High-performance color master batch for automobile engineering plastics and preparation method thereof

Abstract

The invention discloses a high-performance color master batch for automobile engineering plastics and a preparation method of the high-performance color master batch, and belongs to the technical field of color master batches. Comprising the following raw materials in parts by weight: 83-95 parts of polypropylene resin, 33-41 parts of linear low-density polyethylene, 12-16 parts of toner, 6-10 parts of an antioxidant, 7-21 parts of an auxiliary agent and 3-5 parts of a lubricant. Wherein polypropylene is used as a main matrix, so that the color master batch is endowed with excellent mechanical strength; in addition, the linear low-density polyethylene added into the raw materials has good flexibility, and the impact resistance of the color master batch can be improved; in addition, molecules of the auxiliary agent contain various functional groups, so that the anti-ultraviolet performance and the flame-retardant performance of the matrix can be remarkably improved; in conclusion, the color master batch prepared by the invention has excellent mechanical properties, ultraviolet resistance and flame retardance, and has important application value in the technical field of color master batches.

Description

Technical Field

[0001] The present invention belongs to the technical field of masterbatch, and specifically relates to a high-performance masterbatch for automotive engineering plastics and a preparation method thereof. Background Art

[0002] With the rapid development of the automotive industry, lightweight design has become one of the important trends in modern automotive manufacturing. In modern passenger cars, the proportion of plastic materials has reached 12%-15% of the total vehicle mass. Among them, engineering plastics such as polypropylene (PP), nylon (PA), and polycarbonate (PC) are gradually replacing traditional metal materials from interior parts to exterior parts and then to structural parts, becoming one of the key materials for achieving vehicle weight reduction, energy conservation, and emission reduction. However, in order to meet the diverse needs of consumers for the appearance and functionality of automobiles, engineering plastics often need to be colored during actual application, and this process poses extremely high requirements for the performance of masterbatch.

[0003] Masterbatch is a high-concentration colorant in which pigments or dyes are uniformly dispersed in a carrier resin. Its main function is to provide a stable and uniform color effect for plastic products without affecting the physical properties of the base material. In the field of automotive engineering plastics, high-performance masterbatch needs to meet a series of stringent technical indicators. If the performance of the masterbatch is insufficient, it may cause problems such as fading, color change, cracking, and even a decrease in mechanical properties of plastic products, thereby affecting the quality and service life of the entire vehicle.

[0004] Although there are a wide variety of masterbatch products on the market currently, there are still many problems when they are applied to automotive engineering plastics. For example, many masterbatches will show obvious fading when exposed to ultraviolet light for a long time, which is particularly prominent in automotive exterior parts. In addition, the oxygen index of general resin matrices is low, the flammability is high, and a large amount of thick smoke and toxic gases will be generated during combustion. These characteristics not only increase the fire risk but also pose a serious threat to the lives and safety of personnel. In view of the above problems, it is urgent to develop a high-performance masterbatch with both anti-ultraviolet and flame-retardant properties to meet the needs of automotive engineering plastics, which has important practical significance and broad market prospects. Summary of the Invention

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

[0006] The purpose of the present invention can be achieved by the following technical solutions:

[0007] A preparation method of a high-performance masterbatch for automotive engineering plastics, comprising the following steps:

[0008] Mix polypropylene resin, linear low-density polyethylene, color powder, antioxidant, additives and lubricant in a blender. After stirring for 15 - 30 minutes, add them into a twin-screw extruder for melt blending, extrusion and pelletizing to obtain a high-performance color masterbatch for automotive engineering plastics.

[0009] Furthermore, the raw materials are as follows by weight parts: 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 additives, and 3 - 5 parts of 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 additives are prepared through the following steps:

[0014] Step 1: Add phosphoric acid, pentaerythritol, p-toluenesulfonic acid and toluene into a three-necked flask equipped with a magnetic stirrer, a condenser, a thermometer and a water separator. Introduce nitrogen as a protective gas and heat it to 100 °C in an oil bath. Continuously separate the water generated by the reaction through the water separator, keep the reaction for 6 hours. After the reaction is completed, cool it to room temperature, add saturated sodium bicarbonate solution to neutralize the unreacted acid, adjust the pH to 7, separate the aqueous phase by liquid separation, wash it with deionized water for several times, and finally perform rotary evaporation to obtain intermediate product 1. The dosage ratio of phosphoric acid, pentaerythritol, p-toluenesulfonic acid and toluene is 20.7 g: 13.6 g: 0.3 g: 100 mL;

[0015] Under the catalysis of p-toluenesulfonic acid, phosphoric acid and pentaerythritol undergo an esterification reaction to obtain intermediate product 1. The specific reaction process is as follows:

[0016]

[0017] Step 2: Add cyanuric chloride and acetone into a three-necked flask equipped with a magnetic stirrer, a condenser and a thermometer. Then dissolve 2,4-dihydroxybenzophenone and sodium hydroxide in acetone and distilled water respectively. After stirring and mixing them evenly, add them into the three-necked flask in sequence. Control the reaction temperature at 60 °C and reflux for 5 h. After the reaction is completed, perform suction filtration. Wash the filter residue with distilled water and ethanol for multiple times to obtain intermediate 2. The dosage ratio of cyanuric chloride, acetone, 2,4-dihydroxybenzophenone, sodium hydroxide and distilled water is 20.3 g: 150 mL: 42.7 g: 7.9 g: 50 mL;

[0018] Sodium hydroxide can react with the hydroxyl group at the para-position in the 2,4-dihydroxybenzophenone molecule to form a phenolate with stronger nucleophilicity. The phenolate can attack the carbon atom connected to the chlorine atom on cyanuric chloride to generate an ether bond. By adjusting the molar ratio of 2,4-dihydroxybenzophenone to cyanuric chloride to be close to 2:1 (cyanuric chloride is slightly in excess), it can ensure that only two chlorine atoms in the cyanuric chloride molecule undergo substitution reactions, thereby generating intermediate 2. The specific reaction process is as follows:

[0019]

[0020] Step 3: Add intermediate 1, intermediate 2, toluene and triethylamine into a three-necked flask equipped with a magnetic stirrer, a condenser and a thermometer. After mixing and stirring evenly, under the water bath condition of 55 °C, continuously stir for 8 h. After the reaction is completed, filter to remove triethylamine hydrochloride. After concentrating under reduced pressure to remove part of the solvent, use a benzene-ethyl acetate (3:2, v / v) elution system for column chromatography purification. Finally, remove the residual eluent by distillation under reduced pressure to obtain the additive. The dosage ratio of intermediate 1, intermediate 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 be close to 2:1 (intermediate 2 is slightly in excess), it can ensure that two hydroxyl groups in the intermediate 1 molecule undergo nucleophilic substitution reactions to obtain the additive. The structure of the additive is as follows:

[0022]

[0023] R:

[0024] The obtained additive of the present invention contains spirophosphate, triazine ring and benzophenone structure in its molecule. Among them, spirophosphate exhibits excellent flame retardant performance by virtue of its rigid six-membered heterocyclic skeleton. Its action mechanism is as follows: Under high-temperature combustion conditions, the pentaerythritol group generates a dense carbon layer through a catalytic carbonization reaction, forming a physical barrier to block heat transfer and oxygen penetration, thereby inhibiting the thermal-oxidative degradation and flame spread of the matrix material and improving the flame retardant performance of the matrix. In addition, the triazine ring in the additive, belonging to a nitrogen-based flame retardant, will generate nitrogen-containing gases during combustion, dilute and reduce the smoke density, self-condense to form melem at high temperature to make the carbon layer compact, and can cooperate with spirophosphate to greatly enhance the flame retardant performance of the matrix. Finally, two benzophenone structures are introduced into the additive molecule. When ultraviolet light irradiates the benzophenone molecule, its carbonyl group and benzene ring system will 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 internal vibrational or rotational energy of the molecule, thus preventing ultraviolet light from penetrating into the matrix and improving the ultraviolet resistance of the matrix.

[0025] Advantages of the present invention:

[0026] 1. The obtained masterbatch of the present invention uses polypropylene as the main matrix, endowing the masterbatch with excellent mechanical strength;

[0027] 2. Adding linear low-density polyethylene to the raw materials has good 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 various functional groups, which can significantly improve the ultraviolet resistance and flame retardant performance of the matrix;

[0029] In summary, the obtained masterbatch of the present invention has excellent mechanical properties, ultraviolet resistance and flame retardant performance, and has important application value in the field of masterbatch technology. Specific embodiments

[0030] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative work belong to the scope of protection of the present invention.

[0031] Example 1

[0032] Preparation of the additive:

[0033] Step 1: Add 20.7 g of phosphoric acid, 13.6 g of pentaerythritol, 0.3 g of p-toluenesulfonic acid, and 100 mL of toluene into a three-necked flask equipped with a magnetic stirrer, a condenser, a thermometer, and a water separator. Introduce nitrogen as a protective gas, heat the oil bath to 100 °C, continuously separate the water generated by the reaction through the water separator, keep the reaction at a constant temperature for 6 h. After the reaction is completed, cool it to room temperature, add saturated sodium bicarbonate solution to neutralize the unreacted acid, adjust the pH to 7, separate and remove the aqueous phase by liquid separation, wash it with deionized water for several times, and finally perform rotary evaporation to obtain intermediate 1;

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

[0035] Step 3: Add 25.9 g of intermediate 1, 109.4 g of intermediate 2, 200 mL of toluene, and 30 mL of triethylamine into a three-necked flask equipped with a magnetic stirrer, a condenser, and a thermometer. After mixing and stirring evenly, under the condition of a 55 °C water bath, continuously stir for 8 h. After the reaction is completed, filter to remove triethylamine hydrochloride. After concentrating under reduced pressure to remove part of the solvent, use a benzene-ethyl acetate (3:2, v / v) elution system for column chromatography purification, and finally remove the residual eluent by distillation under reduced pressure to obtain the additive.

[0036] Example 2

[0037] Preparation of additive:

[0038] Step 1: Add 41.4 g of phosphoric acid, 27.2 g of pentaerythritol, 0.6 g of p-toluenesulfonic acid, and 200 mL of toluene into a three-necked flask equipped with a magnetic stirrer, a condenser, a thermometer, and a water separator. Introduce nitrogen as a protective gas, heat the oil bath to 100 °C, continuously separate the water generated by the reaction through the water separator, keep the reaction at a constant temperature for 6 h. After the reaction is completed, cool it to room temperature, add saturated sodium bicarbonate solution to neutralize the unreacted acid, adjust the pH to 7, separate and remove the aqueous phase by liquid separation, wash it with deionized water for several times, and finally perform rotary evaporation to obtain intermediate 1;

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

[0040] Step 3: Add 51.8 g of intermediate product 1, 218.8 g of intermediate product 2, 400 mL of toluene and 60 mL of triethylamine into a three-necked flask equipped with a magnetic stirrer, a condenser and a thermometer. After mixing and stirring evenly, under the condition of a 55 °C water bath, continuously stir for 8 h. After the reaction is completed, filter to remove triethylamine hydrochloride. After concentrating under reduced pressure to remove part of the solvent, perform column chromatography purification using a benzene-ethyl acetate (3:2, v / v) elution system, and finally remove the residual eluent by distillation under reduced pressure to obtain the auxiliary agent.

[0041] Example 3

[0042] Mix 83 g of polypropylene resin, 33 g of linear low-density polyethylene, 12 g of phthalocyanine green, 6 g of antioxidant 1010, 7 g of the auxiliary agent prepared in Example 1 and 3 g of paraffin in a blender. After stirring for 15 min, add them into a twin-screw extruder, melt and blend, extrude and pelletize to obtain a high-performance masterbatch for automotive engineering plastics.

[0043] Example 4

[0044] Mix 89 g of polypropylene resin, 39 g of linear low-density polyethylene, 14 g of phthalocyanine blue, 8 g of antioxidant 168, 14 g of the auxiliary agent prepared in Example 2 and 4 g of stearic acid in a blender. After stirring for 30 min, add them into a twin-screw extruder, melt and blend, extrude and pelletize to obtain a high-performance masterbatch for automotive engineering plastics.

[0045] Example 5

[0046] Mix 95 g of polypropylene resin, 41 g of linear low-density polyethylene, 16 g of phthalocyanine red, 10 g of antioxidant 168, 21 g of the auxiliary agent prepared in Example 2 and 5 g of stearic acid in a blender. After stirring for 30 min, add them into a twin-screw extruder, melt and blend, extrude and pelletize to obtain a high-performance masterbatch for automotive engineering plastics.

[0047] Comparative Example 1

[0048] Use a commercially available phosphorus-based flame retardant to replace the auxiliary agent in Example 5, and refer to Example 5 for the remaining process parameters and operation procedures. Finally, prepare the target masterbatch.

[0049] Comparative Example 2

[0050] Use commercially available weather-resistant masterbatch.

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

[0052] Use the national standard GB / T 1843-2008 "Determination of Izod impact strength of plastics" to test the notched impact strength;

[0053] Put the specimen into a xenon lamp aging test chamber to accelerate aging for 15 days. The aging conditions are air atmosphere, xenon lamp wavelength 280 - 800 nm, irradiation intensity 500 W / m 2 , test the notched impact strength (GB / T 1843-2008) of the specimen before and after aging and calculate the retention rate of the notched impact strength; Retention rate of notched impact strength = Notched impact strength after test / Notched impact strength before test × 100%;

[0054] Use the national standard GB / T 2406-2008 "Test method for flammability of plastics" to determine the oxygen index of the specimen;

[0055] The measured results are shown in the following table:

[0056] Test item Example 3 Example 4 Example 5 Comparative example 1 Comparative example 2 <![CDATA[Notched 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] It can be seen from the above table that the masterbatch prepared in the examples of the present invention has excellent impact resistance, and its anti-ultraviolet performance and flame retardant performance are higher than those of the comparative examples. Therefore, the present invention has important application value in the technical field of masterbatch.

[0058] In the description of the specification, the description with reference to terms such as "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in a suitable manner in any one or more embodiments or examples.

[0059] The above content is only an example and explanation of the present invention. Those skilled in the art of the present technology make various modifications or supplements to the described specific embodiments or use similar methods to replace them. As long as they do not deviate from the invention or exceed the scope defined by the claims of the present invention, they should all belong to the protection scope of the present invention.

Claims

1. A method for preparing high-performance masterbatch for automotive engineering plastics, characterized in that: The following steps are involved: The polypropylene resin, linear low-density polyethylene, color powder, antioxidant, additive and lubricant are mixed in a mixer, stirred, and then added into a twin-screw extruder, melt blended, extruded, and granulated to obtain high-performance masterbatch for automotive engineering plastics.

2. The method for preparing a high-performance masterbatch for automotive engineering plastics according to claim 1, characterized in that: The raw materials are calculated in parts by weight as follows: 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, and 3-5 parts of lubricant.

3. 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.

4. 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 and stearic acid.

5. The method for preparing a high-performance masterbatch for automotive engineering plastics according to claim 1, characterized in that: The auxiliary agent is prepared by the following steps: Step 1, phosphoric acid, pentaerythritol, p-toluenesulfonic acid and toluene are added to a flask, nitrogen is introduced, and the oil bath is heated to 100° C., and the reaction is kept warm for 6 hours. After the reaction is completed, the temperature is cooled to room temperature, the pH is adjusted to 7, the liquids are separated, washed, and rotary evaporated to obtain intermediate 1; Step 2, adding cyanuric chloride and acetone into a flask, and then dissolving 2,4-dihydroxybenzophenone and sodium hydroxide in acetone and distilled water respectively, stirring and mixing, and then adding them into the flask in sequence, and reflux reaction at 60° C. for 5 hours. After the reaction is completed, filtering and washing the filter residue to obtain intermediate product 2; Step 3: Add intermediate product 1, intermediate product 2, toluene and triethylamine into a flask, mix and stir evenly, and react for 8 hours in a 55°C water bath with continuous stirring. After the reaction is completed, filter, concentrate under reduced pressure, purify by column chromatography, and distill under reduced pressure to obtain an auxiliary agent.

6. The method for preparing a high-performance masterbatch for automotive engineering plastics according to claim 5, characterized in that: In step 1, the ratio of phosphoric acid, pentaerythritol, p-toluenesulfonic acid and toluene is 20.7 g:13.6 g:0.3 g:100 mL.

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

8. The method for preparing a high-performance masterbatch for automotive engineering plastics according to claim 5, characterized in that: In step 3, the ratio of the amount of intermediate product 1, intermediate product 2, toluene and triethylamine is 25.9 g:109.4 g:200 mL:30 mL.

9. A high-performance masterbatch for automotive engineering plastics, characterized in that: Prepared according to the method according to any one of claims 1 to 8.

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