Efficient polyester color master batch and preparation method thereof

Abstract

The invention discloses an efficient polyester color master batch and a preparation method thereof, and relates to the technical field of polyester color master batches. The high-efficiency polyester color master batch is prepared from the following raw materials in parts by mass: 40-70 parts of a polyamide carrier, 20-50 parts of a coloring agent, 5-15 parts of a dispersing agent, 1-5 parts of a lubricating agent and 0.5-3 parts of an antioxidant. The special antioxidant specially designed for a polyamide carrier is adopted, the compatibility with the carrier is improved based on the principle of similar dissolves, the problem that a traditional antioxidant is uneven in dispersion to form an anti-oxidation blind area is fundamentally solved, meanwhile, volatilization and migration in the processing process are inhibited by means of high thermal stability of the molecular structure of the antioxidant, and the anti-oxidation performance of the carrier is improved. The color master batch endows a polyester product with a longer anti-oxidation protection effect, and the problems of yellowing, chromatic aberration and the like caused by oxidation in the processing and using processes of the product can be effectively reduced.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of polyester color masterbatch, and particularly relates to a high-efficiency polyester color masterbatch and a preparation method thereof. BACKGROUND

[0002] Polyester has become the core substrate in the fields of textiles, packaging, engineering plastics and the like due to excellent mechanical strength, weather resistance and forming processability. As a key material for coloring polyester, the performance of the color masterbatch directly determines the appearance stability and service life of the final product, and the oxidation resistance is one of the core indicators restricting the quality of the color masterbatch. During the extrusion and spinning process of polyester at 200-250 DEG C, and during the use of the finished product in outdoor and high-temperature environments, the polyester is prone to react with oxygen to cause molecular chain oxidative degradation, resulting in yellowing of the product, attenuation of coloring depth, and even significant decrease in mechanical properties such as tensile strength and elongation at break.

[0003] The current polyester color masterbatch mostly uses traditional antioxidants such as hindered phenol and phosphite, which has obvious technical shortcomings. On the one hand, the compatibility of such antioxidants with the polyamide carrier commonly used in the color masterbatch is poor, and uneven dispersion is prone to occur during high-speed mixing and melt extrusion, forming a local "antioxidant blind area". At high temperatures, the antioxidants are also prone to volatilization or migration to the surface of the product, resulting in rapid attenuation of the oxidation resistance protection effect over time. On the other hand, the antioxidant efficiency is difficult to meet the high-end requirements. For example, outdoor polyester fabrics need to withstand ultraviolet-oxygen synergistic aging for a long time, and food packaging polyester needs to maintain color stability after high-temperature sterilization. Due to the insufficient oxidation resistance of traditional color masterbatch, the color and luster of the product decrease significantly after 3-6 months of use, seriously affecting the appearance of the product in use.

[0004] In addition, there is an "antagonistic effect" between the colorants (such as phthalocyanine and quinacridone pigments) and the traditional antioxidants in the existing formula. Some pigments can catalyze the oxidation reaction process, further accelerating the degradation of the product. With the increasing requirements of downstream industries on the weather resistance and durability of polyester products, the oxidation resistance defect of traditional color masterbatch has become a key bottleneck restricting the application of polyester materials in high-end fields such as outdoor building materials and medical packaging. It is urgent to develop a polyester color masterbatch technical solution that is suitable for polyamide carrier, has high antioxidant efficiency and is long-acting and stable. SUMMARY

[0005] The present application aims to solve the problems of insufficient oxidation resistance of existing polyester color masterbatch, poor compatibility of traditional antioxidants with polyamide carrier, easy volatilization and migration, and antagonistic effect with colorants, and provides a high-efficiency polyester color masterbatch. The antioxidant of the polyester color masterbatch is suitable for the carrier, is uniformly dispersed, is long-acting and stable, avoids the adverse effects of the colorants, improves the processing stability of the color masterbatch, prolongs the color retention life of the polyester product, and meets the requirements of high-end fields.

[0006] To achieve the above object, the technical scheme adopted by the present application is as follows: A high-efficiency polyester color master batch is prepared from raw materials including the following components in parts by mass: polyamide carrier 40-70 parts, colorant 20-50 parts, dispersant 5-15 parts, lubricant 1-5 parts, and antioxidant 0.5-3 parts. The antioxidant is a compound shown in formula 1. The formula 1 is: ; R1 in the formula 1 is a substituent. The R1 is selected from any one of fluorine, trifluoromethyl, cyano, alkyl with carbon atom number of 1-5, and alkoxy with carbon atom number of 1-5.

[0007] Further, the polyamide carrier is one or a mixture of several of polyamide 6 (PA6), polyamide 66 (PA66), and polyamide 1010 (PA1010).

[0008] Further, the colorant is one or a mixture of several of high-pigment carbon black, phthalocyanine blue, phthalocyanine green, permanent red, permanent yellow, quinacridone red, and isoindolinone yellow.

[0009] Further, the dispersant is one or a mixture of several of polyethylene wax, oxidized polyethylene wax, polypropylene wax, EVA wax, zinc stearate, and calcium stearate.

[0010] Further, the lubricant is one or a mixture of several of stearic acid, stearic acid amide, oleic acid amide, and ethylene bis-stearic acid amide.

[0011] Further, the antioxidant is any one of the compounds shown in the following structures: ; ; ; .

[0012] A preparation method of the high-efficiency polyester color master batch includes the following steps: (1) Pre-mixing: the polyamide carrier, colorant, dispersant, lubricant, and antioxidant are added into a mixing machine, and mixed at a rotation speed of 600-1200 r / min for 30-45 minutes to obtain a pre-mixed material; (2) Melt extrusion: the pre-mixed material is sent into a double-screw extruder for melt blending and extrusion granulation, and the temperature of each section of the double-screw extruder is set as follows: zone 1 200-220℃, zone 2 220-240℃, zone 3 240-250℃, zone 4 245-255℃, and the head 245-255℃, and the screw rotation speed is 200-400 r / min. (3) Cooling, pelletizing and drying: the extruded strip material is cooled through a water tank, then pelletized through a pelletizer, and dried, to obtain the high-efficiency polyester color master batch.

[0013] Further, the mixing temperature of the mixer in step (1) is 40-60℃.

[0014] Further, the mixing in step (1) is first at 600 rpm for 15 min, and then at 1200 rpm for 15-30 min.

[0015] Further, the length-diameter ratio of the twin-screw extruder in step (2) is 40:1-52:1.

[0016] Further, the drying in step (3) is air-drying at 80-100℃ for 4-6 hours, to make the water content of the particles less than 0.05%.

[0017] The imino (-NH-) in the antioxidant mother nucleus structure of the application can effectively capture and eliminate the peroxide free radicals (ROO·) and alkyl free radicals (R·) generated during the polymer processing and use. By providing a hydrogen atom, the free radical reaction is generated, a stable, less active self free radical, thereby interrupting the auto-oxidation chain reaction leading to polymer aging, delaying the degradation of the material. The aryl group provides a large conjugated system and steric hindrance, which helps to disperse and stabilize the electron cloud of the free radical intermediate formed after the hydrogen atom provided by the imino group, to prevent it from initiating new side reactions. The nitro group is a strong electron-withdrawing group, which can significantly enhance the stability of the entire molecular structure through electron-withdrawing effect, especially the carbon center connected with the imino group, which can reduce its reactivity, so that it is not easy to be further oxidized and decomposed after playing an antioxidant role, thereby maintaining long-term antioxidant ability.

[0018] The application realizes high compatibility with the polyamide carrier (PA6, PA66 or PA1010) based on the principle of "like dissolves like", fundamentally solves the problem of uneven dispersion of "antioxidant blind area", effectively inhibits volatilization and migration in the process by the high thermal stability of the molecular structure, and ensures the long-acting effect of oxidation resistance; By selecting high-performance colorants and the interface wetting effect of dispersants, the micro-uniform dispersion of antioxidants and colorants in the polyamide carrier is realized, and the "antagonistic effect" between colorants and antioxidants and the problem of pigment catalytic oxidation in the traditional system due to insufficient compatibility are avoided; Further introduction of lubricant reduces melt viscosity and shear heat, reduces thermal degradation and promotes dispersion, and through the segmented heating melting blending of high length-diameter ratio twin screw extruder and the deep drying process of 80-100 DEG C, the risk of polyamide hydrolysis degradation is completely eliminated, and finally the color master batch can provide excellent and long-acting heat oxidation resistance and weather resistance while giving polyester products bright color, effectively preventing product yellowing, color difference and other problems.

[0019] Compared with the prior art, the application has the following advantages: 1. The antioxidant performance and long-acting effect are more excellent: the special antioxidant for polyamide carrier is used, the compatibility with the carrier is improved based on the principle of "like dissolves like", the problem of uneven dispersion of traditional antioxidant to form "antioxidant blind area" is fundamentally solved, and the volatilization and migration in the process are inhibited by the high thermal stability of the molecular structure of the antioxidant, so that the color master batch gives the polyester product a longer-acting oxidation resistance effect, which can effectively reduce the yellowing and color difference of the product caused by oxidation during processing and use.

[0020] 2. Eliminate the adverse effects of colorants and antioxidants: by selecting high-performance colorants and the interface wetting effect of dispersants, the micro-uniform dispersion of antioxidants and colorants in the polyamide carrier is realized, the "antagonistic effect" between colorants and antioxidants and the problem of pigment catalytic oxidation in the traditional system due to insufficient compatibility are avoided, the color stability of polyester products is ensured, and the degradation of products caused by the adverse effects is reduced.

[0021] 3. The processing stability and product applicability are improved: the lubricant is introduced to reduce the melt viscosity and shear heat, reduce the thermal degradation in the process and promote the dispersion of each component; at the same time, the segmented heating melting blending of high length-diameter ratio twin screw extruder and the deep drying process are combined to completely eliminate the risk of polyamide hydrolysis degradation, improve the processing stability of color master batch, and finally make the color master batch have more excellent heat oxidation resistance and weather resistance while giving polyester products bright color, which can better meet the performance requirements of polyester products in high-end fields (such as outdoor building materials and medical packaging). BRIEF DESCRIPTION OF DRAWINGS

[0022] Figure 1 NMR chart of antioxidant 1 described in the present application. DETAILED DESCRIPTION

[0023] The technical solutions of the present application will be described clearly and completely below in combination with the drawings in the present application. Obviously, the described embodiments are only some of the embodiments of the present application, but 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 fall within the scope of protection of the present application.

[0024] Preparation example 1 Preparation of antioxidant 1: .

[0025] First step: 10.00 g of compound 1 and 5.32 g of compound 2 are added to 130 ml of dichloromethane, stirred until evenly dispersed, then 0.41 g of triphenylphosphine, 0.10 g of palladium-carbon and 1.90 g of sodium hydroxide are sequentially added under nitrogen atmosphere, and the reaction is continuously carried out at 80℃ for 10 h. After the reaction is completed, the reaction mixture is filtered with silica gel, the organic solvent is spin-dried, and then purified by column chromatography (silica gel column chromatography, mobile phase: mixed solution of petroleum ether and ethyl acetate), spin-dried to obtain 10.05 g of compound 3.

[0026] Second step: 10.05 g of compound 3, 4.95 g of compound 4, 13.27 g of potassium phosphate trihydrate, 0.15 g of pyridine-2-carboxylic acid and 0.23 g of CuI are added to 150 ml of DMSO, heated to 85℃ and reacted for 14 h; after cooling, the reaction mixture is extracted with ammonia solution and methyl tert-butyl ether, the organic phase is retained, the organic solvent is spin-dried, and then purified by column chromatography (silica gel column chromatography, mobile phase: mixed solution of petroleum ether and ethyl acetate), spin-dried to obtain 11.23 g of antioxidant 1.

[0027] Structure identification: Mass spectrum of compound 3: 404, tested by ms+1; Mass spectrum of antioxidant 1: 564, tested by ms+1; NMR of antioxidant 1: 1 HNMR( Figure 1) δ 8.34 (m, 2H), 7.81-7.75 (m, IH), 7.74-7.62 (m, 2H), 7.61-7.46 (m, 2H), 7.25-7.13 (m, 3H), 7.01 (d, IH), 6.61-6.53 (m, IH), 6.46-6.38 (m, 2H), 4.42 (s, 2H), 3.86 (s, 3H), 3.33-3.23 (m, 4H), 3.04-2.94 (m, 4H), 1.97 (p, 2H).

[0028] Preparation Example 2 Antioxidant 2 was prepared in Preparation Example 2, referring to the preparation method of Preparation Example 1, replacing compound 2 therein with The rest was the same as Preparation Example 1, and the mass spectrum of antioxidant 2 was 548, tested by ms+1.

[0029] The structure of antioxidant 2 is: .

[0030] Preparation Example 3 Antioxidant 4 was prepared in Preparation Example 3, referring to the preparation method of Preparation Example 1, replacing compound 2 therein with The rest was the same as Preparation Example 1, and the mass spectrum of antioxidant 4 was 602, tested by ms+1.

[0031] The structure of antioxidant 4 is: .

[0032] Preparation Example 4 Antioxidant 5 was prepared in Preparation Example 4, referring to the preparation method of Preparation Example 1, replacing compound 2 therein with The rest was the same as Preparation Example 1, and the mass spectrum of antioxidant 5 was 559, tested by ms+1.

[0033] The structure of antioxidant 5 is: .

[0034] Preparation Example 5 Antioxidant 7 was prepared in Preparation Example 5, referring to the preparation method of Preparation Example 1, replacing compound 2 therein with The rest was the same as Preparation Example 1, and the mass spectrum of antioxidant 7 was 602, tested by ms+1.

[0035] The structure of antioxidant 7 is: .

[0036] Example 1 A high-efficiency polyester color master batch was prepared: 1. Raw material ratio: Polyamide carrier selected from: PA6, 55 parts, purchased from: Haiyang Science and Technology Co., Ltd.; Colorant selected from: phthalocyanine blue, 30 parts, purchased from: Shuangle Pigment Co., Ltd.; Dispersant selected from: polyethylene wax, 8 parts, purchased from: Qingdao Bony Chemical Co., Ltd.; Lubricant selected from: stearic acid amide, 2 parts, purchased from: Jiangxi Zhilian New Material Co., Ltd.; Antioxidant selected from: antioxidant 1 prepared by preparation example 1, 1.5 parts.

[0037] 2. Preparation method: (1) Premixing: 55 parts of polyamide carrier PA6, 30 parts of phthalocyanine blue, 8 parts of polyethylene wax, 2 parts of stearic acid amide and 1.5 parts of antioxidant 1 are added into a high-speed mixer, and the mixing temperature is controlled at 50℃. First, mix at 600 r / min for 15 min, and then mix at 1200 r / min for 20 min to obtain a uniformly mixed premix; (2) Melt extrusion: the above premix is sent into a double screw extruder with a length-diameter ratio of 48:1 for melt blending and extrusion granulation. The temperature of each section of the double screw extruder is set as follows: zone 1 210℃, zone 2 230℃, zone 3 245℃, zone 4 250℃, and the head 250℃. The screw speed is set at 300 r / min; (3) Cooling, granulating and drying: the extruded strip material is cooled to room temperature through a water tank, and then granulated through a granulator. The obtained particles are placed in a forced air drying oven at 90℃ for 5 hours, and finally a high-efficiency polyester color master batch with water content less than 0.05% is obtained.

[0038] Examples 2-5 A high-efficiency polyester color master batch is prepared by referring to the preparation method of example 1, and replacing the antioxidant therein with the antioxidants prepared in preparation examples 2-5 in turn, and the rest remains the same as example 1.

[0039] Comparative example 1 A high-efficiency polyester color master batch is prepared by referring to the preparation method of example 1, and replacing the antioxidant therein with antioxidant 1010, and the rest remains the same as example 1.

[0040] Comparative example 2 A high-efficiency polyester color master batch is prepared by referring to the preparation method of example 1, and replacing the antioxidant therein with antioxidant CY, and the rest remains the same as example 1.

[0041] Comparative example 3 A high-efficiency polyester color master batch is prepared by referring to the preparation method of example 1, and not adding the antioxidant therein, and the rest remains the same as example 1.

[0042] Comparative Example 4 A high-efficiency polyester color master batch was prepared according to the preparation method of Example 1, without adding the lubricant therein, and the rest was the same as Example 1.

[0043] Performance test: 1. The measurement method of the melt index of the master batch was GB / T3682, the condition was 230℃ / 2.16Kg, and the data were shown in Table 1; 2. The measurement method of the weather resistance color difference was GB / T16422.2-2014, and the data were shown in Table 1; 3. The measurement method of the surface resistivity was GB / T1410-2006, and the data were shown in Table 1.

[0044] Table 1.

[0045]

[0046] The melt index of the master batch of the example group (using the special antioxidant of the application) was more stable as a whole, with less fluctuation. In the comparative examples, the melt index of the group using the traditional antioxidant or without adding the lubricant changed slightly, indicating that the stability would decrease without adding the lubricant. The weather resistance color difference of the example group was significantly better, meaning that the weather resistance performance was better. In the comparative examples, the weather resistance color difference of the group without adding the antioxidant was the worst, the color difference of the group using the traditional antioxidant was also significantly larger than that of the example group, and the color difference of the group without adding the lubricant was better than the previous two comparative examples, but still not as good as the example group. The surface resistivity of the example group was more concentrated as a whole, with better stability. In the comparative examples, the surface resistivity of the group without adding the lubricant was relatively high, and the fluctuation of the surface resistivity of the other comparative examples and the example group was slightly larger.

[0047] Although the embodiments of the application have been shown and described, it is to be understood that for the purpose of the present application, the changes in the embodiments, the modifications, the replacements and the variations can be made by those of ordinary skill in the art without departing from the principles and the spirit of the application, and the scope of the application is defined by the appended claims and their equivalents.

Claims

1. A high efficiency polyester color masterbatch characterized in that, Prepared from raw materials comprising the following parts by mass: polyamide carrier 40-70 parts, colorant 20-50 parts, dispersant 5-15 parts, lubricant 1-5 parts, antioxidant 0.5-3 parts; The antioxidant is a compound shown in formula 1; The formula 1 is: ; R1 in the formula 1 is a substituent; The R1 is selected from any one of fluorine, trifluoromethyl, cyano, alkyl with carbon atom number 1-5, alkoxy with carbon atom number 1-5.

2. The high efficiency polyester color masterbatch as claimed in claim 1, wherein, The polyamide carrier is one or mixture of several of polyamide 6, polyamide 66, polyamide 1010.

3. The high efficiency polyester color masterbatch as claimed in claim 1, wherein, The colorant is one or mixture of several of high-pigment carbon black, phthalocyanine blue, phthalocyanine green, permanent red, permanent yellow, quinacridone red, isoindolinone yellow.

4. The high efficiency polyester color master batch as claimed in claim 1, wherein, The dispersant is one or mixture of several of polyethylene wax, oxidized polyethylene wax, polypropylene wax, EVA wax, zinc stearate, calcium stearate.

5. The high efficiency polyester color masterbatch as claimed in claim 1, wherein, The lubricant is one or mixture of several of stearic acid, stearic acid amide, oleic acid amide, ethylene bis-stearic acid amide.

6. The high efficiency polyester color masterbatch as claimed in claim 1, wherein, The antioxidant is any one of the compounds described in the following structure: ； ； ； 。 7. A method for preparing a high-efficiency polyester masterbatch as described in any one of claims 1-6, characterized in that, Comprising the following steps: (1) Pre-mixing: the polyamide carrier, colorant, dispersant, lubricant and antioxidant are added into a mixer, mixed at a speed of 600-1200 r / min for 30-45 minutes to obtain a pre-mixed material; (2) Melt extrusion: the pre-mixed material is sent into a twin-screw extruder for melt blending and extrusion granulation, the temperature of each section of the twin-screw extruder is set as: zone 1 200-220℃, zone 2 220-240℃, zone 3 240-250℃, zone 4 245-255℃, die head 245-255℃, screw speed 200-400 r / min; (3) Cooling, granulating and drying: the extruded strip material is cooled through a water tank, then granulated through a granulator, and dried, to obtain the high-efficiency polyester color master batch.

8. The method according to claim 7, wherein the method is characterized by, The mixing temperature of the mixer in step (1) is 40-60℃; In step (1), the mixing is first at 600 r / min for 15 min, and then at 1200 r / min for 15-30 min.

9. The method according to claim 7, wherein the method is characterized by, The length-diameter ratio of the twin-screw extruder in step (2) is 40:1-52:

1.

10. The method according to claim 7, wherein the method is characterized by, In step (3), the drying is air-drying at 80-100℃ for 4-6 hours, so that the moisture content of the particles is less than 0.05%.

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