Nylon composition, preparation method therefor and use thereof

Abstract

A nylon composition, a preparation method therefor and the use thereof. The nylon composition comprises the following components in parts by weight: 93-99 parts of nylon; 0.02-0.05 part of pigment red; 0.5-5 parts of PE; 0.5-10 parts of EVA; and 0.1-2 parts of an auxiliary agent. The nylon composition can be used for preparing components of power tools. The nylon composition has the effect of avoiding the transition of pigments into a dye-like state caused by hydrogen bond interaction between pigment particles and amide bonds of nylon, solves the problem of fluorescence of pigments in nylon, and achieves color recovery; and the nylon composition greatly reduces the use amount of pigments so as to reduce the color blending cost, significantly improves cost efficiency, and broadens the application range of other colorants in polar plastics.

Description

Nylon composition, preparation method and application thereof TECHNICAL FIELD

[0001] The present application belongs to the technical field of polymer material coloring, and particularly relates to a nylon composition, a preparation method and application thereof. BACKGROUND

[0002] Nylon, also known as polyamide, is referred to as Nylon or Polyamide (PA) in English. Nylon has the characteristics of high strength, wear resistance, light weight, good insulation, high temperature resistance, and chemical corrosion resistance. These characteristics make nylon widely used in many fields. In the industrial field, nylon is used to manufacture mechanical parts such as bearings, gears, and pipes due to its high strength and wear resistance. In the electronics and electrical industry, nylon is used in wire and cable insulation layers and electrical switch components due to its good insulation and high temperature resistance. In the construction industry, nylon is often used to make building decorations and sealing materials due to its weather resistance and easy processing. In the aerospace field, nylon is used to manufacture lightweight and high-strength parts due to its lightweight and high-strength characteristics.

[0003] During the processing of nylon, color powder is usually added for dyeing to meet the diverse needs of the market and consumers. Through dyeing, nylon products can obtain rich colors and patterns, thereby enhancing their aesthetic appeal and attractiveness.

[0004] However, many pigments can interact with the amide bond of nylon through hydrogen bonding during processing and cause pigment-dyeing phenomenon, changing the color of the pigment and accompanied by strong fluorescence phenomenon [J. Colloid Interface Sci, 1999, 216(1):189], resulting in a significant decrease in the weather resistance and color stability of plastic products. Therefore, the selection of pigments in colored nylon is greatly limited. Currently, the commonly used red pigments in nylon composition color matching are DPP pigments and perylene pigments. Although these two types of pigments have a great advantage in terms of molecular structure stability, they still cannot completely avoid the pigment-dyeing phenomenon. According to public information, dissolved DPP dye monomers can be promoted to aggregate through mechanical force and thermal annealing stimulation, realizing color change and fluorescence quenching. However, in the field of plastic coloring, the pigment / dye molecules in this environment are difficult to realize structural transformation due to the influence of high molecular chain segment movement. DPP molecules dissolved in nylon need to be heat treated at a high temperature of 180℃ for 5h to realize molecular aggregation and restore the original red color. This method has a great impact on the mechanical properties of nylon itself.

[0005] The Chinese patent application with the publication number CN 109735102 A discloses a non-fluorescent red nylon material and a preparation method thereof. The application inhibits the fluorescence of the red nylon by greatly increasing the amount of DPP pigment. The amount of DPP needs to be increased to more than 1.5 wt%, which will damage the material performance and also cause waste of pigment and increase of cost.

[0006] The prior art lacks a red nylon composition with less toner addition amount, no fluorescence, and fast realization of pigment-dye reverse conversion. SUMMARY

[0007] The purpose of the present application is to solve the above technical problems and provide a red nylon composition with less toner addition amount and no fluorescence.

[0008] Another purpose of the present application is to provide a preparation method of the above nylon composition.

[0009] Still another purpose of the present application is to provide an application of the above nylon composition.

[0010] The present application is achieved by the following technical solutions:

[0011] A nylon composition, characterized in that it contains the following components in parts by weight:

[0012] Nylon 93-99 parts;

[0013] Pigment red 0.02-0.05 parts;

[0014] PE 0.5-5 parts;

[0015] EVA 0.5-10 parts;

[0016] The sum of the weight parts of PE and EVA is greater than or equal to 2 parts.

[0017] Preferably, the sum of the weight parts of PE and EVA is 2-5 parts.

[0018] Preferably, the PE is selected from any one or more of HDPE, LDPE; preferably HDPE.

[0019] Preferably, the weight ratio of the PE: EVA is 1: (0.1-10); further preferably 1: (1-7), and more preferably 1: (2-4).

[0020] Preferably, the weight average molecular weight of the PE is preferably 50000-250000, and further preferably 60000-200000.

[0021] Preferably, the melting point of the PE is preferably 90-150°C, and further preferably 100-135°C.

[0022] Preferably, the weight percentage of the VA in the EVA is preferably 15-45%.

[0023] Preferably, the nylon is selected from any one or more of nylon 6, nylon 66, nylon 56, nylon 612, nylon 510, nylon 12, further preferably nylon 6, nylon 66, and more preferably nylon 6.

[0024] The relative viscosity of the nylon is preferably 2.30-37.00, the melting point is preferably 170-270°C, and the density is preferably 0.60-1.20 g / cm 3 .

[0025] Preferably, the pigment is selected from any one or more of bis(p-chlorophenyl)-1,4-diketopyrrolopyrrole, 2,9-dimethyl-5,12-dihydroquinoline[2,3-B]acridine-7,14-dione, 2,9-dichloro-5,12-dihydroquinoline[2,3-B]acridine-7,14-dione, 1-(4-chloro o-sulfonic acid-5-tolylazo)-2-naphthol barium salt, 3-hydroxy-4-[(4-methyl-2-sulfonic acid phenyl)azo]-2-naphthalene carboxylic acid calcium salt, N,N'-1,4-phenylene-di[4-(2,5-dichlorophenyl)azo]-3-hydroxynaphthalene-2-carboxamide, 2,9-bis[4-(phenylazo)phenyl]anthracene[2,1,9-def:6,5,10-d'e'f']diisoquinoline-1,3,8,10(2H,9H)-tetrone, preferably any one or more of bis(p-chlorophenyl)-1,4-diketopyrrolopyrrole, 2,9-bis[4-(phenylazo)phenyl]anthracene[2,1,9-def:6,5,10-d'e'f']diisoquinoline-1,3,8,10(2H,9H)-tetrone, and further preferably bis(p-chlorophenyl)-1,4-diketopyrrolopyrrole.

[0026] When the amount of pigment red is too small, it will cause fluorescence enhancement, and it is also difficult to restore the color; if the amount is too large, it can inhibit fluorescence to a certain extent, which is helpful for color regulation, but it will lead to a substantial increase in cost, and also cause appearance defects such as color powder points on the surface of the colored plastic, and the influence of fluorescence on weather resistance cannot be ignored.

[0027] The person skilled in the art can add 0.1-2 parts of auxiliary agents by weight according to actual needs; the auxiliary agent is selected from any one or more of antioxidants, lubricants, and light stabilizers.

[0028] Preferably, the antioxidant is selected from any one or more of hindered phenolic antioxidants and aromatic amine antioxidants, and the lubricant is selected from any one or more of esters or sodium tannate.

[0029] The application also provides a preparation method of the above-mentioned nylon composition, comprising the following steps:

[0030] S1: drying the nylon sufficiently;

[0031] S2: mixing the components uniformly, and extruding the nylon composition through a screw extruder;

[0032] S3: packaging the nylon composition into a bag.

[0033] Preferably, the drying temperature in S1 is 110-120 DEG C, and the drying time is 2-4 hours.

[0034] The application also provides an application of the above-mentioned nylon composition, which is used for preparing electric tool parts.

[0035] The application has the following beneficial effects: PE and EVA form a melt to wrap the pigment, weaken the contact between the pigment and the nylon, avoid the hydrogen bond interaction between the amide bond of the pigment particles and the nylon, and cause the pigment-dye phenomenon; the low polarity of PE and EVA helps to reduce the solubility of the pigment in the nylon; the lubricity of PE and EVA helps to increase the movement ability of the nylon chain segment, and weaken the heterogeneous nucleation between the pigment molecules and the nylon; EVA helps to adjust the compatibility in the nylon composition, and prevent the precipitation failure.

[0036] In addition to increasing the movement ability of the nylon chain segment through lubricity, PE and EVA can also affect the temperature of thermal annealing, thereby promoting the movement of the nylon chain segment. PE has poor compatibility with PA, and if only PE is added, it is not conducive to the mechanical properties of the nylon composition; if only EVA is added, the melting point of the system is lower than 100 DEG C, at this time, although the movement is promoted, the temperature does not reach the best movement state of the nylon chain segment itself.

[0037] By the cooperation of PE powder and EVA, the fluorescence problem of pigments in nylon is solved, and the color recovery is realized; the technical scheme of the application can greatly reduce the amount of pigments, save the color matching cost, achieve more excellent effect through the compounding of PE and EVA, reduce the cost, significantly improve the cost benefit, and also widen the application range of other coloring agents in polar plastics. DETAILED DESCRIPTION

[0038] The application will be described in detail below in combination with specific embodiments. The following embodiments will help those skilled in the art to further understand the application, but do not limit the application in any form. It should be pointed out that, for those skilled in the art, without departing from the concept of the application, a number of modifications and improvements can be made. These all belong to the protection scope of the application.

[0039] The raw materials used in the application are as follows:

[0040] Nylon 6: purchased from Jiangsu Haiyang Science and Technology Co., Ltd., brand HY-2500A, relative viscosity 2.45±0.04, melting point 215-220℃, density 1.135-1.145 g / cm 3 .

[0041] Nylon 66: purchased from Inventa Nylon Chemicals (China) Co., Ltd., brand PA66 U3200, relative viscosity 30.0-35.0, melting point 263℃, density 0.65-0.70 g / cm 3 .

[0042] Nylon 56: purchased from Shanghai Kaisai Biotechnology Co., Ltd., brand E-6631, relative viscosity 2.37±0.05, melting point 265±3℃, density 1.17 g / cm 3 .

[0043] Nylon 612: purchased from DuPont, brand Zytel-158, melting point 218℃, density 1.06 g / cm 3

[0044] Nylon 12: purchased from Shandong Dongchen Ruisen New Material Technology Co., Ltd., brand PA1212, melting point 178-185℃, density 1.01-1.03 g / cm 3 .

[0045] PE1: HDPE, purchased from Dow Chemical, brand ELITE™ AT 6900, weight average molecular weight 200000, melting point 134℃.

[0046] PE2: LDPE, purchased from Sinopec Chemical Sales (Guangdong) Co., Ltd., brand LDPE MG70, weight average molecular weight 60000, melting point 102℃.

[0047] EVA1: purchased from Taiwan Plastics Industry Co., Ltd., trade name EVA 7350M, VA content 18%.

[0048] EVA2: purchased from Quanzhou Petrochemical Co., Ltd., trade name EVA UL00628, VA content 28%.

[0049] PP: purchased from CNOOC Shell Petrochemicals Co., Ltd., trade name PP EP548R, melting point 164-170°C, density 0.9 g / cm 3 .

[0050] Pigment 1: Bis(p-chlorophenyl)-1,4-diketopyrrolopyrrole, purchased from BASF Corporation, trade name Irgazin® Red K 3840 SQ (Pigment Red 254).

[0051] Pigment 2: 2,9-Dimethyl-5,12-dihydroquinoline[2,3-B]acridine-7,14-dione, purchased from Zhejiang Yongquan Chemical Co., Ltd., trade name 122B (R203) (Pigment Red 122).

[0052] Pigment 3: 2,9-Dichloro-5,12-dihydroquinoline[2,3-B]acridine-7,14-dione, purchased from Titanium Yang Chemical, trade name R252 (Pigment Red 202).

[0053] Pigment 4: 3-Hydroxy-4-[(4-methyl-2-sulfonatophenyl)azo]-2-naphthalenecarboxylic acid calcium salt, purchased from Shenzhen Dingtai Chemical Co., Ltd., trade name L4B (R216) (Pigment Red 57:1).

[0054] Pigment 5: N,N'-1,4-Phenylene-di[4-(2,5-dichlorophenyl)azo]-3-hydroxynaphthalene-2-carboxamide, purchased from BASF Corporation, trade name K3540 (Pigment Red 166).

[0055] Pigment 6: 2,9-Bis[4-(phenylazo)phenyl]anthracene[2,1,9-def:6,5,10-d'e'f']diisoquinoline-1,3,8,10(2H,9H)-tetraone, purchased from BASF Corporation, trade name K3911 (Pigment Red 178).

[0056] Pigment 7: 1-(4-Chloro-o-sulfonate-5-tolylazo)-2-naphthol barium salt, purchased from Shenzhen Tianlaibao Pigment Co., Ltd., trade name Graphtol Red LC-CN09 (Pigment Red 53:1).

[0057] Antioxidant 1: purchased from Tianjin Li'anlong New Material Co., Ltd., hindered phenolic antioxidant, trade name RIANOX 1098.

[0058] Antioxidant 2: purchased from CBITEC, a spiro phosphite antioxidant, trade designation REVONOX® 608.

[0059] Lubricant 1: purchased from Emery Oleochemicals, trade designation LOXIOL G 32.

[0060] Lubricant 2: purchased from Clariant, trade designation Licomont NAV101 PWD.

[0061] Light stabilizer: purchased from Cytec Surface Specialties (Shanghai) Co., Ltd., trade designation CYASORB® UV-3808PP5.

[0062] Preparation method of the nylon compositions of the examples and comparative examples: the nylon was dried thoroughly, the drying temperature was 120°C, and the drying time was 2 hours; the components were mixed uniformly according to the ratio, and the plastic particles were extruded through a screw extruder; the plastic particles were packaged into bags.

[0063] Test methods:

[0064] (1) Fluorescence intensity: the plastic particles were injection molded into a color plate for testing, and a fluorescence spectrometer of Horiba Jobin Yvon LabRAM HR800 model was used for fluorescence intensity determination, wherein the slit was set to 1 nm, the excitation wavelength was 400 nm, and the color plate was placed at 45°.

[0065] (2) Hue: the plastic particles were injection molded into a color plate for testing, and a spectrophotometer of X-rite Color-Eye 7000A model was used for hue determination. The hue h represents the color information, i.e., the position of the spectral color; this parameter is expressed in angular measure, with a value ranging from 0 to 360°: if calculated in the counter-clockwise direction starting from red, red is 0°, green is 120°, and blue is 240°. Their complementary colors are: yellow is 60°, cyan is 180°, and purple is 300°. The smaller the value, the redder the color.

[0066] (3) Two-month outdoor simulated weather resistance test color difference: the color plates were evenly placed in an aging oven, and a 0.80 W / (m 2 nm) irradiance intensity xenon lamp aging was used for 2 months of artificial aging test, and the samples were collected every seven days for color testing. The color difference (ΔΕ) was characterized by a spectrophotometer (X-rite Color-Eye 7000A).

[0067] Table 1: Weight parts of each component of the nylon compositions of Examples 1-10 and test results

[0068] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Nylon 6 93 98 Nylon 66:98 Nylon 5 6:98 Nylon 6 12:96 98 Nylon 5 10 98 Nylon 12:99 98 PE 11.25 1.25 1.25 1.25 1.25 1.25 PE 21.53 51.25 EVA 12 6 10 EVA 23.75 3.75 3.75 3.75 3.75 3.75 3.75 Pigment 1 0.02 0.02 0.02 0.02 0.02 0.02 0.02 Pigment 2 0.02 Pigment 4 0.03 Pigment 6 0.04 Antioxidant 1 0.2 0.4 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Antioxidant 2 0.3 0.1 0.04 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Lubricant 1 0.2 0.4 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Lubricant 2 0.3 0.1 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Light stabilizer 0.3 0.6 1.0 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Fluorescent intensity 0.19 0.23 0.11 0.08 0.13 0.23 0.15 0.16 0.15 0.13 Hue 30.25° 33.20° 29.70° 29.76° 30.09° 30.80° 30.21° 30.19° 29.92° 31.65° Simulated weathering test color difference 15.11 8.71 3.81 3.71 4.01 6.01 5.31 4.51 3.81 4.2

[0069] From Examples 4-9, it is known that when nylon 6 is selected, the prepared nylon composition has better performance in the three test results of fluorescent intensity, hue, and simulated weathering test color difference.

[0070] From Examples 4 and 10, it is known that when HDPE is selected, the prepared nylon composition has better performance in each performance test.

[0071] Table 2: Weight parts of each component of the nylon composition and test results of Examples 11-20

[0072] Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Example 18 Example 19 Example 20 Nylon 6: 98 98 98 98 98 98 98 98 98 98 PE 1 1.25 1.25 1.25 1.25 1.25 1.25 1.25 1.25 1.25 1.25 EVA 2 3.75 3.75 3.75 3.75 3.75 3.75 3.75 3.75 3.75 Pigment 1 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 Pigment 2 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 Pigment 3 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 Pigment 4 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 Pigment 5 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 Pigment 6 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 Pigment 7 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 Antioxidant 1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Antioxidant 2 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Lubricant 1 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Lubricant 2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Light stabilizer 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Fluorescent intensity 0.18 0.20 0.19 0.21 0.10 0.21 0.09 0.17 0.11 0.07 Hue 30.12° 32.73° 31.58° 31.65° 29.53° 31.21° 29.26° 30.18° 29.76° 29.00° Color difference in simulated weathering test 15.31 16.71 15.81 16.31 14.01 15.61 13.11 12.91 13.71 13.4

[0073] From Examples 4, 11-14, it can be seen that the present application can achieve good results with a small amount of PE and EVA added.

[0074] From Examples 4, 15-20, it can be seen that the present application has universality in pigment selection, and the selection of specific pigments has little effect on the technical effect of achieving no fluorescence.

[0075] Table 3: Weight parts of each component of the nylon composition of Comparative Examples 1-4 and test results

[0076] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Nylon 6 98 98 98 98 PE 1 1.25 1.25 1.25 1.25 EVA 2 3.75 3.75 3.75 3.75 PP 3.75 3.75 3.75 3.75 Pigment 1 0.02 0.02 0.02 0.01 Antioxidant 1 0.1 0.1 0.1 0.1 Antioxidant 2 0.4 0.4 0.4 0.4 Lubricant 1 0.3 0.3 0.3 0.3 Lubricant 2 0.2 0.2 0.2 0.2 Light stabilizer 0.5 0.5 0.5 0.5 Fluorescent intensity 0.43 0.45 1.00 0.54 Hue 35.21° 36.03° 58.93° 47.78° Color difference in simulated weathering test 23.65 23.70 44.23 0.2

[0077] Comparative Example 1 only added PE, did not add EVA, the sum of the weight parts of PE and EVA did not reach 2 parts, the fluorescence intensity was greater than 0.4, and the hue was greater than 35, the simulated weather resistance test color difference was greater than 20.

[0078] From Comparative Example 2, by replacing EVA with PP, the test results of the nylon composition were within an acceptable error range, and PP had no effect on achieving the technical effects of the present application.

[0079] Comparative Example 3 is a blank control group without adding PE and EVA.

[0080] In Comparative Example 4, the pigment addition amount is 0.01, which is compared with Example 4, and the three test results are greatly different from Example 4. It can be known that the lower limit of the addition amount of the pigment has a great influence on the results of the fluorescence intensity, the hue and the simulated weather resistance test color difference. It is speculated that the reason is that the red pigment has the phenomenon of aggregation and redness. When the addition amount of the red pigment is low, the red pigment is basically dissolved in the resin, so the smaller the addition amount, the stronger the fluorescence, and the color is also more difficult to recover.

Claims

A nylon composition characterized in that, By weight parts, containing the following ingredients: Nylon 93-99 parts; Pigment red 0.02-0.05 parts; PE 0.5-5 parts; EVA 0.5-10 parts; Wherein, the sum of weight parts of PE and EVA is greater than or equal to 2 parts. A nylon composition according to claim 1, characterized in that The PE is selected from any one or more of HDPE, LDPE; preferably HDPE. A nylon composition according to claim 1, characterized in that The weight ratio of PE: EVA is 1: (0.1-10); preferably 1: (1-7), further preferably 1: (2-4). A nylon composition according to claim 1, characterized in that The nylon is selected from any one or more of nylon 6, nylon 66, nylon 56, nylon 612, nylon 510, nylon 12, preferably nylon 6, nylon 66, further preferably nylon 6. A nylon composition according to claim 1, characterized in that The pigment is selected from any one or more of bis (p-chlorophenyl)-1, 4-diketopyrrolopyrrole, 2, 9-dimethyl-5, 12-dihydroquinoline [2, 3-B] acridine-7, 14-dione, 2, 9-dichloro-5, 12-dihydroquinoline [2, 3-B] acridine-7, 14-dione, 1- (4-chloro o-sulfonic acid-5-tolyl azo)-2-naphthol barium salt, 3-hydroxy-4- [(4-methyl-2-sulfonic acid phenyl) azo]-2-naphthalene carboxylic acid calcium salt, N, N'-1, 4-phenylene-di [4- (2, 5-dichlorophenyl) azo]-3-hydroxy naphthalene-2-formamide, 2, 9-bis [4- (phenylazo) phenyl] anthracene [2, 1, 9-def: 6, 5, 10-d'e'f'] diisoquinoline-1, 3, 8, 10 (2H, 9H)-tetrone, preferably any one or more of bis (p-chlorophenyl)-1, 4-diketopyrrolopyrrole, 2, 9-bis [4- (phenylazo) phenyl] anthracene [2, 1, 9-def: 6, 5, 10-d'e'f'] diisoquinoline-1, 3, 8, 10 (2H, 9H)-tetrone, further preferably bis (p-chlorophenyl)-1, 4-diketopyrrolopyrrole. A nylon composition according to claim 1, characterized in that Further comprising 0.1-2 parts of auxiliary agent by weight parts; the auxiliary agent is selected from any one or more of antioxidant, lubricant, light stabilizer. A nylon composition according to claim 6, characterized in that The antioxidant is selected from any one or more of hindered phenolic antioxidant and aromatic amine antioxidant, the lubricant is selected from any one or more of ester or sodium tannate. Process for the preparation of a nylon composition according to any one of claims 1 to 7, characterized in that, Comprising the following steps: S1: dry the nylon sufficiently; S2: mix the components uniformly, extrude the nylon composition through a screw extruder; S3: package the nylon composition into a bag. The production method according to claim 8, wherein The drying temperature in S1 is 110-120℃, and the drying time is 2-4 hours. The use of a nylon composition according to any one of claims 1-7 for the preparation of electric tool parts.