High-strength pc / abs alloy resistant to perfume and preparation method and application thereof

Abstract

The present application relates to a kind of high-strength PC / ABS alloy resistant to perfume and its preparation method and application, the high-strength PC / ABS alloy is made of the following weight parts of component: PC resin 50~80 parts, ABS resin 10~40 parts, perfume resistant cracking agent 2~8 parts, toughening agent 2~6 parts, compatible agent 1~5 parts, antioxidant 0.1~1.5 parts, lubricant 0.1~1.5 parts, ester exchange inhibitor 0.1~1.5 parts;Wherein, the perfume resistant cracking agent is the composite of montmorillonite and polybutylene terephthalate.Compared with prior art, the present application improves the strength of weld line by adding polymethyl methacrylate, synergizes the effect of montmorillonite and polybutylene terephthalate, and further improves the perfume resistance of weak position of part structure.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, and in particular to a high-strength PC / ABS alloy resistant to perfume, its preparation method, and its application. Background Technology

[0002] PC / ABS alloys combine the excellent properties of both PC and ABS, exhibiting superior impact resistance, processability, and thermal properties, making them widely used in automotive interiors and exteriors, digital products, and home appliances. However, PC / ABS has poor resistance to certain chemicals, making it susceptible to corrosion and potential cracking or cosmetic defects. Perfumes are frequently used in automotive interiors, and most commercially available car perfumes contain esters, alcohols, and fragrances. PC / ABS contains similar molecular structures, making it prone to discoloration and micro-cracks when exposed to highly volatile perfumes, ultimately leading to cracking. The perfume resistance of a material is largely related to the resin's molecular structure. Besides post-treatments such as applying chemical-resistant paints or electroplating, perfume resistance can be improved by adjusting the material's inherent properties.

[0003] Previous work has mostly focused on adding olefin copolymers to improve chemical resistance, but this is not very effective for perfume resistance and can reduce the mechanical properties of the material.

[0004] Chinese patent CN202211710982.4 discloses a PC / ABS composite material for automotive interiors that is resistant to perfumes and colognes, and its preparation method. The method includes the following steps: 60-80 parts PC resin; 20-35 parts ABS resin; 5-10 parts PET; 0-5 parts compatibilizer; 0.1-1 part light stabilizer; 0.1-2 parts antioxidant; and 0.1-0.5 parts lubricant. The PET resin has a viscosity of 0.5-0.8, a terminal hydroxyl content of 30-40 mol / t, and a diethylene glycol content ≤0.8%. This patent improves the perfume and cologne resistance of PC / ABS by adding a small amount of PET resin with specific viscosity and terminal hydroxyl content. However, PET resin requires a high melting temperature, and the crystallization rate of the composite material with added PET is slower, resulting in a long molding cycle, high injection temperature, slow crystallization at commonly used processing temperatures, film sticking, and continued crystallization and warping deformation after demolding. Summary of the Invention

[0005] The purpose of this invention is to overcome the problem that PC / ABS products in the prior art are prone to cracking when exposed to highly volatile perfumes, and to provide a high-strength PC / ABS alloy resistant to perfumes, its preparation method, and its application.

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

[0007] A high-strength PC / ABS alloy resistant to fragrance, comprising the following components in parts by weight:

[0008]

[0009] The perfume-resistant crack-resistant agent is a composite of montmorillonite and polybutylene terephthalate.

[0010] Preferably, the PC resin is bisphenol A type polycarbonate with a melt index of 7 to 15 g / 10 min at 300°C / 1.2 kg.

[0011] Preferably, the ABS resin has a mass-average molecular weight of 13w to 15w and a melt index of 20 to 30 g / min at 220℃ / 10kg.

[0012] Preferably, the silica content in the montmorillonite is 50-80% by mass.

[0013] Preferably, the polybutylene terephthalate has a characteristic viscosity of 0.5 to 2 dL / g and a melt index of 20 to 80 g / min at 250°C / 2.16 kg.

[0014] Preferably, the ratio of montmorillonite to polybutylene terephthalate by weight is 1:1 to 1:1.5.

[0015] Preferably, the toughening agent is a methyl methacrylate-butadiene-styrene terpolymer.

[0016] Preferably, the compatibilizer is polymethyl methacrylate.

[0017] Preferably, the antioxidant is selected from any one or more of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], tris(2,4-di-tert-butyl)phosphite, or dioctadecyl pentaerythritol diphosphite.

[0018] Preferably, the lubricant is selected from any one or more of silicone powder, paraffin wax, stearic acid, butyl stearate, or ethylene bis-stearamide.

[0019] Preferably, the transesterification inhibitor is sodium dihydrogen carbonate.

[0020] As a preferred technical solution, the high-strength PC / ABS alloy is made of the following components in parts by weight:

[0021]

[0022] As a preferred technical solution, the high-strength PC / ABS alloy is made of the following components in parts by weight:

[0023]

[0024] This invention also provides a method for preparing a high-strength PC / ABS alloy resistant to perfume, the specific steps of which are as follows:

[0025] (1) Prepare the components according to the following weight proportions:

[0026]

[0027] (2) The components obtained in step (1) are mixed evenly in a high-speed mixer. The mixed material is added to a twin-screw extruder for melt blending and extrusion. After cooling, pelletizing, and drying, a high-strength PC / ABS alloy resistant to perfume is obtained.

[0028] Preferably, in step (2), the twin screw speed is 250 to 500 rpm.

[0029] Preferably, in step (2), the extrusion temperature is 210 to 270°C.

[0030] Preferably, in step (2), the obtained perfume-resistant high-strength PC / ABS alloy is subjected to performance testing after injection molding.

[0031] In addition, the present invention also provides the application of the above-mentioned fragrance-resistant high-strength PC / ABS alloy in the manufacture of automotive interior and exterior trim parts, such as dashboard trim frames, bumpers, air vents and spoilers.

[0032] Compared with the prior art, the present invention has the following beneficial effects:

[0033] (1) In this invention, montmorillonite and polybutylene terephthalate are selected as perfume cracking resistant agents. Adding semi-crystalline polybutylene terephthalate (PBT) to PC / ABS will reduce the swelling effect of solvent on the material and improve the overall solvent resistance of the alloy.

[0034] (2) In this invention, montmorillonite and polybutylene terephthalate are selected as fragrance crack-resistant agents. The unique lamellar structure inside montmorillonite can form a barrier effect, which hinders the diffusion of solvent molecules. The interlayer material between the silicon-oxygen skeleton of montmorillonite adsorbs volatile fragrances and solvents, which prevents polymer chain segments from breaking and degrading under the action of solvent. The montmorillonite on the surface of the material forms a highly expanded gel in the solvent, which helps to form a tight cross-linked structure between particles and improves the fragrance resistance of the material.

[0035] (3) In this invention, by adding polymethyl methacrylate, the phase separation between PC and ABS is weakened, thereby improving the weld line strength. The synergistic effect of polymethyl methacrylate with montmorillonite and polybutylene terephthalate further improves the fragrance resistance of the weak parts.

[0036] (4) Compared with PET, polybutylene terephthalate (PBT) has a lower glass transition temperature and a lower melting point, and can be processed at a lower temperature. Moreover, PBT generally has better mechanical properties than PET, with higher dimensional stability, good chemical corrosion resistance, excellent electrical insulation, good mechanical properties and elasticity, and lower water absorption. It also has better fluidity in the molten state and is easier to process. Detailed Implementation

[0037] The present invention will now be described in detail with reference to specific embodiments. These embodiments are based on the technical solution of the present invention and provide detailed implementation methods and specific operating procedures. However, the scope of protection of the present invention is not limited to the following embodiments.

[0038] The raw materials used in the embodiments and comparative examples of this invention are all commercially available, including but not limited to the following materials:

[0039] The PC resin used is Lotte's PC-1100;

[0040] The ABS resin is ABS8391 from Takahashi Petrochemical.

[0041] The perfume crack-resistant agent is a blend of montmorillonite (commercially available) and polybutylene terephthalate (Yizheng GX112A) premixed, with a weight ratio of montmorillonite to polybutylene terephthalate of 1:1 to 1:1.5.

[0042] The toughening agent is LG's EM 500;

[0043] The compatibilizer is Asahi Kasei Corporation's 80NM;

[0044] The antioxidant is BASF's IRGANOX 1010;

[0045] The lubricant is Chenguang's GM-100 silicone powder;

[0046] The transesterification inhibitor is commercially available sodium dihydrogen hydrate.

[0047] The above-described embodiments will be described in more detail below with reference to specific examples.

[0048] Example 1

[0049] A method for preparing a high-strength PC / ABS alloy to improve perfume cracking, the specific steps of which are as follows:

[0050] Weigh the following components according to the weight parts in Table 1: 60 parts PC resin, 34 parts ABS resin, 3 parts fragrance-resistant cracking agent, 4 parts toughening agent, 2 parts compatibilizer, 0.3 parts antioxidant, 0.2 parts lubricant, and 0.3 parts transesterification inhibitor. Mix the components evenly in a high-speed mixer. Add the mixed material to a twin-screw extruder for melt blending and extrusion. After cooling, pelletizing, and drying, a high-strength fragrance-resistant PC / ABS alloy is obtained.

[0051] The extruder's process conditions are as follows: Zone 1 temperature 210℃, Zone 2 temperature 230℃, Zone 3 temperature 230℃, Zone 4 temperature 240℃, Zone 5 temperature 240℃, Zone 6 temperature 250℃, Zone 7 temperature 250℃, Zone 8 temperature 255℃, Zone 9 temperature 255℃, twin screw speed 500rpm, extrusion temperature 255℃, and extrusion pressure 3MPa.

[0052] Example 2

[0053] This embodiment provides a method for preparing a high-strength PC / ABS alloy to improve perfume cracking. The weight ratio of the raw materials is shown in Table 1, and the preparation method is the same as in Embodiment 1.

[0054] Example 3

[0055] This embodiment provides a method for preparing a high-strength PC / ABS alloy to improve perfume cracking. The weight ratio of the raw materials is shown in Table 1, and the preparation method is the same as in Embodiment 1.

[0056] Example 4

[0057] This embodiment provides a method for preparing a high-strength PC / ABS alloy to improve perfume cracking. The weight ratio of the raw materials is shown in Table 1, and the preparation method is the same as in Embodiment 1.

[0058] Example 5

[0059] This embodiment provides a method for preparing a high-strength PC / ABS alloy to improve perfume cracking. The weight ratio of the raw materials is shown in Table 1, and the preparation method is the same as in Embodiment 1.

[0060] Comparative Example 1

[0061] This embodiment provides a method for preparing PC / ABS alloy. The weight ratio of the raw materials is shown in Table 1, and the preparation method is the same as in Embodiment 1.

[0062] Comparative Example 2

[0063] This embodiment provides a method for preparing PC / ABS alloy. The weight ratio of the raw materials is shown in Table 1, and the preparation method is the same as in Embodiment 1.

[0064] Comparative Example 3

[0065] This embodiment provides a method for preparing PC / ABS alloy. The weight ratio of the raw materials is shown in Table 1, and the preparation method is the same as in Embodiment 1.

[0066] Comparative Example 4

[0067] This embodiment provides a method for preparing PC / ABS alloy. The weight ratio of the raw materials is shown in Table 1, and the preparation method is the same as in Embodiment 1.

[0068] Table 1 Formulations of Examples 1-5 and Comparative Examples 1-4

[0069]

[0070]

[0071] Note: In Table 1, "-" indicates that the component is not present. The weight ratio of montmorillonite to polybutylene terephthalate in the perfume crack resistant agent is 1:1.

[0072] Performance testing

[0073] The particles obtained from granulation of Comparative Examples 1-4 and Examples 1-5 were dried at 100°C for 4 hours, then injection molded into specimens for tensile strength and notched impact strength tests. The perfume resistance of the injection molded products was evaluated. The experimental results are shown in Table 2.

[0074] Table 2 Performance test results of Examples 1-5 and Comparative Examples 1-4

[0075]

[0076] Note: The method for detecting cracks caused by spraying perfume is as follows: Spray the perfume (choose any 3 commercially available perfumes for the experiment) from the sprayer at a distance of 15cm from the sample and spray for 10s. Then let it stand at 80℃ and 80%RH for 4h, and then let it stand at room temperature (23℃) for 24h to count the crack ratio of the parts.

[0077] The test results of Examples 1-5 and Comparative Examples 1-4 are shown in Table 2. By comparing Comparative Example 1 with Example 1, and Comparative Example 2 with Example 3, it can be found that when the content of perfume cracking agent is increased to 3 parts by weight, the cracking rate of the product after spraying perfume is reduced from more than 70% to about 20%, and the notched impact strength is also significantly improved. The tensile strength of Example 3 is significantly higher than that of Comparative Example 2.

[0078] By comparing Comparative Example 1 with Example 2, and Comparative Example 2 with Example 4, it can be found that when the content of the perfume crack-resistant agent increases to 5 parts by weight, the cracking rate of the product after perfume spraying decreases from over 70% to 0. The tensile strength and notched impact strength of Examples 2 and 4 are significantly greater than those of Comparative Examples 1-2. Therefore, this application selects montmorillonite and polybutylene terephthalate as perfume crack-resistant agents. Adding semi-crystalline polybutylene terephthalate (PBT) to the PC / ABS alloy reduces the swelling effect of the solvent on the material and improves the overall solvent resistance of the alloy; while the unique lamellar structure inside montmorillonite can form a barrier effect, hindering the diffusion of solvent molecules.

[0079] Comparing Example 5 with Example 4, it can be seen that by increasing the content of compatibilizer, the notched impact strength of PC / ABS alloy is significantly increased. Therefore, the compatibilizer polymethyl methacrylate can weaken the phase separation between PC and ABS, thereby improving the weld line strength. The synergistic effect of polymethyl methacrylate with montmorillonite and polybutylene terephthalate further improves the fragrance resistance of weak parts.

[0080] Comparing Comparative Examples 2, 3, and 4, it can be seen that adding PBT or montmorillonite alone significantly increases the tensile strength and notched impact strength of the PC / ABS alloy, and reduces the cracking rate after perfume spraying. Comparing Example 5, 3, and 4, it can be seen that the PC / ABS alloy obtained by adding both PBT and montmorillonite (i.e., perfume-resistant cracking agent) simultaneously has higher tensile strength and notched impact strength than the PC / ABS alloy obtained by adding PBT or montmorillonite alone. Furthermore, the PC / ABS alloy obtained by adding both PBT and montmorillonite (i.e., perfume-resistant cracking agent) simultaneously has a cracking rate of 0 after perfume spraying. Therefore, the synergistic properties of polybutylene terephthalate (PBT) and montmorillonite improve the overall solvent resistance of the alloy.

[0081] Example 6

[0082] A method for preparing a high-strength PC / ABS alloy to improve perfume cracking, the specific steps of which are as follows:

[0083] Weigh the following components according to the weight proportions in Table 1: 60 parts PC resin, 34 parts ABS resin, 3 parts fragrance-resistant cracking agent (montmorillonite to polybutylene terephthalate weight ratio is 1:1.5), 4 parts toughening agent, 2 parts compatibilizer, 0.3 parts antioxidant, 0.2 parts lubricant, and 0.3 parts transesterification inhibitor. Mix the components evenly in a high-speed mixer. Add the mixed material to a twin-screw extruder for melt blending and extrusion. After cooling, pelletizing, and drying, a fragrance-resistant high-strength PC / ABS alloy is obtained.

[0084] The extruder's process conditions are as follows: Zone 1 temperature 210℃, Zone 2 temperature 230℃, Zone 3 temperature 230℃, Zone 4 temperature 240℃, Zone 5 temperature 240℃, Zone 6 temperature 250℃, Zone 7 temperature 250℃, Zone 8 temperature 255℃, Zone 9 temperature 255℃, twin screw speed 500rpm, extrusion temperature 255℃, and extrusion pressure 3MPa.

[0085] The above description of the embodiments is provided to enable those skilled in the art to understand and use the invention. It will be apparent to those skilled in the art that various modifications can be made to these embodiments, and the general principles described herein can be applied to other embodiments without inventive effort. Therefore, the present invention is not limited to the above embodiments, and any improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the invention should be within the protection scope of the present invention.

Claims

1. A high-strength PC / ABS alloy resistant to perfume, characterized in that, It is made from the following components in parts by weight: 50-80 parts of PC resin, 10-40 parts of ABS resin 2-8 parts of perfume-resistant crack-resistant agent 2-6 parts toughening agent 1-5 parts compatibilizer Antioxidant 0.1~1.5 parts, Lubricant 0.1~1.5 parts, Transesterification inhibitor 0.1-1.5 parts; The perfume-resistant crack-resistant agent is a composite of montmorillonite and polybutylene terephthalate. By weight ratio, montmorillonite:polybutylene terephthalate = 1:1~1:1.5; The compatibilizer is polymethyl methacrylate.

2. The high-strength PC / ABS alloy resistant to perfume according to claim 1, characterized in that, The PC resin is bisphenol A type polycarbonate.

3. The high-strength PC / ABS alloy resistant to perfume according to claim 1, characterized in that, The weight-average molecular weight of the ABS resin is 13w to 15w.

4. The high-strength PC / ABS alloy resistant to perfume according to claim 1, characterized in that, The toughening agent is a methyl methacrylate-butadiene-styrene terpolymer.

5. The high-strength PC / ABS alloy resistant to perfume according to claim 1, characterized in that, The antioxidant is selected from any one or more of the following: octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], tris(2,4-di-tert-butyl)phosphite, or dioctadecyl pentaerythritol diphosphite.

6. The high-strength PC / ABS alloy resistant to perfume according to claim 1, characterized in that, The lubricant is selected from any one or more of silicone powder, paraffin wax, stearic acid, butyl stearate, or ethylene bis-stearamide.

7. The high-strength PC / ABS alloy resistant to perfume according to claim 1, characterized in that, The transesterification inhibitor is sodium dihydrogen carbonate.

8. A method for preparing a perfume-resistant high-strength PC / ABS alloy as described in any one of claims 1-7, characterized in that, The specific steps are as follows: (1) Prepare the components according to the following parts by weight: 50-80 parts of PC resin, 10-40 parts of ABS resin 2-8 parts of perfume-resistant crack-resistant agent 2-6 parts toughening agent 1-5 parts compatibilizer Antioxidant 0.1~1.5 parts, Lubricant 0.1~1.5 parts, Transesterification inhibitor 0.1-1.5 parts; (2) Mix the components obtained in step (1) evenly in a high-speed mixer, add the evenly mixed material to a twin-screw extruder for melt blending and extrusion, the extrusion temperature is 210~270℃, the twin-screw speed is 250~500rpm, after cooling and pelletizing, and after drying, obtain a high-strength PC / ABS alloy resistant to perfume.

9. The application of the perfume-resistant high-strength PC / ABS alloy according to any one of claims 1-7 in the manufacture of automotive interior and exterior trim parts.

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