSO, heating to 60 ℃ while stirring, adding 12g of the polystyrene seed microspheres obtained in the step S1 and a mixed solution in which 0.5g of diisopropyl peroxydicarbonate, 27g of p-divinylbenzene and 22g of methacrylic acid are dissolved, heating to 75 ℃ for polymerization, reacting for 1h, swelling the coated core-shell structure microspheres by using anhydrous ether to remove cores, and preparing carboxymethylated polystyrene hollow microspheres;

s3, dispersing 25g of carboxymethylated polystyrene hollow microspheres in 50ml of THF, adding 1g of amino-containing silane coupling agent KH602, and uniformly stirring to obtain a first oil phase; dissolving 35g of tetraethoxysilane in 50ml of THF, and uniformly stirring and mixing to obtain a second oil phase; dissolving 2g of sodium dodecyl sulfate and 3g of pore-foaming agent in 200mL of water to obtain a water phase; the first oil phase is dropwise added into the water phase to be mixed, the mixture is ultrasonically dispersed uniformly, the second oil phase is continuously dropwise added, the mixture is homogenized for 2min at 10000r/min to obtain emulsion, 1mol/LNaOH solution is dropwise added to adjust the pH value of the solution to be 7.5, the reaction lasts for 2h to obtain porous silica/carboxylated polystyrene double-layer hollow sphere emulsion, the porous silica/carboxylated polystyrene double-layer hollow sphere is obtained through pumping filtration and drying, the attached drawing 1 is an SEM image of the porous silica/carboxylated polystyrene double-layer hollow sphere prepared through the method, a figure shows that a plurality of macropores and mesopores are formed on the surface of the figure, the attached drawing 2 is a TEM image of the porous silica/carboxylated polystyrene double-layer hollow sphere prepared through the method, and the interior of the sphere formed through the method is hollow.

The pore-foaming agent is prepared from a macroporous pore-foaming agent polyoxyethylene sorbitan fatty acid ester and a mesoporous pore-foaming agent oxyethylene-oxypropylene triblock copolymer P123 according to the mass ratio of 1: 1 are mixed to obtain the product.

Preparation example 2 preparation of porous silica/carboxylated polystyrene double-layer hollow sphere

The preparation method comprises the following steps:

s1, mixing 100g of water, 30g of ethanol and 37g of styrene, heating the system to 80 ℃ under the protection of nitrogen, adding 1g of ammonium persulfate, reacting for 5 hours, stopping the reaction to obtain polystyrene seed microspheres, centrifuging and washing for multiple times, and collecting the polystyrene seed microspheres for later use;

s2, uniformly mixing 70g of water, 1-3g of sodium dodecyl benzene sulfonate, 30g of ethanol and 120g of DMSO (dimethylsulfoxide), heating to 70 ℃ while stirring, adding 20g of the polystyrene seed microspheres obtained in the step S1 and a mixed solution in which 1.5g of tert-butyl peroxypivalate, 45g of p-divinylbenzene and 30g of methacrylic acid are dissolved, heating to 80 ℃ for polymerization, reacting for 3 hours, swelling the coated core-shell structure microspheres by using anhydrous ether to remove cores, and preparing carboxymethylated polystyrene hollow microspheres;

s3, dispersing 40g of carboxymethylated polystyrene hollow microspheres in 50mL of dichloromethane, adding 4g of amino-containing silane coupling agent KH550, and uniformly stirring to obtain a first oil phase; dissolving 50g of tetraethoxysilane in 50mL of dichloromethane, and uniformly stirring and mixing to obtain a second oil phase; dissolving 5g of sodium stearate and 7g of pore-foaming agent in 200mL of water to obtain a water phase; and dropwise adding the first oil phase into the water phase, mixing, performing ultrasonic dispersion uniformly, continuously dropwise adding the second oil phase, homogenizing at 10000r/min for 2min, emulsifying to obtain an emulsion, dropwise adding a 3mol/LKOH solution to adjust the pH value of the solution to 8.5, reacting for 4h to obtain a porous silicon dioxide/carboxylated polystyrene double-layer hollow sphere emulsion, performing suction filtration, and drying to obtain the porous silicon dioxide/carboxylated polystyrene double-layer hollow sphere.

The pore-foaming agent is prepared from a macroporous pore-foaming agent polyethylene glycol octyl phenyl ether and a mesoporous pore-foaming agent oxyethylene-oxypropylene triblock copolymer F127 according to the mass ratio of 1: 3, and mixing to obtain the product.

Example 1

The cable comprises a cable core and a sheath wrapped outside the cable core, wherein the sheath comprises the following raw materials in parts by weight: 10 parts of porous silicon dioxide/carboxylated polystyrene double-layer hollow sphere prepared in preparation example 1, 2 parts of n-nonanoic vanillylamide, 100 parts of polyethylene, 2 parts of composite flame retardant, 1 part of toughening agent carboxyl liquid nitrile rubber, 0.5 part of antioxidant tetra [ beta- (3, 5-tertiary butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, 0.1 part of dispersant zinc stearate and 2 parts of microcrystalline cellulose. The composite flame retardant is a mixture of expanded graphite and chlorinated paraffin, and the mass ratio is 2: 1.

the method comprises the following steps:

s1, dissolving n-nonanoic vanillylamide in DMSO, adding a porous silica/carboxylated polystyrene double-layer hollow sphere, carrying out ultrasonic dispersion uniformly, heating to 45 ℃, reacting for 1h, centrifuging, washing the solid with water and DMSO, and obtaining the porous silica/carboxylated polystyrene double-layer sphere coated with the n-nonanoic vanillylamide;

s2, adding polyethylene, a composite flame retardant, a toughening agent carboxyl liquid nitrile rubber, an antioxidant tetra [ beta- (3, 5-tertiary butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, a dispersing agent zinc stearate, microcrystalline cellulose and porous silicon dioxide/carboxylated polystyrene double-layer balls wrapping n-nonanoic acid vanillylamide into a double-screw extruder to be extruded into a molten state, extruding into an injection molding machine after the mixed materials are completely molten, and performing extrusion molding at the injection molding temperature of 200 ℃ to obtain the ant-proof rat cable sheath material;

and S3, extruding the sheath material of the termite and rat proof cable outside the cable core to obtain the termite and rat proof cable.

Example 2

The cable comprises a cable core and a sheath wrapped outside the cable core, wherein the sheath comprises the following raw materials in parts by weight: 20 parts of the porous silica/carboxylated polystyrene double-layer hollow sphere prepared in preparation example 1, 7 parts of n-nonanoic oxalamide, 200 parts of polyethylene, 5 parts of a composite flame retardant, 2 parts of a toughening agent carboxyl-terminated liquid nitrile rubber, 1.5 parts of antioxidant tetra [ beta- (3, 5-tertiary butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, 1 part of dispersant calcium stearate and 5 parts of microcrystalline cellulose. The composite flame retardant is a mixture of expanded graphite and chlorinated paraffin, and the mass ratio is 5: 1.

the method comprises the following steps:

s1, dissolving n-nonanoic vanillylamide in DMSO, adding a porous silica/carboxylated polystyrene double-layer hollow sphere, carrying out ultrasonic dispersion uniformly, heating to 65 ℃, reacting for 2 hours, centrifuging, washing the solid with water and DMSO, and obtaining the porous silica/carboxylated polystyrene double-layer sphere coated with the n-nonanoic vanillylamide;

s2, adding polyethylene, a composite flame retardant, a toughening agent carboxyl-terminated liquid nitrile rubber, an antioxidant pentaerythrityl tetrakis [ beta- (3, 5-tertiary butyl-4-hydroxyphenyl) propionate ], a dispersant calcium stearate, microcrystalline cellulose and porous silicon dioxide/carboxylated polystyrene double-layer balls wrapping n-nonanoic acid vanillylamide into a double-screw extruder to be extruded into a molten state, extruding the mixture into an injection molding machine after the mixture is completely molten, and performing extrusion molding at the injection molding temperature of 220 ℃ to obtain the ant-proof rat cable sheath material;

and S3, extruding the sheath material of the termite and rat proof cable outside the cable core to obtain the termite and rat proof cable.

Example 3

The cable comprises a cable core and a sheath wrapped outside the cable core, wherein the sheath comprises the following raw materials in parts by weight: 12 parts of porous silicon dioxide/carboxylated polystyrene double-layer hollow spheres prepared in preparation example 2, 3 parts of n-nonanoic vanilloylamine, 120 parts of polyethylene, 3 parts of a composite flame retardant, 1.2 parts of a toughening agent polyimide, 0.7 part of antioxidant tridodecylol ester, 0.2 part of dispersant potassium stearate and 3 parts of microcrystalline cellulose. The composite flame retardant is a mixture of expanded graphite and chlorinated paraffin, and the mass ratio is 3: 1.

the method comprises the following steps:

s1, dissolving n-nonanoic vanillylamide in DMSO, adding a porous silica/carboxylated polystyrene double-layer hollow sphere, performing ultrasonic dispersion uniformly, heating to 50 ℃, reacting for 1.5h, centrifuging, washing the solid with water and DMSO, and obtaining the porous silica/carboxylated polystyrene double-layer sphere coated with the n-nonanoic vanillylamide;

s2, adding polyethylene, a composite flame retardant, a toughening agent polyimide, an antioxidant tri (dodecyl alcohol) ester, a dispersing agent potassium stearate, microcrystalline cellulose and porous silicon dioxide/carboxylated polystyrene double-layer balls wrapping n-nonanoic vanillylamide into a double-screw extruder, extruding into a molten state, extruding into an injection molding machine after the mixed materials are completely molten, and performing extrusion molding at the injection molding temperature of 210 ℃ to obtain the ant and rat prevention cable sheath material;

and S3, extruding the sheath material of the termite and rat proof cable outside the cable core to obtain the termite and rat proof cable.

Example 4

The cable comprises a cable core and a sheath wrapped outside the cable core, wherein the sheath comprises the following raw materials in parts by weight: 17 parts of porous silicon dioxide/carboxylated polystyrene double-layer hollow spheres prepared in preparation example 2, 6 parts of n-nonanoic acid vanillimide, 180 parts of polyethylene, 4 parts of a composite flame retardant, 1.8 parts of a toughening agent carboxyl-terminated liquid nitrile rubber, 1.2 parts of an antioxidant ditetradecanol ester, 0.8 part of a dispersant potassium stearate and 4 parts of microcrystalline cellulose. The composite flame retardant is a mixture of expanded graphite and chlorinated paraffin, and the mass ratio is 4: 1.

the method comprises the following steps:

s1, dissolving n-nonanoic vanillylamide in DMSO, adding a porous silica/carboxylated polystyrene double-layer hollow sphere, carrying out ultrasonic dispersion uniformly, heating to 55 ℃, reacting for 2 hours, centrifuging, washing the solid with water and DMSO, and obtaining the porous silica/carboxylated polystyrene double-layer sphere coated with the n-nonanoic vanillylamide;

s2, adding polyethylene, a composite flame retardant, a toughening agent carboxyl-terminated liquid nitrile rubber, an antioxidant ditetradecanol ester, a dispersing agent potassium stearate, microcrystalline cellulose and porous silicon dioxide/carboxylated polystyrene double-layer balls wrapping n-nonanoic vanilloylamine into a double-screw extruder, extruding the mixture into a molten state, extruding the mixture into an injection molding machine after the mixture is completely molten, and performing extrusion molding at the injection molding temperature of 200 ℃ to obtain the ant and rat prevention cable sheath material;

and S3, extruding the sheath material of the termite and rat proof cable outside the cable core to obtain the termite and rat proof cable.

Example 5

Compared with the embodiment 4, the composite flame retardant is expanded graphite, and other conditions are not changed.

The cable comprises a cable core and a sheath wrapped outside the cable core, wherein the sheath comprises the following raw materials in parts by weight: 17 parts of porous silicon dioxide/carboxylated polystyrene double-layer hollow spheres prepared in preparation example 2, 6 parts of n-nonanoic acid vanillimide, 180 parts of polyethylene, 4 parts of a composite flame retardant, 1.8 parts of a toughening agent carboxyl-terminated liquid nitrile rubber, 1.2 parts of an antioxidant ditetradecanol ester, 0.8 part of a dispersant potassium stearate and 4 parts of microcrystalline cellulose. The composite flame retardant is expanded graphite.

Example 6

Compared with the example 4, the composite flame retardant is chlorinated paraffin, and other conditions are not changed.

The cable comprises a cable core and a sheath wrapped outside the cable core, wherein the sheath comprises the following raw materials in parts by weight: 17 parts of porous silicon dioxide/carboxylated polystyrene double-layer hollow spheres prepared in preparation example 2, 6 parts of n-nonanoic acid vanillimide, 180 parts of polyethylene, 4 parts of a composite flame retardant, 1.8 parts of a toughening agent carboxyl-terminated liquid nitrile rubber, 1.2 parts of an antioxidant ditetradecanol ester, 0.8 part of a dispersant potassium stearate and 4 parts of microcrystalline cellulose. The composite flame retardant is chlorinated paraffin.

Comparative example 1

Compared with example 4, the porous silica/carboxylated polystyrene double-layer hollow spheres prepared in preparation example 2 are not added, and other conditions are not changed.

The cable comprises a cable core and a sheath wrapped outside the cable core, wherein the sheath comprises the following raw materials in parts by weight: 6 parts of n-nonanoic acid vanillimide, 180 parts of polyethylene, 4 parts of a composite flame retardant, 1.8 parts of a toughening agent carboxyl-terminated liquid nitrile rubber, 1.2 parts of an antioxidant ditetradecanol, 0.8 part of a dispersant potassium stearate and 4 parts of microcrystalline cellulose. The composite flame retardant is a mixture of expanded graphite and chlorinated paraffin, and the mass ratio is 4: 1.

the method comprises the following steps:

adding n-nonanoic vanilloylamine, polyethylene, a composite flame retardant, a toughening agent carboxyl-terminated liquid nitrile rubber, an antioxidant ditetradecanol ester, a dispersing agent potassium stearate, microcrystalline cellulose and porous silicon dioxide/carboxylated polystyrene double-layer balls wrapping the n-nonanoic vanilloylamine into a double-screw extruder to be extruded into a molten state, extruding the mixture into an injection molding machine after the mixture is completely molten, and performing extrusion molding at the injection molding temperature of 200 ℃ to obtain the ant and mouse prevention cable.

Comparative example 2

Compared with the example 4, the carboxyl-terminated liquid nitrile rubber without the toughening agent is not added, and other conditions are not changed.

The cable comprises a cable core and a sheath wrapped outside the cable core, wherein the sheath comprises the following raw materials in parts by weight: 17 parts of porous silicon dioxide/carboxylated polystyrene double-layer hollow spheres prepared in preparation example 2, 6 parts of n-nonanoic acid vanillylamide, 180 parts of polyethylene, 4 parts of a composite flame retardant, 1.2 parts of antioxidant ditetradecanol ester, 2.6 parts of dispersant potassium stearate and 4 parts of microcrystalline cellulose.

Comparative example 3

Compared with example 4, no dispersant potassium stearate was added, and other conditions were not changed.

The cable comprises a cable core and a sheath wrapped outside the cable core, wherein the sheath comprises the following raw materials in parts by weight: 17 parts of porous silicon dioxide/carboxylated polystyrene double-layer hollow spheres prepared in preparation example 2, 6 parts of n-nonanoic acid vanillimide, 180 parts of polyethylene, 4 parts of a composite flame retardant, 2.6 parts of a toughening agent carboxyl-terminated liquid nitrile rubber, 1.2 parts of an antioxidant ditetradecanol ester and 4 parts of microcrystalline cellulose.

Test example 1 rat-proof Effect test

Test objects: termite-proof rat cables prepared in examples 1 to 6 and comparative examples 1 to 3 and the same type of sheath commercially available.

The rats (250-300 g) used in the experiment were randomly divided into 5 groups per cage. During the test, the test specimen is freely drunk and limitedly eaten, 2 specimens of the same group are placed in each cage and are respectively fixed at different positions in the cage, the positions of the cages are the same, the weight of the specimens is weighed every 24 hours, and the areas of the specimen bitten and damaged, the rat repelling effect and the poisoning condition are checked and recorded. This experiment was continued for 2 weeks.

The evaluation methods are shown in Table 1.

TABLE 1

Evaluation results	Area of bite
		-	<0.5/10
+	<1/10
		++	<5/10
+++	>5/10
		++++	<8/10
+++++	<9.5/10

The test results are shown in Table 2.

TABLE 2

As can be seen from table 2, the ant-proof rat cable prepared in the example of the present invention has an excellent rat-proof effect.

Test example 2 insect-proofing effect test

Test objects: termite-proof rat cables prepared in examples 1 to 6 and comparative examples 1 to 3 and the same type of sheath commercially available.

The method is carried out according to the national standard GBT2951.38-1986 termite test method for electric wires and cables. 3 test pieces are tested each time, each test piece is used for testing 20 termites and is independently carried out in three testing devices respectively, the temperature is 27 +/-1 ℃, the relative humidity is 95-97 percent, and the performance of preventing the termites is taken as the judgment standard of a knock-down method according to half knock-down time (Kt50) of 60 termites tested each time by 3 test pieces; the observation is carried out once every 12h until all the termites die, the state of the termite-eaten test piece is used as the colony method judgment standard, and the test result is shown in table 3.

TABLE 3

As can be seen from Table 3, knock-down method K is the termite resistance of the examples of the present invention_t50 are all less than 100 min; the experimental colony methods are all level 1 corrosion, the dead days of colony termites are less than 4 days, and no termite corrosion tooth marks are found on the surface of the sample, which shows that the sheath material can prevent the termites while preventing the rats.

Test example 3 Performance test

The ant-proof rat cables obtained in examples 1 to 6 and comparative examples 1 to 3 and the commercially available sheath of the same kind were subjected to a test according to the ASTM standard, and the results are shown in table 4.

TABLE 4

The above table shows that the ant and rat prevention cable prepared by the embodiment of the invention has better mechanical property, flame retardance and high temperature resistance.

Compared with the prior art, the invention adopts a sol-gel method and a template method to prepare the porous silica/carboxylated polystyrene double-layer hollow sphere with a large number of mesopores on the surface, the inner layer is a wall layer containing a carboxyl structure, amino in n-nonanoic acid vanilloylamine is condensed with carboxyl on the wall layer of the inner layer, and the most spicy n-nonanoic acid vanilloylamine in capsaicin is wrapped in the hollow sphere and fixed in the hollow sphere, thereby playing a slow-release effect and having a long-acting repellent effect on the rat and ant; the silicon dioxide hollow spheres form a large number of mesopores and macropores on the surface through the pore-forming agent, the macropores have the function of enabling a polyethylene molecular chain to pass through the microspheres so as not to break, and the mechanical property of the polyethylene resin is prevented from being influenced, and the mesopores have the function of adsorbing modifiers such as a flame retardant, an antioxidant, a toughening agent and the like, so that the mechanical property of the resin is prevented from being changed due to different phases of the modifiers and matrix resin.

The composite flame retardant additionally added in the invention comprises expanded graphite and chlorinated paraffin, so that the flame retardant property of the sheathing material can be obviously improved, and the situation that fire is caused by possible short circuit of the sheathing material after the sheathing material is gnawed by rats and ants is avoided, thus improving the safety performance of the sheathing material, improving the high and low temperature resistance of the sheathing material and having the synergistic effect;

the porous silicon dioxide double-layer hollow spheres added in the polyethylene material have large specific surface area, and can adsorb composite flame retardant, toughening agent and other modified materials, so that the compatibility and the dispersibility of the additives in the polyethylene material are improved, and the comprehensive performance of the polyethylene material can be effectively improved.

The invention prepares a porous silicon dioxide/carboxylated polystyrene double-layer hollow sphere with a large number of mesopores on the surface, the inner layer is a wall layer containing a carboxyl structure, amino in n-nonanoic vanilloylamine is condensed with carboxyl on the wall layer of the inner layer, a slow release effect is achieved, a long-acting repellent effect on rats and ants is achieved, a composite flame retardant, a toughening agent and other modifying materials are adsorbed on the surface, the comprehensive performance of a polyethylene material is effectively improved, and the porous silicon dioxide/carboxylated polystyrene double-layer hollow sphere has a wide application prospect.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.