A preparation process of wear-resistant flame-retardant woven fabric

Abstract

The invention relates to the technical field of woven fabrics, and discloses a preparation process of a wear-resistant flame-retardant woven fabric, wherein polyethylene resin, organosilicon DOPO flame retardant, maleic anhydride grafted polyethylene, and antioxidant are placed in a twin-screw extruder for melt extrusion, a film sheet is formed by a cast film machine, and then the film is divided into embryonic yarns by a flat yarn machine, stretched, and shaped to obtain wear-resistant flame-retardant polyethylene flat yarns. The organosilicon DOPO flame retardant of the invention contains DOPO and siloxane flame retardant structures in the polymer molecular chain of the flame retardant to form a phosphorus silicon flame retardant system, thereby improving the limiting oxygen index of the flat yarn woven fabric and having better flame retardant properties. The invention adds a compatibilizer maleic anhydride grafted polyethylene to make the organosilicon DOPO flame retardant and the polyethylene resin have better compatibility, which is beneficial to improving the mechanical properties of the woven fabric, and showing higher tensile strength, elongation at break, and wear resistance.

Description

Technical Field

[0001] The invention relates to the technical field of woven fabrics, in particular to a preparation process of wear-resistant and flame-retardant woven fabrics. Background Art

[0002] Polyethylene woven fabric is mainly a woven fabric material made of polyethylene and other resins through stretching, weaving and other processes. It is widely used in civil engineering fields such as building reinforcement, bank protection and slope protection. Developing high-performance polyethylene woven fabrics and improving their mechanical strength, wear resistance, flame retardancy and other properties are research hotspots. Patent CN103397443B discloses halogen-free flame-retardant polyethylene plastic woven fabric and its preparation method. The polyethylene plastic woven fabric prepared by using polyethylene, ethylene-vinyl acetate elastomer, nano inorganic flame retardant and the like as raw materials has the advantages of good flame retardancy, strength and toughness. Compared with traditional inorganic flame retardants, organic flame retardants have the advantages of diverse preparation methods, small dosage, high flame retardancy, and good compatibility with the material matrix. Common organic flame retardants are mainly phosphorus flame retardants, nitrogen flame retardants, silicon flame retardants, etc.

[0003] Organic siloxane polymers have the advantages of good chemical stability, high toughness, high weather resistance, strong wear resistance, etc. They can be used as toughening agents, flame retardants and other additives, and are widely used in plastics, fiber textiles, etc. The present invention uses organic silicon DOPO flame retardant to improve the mechanical properties, wear resistance and flame retardancy of polyethylene flat yarn and its woven fabric. Summary of the invention

[0004] The invention solves the problem that the polyethylene flat yarn and the woven fabric thereof have poor wear resistance and poor flame retardancy.

[0005] The technical solution of the present invention is a preparation process of a wear-resistant and flame-retardant woven cloth, which is woven by a wear-resistant and flame-retardant polyethylene flat wire through a weaving machine.

[0006] The preparation process of wear-resistant and flame-retardant polyethylene flat wire is:

[0007] Step S1, adding 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane and a structural formula After the reaction, the solution is poured into ethanol, filtered, washed with ethanol, and dried to obtain an organosilicon DOPO flame retardant. The reaction formula is: .

[0008] Step S2, placing 100 parts by weight of polyethylene resin, 5-25 parts by weight of silicone DOPO flame retardant, 1.5-8 parts by weight of maleic anhydride grafted polyethylene and 0.3-0.6 parts by weight of antioxidant in a twin-screw extruder for melt extrude, the temperature of each section is 120°C, 155°C, 170°C, 185°C, 185°C, 180°C, and the screw speed is 60-100r / min; forming a film sheet through a cast film machine, and then dividing it into embryonic wires through a flat wire machine, stretching and shaping, the temperature during stretching is 110-120°C, and the stretching ratio is 2-3, to obtain wear-resistant and flame-retardant polyethylene flat wire.

[0009] Preferably, in step S1, the molar ratio of 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane to diglycidyl succinate-based DOPO is 1:(1-1.1).

[0010] Preferably, in step S1, the reaction temperature is 55-70° C., and the reaction time is 8-12 h.

[0011] Preferably, the preparation process of diglycidyl succinate-based DOPO is as follows: add N,N-dimethylformamide, succinate-based DOPO, 4-dimethylaminopyridine, N,N-dicyclohexylcarbodiimide and glycidol in a molar ratio of 1: (0.2-0.26): (2.2-2.4): (2.6-3.2) to a flask, stir and react for 12-18 hours, add water to dilute, then extract with ethyl acetate, add anhydrous sodium sulfate to the ethyl acetate extract phase for drying, filter, heat the filtrate to volatilize and precipitate, then cool and recrystallize in an ice water bath to obtain diglycidyl succinate-based DOPO. The reaction formula is: .

[0012] Technical effect: The present invention conducts an esterification reaction of succinic acid-based DOPO and glycidol, and then conducts an amino-epoxy ring-opening reaction with 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane to obtain an organosilicon DOPO flame retardant.

[0013] The polyethylene flat yarn and the woven fabric thereof are added with an organic silicon DOPO flame retardant. The polymer molecular chain of the flame retardant contains DOPO and siloxane flame retardant structures to form a phosphorus silicon flame retardant system. During combustion, DOPO is pyrolyzed to generate phosphorus-containing free radicals, which can capture combustion chain reaction free radicals and inhibit the combustion reaction process. At the same time, high-temperature pyrolysis generates phosphoric acid substances, which promotes the dehydration of the flat yarn woven fabric to form a carbon layer. Siloxane is oxidized at high temperature to generate inorganic silicon dioxide, which is combined with the carbon layer to form a continuous and stable carbon silicon barrier layer, which has the flame retardant effects of isolating oxygen and inhibiting smoke escape, thereby improving the limiting oxygen index of the flat yarn woven fabric and having better flame retardant properties.

[0014] The molecular chain of the organosilicon DOPO flame retardant of the present invention contains active groups such as hydroxyl groups and imino groups, which can react with the compatibilizer maleic anhydride grafted polyethylene, so that the organosilicon DOPO flame retardant and the polyethylene resin have better compatibility and will not affect the mechanical properties of the polyethylene resin. In addition, the flame retardant contains flexible and wear-resistant siloxane segments, which have a certain toughening effect, are beneficial to improving the mechanical properties of the woven fabric, show higher tensile strength and elongation at break, reduce wear mass loss, and improve wear resistance. DETAILED DESCRIPTION

[0015] In order to more clearly understand the above-mentioned purpose, features and advantages of the present invention, the present invention is further described in detail below in conjunction with specific embodiments. It should be noted that the embodiments of the present application and the features in the embodiments can be combined with each other without conflict.

[0016] The polyethylene resin model of the present invention is SABIC 118P, produced by Dongguan Longhuang Plastic Raw Materials Co., Ltd.

[0017] Maleic anhydride grafted polyethylene, Dongguan Shengli New Materials Co., Ltd.

[0018] The preparation process of succinic acid-DOPO is as follows: add 30 mL of xylene, 30 mL of tetrahydrofuran and 10 g of DOPO 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to a flask containing a condenser reflux tube, introduce nitrogen, heat to 95°C, add 5.37 g of maleic acid dropwise after stirring, react for 10 hours, cool and filter, wash the product with a mixed solution of tetrahydrofuran and xylene, and dry to obtain succinic acid-DOPO. The structural formula is .

[0019] Embodiment 1:

[0020] (1) Add 40 mL of N,N-dimethylformamide, 15 mmol of succinic acid-based DOPO, 3.6 mmol of 4-dimethylaminopyridine, 36 mmol of N,N-dicyclohexylcarbodiimide and 45 mmol of glycidol into a flask, stir and react for 18 h, add water to dilute, then extract with ethyl acetate, add anhydrous sodium sulfate to the ethyl acetate extract to dry, filter, heat the filtrate to evaporate and precipitate, then cool in an ice-water bath and recrystallize to obtain succinic acid diglycidyl DOPO.

[0021] (2) Add 40 mmol 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane and 40 mmol diglycidyl succinate-based DOPO to 250 mL N,N-dimethylformamide, heat to 60°C, stir and react for 12 h, pour the solution into ethanol, filter, wash with ethanol, and dry to obtain an organosilicon DOPO flame retardant.

[0022] (3) Place 1 kg of polyethylene resin, 50 g of silicone DOPO flame retardant, 15 g of maleic anhydride grafted polyethylene and 6 g of antioxidant 168 in a twin-screw extruder for melt extrusion, with the temperatures of each section being 120°C, 155°C, 170°C, 185°C, 185°C, and 180°C, and the screw speed being 100 r / min; form a film sheet through a cast film machine, and then divide it into embryonic filaments through a flat yarn machine, stretch and shape them, with the stretching temperature being 120°C and the stretching ratio being 2.5, to obtain wear-resistant and flame-retardant polyethylene flat yarn.

[0023] Embodiment 2:

[0024] (1) Add 40 mL of N,N-dimethylformamide, 15 mmol of succinic acid-based DOPO, 3 mmol of 4-dimethylaminopyridine, 33 mmol of N,N-dicyclohexylcarbodiimide and 39 mmol of glycidol into a flask, stir and react for 18 h, add water to dilute, and then extract with ethyl acetate. Add anhydrous sodium sulfate to the ethyl acetate extract to dry, filter, heat the filtrate to evaporate and precipitate, and then cool in an ice-water bath for recrystallization to obtain succinic acid diglycidyl DOPO.

[0025] (2) Add 40 mmol 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane and 40 mmol diglycidyl succinate-based DOPO to 300 mL N,N-dimethylformamide, heat to 70°C, stir and react for 8 h, pour the solution into ethanol, filter, wash with ethanol, and dry to obtain an organosilicon DOPO flame retardant.

[0026] (3) Place 1 kg of polyethylene resin, 150 g of silicone DOPO flame retardant, 48 g of maleic anhydride grafted polyethylene and 3 g of antioxidant 168 in a twin-screw extruder for melt extrusion, with the temperatures of each section being 120°C, 155°C, 170°C, 185°C, 185°C, and 180°C, and the screw speed being 100 r / min; form a film sheet through a cast film machine, and then divide it into embryonic filaments through a flat yarn machine, stretch and shape them, with the stretching temperature being 120°C and the stretching ratio being 2, to obtain wear-resistant and flame-retardant polyethylene flat yarn.

[0027] Embodiment 3:

[0028] (1) Add 50 mL of N,N-dimethylformamide, 15 mmol of succinic acid-based DOPO, 3.9 mmol of 4-dimethylaminopyridine, 36 mmol of N,N-dicyclohexylcarbodiimide and 48 mmol of glycidol into a flask, stir and react for 12 h, add water to dilute, and then extract with ethyl acetate. Add anhydrous sodium sulfate to the ethyl acetate extract to dry, filter, heat the filtrate to evaporate and precipitate, and then cool in an ice-water bath for recrystallization to obtain succinic acid diglycidyl DOPO.

[0029] (2) Add 40 mmol 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane and 44 mmol diglycidyl succinate-based DOPO to 300 mL N,N-dimethylformamide, heat to 55 °C, stir and react for 12 h, pour the solution into ethanol, filter, wash with ethanol, and dry to obtain an organosilicon DOPO flame retardant.

[0030] (3) Place 1 kg of polyethylene resin, 250 g of silicone DOPO flame retardant, 80 g of maleic anhydride grafted polyethylene and 6 g of antioxidant 168 in a twin-screw extruder for melt extrusion, with the temperatures of each section being 120°C, 155°C, 170°C, 185°C, 185°C, and 180°C, and the screw speed being 60 r / min; form a film sheet through a cast film machine, and then divide it into embryonic filaments through a flat yarn machine, stretch and shape them, with the stretching temperature being 110°C and the stretching ratio being 3, to obtain wear-resistant and flame-retardant polyethylene flat yarn.

[0031] Comparative Example 1

[0032] (1) Place 1 kg of polyethylene resin, 15 g of maleic anhydride grafted polyethylene and 6 g of antioxidant 168 in a twin-screw extruder for melt extrusion, with the temperatures of each section being 120°C, 155°C, 170°C, 185°C, 185°C, and 180°C, and the screw speed being 100 r / min; form a film sheet through a cast film machine, and then divide it into embryonic filaments through a flat yarn machine, stretch and shape them, with the temperature during stretching being 120°C and the stretching ratio being 2.5, to obtain polyethylene flat yarn.

[0033] Comparative Example 2

[0034] (1) Place 1 kg of polyethylene resin, 50 g of silicone DOPO flame retardant (prepared according to the method of Example 1) and 6 g of antioxidant 168 in a twin-screw extruder for melt extrusion, with the temperatures of each section being 120°C, 155°C, 170°C, 185°C, 185°C, and 180°C, and the screw speed being 100 r / min; form a film sheet through a cast film machine, and then divide it into embryonic filaments through a flat yarn machine, stretch and shape them, with the stretching temperature being 120°C and the stretching ratio being 2.5, to obtain polyethylene flat yarn.

[0035] Comparative Example 3

[0036] (1) Place 1 kg of polyethylene resin, 50 g of diglycidyl succinate-based DOPO (prepared according to the method of Example 1), 15 g of maleic anhydride grafted polyethylene and 6 g of antioxidant 168 in a twin-screw extruder for melt extrusion, with the temperatures of each section being 120°C, 155°C, 170°C, 185°C, 185°C, and 180°C, and the screw speed being 100 r / min; form a film sheet through a cast film machine, and then divide it into embryonic filaments through a flat yarn machine, stretch and shape them, with the stretching temperature being 120°C and the stretching ratio being 2.5, to obtain polyethylene flat yarn.

[0037] Comparative Example 4

[0038] (1) Add 40 mmol of 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane and 40 mmol of ethylene glycol diglycidyl ether to 250 mL of N,N-dimethylformamide, heat to 60°C, stir and react for 12 h, pour the solution into ethanol, filter, wash with ethanol, and dry to obtain an organosilicon polymer.

[0039] (2) Place 1 kg of polyethylene resin, 50 g of silicone polymer, 15 g of maleic anhydride grafted polyethylene and 6 g of antioxidant 168 in a twin-screw extruder for melt extrusion. The temperatures of each section are 120°C, 155°C, 170°C, 185°C, 185°C, and 180°C, and the screw speed is 100 r / min; form a film sheet through a cast film machine, and then divide it into embryonic filaments through a flat yarn machine, stretch and shape them. The stretching temperature is 120°C and the stretching ratio is 2.5 to obtain polyethylene flat yarn.

[0040] The mechanical properties of wear-resistant and flame-retardant polyethylene flat yarn were tested using an electronic fabric strength tester. The clamp distance was 200mm and the tensile speed was 50mm / min. Each sample was tested 5 times and the average value was taken. Specifically: start the tensile tester, the distance between the two clamps was 200mm, and the tensile force was applied to the flat yarn sample at a tensile speed of 50mm / min until the flat yarn sample broke. During the test, the tensile tester recorded the tensile force applied to the flat yarn sample. When the sample broke, the tensile tester would record the maximum tensile force at the time of breaking, i.e. the breaking force, in Newton (N). And calculate the elongation at break. Elongation at break = (E / L) × 100%. L is the starting length of the flat yarn, in millimeters (mm). E is the elongation value of the flat yarn from the starting length to the time of breaking, in millimeters (mm).

[0041] Wear-resistant flame-retardant polyethylene flat yarn is used as warp yarn and weft yarn, and is woven into a cloth shape by a weaving machine to obtain wear-resistant flame-retardant woven cloth. Specifically, the polyethylene flat yarn warp yarn and weft yarn are collected into spindles, the warp yarn width is 2.3 mm; the weft yarn width is 2.5 mm, and the yarns are arranged and woven in a circular loom. The warp density of the woven cloth is 36 strands / 100mm, and the weft density is 31 strands / 100mm.

[0042] According to GB T 5454-1997 method, the oxygen index tester is used to test the limiting oxygen index of wear-resistant flame-retardant woven fabrics. The larger the limiting oxygen index, the better the flame retardancy.

[0043] The wear resistance of the wear-resistant flame-retardant woven fabric was tested using a friction and wear tester. The counterpiece was a 45# steel ring, the load was 1kg, the speed was 200r / min, and the wear time was 10min. The mass loss before and after wear was tested. The smaller the wear mass loss, the better the wear resistance.

[0044] Table 1

[0045] Breaking force (N) Elongation at break (%) Limiting oxygen index (%) Wear mass loss (mg) Example 1 27.9 152.0 27.9 61.8 Example 2 33.2 175.4 29.5 49.5 Example 3 32.0 180.8 30.8 36.2 Comparative Example 1 24.8 126.5 18.1 72.3 Comparative Example 2 25.7 131.2 27.7 67.5 Comparative Example 3 24.2 122.3 26.4 72.9 Comparative Example 4 27.1 156.6 18.7 63.6

[0046] Organic silicon DOPO flame retardant is added to the polyethylene flat yarn woven cloth of Examples 1-3. The polymer molecular chain of the flame retardant contains DOPO and siloxane flame retardant structures to form a phosphorus-silicon flame retardant system. During combustion, DOPO pyrolyzes to produce phosphorus-containing free radicals, which can capture the combustion chain reaction free radicals and inhibit the combustion reaction process. At the same time, high-temperature pyrolysis produces phosphoric acid substances, which promote the dehydration of the flat yarn woven cloth to form a carbon layer, and high-temperature oxidation of siloxane produces inorganic silicon dioxide, which is combined with the carbon layer to form a continuous and stable carbon-silicon barrier layer, which has the flame retardant effects of isolating oxygen and inhibiting smoke escape, thereby improving the limiting oxygen index of the flat yarn woven cloth and having better flame retardant properties.

[0047] The molecular chain of the organosilicon DOPO flame retardant of the present invention contains active groups such as hydroxyl groups and imino groups, which can react with the compatibilizer maleic anhydride grafted polyethylene, so that the organosilicon DOPO flame retardant and the polyethylene resin have better compatibility and will not affect the mechanical properties of the polyethylene resin. In addition, the flame retardant contains flexible and wear-resistant siloxane segments, which have a certain toughening effect, are beneficial to improving the mechanical properties of the woven fabric, show higher tensile strength and elongation at break, reduce wear mass loss, and improve wear resistance.

[0048] Comparative Example 1 does not add the organosilicon DOPO flame retardant, the limiting oxygen index of the flat yarn woven fabric is low, the flame retardancy is poor, and the tensile strength and elongation at break are low, the wear mass loss is large, and the mechanical properties and wear resistance are poor.

[0049] In Comparative Example 2, no compatibilizer maleic anhydride grafted polyethylene was added, and the compatibility between the silicone DOPO flame retardant and the polyethylene resin was poor, making it difficult to effectively improve the mechanical properties and wear resistance of the flat woven fabric.

[0050] In Comparative Example 3, only diglycidyl succinate-based DOPO was added as a flame retardant, which does not contain a siloxane structure. The limiting oxygen index of the woven fabric is low, only 26.5%, the flame retardancy is poor, and the tensile strength and elongation at break are low, the wear mass loss is large, and the mechanical properties and wear resistance are poor.

[0051] Comparative Example 4 uses 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane and ethylene glycol diglycidyl ether for ring-opening polymerization, and the obtained silicone polymer does not contain DOPO flame retardant structure. The limiting oxygen index of the woven fabric is very low and the flame retardancy is poor.

[0052] The embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications made without departing from the spirit and principle of the present invention shall be equivalent replacement modes and shall be included in the protection scope of the present invention.

Claims

1. A process for preparing a wear-resistant flame-retardant woven fabric, characterized in that: The wear-resistant and flame-retardant woven fabric is woven from wear-resistant and flame-retardant polyethylene flat wires through a weaving machine; The preparation process of the wear-resistant and flame-retardant polyethylene flat wire is as follows: Step S1, adding 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane and a structural formula The diglycidyl succinate-based DOPO is prepared, and after the reaction, the solution is poured into ethanol, filtered, washed, and dried to obtain an organosilicon DOPO flame retardant; Step S2, placing 100 parts by weight of polyethylene resin, 5-25 parts by weight of silicone DOPO flame retardant, 1.5-8 parts by weight of maleic anhydride grafted polyethylene and 0.3-0.6 parts by weight of antioxidant in a twin-screw extruder for melt extrusion, forming a film sheet through a cast film machine, and then dividing it into embryonic yarns through a flat yarn machine, stretching and shaping, to obtain wear-resistant flame-retardant polyethylene flat yarns.

2. The preparation process of the wear-resistant flame-retardant woven fabric according to claim 1, characterized in that: In the step S1, the molar ratio of 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane to diglycidyl succinate-based DOPO is 1:(1-1.1).

3. The preparation process of the wear-resistant flame-retardant woven fabric according to claim 1, characterized in that: In the step S1, the reaction temperature is 55-70° C., and the reaction time is 8-12 hours.

4. The preparation process of the wear-resistant flame-retardant woven fabric according to claim 1, characterized in that: In step S2, the temperatures of each section of the twin-screw extruder are 120° C., 155° C., 170° C., 185° C., 185° C., and 180° C., and the screw speed is 60-100 r / min.

5. The preparation process of the wear-resistant flame-retardant woven fabric according to claim 1, characterized in that: In the step S2, the temperature during stretching is 110-120°C, and the stretching ratio is 2-3.

6. The process for preparing the wear-resistant flame-retardant woven fabric according to claim 1, characterized in that: The preparation process of the diglycidyl succinate-based DOPO is as follows: N,N-dimethylformamide and a structural formula of Succinic acid-based DOPO, 4-dimethylaminopyridine, N,N-dicyclohexylcarbodiimide and glycidol are stirred for reaction for 12-18 hours, and water is added for dilution, extraction and recrystallization to obtain succinic acid diglycidyl ester-based DOPO.

7. The process for preparing the wear-resistant flame-retardant woven fabric according to claim 6, characterized in that: The molar ratio of the succinic acid-DOPO, 4-dimethylaminopyridine, N,N-dicyclohexylcarbodiimide and glycidol is 1:(0.2-0.26):(2.2-2.4):(2.6-3.2).

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