High-flame-retardant environment-friendly material for cable wrapping tape and preparation process thereof

Abstract

The invention discloses a high-flame-retardant environment-friendly material for a cable belting and a preparation process of the high-flame-retardant environment-friendly material, and relates to the field of plastics for cables, and the high-flame-retardant environment-friendly material for the cable belting is prepared from polypropylene, modified SBS, nitrile rubber, a flame retardant and other raw materials. The stability of cyanuric acid in the flame retardant is enhanced, the phenomena of strong water solubility of cyanuric acid and high water absorption of zinc borate powder are improved, and the flame retardant endows the material for the cable belting with high flame retardance, waterproofness and environmental friendliness. The modified SBS is obtained by grafting a functional monomer containing triazinobenzimidazole, thiophene and hydroxyl with SBS through a reaction, so that the material for the cable belting is endowed with good ultraviolet resistance and oil resistance.

Description

Technical Field

[0001] The present invention relates to the field of materials for cables, and particularly to a highly flame-retardant and environmentally friendly material for cable wrapping tapes and its preparation process. Background Art

[0002] Polypropylene (PP) is widely used in cable wrapping tapes, filling layers and insulating layers, such as pp woven winding tapes, cable wrapping tapes, etc., and has the characteristics of high corrosion resistance and high tensile strength. However, at low temperatures (below -30°C), the impact strength of polypropylene drops significantly, which may cause the wrapping tape to become brittle and fail; the use of olefin copolymers such as SBS blended with PP can significantly improve the low-temperature toughness of the material, but the defects of high flammability, poor ultraviolet resistance of PP and SBS, and poor oil resistance of the PP and SBS blend limit their use in cable wrapping tape materials.

[0003] The use of halogen-free flame retardants in cable wrapping tape materials can avoid the release of toxic gases during combustion and enhance the environmental protection of cable wrapping tape materials. The flame retardant effect of 1,3,5-tris(2-hydroxyethyl) cyanuric acid (THEIC) used alone as a plastic flame retardant is not ideal, and it has disadvantages such as high water solubility, low molecular weight, and easy migration, which limit its use in cable wrapping tapes with relatively high waterproof requirements. Although zinc borate has advantages such as environmental protection and high thermal stability as a flame retardant, zinc borate is prone to moisture absorption in a high-humidity environment, resulting in a decrease in flame retardancy.

[0004] Based on this, appropriate modification methods are needed to improve the hydrophobicity and stability of THEIC and zinc borate, improve the defects of poor oil resistance and poor ultraviolet resistance of the PP and SBS blend, and apply them to cable wrapping tape materials to obtain cable wrapping tape materials with excellent properties such as flame retardancy, waterproofness, oil resistance, and ultraviolet resistance. Summary of the Invention

[0005] In order to solve the above technical problems, the present invention provides a highly flame-retardant and environmentally friendly material for cable wrapping tapes and its preparation process.

[0006] The object of the present invention can be achieved by the following technical solutions: A highly flame-retardant and environmentally friendly material for cable wrapping tapes, comprising the following raw materials in parts by weight: 90-100 parts of polypropylene, 20-25 parts of modified SBS, 5-7 parts of nitrile rubber, 2.5-4.5 parts of flame retardant, and 0.02-0.04 parts of calcium stearate; The preparation of the highly flame-retardant and environmentally friendly material for cable wrapping tapes comprises the following steps: Mix polypropylene, modified SBS, nitrile rubber, flame retardant and calcium stearate at 400 - 500 r / min for 20 - 30 min to obtain a mixture, and then melt - extrude and pelletize the mixture at 190 - 210 °C to obtain a highly flame - retardant and environmentally friendly material for cable wrapping tapes; The preparation of the flame retardant includes the following steps: Step A1: Mix a silane coupling agent and absolute ethanol, adjust the pH and stir for hydrolysis, then add zinc borate and stir to obtain product 1; Mix product 1, ethanol, and 3 - chloroperoxybenzoic acid and stir to obtain product 2; Step A2: Mix product 2, 1,3,5 - tris(2 - hydroxyethyl) cyanuric acid, methanol, and trimethylamine, and reflux and stir to obtain product 3; Step A3: Mix enantiomeric pectodiene acid, DMF, and thionyl chloride, and reflux and stir to obtain product 4; Mix product 3, pyridine, triethylamine, and dimethyl sulfoxide to obtain mixture a; Mix product 4 and dimethyl sulfoxide to obtain mixture b; Drop mixture b into mixture a in an ice - water bath and stir to obtain product 5; Step A4: Mix product 5, ethyl acetate, and 3 - chloroperoxybenzoic acid, heat and stir to obtain the flame retardant; Furthermore, the preparation of the flame retardant includes the following specific steps: Step A1: Add the silane coupling agent to absolute ethanol, adjust the pH to 5.5 - 6.0, stir at a speed of 900 - 1000 r / min and a temperature of 50 - 60 °C for 0.5 - 1 h; Then add zinc borate and continue to stir for 1 - 1.5 h, filter and dry to obtain product 1; Mix product 1, ethanol, and 3 - chloroperoxybenzoic acid, and stir at room temperature for 5.5 - 6 h, extract and separate to obtain product 2; Furthermore, zinc borate is used after being ground through a 400 - 600 - mesh sieve; Acetic acid is used to adjust the pH; The dosage ratio of the silane coupling agent, absolute ethanol, and zinc borate is 0.1 - 0.3 g: 80 - 90 mL: 10 - 15 g; The silane coupling agent is 10 - alkenylundecyltrimethoxysilane; The dosage ratio of product 1, ethanol, and 3 - chloroperoxybenzoic acid is 5 - 7 g: 90 - 100 mL: 20 - 22 g; The volume fraction of ethanol is 95%; During the reaction process of Step A1, the silane modifies the surface of zinc borate to obtain zinc borate with terminal carbon - carbon double bonds and alkane long chains on the surface, that is, product 1; The double bond of product 1 is oxidized to an epoxy group to obtain product 2; Step A2: Add product 2 and 1,3,5 - tris(2 - hydroxyethyl) cyanuric acid to methanol, add trimethylamine under stirring, and reflux and stir at 110 - 115 °C for 8 - 8.5 h, extract, dry, and separate to obtain product 3; Furthermore, the dosage ratio of Product 2, 1,3,5-tris(2-hydroxyethyl)cyanuric acid, methanol, and trimethylamine is 8 - 10 g : 36 - 40 g : 100 - 120 mL : 0.6 - 0.8 g; During the reaction process of Step A2, the epoxy group of Product 2 reacts with the hydroxyl group of 1,3,5-tris(2-hydroxyethyl)cyanuric acid to obtain a hydroxyl-containing zinc borate and cyanuric acid grafted product, namely Product 3; Step A3: Add enantioprotodione to DMF, add thionyl chloride under stirring, and reflux and stir at 50 - 60 °C for 5 - 5.5 h to obtain Product 4; Mix Product 3, pyridine, triethylamine, and dimethyl sulfoxide to obtain mixture a; Add Product 4 to dimethyl sulfoxide and mix to obtain mixture b; Dropwise add mixture b to mixture a in an ice-water bath, then raise the temperature to 40 - 45 °C and stir for 6 - 7 h to obtain Product 5; Furthermore, the dosage ratio of enantioprotodione, DMF, and thionyl chloride is 31 - 33 g : 105 - 115 mL : 18 - 20 g; The dosage ratio of Product 3, pyridine, triethylamine, and dimethyl sulfoxide in mixture a is 10 - 12 g : 0.07 - 0.09 g : 10.5 - 11.0 g : 130 - 150 mL; The dosage ratio of Product 4 and dimethyl sulfoxide in mixture b is 35 - 37 g : 80 - 90 mL; The dosage ratio of mixture a and mixture b is 155 - 165 mL : 120 - 130 mL; During the reaction process of Step A3, enantioprotodione reacts with thionyl chloride to obtain an acyl chloride product, namely Product 4; The acyl chloride of Product 4 reacts with the hydroxyl group of Product 3 to obtain a grafted product of zinc borate, cyanuric acid, and tetracyclic diterpene, namely Product 5; Step A4: Mix Product 5, ethyl acetate, and 3-chloroperoxybenzoic acid, and stir at 50 - 60 °C for 7 - 7.5 h to obtain a flame retardant; Furthermore, the dosage ratio of Product 5, ethyl acetate, and 3-chloroperoxybenzoic acid is 5.5 - 6.5 g : 100 - 110 mL : 12 - 13 g; During the reaction process of Step A4, the exocyclic isolated carbon-carbon double bond of the tetracyclic diterpene in Product 5 is oxidized to an epoxy group to obtain a grafted product containing epoxy group, zinc borate, cyanuric acid, and tetracyclic diterpene, which is the flame retardant.

[0007] The modified SBS is prepared by the following steps: Step B1: Mix a primary amine compound, epichlorohydrin, tetrabutylammonium bromide, and toluene and stir, then cool and add an alkali solution, and stir to obtain Product a; Step B2: Mix methyl 3-amino-2-thiophenecarboxylate, Product a, and dimethyl sulfoxide, and heat and stir to obtain Product b; Step B3: In an inert gas atmosphere, heat and stir product b, then cool down the temperature and add methanol, 5-hexen-1-amine and sodium methoxide, and stir to obtain a functional monomer; mix SBS, toluene, the functional monomer and an initiator, heat and stir to obtain modified SBS; Further, the preparation of the modified SBS includes the following specific steps: Step B1: Add a primary amine compound, epichlorohydrin and tetrabutylammonium bromide into toluene, reflux and stir at 100 - 110 °C for 4 - 4.5 h, cool to room temperature, add an alkali solution, and stir for 5 - 5.5 h to obtain product a; Further, the primary amine compound is 4-methyl[1,3,5]triazino[1,2-a]benzimidazol-2-amine; the dosage ratio of the primary amine compound, epichlorohydrin, tetrabutylammonium bromide, toluene and the alkali solution is 20 - 20.5 g : 9.5 - 10 g : 6 - 6.5 g : 85 - 95 mL : 20 - 25 mL; the alkali solution is a sodium hydroxide solution with a mass fraction of 40 - 50%; During the reaction process of Step B1, the primary amino group of the primary amine compound undergoes ring-opening and then ring-closing with epichlorohydrin to obtain a triazino-benzimidazole containing an epoxy group, namely product a; Step B2: Add methyl 3-aminothiophene-2-carboxylate and product a into dimethyl sulfoxide, stir at 50 - 60 °C for 24 - 25 h, extract and dry to obtain product b; Further, the dosage ratio of methyl 3-aminothiophene-2-carboxylate, product a and dimethyl sulfoxide is 16 - 16.5 g : 30 - 32 g : 100 - 110 mL; During the reaction process of Step B2, the amino group of methyl 3-aminothiophene-2-carboxylate undergoes ring-opening with the epoxy group of product a to obtain a triazino-benzimidazole and thiophene grafted product containing a hydroxyl group and an ester group, namely product b; Step B3: In an inert gas atmosphere, heat product b under reflux stirring to 100 - 110 °C, stir for 35 - 45 min, cool to 50 - 60 °C, add methanol, 5-hexen-1-amine and sodium methoxide, stir and react for 24 - 25 h to obtain a functional monomer; add SBS into toluene and stir for 30 - 40 min, then add the functional monomer and an initiator, and stir at 100 - 120 °C for 2 - 2.5 h to obtain modified SBS; Further, the dosage ratio of product b, methanol, 5-hexen-1-amine and sodium methoxide is 48 - 50 g : 125 - 135 mL : 10 - 12 g : 0.25 - 0.4 g; the dosage ratio of SBS, toluene, the functional monomer and the initiator is 100 - 105 g : 300 - 350 mL : 3 - 5 g : 0.5 - 0.7 g; the initiator is dibenzoyl peroxide; During the reaction process of Step B3, the ester group of product b undergoes an ammonolysis reaction with 5-hexen-1-amine to obtain a functional monomer containing a terminal carbon-carbon double bond, triazine-benzimidazole, thiophene, and hydroxyl group; under the action of an initiator, the functional monomer is grafted onto SBS to obtain modified SBS.

[0008] Advantages of the present invention: The present invention discloses a highly flame-retardant and environmentally friendly material for cable tape and its preparation process. The highly flame-retardant and environmentally friendly material for cable tape is prepared from raw materials such as polypropylene, modified SBS, nitrile rubber, and flame retardant.

[0009] The flame retardant is obtained by grafting 1,3,5-tris(2-hydroxyethyl) cyanuric acid with zinc borate treated with a silane coupling agent and enantiopimaric acid. The flame retardant contains zinc borate, an alkane long chain, cyanuric acid, tetracyclic diterpenoids, and epoxy groups; after grafting 1,3,5-tris(2-hydroxyethyl) cyanuric acid with zinc borate and tetracyclic diterpenoids, the molecular weight of 1,3,5-tris(2-hydroxyethyl) cyanuric acid is increased, enhancing the stability of the flame retardant; the tetracyclic diterpenoids and the alkane long chain synergistically enhance the hydrophobicity of the flame retardant, endowing the material for cable tape with good waterproofness and improving the adverse effects of the strong water absorption of zinc borate powder and the high water solubility of cyanuric acid on the insulation of the material for cable tape; cyanuric acid can promote the formation of a dense carbon layer on the material surface, isolating oxygen and heat, while zinc borate decomposes at high temperatures to form glassy boron oxides, covering the surface of the carbon layer and inhibiting the release of smoke and combustible gases. The synergy within the molecules of cyanuric acid and zinc borate makes the carbon layer more stable and has a significant smoke suppression effect, endowing the material for cable tape with high flame retardancy; the use of enantiopimaric acid, which belongs to natural products, also enhances the environmental friendliness of the material for cable tape.

[0010] The modified SBS is obtained by grafting a functional monomer containing triazine-benzimidazole, thiophene, and hydroxyl group onto SBS through a reaction; triazine-benzimidazole contains a large double bond conjugate system, enhancing the ability to absorb ultraviolet light, while the sulfur atom and conjugate structure of thiophene can disperse energy, reducing the damage caused by ultraviolet light to the material for cable tape; the hydroxyl group can enhance the polarity of the modified SBS, improving the defect of poor oil resistance of the material after mixing polypropylene and modified SBS; the hydroxyl group in the modified SBS and the epoxy group in the flame retardant undergo a reaction crosslinking during the mixing process of the raw materials of the material for cable tape, densifying the crosslinking network inside the material, preventing oil stains and the like from entering, and further enhancing the oil resistance of the material for cable tape. Detailed implementation manners

[0011] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts belong to the scope of protection of the present invention.

[0012] Example 1

[0013] A flame retardant, the preparation of which comprises the following steps: Step A1: Add 10 - alkenylundecyltrimethoxysilane to absolute ethanol, adjust the pH to 5.6, stir at a rotation speed of 1000 r / min and a temperature of 50 °C for 0.5 h; then add zinc borate and continue to stir for 1 h, filter and dry to obtain Product 1; mix Product 1, ethanol, and 3 - chloroperoxybenzoic acid, and stir at room temperature for 5.5 h, extract and separate to obtain Product 2; zinc borate (supplier: Dongguan Hongrui Plastic Raw Materials Co., Ltd.) is used after being ground through a 500 - mesh sieve; acetic acid is used to adjust the pH; the dosage ratio of 10 - alkenylundecyltrimethoxysilane, absolute ethanol, and zinc borate is 0.1 g: 80 mL: 10 g; the dosage ratio of Product 1, ethanol, and 3 - chloroperoxybenzoic acid is 5 g: 90 mL: 20 g; the volume fraction of ethanol is 95%; Step A2: Add Product 2 and 1,3,5 - tris(2 - hydroxyethyl)cyanuric acid to methanol, add trimethylamine with stirring, reflux and stir at 110 °C for 8 h, extract, dry, and separate to obtain Product 3; the dosage ratio of Product 2, 1,3,5 - tris(2 - hydroxyethyl)cyanuric acid, methanol, and trimethylamine is 8 g: 36 g: 100 mL: 0.6 g; Step A3: Add enantiomeric pectodiene acid to DMF, add thionyl chloride with stirring, reflux and stir at 50 °C for 5 h to obtain Product 4; mix Product 3, pyridine, triethylamine, and dimethyl sulfoxide to obtain mixture a; add Product 4 to dimethyl sulfoxide to obtain mixture b; dropwise add mixture b to mixture a in an ice - water bath, then heat up to 40 °C and stir for 6 h to obtain Product 5; the dosage ratio of enantiomeric pectodiene acid, DMF, and thionyl chloride is 31 g: 105 mL: 18 g; the dosage ratio of Product 3, pyridine, triethylamine, and dimethyl sulfoxide in mixture a is 10 g: 0.07 g: 10.5 g: 130 mL; the dosage ratio of Product 4 and dimethyl sulfoxide in mixture b is 35 g: 80 mL; the dosage ratio of mixture a and mixture b is 155 mL: 120 mL; Step A4: Mix Product 5, ethyl acetate, and 3 - chloroperoxybenzoic acid, and stir at 50 °C for 7 h to obtain the flame retardant; the dosage ratio of Product 5, ethyl acetate, and 3 - chloroperoxybenzoic acid is 5.5 g: 100 mL: 12 g.

[0014] Example 2

[0015] A flame retardant, the preparation of which comprises the following steps: Step A1: Add 10 - alkenyl undecyltrimethoxysilane into absolute ethanol, adjust the pH to 5.7, stir at a rotation speed of 1000 r / min and a temperature of 55 °C for 0.8 h; then add zinc borate and continue stirring for 1.3 h, filter and dry to obtain Product 1; mix Product 1, ethanol, and 3 - chloroperoxybenzoic acid, and stir at room temperature for 5.8 h, then extract and separate to obtain Product 2; zinc borate (supplier: Dongguan Hongrui Plastic Raw Materials Co., Ltd.) is used after being ground through a 500 - mesh sieve; acetic acid is used to adjust the pH; the dosage ratio of the silane coupling agent, absolute ethanol, and zinc borate is 0.2 g:85 mL:13 g; the dosage ratio of Product 1, ethanol, and 3 - chloroperoxybenzoic acid is 6 g:95 mL:21 g; the volume fraction of ethanol is 95%; Step A2: Add Product 2 and 1,3,5 - tris(2 - hydroxyethyl) cyanuric acid into methanol, add trimethylamine while stirring, and reflux and stir at 113 °C for 8.3 h, then extract, dry, and separate to obtain Product 3; the dosage ratio of Product 2, 1,3,5 - tris(2 - hydroxyethyl) cyanuric acid, methanol, and trimethylamine is 9 g:38 g:110 mL:0.7 g; Step A3: Add enantiomeric pectodiene acid into DMF, add thionyl chloride while stirring, and reflux and stir at 55 °C for 5.3 h to obtain Product 4; mix Product 3, pyridine, triethylamine, and dimethyl sulfoxide to obtain mixture a; add Product 4 into dimethyl sulfoxide to obtain mixture b; drop - wise add mixture b into mixture a in an ice - water bath, then raise the temperature to 43 °C and stir for 6.5 h to obtain Product 5; the dosage ratio of enantiomeric pectodiene acid, DMF, and thionyl chloride is 32 g:110 mL:19 g; the dosage ratio of Product 3, pyridine, triethylamine, and dimethyl sulfoxide in mixture a is 11 g:0.08 g:10.8 g:140 mL; the dosage ratio of Product 4 and dimethyl sulfoxide in mixture b is 36 g:85 mL; the dosage ratio of mixture a and mixture b is 160 mL:125 mL; Step A4: Mix Product 5, ethyl acetate, and 3 - chloroperoxybenzoic acid, and stir at 55 °C for 7.3 h to obtain the flame retardant; the dosage ratio of Product 5, ethyl acetate, and 3 - chloroperoxybenzoic acid is 6.0 g:105 mL:12.5 g.

[0016] Example 3

[0017] A flame retardant, the preparation of which comprises the following steps: Step A1: Add 10 - alkenylundecyltrimethoxysilane into absolute ethanol, adjust the pH to 5.9, stir at a rotation speed of 1000 r / min and a temperature of 60 °C for 1 h; then add zinc borate and continue stirring for 1.5 h, filter and dry to obtain Product 1; mix Product 1, ethanol, and 3 - chloroperoxybenzoic acid, stir at room temperature for 6 h, extract and separate to obtain Product 2; zinc borate (supplier: Dongguan Hongrui Plastic Raw Material Co., Ltd.) is used after being ground through a 500 - mesh sieve; acetic acid is used to adjust the pH; the dosage ratio of the silane coupling agent, absolute ethanol, and zinc borate is 0.3 g: 90 mL: 15 g; the dosage ratio of Product 1, ethanol, and 3 - chloroperoxybenzoic acid is 7 g: 100 mL: 22 g; the volume fraction of ethanol is 95%; Step A2: Add Product 2 and 1,3,5 - tris(2 - hydroxyethyl)cyanuric acid into methanol, add trimethylamine while stirring, reflux and stir at 115 °C for 8.5 h, extract, dry, and separate to obtain Product 3; the dosage ratio of Product 2, 1,3,5 - tris(2 - hydroxyethyl)cyanuric acid, methanol, and trimethylamine is 10 g: 40 g: 120 mL: 0.8 g; Step A3: Add enantiomeric pectodiene acid into DMF, add thionyl chloride while stirring, reflux and stir at 60 °C for 5.5 h to obtain Product 4; mix Product 3, pyridine, triethylamine, and dimethyl sulfoxide to obtain mixture a; add Product 4 into dimethyl sulfoxide to obtain mixture b; drop - wise add mixture b into mixture a in an ice - water bath, then raise the temperature to 45 °C and stir for 7 h to obtain Product 5; the dosage ratio of enantiomeric pectodiene acid, DMF, and thionyl chloride is 33 g: 115 mL: 20 g; the dosage ratio of Product 3, pyridine, triethylamine, and dimethyl sulfoxide in mixture a is 12 g: 0.09 g: 11.0 g: 150 mL; the dosage ratio of Product 4 and dimethyl sulfoxide in mixture b is 37 g: 90 mL; the dosage ratio of mixture a and mixture b is 165 mL: 130 mL; Step A4: Mix Product 5, ethyl acetate, and 3 - chloroperoxybenzoic acid, stir at 60 °C for 7.5 h to obtain the flame retardant; the dosage ratio of Product 5, ethyl acetate, and 3 - chloroperoxybenzoic acid is 6.5 g: 110 mL: 13 g.

[0018] Example 4

[0019] A modified SBS, its preparation includes the following steps: Step B1: Add 4-methyl-[1,3,5]triazino[1,2-a]benzimidazol-2-amine, epichlorohydrin, and tetrabutylammonium bromide into toluene, reflux and stir at 100 °C for 4 h. Cool to room temperature and add the alkali solution, then stir for 5 h to obtain product a. The dosage ratio of 4-methyl-[1,3,5]triazino[1,2-a]benzimidazol-2-amine, epichlorohydrin, tetrabutylammonium bromide, toluene, and the alkali solution is 20 g: 9.5 g: 6 g: 85 mL: 20 mL. The alkali solution is a sodium hydroxide solution with a mass fraction of 40%. Step B2: Add methyl 3-aminothiophene-2-carboxylate and product a into dimethyl sulfoxide, stir at 50 °C for 24 h, then extract and dry to obtain product b. The dosage ratio of methyl 3-aminothiophene-2-carboxylate, product a, and dimethyl sulfoxide is 16 g: 30 g: 100 mL. Step B3: Under a nitrogen atmosphere, heat product b to 100 °C with stirring under reflux, stir for 35 min, then cool to 50 °C, add methanol, 5-hexen-1-amine, and sodium methoxide, and stir and react for 24 h to obtain the functional monomer. After adding SBS (supplier: Dongguan Chaorong Plastic Raw Materials Co., Ltd.) into toluene and stirring for 30 min, add the functional monomer and dibenzoyl peroxide, and stir at 100 °C for 2 h to obtain the modified SBS. The dosage ratio of product b, methanol, 5-hexen-1-amine, and sodium methoxide is 48 g: 125 mL: 10 g: 0.25 g. The dosage ratio of SBS, toluene, the functional monomer, and dibenzoyl peroxide is 100 g: 300 mL: 3 g: 0.5 g.

[0020] Example 5

[0021] A modified SBS, the preparation of which comprises the following steps: Step B1: Add 4-methyl-[1,3,5]triazino[1,2-a]benzimidazol-2-amine, epichlorohydrin, and tetrabutylammonium bromide into toluene, reflux and stir at 105 °C for 4.3 h. Cool to room temperature and add the alkali solution, then stir for 5.3 h to obtain product a. The dosage ratio of 4-methyl-[1,3,5]triazino[1,2-a]benzimidazol-2-amine, epichlorohydrin, tetrabutylammonium bromide, toluene, and the alkali solution is 20.3 g: 9.8 g: 6.3 g: 90 mL: 23 mL. The alkali solution is a sodium hydroxide solution with a mass fraction of 45%. Step B2: Add methyl 3-aminothiophene-2-carboxylate and product a into dimethyl sulfoxide, stir at 55 °C for 24.5 h, then extract and dry to obtain product b. The dosage ratio of methyl 3-aminothiophene-2-carboxylate, product a, and dimethyl sulfoxide is 16.3 g: 31 g: 105 mL. Step B3: In a nitrogen atmosphere, heat the product b to 105 °C with reflux stirring, stir for 40 min, cool to 55 °C, add methanol, 5-hexen-1-amine and sodium methoxide, and stir and react for 24.5 h to obtain a functional monomer; After adding SBS (supplier: Dongguan Chaorong Plastic Raw Materials Co., Ltd.) to toluene and stirring for 35 min, add the functional monomer and benzoyl peroxide, and stir at 110 °C for 2.3 h to obtain modified SBS; The dosage ratio of product b, methanol, 5-hexen-1-amine and sodium methoxide is 49 g: 130 mL: 11 g: 0.32 g; The dosage ratio of SBS, toluene, functional monomer and benzoyl peroxide is 103 g: 325 mL: 4 g: 0.6 g.

[0022] Example 6

[0023] A modified SBS, the preparation thereof comprises the following steps: Step B1: Add 4-methyl[1,3,5]triazino[1,2-a]benzimidazol-2-amine, epichlorohydrin and tetrabutylammonium bromide to toluene, reflux and stir at 110 °C for 4.5 h, cool to room temperature, add an alkali solution, and stir for 5.5 h to obtain product a; The dosage ratio of 4-methyl[1,3,5]triazino[1,2-a]benzimidazol-2-amine, epichlorohydrin, tetrabutylammonium bromide, toluene and alkali solution is 20.5 g: 10 g: 6.5 g: 95 mL: 25 mL; The alkali solution is a sodium hydroxide solution with a mass fraction of 50%; Step B2: Add methyl 3-aminothiophene-2-carboxylate and product a to dimethyl sulfoxide, stir at 60 °C for 25 h, extract and dry to obtain product b; The dosage ratio of methyl 3-aminothiophene-2-carboxylate, product a and dimethyl sulfoxide is 16.5 g: 32 g: 110 mL; Step B3: In a nitrogen atmosphere, heat the product b to 110 °C with reflux stirring, stir for 45 min, cool to 60 °C, add methanol, 5-hexen-1-amine and sodium methoxide, and stir and react for 25 h to obtain a functional monomer; After adding SBS (supplier: Dongguan Chaorong Plastic Raw Materials Co., Ltd.) to toluene and stirring for 40 min, add the functional monomer and benzoyl peroxide, and stir at 120 °C for 2.5 h to obtain modified SBS; The dosage ratio of product b, methanol, 5-hexen-1-amine and sodium methoxide is 50 g: 135 mL: 12 g: 0.4 g; The dosage ratio of SBS, toluene, functional monomer and benzoyl peroxide is 105 g: 350 mL: 5 g: 0.7 g.

[0024] Example 7

[0025] A highly flame-retardant and environmentally friendly material for cable wrapping tapes, comprising the following raw materials in parts by weight: 90 parts of polypropylene, 20 parts of modified SBS, 5 parts of nitrile rubber, 2.5 parts of flame retardant, 0.02 part of calcium stearate; The high flame-retardant and environmentally friendly material for cable wrapping tape, its preparation includes the following steps: Mix polypropylene (brand: Sabic, supplier: Shanghai Haikuo International Trading Co., Ltd.), the modified SBS obtained in Example 4, nitrile rubber (supplier: Kaiming Plastic (Dongguan) Co., Ltd., specification: 20 kg / barrel), the flame retardant obtained in Example 1, and calcium stearate at 400 r / min for 20 min to obtain a mixture, and then melt-extrude and pelletize the mixture at 200 °C to obtain the high flame-retardant and environmentally friendly material for cable wrapping tape.

[0026] Example 8

[0027] A high flame-retardant and environmentally friendly material for cable wrapping tape, comprising the following raw materials in parts by weight: 95 parts of polypropylene, 23 parts of modified SBS, 6 parts of nitrile rubber, 3.5 parts of flame retardant, 0.03 part of calcium stearate; The high flame-retardant and environmentally friendly material for cable wrapping tape, its preparation includes the following steps: Mix polypropylene (brand: Sabic, supplier: Shanghai Haikuo International Trading Co., Ltd.), the modified SBS obtained in Example 5, nitrile rubber (supplier: Kaiming Plastic (Dongguan) Co., Ltd., specification: 20 kg / barrel), the flame retardant obtained in Example 2, and calcium stearate at 400 r / min for 25 min to obtain a mixture, and then melt-extrude and pelletize the mixture at 200 °C to obtain the high flame-retardant and environmentally friendly material for cable wrapping tape.

[0028] Example 9

[0029] A high flame-retardant and environmentally friendly material for cable wrapping tape, comprising the following raw materials in parts by weight: 100 parts of polypropylene, 25 parts of modified SBS, 7 parts of nitrile rubber, 4.5 parts of flame retardant, 0.04 part of calcium stearate; The high flame-retardant and environmentally friendly material for cable wrapping tape, its preparation includes the following steps: Mix polypropylene (brand: Sabic, supplier: Shanghai Haikuo International Trading Co., Ltd.), the modified SBS obtained in Example 6, nitrile rubber (supplier: Kaiming Plastic (Dongguan) Co., Ltd., specification: 20 kg / barrel), the flame retardant obtained in Example 3, and calcium stearate at 400 r / min for 30 min to obtain a mixture, and then melt-extrude and pelletize the mixture at 200 °C to obtain the high flame-retardant and environmentally friendly material for cable wrapping tape.

[0030] Comparative Example 1 Compared with Example 9, replace zinc borate in the preparation process of the flame retardant with magnesium oxide, and the rest is exactly the same as Example 9 to prepare the high flame-retardant and environmentally friendly material for cable wrapping tape.

[0031] Comparative Example 2 Compared with Example 9, the flame retardant was replaced with zinc borate (ground through a 500-mesh sieve) and 1,3,5-tris(2-hydroxyethyl) cyanuric acid, which were mixed and compounded in a mass ratio of 1:4, and the rest was exactly the same as in Example 9, to obtain a highly flame-retardant and environmentally friendly material for cable wrapping tapes.

[0032] Comparative Example 3 Compared with Example 9, the enantiomeric phellodienoic acid in the preparation process of the flame retardant was replaced with neoabietic acid, and the rest was exactly the same as in Example 9, to obtain a highly flame-retardant and environmentally friendly material for cable wrapping tapes.

[0033] Comparative Example 4 Compared with Example 9, the enantiomeric phellodienoic acid in the preparation process of the flame retardant was replaced with 4-pentenoic acid, and the rest was exactly the same as in Example 9, to obtain a highly flame-retardant and environmentally friendly material for cable wrapping tapes.

[0034] Comparative Example 5 Compared with Example 9, 4-methyl[1,3,5]triazino[1,2-a]benzimidazol-2-amine in the preparation process of the modified SBS was replaced with 5-aminobenzimidazole, and the rest was exactly the same as in Example 9, to obtain a highly flame-retardant and environmentally friendly material for cable wrapping tapes.

[0035] Comparative Example 6 Compared with Example 9, 4-methyl[1,3,5]triazino[1,2-a]benzimidazol-2-amine in the preparation process of the modified SBS was replaced with 2-amino-4-methyl-6-phenyl-1,3,5-triazine, and the rest was exactly the same as in Example 9, to obtain a highly flame-retardant and environmentally friendly material for cable wrapping tapes.

[0036] Comparative Example 7 Compared with Example 9, the functional monomer in the preparation process of the modified SBS was replaced with functional monomer 1, and the rest was exactly the same as in Example 9, to obtain a highly flame-retardant and environmentally friendly material for cable wrapping tapes; Preparation of functional monomer 1: The functional monomer prepared by the same preparation process as the functional monomer used in Example 9 was mixed and stirred with toluene and a 10% sodium hydroxide solution by mass for 10 min, then epichlorohydrin was added, and the mixture was stirred and reacted at room temperature for 7 h to convert the hydroxyl group in the functional monomer into an epoxy group, obtaining functional monomer 1.

[0037] The following is a further effect test on the highly flame-retardant and environmentally friendly material for cable wrapping tapes prepared by the present invention, and the test results are as follows.

[0038] Flame retardancy: The obtained material was soaked in water at 25°C for 3 d, and the limiting oxygen index before and after water soaking was measured with reference to GB / T 2406.2-2009 "Determination of burning behavior by the oxygen index method" and recorded in Table 1; Oil resistance: Refer to GB / T 1690-2010 to conduct an oil resistance test on the material. Make dumbbell strips with a width of 4 mm and a gauge length of 25 mm from the obtained material and immerse them in 3 # standard oil (IRM903) at (23±2)°C for 24 h. According to GB / T 1040.2-2022, use a tensile testing machine to measure the tensile strength before and after oil immersion at a tensile speed of 200 mm / min, calculate the retention rate of tensile strength after oil immersion and record it in Table 1; Retention rate of tensile strength = Tensile strength after oil immersion / Tensile strength before oil immersion × 100%; Waterproofness: Make dumbbell strips of the same size as those in the oil resistance test from the obtained material, immerse them in water at 25°C for 3 d, measure the mass before and after water immersion, calculate the water absorption rate and record it in Table 1; Water absorption rate = (Mass after water immersion - Mass before water immersion) / Mass before water immersion × 100%; UV resistance: Refer to GB / T 16422.2-2014 for testing. Use a xenon lamp testing machine to conduct artificial aging for 60 d and measure the retention rate of tensile strength after aging; Table 1: Test results

[0039] According to the data in Table 1, the high-flame-retardant and environmentally friendly material for cable tape of the present invention has excellent flame retardancy, oil resistance and waterproofness. Comparing Example 9 with Comparative Example 1, it can be seen that when zinc borate in the preparation process of the flame retardant is replaced with magnesium oxide, the synergistic flame retardancy of magnesium oxide and 1,3,5-tris(2-hydroxyethyl) cyanuric acid decreases. Comparing Example 9 with Comparative Example 2, it can be seen that the flame retardant is replaced with a compound prepared by mixing zinc borate (ground through a 500-mesh sieve) and 1,3,5-tris(2-hydroxyethyl) cyanuric acid in a mass ratio of 1:4. The zinc borate powder has strong water absorption, high water solubility of cyanuric acid, a relatively large increase in water absorption rate, and a relatively large decrease in waterproofness. The flame retardancy of the compound of zinc borate and cyanuric acid is weaker than the synergistic flame retardant effect of the two in the flame retardant, and the oxygen index before and after water immersion decreases significantly. Comparing Example 9 with Comparative Example 3, it can be seen that when enantiomeric phellandrene acid in the preparation process of the flame retardant is replaced with abietic acid, the hydrophobicity decreases, the water absorption rate increases, the waterproofness decreases, and the oxygen index after water immersion decreases significantly, and the flame retardancy decreases. Comparing Example 9 with Comparative Example 4, it can be seen that when enantiomeric phellandrene acid in the preparation process of the flame retardant is replaced with 4-pentenoic acid, the hydrophobicity weakens, the water absorption rate increases relatively much, the waterproofness decreases relatively much, the oxygen index after water immersion decreases, and the flame retardancy decreases. Comparing Example 9 with Comparative Example 5, it can be seen that when 4-methyl[1,3,5]triazino[1,2-a]benzimidazol-2-amine in the preparation process of modified SBS is replaced with 5-aminobenzimidazole, the ultraviolet resistance decreases, and the nitrogen content decreases, and the flame retardancy decreases somewhat. Comparing Example 9 with Comparative Example 6, it can be seen that when 4-methyl[1,3,5]triazino[1,2-a]benzimidazol-2-amine in the preparation process of modified SBS is replaced with 2-amino-4-methyl-6-phenyl-1,3,5-triazine, the ultraviolet resistance decreases, and the nitrogen content decreases, and the flame retardancy decreases somewhat. Comparing Example 9 with Comparative Example 7, it can be seen that when the functional monomer in the preparation process of modified SBS is replaced with functional monomer 1, the hydroxyl group of the functional monomer is replaced with the epoxy group in functional monomer 1, the polarity weakens, and the crosslinking with the epoxy group in the flame retardant weakens, resulting in a relatively large decrease in oil resistance, a somewhat decrease in waterproofness, and a somewhat decrease in flame retardancy after water immersion.

[0040] The above content is only an example and illustration of the concept of the present invention. Those skilled in the art of this technology can make various modifications or supplements to the described specific embodiments or use similar methods for substitution. As long as they do not deviate from the concept of the invention or exceed the scope defined by this claim book, they should all fall within the protection scope of the present invention.

Claims

1. A highly flame-retardant and environmentally friendly material for cable wrapping tapes, characterized in that: It includes the following raw materials in parts by weight: 90 - 100 parts of polypropylene, 20 - 25 parts of modified SBS, 5 - 7 parts of nitrile rubber, 2.5 - 4.5 parts of flame retardant, and 0.02 - 0.04 parts of calcium stearate; The preparation of the flame retardant includes the following steps: Step A1: Mix the silane coupling agent and absolute ethanol, adjust the pH and stir for hydrolysis, then add zinc borate and stir to obtain Product 1; Mix Product 1, ethanol, and 3 - chloroperoxybenzoic acid, and stir to obtain Product 2; Step A2: Mix Product 2, 1,3,5 - tris(2 - hydroxyethyl) cyanuric acid, methanol, and trimethylamine, and reflux and stir to obtain Product 3; Step A3: Mix enantiomeric pectodiene acid, DMF, and thionyl chloride, and reflux and stir to obtain Product 4; Mix Product 3, pyridine, triethylamine, and dimethyl sulfoxide to obtain mixture a; Mix Product 4 and dimethyl sulfoxide to obtain mixture b; Dropwise add mixture b to mixture a in an ice - water bath and stir to obtain Product 5; Step A4: Mix Product 5, ethyl acetate, and 3 - chloroperoxybenzoic acid, heat and stir to obtain the flame retardant.

2. The high-flame-retardant and environmentally friendly material for cable tape according to claim 1, wherein: In Step A1, zinc borate is ground and passed through a 400 - 600 - mesh sieve before use; The pH is adjusted to 5.5 - 6.0 with acetic acid; The dosage ratio of the silane coupling agent, absolute ethanol, and zinc borate is 0.1 - 0.3 g : 80 - 90 mL : 10 - 15 g.

3. The high flame-retardant and environmentally friendly material for cable tape according to claim 1, wherein: In Step A1, the dosage ratio of Product 1, ethanol, and 3 - chloroperoxybenzoic acid is 5 - 7 g : 90 - 100 mL : 20 - 22 g.

4. A highly flame-retardant and environmentally friendly material for cable wrapping tape according to claim 1, characterized in that: In Step A2, the dosage ratio of Product 2, 1,3,5 - tris(2 - hydroxyethyl) cyanuric acid, methanol, and trimethylamine is 8 - 10 g : 36 - 40 g : 100 - 120 mL : 0.6 - 0.8 g; In Step A4, the dosage ratio of Product 5, ethyl acetate, and 3 - chloroperoxybenzoic acid is 5.5 - 6.5 g : 100 - 110 mL : 12 - 13 g.

5. The high flame-retardant and environmentally friendly material for cable wrapping tape according to claim 1, wherein: In Step A3, the dosage ratio of enantiomeric pectodiene acid, DMF, and thionyl chloride is 31 - 33 g : 105 - 115 mL : 18 - 20 g; In mixture a, the dosage ratio of Product 3, pyridine, triethylamine, and dimethyl sulfoxide is 10 - 12 g : 0.07 - 0.09 g : 10.5 - 11.0 g : 130 - 150 mL; In mixture b, the dosage ratio of Product 4 and dimethyl sulfoxide is 35 - 37 g : 80 - 90 mL; The dosage ratio of mixture a and mixture b is 155 - 165 mL : 120 - 130 mL.

6. A highly flame-retardant and environmentally friendly material for cable wrapping tapes according to claim 1, characterized in that: The preparation of the modified SBS includes the following steps: Step B1: Mix the primary amine compound, epichlorohydrin, tetrabutylammonium bromide, and toluene and stir, then cool and add the alkali solution, and stir to obtain Product a; Step B2: Mix methyl 3 - amino - 2 - thiophenecarboxylate, Product a, and dimethyl sulfoxide, and heat and stir to obtain Product b; Step B3: In an atmosphere of protective gas, heat and stir Product b, then cool down and add methanol, 5 - hexen - 1 - amine, and sodium methoxide, and stir to obtain the functional monomer; Mix SBS, toluene, the functional monomer, and the initiator, and heat and stir to obtain the modified SBS.

7. An environmentally friendly high flame retardant material for cable wrapping tape according to claim 6, characterized in that: In step B1, the primary amine compound is 4-methyl[1,3,5]triazino[1,2-a]benzimidazol-2-amine; the dosage ratio of the primary amine compound, epichlorohydrin, tetrabutylammonium bromide, toluene, and lye is 20-20.5 g: 9.5-10 g: 6-6.5 g: 85-95 mL: 20-25 mL.

8. The high flame-retardant and environmentally friendly material for cable wrapping tape according to claim 6, characterized in that: In step B2, the dosage ratio of methyl 3-aminothiophene-2-carboxylate, product a, and dimethyl sulfoxide is 16-16.5 g: 30-32 g: 100-110 mL.

9. The high flame-retardant and environmentally friendly material for cable tape according to claim 6, characterized in that: In step B3, the dosage ratio of product b, methanol, 5-hexen-1-amine, and sodium methoxide is 48-50 g: 125-135 mL: 10-12 g: 0.25-0.4 g; the dosage ratio of SBS, toluene, functional monomer, and initiator is 100-105 g: 300-350 mL: 3-5 g: 0.5-0.7 g.

10. A preparation process of a highly flame-retardant and environmentally friendly material for cable wrapping tapes according to any one of claims 1-9, characterized in that: It includes the following steps: Mix polypropylene, modified SBS, nitrile rubber, flame retardant, and calcium stearate at 400-500 r / min for 20-30 min to obtain a mixture, and then melt-extrude and pelletize the mixture at 190-210 °C to obtain a highly flame-retardant and environmentally friendly material for cable wrapping tapes.

Images