An unfading color masterbatch for lawns and its preparation method

Abstract

The present invention provides a lawn-use color masterbatch that is not prone to fading and a preparation method thereof, comprising the following steps: high-speed stirring and mixing low-density polyethylene, polyethylene wax, and magnesium stearate, heating and maintaining a constant temperature until the polyethylene wax is completely melted; adding high-stability pigment particles, and stirring until a large amount of high-stability pigment particles are coated on the surface of the low-density polyethylene to obtain a mixture; after the twin-screw extruder is heated to 130 °C, adding the mixture, extruding, and granulating to obtain the lawn-use color masterbatch that is not prone to fading. The present invention uses the electrospinning method to make fibers from modified porous materials with different pore sizes loaded with pigments, and then utilizes the electrostatic interaction between positively charged chitosan and negatively charged attapulgite nanorods to form an interphase between the electrospun membrane fibers, which wraps around each fiber to form a nano-coating, constituting a strong and dense interface, thereby protecting the stability of the pigments, improving the light resistance and aging resistance stability, and at the same time, also improving the compatibility and dispersibility with the matrix resin.

Description

Technical Field

[0001] The invention relates to the technical field of masterbatch materials, and in particular to a non-fading masterbatch for lawns and a preparation method thereof. Background Art

[0002] Human beings have a long history of using pigments to color plastics, but it has only been about 40 to 50 years since pigments were made into masterbatches for coloring. The first industries to use masterbatches were the cable and synthetic fiber industries. Due to the continuous improvement of masterbatch production technology and the advanced application of masterbatches, they have been widely used in packaging materials, automotive plastics, household appliances and agricultural plastics, making the masterbatch industry have made great progress. The research and development of masterbatches in my country began in the mid-1970s. At that time, due to the start of construction of Yanshan and Liaohua polypropylene production facilities in my country, my country's polypropylene fiber has developed rapidly. Since polypropylene fiber does not have a dye that can be dyed, the use of masterbatches for stock coloring is the only way to solve its coloring. Since then, various parts of my country have begun to study masterbatches, taking the first step in the development of masterbatches in my country. At present, masterbatch coloring is widely used in the fields of plastic products such as films, plastic products, and chemical fibers, including artificial turf materials. Since masterbatches for artificial turf are used outdoors, they must be exposed to the sun and rain, and their fading is a problem that must be solved. How to improve its fading resistance and anti-aging performance is a problem that needs to be solved at present. Summary of the invention

[0003] Technical problem to be solved: The purpose of the present invention is to provide a non-fading masterbatch for lawns and a preparation method thereof, wherein porous materials with different pore sizes are used to adsorb pigments, and the pores with different pore sizes can promote the internal diffusion of pigment molecules, reduce external mass transfer resistance, and allow pigment molecules to reach the adsorption site faster, thereby accelerating the adsorption rate and loading amount; and an electrostatic spinning method is used to make fibers with modified porous materials with different pore sizes loaded with pigments, and then the electrostatic interaction between positively charged chitosan and negatively charged attapulgite nanorods is utilized to form an interphase between the electrospinning membrane fibers, which is wrapped around each fiber to form a nano coating, forming a strong and dense interface, thereby protecting the stability of the pigment, improving the light resistance and aging resistance, and at the same time improving the compatibility and dispersibility with the matrix resin.

[0004] Technical solution: A non-fading masterbatch for lawns, comprising the following raw materials in parts by weight: 10 to 18 parts of high-stability pigment particles, 100 parts of low-density polyethylene, 12 parts of polyethylene wax, and 8 parts of magnesium stearate.

[0005] Furthermore, the preparation method of the high stability pigment particles is as follows:

[0006] Step 1: Dissolve chitosan in 3% acetic acid solution to prepare a chitosan acetate solution with a concentration of 0.5 - 2 g / L. Add porous materials with different pore sizes, and carry out a magnetic stirring reaction for 6 h. Centrifuge at 9000 rpm for 5 min to separate the solid and liquid phases. After washing the solid, dry it at 70 °C and grind it to obtain modified porous materials with different pore sizes;

[0007] Step 2: Dissolve / disperse 25 - 50 mg of pigment in 1 L of ultrapure water to form a pigment solution / suspension. Take 2 - 4 g of modified porous materials with different pore sizes and disperse them in the pigment solution. Carry out a magnetic stirring for 2 - 4 h. Centrifuge at 9000 rpm for 5 min to separate the solid and liquid phases. After washing the solid, dry it at 70 °C and grind it to obtain modified porous materials with different pore sizes loaded with pigment;

[0008] Step 3: Prepare a PVP / ethanol solution with a mass concentration of 10 - 14%. Add the modified porous materials with different pore sizes loaded with pigment, stir evenly, and then place them in an electrospinning device for electrospinning to obtain a porous fiber membrane coated with pigment;

[0009] Step 4: Remove the porous fiber membrane coated with pigment, put it into a vacuum drying oven at 70 °C for drying, crush it, and sieve it through a 200 - mesh sieve to obtain porous fiber membrane particles coated with pigment with a porosity of 60 - 80% and a pore size of 10 - 50 μm;

[0010] Step 5: Dissolve chitosan in 3% acetic acid solution to prepare a chitosan acetate solution with a concentration of 0.5 - 2 g / L. Take 50 mg of attapulgite nanorods, add 50 mL of PBS buffer solution, and carry out ultrasonic dispersion to obtain an attapulgite nanorod suspension;

[0011] Step 6: Immerse 50 mg of porous fiber membrane particles coated with pigment in 100 mL of chitosan acetate solution for 1 - 2 h;

[0012] Step 7: Add the attapulgite nanorod suspension, stir and mix evenly, and carry out an electrostatic assembly reaction at room temperature for 4 - 5 h;

[0013] Step 8: Take out the reaction product, wash it with water, and carry out freeze - drying to obtain highly stable pigment particles.

[0014] Furthermore, the preparation method of the porous materials with different pore sizes in Step 1 is as follows:

[0015] S1: Take 3 g of MgO, 18 g of Al2O3, and 80 g of SiC powder, mix them evenly, add a 0.8 wt.% sodium carboxymethyl cellulose solution, and adjust the pH to 10 to obtain a ceramic slurry with a solid content of 25 - 40 vol.%;

[0016] S2: Place the ceramic slurry in a ball - milling tank for ball - milling. The ball - milling time is 10 h and the rotation speed is 100 r / min;

[0017] S3: Add PS microspheres with different particle sizes to the ball-milled ceramic slurry, stir evenly, inject it into a mold, and centrifuge it on a centrifuge at a speed of 4000 - 6000 rpm for 30 - 50 min;

[0018] S4: Immerse the bottom of the mold in a liquid cold source at -120°C to -30°C for rapid freezing;

[0019] S5: Freeze-dry at a temperature of -50°C and a pressure of 0 - 50 Pa to obtain porous ceramic preforms with different pore sizes;

[0020] S6: Place the porous ceramic preforms with different pore sizes in an atmosphere box furnace, keep it at 385°C in air for 20 min, then raise the temperature to 1200°C and keep it for 1 h, evacuate and then introduce argon for liquid-phase sintering, raise the temperature to 1500°C and keep it for 2 h, and the heating rate is 5°C / min.

[0021] Further, the addition amount of the PS microspheres with different particle sizes is 1 - 2% of the volume of the ceramic slurry, the particle sizes are 10 - 30 nm and 100 - 170 nm respectively, and the volume ratio is 1:1.

[0022] Further, the volume-mass ratio of the chitosan acetate solution and the porous material with different pore sizes in step 1 is 1 L:(50 - 130) g.

[0023] Further, the particle size of the modified porous material with different pore sizes loaded with pigments in step 2 is 2 - 20 μm.

[0024] Further, the volume-mass ratio of the PVP / ethanol solution and the modified porous material with different pore sizes in step 3 is 20 mL:(1 - 2) g.

[0025] Further, the electrospinning conditions in step 3 are: the spinning temperature is 20 - 26°C, the humidity is 20 - 30%, the flow rate of the spinning solution is 0.5 - 0.8 mL / h, the outer diameter of the needle is 0.8 mm, the inner diameter is 0.5 mm, and the receiving distance is 13 - 16 cm.

[0026] The preparation method of the above-mentioned non-fading color masterbatch for lawns includes the following steps:

[0027] Step 1: Stir and mix low-density polyethylene, polyethylene wax, and magnesium stearate at high speed, and heat to 80°C, and keep the temperature constant until the polyethylene wax is completely melted;

[0028] Step 2: Add high-stability pigment particles, and stir until a large number of high-stability pigment particles are coated on the surface of the low-density polyethylene to obtain a mixture;

[0029] Step 3: After the twin-screw extruder is heated to 130°C, the mixed material is added, and extrusion and pelletization are carried out at a temperature of 120 - 140°C to obtain the non-fading color masterbatch for lawns.

[0030] Beneficial effects:

[0031] 1. In the present invention, porous materials with different pore diameters are used to adsorb pigments. The porous materials with different pore diameters can promote the internal diffusion of pigment molecules, reduce the external mass transfer resistance, enable the pigment molecules to reach the adsorption sites faster, and thus accelerate the adsorption rate and loading capacity.

[0032] 2. In the present invention, chitosan is used to modify the porous materials with different pore diameters, thereby providing more adsorption sites, which can adsorb more pigments, and further improving the pigment loading capacity of the porous materials.

[0033] 3. In the present invention, the modified porous materials with different pore diameters loaded with pigments are made into fibers by electrospinning. Then, by using the electrostatic interaction between positively charged chitosan and negatively charged attapulgite nanorods, an interphase is formed between the electrospun membrane fibers, which wraps around each fiber to form a nano-coating, constituting a strong and dense interface, thereby protecting the stability of the pigments, improving the light resistance and aging resistance stability, and at the same time, also improving the compatibility and dispersibility with the matrix resin. Description of the drawings

[0034] Figure 1 It is a graph showing the test results of the light resistance stability of the pigment particles prepared in Examples 7 - 9, Comparative Example 3, and Comparative Example 5. Detailed implementation manners

[0035] Example 1

[0036] The preparation method of the porous materials with different pore diameters is as follows:

[0037] S1: Take 3 g of MgO, 18 g of Al2O3, and 80 g of SiC powder, mix them evenly, add a 0.8 wt.% sodium carboxymethyl cellulose solution, and adjust the pH to 10 to obtain a ceramic slurry with a solid content of 30 vol.%.

[0038] S2: Place the ceramic slurry in a ball mill tank for ball milling. The ball milling time is 10 h, and the rotation speed is 100 r / min.

[0039] S3: Add PS microspheres with different particle sizes to the ball-milled ceramic slurry, stir evenly, inject it into a mold, and centrifuge it at a rotation speed of 4000 rpm for 50 min on a centrifuge; the addition amount of PS microspheres with different particle sizes is 1% of the volume of the ceramic slurry, and the particle sizes are 10 - 30 nm and 100 - 170 nm respectively, and the volume ratio is 1:1.

[0040] S4: Immerse the bottom of the mold in a liquid cold source at -100 °C for rapid freezing;

[0041] S5: Freeze-dry at a temperature of -50 °C and a pressure of 5 Pa to obtain porous ceramic preforms with different pore sizes;

[0042] S6: Place the porous ceramic preforms with different pore sizes in an atmosphere box furnace, hold at 385 °C in air for 20 min, then raise the temperature to 1200 °C and hold for 1 h. After evacuating, introduce argon for liquid-phase sintering, raise the temperature to 1500 °C and hold for 2 h, with a heating rate of 5 °C / min.

[0043] After testing, the different pore size distributions of the porous materials with different pore sizes are relatively uniform, and they have pore sizes of 2 - 5 nm, 10 - 30 nm, and 100 - 170 nm.

[0044] Example 2

[0045] The preparation method of the porous material with different pore sizes is as follows:

[0046] S1: Take 3 g of MgO, 18 g of Al2O3, and 80 g of SiC powder, mix them evenly, add a 0.8 wt.% sodium carboxymethylcellulose solution, and adjust the pH to 10 to obtain a ceramic slurry with a solid content of 30 vol.%;

[0047] S2: Place the ceramic slurry in a ball mill tank for ball milling. The ball milling time is 10 h and the rotation speed is 100 r / min;

[0048] S3: Add PS microspheres with different particle sizes to the ball-milled ceramic slurry, stir evenly, inject it into the mold, and centrifuge at a speed of 5000 rpm on a centrifuge for 40 min; The addition amount of PS microspheres with different particle sizes is 1.5% of the volume of the ceramic slurry, and the particle sizes are 10 - 30 nm and 100 - 170 nm respectively, with a volume ratio of 1:1;

[0049] S4: Immerse the bottom of the mold in a liquid cold source at -100 °C for rapid freezing;

[0050] S5: Freeze-dry at a temperature of -50 °C and a pressure of 5 Pa to obtain porous ceramic preforms with different pore sizes;

[0051] S6: Place the porous ceramic preforms with different pore sizes in an atmosphere box furnace, hold at 385 °C in air for 20 min, then raise the temperature to 1200 °C and hold for 1 h. After evacuating, introduce argon for liquid-phase sintering, raise the temperature to 1500 °C and hold for 2 h, with a heating rate of 5 °C / min.

[0052] After testing, the different pore size distributions of the porous materials with different pore sizes are uniform, and they have pore sizes of 1 - 3 nm, 10 - 30 nm, and 100 - 170 nm.

[0053] Example 3

[0054] The preparation method of porous materials with different pore sizes is as follows:

[0055] S1: Take 3 g of MgO, 18 g of Al2O3 and 80 g of SiC powder, mix them evenly, add a 0.8 wt.% sodium carboxymethyl cellulose solution, adjust the pH to 10, and obtain a ceramic slurry with a solid content of 30 vol.%;

[0056] S2: Place the ceramic slurry in a ball mill jar for ball milling. The ball milling time is 10 h and the rotation speed is 100 r / min;

[0057] S3: Add PS microspheres with different particle sizes to the ball-milled ceramic slurry, stir evenly, inject it into a mold, and centrifuge it at a rotation speed of 6000 rpm for 30 min on a centrifuge; The addition amount of PS microspheres with different particle sizes is 2% of the volume of the ceramic slurry, and the particle sizes are 10 - 30 nm and 100 - 170 nm respectively, and the volume ratio is 1:1;

[0058] S4: Immerse the bottom of the mold in a liquid cold source at -100 °C for rapid freezing;

[0059] S5: Freeze-dry at a temperature of -50 °C and a pressure of 5 Pa to obtain porous ceramic preforms with different pore sizes;

[0060] S6: Place the porous ceramic preforms with different pore sizes in an atmosphere box furnace, keep them at 385 °C in air for 20 min, then raise the temperature to 1200 °C and keep it for 1 h, evacuate and then introduce argon for liquid phase sintering, raise the temperature to 1500 °C and keep it for 2 h, and the heating rate is 5 °C / min.

[0061] After testing, the different pore size distributions of the porous materials with different pore sizes are relatively uniform, and they have pore sizes of 1 - 2 nm, 10 - 30 nm and 100 - 170 nm.

[0062] Comparative Example 1

[0063] The preparation method of the porous material is as follows:

[0064] S1: Take 3 g of MgO, 18 g of Al2O3 and 80 g of SiC powder, mix them evenly, add a 0.8 wt.% sodium carboxymethyl cellulose solution, adjust the pH to 10, and obtain a ceramic slurry with a solid content of 30 vol.%;

[0065] S2: Place the ceramic slurry in a ball mill jar for ball milling. The ball milling time is 10 h and the rotation speed is 100 r / min;

[0066] S3: Add PS microspheres of the same particle size to the ball-milled ceramic slurry, stir evenly, inject into a mold, and centrifuge at 5000 rpm for 40 min on a centrifuge; the addition amount of PS microspheres is 1.5% of the volume of the ceramic slurry, and the particle size is 100 - 170 nm; S4: Immerse the bottom of the mold in a liquid cold source at -100 °C for rapid freezing;

[0067] S5: Freeze-dry at a temperature of -50 °C and a pressure of 5 Pa to obtain porous ceramic preforms with different pore sizes;

[0068] S6: Place the porous ceramic preforms with different pore sizes in an atmosphere box furnace, keep them at 385 °C in air for 20 min, then raise the temperature to 1200 °C and keep it for 1 h, evacuate and then introduce argon for liquid-phase sintering, raise the temperature to 1500 °C and keep it for 2 h, and the heating rate is 5 °C / min.

[0069] After testing, the pore size distribution of the porous material is uniform, and it has pore sizes of 1 - 3 nm and 100 - 170 nm.

[0070] Example 4

[0071] Carry out the following tests on the porous materials with different pore sizes prepared by Example 1 (result named: Example 4-1), Example 2 (result named: Example 4-2), Example 3 (result named: Example 4-3) and Comparative Example 1 (result named: Comparative Example 2) respectively:

[0072] Preparation of modified porous materials with different pore sizes loaded with pigments:

[0073] Step 1: Dissolve chitosan in a 3% acetic acid solution to prepare a 1 L chitosan acetate solution with a concentration of 0.5 g / L, add 100 g of porous materials with different pore sizes, react with magnetic stirring for 6 h, centrifuge at 9000 rpm for 5 min to separate the solid and liquid, wash the solid and dry it at 70 °C, and grind it to obtain modified porous materials with different pore sizes;

[0074] Step 2: Disperse 400 mg of phthalocyanine green G in 10 L of ultrapure water to form a phthalocyanine green G suspension. Take 20 g of modified porous materials with different pore sizes and disperse them in the pigment solution, stir magnetically for 3 h, centrifuge at 9000 rpm for 5 min to separate the solid and liquid, wash the solid and dry it at 70 °C, and grind it to obtain modified porous materials with different pore sizes loaded with pigments with a particle size of 2 - 20 μm.

[0075] Example 5

[0076] Carry out the following tests on the porous materials with different pore sizes prepared by Example 1 (result named: Example 5-1), Example 2 (result named: Example 5-2), Example 3 (result named: Example 5-3) and Comparative Example 1 (result named: Comparative Example 3) respectively:

[0077] Preparation of Modified Porous Materials with Different Pore Sizes Loaded with Pigments:

[0078] Step 1: Dissolve chitosan in 3% acetic acid solution to prepare 1 L of 1.5 g / L chitosan acetate solution. Add 100 g of the porous materials with different pore sizes prepared in Example 2, and react under magnetic stirring for 6 h. Centrifuge at 9000 rpm for 5 min to separate the solid and liquid. After washing the solid, dry it at 70 °C and grind it to obtain modified porous materials with different pore sizes.

[0079] Step 2: Disperse 400 mg of phthalocyanine green G in 10 L of ultrapure water to form a phthalocyanine green G suspension. Take 30 g of the modified porous materials with different pore sizes and disperse them in the pigment solution. Stir magnetically for 3 h, centrifuge at 9000 rpm for 5 min to separate the solid and liquid. After washing the solid, dry it at 70 °C and grind it to obtain modified porous materials with different pore sizes loaded with pigments with a particle size of 2 - 20 μm.

[0080] Example 6

[0081] Use the porous materials with different pore sizes prepared in Example 1 (result named: Example 6 - 1), Example 2 (result named: Example 6 - 2), Example 3 (result named: Example 6 - 3) and Comparative Example 1 (result named: Comparative Example 4) to conduct the following tests:

[0082] Preparation of Modified Porous Materials with Different Pore Sizes Loaded with Pigments:

[0083] Step 1: Dissolve chitosan in 3% acetic acid solution to prepare 1 L of 2 g / L chitosan acetate solution. Add 100 g of the porous materials with different pore sizes prepared in Example 2, and react under magnetic stirring for 6 h. Centrifuge at 9000 rpm for 5 min to separate the solid and liquid. After washing the solid, dry it at 70 °C and grind it to obtain modified porous materials with different pore sizes.

[0084] Step 2: Disperse 400 mg of phthalocyanine green G in 10 L of ultrapure water to form a phthalocyanine green G suspension. Take 40 g of the modified porous materials with different pore sizes and disperse them in the pigment solution. Stir magnetically for 3 h, centrifuge at 9000 rpm for 5 min to separate the solid and liquid. After washing the solid, dry it at 70 °C and grind it to obtain modified porous materials with different pore sizes loaded with pigments with a particle size of 2 - 20 μm. Measure the pigment loading amount of the modified porous materials with different pore sizes loaded with pigments. The results are shown in Table 1 below:

[0085] Table 1

[0086]

[0087]

[0088] From the perspectives of pigment loading and economy, the modified porous materials with different pore sizes loaded with pigments in the results of Example 5-2 were selected for the next experiment.

[0089] Example 7

[0090] Preparation of highly stable pigment particles:

[0091] Step 1: Prepare 200 mL of a PVP / ethanol solution with a mass concentration of 10%. Add 10 g of the modified porous materials with different pore sizes loaded with pigments, stir evenly, and place them in an electrospinning device for electrospinning. The electrospinning conditions are as follows: the spinning temperature is 24 °C, the humidity is 26%, the flow rate of the spinning solution is 0.5 mL / h, the outer diameter of the needle is 0.8 mm, the inner diameter is 0.5 mm, and the receiving distance is 13 cm to obtain a porous fiber membrane coated with pigments;

[0092] Step 2: Remove the porous fiber membrane coated with pigments, place it in a vacuum drying oven at 70 °C for drying, crush it, and pass through a 200-mesh sieve to obtain porous fiber membrane particles coated with pigments with a porosity of 67.2% and a pore size of 10-30 μm;

[0093] Step 3: Dissolve chitosan in a 3% acetic acid solution to prepare a 1.5 g / L chitosan acetate solution; take 5 g of attapulgite nanorods, add 5 L of PBS buffer solution, and ultrasonically disperse to obtain an attapulgite nanorod suspension;

[0094] Step 4: Immerse 5 g of the porous fiber membrane particles coated with pigments in 10 L of the chitosan acetate solution for 2 h;

[0095] Step 5: Add the attapulgite nanorod suspension, stir and mix evenly, and carry out an electrostatic assembly reaction at room temperature for 4.5 h;

[0096] Step 6: Take out the reactants, wash them with water, and freeze-dry to obtain highly stable pigment particles.

[0097] Example 8

[0098] Preparation of highly stable pigment particles:

[0099] Step 1: Prepare 200 mL of a PVP / ethanol solution with a mass concentration of 12%. Add 15 g of the modified porous materials with different pore sizes loaded with pigments, stir evenly, and place them in an electrospinning device for electrospinning. The electrospinning conditions are as follows: the spinning temperature is 24 °C, the humidity is 26%, the flow rate of the spinning solution is 0.7 mL / h, the outer diameter of the needle is 0.8 mm, the inner diameter is 0.5 mm, and the receiving distance is 15 cm to obtain a porous fiber membrane coated with pigments;

[0100] Step 2: Remove the porous fiber membrane coated with pigment, place it in a vacuum drying oven at 70 °C for drying, crush it, and pass it through a 200-mesh sieve to obtain porous fiber membrane particles coated with pigment with a porosity of 71.3% and a pore size of 15 - 40 μm;

[0101] Step 3: Dissolve chitosan in a 3% acetic acid solution to prepare a 1.5 g / L chitosan acetate solution; Take 5 g of attapulgite nanorods, add 5 L of PBS buffer solution, and ultrasonically disperse to obtain an attapulgite nanorod suspension;

[0102] Step 4: Immerse 5 g of porous fiber membrane particles coated with pigment in 10 L of chitosan acetate solution for 2 h;

[0103] Step 5: Add the attapulgite nanorod suspension, stir and mix evenly, and carry out an electrostatic assembly reaction at room temperature for 4.5 h;

[0104] Step 6: Take out the reactant, wash it with water, and freeze-dry to obtain highly stable pigment particles.

[0105] Example 9

[0106] Preparation of highly stable pigment particles:

[0107] Step 1: Prepare 200 mL of a PVP / ethanol solution with a mass concentration of 14%, add 20 g of modified porous materials with different pore sizes loaded with pigment, stir evenly, and place it in an electrospinning device for electrospinning. The electrospinning conditions are: spinning temperature is 24 °C, humidity is 26%, the flow rate of the spinning solution is 0.8 mL / h, the outer diameter of the needle is 0.8 mm, the inner diameter is 0.5 mm, and the receiving distance is 16 cm to obtain a porous fiber membrane coated with pigment;

[0108] Step 2: Remove the porous fiber membrane coated with pigment, place it in a vacuum drying oven at 70 °C for drying, crush it, and pass it through a 200-mesh sieve to obtain porous fiber membrane particles coated with pigment with a porosity of 75.6% and a pore size of 20 - 50 μm;

[0109] Step 3: Dissolve chitosan in a 3% acetic acid solution to prepare a 1.5 g / L chitosan acetate solution; Take 5 g of attapulgite nanorods, add 5 L of PBS buffer solution, and ultrasonically disperse to obtain an attapulgite nanorod suspension;

[0110] Step 4: Immerse 5 g of porous fiber membrane particles coated with pigment in 10 L of chitosan acetate solution for 2 h;

[0111] Step 5: Add the attapulgite nanorod suspension, stir and mix evenly, and carry out an electrostatic assembly reaction at room temperature for 4.5 h;

[0112] Step 6: Take out the reactant, wash it with water, and freeze-dry to obtain highly stable pigment particles.

[0113] Comparative Example 5

[0114] The difference between this comparative example and Example 9 is that instead of using the modified porous materials with different pore sizes loaded with pigments obtained from the results of Example 5-2 for the next test, the modified porous materials with different pore sizes loaded with pigments prepared in Comparative Example 3 are used, and the other conditions remain unchanged.

[0115] Lightfastness stability test: The light stability of the highly stable pigment particles was tested by ultraviolet diffuse reflection-visible spectrophotometry. The sample was irradiated with a UV lamp with a wavelength of 395 nm, the power of the UV lamp was 50 W, and the light intensity was 550 mW / cm 2 , and after irradiating for 120 h, the color difference was calculated. The smaller the color difference, the better the lightfastness stability.

[0116] The results are shown in Table 2 and Figure 1 as follows.

[0117] Table 2

[0118]

[0119] After comparison, the highly stable pigment particles prepared in Example 9 were used to prepare the non-fading masterbatch for lawns.

[0120] Example 10

[0121] A method for preparing a non-fading masterbatch for lawns, comprising the following steps:

[0122] Step 1: Mix 1000 g of low-density polyethylene, 120 g of polyethylene wax, and 80 g of magnesium stearate by high-speed stirring, and heat to 80 °C, and keep the temperature constant until the polyethylene wax is completely melted;

[0123] Step 2: Add 100 g of highly stable pigment particles, and stir until a large amount of highly stable pigment particles are coated on the surface of the low-density polyethylene to obtain a mixture;

[0124] Step 3: After the twin-screw extruder is heated to 130 °C, add the mixture, and control the temperatures of the first to sixth zones of the twin-screw extruder to be: 130 °C in the first zone, 135 °C in the second zone, 140 °C in the third zone, 135 °C in the fourth zone, 125 °C in the fifth zone, and 120 °C in the sixth zone, and extrude and pelletize to obtain the non-fading masterbatch for lawns.

[0125] Example 11

[0126] A method for preparing a non-fading masterbatch for lawns, comprising the following steps:

[0127] Step 1: Mix 1000 g of low-density polyethylene, 120 g of polyethylene wax, and 80 g of magnesium stearate by high-speed stirring, and heat to 80 °C, and keep the temperature constant until the polyethylene wax is completely melted;

[0128] Step 2: Add 150 g of highly stable pigment particles and stir until a large amount of highly stable pigment particles are coated on the surface of low-density polyethylene to obtain a mixture.

[0129] Step 3: After the twin-screw extruder is heated to 130 °C, add the mixture, and control the temperatures of the first to sixth zones of the twin-screw extruder to be: 130 °C in the first zone, 135 °C in the second zone, 140 °C in the third zone, 135 °C in the fourth zone, 125 °C in the fifth zone, and 120 °C in the sixth zone. Extrude and pelletize to obtain the non-fading masterbatch for lawn.

[0130] Example 12

[0131] A method for preparing a non-fading masterbatch for lawn, comprising the following steps:

[0132] Step 1: High-speed stir and mix 1000 g of low-density polyethylene, 120 g of polyethylene wax, and 80 g of magnesium stearate, and heat to 80 °C, and keep the temperature constant until the polyethylene wax is completely melted.

[0133] Step 2: Add 180 g of highly stable pigment particles and stir until a large amount of highly stable pigment particles are coated on the surface of low-density polyethylene to obtain a mixture.

[0134] Step 3: After the twin-screw extruder is heated to 130 °C, add the mixture, and control the temperatures of the first to sixth zones of the twin-screw extruder to be: 130 °C in the first zone, 135 °C in the second zone, 140 °C in the third zone, 135 °C in the fourth zone, 125 °C in the fifth zone, and 120 °C in the sixth zone. Extrude and pelletize to obtain the non-fading masterbatch for lawn.

[0135] Comparative Example 6

[0136] The difference between this comparative example and Example 11 is that instead of using the highly stable pigment particles prepared in Example 9 for the next test, the modified porous materials with different pore sizes loaded with pigments prepared in Comparative Example 3 are used, and the other conditions remain unchanged.

[0137] Comparative Example 7

[0138] The difference between this comparative example and Example 11 is that instead of using the highly stable pigment particles prepared in Example 9 for the next test, the pigment particles prepared in Comparative Example 5 are used, and the other conditions remain unchanged.

[0139] Test the performance of the non-fading masterbatch for lawn prepared in each example:

[0140] Color difference and UV aging resistance test: At a wavelength of 315 - 400 nm and a light intensity of 6000 μW / cm 2Exposed under ultraviolet light for 30 days, and the color difference (△E) and elongation at break retention rate of each masterbatch after 30 days of exposure were measured according to GB / T 1040 "Determination of Tensile Properties of Plastics". The test results are shown in Table 3 below:

[0141] Table 3

[0142]

[0143] The above embodiments are for a clear and complete description of the technical solution, and are partial embodiments of the present invention, rather than all embodiments. However, the embodiments of the present invention are not limited by the above embodiments. Any other changes, modifications, substitutions, combinations or simplifications made without departing from the spirit and principle of the present invention shall be equivalent replacement methods and are all included in the protection scope of the present invention.

Claims

1. An unfading color masterbatch for lawns, characterized in that: It comprises the following raw materials in parts by weight: 10 - 18 parts of high-stability pigment particles, 100 parts of low-density polyethylene, 12 parts of polyethylene wax, and 8 parts of magnesium stearate; The preparation method of the high-stability pigment particles is as follows: Step 1: Dissolve chitosan in a 3% acetic acid solution to prepare a chitosan acetic acid solution with a concentration of 0.5 - 2 g / L. Add porous materials with different pore sizes, and carry out magnetic stirring reaction for 6 h. Centrifuge at 9000 rpm for 5 min to separate the solid and liquid. After washing the solid, dry it at 70 °C, and grind it to obtain modified porous materials with different pore sizes; Step 2: Dissolve / disperse 25 - 50 mg of pigment in 1 L of ultrapure water to form a pigment solution / suspension. Take 2 - 4 g of modified porous materials with different pore sizes and disperse them in the pigment solution, and carry out magnetic stirring for 2 - 4 h. Centrifuge at 9000 rpm for 5 min to separate the solid and liquid. After washing the solid, dry it at 70 °C, and grind it to obtain modified porous materials with different pore sizes loaded with pigment; Step 3: Prepare a PVP / ethanol solution with a mass concentration of 10 - 14%. Add the modified porous materials loaded with pigment, stir evenly, and place it in an electrospinning device for electrospinning to obtain a porous fiber membrane coated with pigment; Step 4: Remove the porous fiber membrane coated with pigment, put it into a vacuum drying oven at 70 °C for drying, crush it, and pass it through a 200-mesh sieve to obtain porous fiber membrane particles coated with pigment with a porosity of 60 - 80% and a pore size of 10 - 50 μm; Step 5: Dissolve chitosan in a 3% acetic acid solution to prepare a chitosan acetic acid solution with a concentration of 0.5 - 2 g / L. Take 50 mg of attapulgite nanorods, add 50 mL of PBS buffer solution, and carry out ultrasonic dispersion to obtain an attapulgite nanorod suspension; Step 6: Immerse 50 mg of porous fiber membrane particles coated with pigment in 100 mL of chitosan acetic acid solution for 1 - 2 h; Step 7: Add the attapulgite nanorod suspension, stir and mix evenly, and carry out electrostatic assembly reaction at room temperature for 4 - 5 h; Step 8: Take out the reactant, wash it with water, and freeze-dry it to obtain high-stability pigment particles.

2. The non-fading color masterbatch for lawn according to claim 1, characterized in that: The preparation method of the porous materials with different pore sizes in Step 1 is as follows: S1: Take 3 g of MgO, 18 g of Al2O3, and 80 g of SiC powder and mix them evenly. Add a 0.8 wt.% sodium carboxymethyl cellulose solution, and adjust the pH to 10 to obtain a ceramic slurry with a solid content of 25 - 40 vol.%; S2: Place the ceramic slurry in a ball mill jar for ball milling. The ball milling time is 10 h, and the rotation speed is 100 r / min; S3: Add PS microspheres with different particle sizes to the ball-milled ceramic slurry, stir evenly, inject it into a mold, and centrifuge it at a rotation speed of 4000 - 6000 rpm for 30 - 50 min on a centrifuge; S4: Immerse the bottom of the mold in a liquid cold source at -120 °C to -30 °C for rapid freezing; S5: Carry out freeze-drying at a temperature of -50 °C and a pressure of 0 - 50 Pa to obtain a porous ceramic preform with different pore sizes; S6: Place the porous ceramic preforms with different pore sizes into an atmosphere box furnace, keep them at 385 °C in air for 20 min, then raise the temperature to 1200 °C and keep it for 1 h. After evacuating, introduce argon for liquid-phase sintering, raise the temperature to 1500 °C and keep it for 2 h, with a heating rate of 5 °C / min.

3. A non-fading color masterbatch for lawns according to claim 1, characterized in that: The addition amount of PS microspheres with different particle sizes is 1-2% of the volume of the ceramic slurry, and the particle sizes are 10-30 nm and 100-170 nm respectively, with a volume ratio of 1:

1.

4. A color masterbatch for lawn that is not prone to fading according to claim 1, characterized in that: In step 1, the volume-mass ratio of the chitosan acetate solution to the porous material with different pore sizes is 1L: (50-130) g.

5. The non-fading color masterbatch for lawn according to claim 1, characterized in that: In step 2, the particle size of the modified porous material with different pore sizes loaded with pigments is 2-20 μm.

6. A non-fading color masterbatch for lawns according to claim 1, characterized in that: In step 3, the volume-mass ratio of the PVP / ethanol solution to the modified porous material with different pore sizes is 20mL: (1-2) g.

7. The non-fading color masterbatch for lawn according to claim 1, characterized in that: In step 3, the electrospinning conditions are: the spinning temperature is 20-26 °C, the humidity is 20-30%, the flow rate of the spinning solution is 0.5-0.8 mL / h, the outer diameter of the needle is 0.8 mm, the inner diameter is 0.5 mm, and the receiving distance is 13-16 cm.

8. The preparation method of a non-fading color masterbatch for lawn according to any one of claims 1 to 7, characterized in that: It includes the following steps: Step 1: Stir and mix low-density polyethylene, polyethylene wax, and magnesium stearate at high speed, and heat to 80 °C, keep the temperature constant until the polyethylene wax is completely melted; Step 2: Add high-stability pigment particles and stir until a large number of high-stability pigment particles are coated on the surface of the low-density polyethylene to obtain a mixture; Step 3: After the twin-screw extruder is heated to 130 °C, add the mixture and extrude and pelletize at a temperature of 120-140 °C to obtain the color masterbatch for lawns that is not easy to fade.

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