A highly flame-retardant and environmentally friendly material for cable wrapping tape and its preparation process

Abstract

The present invention discloses a highly flame-retardant, environmentally friendly material for cable tape and its preparation process, relating to the field of plastics for cables. The highly flame-retardant, environmentally friendly material for cable tape is prepared from raw materials such as polypropylene, modified SBS, nitrile rubber, and a flame retardant. The flame retardant enhances the stability of cyanuric acid, improves the strong water solubility of cyanuric acid, and improves the high water absorption of zinc borate powder. The flame retardant imparts high flame retardancy, water resistance, and environmental friendliness to the cable tape material. The modified SBS is obtained by grafting functional monomers containing triazine benzimidazole, thiophene, and hydroxyl groups onto SBS, imparting excellent UV resistance and oil resistance to the cable tape material.

Description

Technical Field

[0001] The present invention relates to the field of cable materials, and in particular to a highly flame-retardant and environmentally friendly material for cable tape and a preparation process thereof. Background Art

[0002] Polypropylene (PP) is widely used in cable wrapping tapes, filling layers, and insulation layers, such as PP braided wrapping tapes and cable wrapping tapes. It exhibits corrosion resistance and high tensile strength. However, at low temperatures (below -30°C), PP's impact strength decreases significantly, potentially leading to brittle failure of the tape. While blending olefin copolymers such as SBS with PP significantly improves the material's low-temperature toughness, drawbacks such as the high flammability and poor UV resistance of PP and SBS, as well as the poor oil resistance of PP / SBS blends, limit their use in cable wrapping tapes.

[0003] Halogen-free flame retardants are used in cable tape materials to prevent the release of toxic gases during combustion, enhancing the environmental friendliness of cable tape materials. 1,3,5-Tris(2-hydroxyethyl)cyanuric acid (THEIC) alone is not ideal as a flame retardant for plastics. Its high water solubility, low molecular weight, and migration limits its use in cable tapes requiring high water resistance. While zinc borate offers advantages as a flame retardant, such as environmental friendliness and high thermal stability, it readily absorbs moisture in high-humidity environments, reducing its flame retardancy.

[0004] Based on this, a suitable modification method is needed to improve the hydrophobicity and stability of THEIC and zinc borate, improve the defects of poor oil resistance and UV resistance of PP and SBS blends, and apply them to cable tape materials to obtain cable tape materials with excellent properties such as flame retardancy, waterproofness, oil resistance, and UV 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 tape and a preparation process thereof.

[0006] The purpose of the present invention can be achieved through the following technical solutions:

[0007] A highly flame-retardant and environmentally friendly material for cable tape, 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;

[0008] The cable tape is made of highly flame-retardant and environmentally friendly material, and its preparation comprises the following steps:

[0009] Polypropylene, modified SBS, nitrile rubber, flame retardant and calcium stearate are stirred and mixed at 400-500 r / min for 20-30 minutes to obtain a mixture, and then the mixture is melt-extruded and granulated at 190-210° C. to obtain a highly flame-retardant and environmentally friendly material for cable tape;

[0010] The flame retardant is prepared by the following steps:

[0011] Step A1: Mix a silane coupling agent and anhydrous ethanol, adjust the pH, stir and hydrolyze, add zinc borate and stir to obtain product 1; mix product 1, ethanol and 3-chloroperoxybenzoic acid, and stir to obtain product 2;

[0012] Step A2, mixing product 2, 1,3,5-tris(2-hydroxyethyl)cyanuric acid, methanol, and trimethylamine, and refluxing with stirring to obtain product 3;

[0013] Step A3: Mix enantioconchadienoic acid, DMF, and dichlorothionyl, and reflux with stirring to obtain product 4; mix product 3, pyridine, triethylamine, and dimethyl sulfoxide to obtain a mixture a; mix product 4 and dimethyl sulfoxide to obtain a mixture b; add mixture b dropwise to mixture a in an ice-water bath, and stir to obtain product 5;

[0014] Step A4: mixing the product 5, ethyl acetate, and 3-chloroperbenzoic acid, heating and stirring to obtain a flame retardant;

[0015] Furthermore, the preparation of the flame retardant includes the following specific steps:

[0016] Step A1, adding a silane coupling agent to anhydrous ethanol, adjusting the pH to 5.5-6.0, and stirring at a speed of 900-1000 r / min and a temperature of 50-60° C. for 0.5-1 hour; then adding zinc borate, continuing stirring for 1-1.5 hours, filtering, and drying to obtain product 1; mixing product 1, ethanol, and 3-chloroperoxybenzoic acid, stirring at room temperature for 5.5-6 hours, extracting, and separating to obtain product 2;

[0017] Furthermore, zinc borate is ground through a 400-600 mesh sieve before use; acetic acid is used to adjust the pH; the dosage ratio of the silane coupling agent, anhydrous 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 the product 1, ethanol, and 3-chloroperoxybenzoic acid is 5-7 g:90-100 mL:20-22 g; and the volume fraction of ethanol is 95%.

[0018] During the reaction of step A1, silane modifies the surface of zinc borate to obtain zinc borate having a terminal carbon-carbon double bond and a long alkane chain on the surface, i.e., product 1; the double bond of product 1 is oxidized to an epoxy group to obtain product 2;

[0019] Step A2, adding product 2 and 1,3,5-tris(2-hydroxyethyl)cyanuric acid to methanol, adding trimethylamine with stirring, reacting under reflux and stirring at 110-115° C. for 8-8.5 hours, extracting, drying, and separating to obtain product 3;

[0020] Furthermore, the usage 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;

[0021] During the reaction 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;

[0022] Step A3: Add enantio-conchiodienoic acid to DMF, add dichlorothionyl with stirring, and reflux with stirring at 50-60°C for 5-5.5 hours to obtain product 4; mix product 3, pyridine, triethylamine, and dimethyl sulfoxide to obtain a mixture a; add product 4 to dimethyl sulfoxide and mix to obtain a mixture b; add mixture b dropwise to mixture a in an ice-water bath, then raise the temperature to 40-45°C and stir for 6-7 hours to obtain product 5;

[0023] Furthermore, the amount ratio of enantioconchodienoic acid, DMF, and dichlorothionyl is 31-33 g: 105-115 mL: 18-20 g; the amount ratio of product 3, pyridine, triethylamine, and dimethyl sulfoxide in the mixed solution a is 10-12 g: 0.07-0.09 g: 10.5-11.0 g: 130-150 mL; the amount ratio of product 4 and dimethyl sulfoxide in the mixed solution b is 35-37 g: 80-90 mL; the amount ratio of the mixed solution a to the mixed solution b is 155-165 mL: 120-130 mL;

[0024] During the reaction of step A3, the enantioconchodienoic acid 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 graft product of zinc borate, cyanuric acid, and tetracyclic diterpene, namely, product 5;

[0025] Step A4: Mix product 5, ethyl acetate, and 3-chloroperbenzoic acid, and stir at 50-60° C. for 7-7.5 hours to obtain a flame retardant;

[0026] Furthermore, the usage ratio of product 5, ethyl acetate, and 3-chloroperoxybenzoic acid is 5.5-6.5 g:100-110 mL:12-13 g;

[0027] During the reaction of step A4, the isolated carbon-carbon double bond outside the ring of the tetracyclic diterpene of product 5 is oxidized into an epoxy group, thereby obtaining a grafted product containing epoxy groups, zinc borate, cyanuric acid, and tetracyclic diterpene, which is a flame retardant.

[0028] The modified SBS is prepared by the following steps:

[0029] Step B1, mixing a primary amine compound, epichlorohydrin, tetrabutylammonium bromide, and toluene, cooling, adding alkali solution, and stirring to obtain product a;

[0030] Step B2, mixing methyl 3-amino-2-thiophenecarboxylate, product a, and dimethyl sulfoxide, heating and stirring to obtain product b;

[0031] Step B3: In a protective gas atmosphere, heat and stir the product b, then cool it and add methanol, 5-hexen-1-amine and sodium methoxide, and stir to obtain a functional monomer; mix SBS, toluene, the functional monomer and the initiator, and heat and stir to obtain a modified SBS;

[0032] Furthermore, the preparation of the modified SBS includes the following specific steps:

[0033] Step B1, adding a primary amine compound, epichlorohydrin, and tetrabutylammonium bromide to toluene, reflux and stir at 100-110° C. for 4-4.5 hours, cool to room temperature, add alkali solution, and stir for 5-5.5 hours to obtain product a;

[0034] Furthermore, the primary amine compound is 4-methyl[1,3,5]triazine[1,2-A]benzimidazol-2-amine; the dosage ratio of the primary amine compound, epichlorohydrin, tetrabutylammonium bromide, toluene, and alkali solution is 20-20.5g:9.5-10g:6-6.5g:85-95mL:20-25mL; the alkali solution is a sodium hydroxide solution with a mass fraction of 40-50%;

[0035] During the reaction process of step B1, the primary amino group of the primary amine compound and epichlorohydrin undergo ring opening and then ring closing to obtain a triazine benzimidazole containing an epoxy group, i.e., product a;

[0036] Step B2, adding methyl 3-amino-2-thiophenecarboxylate and product a to dimethyl sulfoxide, stirring at 50-60° C. for 24-25 h, extracting, and drying to obtain product b;

[0037] Furthermore, the usage ratio of methyl 3-amino-2-thiophenecarboxylate, product a, and dimethyl sulfoxide is 16-16.5 g: 30-32 g: 100-110 mL;

[0038] During the reaction of step B2, the amino group of methyl 3-amino-2-thiophenecarboxylate and the epoxy group of product a undergo ring-opening to obtain a triazine benzimidazole-thiophene grafted product containing hydroxyl and ester groups, namely product b;

[0039] Step B3, in a protective gas atmosphere, heating the product b to 100-110° C. with stirring under reflux, stirring for 35-45 minutes, cooling to 50-60° C., adding methanol, 5-hexen-1-amine and sodium methoxide, and stirring for 24-25 hours to obtain a functional monomer; adding SBS to toluene and stirring for 30-40 minutes, adding the functional monomer and initiator, and stirring at 100-120° C. for 2-2.5 hours to obtain a modified SBS;

[0040] Furthermore, the usage 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 usage ratio of SBS, toluene, functional monomer, and initiator is 100-105 g: 300-350 mL: 3-5 g: 0.5-0.7 g; and the initiator is dibenzoyl peroxide.

[0041] During the reaction of step B3, the ester group of product b undergoes an aminolysis reaction with 5-hexen-1-amine to obtain a functional monomer containing a terminal carbon-carbon double bond, triazine benzimidazole, thiophene and hydroxyl groups; the functional monomer is grafted with SBS under the action of an initiator to obtain a modified SBS.

[0042] Beneficial effects of the present invention: The present invention discloses a highly flame-retardant and environmentally friendly material for cable tape and a preparation process thereof. The highly flame-retardant and environmentally friendly material for cable tape is prepared from raw materials such as polypropylene, modified SBS, nitrile rubber, and a flame retardant.

[0043] The flame retardant is obtained by grafting 1,3,5-tris(2-hydroxyethyl)cyanuric acid with zinc borate and enantio-conchodienoic acid treated with a silane coupling agent. The flame retardant contains zinc borate, long-chain alkanes, cyanuric acid, tetracyclic diterpenes, and epoxy groups. After 1,3,5-tris(2-hydroxyethyl)cyanuric acid is grafted with zinc borate and tetracyclic diterpenes, the molecular weight of 1,3,5-tris(2-hydroxyethyl)cyanuric acid is increased, thereby enhancing the stability of the flame retardant. The tetracyclic diterpenes and long-chain alkanes synergistically enhance the hydrophobicity of the flame retardant, thereby giving the cable tape material good waterproofness. The strong water absorption of zinc borate powder and the high water solubility of cyanuric acid have an adverse effect on the insulation of cable tape materials. Cyanuric acid can promote the formation of a dense carbon layer on the surface of the material to isolate oxygen and heat, while zinc borate decomposes at high temperature to form glassy boron oxide, which covers the surface of the carbon layer and inhibits the release of smoke and combustible gases. The synergistic effect of cyanuric acid and zinc borate molecules makes the carbon layer more stable and has a significant smoke suppression effect, making the cable tape material highly flame retardant. The use of enantio-conchodienoic acid, which is a natural product, also enhances the environmental friendliness of the cable tape material.

[0044] The modified SBS is obtained by grafting a functional monomer containing triazine benzimidazole, thiophene, and hydroxyl groups onto SBS through a reaction; the triazine benzimidazole contains a larger double bond conjugated system, which enhances the ability to absorb ultraviolet rays, while the sulfur atom and conjugated structure of thiophene can disperse energy and reduce the damage caused by ultraviolet rays to the cable tape material; the hydroxyl group can enhance the polarity of the modified SBS and improve the defect of poor oil resistance of the material obtained by mixing polypropylene and modified SBS; the hydroxyl group in the modified SBS and the epoxy group in the flame retardant react and crosslink during the mixing process of the raw materials of the cable tape material, thereby densifying the crosslinked network inside the material, preventing oil stains and the like from entering, and further improving the oil resistance of the cable tape material. DETAILED DESCRIPTION

[0045] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0046] Example 1

[0047] A flame retardant, the preparation of which comprises the following steps:

[0048] Step A1, 10-alkenyl undecyl trimethoxy silane was added to anhydrous ethanol, the pH was adjusted to 5.6, and the mixture was stirred at a speed of 1000 r / min and a temperature of 50°C for 0.5 h; zinc borate was then added, the mixture was stirred for 1 h, filtered, and dried to obtain product 1; product 1, ethanol, and 3-chloroperoxybenzoic acid were mixed, stirred at room temperature for 5.5 h, extracted, and separated to obtain product 2; zinc borate (supplier: Dongguan Hongrui Plastic Raw Materials Co., Ltd.) was ground through a 500-mesh sieve before use; acetic acid was used to adjust the pH; the amount ratio of 10-alkenyl undecyl trimethoxy silane, anhydrous ethanol, and zinc borate was 0.1 g:80 mL:10 g; the amount ratio of product 1, ethanol, and 3-chloroperoxybenzoic acid was 5 g:90 mL:20 g; the volume fraction of ethanol was 95%;

[0049] Step A2, adding product 2 and 1,3,5-tris(2-hydroxyethyl)cyanuric acid to methanol, adding trimethylamine with stirring, reacting under reflux and stirring at 110°C for 8 hours, extracting, drying, and separating to obtain product 3; the amount 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;

[0050] Step A3, adding enantioconchadienoic acid to DMF, adding dichlorothionyl with stirring, and refluxing and stirring at 50°C for 5h to obtain product 4; mixing product 3, pyridine, triethylamine, and dimethyl sulfoxide to obtain a mixed solution a; adding product 4 to dimethyl sulfoxide to obtain a mixed solution b; adding mixed solution b dropwise to mixed solution a in an ice-water bath, and then heating to 40°C and stirring for 6h to obtain product 5; the amount ratio of enantioconchadienoic acid, DMF, and dichlorothionyl is 31g:105mL:18g; the amount ratio of product 3, pyridine, triethylamine, and dimethyl sulfoxide in mixed solution a is 10g:0.07g:10.5g:130mL; the amount ratio of product 4 and dimethyl sulfoxide in mixed solution b is 35g:80mL; the amount ratio of mixed solution a to mixed solution b is 155mL:120mL;

[0051] Step A4: Mix the product 5, ethyl acetate, and 3-chloroperbenzoic acid, and stir at 50° C. for 7 h to obtain a flame retardant; the amount ratio of the product 5, ethyl acetate, and 3-chloroperbenzoic acid is 5.5 g:100 mL:12 g.

[0052] Example 2

[0053] A flame retardant, the preparation of which comprises the following steps:

[0054] Step A1. Add 10-alkenylundecyltrimethoxysilane to anhydrous ethanol, adjust the pH to 5.7, and stir at a speed of 1000 r / min and a temperature of 55°C for 0.8 h; then add zinc borate, continue stirring for 1.3 h, filter, and dry to obtain product 1; mix product 1, ethanol, and 3-chloroperbenzoic acid, stir at room temperature for 5.8 h, extract, and separate to obtain product 2; zinc borate (supplier: Dongguan Hongrui Plastic Raw Materials Co., Ltd.) was ground through a 500-mesh sieve before use; acetic acid was used to adjust the pH; the amount ratio of silane coupling agent, anhydrous ethanol, and zinc borate was 0.2 g:85 mL:13 g; the amount ratio of product 1, ethanol, and 3-chloroperbenzoic acid was 6 g:95 mL:21 g; the volume fraction of ethanol was 95%;

[0055] Step A2, adding product 2 and 1,3,5-tris(2-hydroxyethyl)cyanuric acid to methanol, adding trimethylamine with stirring, reacting under reflux and stirring at 113°C for 8.3 hours, extracting, drying, and separating to obtain product 3; the amount 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;

[0056] Step A3, add enantioconchadienoic acid to DMF, add dichlorothionyl while stirring, and reflux and stir at 55°C for 5.3h to obtain product 4; mix product 3, pyridine, triethylamine, and dimethyl sulfoxide to obtain a mixed solution a; add product 4 to dimethyl sulfoxide and mix to obtain a mixed solution b; add mixed solution b dropwise to mixed solution a in an ice-water bath, then raise the temperature to 43°C and stir for 6.5h to obtain product 5; the amount ratio of enantioconchadienoic acid, DMF, and dichlorothionyl is 32g:110mL:19g; the amount ratio of product 3, pyridine, triethylamine, and dimethyl sulfoxide in mixed solution a is 11g:0.08g:10.8g:140mL; the amount ratio of product 4 and dimethyl sulfoxide in mixed solution b is 36g:85mL; the amount ratio of mixed solution a to mixed solution b is 160mL:125mL;

[0057] Step A4: Mix the product 5, ethyl acetate, and 3-chloroperbenzoic acid, and stir at 55° C. for 7.3 h to obtain a flame retardant; the amount ratio of the product 5, ethyl acetate, and 3-chloroperbenzoic acid is 6.0 g:105 mL:12.5 g.

[0058] Example 3

[0059] A flame retardant, the preparation of which comprises the following steps:

[0060] Step A1. Add 10-alkenylundecyltrimethoxysilane to anhydrous ethanol, adjust the pH to 5.9, and stir at a speed of 1000 r / min and a temperature of 60°C for 1 hour; then add zinc borate, continue stirring for 1.5 hours, filter, and dry to obtain product 1; mix product 1, ethanol, and 3-chloroperbenzoic acid, stir at room temperature for 6 hours, extract, and separate to obtain product 2; zinc borate (supplier: Dongguan Hongrui Plastic Raw Materials Co., Ltd.) is ground through a 500-mesh sieve before use; acetic acid is used to adjust the pH; the amount ratio of silane coupling agent, anhydrous ethanol, and zinc borate is 0.3g:90mL:15g; the amount ratio of product 1, ethanol, and 3-chloroperbenzoic acid is 7g:100mL:22g; the volume fraction of ethanol is 95%;

[0061] Step A2, adding product 2 and 1,3,5-tris(2-hydroxyethyl)cyanuric acid to methanol, adding trimethylamine with stirring, reacting under reflux and stirring at 115°C for 8.5 hours, extracting, drying, and separating to obtain product 3; the amount 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;

[0062] Step A3, add enantioconchadienoic acid to DMF, add dichlorothionyl while stirring, and reflux and stir at 60°C for 5.5h to obtain product 4; mix product 3, pyridine, triethylamine, and dimethyl sulfoxide to obtain a mixed solution a; add product 4 to dimethyl sulfoxide and mix to obtain a mixed solution b; add mixed solution b dropwise to mixed solution a in an ice-water bath, then raise the temperature to 45°C and stir for 7h to obtain product 5; the amount ratio of enantioconchadienoic acid, DMF, and dichlorothionyl is 33g:115mL:20g; the amount ratio of product 3, pyridine, triethylamine, and dimethyl sulfoxide in mixed solution a is 12g:0.09g:11.0g:150mL; the amount ratio of product 4 and dimethyl sulfoxide in mixed solution b is 37g:90mL; the amount ratio of mixed solution a to mixed solution b is 165mL:130mL;

[0063] Step A4: Mix product 5, ethyl acetate, and 3-chloroperbenzoic acid, and stir at 60° C. for 7.5 h to obtain a flame retardant; the usage ratio of product 5, ethyl acetate, and 3-chloroperbenzoic acid is 6.5 g:110 mL:13 g.

[0064] Example 4

[0065] A modified SBS, the preparation of which comprises the following steps:

[0066] Step B1, 4-methyl[1,3,5]triazine[1,2-A]benzimidazol-2-amine, epichlorohydrin, and tetrabutylammonium bromide were added to toluene, refluxed and stirred at 100°C for 4 hours, cooled to room temperature, added with alkali solution, and stirred for 5 hours to obtain product a; the dosage ratio of 4-methyl[1,3,5]triazine[1,2-A]benzimidazol-2-amine, epichlorohydrin, tetrabutylammonium bromide, toluene, and alkali solution was 20g:9.5g:6g:85mL:20mL; the alkali solution was a sodium hydroxide solution with a mass fraction of 40%;

[0067] Step B2, methyl 3-amino-2-thiophenecarboxylate and product a were added to dimethyl sulfoxide, stirred at 50°C for 24 hours, extracted, and dried to obtain product b; the amount ratio of methyl 3-amino-2-thiophenecarboxylate, product a, and dimethyl sulfoxide was 16g:30g:100mL;

[0068] Step B3. Under a nitrogen atmosphere, the product b was refluxed and stirred, heated to 100°C, stirred for 35 minutes, cooled to 50°C, and methanol, 5-hexen-1-amine and sodium methoxide were added. The reaction was stirred for 24 hours to obtain a functional monomer; SBS (supplier: Dongguan Chaorong Plastic Raw Materials Co., Ltd.) was added to toluene and stirred for 30 minutes, and then the functional monomer and dibenzoyl peroxide were added. The mixture was stirred at 100°C for 2 hours to obtain a modified SBS; the amount ratio of product b, methanol, 5-hexen-1-amine, and sodium methoxide was 48 g:125 mL:10 g:0.25 g; the amount ratio of SBS, toluene, functional monomer, and dibenzoyl peroxide was 100 g:300 mL:3 g:0.5 g.

[0069] Example 5

[0070] A modified SBS, the preparation of which comprises the following steps:

[0071] Step B1, 4-methyl[1,3,5]triazine[1,2-A]benzimidazol-2-amine, epichlorohydrin, and tetrabutylammonium bromide were added to toluene, refluxed and stirred at 105°C for 4.3 hours, cooled to room temperature, added with alkali solution, and stirred for 5.3 hours to obtain product a; the dosage ratio of 4-methyl[1,3,5]triazine[1,2-A]benzimidazol-2-amine, epichlorohydrin, tetrabutylammonium bromide, toluene, and alkali solution was 20.3 g:9.8 g:6.3 g:90 mL:23 mL; the alkali solution was a sodium hydroxide solution with a mass fraction of 45%;

[0072] Step B2, methyl 3-amino-2-thiophenecarboxylate and product a were added to dimethyl sulfoxide, stirred at 55°C for 24.5h, extracted, and dried to obtain product b; the amount ratio of methyl 3-amino-2-thiophenecarboxylate, product a, and dimethyl sulfoxide was 16.3g:31g:105mL;

[0073] Step B3. Under a nitrogen atmosphere, the product b was refluxed and stirred, heated to 105°C, stirred for 40 minutes, cooled to 55°C, and methanol, 5-hexen-1-amine and sodium methoxide were added. The mixture was stirred and reacted for 24.5 hours to obtain a functional monomer. SBS (supplier: Dongguan Chaorong Plastic Raw Materials Co., Ltd.) was added to toluene and stirred for 35 minutes. Then, the functional monomer and dibenzoyl peroxide were added and stirred at 110°C for 2.3 hours to obtain a modified SBS. The dosage ratio of product b, methanol, 5-hexen-1-amine, and sodium methoxide was 49 g:130 mL:11 g:0.32 g; the dosage ratio of SBS, toluene, functional monomer, and dibenzoyl peroxide was 103 g:325 mL:4 g:0.6 g.

[0074] Example 6

[0075] A modified SBS, the preparation of which comprises the following steps:

[0076] Step B1, 4-methyl[1,3,5]triazine[1,2-A]benzimidazol-2-amine, epichlorohydrin, and tetrabutylammonium bromide were added to toluene, refluxed and stirred at 110°C for 4.5 hours, cooled to room temperature, added with alkali solution, and stirred for 5.5 hours to obtain product a; the dosage ratio of 4-methyl[1,3,5]triazine[1,2-A]benzimidazol-2-amine, epichlorohydrin, tetrabutylammonium bromide, toluene, and alkali solution was 20.5g:10g:6.5g:95mL:25mL; the alkali solution was a sodium hydroxide solution with a mass fraction of 50%;

[0077] Step B2, methyl 3-amino-2-thiophenecarboxylate and product a were added to dimethyl sulfoxide, stirred at 60°C for 25 hours, extracted, and dried to obtain product b; the amount ratio of methyl 3-amino-2-thiophenecarboxylate, product a, and dimethyl sulfoxide was 16.5g:32g:110mL;

[0078] Step B3. Under a nitrogen atmosphere, the product b was refluxed and stirred, heated to 110°C, stirred for 45 minutes, cooled to 60°C, and methanol, 5-hexen-1-amine and sodium methoxide were added. The mixture was stirred for 25 hours to obtain a functional monomer. SBS (supplier: Dongguan Chaorong Plastic Raw Materials Co., Ltd.) was added to toluene and stirred for 40 minutes. Then, the functional monomer and dibenzoyl peroxide were added and stirred at 120°C for 2.5 hours to obtain a modified SBS. The amount ratio of product b, methanol, 5-hexen-1-amine, and sodium methoxide was 50 g:135 mL:12 g:0.4 g; the amount ratio of SBS, toluene, functional monomer, and dibenzoyl peroxide was 105 g:350 mL:5 g:0.7 g.

[0079] Example 7

[0080] A highly flame-retardant and environmentally friendly material for cable tape, 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, and 0.02 parts of calcium stearate;

[0081] The cable tape is made of highly flame-retardant and environmentally friendly material, and its preparation comprises the following steps:

[0082] Polypropylene (brand: Saudi Basel, supplier: Shanghai Haikuo International Trade 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 were stirred and mixed at 400 r / min for 20 minutes to obtain a mixture, and then the mixture was melt-extruded and granulated at 200°C to obtain a highly flame-retardant and environmentally friendly material for cable tape.

[0083] Example 8

[0084] A highly flame-retardant and environmentally friendly material for cable 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, and 0.03 parts of calcium stearate;

[0085] The cable tape is made of highly flame-retardant and environmentally friendly material, and its preparation comprises the following steps:

[0086] Polypropylene (brand: Saudi Basel, supplier: Shanghai Haikuo International Trade 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 were stirred and mixed at 400 r / min for 25 minutes to obtain a mixture, and then the mixture was melt-extruded and granulated at 200°C to obtain a highly flame-retardant and environmentally friendly material for cable tape.

[0087] Example 9

[0088] A highly flame-retardant and environmentally friendly material for cable 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, and 0.04 parts of calcium stearate;

[0089] The cable tape is made of highly flame-retardant and environmentally friendly material, and its preparation comprises the following steps:

[0090] Polypropylene (brand: Saudi Basel, supplier: Shanghai Haikuo International Trade 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 were stirred and mixed at 400 r / min for 30 minutes to obtain a mixture, and then the mixture was melt-extruded and granulated at 200°C to obtain a highly flame-retardant and environmentally friendly material for cable tape.

[0091] Comparative Example 1

[0092] Compared with Example 9, the zinc borate in the flame retardant preparation process is replaced with magnesium oxide, and the rest is exactly the same as Example 9 to prepare a highly flame retardant and environmentally friendly material for cable wrapping.

[0093] Comparative Example 2

[0094] Compared with Example 9, the flame retardant was replaced with zinc borate (ground and passed through a 500-mesh sieve) and 1,3,5-tris(2-hydroxyethyl)cyanuric acid in a mass ratio of 1:4, and the rest was exactly the same as Example 9 to prepare a highly flame-retardant and environmentally friendly material for cable tape.

[0095] Comparative Example 3

[0096] Compared with Example 9, the enantiomeric shell dienoic acid in the flame retardant preparation process is replaced with neorosinic acid, and the rest is exactly the same as Example 9 to prepare a highly flame retardant and environmentally friendly material for cable wrapping.

[0097] Comparative Example 4

[0098] Compared with Example 9, the enantiomeric shell dienoic acid in the flame retardant preparation process is replaced with 4-pentenoic acid, and the rest is exactly the same as Example 9 to prepare a highly flame-retardant and environmentally friendly material for cable wrapping.

[0099] Comparative Example 5

[0100] Compared with Example 9, the 4-methyl[1,3,5]triazine[1,2-A]benzimidazole-2-amine in the preparation process of the modified SBS was replaced with 5-aminobenzimidazole, and the rest was exactly the same as Example 9 to prepare a highly flame-retardant and environmentally friendly material for cable tape.

[0101] Comparative Example 6

[0102] Compared with Example 9, the 4-methyl[1,3,5]triazine[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 prepare a highly flame-retardant and environmentally friendly material for cable tape.

[0103] Comparative Example 7

[0104] 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 prepare a highly flame-retardant and environmentally friendly material for cable tape;

[0105] Preparation of Functional Monomer 1: The functional monomer prepared in the same manner as in Example 9 was mixed with toluene and a 10% by mass sodium hydroxide solution and stirred for 10 minutes. Epichlorohydrin was then added and stirred at room temperature for 7 hours to convert the hydroxyl groups in the functional monomer into epoxy groups, thereby obtaining Functional Monomer 1.

[0106] The effects of the highly flame-retardant and environmentally friendly material for cable wrapping tape prepared by the present invention are further tested below, and the test results are described as follows.

[0107] Flame retardancy: The obtained materials were immersed in water at 25°C for 3 days. The limiting oxygen index before and after water immersion was measured with reference to GB / T2406.2-2009 "Determination of combustion behavior by oxygen index method" and recorded in Table 1.

[0108] Oil resistance: The material was tested for oil resistance according to GB / T1690-2010. The obtained material was made into dumbbell bars with a width of 4mm and a gauge length of 25mm and placed in a 3 # Immerse the specimens in standard oil (IRM903) for 24 h. Measure the tensile strength before and after oil immersion using a tensile testing machine at a tensile speed of 200 mm / min according to GB / T1040.2-2022. Calculate the tensile strength retention rate after oil immersion and record it in Table 1; tensile strength retention rate = tensile strength after oil immersion / tensile strength before oil immersion × 100%.

[0109] Waterproofness: The obtained material was made into dumbbell bars of the same size as those used in the oil resistance test and immersed in 25°C water for 3 days. The mass before and after immersion was measured, and the water absorption rate was calculated and recorded in Table 1; water absorption rate = (mass after immersion - mass before immersion) / mass before immersion × 100%;

[0110] UV resistance: Tested in accordance with GB / T16422.2-2014, artificial aging was performed using a xenon lamp testing machine for 60 days, and the tensile strength retention rate after aging was measured;

[0111] Table 1: Test results

[0112]

[0113] According to the data in Table 1, the highly flame-retardant and environmentally friendly material for cable tape of the present invention has excellent flame retardancy, oil resistance and water resistance. Comparison of Example 9 with Comparative Example 1 shows that when zinc borate in the flame retardant preparation process is replaced with magnesium oxide, the synergistic flame retardancy of magnesium oxide and 1,3,5-tris(2-hydroxyethyl)cyanuric acid decreases. Comparison of Example 9 with Comparative Example 2 shows that when the flame retardant is replaced with 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 and cyanuric acid is highly water-soluble, the water absorption rate increases significantly, and the water resistance decreases significantly. The flame retardancy of the compound of zinc borate and cyanuric acid is weaker than the synergistic flame retardancy of the two in the flame retardant, and the oxygen index before and after water immersion decreases significantly. Comparison of Example 9 with Comparative Example 3 shows that when the enantiomer-conchodienoic acid in the flame retardant preparation process is replaced with neorosinic acid, the hydrophobicity decreases, the water absorption rate increases, the water resistance decreases, the oxygen index after water immersion decreases more, and the flame retardancy decreases. Comparison of Example 9 with Comparative Example 4 shows that when the enantiomer-conchodienoic acid in the flame retardant preparation process is replaced with 4-pentenoic acid, the hydrophobicity is weakened, the water absorption rate increases more, the water resistance decreases more, the oxygen index after water immersion decreases, and the flame retardancy decreases. Comparison of Example 9 with Comparative Example 5 shows that when the 4-methyl[1,3,5]triazin[1,2-A]benzimidazol-2-amine in the modified SBS preparation process is replaced with 5-aminobenzimidazole, the UV resistance decreases, the nitrogen content decreases, and the flame retardancy decreases. Comparing Example 9 with Comparative Example 6, it can be seen that replacing 4-methyl[1,3,5]triazino[1,2-A]benzimidazol-2-amine in the preparation of the modified SBS with 2-amino-4-methyl-6-phenyl-1,3,5-triazine reduces UV resistance, decreases nitrogen content, and slightly reduces flame retardancy. Comparing Example 9 with Comparative Example 7, it can be seen that replacing the functional monomer in the preparation of the modified SBS with Functional Monomer 1 and replacing the hydroxyl group of the functional monomer with the epoxy group in Functional Monomer 1 weakens polarity and weakens crosslinking with the epoxy group in the flame retardant, resulting in a significant decrease in oil resistance, a slight decrease in water resistance, and a decrease in flame retardancy after water immersion.

[0114] The above content is merely an example and explanation of the concept of the present invention. Those skilled in the art may make various modifications or additions to the described specific embodiments or replace them in a similar manner. As long as they do not deviate from the concept of the invention or exceed the scope defined by the claims, they should all fall within the scope of protection of the present invention.

Claims

1. A highly flame-retardant and environmentally friendly material for cable wrapping, characterized by: The invention comprises 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 flame retardant is prepared by the following steps: Step A1: Mix a silane coupling agent and anhydrous ethanol, adjust the pH, stir and hydrolyze, 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, mixing product 2, 1,3,5-tris(2-hydroxyethyl)cyanuric acid, methanol, and trimethylamine, and refluxing with stirring to obtain product 3; Step A3, mixing enantioconchadienoic acid, DMF, and thionyl chloride, and reflux with stirring to obtain product 4; Mix product 3, pyridine, triethylamine, and dimethyl sulfoxide to obtain a mixture a; mix product 4 and dimethyl sulfoxide to obtain a mixture b; add mixture b dropwise to mixture a in an ice-water bath and stir to obtain product 5; Step A4: mixing the product 5, ethyl acetate, and 3-chloroperbenzoic acid, heating and stirring to obtain a flame retardant; The modified SBS is prepared by the following steps: Step B1, mixing a primary amine compound, epichlorohydrin, tetrabutylammonium bromide, and toluene, cooling, adding alkali solution, and stirring to obtain product a; Step B2, mixing methyl 3-amino-2-thiophenecarboxylate, product a, and dimethyl sulfoxide, heating and stirring to obtain product b; Step B3: In a protective gas atmosphere, heat and stir the product b, then cool it and add methanol, 5-hexen-1-amine and sodium methoxide, and stir to obtain a functional monomer; mix SBS, toluene, functional monomer and initiator, and heat and stir to obtain modified SBS.

2. The highly flame-retardant and environmentally friendly material for cable wrapping according to claim 1, characterized in that: In step A1, zinc borate is ground and passed through a 400-600 mesh sieve before use; acetic acid is used to adjust the pH to 5.5-6.0; and the dosage ratio of the silane coupling agent, anhydrous ethanol, and zinc borate is 0.1-0.3 g: 80-90 mL: 10-15 g.

3. The highly flame-retardant and environmentally friendly material for cable tape according to claim 1, characterized in that: In step A1, the usage ratio of product 1, ethanol, and 3-chloroperbenzoic acid is 5-7 g:90-100 mL:20-22 g.

4. The highly flame-retardant and environmentally friendly material for cable tape according to claim 1, characterized in that: In step A2, the amount 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 amount ratio of product 5, ethyl acetate, and 3-chloroperbenzoic acid is 5.5-6.5 g:100-110 mL:12-13 g.

5. The highly flame-retardant and environmentally friendly material for cable tape according to claim 1, characterized in that: In step A3, the amount ratio of enantio-conchiodienoic acid, DMF, and dichlorothionyl is 31-33 g: 105-115 mL: 18-20 g; the amount ratio of product 3, pyridine, triethylamine, and dimethyl sulfoxide in the mixed solution a is 10-12 g: 0.07-0.09 g: 10.5-11.0 g: 130-150 mL; the amount ratio of product 4 and dimethyl sulfoxide in the mixed solution b is 35-37 g: 80-90 mL; the amount ratio of mixed solution a and mixed solution b is 155-165 mL: 120-130 mL.

6. The highly flame-retardant and environmentally friendly material for cable tape according to claim 1, characterized in that: In step B1, the primary amine compound is 4-methyl[1,3,5]triazine[1,2-A]benzimidazol-2-amine; the usage ratio of the primary amine compound, epichlorohydrin, tetrabutylammonium bromide, toluene, and alkali solution is 20-20.5 g: 9.5-10 g: 6-6.5 g: 85-95 mL: 20-25 mL.

7. The highly flame-retardant and environmentally friendly material for cable tape according to claim 1, characterized in that: In step B2, the usage ratio of methyl 3-amino-2-thiophenecarboxylate, product a, and dimethyl sulfoxide is 16-16.5 g: 30-32 g: 100-110 mL.

8. The highly flame-retardant and environmentally friendly material for cable wrapping according to claim 1, characterized in that: In step B3, the usage 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 usage ratio of SBS, toluene, functional monomer, and initiator is 100-105 g: 300-350 mL: 3-5 g: 0.5-0.7 g.

9. A process for preparing a highly flame-retardant and environmentally friendly material for cable tape according to any one of claims 1 to 8, characterized in that: The steps include: Polypropylene, modified SBS, nitrile rubber, flame retardant and calcium stearate are stirred and mixed at 400-500 r / min for 20-30 minutes to obtain a mixture, and then the mixture is melt-extruded and granulated at 190-210° C. to obtain a highly flame-retardant and environmentally friendly material for cable wrapping tape.

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