Flame-retardant data connecting line and preparation method thereof

Abstract

The invention discloses a flame-retardant data connecting line and a preparation method thereof, and belongs to the technical field of data connecting lines. The preparation method comprises the following steps: weighing 90-100 parts by weight of polyvinyl chloride resin, 15-25 parts by weight of a modified filler, 10-15 parts by weight of a plasticizer, 6-12 parts by weight of a flame retardant, 2-5 parts by weight of a lubricant, 0.5-1 part by weight of a stabilizer, 0.5-1 part by weight of an antioxidant and 0.05-0.1 part by weight of a cross-linking agent, stirring, feeding into a press vulcanizer, carrying out hot pressing, cold pressing, sheet discharging and crushing, feeding into a twin-screw extruder, carrying out extrusion granulation, drying, adding into a machine barrel, melting, and carrying out extrusion granulation. And extruding the molten sheath material into a machine head mold, coating the passing conductive wire core, and cooling to obtain the data connecting wire. The flame retardant, the modified filler and the polyvinyl chloride resin form a mutually cross-linked spatial network structure, and the flame retardant and the modified filler stably exist in the data connection line and are not easy to migrate, so that the data connection line disclosed by the invention has excellent flame-retardant smoke suppression property, antibacterial property and mechanical strength.

Description

Technical Field

[0001] The present invention belongs to the technical field of data connection lines, and in particular, relates to a flame retardant data connection line and a preparation method thereof. Background Art

[0002] With the rapid development of the electronics industry, data cables have become an indispensable part of our lives. Data cables generate heat during use. If they reach a certain temperature due to improper operation, they can easily cause fires and endanger life and property safety.

[0003] Chinese patent CN111675873A discloses a flame retardant data connection line and a preparation method thereof. The flame retardant data connection line includes a conductive core wire and a sheath layer coated on the surface of the conductive core wire. The sheath layer is made of the following raw materials in parts by weight: 50-60 parts of polyvinyl chloride resin, 3-5 parts of composite flame retardant, 0.8-1 part of stabilizer, 4-6 parts of calcium carbonate, 8-10 parts of calcium stearate, 4-5 parts of plasticizer, and 0.3-0.5 parts of antioxidant. The composite flame retardant has good compatibility with the remaining raw materials and has good flame retardant properties. However, the composite flame retardant cannot be stably present in the sheath layer, cannot exert a flame retardant effect for a long time, and the flame retardant effect needs to be further improved. Summary of the invention

[0004] The purpose of the present invention is to overcome the defects of the prior art and provide a flame retardant data connecting line and a preparation method thereof.

[0005] The purpose of the present invention can be achieved through the following technical solutions: A method for preparing a flame retardant data connection line comprises the following steps: Weigh 90-100 parts of polyvinyl chloride resin, 15-25 parts of modified filler, 10-15 parts of plasticizer, 6-12 parts of flame retardant, 2-5 parts of lubricant, 0.5-1 part of stabilizer, 0.5-1 part of antioxidant and 0.05-0.1 part of cross-linking agent by weight, add all the raw materials into a mixer and stir, and after mixing evenly, send them into a flat vulcanizer, hot press at 180°C, cold press at room temperature, sheet out, crush, and then send them into a twin-screw extruder for extrusion and granulation. After drying, add them into the barrel of the twin-screw extruder to melt, extrude the molten sheath material into the head mold of the twin-screw extruder, cover the conductive wire core passing through the head mold, cool, and obtain a flame-retardant data connecting line.

[0006] Furthermore, the modified filler is prepared by the following steps: The inorganic filler and deionized water were mixed evenly in a three-necked flask, and acetic acid was slowly added to adjust the pH to 4. Subsequently, a mixed solution of coupling agent and anhydrous ethanol was slowly added while stirring. After the addition was completed, the temperature was raised to 65°C and the reaction was kept warm for 1 hour. After the reaction was completed, the mixture was cooled to room temperature and centrifuged. After centrifugation, the lower precipitate was taken and dispersed in anhydrous ethanol, and then ultrasonicated for 1 hour. Finally, it was dried at 80°C for 12 hours to obtain a modified filler. The mass ratio of inorganic filler to coupling agent was 10:1.

[0007] Furthermore, the inorganic filler is a mixture of magnesium hydroxide, nano titanium dioxide and calcium carbonate in a mass ratio of 2:1:(1-2).

[0008] Furthermore, the coupling agent is one or more of vinyl trimethoxy silane, vinyl triethoxy silane, 3-(methacryloyloxy)propyl trimethoxy silane, and methacryloxypropyl triethoxy silane.

[0009] Magnesium hydroxide has flame retardant and smoke suppression effects; nano titanium dioxide has both antibacterial and anti-ultraviolet effects; calcium carbonate can improve the mechanical strength and heat resistance of the sheath material, and the decomposition products of calcium carbonate, carbon dioxide and water vapor, can inhibit the spread of fire sources and prevent the spread of fire. The modified fillers prepared by the treatment of these three inorganic fillers with coupling agents can be evenly dispersed in the sheath material, and at the same time, abundant carbon-carbon double bonds are grafted on the surface. The carbon-carbon double bonds can react chemically with the carbon-carbon double bonds in the flame retardant and the unreacted carbon-carbon double bonds at the end of the polyvinyl chloride resin during the melting process and under the action of the cross-linking agent, and then the modified fillers can be further dispersed in the sheath material and give full play to their role, giving the sheath material excellent and stable antibacterial, flame retardant and smoke suppression properties and good mechanical strength.

[0010] Furthermore, the plasticizer is one or more of triisooctyl phosphite, diisooctyl phthalate, di-n-octyl adipate, and dioctyl sebacate.

[0011] Furthermore, the flame retardant is prepared by the following steps: S1. Blow nitrogen gas into a dry three-necked flask for 30 minutes to expel air and moisture from the flask, then add 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane, triethylamine and benzene, stir and dissolve, heat to 60°C, slowly add diallylamine, and continue to react at 60°C for 3 hours after the addition. After the reaction is completed, cool to room temperature, and distill under reduced pressure to obtain intermediate 1; the dosage ratio of 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane, diallylamine, triethylamine and benzene is 22mL:13.3mL:16.7mL:150mL; Triethylamine is used as an acid binding agent, and the molar ratio of 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane and diallylamine is controlled to be 1:1.05-1.1. 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane and diallylamine undergo a substitution reaction under heating. The reaction process is shown below:

[0012] S2, nitrogen blowing dry three-necked flask for 30 minutes to expel air and moisture in the flask, then add melamine, triethylamine and dimethyl sulfoxide, stir and dissolve, heat to 65 ° C, then slowly add intermediate 1, keep warm for 4 hours after the addition is complete, and distill under reduced pressure after the reaction is completed to obtain intermediate 2; the amount ratio of intermediate 1, melamine, triethylamine and dimethyl sulfoxide is 26.3g:12.3g:15mL:200mL; Triethylamine is used as an acid binding agent, and the molar ratio of intermediate 1 to melamine is controlled to be 1:1.05-1.1. Intermediate 1 and melamine undergo a substitution reaction under heating. The reaction process is as follows:

[0013] S3. Under nitrogen protection, add 3-hydroxyphenylphosphoryl propionic acid, EDC (1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride), NHS (N-hydroxysuccinimide) and DMF (N,N-dimethylformamide) into a dry three-necked flask, stir to dissolve and then heat to 50°C, then slowly add intermediate 2, keep warm and react for 6 hours, cool to room temperature after the reaction, and distill under reduced pressure to obtain a flame retardant; the dosage ratio of 3-hydroxyphenylphosphoryl propionic acid, intermediate 2, EDC, NHS and DMF is 19.1g:23.2g:4.1g:2.5g:240mL.

[0014] The molar ratio of intermediate 2 to 3-hydroxyphenylphosphoryl propionic acid is controlled to be 1:2.1-2.2, and the -NH 2 The -COOH of 3-hydroxyphenylphosphoryl propionic acid undergoes an amidation reaction under the action of EDC and NHS. The reaction equation is shown below:

[0015] The phosphorus element in the flame retardant provides an acid source, reacting with the polyvinyl chloride resin to promote the formation of carbonized products; the nitrogen element provides a gas source, which can make the system expand and foam, and also promotes the formation of a carbonized layer, forming a porous foam carbon; the silicon element generates an inorganic thermal insulation protective layer containing -Si-O bonds and -Si-C- bonds during combustion, which not only prevents the decomposition products generated by combustion from escaping, but also inhibits the thermal decomposition of polymer materials, achieving the purpose of high flame retardancy, low smoke emission and low harmfulness.

[0016] The flame retardant contains multiple carbon-carbon double bonds, which can react chemically with the carbon-carbon double bonds on the surface of the modified filler and the unreacted carbon-carbon double bonds at the end of the polyvinyl chloride resin under the action of the cross-linking agent, so that the flame retardant can be firmly present in the sheath material, not easy to migrate or escape, and can give full play to the efficient and safe flame retardant and smoke suppression effect. The chemical reaction between the raw materials forms a mutually cross-linked spatial network structure between the flame retardant, polyvinyl chloride resin, and modified filler, which makes the flame retardant and modified filler highly dispersed and stably present in the sheath material, not easy to migrate or escape, thereby maximizing their role and giving the sheath material excellent and stable antibacterial properties, flame retardant and smoke suppression properties, and good mechanical strength.

[0017] Furthermore, the lubricant is one or more of zinc stearate, calcium stearate, oleamide, and erucamide.

[0018] Furthermore, the stabilizer is one or more of the ultraviolet absorber UV-531, ultraviolet absorber UV-9, ultraviolet absorber UV-P, light stabilizer AM-101, light stabilizer GW-540, and light stabilizer 744.

[0019] Furthermore, the antioxidant is one or more of antioxidant 1010, antioxidant 1098, antioxidant 245, antioxidant 168, antioxidant 1076, and antioxidant DLTP.

[0020] Furthermore, the cross-linking agent is one or two of benzoyl peroxide, di-tert-butyl peroxide, triallyl isocyanurate, and azobisisobutyronitrile.

[0021] The present invention also discloses a flame retardant data connecting line, which is prepared according to the preparation method of the flame retardant data connecting line.

[0022] The beneficial effects of the present invention are as follows: a mutually cross-linked spatial network structure is formed between the flame retardant containing halogen-free flame retardant elements of nitrogen, phosphorus and silicon, the modified filler and the polyvinyl chloride resin; the flame retardant and the modified filler are both stably present in the data connection line, are not easy to migrate and fall out, and can fully play their role, thereby making the data connection line of the present invention have efficient and safe flame retardant and smoke suppression effects, excellent and stable antibacterial properties and good mechanical strength. DETAILED DESCRIPTION

[0023] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0024] Example 1, preparing the modified filler, the specific steps are as follows: 15g magnesium hydroxide, 7.5g nano titanium dioxide, 7.5g calcium carbonate and 250mL deionized water were mixed evenly in a 500mL three-necked flask, and acetic acid was slowly added to adjust the pH to 4. Subsequently, a mixed solution of 1.5g vinyltrimethoxysilane, 1.5g 3-(methacryloyloxy)propyltrimethoxysilane and 10mL anhydrous ethanol was slowly added while stirring. After the addition was completed, the temperature was raised to 65°C and the reaction was kept warm for 1h. After the reaction was completed, it was cooled to room temperature and centrifuged. After centrifugation, the lower layer of precipitate was taken and dispersed in anhydrous ethanol, then ultrasonicated for 1h, and finally dried at 80°C for 12h to obtain a modified filler.

[0025] Example 2, preparing the modified filler, the specific steps are as follows: 13.3g magnesium hydroxide, 6.7g nano titanium dioxide, 10g calcium carbonate and 250mL deionized water were mixed evenly in a 500mL three-necked flask, and acetic acid was slowly added to adjust the pH to 4. Subsequently, a mixed solution of 3g methacryloxypropyltriethoxysilane and 10mL anhydrous ethanol was slowly added while stirring. After the addition was completed, the temperature was raised to 65°C and the reaction was kept warm for 1h. After the reaction was completed, it was cooled to room temperature and centrifuged. After centrifugation, the lower layer of precipitate was taken and dispersed in anhydrous ethanol, and then ultrasonicated for 1h. Finally, it was dried at 80°C for 12h to obtain a modified filler.

[0026] Example 3, preparing the modified filler, the specific steps are as follows: Mix 12g magnesium hydroxide, 6g nano titanium dioxide, 12g calcium carbonate and 250mL deionized water in a 500mL three-necked flask, then slowly add acetic acid to adjust the pH to 4, then slowly add a mixed solution of 3g vinyltrimethoxysilane and 10mL anhydrous ethanol while stirring. After the addition is completed, heat to 65°C and keep the reaction for 1h. After the reaction is completed, cool to room temperature and centrifuge. After centrifugation, take the lower layer of precipitate and disperse it in anhydrous ethanol, then ultrasonicate for 1h, and finally dry at 80°C for 12h to obtain a modified filler.

[0027] Example 4, preparing the modified filler, the specific steps are as follows: The remaining steps remained unchanged, except that 1.5 g of vinyltrimethoxysilane and 1.5 g of 3-(methacryloyloxy)propyltrimethoxysilane in Example 1 were replaced with 3 g of 3-aminopropyltrimethoxysilane to prepare a modified filler.

[0028] Example 5, preparing a flame retardant, the specific steps are as follows: S1. Blow nitrogen gas into a 500 mL dry three-necked flask for 30 min to expel air and moisture in the flask, then add 22 mL of 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane, 16.7 mL of triethylamine and 150 mL of benzene, stir and dissolve, then heat to 60°C, then slowly add 13.3 mL of diallylamine, and continue to react at 60°C for 3 h after the addition is completed. After the reaction is completed, cool to room temperature and distill under reduced pressure to obtain intermediate 1; S2, nitrogen was blown into a 500 mL dry three-necked flask for 30 min to expel air and moisture in the flask, then 12.3 g of melamine, 15 mL of triethylamine and 200 mL of dimethyl sulfoxide were added, stirred and dissolved, and the temperature was raised to 65°C, and then 26.3 g of intermediate 1 was slowly added. After the addition was completed, the temperature was kept for 4 h. After the reaction was completed, distillation was carried out under reduced pressure to obtain intermediate 2; S3. Under nitrogen protection, add 19.1 g of 3-hydroxyphenylphosphorylpropionic acid, 4.1 g of EDC, 2.5 g of NHS and 240 mL of DMF into a 500 mL dry three-necked flask, stir to dissolve and then heat to 50°C, then slowly add 23.2 g of intermediate 2, keep warm and react for 6 hours, cool to room temperature after the reaction is completed, and distill under reduced pressure to obtain a flame retardant.

[0029] Example 6, preparing a flame retardant data connection line, the specific steps are as follows: 90 parts of polyvinyl chloride resin, 15 parts of modified filler prepared in Example 1, 10 parts of triisooctyl phosphite, 6 parts of flame retardant prepared in Example 4, 2 parts of zinc stearate, 0.5 parts of ultraviolet absorber UV-531, 0.5 parts of antioxidant 1010 and 0.05 parts of benzoyl peroxide are weighed by weight, and each raw material is added to a mixer for stirring. After mixing evenly, it is sent to a flat vulcanizer, hot-pressed at 180°C, cold-pressed at room temperature, sheeted, crushed, and then sent to a twin-screw extruder for extrusion granulation. After drying, it is added to the barrel of the twin-screw extruder for melting, and the molten sheath material is extruded into the head mold of the twin-screw extruder to cover the conductive wire core passing through the head mold, and cooled to obtain a flame-retardant data connection line.

[0030] Example 7, preparing a flame retardant data connection line, the specific steps are as follows: Weigh 95 parts of polyvinyl chloride resin, 20 parts of modified filler prepared in Example 2, 6 parts of dioctyl phthalate, 7 parts of dioctyl adipate, 10 parts of flame retardant prepared in Example 4, 2 parts of zinc stearate, 1 part of oleic acid amide, 0.4 parts of ultraviolet absorber UV-9, 0.2 parts of light stabilizer AM-101, 0.2 parts of light stabilizer GW-540, 0.4 parts of antioxidant 1098, 0.2 parts of antioxidant 245, 0.2 parts of Antioxidant 168 and 0.08 parts of triallyl isocyanurate, the raw materials are added into a mixer and stirred, and after being evenly mixed, they are sent to a flat vulcanizer, hot-pressed at 180°C, cold-pressed at room temperature, sheeted, and crushed, and then sent to a twin-screw extruder for extrusion and granulation. After drying, the obtained material is added into the barrel of the twin-screw extruder for melting, and the molten sheath material is extruded into the die of the twin-screw extruder to cover the conductive wire core passing through the die, and cooled to obtain a flame-retardant data cable.

[0031] Example 8, preparing a flame retardant data connection line, the specific steps are as follows: Weigh 100 parts of polyvinyl chloride resin, 25 parts of modified filler prepared in Example 3, 7 parts of triisooctyl phosphite, 8 parts of dioctyl sebacate, 12 parts of flame retardant prepared in Example 4, 2 parts of calcium stearate, 3 parts of erucic acid amide, 0.5 parts of ultraviolet absorber UV-P, 0.2 parts of light stabilizer GW-540, 0.3 parts of light stabilizer 744, 0.5 parts of antioxidant 1010, 0.2 parts of antioxidant 1076, 0.3 parts of Antioxidant DLTP and 0.1 parts of azobisisobutyronitrile are added into a mixer and stirred. After being evenly mixed, they are sent to a flat vulcanizer, hot-pressed at 180°C, cold-pressed at room temperature, sheeted, and crushed. Subsequently, they are sent to a twin-screw extruder for extrusion granulation. After drying, they are added into the barrel of the twin-screw extruder for melting. The molten sheath material is extruded into the die of the twin-screw extruder to cover the conductive wire core passing through the die, and cooled to obtain a flame-retardant data cable.

[0032] Comparative Example 1: preparing a data connection line, the specific steps are as follows: The remaining steps remain unchanged, except that the flame retardant in Example 6 is replaced by 3 parts of melamine cyanurate and 3 parts of diethyl aluminum hypophosphite to prepare a data connection line.

[0033] Comparative Example 2: preparing a data connection line, the specific steps are as follows: The remaining steps remain unchanged, only the modified filler in Example 6 is replaced by 15 parts of the modified filler prepared in Example 4 to prepare a data connection line.

[0034] Comparative Example 3: preparing a data connection line, the specific steps are as follows: The remaining steps remain unchanged, the flame retardant in Example 6 is replaced by 3 parts of melamine cyanurate and 3 parts of diethylaluminum hypophosphite, and the modified filler in Example 6 is replaced by 15 parts of the modified filler prepared in Example 4, to prepare a data connection line.

[0035] Performance Testing The molten sheath materials in Examples 6-8 and Comparative Examples 1-3 were extruded, cooled, and processed into test specimens, and the following performance tests were performed: tensile properties were tested according to GB / T 1040.2-2006; flame retardancy (limiting oxygen index LOI) was tested according to GB / T 10707-2008; and smoke suppression performance was tested according to GB / T 8323.1-2008. The test results of all items are shown in Table 1 below: Table 1

[0036] In the description of the specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0037] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the invention or exceed the scope defined by the claims, they shall all fall within the protection scope of the present invention.

Claims

1. A method for preparing a flame retardant data connection line, characterized in that: The following steps are involved: 90-100 parts of polyvinyl chloride resin, 15-25 parts of modified filler, 10-15 parts of plasticizer, 6-12 parts of flame retardant, 2-5 parts of lubricant, 0.5-1 parts of stabilizer, 0.5-1 parts of antioxidant and 0.05-0.1 parts of cross-linking agent are weighed by weight, added to a mixer, stirred, and then sent to a flat vulcanizer, hot pressed, cold pressed, sliced, crushed, and then sent to a twin-screw extruder for extrusion granulation, dried, added to the barrel for melting, and the molten sheath material is extruded into a die mold to cover the conductive wire core passing through the die mold, cooled, and obtained a flame-retardant data connection line; Wherein, the modified filler is prepared by the following steps: The inorganic filler and deionized water were mixed in a flask, the pH was adjusted to 4, a coupling agent and anhydrous ethanol were added, the mixture was reacted at 65°C for 1 hour, the mixture was cooled, centrifuged, the lower precipitate was taken and dispersed in anhydrous ethanol, ultrasonicated, and dried to obtain a modified filler; The flame retardant is prepared by the following steps: S1. After nitrogen is blown into the flask, 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane, triethylamine and benzene are added, the temperature is raised to 60°C with stirring, diallylamine is added, the reaction is carried out for 3 hours, the reaction is cooled, and the reaction is carried out under reduced pressure distillation to obtain intermediate 1; S2, after nitrogen blowing into the flask, add melamine, triethylamine and dimethyl sulfoxide, stir and heat to 65°C, add intermediate 1, react for 4 hours, and distill under reduced pressure to obtain intermediate 2; S3. Under nitrogen protection, add 3-hydroxyphenylphosphorylpropionic acid, EDC, NHS and DMF into a flask, stir and heat to 50°C, add intermediate 2, react for 6 hours, cool, and distill under reduced pressure to obtain a flame retardant.

2. The method for preparing a flame retardant data connection line according to claim 1, characterized in that: The mass ratio of the inorganic filler to the coupling agent is 10:1; the inorganic filler is a mixture of magnesium hydroxide, nano-titanium dioxide and calcium carbonate in a mass ratio of 2:1:(1-2); the coupling agent is one or more of vinyltrimethoxysilane, vinyltriethoxysilane, 3-(methacryloyloxy)propyltrimethoxysilane and methacryloxypropyltriethoxysilane.

3. The method for preparing a flame retardant data connection line according to claim 1, characterized in that: The amount ratio of 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane, diallylamine, triethylamine and benzene in step S1 is 22 mL:13.3 mL:16.7 mL:150 mL; the amount ratio of intermediate 1, melamine, triethylamine and dimethyl sulfoxide in step S2 is 26.3 g:12.3 g:15 mL:200 mL; the amount ratio of 3-hydroxyphenylphosphatopropionic acid, intermediate 2, EDC, NHS and DMF in step S3 is 19.1 g:23.2 g:4.1 g:2.5 g:240 mL.

4. The method for preparing a flame retardant data connection line according to claim 1, characterized in that: The plasticizer is one or more of triisooctyl phosphite, diisooctyl phthalate, di-n-octyl adipate, and dioctyl sebacate.

5. The method for preparing a flame retardant data connecting line according to claim 1, characterized in that: The lubricant is one or more of zinc stearate, calcium stearate, oleamide and erucamide.

6. The method for preparing a flame retardant data connection line according to claim 1, characterized in that: The stabilizer is one or more of the ultraviolet absorber UV-531, ultraviolet absorber UV-9, ultraviolet absorber UV-P, light stabilizer AM-101, light stabilizer GW-540, and light stabilizer 744.

7. The method for preparing a flame retardant data connection line according to claim 1, characterized in that: The antioxidant is one or more of antioxidant 1010, antioxidant 1098, antioxidant 245, antioxidant 168, antioxidant 1076, and antioxidant DLTP.

8. The method for preparing a flame retardant data connection line according to claim 1, characterized in that: The cross-linking agent is one or two of benzoyl peroxide, di-tert-butyl peroxide, triallyl isocyanurate, and azobisisobutyronitrile.

9. A flame retardant data connection line, characterized in that: The flame retardant data connecting line is prepared according to the method for preparing the flame retardant data connecting line according to any one of claims 1 to 8.

Images