Environment-friendly smoke suppression type rare earth synergistic flame-retardant PA6 fiber and preparation method thereof
By combining nano rare earth and phosphorus-silicon synergistic flame retardants, environmentally friendly smoke-suppressing rare earth synergistic flame retardant PA6 fiber is prepared, which solves the problem of poor flame retardant ability of PA6 fiber and achieves significant improvement in flame retardant performance and safety.
Patent Information
- Application Number
- CN202410463129.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-04-17
- Publication Date
- 2025-10-24
AI Technical Summary
PA6 fiber has poor flame retardancy and poses a fire safety hazard, especially at high temperatures where it is easy to ignite and drip, resulting in a high fire risk factor. The current production of flame-retardant fibers is insufficient and the market demand is huge.
Nano rare earth and phosphorus-silicon synergistic flame retardants are mixed with PA6 chips, and environmentally friendly smoke-suppressing rare earth synergistic flame retardant PA6 fibers are prepared through melt extrusion, spinning and other processes. The synergistic effect of nano rare earth and phosphorus-silicon synergistic flame retardants is used to improve the flame retardant properties.
The prepared environmentally friendly smoke-suppressing rare earth synergistic flame-retardant PA6 fiber has the advantages of being halogen-free, smoke-suppressing, and having low heat release. The flame retardant performance is significantly improved, the total heat release and smoke release are reduced, the breaking strength is basically maintained, and the LOI value is significantly improved.
Smart Images
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Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the technical field of high molecular flame-retardant materials, and particularly relates to an environment-friendly smoke-suppressing rare earth synergistic flame-retardant PA6 fiber and a preparation method thereof. BACKGROUND
[0002] PA6 fiber is one of the earliest synthetic fibers to realize industrial production, is light, soft, wear-resistant, and low in price, and has penetrated into various fields of national production and life, occupies an irreplaceable position in the fields of building construction, machinery manufacturing, aerospace and textile clothing, and has a huge market share. However, the PA6 fiber with excellent comprehensive performance has extremely serious fire safety hazards. The PA6 fiber is an aliphatic macromolecular polymer with -NH-(CH2)5-CO- as a repeating unit. Because the amide bond has low bond energy, the macromolecular chain is easily decomposed into flammable small molecular fragments under heat and is quickly ignited. In addition, the highly linear molecular structure also causes low carbonization rate and serious melting drops during combustion, which has the dual hazards of "high-temperature scalding" and "causing secondary fire", especially affected by the fiber morphology structure, compared with engineering plastics, the fiber is more easily ignited, melted, and spread with flame when attacked by heat flow, and has a higher risk coefficient. Fire data shows that more than half of the 2 million fires in the past decade are related to the ignition and combustion of high molecular fiber products, causing heavy casualties and economic losses. According to the conservative estimate of the relevant departments, the current demand for flame-retardant fibers in the world is as high as 5 million tons, but the current production of flame-retardant fibers is less than 100,000 tons, the gap is huge, and the research and development demand is very urgent. Based on this, as an important basic material closely related to the national livelihood, the high-quality flame-retardant modification of PA6 fiber is undoubtedly a basic research topic with great practical significance. Therefore, how to provide a PA6 fiber with excellent flame-retardant performance has become a problem to be solved by the technical personnel in the field. SUMMARY
[0003] Therefore, the present application provides an environment-friendly smoke-suppressing rare earth synergistic flame-retardant PA6 fiber and a preparation method thereof.
[0004] In order to achieve the above-mentioned purpose, the present application adopts the following technical scheme:
[0005] The present application provides an environment-friendly smoke-suppressing rare earth synergistic flame-retardant PA6 fiber, which is prepared from raw materials containing the following weight parts:
[0006] PA6 chip 85-95 parts, nano rare earth 0.5-2 parts, phosphorus-silicon synergistic flame retardant 4-13 parts, and antioxidant 0-0.5 parts.
[0007] Further, the nano rare earth includes one or more of nano lanthanum oxide, nano cerium oxide and nano neodymium oxide.
[0008] Further, the structural formula of the phosphorus-silicon synergistic flame retardant includes formula 1 or formula 2:
[0009]
[0010] Wherein, x = 5-10, y = 5-10.
[0011] Further, the antioxidant includes Doverphos S-9228.
[0012] Further, the water content of the PA6 chip is ≤100 ppm.
[0013] The application also provides a preparation method of the above-mentioned environmentally-friendly smoke-suppressing rare earth synergistic flame-retardant PA6 fiber.
[0014] S1, mixing all raw materials to obtain a mixture, and the mixture is sequentially subjected to melt extrusion, water cooling, granulation, extraction, drying, and granulation to obtain a flame-retardant PA6 masterbatch;
[0015] S2, sequentially drying, spinning, extruding, side-blowing, bundling, drawing, and winding the flame-retardant PA6 masterbatch to obtain the environmentally-friendly smoke-suppressing rare earth synergistic flame-retardant PA6 fiber.
[0016] Further, in the step S1, the temperature for melt extrusion is 225-250℃.
[0017] Further, in the step S2, the temperature for drying is 100-120℃, and the time for drying is 8-12h; the water content of the flame-retardant PA6 masterbatch after drying is ≤100 ppm.
[0018] Further, in the step S2, the parameters for spinning are as follows: the temperature of the first zone is 235-245℃, the temperature of the second zone is 245-255℃, the temperature of the third zone is 245-260℃, and the temperature of the fourth zone is 250-260℃; the speed for spinning is 2500-4500m / min.
[0019] Further, in the step S2, the temperature for side-blowing is 18-22℃, the wind speed is 0.4-0.6m / s; and the drawing multiple is 3-5 times.
[0020] According to the above technical solution, compared with the prior art, the application has the following advantages:
[0021] The application realizes the controllable preparation of the environmentally-friendly smoke-suppressing rare earth synergistic flame-retardant PA6 fiber by synergizing the smoke-suppressing nano rare earth with the high-efficiency phosphorus-silicon synergistic flame retardant. DETAILED DESCRIPTION
[0022] The application provides an environment-friendly smoke-suppressing rare earth synergistic flame-retardant PA6 fiber, which is prepared from raw materials containing the following components by weight:
[0023] PA6 chips 85-95 parts, nano rare earth 0.5-2 parts, phosphorus-silicon synergistic flame retardant 4-13 parts, and antioxidant 0-0.5 part.
[0024] In the application, the PA6 chips are preferably used in an amount of 86-94 parts, and further preferably in an amount of 88-92 parts.
[0025] In the application, the nano rare earth is preferably used in an amount of 0.8-1.6 parts, and further preferably in an amount of 1.0-1.2 parts.
[0026] In the application, the phosphorus-silicon synergistic flame retardant is preferably used in an amount of 5-12 parts, and further preferably in an amount of 8-10 parts.
[0027] In the application, the nano rare earth includes one or more of nano lanthanum oxide, nano cerium oxide and nano neodymium oxide, and is preferably nano lanthanum oxide and / or nano cerium oxide, and is further preferably nano lanthanum oxide.
[0028] In the application, the structural formula of the phosphorus-silicon synergistic flame retardant includes formula 1 or formula 2:
[0029]
[0030] In the formula, x=5-10, preferably 6-9, and further preferably 7-8; y=5-10, preferably 6-9, and further preferably 7-8.
[0031] In the application, the antioxidant includes Doverphos S-9228.
[0032] In the application, the PA6 chips have a water content of ≤100 ppm, preferably ≤90 ppm, and further preferably ≤80 ppm.
[0033] The application further provides a preparation method of the environment-friendly smoke-suppressing rare earth synergistic flame-retardant PA6 fiber.
[0034] S1, mixing all the raw materials to obtain a mixture, and then sequentially performing melt extrusion, water cooling, granulation, extraction, drying and granulation on the mixture to obtain flame-retardant PA6 masterbatch;
[0035] S2, sequentially performing drying, spinning, extrusion, side blowing, bundling, drawing and winding on the flame-retardant PA6 masterbatch to obtain the environment-friendly smoke-suppressing rare earth synergistic flame-retardant PA6 fiber.
[0036] In the present application, the temperature of melt extrusion in step S1 is 225-250℃, preferably 230-245℃, and further preferably 235-240℃.
[0037] In the present application, the temperature of drying in step S2 is 100-120℃, preferably 105-115℃, and further preferably 108-112℃; the time of drying is 8-12h, preferably 8.5-11.5h, and further preferably 9-10h; the water content of the flame-retardant PA6 masterbatch after drying is ≤100ppm, preferably ≤90ppm, and further preferably ≤80ppm.
[0038] In the present application, the parameters of spinning in step S2 are as follows: the temperature of the first zone is 235-245℃, preferably 236-244℃, and further preferably 238-242℃; the temperature of the second zone is 245-255℃, preferably 247-253℃, and further preferably 249-251℃; the temperature of the third zone is 245-260℃, preferably 248-257℃, and further preferably 250-255℃; the temperature of the fourth zone is 250-260℃, preferably 252-258℃, and further preferably 254-256℃; the speed of spinning is 2500-4500m / min, preferably 2800-4200m / min, and further preferably 3000-4000m / min.
[0039] In the present application, the temperature of side blowing in step S2 is 18-22℃, preferably 19-21℃, and further preferably 20℃; the wind speed is 0.4-0.6m / s, preferably 0.5m / s; the multiple of traction is 3-5, preferably 4.
[0040] The technical solutions provided by the present application will be described in detail below in combination with examples, but they should not be understood as limiting the scope of protection of the present application.
[0041] Example 1
[0042] The structural formula of the phosphorus-silicon synergistic flame retardant used in this example is as follows:
[0043] x=5.
[0044] 90 parts of PA6 chips with water content of ≤100 ppm, 1 part of nano lanthanum oxide, 8.5 parts of phosphorus-silicon synergistic flame retardant, and 0.5 parts of antioxidant (Doverphos S-9228) are uniformly mixed; then, the mixture is fed into a twin-screw melt extruder, and after melt extrusion, water cooling, granulation, extraction, and drying, a flame-retardant PA6 master batch is prepared by granulation, wherein the melt extrusion temperature setting parameters of the twin-screw melt extruder are as follows: zone 1 temperature: 225°C; zone 2 temperature: 225°C; zone 3 temperature: 240°C; zone 4 temperature: 240°C; and zone 5 temperature: 240°C.
[0045] The flame-retardant PA6 master batch is placed in a drum dryer and dried at 100°C for 12 h until the water content of the master batch is less than 100 ppm. Then, the dried flame-retardant PA6 master batch is put into a spinning box, and the spinning parameters are set as follows: zone 1 temperature: 235°C; zone 2 temperature: 245°C; zone 3 temperature: 245°C; zone 4 temperature: 250°C; and spinning speed: 4000 m / min; then, after extrusion, side blowing, bunching, drawing, and winding, an environmentally friendly smoke-suppressing rare earth synergistic flame-retardant PA6 fiber is obtained. The side blowing temperature is 20°C, the wind speed is 0.4 m / s, and the drawing multiple is 5 times.
[0046] A micro-combustion calorimeter (MCC, Novmark) is used to evaluate the heat release behavior of the sample. The test standard is ASTM D7309-7, the temperature range is 30-900°C, and the heating rate is 1°C / s. The test results show that compared with pure PA6 fiber, the total heat release (THR) of the environmentally friendly smoke-suppressing rare earth synergistic flame-retardant PA6 fiber obtained in this embodiment is reduced by 30.5%, and the total smoke release (TSR) is reduced by 31.8%; the flame-retardant performance of the environmentally friendly smoke-suppressing rare earth synergistic flame-retardant PA6 fiber is further studied by limiting oxygen index test and UL94 vertical burning test, and compared with pure PA6 fiber, the LOI value is significantly increased and can be increased to 31.5%; the strength test shows that the breaking strength of the environmentally friendly smoke-suppressing rare earth synergistic flame-retardant PA6 fiber is 3.0 cN / dtex.
[0047] Example 2
[0048] The structure of the phosphorus-silicon synergistic flame retardant used in this embodiment is as follows:
[0049] wherein x = 10.
[0050] 85 parts of PA6 chips with water content of ≤100 ppm, 1.5 parts of nano lanthanum oxide, 13 parts of phosphorus-silicon synergistic flame retardant, and 0.5 parts of antioxidant (Doverphos S-9228) were uniformly mixed; then, the mixture was fed into a twin-screw melt extruder, and after melt extrusion, water cooling, granulation, extraction, and drying, a flame-retardant PA6 master batch was prepared by granulation, wherein the melt extrusion temperature setting parameters of the twin-screw melt extruder were as follows: zone 1 temperature: 230°C; zone 2 temperature: 230°C; zone 3 temperature: 230°C; zone 4 temperature: 240°C; and zone 5 temperature: 240°C.
[0051] The flame-retardant PA6 master batch was placed in a drum dryer and dried at 110°C for 10 h until the water content of the master batch was less than 100 ppm. Then, the dried flame-retardant PA6 master batch was fed into a spinning box, and the spinning parameters were set as follows: zone 1 temperature: 240°C; zone 2 temperature: 245°C; zone 3 temperature: 250°C; zone 4 temperature: 255°C; and spinning speed: 3800 m / min; then, after extrusion, side blowing, bunching, drawing, and winding, an environmentally friendly smoke-suppressing rare earth synergistic flame-retardant PA6 fiber was obtained. The side blowing temperature was 20°C, the air speed was 0.4 m / s, and the drawing multiple was 3 times.
[0052] A micro-combustion calorimeter (MCC, Novmark) was used to evaluate the heat release behavior of the sample. The test standard was ASTM D7309-7, the temperature range was 30-900°C, and the heating rate was 1°C / s. It was detected that compared with pure PA6 fiber, the total heat release (THR) of the environmentally friendly smoke-suppressing rare earth synergistic flame-retardant PA6 fiber obtained in this embodiment decreased by 30.5%, and the total smoke release (TSR) decreased by 31.8%; the flame-retardant performance of the environmentally friendly smoke-suppressing rare earth synergistic flame-retardant PA6 fiber was further studied by limiting oxygen index test and UL94 vertical burning test, and compared with pure PA6 fiber, the LOI value increased significantly and could increase to 31.4%; through strength detection, the breaking strength of the environmentally friendly smoke-suppressing rare earth synergistic flame-retardant PA6 fiber was 3.0 cN / dtex.
[0053] Example 3
[0054] The structure of the phosphorus-silicon synergistic flame retardant used in this embodiment is as follows:
[0055] y = 8.
[0056] 92 parts of PA6 chips with water content of ≤100 ppm, 0.5 parts of nano lanthanum oxide, 7.3 parts of phosphorus-silicon synergistic flame retardant, and 0.2 parts of antioxidant (Doverphos S-9228) were uniformly mixed; then, the mixture was fed into a twin-screw melt extruder, and after melt extrusion, water cooling, granulation, extraction, and drying, a flame-retardant PA6 master batch was prepared by granulation, wherein the melt extrusion temperature setting parameters of the twin-screw melt extruder were as follows: zone 1 temperature: 230°C; zone 2 temperature: 235°C; zone 3 temperature: 235°C; zone 4 temperature: 245°C; and zone 5 temperature: 245°C.
[0057] The flame-retardant PA6 master batch was placed in a drum dryer and dried at 120°C for 8h until the water content of the master batch was less than 100 ppm. Then, the dried flame-retardant PA6 master batch was fed into a spinning box, and the spinning parameters were set as follows: zone 1 temperature: 245°C; zone 2 temperature: 250°C; zone 3 temperature: 255°C; zone 4 temperature: 255°C; spinning speed: 4500 m / min; and then, after extrusion, side blowing, bunching, drawing, and winding, an environmentally friendly smoke-suppressing rare earth synergistic flame-retardant PA6 fiber was obtained. The side blowing temperature was 18°C, the air speed was 0.6 m / s, and the drawing ratio was 5 times.
[0058] A micro-combustion calorimeter (MCC, Novmark) was used to evaluate the heat release behavior of the sample. The test standard was ASTM D7309-7, the temperature range was 30-900°C, and the heating rate was 1°C / s. The test results showed that compared with pure PA6 fiber, the total heat release (THR) of the environmentally friendly smoke-suppressing rare earth synergistic flame-retardant PA6 fiber obtained in this embodiment decreased by 20.2%, and the total smoke release (TSR) decreased by 21.5%; the flame-retardant performance of the environmentally friendly smoke-suppressing rare earth synergistic flame-retardant PA6 fiber was further studied by limiting oxygen index test and UL94 vertical burning test, and compared with pure PA6 fiber, the LOI value increased significantly and could reach 28.6%; the strength test showed that the breaking strength of the environmentally friendly smoke-suppressing rare earth synergistic flame-retardant PA6 fiber was 3.3 cN / dtex.
[0059] Example 4
[0060] The structure of the phosphorus-silicon synergistic flame retardant used in this embodiment is as follows:
[0061] wherein y = 5.
[0062] 88 parts of PA6 chips with water content ≤100 ppm, 1 part of nano lanthanum oxide, 10.5 parts of phosphorus-silicon synergistic flame retardant, and 0.5 parts of antioxidant (Doverphos S-9228) are uniformly mixed; then, the mixture is fed into a twin-screw melt extruder, and after melt extrusion, water cooling, granulation, extraction, and drying, a flame-retardant PA6 master batch is prepared by granulation, wherein the melt extrusion temperature setting parameters of the twin-screw melt extruder are: zone 1 temperature: 230℃; zone 2 temperature: 230℃; zone 3 temperature: 240℃; zone 4 temperature: 240℃; zone 5 temperature: 245℃.
[0063] The flame-retardant PA6 master batch is placed in a drum dryer and dried at 120℃ for 8h until the water content of the master batch is less than 100 ppm. Then, the dried flame-retardant PA6 master batch is fed into a spinning box, and the spinning parameters are set as follows: zone 1 temperature: 240℃; zone 2 temperature: 245℃; zone 3 temperature: 250℃; zone 4 temperature: 255℃; spinning speed: 3500m / min; then, after extrusion, side blowing, bunching, drawing, and winding, an environmentally friendly smoke-suppressing rare earth synergistic flame-retardant PA6 fiber is obtained. Among them, the side blowing temperature is 22℃, the wind speed is 0.5m / s; the drawing ratio is 3 times.
[0064] A micro-combustion calorimeter (MCC, Novmark) is used to evaluate the heat release behavior of the sample. Test standard: ASTM D7309-7, temperature range: 30-900℃, heating rate: 1℃ / s. It is detected that compared with pure PA6 fiber, the total heat release (THR) of the environmentally friendly smoke-suppressing rare earth synergistic flame-retardant PA6 fiber obtained in the embodiment is reduced by 28.9%, and the total smoke release (TSR) is reduced by 29.2%; the flame-retardant performance of the environmentally friendly smoke-suppressing rare earth synergistic flame-retardant PA6 fiber is further studied by limiting oxygen index test and UL94 vertical burning test, and compared with pure PA6 fiber, the LOI value is increased significantly and can be increased to 30.4%; through strength detection, the breaking strength of the environmentally friendly smoke-suppressing rare earth synergistic flame-retardant PA6 fiber is 2.9cN / dtex.
[0065] The above only describes the preferred embodiments of the present application, and it should be noted that for ordinary skilled persons in the art, without departing from the principles of the present application, several improvements and refinements can be made, and these improvements and refinements should also be considered as the protection scope of the present application.
Claims
1. An environmentally friendly smoke-suppressing rare earth synergistic flame-retardant PA6 fiber, characterized in that, Prepared from raw materials comprising the following parts by weight: PA6 chips 85-95 parts, nano-rare earth 0.5-2 parts, phosphorus-silicon synergistic flame retardant 4-13 parts, antioxidant 0-0.5 parts.
2. The environmentally friendly smoke suppressing rare earth synergistic flame-retardant PA6 fiber according to claim 1, characterized in that, The nano-rare earth includes one or several of nano lanthanum oxide, nano cerium oxide and nano neodymium oxide. 3.The environmentally-friendly smoke-reducing rare earth synergistic flame-retardant PA6 fiber according to claim 2, characterized in that, The structural formula of the phosphorus-silicon synergistic flame retardant includes formula 1 or formula 2: Wherein, x = 5-10, y = 5-10.
4. The environmentally friendly smoke suppressing rare earth synergistic flame-retardant PA6 fiber according to any one of claims 1-3, characterized in that, The antioxidant includes Doverphos S-9228.
5. The environmentally friendly smoke suppressing rare earth synergistic flame-retardant PA6 fiber according to claim 4, characterized in that, The water content of the PA6 chips is ≤100 ppm.
6. The preparation method of the environmentally friendly smoke-suppressing rare earth synergistic flame-retardant PA6 fiber according to any one of claims 1-5, characterized in that, Comprising the following steps: S1, after mixing all raw materials to obtain a mixture, the mixture is sequentially melt extruded, water cooled, granulated, extracted, dried, and granulated to obtain a flame-retardant PA6 masterbatch; S2, the flame-retardant PA6 masterbatch is sequentially dried, spun, extruded, side blown, bundled, drawn, and wound to obtain an environmentally friendly smoke-suppressing rare earth synergistic flame-retardant PA6 fiber.
7. The preparation method according to claim 6, characterized in that In the step S1, the temperature of melt extrusion is 225-250℃.
8. The production method according to claim 6 or 7, characterized by, In the step S2, the temperature of drying is 100-120℃, and the time of drying is 8-12h; the water content of the flame-retardant PA6 masterbatch after drying is ≤100 ppm.
9. The production method according to claim 8, characterized by, In the step S2, the parameters of spinning are as follows: the temperature of the first zone is 235-245℃, the temperature of the second zone is 245-255℃, the temperature of the third zone is 245-260℃, and the temperature of the fourth zone is 250-260℃; the speed of spinning is 2500-4500 m / min.
10. The production method according to claim 6, 7 or 9, characterized in that, In the step S2, the temperature of side blowing is 18-22℃, the wind speed is 0.4-0.6 m / s; the draw ratio is 3-5 times.