High performance color masterbatch for automotive engineering plastics and method for its preparation

Abstract

The application discloses a kind of high-performance color master batch for automotive engineering plastics and preparation method thereof, belong to color master batch technical field.It includes the following weight parts of raw materials:83-95 parts of polypropylene resin, 33-41 parts of linear low density polyethylene, 12-16 parts of color powder, 6-10 parts of antioxidant, 7-21 parts of auxiliary agent, 3-5 parts of lubricant.Among them, polypropylene is used as the main matrix, which gives the color master batch excellent mechanical strength;In addition, the raw material is added with linear low density polyethylene, which has good flexibility and can improve the impact resistance of the color master batch;In addition, the auxiliary agent molecule contains a variety of functional groups, which can significantly improve the ultraviolet resistance and flame retardant properties of the matrix;In conclusion, the color master batch prepared by the application has excellent mechanical properties, ultraviolet resistance and flame retardant properties, and has important application value in the field of color master batch technology.

Description

Technical Field

[0001] This invention belongs to the field of color masterbatch technology, specifically, it relates to a high-performance color masterbatch for automotive engineering plastics and its preparation method. Background Technology

[0002] With the rapid development of the automotive industry, lightweight design has become one of the important trends in modern automobile manufacturing. In modern passenger vehicles, plastic materials now account for 12%-15% of the total vehicle weight. Among them, engineering plastics such as polypropylene (PP), nylon (PA), and polycarbonate (PC) are gradually replacing traditional metal materials, becoming one of the key materials for achieving weight reduction, energy conservation, and emission reduction in automobiles, from interior parts to exterior parts and structural components. However, to meet the diverse needs of consumers for the appearance and functionality of automobiles, engineering plastics often require coloring treatment in practical applications, and this process places extremely high demands on the performance of color masterbatches.

[0003] Color masterbatch is a high-concentration colorant made by uniformly dispersing pigments or dyes in a carrier resin. Its main function is to provide stable and uniform color effects for plastic products without affecting the physical properties of the substrate. In the field of automotive engineering plastics, high-performance color masterbatches need to meet a series of stringent technical specifications. If the performance of the color masterbatch is insufficient, it may lead to problems such as fading, discoloration, cracking, and even a decline in mechanical properties in plastic products, thereby affecting the quality and service life of the entire vehicle.

[0004] While a wide variety of color masterbatches are currently available on the market, numerous problems remain when applied to automotive engineering plastics. For example, many color masterbatches exhibit significant fading upon prolonged exposure to ultraviolet light, particularly noticeable in automotive exterior parts. Furthermore, typical resin matrices have low oxygen indexes, high flammability, and produce large amounts of dense smoke and toxic gases during combustion. These characteristics not only increase fire risks but also pose a serious threat to human safety. Therefore, there is an urgent need to develop a high-performance color masterbatch that combines UV resistance and flame retardancy to meet the demands of automotive engineering plastics, which has significant practical implications and broad market prospects. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of the prior art and provide a high-performance masterbatch for automotive engineering plastics and its preparation method.

[0006] The objective of this invention can be achieved through the following technical solutions:

[0007] A method for preparing high-performance masterbatch for automotive engineering plastics includes the following steps:

[0008] Polypropylene resin, linear low-density polyethylene, color powder, antioxidant, additives and lubricant are mixed in a mixer and stirred for 15-30 minutes. Then, the mixture is added to a twin-screw extruder for melt blending, extrusion and granulation to obtain high-performance color masterbatch for automotive engineering plastics.

[0009] Furthermore, the raw materials are as follows by weight: 83-95 parts polypropylene resin, 33-41 parts linear low-density polyethylene, 12-16 parts color powder, 6-10 parts antioxidant, 7-21 parts additives, and 3-5 parts lubricant.

[0010] Furthermore, the antioxidant is one of antioxidant 1010, antioxidant 168, antioxidant DNP, and antioxidant TNP.

[0011] Furthermore, the lubricant is one of paraffin wax and stearic acid.

[0012] Using polypropylene as the main matrix endows the color masterbatch with excellent mechanical strength. The added linear low-density polyethylene has very fine crystals and good flexibility, which can improve the impact resistance of the color masterbatch.

[0013] Furthermore, the additive is prepared through the following steps:

[0014] Step 1: Add phosphoric acid, pentaerythritol, p-toluenesulfonic acid, and toluene to a three-necked flask equipped with a magnetic stirrer, condenser, thermometer, and water separator. Purge with nitrogen as a protective gas and heat in an oil bath to 100°C. Continuously separate the water produced by the reaction using the water separator. Maintain the temperature for 6 hours until the reaction is complete. Cool to room temperature, add saturated sodium bicarbonate solution to neutralize the unreacted acid, adjust the pH to 7, separate the aqueous phase, wash several times with deionized water, and finally rotary evaporate to obtain intermediate product 1. The ratio of phosphoric acid, pentaerythritol, p-toluenesulfonic acid, and toluene is 20.7g:13.6g:0.3g:100mL.

[0015] Under the catalysis of p-toluenesulfonic acid, phosphoric acid and pentaerythritol undergo an esterification reaction to give intermediate 1; the specific reaction process is shown below:

[0016]

[0017] Step 2: Add cyanuric chloride and acetone to a three-necked flask equipped with a magnetic stirrer, condenser, and thermometer. Dissolve 2,4-dihydroxybenzophenone and sodium hydroxide in acetone and distilled water, respectively. Stir and mix thoroughly, then add the solutions sequentially to the three-necked flask. Control the reaction temperature at 60°C and reflux for 5 hours. After the reaction is complete, filter the solution. Wash the residue several times with distilled water and ethanol to obtain intermediate product 2. The ratio of cyanuric chloride, acetone, 2,4-dihydroxybenzophenone, sodium hydroxide, and distilled water is 20.3g:150mL:42.7g:7.9g:50mL.

[0018] Sodium hydroxide reacts with the para-hydroxyl group in the 2,4-dihydroxybenzophenone molecule to form sodium phenolate, which has stronger nucleophilicity. Sodium phenolate can attack the carbon atom bonded to the chlorine atom in cyanuric chloride, forming an ether bond. By adjusting the molar ratio of 2,4-dihydroxybenzophenone to cyanuric chloride to approximately 2:1 (with a slight excess of cyanuric chloride), it can be ensured that only two chlorine atoms in the cyanuric chloride molecule undergo substitution reaction, thereby generating intermediate product 2. The specific reaction process is shown below:

[0019]

[0020] Step 3: Add intermediate product 1, intermediate product 2, toluene, and triethylamine to a three-necked flask equipped with a magnetic stirrer, condenser, and thermometer. After mixing and stirring evenly, react continuously for 8 hours under a 55°C water bath. Once the reaction is complete, filter to remove triethylamine hydrochloride, concentrate under reduced pressure to remove some solvent, and then perform column chromatography purification using a benzene-ethyl acetate (3:2, v / v) elution system. Finally, remove residual eluent by reduced pressure distillation to obtain the auxiliary agent. The ratio of intermediate product 1, intermediate product 2, toluene, and triethylamine is 25.9 g: 109.4 g: 200 mL: 30 mL.

[0021] Triethylamine is used as an acid-binding agent. By adjusting the molar ratio of intermediate 2 to intermediate 1 to approximately 2:1 (with a slight excess of intermediate 2), the affinity substitution reaction of the two hydroxyl groups in intermediate 1 molecule can be ensured, yielding the auxiliary agent. The structure of the auxiliary agent is shown below:

[0022]

[0023] R:

[0024] The additive molecule prepared by this invention contains spirocyclic phosphate, triazine ring, and benzophenone structures. The spirocyclic phosphate exhibits excellent flame-retardant properties due to its rigid six-membered heterocyclic skeleton. Its mechanism of action is as follows: under high-temperature combustion conditions, the pentaerythritol group catalyzes a char formation reaction to generate a dense char layer, forming a physical barrier to block heat transfer and oxygen penetration, thereby inhibiting the thermo-oxidative degradation of the matrix material and flame spread, and improving the flame-retardant properties of the matrix. Furthermore, the triazine ring in the additive is a nitrogen-based flame retardant that produces [flame retardants] during combustion. Nitrogen gas dilutes and reduces smoke density. At high temperatures, it self-condenses to form melamine, making the char layer dense. It can synergistically work with spirocyclic phosphate to significantly enhance the flame retardant properties of the matrix. Finally, the additive molecules introduce two benzophenone structures. When ultraviolet light irradiates the benzophenone molecule, its carbonyl and benzene ring systems absorb the energy of ultraviolet photons, causing the molecule to transition from the ground state to the excited state. This absorption process converts ultraviolet light into vibrational or rotational energy within the molecule, thereby preventing ultraviolet light from penetrating into the matrix and improving the matrix's UV resistance.

[0025] The beneficial effects of this invention are:

[0026] 1. The color masterbatch prepared by this invention uses polypropylene as the main matrix, which gives the color masterbatch excellent mechanical strength.

[0027] 2. Adding linear low-density polyethylene to the raw materials provides better flexibility and can improve the impact resistance of the masterbatch.

[0028] 3. An additive is prepared through a series of reactions. The additive molecule contains a variety of functional groups, which can significantly improve the UV resistance and flame retardant properties of the matrix.

[0029] In summary, the color masterbatch prepared by this invention has excellent mechanical properties, UV resistance, and flame retardant properties, and has important application value in the field of color masterbatch technology. Detailed Implementation

[0030] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0031] Example 1

[0032] Preparation aids:

[0033] Step 1: Add 20.7g phosphoric acid, 13.6g pentaerythritol, 0.3g p-toluenesulfonic acid and 100mL toluene to a three-necked flask equipped with a magnetic stirrer, condenser, thermometer and water separator. Purge with nitrogen as a protective gas and heat in an oil bath to 100℃. Continuously separate the water produced by the reaction through the water separator. Keep the reaction at this temperature for 6 hours until the reaction is complete. Cool to room temperature, add saturated sodium bicarbonate solution to neutralize the unreacted acid, adjust the pH to 7, separate the aqueous phase, wash several times with deionized water, and finally rotary evaporate to obtain intermediate product 1.

[0034] Step 2: Add 20.3g of cyanuric chloride and 50mL of acetone to a three-necked flask equipped with a magnetic stirrer, a condenser and a thermometer. Then dissolve 42.7g of 2,4-dihydroxybenzophenone and 7.9g of sodium hydroxide in 100mL of acetone and 50mL of distilled water respectively. After stirring and mixing evenly, add them to the three-necked flask in sequence. Control the reaction temperature at 60℃ and reflux for 5h. After the reaction is completed, filter and wash the residue with distilled water and ethanol several times to obtain intermediate product 2.

[0035] Step 3: Add 25.9g of intermediate product 1, 109.4g of intermediate product 2, 200mL of toluene and 30mL of triethylamine to a three-necked flask equipped with a magnetic stirrer, a condenser and a thermometer. After mixing and stirring evenly, the mixture is stirred continuously in a 55℃ water bath for 8 hours until the reaction is complete. After filtering to remove triethylamine hydrochloride, the solvent is removed by vacuum concentration. Then, column chromatography is performed using a benzene-ethyl acetate (3:2, v / v) elution system to purify the mixture. Finally, residual eluent is removed by vacuum distillation to obtain the auxiliary agent.

[0036] Example 2

[0037] Preparation aids:

[0038] Step 1: Add 41.4g of phosphoric acid, 27.2g of pentaerythritol, 0.6g of p-toluenesulfonic acid and 200mL of toluene to a three-necked flask equipped with a magnetic stirrer, condenser, thermometer and water separator. Purge with nitrogen as a protective gas and heat in an oil bath to 100℃. Continuously separate the water produced by the reaction through the water separator. Keep the reaction at this temperature for 6 hours until the reaction is complete. Cool to room temperature, add saturated sodium bicarbonate solution to neutralize the unreacted acid, adjust the pH to 7, separate the aqueous phase, wash several times with deionized water, and finally rotary evaporate to obtain intermediate product 1.

[0039] Step 2: Add 40.6g of cyanuric chloride and 100mL of acetone to a three-necked flask equipped with a magnetic stirrer, a condenser and a thermometer. Then dissolve 85.4g of 2,4-dihydroxybenzophenone and 15.8g of sodium hydroxide in 200mL of acetone and 100mL of distilled water respectively. After stirring and mixing evenly, add them to the three-necked flask in sequence. Control the reaction temperature at 60℃ and reflux for 5h. After the reaction is completed, filter and wash the residue with distilled water and ethanol several times to obtain intermediate product 2.

[0040] Step 3: Add 51.8g of intermediate product 1, 218.8g of intermediate product 2, 400mL of toluene and 60mL of triethylamine to a three-necked flask equipped with a magnetic stirrer, a condenser and a thermometer. After mixing and stirring evenly, the mixture is stirred continuously in a 55℃ water bath for 8 hours until the reaction is complete. After filtering to remove triethylamine hydrochloride, the solvent is removed by vacuum concentration. Then, column chromatography is performed using a benzene-ethyl acetate (3:2, v / v) elution system to purify the mixture. Finally, residual eluent is removed by vacuum distillation to obtain the auxiliary agent.

[0041] Example 3

[0042] 83g of polypropylene resin, 33g of linear low-density polyethylene, 12g of phthalocyanine green, 6g of antioxidant 1010, 7g of the additives prepared in Example 1, and 3g of paraffin wax were mixed in a mixer and stirred for 15 minutes. Then, the mixture was added to a twin-screw extruder for melt blending, extrusion, and granulation to obtain a high-performance masterbatch for automotive engineering plastics.

[0043] Example 4

[0044] 89g of polypropylene resin, 39g of linear low-density polyethylene, 14g of phthalocyanine blue, 8g of antioxidant 168, 14g of the additives prepared in Example 2, and 4g of stearic acid were mixed in a mixer and stirred for 30 minutes. Then, the mixture was added to a twin-screw extruder for melt blending, extrusion, and granulation to obtain a high-performance masterbatch for automotive engineering plastics.

[0045] Example 5

[0046] 95g of polypropylene resin, 41g of linear low-density polyethylene, 16g of phthalocyanine red, 10g of antioxidant 168, 21g of the additives prepared in Example 2, and 5g of stearic acid were mixed in a mixer and stirred for 30 minutes. Then, the mixture was added to a twin-screw extruder for melt blending, extrusion, and granulation to obtain a high-performance masterbatch for automotive engineering plastics.

[0047] Comparative Example 1

[0048] Commercially available phosphorus-based flame retardants were used to replace the additives in Example 5, and the remaining process parameters and operating procedures were the same as in Example 5. The target color masterbatch was finally prepared.

[0049] Comparative Example 2

[0050] Use commercially available weather-resistant masterbatch.

[0051] The following performance tests were conducted on Examples 3, 4, and 5, and Comparative Examples 1 and 2, according to different test standards:

[0052] The notched impact strength was tested according to the national standard GB / T 1843-2008 "Determination of Impact Strength of Plastic Cantilever Beams";

[0053] The samples were placed in a xenon lamp aging test chamber for accelerated aging for 15 days. The aging conditions were an air atmosphere, a xenon lamp wavelength of 280-800 nm, and an irradiation intensity of 500 W / m². 2 The notched impact strength of the specimens before and after aging was tested (GB / T 1843-2008), and the retention rate of notched impact strength was calculated; the retention rate of notched impact strength = notched impact strength after testing / notched impact strength before testing × 100%;

[0054] The oxygen index of the samples was determined according to the national standard GB / T 2406-2008 "Test Method for Burning Performance of Plastics";

[0055] The measurement results are shown in the table below:

[0056] Test Project Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 <![CDATA[Izod impact strength / (kJ / m 2 )]]> 6.89 7.12 7.26 7.05 6.07 Notched impact strength retention rate / % 93.0 93.7 94.6 68.5 89.7 Limiting oxygen index / % 28.6 29.5 29.9 27.2 18.2

[0057] As can be seen from the table above, the color masterbatch prepared by the embodiments of the present invention has excellent impact resistance, and its UV resistance and flame retardant properties are higher than those of the comparative example. Therefore, the present invention has important application value in the field of color masterbatch technology.

[0058] In the description of this specification, the references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0059] The above description is merely an example and illustration of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described, or use similar methods to replace them, as long as they do not deviate from the invention or exceed the scope defined in the claims, all of which should fall within the protection scope of the present invention.

Claims

1. A method for preparing high-performance masterbatch for automotive engineering plastics, characterized in that, Includes the following steps: Polypropylene resin, linear low-density polyethylene, color powder, antioxidant, additives and lubricant are mixed in a mixer, stirred and then added to a twin-screw extruder for melt blending, extrusion and granulation to obtain high-performance color masterbatch for automotive engineering plastics. The auxiliary agent is prepared through the following steps: Step 1: Add phosphoric acid, pentaerythritol, p-toluenesulfonic acid and toluene to a flask, purge with nitrogen, heat in an oil bath to 100°C, keep the temperature for 6 hours until the reaction is complete, cool to room temperature, adjust the pH to 7, separate the contents, wash, and rotary evaporate to obtain intermediate product 1. Step 2: Add cyanuric chloride and acetone to the flask, then dissolve 2,4-dihydroxybenzophenone and sodium hydroxide in acetone and distilled water respectively, stir and mix, and add them to the flask in sequence. Reflux at 60°C for 5 hours. After the reaction is complete, filter, wash the filter residue, and obtain intermediate product 2. Step 3: Add intermediate product 1, intermediate product 2, toluene and triethylamine to a flask, mix and stir evenly, and react continuously for 8 hours under a 55°C water bath. After the reaction is complete, filter, concentrate under reduced pressure, purify by column chromatography, and distill under reduced pressure to obtain the auxiliary agent. The raw materials are as follows by weight: 83-95 parts polypropylene resin, 33-41 parts linear low-density polyethylene, 12-16 parts color powder, 6-10 parts antioxidant, 7-21 parts additives, and 3-5 parts lubricant.

2. The method for preparing a high-performance masterbatch for automotive engineering plastics according to claim 1, characterized in that, The antioxidant is one of antioxidant 1010, antioxidant 168, antioxidant DNP, and antioxidant TNP.

3. The method for preparing a high-performance masterbatch for automotive engineering plastics according to claim 1, characterized in that, The lubricant is one of paraffin wax and stearic acid.

4. The method for preparing a high-performance masterbatch for automotive engineering plastics according to claim 1, characterized in that, In step 1, the ratio of phosphoric acid, pentaerythritol, p-toluenesulfonic acid, and toluene is 20.7g:13.6g:0.3g:100mL.

5. The method for preparing a high-performance masterbatch for automotive engineering plastics according to claim 1, characterized in that, In step 2, the ratio of cyanuric chloride, acetone, 2,4-dihydroxybenzophenone, sodium hydroxide, and distilled water is 20.3g:150mL:42.7g:7.9g:50mL.

6. The method for preparing a high-performance masterbatch for automotive engineering plastics according to claim 1, characterized in that, In step 3, the ratio of intermediate product 1, intermediate product 2, toluene, and triethylamine is 25.9g:109.4g:200mL:30mL.

7. A high-performance masterbatch for automotive engineering plastics, characterized in that, Prepared according to the method according to any one of claims 1-6.

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