High-efficiency cool-feeling nylon special color master batch and preparation method thereof

Abstract

The application discloses a high-efficiency cool-feeling special color master batch for nylon and a preparation method thereof, and relates to the technical field of functional master batches and resin modification. The high-efficiency cool-feeling special color master batch for nylon is prepared from the following components in parts by mass: carrier resin 40-70 parts, cool-feeling functional material 15-25 parts, dispersing agent 3-10 parts, pigment 5-25 parts, auxiliary processing aid 0.5-5 parts, and antioxidant 1.5-1.5 parts. The antioxidant can effectively inhibit the oxidative degradation of the color master batch in high-temperature processing and long-term use of the fabric, reduces problems such as yellowing and mechanical property reduction, and prolongs the stable use period of the color master batch and the fabric.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of functional masterbatch and resin modification, and particularly relates to a high-efficiency cooling special color masterbatch for nylon and a preparation method thereof. BACKGROUND

[0002] Nylon (polyamide) is a high-performance fiber commonly used in the textile field, and is widely used in cooling fabrics (such as summer clothes and sportswear) due to its excellent mechanical strength and spinning adaptability. The function of cooling nylon fabric is realized by relying on special color masterbatch, which needs to meet the core requirements of uniform coloring, long-lasting cooling and stable base material, and the antioxidant performance is a key factor to ensure the long-term stability of the color masterbatch and the subsequent fabric.

[0003] The nylon molecular chain contains amide bonds, which are easily oxidized and degraded by external factors during processing and use: on the one hand, the preparation of color masterbatch needs to be melt blended by a double-screw extruder (processing temperature 210-250 DEG C), and the high-temperature environment will accelerate the breakage of nylon molecular chain, causing the color masterbatch to turn yellow and the mechanical properties to decrease, and it may also cause broken yarn and loose yarn during subsequent spinning; on the other hand, the cooling fabric is in long-term contact with light and oxygen during use, which is easy to cause the cooling function to attenuate (such as the decrease of the bonding force between the cooling particles and the oxidized nylon base material), the fabric to become hard, and the service life to be shortened.

[0004] The compatibility problem of the dispersant, pigment and other components in the color masterbatch with the traditional antioxidant may also cause the poor formability of the color masterbatch (the appearance of burrs during granulation), the easy caking after drying, and the increase of subsequent processing cost. In summary, the existing antioxidant system cannot meet the comprehensive requirements of high-temperature resistance and long-term antioxidant of the high-efficiency cooling special color masterbatch for nylon, and the development of a new type of antioxidant and a matching system becomes the key to solving the stability problem of the cooling nylon color masterbatch. SUMMARY

[0005] In view of the problems of insufficient high-temperature resistance and long-term antioxidant of the existing antioxidant, which leads to weak antioxidant performance of the color masterbatch, yellowing of the color masterbatch, and performance attenuation of the color masterbatch, a high-efficiency cooling special color masterbatch for nylon and a preparation method thereof are provided to realize excellent antioxidant performance, uniform coloring, excellent performance, and adapt to nylon processing, and improve the stability of the color masterbatch and the fabric.

[0006] To achieve the above-mentioned purpose, the technical scheme adopted by the present application is that a high-efficiency cooling special color masterbatch for nylon is prepared from the following components by mass fraction: carrier resin 40-70 parts, cooling functional material 15-25 parts, dispersant 3-10 parts, pigment 5-25 parts, auxiliary processing aid 0.5-5 parts, and antioxidant 1.5-1.5 parts.

[0007] The antioxidant is a compound shown in formula 1.

[0008] Formula 1: ;

[0009] R1 in the Formula 1 is a substituent, and n is the number of substituents;

[0010] R1 is selected from H, alkyl with carbon atoms number in the range of 1-4, alkoxy with carbon atoms number in the range of 1-5;

[0011] n is selected from 1, 2.

[0012] Further, the carrier resin is selected from one or mixture of both of polycaprolactam (PA6) and polyhexamethylene adipamide (PA66).

[0013] Further, the cool-feeling functional material is selected from one or mixture of more than one of natural mica, silicon dioxide, boron nitride with particle size in the range of 1-10 μm.

[0014] Further, the dispersant is selected from one or more than one of polyethylene wax, oxidized polyethylene wax, zinc stearate, calcium stearate, ethylene bis-stearamide.

[0015] Further, the auxiliary processing aid is selected from one or more than one of oleic acid amide and erucic acid amide.

[0016] Further, the pigment is selected from one or more than one of titanium dioxide, iron oxide, carbon black, phthalocyanine blue, phthalocyanine green, permanent yellow, permanent red, quinacridone red.

[0017] Further, the antioxidant is selected from any one of the compounds shown in the following structures:

[0018] ;

[0019] ;

[0020] .

[0021] A preparation method of a high-efficiency cool-feeling special color master batch for polyamide fiber, comprising the following steps:

[0022] a) adding the carrier resin, cool-feeling functional material, dispersant, pigment, auxiliary processing aid and antioxidant into a mixing machine, mixing at a rotating speed of 600-1200 rpm for 30-45 minutes to obtain a premix;

[0023] b) feeding the premix into a twin-screw extruder for melt blending and extrusion granulation, and the processing temperature of the twin-screw extruder is controlled in the range of 210-250℃;

[0024] c) the extruded melt strip is cooled and solidified through a water tank, and then cut into particles by a particle cutter, and the cut particles are dried and sieved to obtain the high-efficiency cool-feeling special color master batch for nylon.

[0025] Further, the step a) is carried out under nitrogen atmosphere.

[0026] Further, the mixing temperature of the mixing machine in the step a) is 40-60℃.

[0027] Further, the mixing in the step a) is first carried out at 600 rpm for 15 min, and then carried out at 1200 rpm for 15-30 min.

[0028] Further, the screw rotation speed of the twin-screw extruder in the step b) is 250-350 rpm.

[0029] The total hydroxyl group of the antioxidant molecule in the application can provide active hydrogen atoms (H•), directly capture active free radicals such as alkoxy radicals (RO•) and peroxide radicals (ROO•) generated in the process or use, and convert them into stable hydroperoxide (ROOH), thereby blocking the free radical chain reaction. The imino group can decompose the hydrogen peroxide (ROOH) generated in the oxidation process, and convert it into inert products such as alcohol and ketone, thereby reducing the source of free radical generation. The imino nitrogen atom can be chelated with trace metal ions (such as Fe 2+ , Cu + ) in the nylon processing equipment, thereby blocking the path of metal ion catalyzed oxidation reaction. The aromatic ring provides a large π conjugated system as a rigid planar structure, promotes the electron synergistic transmission between the phenolic hydroxyl group and the imino group, and enhances the overall molecular stability. The stereoscopic structure of the aromatic ring can protect the phenolic hydroxyl group and the imino group, and reduce the probability of oxidation, especially maintaining activity in high-temperature processing environment.

[0030] The application utilizes the triple antioxidant mechanism of the antioxidant, i.e. the phenolic hydroxyl group captures alkoxy radicals (RO·) and peroxide radicals (ROO·), the imino group decomposes hydrogen peroxide (ROOH) into inert small molecules, and the imino nitrogen atom chelates Fe 2+ / Cu +Metal ions - synergistic inhibition of oxidative chain reaction; and with the help of its aromatic ring large pi conjugated structure to ensure the thermal stability in 210-250℃ high temperature processing. By selecting poly (caprolactam) / poly (hexamethylene adipamide) carrier resin, realize the chemical structure consistency and high melting point (> 210℃) compatibility with nylon base material, avoid local oxidation; at the same time, with the synergistic effect of particle size of 1-10μm natural mica / silicon dioxide / boron nitride cooling material and polyethylene wax / stearate dispersant, prevent agglomeration to form oxidation hot spot, and through the auxiliary passivation of zinc / calcium stearate, the metal ions. Oleic acid amide / erucic acid amide and other processing aids reduce the friction heat and shear oxidation stress of the melt, and carbon black / titanium dioxide and other pigments provide ultraviolet shielding function to block the photooxidation path, finally in the process of nitrogen protection mixing, 40-60℃ temperature control premixing and 250-350rpm screw speed, the system solves the yellowing, degradation, cooling attenuation, spinning broken filament, caking and aging problems of nylon color master batch in high temperature processing and long-term use.

[0031] Compared with the prior art, the beneficial effects of the present application are:

[0032] 1. The oxidation resistance and stability are significantly improved: the color master batch can effectively inhibit the oxidative degradation of the color master batch in high temperature processing and long-term use of the fabric, reduce the yellowing, mechanical property decline and other problems, and prolong the stable use period of the color master batch and the fabric.

[0033] 2. The cooling function and coloring effect are better: the cooling functional material can be uniformly dispersed, avoiding the cooling attenuation caused by agglomeration, and the coloring is uniform, which can stably maintain the core function and appearance performance of the cooling nylon fabric.

[0034] 3. The processing adaptability and application reliability are improved: through component collocation optimization (such as auxiliary processing aid) and process improvement (such as nitrogen protection mixing), the forming problems such as burr and caking of the color master batch during processing are reduced, the risk of broken filament and hair in subsequent spinning is reduced, and the application stability is improved. DETAILED DESCRIPTION

[0035] Figure 1 The nuclear magnetic resonance spectrum of the antioxidant 1 described in the present application. DETAILED DESCRIPTION

[0036] The technical solutions of the present application will be described clearly and completely in combination with the drawings in the present application. Obviously, the described embodiments are only part of the embodiments of the present application, not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor belong to the scope of protection of the present application.

[0037] Example 1-1

[0038] Synthesis of antioxidant 1:

[0039] ;

[0040] 10 g of raw material 1, 5.93 g of raw material 2, and 19.62 g of triphenylphosphine were dissolved in 120 ml of dichloromethane. The reaction system was then purged under a nitrogen atmosphere and cooled to 0°C in an ice bath. 15.13 g of diisopropyl azodicarbonate was added to the reaction system, and the mixture was heated to room temperature for 4 hours. The solvent was evaporated to dryness, and the mixture was purified by silica gel column chromatography (mobile phase: petroleum ether: ethyl acetate = 3:1, v / v). The purified product was then evaporated to dryness to obtain 6.56 g of intermediate 1. The mass spectrometry (MS) of intermediate 1 was analyzed at m / z = 382 [MS+H]. + ].

[0041] ;

[0042] Under nitrogen protection, 6.56 g of intermediate 1 and 4.20 g of raw material 3 were dissolved in 90 mL of a mixed solvent of 1,4-dioxane / diisopropylamine (60 mL / 30 mL). 0.08 g of palladium acetate, 0.4 g of 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl, and 0.16 g of CuI were added to the above system, and the reaction was carried out at 90 °C for 5 h. After the reaction was completed, the temperature was slightly lowered, and the mixture was filtered through diatomaceous earth to remove salts and catalyst. The reaction solution was concentrated, separated by silica gel column chromatography, using a mixed solvent of n-heptane and ethyl acetate as the eluent, and evaporated to dryness to obtain 7.61 g of antioxidant 1. Antioxidant 1 was analyzed by mass spectrometry (MS, m / z = 549 [MS+H). + ].

[0043] Antioxidant 1 1 H NMR (Chloroform-d, Figure 1 ) δ 7.41 (d,1H), 7.12-7.05 (m, 2H),6.86-6.70 (m, 4H), 6.11 (q, 1H), 4.57 (d, 1H), 4.45 (p, 1H), 4.32 (dd, 1H),4.22 (s, 1H), 4.16 (m, 1H), 4.08 (dd, 1H), 4.03-3.94 (m, 2H), 3.79-3.66 (m,1H), 3.54 (t, 2H), 3.28 (m, 1H), 3.20 (s, 3H), 3.14-2.97 (m, 2H), 2.80 (m,2H), 2.66 (mt, 1H), 2.36 (d,3H), 1.24 (d, 3H), 1.13 (dd, 6H).

[0044] Example 1-2 to Example 1-6

[0045] Antioxidants 2-6 were prepared in Example 1-2 to Example 1-6 in turn, referring to the preparation method of Example 1-1, replacing the raw material 2 therein, and the rest being the same as Example 1-1, for details, see Table 1.

[0046] Table 1.

[0047]

[0048] Example 2

[0049] Preparation of a high-efficiency cool-feeling special color master batch for nylon:

[0050] 1. Raw material components:

[0051] Carrier resin, selected from: polycaprolactam, 60 parts, purchased from: Shanghai Dingfen Chemical Technology Co., Ltd.;

[0052] Cool-feeling functional material, selected from: silicon dioxide, particle size 5 μm, 15 parts, purchased from: Shijiazhuang Shuanglian Chemical Industry Co., Ltd.;

[0053] Dispersant, selected from: polyethylene wax, 6 parts, purchased from: Shanghai Dingfen Chemical Technology Co., Ltd.;

[0054] Pigment, selected from: titanium white, 15 parts, purchased from: Shanghai Yuejiang Titanium Dioxide Chemical Products Co., Ltd.;

[0055] Auxiliary processing aid, selected from: oleic acid amide, 2 parts, purchased from: Jiangxi Zhilian New Materials Co., Ltd.;

[0056] Antioxidant, selected from: antioxidant 1, 1.5 parts.

[0057] 2. Preparation method:

[0058] a) The carrier resin, cool-feeling functional material, dispersant, pigment, auxiliary processing aid and antioxidant were added to a high-speed mixer, mixed at 600 rpm for 15 min under nitrogen atmosphere protection, and then mixed at 1200 rpm for 20 min, the mixing temperature was controlled at 50°C, to obtain a premix;

[0059] b) The premix was sent into a twin-screw extruder, the screw speed was set at 300 rpm, the processing temperature was controlled according to four zones: Zone 1: 220°C, Zone 2: 230°C, Zone 3: 245°C, Zone 4: 235°C, and then extruded and granulated after melt blending;

[0060] c) extruded melt strands are cooled and solidified in a water tank, cut by a cutter, the granules are dried at 80℃ for 4 hours, and screened to remove granules with a size <0.5mm and >3mm, to obtain a high-efficiency cool-feeling special color master batch for nylon.

[0061] Examples 2 to 7

[0062] A high-efficiency cool-feeling special color master batch for nylon is prepared according to the preparation method of Example 2, wherein the antioxidant is replaced by antioxidant 2-antioxidant 6 in turn, and the rest is the same as Example 2.

[0063] Comparative Example 1

[0064] A high-efficiency cool-feeling special color master batch for nylon is prepared according to the preparation method of Example 2, wherein the antioxidant is replaced by antioxidant SP (CAS: 61788-44-1), and the rest is the same as Example 2.

[0065] Comparative Example 2

[0066] A high-efficiency cool-feeling special color master batch for nylon is prepared according to the preparation method of Example 2, wherein the antioxidant is replaced by antioxidant 330 (CAS: 1709-70-2), and the rest is the same as Example 2.

[0067] Comparative Example 3

[0068] A high-efficiency cool-feeling special color master batch for nylon is prepared according to the preparation method of Example 2, wherein the antioxidant is not added, and the rest is the same as Example 2.

[0069] Comparative Example 4

[0070] A high-efficiency cool-feeling special color master batch for nylon is prepared according to the preparation method of Example 2, wherein the auxiliary processing aid is not added, and the rest is the same as Example 2.

[0071] Performance test:

[0072] A high-efficiency cool-feeling special color master batch for nylon prepared in the examples and comparative examples is prepared into a fiber fabric through a color master batch fiber preparation process.

[0073] 1) Using a contact cold and warm feeling tester, in an environment with a temperature of 20℃±2℃ and a relative humidity of 65%±4%, cut 5 pieces of the sample to be tested, each with an area of 500pxx500px, and place them in a standard atmospheric environment for at least 1 hour. The test procedure is as follows: turn on the power supply and preheat for 15 minutes; turn on the hot plate heater switch and set the hot plate temperature to 35℃±0.1℃, and then turn on the guard ring heater switch after the temperature reaches the set value; set the cold plate to the desired temperature, which is generally 25℃, and then place the test sample on the cold plate with the skin facing up; when the hot plate temperature reaches 35℃, press the "qm" key and quickly place the hot plate vertically on the test sample; record the qm value, which is the contact cool feeling (transient maximum heat flow) of the test sample, with the unit being W / cm 2 Take the average of 5 test data and round to three decimal places. The data is shown in Table 2.

[0074] 2) Tensile strength test: The test method is GB / T 14337-2008, and the data is shown in Table 2.

[0075] 3) Aging resistance test: Place the fiber fabric in an aging oven, set the aging temperature to 60℃, the wind speed to 1m / s, the UV-A light source to irradiation, and the humidity to 75%RH, and then test the tensile strength after aging for 1200h and calculate the tensile strength retention rate. The data is shown in Table 2.

[0076] Table 2.

[0077]

[0078] The instant cool feeling value, tensile strength of each embodiment using the specific antioxidant of the application is slightly better than that of the comparative examples using traditional antioxidants or without adding antioxidants; the advantage of the embodiment is particularly significant in the tensile strength retention rate, which is much higher than that of various comparative examples. The performance of the comparative example without adding auxiliary processing aids is better than that of the comparative examples using traditional antioxidants or without antioxidants, but still not as good as that of the embodiment with auxiliary processing aids. In addition, the instant cool feeling value, tensile strength and tensile strength retention rate of each embodiment have small overall fluctuations and stable performance.

[0079] Although embodiments of the application have been shown and described, it is to be understood that the application is not limited to the details of the foregoing embodiment, and that various changes in the form and details thereof can be made without departing from the spirit and scope of the application. The scope of the application is defined by the appended claims and their equivalents.

Claims

1. A high-efficiency, cooling-feeling nylon-specific masterbatch, characterized in that, It is prepared from the following components in parts by weight: 40-70 parts carrier resin, 15-25 parts cooling functional material, 3-10 parts dispersant, 5-25 parts pigment, 0.5-5 parts auxiliary processing aid, and 1.5 parts antioxidant. The antioxidant is a compound represented by Formula 1; Formula 1: ; In Formula 1, R1 is a substituent and n is the number of substituents; The R1 is selected from: H, alkyl groups having 1-4 carbon atoms, and alkoxy groups having 1-5 carbon atoms; The n is selected from: 1, 2; The auxiliary processing agent is selected from one or more of oleamide and erucamide.

2. The high-efficiency cooling nylon masterbatch according to claim 1, characterized in that, The carrier resin is selected from one or a mixture of two of polycaprolactam and polyhexamethylene adipamide.

3. The high-efficiency cooling nylon masterbatch according to claim 1, characterized in that, The cooling functional material is selected from one or more of the following: natural mica, silicon dioxide, and boron nitride with a particle size in the range of 1-10 μm.

4. The high-efficiency cooling nylon masterbatch according to claim 1, characterized in that, The dispersant is selected from one or more of the following: polyethylene wax, oxidized polyethylene wax, zinc stearate, calcium stearate, and ethylene bis-stearamide.

5. The high-efficiency cooling nylon masterbatch according to claim 1, characterized in that, The antioxidant is selected from any one of the compounds shown in the following structures: ； ； 。 6. A method for preparing a high-efficiency cooling nylon masterbatch according to any one of claims 1-5, characterized in that, Includes the following steps: a) Add the carrier resin, cooling functional material, dispersant, pigment, auxiliary processing agent and antioxidant into a mixer and mix at a speed of 600-1200 rpm for 30-45 minutes to obtain a premix; b) The premixed material is fed into a twin-screw extruder for melt blending, extrusion granulation, and the processing temperature of the twin-screw extruder is controlled at 210-250℃; c) The extruded molten strip is cooled and solidified in a water tank, and then granulated by a pelletizer. After drying and screening, a high-efficiency cool-feeling nylon-specific masterbatch is obtained.

7. The method for preparing a high-efficiency cooling nylon masterbatch according to claim 6, characterized in that, Step a) is performed under a nitrogen atmosphere.

8. The method for preparing a high-efficiency cooling nylon masterbatch according to claim 6, characterized in that, The mixing temperature of the mixer in step a) is 40-60℃; In step a), the mixture is first mixed at 600 rpm for 15 minutes, and then mixed at 1200 rpm for 15-30 minutes.

9. The method for preparing a high-efficiency cooling nylon masterbatch according to claim 6, characterized in that, The screw speed of the twin-screw extruder in step b) is 250-350 rpm.

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