Special color master batch for high-efficiency cool chinlon and preparation method of special color master batch

Abstract

The invention discloses a special color master batch for high-efficiency cool chinlon and a preparation method of the special color master batch, and relates to the technical field of functional master batch and resin modification. The invention relates to a special color master batch for high-efficiency cool chinlon. The special color master batch is prepared from the following components in parts by mass: 40-70 parts of carrier resin, 15-25 parts of a cool functional material, 3-10 parts of a dispersing agent, 5-25 parts of pigment, 0.5-5 parts of an auxiliary processing aid and 1.5-1.5 parts of an antioxidant. Oxidation degradation of the color master batch in high-temperature processing and long-term use of the fabric can be effectively inhibited through oxidation resistance, the problems of yellowing, mechanical property reduction and the like are reduced, and the stable service cycle of the color master batch and the fabric is prolonged.

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 color masterbatch preparation 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 the nylon molecular chain, causing the color masterbatch to turn yellow, the mechanical properties to decrease, and possibly leading to 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 easily causes the cooling function to attenuate (such as the decreased 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 color masterbatch to have poor formability (with burrs during granulation), to be easy to cake after drying, and to increase the 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, leading 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 to 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: a high-efficiency cooling special color masterbatch for nylon is prepared from the following components by mass: 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. The antioxidant is a compound shown in formula 1. Formula 1: ; R1 in the formula 1 is a substituent, and n is the number of substituents; R1 is selected from H, alkyl with carbon atoms in the range of 1-4, and alkoxy with carbon atoms in the range of 1-5; n is selected from 1 and 2.

[0007] Further, the carrier resin is selected from one or mixture of both of polycaprolactam (PA6) and polyhexamethylene adipamide (PA66).

[0008] Further, the cool-feeling functional material is selected from one or mixture of two or more of natural mica, silicon dioxide, and boron nitride with particle size in the range of 1-10 μm.

[0009] Further, the dispersant is selected from one or more of polyethylene wax, oxidized polyethylene wax, zinc stearate, calcium stearate, and ethylene bis-stearamide.

[0010] Further, the auxiliary processing aid is selected from one or more of oleic acid amide and erucic acid amide.

[0011] Further, the pigment is selected from one or more of titanium dioxide, iron oxide, carbon black, phthalocyanine blue, phthalocyanine green, permanent yellow, permanent red, and quinacridone red.

[0012] Further, the antioxidant is selected from any one of the compounds shown in the following structures: ; ; .

[0013] A preparation method of a high-efficiency cool-feeling special color master batch for polyamide fiber, comprising the following steps: a) adding the carrier resin, cool-feeling functional material, dispersant, pigment, auxiliary processing aid, and antioxidant into a mixing machine, and mixing at a rotation speed of 600-1200 rpm for 30-45 minutes to obtain a premix; b) feeding the premix into a twin-screw extruder for melt blending and extrusion granulation, and controlling the processing temperature of the twin-screw extruder at 210-250℃; c) cooling and solidifying the extruded melt strip through a water tank, and then cutting the granules through a granulator, and then drying and screening the cut granules to obtain a high-efficiency cool-feeling special color master batch for polyamide fiber.

[0014] Further, the step a) is performed under a nitrogen atmosphere.

[0015] Further, the mixing temperature of the mixing machine in the step a) is 40-60℃.

[0016] Further, the mixing in step a) is first mixed at 600 rpm for 15 min, and then mixed at 1200 rpm for 15-30 min.

[0017] Further, the screw rotation speed of the twin-screw extruder in step b) is 250-350 rpm.

[0018] The total hydroxyl group of the antioxidant molecule in the present application can provide active hydrogen atoms (H•), directly capture active free radicals such as alkoxy radicals (RO•) and peroxy radicals (ROO•) generated during processing or use, and convert them into stable hydroperoxides (ROOH), thereby blocking the free radical chain reaction. The imino group can decompose the hydrogen peroxide (ROOH) generated during 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 chelate 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 rigid planar structure and a large π conjugated system, which promotes the electron synergistic transmission between the phenolic hydroxyl group and the imino group, and enhances the overall molecular stability. The stereostructure of the aromatic ring can protect the phenolic hydroxyl group and the imino group, thereby reducing the probability of oxidation, especially maintaining activity under high-temperature processing environment.

[0019] The present application cooperatively inhibits the oxidation chain reaction through the triple antioxidant mechanism of the antioxidant, i.e. the phenolic hydroxyl group captures alkoxy radicals (RO•) and peroxy radicals (ROO•), the imino group decomposes hydrogen peroxide (ROOH) into inert small molecules, and the imino nitrogen atom chelates with metal ions such as Fe 2+ / Cu + . The large π conjugated structure of the aromatic ring ensures the thermal stability during high-temperature processing at 210-250℃. By selecting polyhexamethylene adipamide / polyhexamethylene adipamide carrier resin, the chemical structure consistency and high melting point (>210℃) compatibility with nylon base material are realized, thereby avoiding local oxidation. Meanwhile, through the synergistic effect of natural mica / silicon dioxide / boron nitride cooling materials with a particle size of 1-10 μm and polyethylene wax / stearate dispersant, agglomeration to form oxidation hot spots is prevented, and zinc / calcium stearate is used to assist in passivating metal ions. Processing aids such as oleic acid amide / erucic acid amide reduce the heat generated by friction and shear oxidation stress of the melt, and pigments such as carbon black / titanium dioxide provide ultraviolet shielding function to block the photo-oxidation path. Ultimately, under the synergistic effect of nitrogen protection mixing, 40-60℃ temperature control premixing, and 250-350 rpm screw rotation speed, the yellowing, degradation, cooling attenuation, spinning broken filament, caking and aging problems of nylon color master batch during high-temperature processing and long-term use are solved.

[0020] Compared with the prior art, the present application has the following beneficial effects: 1. Oxidation resistance and stability are significantly improved: It can effectively inhibit the oxidative degradation of color masterbatch in high temperature processing and long-term use of fabric, reduce yellowing, mechanical property decline and other problems, and prolong the stable use period of color masterbatch and fabric.

[0021] 2. Cooling function and coloring effect are better: The cooling functional material can be uniformly dispersed, avoiding the attenuation of cooling caused by aggregation, and the coloring is uniform, which can stably maintain the core function and appearance performance of cooling nylon fabric.

[0022] 3. Processing adaptability and application reliability are improved: Through component matching optimization (such as auxiliary processing aid) and process improvement (such as nitrogen protection mixing), the forming problems such as burr and caking of color masterbatch during processing are reduced, the risk of broken and hairy yarn during subsequent spinning is reduced, and the application stability is improved. BRIEF DESCRIPTION OF DRAWINGS

[0023] Figure 1 The nuclear magnetic chart of the antioxidant 1 described in the application. DETAILED DESCRIPTION

[0024] The technical solutions of the application will be described clearly and completely below in combination with the drawings in the application. Obviously, the described embodiments are only part of the embodiments of the application, not all the embodiments. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative labor belong to the scope of protection of the application.

[0025] Example 1-1 Synthesis of antioxidant 1: ; Dissolve 10 g of raw material 1, 5.93 g of raw material 2 and 19.62 g of triphenylphosphine in 120 ml of dichloromethane, replace the reaction system with nitrogen atmosphere, cool to 0℃ in ice bath, add 15.13 g of diisopropyl azodicarboxylate to the reaction system, warm to room temperature and react for 4 hours, spin dry the solvent, purify by silica gel column chromatography (mobile phase is petroleum ether: ethyl acetate = 3:1, v / v), spin dry to obtain 6.56 g of intermediate 1. The mass spectrum MS of intermediate 1 is m / z = 382 [MS+H + ].

[0026] ; Under nitrogen protection, 6.56 g of intermediate 1, 4.20 g of raw material 3 were dissolved in a mixed solvent of 90 mL of 1,4-dioxane / diisopropylamine (60 mL / 30 mL), 0.08 g of palladium acetate, 0.4 g of 2-dicyclohexylphosphine-2',4',6'-triisopropyl biphenyl, 0.16 g of CuI were added to the above system, and the reaction was carried out at 90°C for 5h. After the reaction was completed, the temperature was slightly lowered, and diatomite was used for filtration to remove the salt and catalyst. The reaction solution was concentrated and separated by silica gel column chromatography, using a mixed solvent of n-heptane and ethyl acetate as the eluent, and then rotary evaporation was performed to obtain 7.61 g of antioxidant 1. Mass spectrum MS, m / z = 549 [MS+H + ]。

[0027] 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), 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)。

[0028] Examples 1-2 to 1-6 Antioxidants 2-6 were prepared in Examples 1-2 to 1-6 in turn, referring to the preparation method of Example 1-1, replacing raw material 2 therein, and the rest being the same as Example 1-1. See Table 1 for details.

[0029] Table 1.

[0030]

[0031] Example 2 Preparation of a high-efficiency cool-feeling special color master batch for nylon: 1. Raw material components: Carrier resin, selected from: polyhexalactam, 60 parts, purchased from Shanghai Dingfen Chemical Technology Co., Ltd. Cooling functional material, selected from: silicon dioxide, particle size 5 μm, 15 parts, purchased from: Shijiazhuang Shuanglian Chemical Industry Co., Ltd.; Dispersant, selected from: polyethylene wax, 6 parts, purchased from: Shanghai Dingfen Chemical Technology Co., Ltd.; Pigment, selected from: titanium dioxide, 15 parts, purchased from: Shanghai Yuejiang Titanium Dioxide Chemical Products Co., Ltd.; Auxiliary processing aid, selected from: oleic acid amide, 2 parts, purchased from: Jiangxi Zhilian New Material Co., Ltd.; Antioxidant, selected from: antioxidant 1, 1.5 parts.

[0032] 2. Preparation method: a) The carrier resin, cooling functional material, dispersant, pigment, auxiliary processing aid and antioxidant are added to a high-speed mixer, mixed at 600 rpm for 15 min, and then mixed at 1200 rpm for 20 min under the protection of nitrogen atmosphere, and the mixing temperature is controlled at 50°C, to obtain a premix; b) The premix is sent into a twin-screw extruder, and the screw speed is set to 300 rpm, and the processing temperature is controlled by four zones: zone 1: 220°C, zone 2: 230°C, zone 3: 245°C, and zone 4: 235°C. After melt blending, extrusion granulation is performed; c) The extruded melt strip is cooled and solidified in a water tank, and then cut into particles by a granulator. The granules are dried at 80°C for 4 hours, and the particles with a particle size of <0.5 mm and >3 mm are removed by screening, to obtain a high-efficiency cooling nylon special color master batch.

[0033] Examples 2 to 7 A high-efficiency cooling nylon special color master batch is prepared by referring to the preparation method of Example 2, and replacing the antioxidant therein with antioxidants 2-6 in turn, and the rest remains the same as Example 2.

[0034] Comparative Example 1 A high-efficiency cooling nylon special color master batch is prepared by referring to the preparation method of Example 2, and replacing the antioxidant therein with antioxidant SP (CAS: 61788-44-1), and the rest remains the same as Example 2.

[0035] Comparative Example 2 A high-efficiency cooling nylon special color master batch is prepared by referring to the preparation method of Example 2, and replacing the antioxidant therein with antioxidant 330 (CAS: 1709-70-2), and the rest remains the same as Example 2.

[0036] Comparative Example 3 A high-efficiency cooling nylon special color master batch is prepared by referring to the preparation method of Example 2, and not adding the antioxidant therein, and the rest remains the same as Example 2.

[0037] Comparative Example 4 A high-efficiency cool-feeling special color master batch for nylon was prepared according to the preparation method of Example 2, without adding the auxiliary processing aid therein, and the rest was the same as that of Example 2.

[0038] Performance test: A high-efficiency cool-feeling special color master batch for nylon prepared in the examples and comparative examples was prepared into a fiber fabric through a color master batch fiber preparation process.

[0039] 1) A contact cold and warm feeling tester was used, 5 pieces of sample to be tested were cut at a temperature of 20℃±2℃ and a relative humidity of 65%±4%, and the area was 500pxx500px. The test steps were 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; set the cold plate to the required temperature, generally 25℃, and then place the sample on the cold plate with the body facing up. When the hot plate temperature reaches 35℃, press the “qm” key, and at the same time, quickly place the hot plate vertically on the sample. Record the qm value, which is the contact cool feeling (transient maximum heat flow) of the sample, and the unit is W / cm 2 . Take the average of 5 test data, and round to three decimal places. The data are shown in Table 2.

[0040] 2) Tensile strength test: the test method was GB / T 14337-2008, and the data are shown in Table 2.

[0041] 3) Aging resistance experiment: the fiber fabric was placed in an aging oven, the aging temperature was set to 60℃, the wind speed was 1m / s, the UV-A light source was irradiated, the humidity was 75%RH, and the aging time was 1200h. The tensile strength was tested, and the tensile strength retention rate was calculated. The data are shown in Table 2.

[0042] Table 2.

[0043]

[0044] The instant cool feeling value and tensile strength of each example using the specific antioxidant of the application are slightly better than those of the comparative examples using traditional antioxidants or without adding antioxidants. The advantage of the examples is particularly significant in the tensile strength retention rate, which is much higher than that of various comparative examples. The comparative examples without adding auxiliary processing aids have better performance than the comparative examples using traditional antioxidants or without adding antioxidants, but still not as good as the examples with auxiliary processing aids. In addition, the instant cool feeling value, tensile strength and tensile strength retention rate of each example have small overall fluctuations, and the performance is stable.

[0045] While embodiments of the application have been shown and described, it is to be understood that the embodiments described are merely exemplary of the principles and application of the present application. Numerous modifications and adaptions can be effected without departing from the spirit and scope of the present application, which is not limited to the exact construction and arrangement described. It is intended, therefore, to cover all modifications and adaptions that fall within the scope of the claims and their equivalents.

Claims

1. A high-efficiency cool-feeling special color master batch for nylon, characterized in that, Prepared from the following components by mass parts: carrier resin 40-70 parts, cool functional material 15-25 parts, dispersant 3-10 parts, pigment 5-25 parts, auxiliary processing aid 0.5-5 parts, antioxidant 1.5-1.5 parts; The antioxidant is a compound shown in formula 1; Formula 1: ; R1 in formula 1 is a substituent, and n is the number of substituents; R1 is selected from H, alkyl with carbon atom number 1-4, alkoxy with carbon atom number 1-5; n is selected from 1, 2.

2. The high-efficiency cool-feeling nylon special color master batch according to claim 1, characterized in that, The carrier resin is selected from one or mixture of both of polycaprolactam, poly(hexamethylene adipamide).

3. The high-efficiency cool-feeling nylon special color master batch according to claim 1, characterized in that, The cool functional material is selected from one or mixture of two or more of natural mica, silicon dioxide, boron nitride with particle size in the range of 1-10 μm.

4. The high-efficiency cool-feeling nylon special color master batch according to claim 1, characterized in that, The dispersant is selected from one or more of polyethylene wax, oxidized polyethylene wax, zinc stearate, calcium stearate, ethylene bis-stearamide.

5. The high-efficiency cool-feeling nylon special color master batch according to claim 1, characterized in that, The auxiliary processing aid is selected from one or more of oleic acid amide, erucic acid amide.

6. The high-efficiency cool-feeling nylon special color master batch according to claim 1, characterized in that, The antioxidant is selected from any one of the compounds shown in the following structure: ； ； 。 7. A method for preparing a high-efficiency cool-feeling nylon-specific masterbatch according to any one of claims 1-6, characterized in that, Comprising the following steps: a) adding the carrier resin, cool functional material, dispersant, pigment, auxiliary processing aid and antioxidant into a mixer, mixing at a speed of 600-1200 rpm for 30-45 minutes to obtain a premix; b) feeding the premix into a twin-screw extruder for melt blending, extruding and granulating, the processing temperature of the twin-screw extruder is controlled at 210-250℃; c) cooling and solidifying the extruded melt strip through a water tank, then cutting the granules through a granulator, and after drying and screening, a high-efficiency cool nylon special color master batch is obtained.

8. The preparation method of the high-efficiency cool-feeling nylon special color master batch according to claim 7, characterized in that, The step a) is carried out under nitrogen atmosphere.

9. The method for preparing the high-efficiency cool-feeling nylon special color master batch according to claim 7, characterized in that, The mixing temperature of the mixer in step a) is 40-60℃; In step a), the mixing is first carried out at 600 rpm for 15 min, and then at 1200 rpm for 15-30 min.

10. The method for preparing the high-efficiency cool-feeling nylon special color master batch according to claim 7, characterized in that, The screw speed of the twin-screw extruder in step b) is 250-350 rpm.

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