Weather-resistant highlight color master batch and preparation method thereof

Abstract

The invention relates to the technical field of plastics, in particular to a weather-resistant highlight color master batch and a preparation method thereof. The weather-resistant highlight color master batch is prepared from 80 to 100 parts of PP (Polypropylene) resin, 2 parts of siloxane modified polypeptide and 35 parts of C.I. Pigment violet, the preparation method of the weather-resistant highlight color master batch comprises the following steps: preparing siloxane modified polypeptide; the preparation method comprises the following steps: weighing PP resin, siloxane modified polypeptide and C.I. Pigment violet 3; the preparation method comprises the following steps: uniformly mixing the raw materials, putting into a double-screw extruder, and extruding at the processing temperature of 180-200 DEG C to obtain the weather-resistant highlight color master batch; the siloxane modified polypeptide obtained by the invention can reduce the probability of decomposition of C.I. Pigment violet 3 in the color master batch when encountering heat; and the addition of the siloxane modified polypeptide is accidentally found to improve the glossiness of the resin product.

Description

Technical Field

[0001] The present invention relates to the technical field of plastics, in particular to a weather-resistant high-gloss masterbatch and a preparation method thereof. Background Art

[0002] Masterbatches, also called color seeds or masterbatches, are primarily used in plastics. Composed of three basic elements: pigment or dye, carrier, and additives, masterbatches are aggregates of pigment uniformly loaded onto a resin. These aggregates are also known as pigment concentrates. During processing, a small amount of masterbatch is blended with uncolored resin to achieve the desired pigment concentration in the desired resin or product.

[0003] Adding CI Pigment Violet 3 to a masterbatch creates a common purple masterbatch. However, CI Pigment Violet 3 is known to contain hydrophilic groups, resulting in poor compatibility with resin substrates. Furthermore, CI Pigment Violet 3 is susceptible to thermal decomposition, leading to brittle cracking in resin products obtained through hot extrusion of this masterbatch. Furthermore, due to the susceptibility of CI Pigment Violet 3 to thermal decomposition, the masterbatch is prone to cracking during drying during transportation and storage, resulting in poor weather resistance. Summary of the Invention

[0004] In view of the deficiencies of the prior art, one of the objects of the present invention is to provide a weather-resistant high-gloss masterbatch, and the second object of the present invention is to provide a method for preparing the weather-resistant high-gloss masterbatch.

[0005] One of the objectives of the present invention is achieved through the following technical solutions:

[0006] A weather-resistant high-gloss masterbatch is prepared by including the following components in parts by weight:

[0007] 80-100 parts of PP resin, 2 parts of silicone modified polypeptide and 35 parts of CI pigment violet.

[0008] In a preferred embodiment, 0.1 parts of dibutyltin dilaurate is further included.

[0009] The second object of the present invention is achieved through the following technical solutions:

[0010] A method for preparing a weather-resistant high-gloss masterbatch comprises the following steps:

[0011] Step 1: Preparation of siloxane-modified polypeptides:

[0012] (1) Dissolve 1 kg of polylysine in 20 L of anhydrous DMF, then add 0.2 kg of NHS and 0.3 kg of EDC-HCl, and stir at room temperature for 2-2.5 hours to obtain a solution; the significance of this step is to activate the amino / carboxyl groups;

[0013] (2) KH-550 was added dropwise to the solution in an amount of 0.5-1.5 L, and the temperature was raised to 60-80° C. under nitrogen protection, and the reaction was carried out for 6-12 hours to obtain a reaction solution; the significance of this step is siloxane grafting;

[0014] (3) The reaction solution was poured into cold ether for precipitation, and the solid was collected by centrifugation. The solid was washed three times with 70% ethanol aqueous solution to remove unreacted siloxane, and then vacuum dried to obtain a light yellow powder, which is the siloxane-modified polypeptide;

[0015] Step 2: weigh PP resin, silicone-modified polypeptide and CI pigment violet 3;

[0016] Step 3: After mixing the raw materials evenly, put them into a twin-screw extruder for extrusion at a processing temperature of 180-200°C to obtain a weather-resistant high-gloss masterbatch.

[0017] In a preferred embodiment, after the addition of KH-550 is completed, triethylamine is used to adjust the pH of the solution to 8-9 to promote siloxane condensation.

[0018] In a preferred embodiment, the vacuum drying temperature is 50° C. and the drying time is 24 hours.

[0019] In a preferred embodiment, the extrusion diameter is 1-2 mm ± 0.2 mm, and the length is 1-2 mm ± 0.2 mm. Since the present invention solves the technical problem of masterbatch brittleness, and since it is known that smaller masterbatch particles make it easier to evenly disperse the pigment into the resin to be colored, the present invention uses a smaller masterbatch particle size to improve coloring uniformity.

[0020] The beneficial effects of the present invention are: the siloxane-modified polypeptide obtained by the present invention can reduce the probability of thermal decomposition of CI Pigment Violet 3 in the masterbatch; and it is unexpectedly found that the addition of the siloxane-modified polypeptide improves the glossiness of the resin product. DETAILED DESCRIPTION

[0021] The following is further explained in conjunction with specific implementation methods:

[0022] Example 1

[0023] Preparation of weather-resistant high-gloss masterbatch:

[0024] Step 1: Preparation of siloxane-modified polypeptides:

[0025] (1) Dissolve 1 kg of polylysine in 20 L of anhydrous DMF, then add 0.2 kg of NHS and 0.3 kg of EDC-HCl, and stir at room temperature for 2 h to obtain a solution;

[0026] (2) KH-550 was added dropwise to the solution in an amount of 0.5 L. After the addition of KH-550 was completed, the pH of the solution was adjusted to 8 using triethylamine. The solution was heated to 60° C. under nitrogen protection and reacted for 6 h to obtain a reaction solution.

[0027] (3) The reaction solution was poured into cold ether for precipitation, and the solid was collected by centrifugation, washed three times with 70% ethanol aqueous solution, and then vacuum dried (vacuum drying temperature 50°C, drying time 24 hours) to obtain a light yellow powder, which is the siloxane-modified polypeptide;

[0028] Step 2: Weigh 80 parts of PP resin, 2 parts of siloxane-modified polypeptide, and 35 parts of CI pigment violet according to weight;

[0029] Step 3: After mixing the raw materials evenly, put them into a twin-screw extruder for extrusion at a processing temperature of 180° C., an extrusion diameter of 1 mm ± 0.2 mm, and a length of 1 mm ± 0.2 mm to obtain a weather-resistant and high-gloss masterbatch.

[0030] Preparation of resin products:

[0031] After heat drying, weather-resistant high-gloss masterbatch and PP resin were mixed in a weight ratio of 1:1 and then injection molded into a sheet with a total length of 150mm, a width of 20mm at the end, a width of 10mm at the measuring section, a length of 50mm at the measuring section, and a thickness of 2mm (this is the 1B type specimen commonly used in elongation at break test). The injection molding parameters are as follows:

[0032] Barrel temperature: 170°C (rear section), 190°C (middle section), and 230°C (front section). Mold temperature: 60°C (mold temperature). Melt temperature: 250°C (injection processing). Injection pressure: 1500 bar. Holding pressure: 80% of injection pressure. Back pressure: 0.5 MPa. Screw speed and plasticizing back pressure: 50 rpm, plasticizing back pressure: 0.3 MPa.

[0033] Example 2

[0034] Preparation of weather-resistant high-gloss masterbatch:

[0035] Step 1: Preparation of siloxane-modified polypeptides:

[0036] (1) Dissolve 1 kg of polylysine in 20 L of anhydrous DMF, then add 0.2 kg of NHS and 0.3 kg of EDC-HCl, and stir at room temperature for 2.5 h to obtain a solution;

[0037] (2) KH-550 was added dropwise to the solution in an amount of 1.5 L. After the addition of KH-550 was completed, the pH of the solution was adjusted to 9 using triethylamine. The solution was heated to 80° C. under nitrogen protection and reacted for 12 h to obtain a reaction solution.

[0038] (3) The reaction solution was poured into cold ether for precipitation, and the solid was collected by centrifugation, washed three times with 70% ethanol aqueous solution, and then vacuum dried (vacuum drying temperature 50°C, drying time 24 hours) to obtain a light yellow powder, which is the siloxane-modified polypeptide;

[0039] Step 2: Weigh 100 parts of PP resin, 2 parts of siloxane-modified polypeptide, and 35 parts of CI pigment violet according to weight;

[0040] Step 3: After mixing the raw materials evenly, put them into a twin-screw extruder for extrusion at a processing temperature of 200° C., an extrusion diameter of 2 mm ± 0.2 mm, and a length of 2 mm ± 0.2 mm to obtain a weather-resistant and high-gloss masterbatch.

[0041] Preparation of resin products:

[0042] After heat drying, weather-resistant high-gloss masterbatch and PP resin are mixed in a weight ratio of 1:1 and then injection molded into a sheet with a total length of 150mm, a width of 20mm at the end, a width of 10mm at the measuring section, a length of 50mm at the measuring section, and a thickness of 2mm. The injection molding parameters are as follows:

[0043] Barrel temperature: 170°C (rear section), 190°C (middle section), and 230°C (front section). Mold temperature: 60°C (mold temperature). Melt temperature: 250°C (injection processing). Injection pressure: 1500 bar. Holding pressure: 80% of injection pressure. Back pressure: 0.5 MPa. Screw speed and plasticizing back pressure: 50 rpm, plasticizing back pressure: 0.3 MPa.

[0044] Example 3

[0045] Preparation of weather-resistant high-gloss masterbatch:

[0046] Step 1: Preparation of siloxane-modified polypeptides:

[0047] (1) Dissolve 1 kg of polylysine in 20 L of anhydrous DMF, then add 0.2 kg of NHS and 0.3 kg of EDC-HCl, and stir at room temperature for 2.3 h to obtain a solution;

[0048] (2) KH-550 was added dropwise to the solution in an amount of 1.3 L. After the addition of KH-550 was completed, the pH of the solution was adjusted to 8.5 using triethylamine. The solution was heated to 70° C. under nitrogen protection and reacted for 10 h to obtain a reaction solution.

[0049] (3) The reaction solution was poured into cold ether for precipitation, and the solid was collected by centrifugation, washed three times with 70% ethanol aqueous solution, and then vacuum dried (vacuum drying temperature 50°C, drying time 24 hours) to obtain a light yellow powder, which is the siloxane-modified polypeptide;

[0050] Step 2: Weigh 90 parts of PP resin, 2 parts of siloxane-modified polypeptide, and 35 parts of CI pigment violet according to weight;

[0051] Step 3: After mixing the raw materials evenly, put them into a twin-screw extruder for extrusion at a processing temperature of 190° C., an extrusion diameter of 1.5 mm ± 0.2 mm, and a length of 1.5 mm ± 0.2 mm to obtain a weather-resistant and high-gloss masterbatch.

[0052] Preparation of resin products:

[0053] After heat drying, weather-resistant high-gloss masterbatch and PP resin are mixed in a weight ratio of 1:1 and then injection molded into a sheet with a total length of 150mm, a width of 20mm at the end, a width of 10mm at the measuring section, a length of 50mm at the measuring section, and a thickness of 2mm. The injection molding parameters are as follows:

[0054] Barrel temperature: 170°C (rear section), 190°C (middle section), and 230°C (front section). Mold temperature: 60°C (mold temperature). Melt temperature: 250°C (injection processing). Injection pressure: 1500 bar. Holding pressure: 80% of injection pressure. Back pressure: 0.5 MPa. Screw speed and plasticizing back pressure: 50 rpm, plasticizing back pressure: 0.3 MPa.

[0055] Example 4

[0056] The step 2 further includes weighing 0.1 parts of dibutyltin dilaurate, and the remaining steps are the same as those in Example 1.

[0057] Comparative Example 1

[0058] In step 2, the siloxane-modified polypeptide is replaced with an equal weight of PP resin, and the remaining steps are the same as those in Example 3.

[0059] Comparative Example 2

[0060] In step 2, the siloxane-modified polypeptide was replaced with polylysine of equal weight, and the remaining steps were the same as those in Example 3.

[0061] The materials used in the above embodiments and comparative examples are as follows:

[0062] (1) Polylysine, purchased from Shanghai Hongshun Biotechnology Co., Ltd., molecular weight 1000-5000, specification 500g / bottle.

[0063] (2) Anhydrous DMF, purchased from Tianjin Renyida Chemical Co., Ltd., trade name: super dry N,N-dimethylformamide, purity 99.9%.

[0064] (3) NHS (N-hydroxysuccinimide) was purchased from Wuhan Kemik Biopharmaceutical Technology Co., Ltd. with a purity of 99%.

[0065] (4) EDC-HCl, purchased from Jinan Fannuo Chemical Co., Ltd., purity 99%.

[0066] (5) KH-550, purchased from Qingdao Xuxin Chemical Co., Ltd., is a colorless transparent liquid with a purity of ≥98.0%.

[0067] (6) Triethylamine, purchased from Shandong Zhuoxuan New Materials Co., Ltd., purity 99%.

[0068] (7) PP resin, purchased from Shaanxi Yanchang China Coal Yulin Energy Chemical Co., Ltd., model EPS30R.

[0069] (8) CI Pigment Violet 3, purchased from Tianjin Alta Technology Co., Ltd., CAS#1325-82-2, product number 1ST5866, purity 99%.

[0070] (9) All other materials not specified were purchased through conventional channels.

[0071] Mechanical properties test

[0072] 1. Experimental purpose: To verify that the resin product obtained by the present invention can effectively reduce brittle cracking compared with the prior art.

[0073] 2. Experimental Method: The sheets obtained in Examples 1-3 and Comparative Examples 1-2 were conditioned at 23±2°C and 50±5% relative humidity for 48 hours (to avoid temperature and humidity affecting the test) and subjected to elongation at break testing. The test standard was ASTM D638, with a tensile speed of 50 mm / min. Five valid specimens (sheets) were tested for each condition, and the average value was calculated.

[0074] 3. Experimental results, see Table 1.

[0075] Table 1 Statistics of elongation at break

[0076] Spline Type Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Elongation at break (%) 480.39 488.45 490.74 451.11 399.56

[0077] As shown in Table 1, after high-temperature injection molding, the elongation at break of Comparative Examples 1 and 2 significantly lags behind that of Examples 1-3. This demonstrates that the siloxane-modified polypeptide prepared in the present invention overcomes the defects of CI Pigment Violet 3, such as its hydrophilicity and susceptibility to high-temperature decomposition. This in turn enhances the mechanical strength of the masterbatch and resin products prepared therefrom, making them less susceptible to brittle cracking and providing the masterbatch or resin products with weather resistance to high outdoor temperatures.

[0078] Optical performance test

[0079] 1. Experimental purpose: To verify that the masterbatch obtained by the present invention has higher gloss and lower color difference after being made into resin products.

[0080] 2. Experimental Method: The gloss of the sheets obtained in each Example and Comparative Example was measured using a 60° angle gloss meter. The color difference values ​​of the sheets obtained in each Example and Comparative Example were measured using a colorimeter. Repeat this three times and take the average value.

[0081] 3. Experimental results, see Table 2.

[0082] Table 2 Statistics of optical performance test results

[0083] Spline Type Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Glossiness (GU) 50 46 49 41 34 Color difference (ΔE) 1.6 1.7 1.5 2.7 3.2

[0084] As shown in Table 2, the glossiness of the resin products obtained in the present invention is significantly improved compared to Comparative Examples 1 and 2. In addition, the glossiness is ranked from high to low as follows: Example 1, 3, and 2, indicating that the higher the content of siloxane-modified polypeptide and CI Pigment Violet 3, the higher the glossiness.

[0085] Table 2 also shows that the resin products obtained by the present invention have very high color consistency compared to Comparative Examples 1 and 2. It is known that a color difference of 3.0 or greater can be clearly perceived by the naked eye. However, the color difference of Examples 1-3 is only 1.5-1.7. This shows that the present invention helps reduce the color difference of CI Pigment Violet 3 masterbatches or resin products.

[0086] The above embodiments and descriptions are only for explaining the principles and best embodiments of the present invention. Without departing from the spirit and scope of the present invention, the present invention may be subject to various changes and improvements, which shall fall within the scope of the invention to be protected.

Claims

1. A weather-resistant high-gloss masterbatch, characterized in that: The preparation comprises the following components in parts by weight: 80-100 parts of PP resin, 2 parts of silicone modified polypeptide and 35 parts of CI pigment violet.

2. The weather-resistant high-gloss masterbatch according to claim 1, characterized in that: Including 0.1 parts of dibutyltin dilaurate.

3. A method for preparing the weather-resistant high-gloss masterbatch according to claim 1, characterized in that: The following steps are involved: Step 1: Preparation of siloxane-modified polypeptides: (1) Dissolve 1 kg of polylysine in 20 L of anhydrous DMF, then add 0.2 kg of NHS and 0.3 kg of EDC-HCl, and stir at room temperature for 2-2.5 h to obtain a solution; (2) KH-550 was added dropwise to the solution in an amount of 0.5-1.5 L, and the temperature was raised to 60-80°C under nitrogen protection, and the reaction was carried out for 6-12 hours to obtain a reaction solution; (3) The reaction solution was poured into cold ether for precipitation, and the solid was collected by centrifugation, washed three times with 70% ethanol aqueous solution, and then vacuum dried to obtain a light yellow powder, which is the siloxane-modified polypeptide; Step 2: weigh PP resin, silicone-modified polypeptide and CI pigment violet 3; Step 3: After mixing the raw materials evenly, put them into a twin-screw extruder for extrusion at a processing temperature of 180-200°C to obtain a weather-resistant high-gloss masterbatch.

4. The method for preparing weather-resistant high-gloss masterbatch according to claim 3, characterized in that: After the KH-550 was added dropwise, the pH of the solution was adjusted to 8-9 using triethylamine.

5. The method for preparing weather-resistant high-gloss masterbatch according to claim 3, characterized in that: The vacuum drying temperature is 50° C. and the drying time is 24 h.

6. The method for preparing weather-resistant high-gloss masterbatch according to claim 3, characterized in that: The extrusion diameter is 1-2 mm ± 0.2 mm, and the length is 1-2 mm ± 0.2 mm.