Polyester composite material modified master batch, preparation method and application thereof, and vehicle-mounted part

Abstract

The invention discloses a polyester composite material modified master batch which comprises the following components in parts by weight: 80-90 parts of low-viscosity polyester; 3 to 10 parts of sodium alginate; 0.3-2 parts of calcium chloride; the low-viscosity polyester is selected from at least one of low-viscosity PBT (Polybutylene Terephthalate) and low-viscosity PET (Polyethylene Terephthalate); the sum of the contents of the sodium alginate and the anhydrous calcium chloride is not less than 5 parts; the intrinsic viscosity of the low-viscosity PBT is 0.80 to 0.86 dL / g, and the intrinsic viscosity of the low-viscosity PET is 0.60 to 0.75 dL / g; the average particle size range of the sodium alginate is 90-600 microns; the average particle size range of the calcium chloride is 1-6mm. The low-viscosity polyester with specific viscosity, the sodium alginate with specific average particle size and the anhydrous calcium chloride cooperate to obtain the modified master batch capable of improving the warping performance defect of the glass fiber reinforced polyester material, and meanwhile, the heat aging resistance can be improved.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, and in particular to a polyester composite material modified masterbatch, its preparation method and application, and an automotive component. Background Technology

[0002] Polyester (PBT, PET) is a common polyester material with numerous applications in daily life. Polyester possesses excellent heat resistance, electrical insulation, and chemical corrosion resistance, making it widely used in fibers, films, and other fields. In automotive materials, the rapid development of new energy vehicles in recent years has greatly expanded the application areas of polyester. In particular, glass fiber reinforced polyester products, with their excellent insulation and low water absorption properties, have surpassed traditional engineering materials such as nylon in some applications. Furthermore, due to its low cost, polyester materials have significant economic value in the modified plastics industry. However, because polyester is a crystalline material, glass fiber reinforced polyester materials often exhibit warping deformation, which greatly limits their use. This invention focuses on solving the technical challenge of warping deformation in glass fiber reinforced polyester materials through formulation design.

[0003] Existing technologies mainly improve warpage through the following methods: Existing methods to improve warpage either involve adding a completely incompatible third component, such as adding PC or ABS to PBT materials. The addition of these third components will reduce the warpage of the material, but at the same time, it will also have various effects on the mechanical properties of the material, such as heat resistance. Summary of the Invention

[0004] The purpose of this invention is to overcome the above-mentioned technical defects and provide a polyester composite material modified masterbatch that can improve warpage and heat aging resistance, as well as its preparation method and application.

[0005] This invention is achieved through the following technical solution: A polyester composite material modified masterbatch, comprising the following components by weight: 80-90 parts of low-viscosity polyester; 3-10 parts sodium alginate; 0.3-2 parts calcium chloride; The combined content of sodium alginate and calcium chloride shall not be less than 5 parts; The low-viscosity polyester is selected from at least one of low-viscosity PBT and low-viscosity PET; The intrinsic viscosity of low-viscosity PBT is 0.80-0.86 dL / g, and the intrinsic viscosity of low-viscosity PET is 0.60-0.75 dL / g. The average particle size range of the sodium alginate is 90-600 micrometers; The average particle size range of the calcium chloride is 1-6 mm.

[0006] The weight ratio of sodium alginate to calcium chloride ranges from 1.5 to 33.3:1.

[0007] In the polyester composite material modified masterbatch of the present invention, the content of low-viscosity polyester can be any value or a range between 80 parts, 81 parts, 82 parts, 83 parts, 84 parts, 85 parts, 86 parts, 87 parts, 88 parts, 89 parts, and 90 parts; the content of sodium alginate can be any value or a range between 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts, 8.5 parts, 9 parts, 9.5 parts, and 10 parts; and the content of calcium chloride can be any value or a range between 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1.0 parts, 1.1 parts, 1.2 parts, 1.3 parts, 1.4 parts, 1.5 parts, 1.6 parts, 1.7 parts, 1.8 parts, 1.9 parts, and 2.0 parts.

[0008] Based on the weight percentage of the polyester composite material modified masterbatch of the present invention, the low-viscosity polyester accounts for no less than 85 wt%, and the total content of sodium alginate and calcium chloride in the masterbatch ranges from 5 to 13 wt%.

[0009] The intrinsic viscosity of the low-viscosity polyester was measured according to GB / T 14190-2008 standard (the solvent is phenol and tetrachloroethane in a mass ratio of 1:1).

[0010] Preferably, the average particle size range of the sodium alginate is 125-250 micrometers.

[0011] Preferably, the average particle size of the calcium chloride is in the range of 2-4 mm.

[0012] The calcium chloride can be hydrated calcium chloride or anhydrous calcium chloride, with anhydrous calcium chloride being preferred.

[0013] The average particle size was obtained by laser particle size analyzer.

[0014] 0-2 parts of additives may be added as needed; the additives are selected from at least one of antioxidants, lubricants, and heat stabilizers.

[0015] Antioxidants can be tris(2,4-di-tert-butylphenyl) phosphite; 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene; 2,5-di-tert-butyl-4-hydroxybenzyl dimethylamine; diethyl-3,5-di-tert-butyl-4-hydroxybenzyl phosphate; stearyl-3,5-di-tert-butyl-4-hydroxybenzyl phosphate; 3,5-di-tert-butyl-4-hydroxyphenyl-3,5-distearate-thiotriazolylamine; 2,6-di-tert-butyl-4-hydroxymethylphenol; 2,4-di-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylglycerol allyl ether)-1,3,5-triazine; N,N'-Hexamethylene di(3,5-di-tert-butyl-4-hydroxy-hydrogenated cinnamamide); N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexamethylenediamine; β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate n-octadecyl ester; triethylene glycol di[3-(3,5-dimethyl-4-hydroxyphenyl)propionate]; triethylene glycol di[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate]; 2,2'-thiodiethyl-di[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]; pentaerythritol tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], etc.

[0016] The lubricant may be at least one of stearate lubricants, fatty acid lubricants, and stearate ester lubricants; the stearate lubricant is selected from at least one of calcium stearate, magnesium stearate, and zinc stearate; the fatty acid lubricant is selected from at least one of fatty acids, fatty acid derivatives, and fatty acid esters; and the stearate ester lubricant is selected from pentaerythritol stearate.

[0017] The preparation method of the polyester composite material modified masterbatch of the present invention includes the following steps: mixing the components evenly according to the formula, and granulating by extrusion through a twin-screw extruder to obtain the polyester composite material modified masterbatch. The processing temperature range is 170-240℃, and the rotation speed range is 400-600 rpm.

[0018] The present invention also relates to a glass fiber reinforced polyester composite material, comprising the following components by weight: 40-90 parts of polyester resin; 5-50 parts glass fiber; 1-10 parts of the above-mentioned polyester composite material modified masterbatch.

[0019] In the glass fiber reinforced polyester composite material of the present invention, the content of polyester resin can be any value or a range between 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, and 90 parts; the content of glass fiber can be any value or a range between 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, and 50 parts; and the content of polyester composite material modified masterbatch can be any value or a range between 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, and 10 parts.

[0020] The modified masterbatch for the polyester composite material accounts for 0.5-18.2 wt% of the total weight of the glass fiber reinforced polyester composite material, and the glass fiber accounts for 4-55 wt% of the total weight of the glass fiber reinforced polyester composite material. Preferably, in one embodiment, the glass fiber accounts for no more than 30 wt% of the total weight of the glass fiber reinforced polyester composite material.

[0021] The polyester resin is selected from at least one of PBT and PET. The intrinsic viscosity of the polyester resin is in the range of 0.5-1.0 dL / g, preferably 0.67-1.0 dL / g.

[0022] Depending on actual needs, you can choose to add 0-20 parts flame retardant, 0-10 parts inorganic filler, 0-1 parts heat stabilizer, 0-1 parts lubricant, 0-1 parts UV stabilizer, etc.

[0023] The preparation method of the glass fiber reinforced polyester composite material of the present invention is as follows: The components are mixed evenly according to the specified ratio, and then extruded and granulated using a twin-screw extruder (glass fiber side-feed) to obtain the glass fiber reinforced polyester composite material. The barrel temperature range is 170-280℃, and the rotation speed range is 400-600 rpm.

[0024] The application of the glass fiber reinforced polyester composite material of the present invention is used to prepare automotive parts.

[0025] The present invention has the following beneficial effects: This invention utilizes a low-viscosity polyester with a specific viscosity, sodium alginate with a specific average particle size, and anhydrous calcium chloride. By leveraging the complexation effect of sodium alginate and calcium ions, a network structure is formed within the material, reducing its anisotropy. This allows for significant improvement in warpage even with relatively low additive content, without affecting the material's mechanical properties. The synergistic effect of these three components yields a modified masterbatch that effectively improves the warpage performance of glass fiber reinforced polyester materials. Furthermore, due to the excellent film-forming properties of sodium alginate, it effectively isolates oxygen within the material, enhancing its resistance to heat aging. Detailed Implementation

[0026] The present invention will now be described in detail with reference to specific embodiments. These embodiments will help those skilled in the art to further understand the present invention, but do not limit the invention in any way. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention. These all fall within the scope of protection of the present invention.

[0027] The raw materials for this invention are sourced as follows: Low viscosity PBT-1: intrinsic viscosity 0.86 dL / g, supplied by Nantong Xingchen, grade PBT 1084; Low viscosity PBT-2: intrinsic viscosity 0.80 dL / g, supplied by Weifang Zhenxing Risheng, grade PBT ZX90800; Ultra-low viscosity PBT: intrinsic viscosity 0.73 dL / g, Yizheng Chemical Fiber, PBT GX111; Low viscosity PET-1: intrinsic viscosity 0.67 dL / g, provided by Sichuan Dongfang Insulation Co., Ltd., grade FG600; Low viscosity PET-2: Intrinsic viscosity 0.64 dL / g, ChemSpace, grade PET SBR; Ultra-low viscosity PET: intrinsic viscosity 0.50 dL / g, PET CR-7702, supplied by Zhuhai Huaren; Medium viscosity PBT: intrinsic viscosity 0.98 dL / g, supplied by Yizheng Chemical Fiber, grade PBT GX121; Medium viscosity PET: intrinsic viscosity 0.8 dL / g, supplied by Yizheng Chemical Fiber, grade PET BG80; Sodium alginate was purchased from Qingdao Mingyue Seaweed Group, and raw materials with different average particle sizes were obtained through grinding and screening.

[0028] Sodium alginate A: Average particle size 90 micrometers; Sodium alginate B: Average particle size 125 micrometers; Sodium alginate C: Average particle size 250 micrometers; Sodium alginate D: Average particle size 600 micrometers; Sodium alginate E: Average particle size 48 micrometers; Sodium alginate F: average particle size 850 micrometers; Anhydrous calcium chloride was purchased from Kailong Chemical, and raw materials with different average particle sizes were obtained through grinding and screening.

[0029] Anhydrous calcium chloride A: average particle size 1 mm; Anhydrous calcium chloride B: average particle size 2 mm; Anhydrous calcium chloride C: average particle size 4 mm; Anhydrous calcium chloride D: average particle size 6 mm; Anhydrous calcium chloride E: average particle size 0.2 mm; Anhydrous calcium chloride F: average particle size 11 mm; Fiberglass: sourced from Jushi Group, brand name ECS11-4.5-534A; Preparation method of polyester composite material modified masterbatch: According to the formula, the components are mixed evenly, and then extruded and granulated through a twin-screw extruder to obtain polyester composite material modified masterbatch. The processing temperature range is 170-240℃, and the rotation speed range is 400-600 rpm.

[0030] Preparation method of glass fiber reinforced polyester composite material in the examples and comparative examples: The components were mixed evenly according to the formula, and then extruded and granulated using a twin-screw extruder (glass fiber side-feed) to obtain the glass fiber reinforced polyester composite material. Screw temperatures: Zone 1 170℃, Zone 2 190℃, Zone 3 230℃, Zone 4 260℃, Zone 5 280℃, Zone 6 280℃, Zone 7 280℃, Zone 8 260℃, Zone 9 260℃; Rotation speed: 500 rpm.

[0031] Test methods: (1) CLTE: The linear expansion coefficient CLTE of the sample in the flow and vertical directions was determined according to ISO 11359-2023. The closer the CLTE ratio in the two directions is to 1, the closer the lateral and longitudinal shrinkage rates of the sample are, and the smaller the material warpage. Temperature range: -30℃ to 80℃.

[0032] (2) Heat aging resistance: The tensile strength before and after aging was tested according to ISO 527-2019 and the performance retention rate was calculated. The aging conditions were 150℃ for 500h. The higher the performance retention rate, the better the heat aging resistance.

[0033] Table 1: Content of each component in polyester composite modified masterbatch A A-1 A-2 A-3 A-4 A-5 A-6 A-7 A-8 A-9 A-10 A-11 Low viscosity PBT-1 80 85 90 85 85 85 85 85 Low viscosity PBT-2 85 Ultra-low viscosity PBT 85 Medium viscosity PBT 85 Sodium alginate grade A A A A B C D A A E F Sodium alginate content 3 5 10 5 5 5 5 5 5 5 5 Anhydrous calcium chloride grade A A A A B C D A A E F Anhydrous calcium chloride content 2 1 0.3 1 1 1 1 1 1 1 1 Table 2: Content of each component in polyester composite modified masterbatch B B-1 B-2 B-3 B-4 B-5 B-6 B-7 B-8 B-9 B-10 B-11 Low viscosity PET-1 80 85 90 85 85 85 85 85 Low viscosity PET-2 85 Ultra-low viscosity PET 85 Medium viscosity PET 85 Sodium alginate grade A A A A B C D A A E F Sodium alginate content 3 6 10 6 6 6 6 6 6 6 6 Anhydrous calcium chloride grade A A A A B C D A A E F Anhydrous calcium chloride content 2 1.2 0.3 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 Table 3: Component content and test results of glass fiber reinforced polyester composites Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Medium viscosity PBT 40 70 90 70 70 70 70 Medium viscosity PET Fiberglass 50 30 10 30 30 30 30 Modified Masterbatch Number A-1 A-1 A-1 A-2 A-3 A-4 A-5 Modified masterbatch content 10 5 1 5 5 5 5 CLTE ratio in the flow direction / vertical direction 0.170 0.194 0.473 0.192 0.200 0.187 0.234 Heat aging resistance, % 93% 91% 92% 93% 94% 95% 95% As can be seen from Examples 2 / 7-9, when sodium alginate and anhydrous calcium chloride with preferred average particle size are used, the glass fiber reinforced polyester composite material exhibits better warping resistance and heat aging resistance.

[0034] Continued from Table 3: Example 8 Example 9 Example 10 Medium viscosity PBT 70 70 Medium viscosity PET 70 Fiberglass 30 30 30 Modified Masterbatch Number A-6 A-7 B-1 Modified masterbatch content 5 5 5 CLTE ratio in the flow direction / vertical direction 0.255 0.197 0.209 Heat aging resistance, % 94% 93% 96% Continued from Table 3: Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Medium viscosity PBT Medium viscosity PET 70 70 70 70 70 70 Fiberglass 30 30 30 30 30 30 Modified Masterbatch Number B-2 B-3 B-4 B-5 B-6 B-7 Modified masterbatch content 5 5 5 5 5 5 CLTE ratio in the flow direction / vertical direction 0.189 0.175 0.192 0.234 0.241 0.195 Heat aging resistance, % 97% 98% 95% 97% 96% 93% As can be seen from Examples 11 / 14 / 15 / 16, when sodium alginate and anhydrous calcium chloride with preferred average particle size are used, the glass fiber reinforced polyester composite material exhibits better warping resistance and heat aging resistance.

[0035] The polyester composite material of the present invention has a heat aging retention rate of more than 90%, and the flow direction / vertical direction CLTE ratio is >0.450 when the glass fiber content is 10 parts, >0.170 when the glass fiber content is 30 parts, and >0.160 when the glass fiber content is 50 parts.

[0036] Continued from Table 3: Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Medium viscosity PBT 70 70 70 70 Medium viscosity PET 70 70 70 70 Fiberglass 30 30 30 30 30 30 30 30 Modified Masterbatch Number A-8 A-9 A-10 A-11 B-8 B-9 B-10 B-11 Modified masterbatch content 5 5 5 5 5 5 5 5 CLTE ratio in the flow direction / vertical direction 0.136 0.113 0.138 0.120 0.131 0.123 0.122 0.109 Heat aging resistance, % 81% 80% 84% 80% 85% 83% 83% 84% As shown in Comparative Example 1 / 2, when ultra-low viscosity PBT or medium viscosity PBT is selected as the masterbatch, the anti-warping performance and heat aging resistance are poor.

[0037] As can be seen from Comparative Examples 3 / 4 / 7 / 8, when the average particle size of sodium alginate and anhydrous calcium chloride in the masterbatch is not within the range of the present invention, the anti-warping performance and heat aging resistance are poor.

[0038] As can be seen from Comparative Example 5 / 6, when ultra-low viscosity PET or medium viscosity PET is selected as the masterbatch, the anti-warping performance and heat aging resistance are poor.

Claims

1. A polyester composite modifying masterbatch characterized in that, By weight parts, comprising the following components: Low viscosity polyester 80-90 parts; Sodium alginate 3-10 parts; Calcium chloride 0.3-2 parts; The content of sodium alginate and calcium chloride is not less than 5 parts; The low viscosity polyester is selected from at least one of low viscosity PBT and low viscosity PET; The intrinsic viscosity of low viscosity PBT is 0.80-0.86 dL / g, and the intrinsic viscosity of low viscosity PET is 0.60-0.75 dL / g; The average particle size of the sodium alginate is in the range of 90-600 microns; The average particle size of the anhydrous calcium chloride is in the range of 1-6 mm.

2. The polyester composite modifier masterbatch according to claim 1, characterized in that, The average particle size of the sodium alginate is in the range of 125-250 microns.

3. The polyester composite modifier masterbatch according to claim 1, characterized in that, The average particle size of the calcium chloride is in the range of 2-4 mm.

4. The polyester composite modifier masterbatch of claim 1, wherein, By weight parts, further comprising 0-2 parts of auxiliary agent; the auxiliary agent is selected from at least one of antioxidant, lubricant, and thermal stabilizer.

5. The method of producing a polyester composite modifier master batch according to any one of claims 1 to 4, characterized in that, The method comprises the following steps: mixing the components uniformly according to the ratio, and extruding and granulating through a double-screw extruder to obtain a polyester composite material modification master batch.

6. A glass fiber reinforced polyester composite material, characterized by, By weight parts, comprising the following components: Polyester resin 40-90 parts; Glass fiber 5-50 parts; The polyester composite material modification master batch of any one of claims 1-4 1-10 parts.

7. The glass fiber reinforced polyester composite of claim 6, wherein, The polyester resin is selected from at least one of PBT and PET; the intrinsic viscosity of the polyester resin is in the range of 0.5-1.0 dL / g.

8. The glass fiber reinforced polyester composite of claim 6, wherein, By weight parts, further comprising 0-20 parts of flame retardant, 0-10 parts of inorganic filler, 0-1 parts of thermal stabilizer, 0-1 parts of lubricant, and 0-1 parts of anti-ultraviolet agent.

9. A vehicle interior component, characterized by Made of the glass fiber reinforced polyester composite material of any one of claims 6-8.