High surface finish hydrolysis resistant reinforced polyamide composite material and method of making

Abstract

The present application relates to a kind of high finish hydrolysis-resistant reinforced polyamide composite and its preparation method.The present application provides a kind of high finish hydrolysis-resistant reinforced polyamide composite, based on 100 parts by weight, including the following weight parts of each component: polyamide 25-75 parts, chopped glass fiber 30-70 parts, antioxidant 0.1-0.6 parts, ultraviolet absorber 0.1-0.5 parts, hindered amine light stabilizer 0.1-0.5 parts, dispersing agent 0.1-0.5 parts, toner 1-3 parts, wherein toner includes two or more selected from the following: pigment carbon black 7, pigment manganese iron black 26, pigment copper chromium black 28, dye solvent black 5.

Description

Technical Field

[0001] This application relates to the field of polymer materials, and in particular to a high-gloss, hydrolysis-resistant reinforced polyamide composite material and its preparation method. Background Technology

[0002] Polyamide is a high-molecular-weight engineering plastic with multiple repeating amide units in its molecular backbone. As one of the five major engineering plastics, polyamide possesses excellent high-temperature resistance, chemical resistance, and ease of processing, and is widely used in automotive powertrains, fuel systems, cooling systems, and interior and exterior trim components. Thermal management systems play a crucial role in hybrid and electric vehicle applications. With the increasing market share of hybrid and electric vehicles, the development of high-performance polyamide materials with excellent hydrolysis resistance and dimensional stability is urgently needed. This material needs to meet the requirements of excellent resistance to water / glycol coolants, good dimensional stability, and excellent rubber bonding and sealing properties. The high-gloss, hydrolysis-resistant reinforced polyamide composite of this invention exhibits high gloss, good resistance to water / glycol coolants, and excellent dimensional stability.

[0003] Chinese invention patent CN106987122A (application number CN201710356347.3) describes a method for preparing hydrolysis-resistant short glass fiber reinforced nylon 66. This invention improves the hydrolysis resistance of nylon 66 by adding high molecular weight maleic anhydride polyethylene wax to increase the material's polarity and reduce the polymer's water absorption rate. However, this method reduces the material's toughness and impact strength, and the surface quality and smoothness are significantly affected by the high processing temperature of nylon. Therefore, there is an urgent need to develop reinforced polyamide materials with high surface finish requirements.

[0004] This invention patent utilizes the synergistic effect between a combination of high-coloring-strength nano-sized pigments and a dispersant to achieve both enhanced hydrolysis resistance of polyamide and good surface finish. The hydrolysis resistance mechanical properties retain 60% at 2000 hours and 135℃, and the surface roughness Ra is <2μm. Summary of the Invention

[0005] To address the shortcomings of existing technologies, one objective of this invention is to provide a high-gloss, hydrolysis-resistant reinforced polyamide composite and its preparation method.

[0006] To achieve the above objectives, the present invention provides a method for preparing a high-gloss, hydrolysis-resistant reinforced polyamide composite.

[0007] According to one aspect of the present invention, the high-gloss hydrolysis-resistant reinforced polyamide composite of the present invention can maintain 60% of its initial tensile strength and have an average surface roughness Ra < 2 μm after a 2000-hour coolant aging test at 135°C.

[0008] One aspect of the present invention provides a high-gloss, hydrolysis-resistant reinforced polyamide composite, comprising, based on 100 parts by weight, the following components in parts by weight:

[0009] 25-75 parts of polyamide

[0010] 30-70 parts chopped glass fiber

[0011] Antioxidant 0.1–0.6 parts

[0012] 0.1 to 0.5 parts of ultraviolet absorber

[0013] 0.1–0.5 parts of hindered amine light stabilizer

[0014] Dispersant 0.1 to 0.5 parts

[0015] 1-3 parts of color powder,

[0016] The pigments mentioned therein include two or more selected from the following: pigment carbon black 7, pigment manganese iron black 26, pigment copper chromium black 28, and dye solvent black 5.

[0017] Another aspect of the present invention provides a method for preparing a high-gloss, hydrolysis-resistant reinforced polyamide composite, comprising the following steps:

[0018] Step 1, Prepare raw materials: The raw materials consist of the following components in parts by weight based on a total of 100 parts by weight:

[0019] 25-75 parts of polyamide

[0020] 30-70 parts chopped glass fiber

[0021] Antioxidant 0.1–0.6 parts

[0022] 0.1 to 0.5 parts of ultraviolet absorber

[0023] 0.1–0.5 parts of hindered amine light stabilizer

[0024] Dispersant 0.1 to 0.5 parts

[0025] 1 to 3 parts of pigment powder, wherein the pigment powder includes two or more selected from the following: pigment carbon black 7, pigment manganese iron black 26, pigment copper chromium black 28, and dye solvent black 5.

[0026] Step 2, Mixed Extrusion: Mix and extrude the prepared raw materials.

[0027] Beneficial effects

[0028] The high-gloss hydrolysis-resistant reinforced polyamide composite of the present invention enhances the material's resistance to cooling liquids. Under the condition of 135℃@2000 hours, the mechanical property retention rate is 60%, and the surface finish is Ra<2μm (surface roughness), thus expanding the application range of hydrolysis-resistant polyamide materials. Detailed Implementation

[0029] The products and methods of the present invention will be described in more detail below. The present invention is not limited to the following specific embodiments, and other features and advantages of the inventive concept will become apparent from the following specific embodiments.

[0030] Regarding terminology definitions, unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In case of conflict, this document (including the definitions) shall prevail. Preferred methods and materials are described below, but similar or equivalent methods and materials may also be used in the practice or testing of the invention. The materials, methods, and examples disclosed herein are illustrative only and not intended to be limiting.

[0031] As used herein, the terms “comprising,” “including,” “having,” “having,” “may,” “containing,” and variations thereof are intended to refer to open transitional phrases, terms, or words that do not exclude the presence or addition of one or more additional features, steps, operations, elements, or components. Unless the context explicitly indicates otherwise, objects without quantifiers include plural objects. However, whether explicitly stated or not, this disclosure also includes other embodiments that “include the embodiments or elements shown herein,” “consist of the embodiments or elements shown herein,” and “consist substantially of the embodiments or elements shown herein.”

[0032] Any range given in absolute or approximate terms is intended to include both, and any definitions used herein are intended to be illustrative rather than limiting. While the numerical ranges and parameters stating a wide range of the invention are approximate, the numerical values ​​stated in the specific embodiments are as precise as possible. However, any numerical value inherently includes some error that must be caused by the standard deviation found in the measurements of the respective tests. Furthermore, all ranges disclosed herein are to be understood to include any and all subranges (including all fractions and integers) included therein.

[0033] All ranges and parameters disclosed herein should be understood to encompass any and all subranges contained therein, and every number between the endpoints. For example, the specified range “1 to 10” should be considered to include any and all subranges between (and including) the minimum value of 1 and the maximum value of 10; that is, all subranges that begin with a minimum value of 1 or greater (e.g., 1 to 6.1) and end with a maximum value of 10 or less (e.g., 2.3 to 9.4, 3 to 8, 4 to 7), and finally the individual numbers 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10 contained within that range. Unless otherwise stated, all percentages, ratios, and proportions herein are by weight.

[0034] Furthermore, this invention includes any and all possible combinations of some or all of the various embodiments described herein. Any and all documents referenced in this application are incorporated herein by reference in their entirety.

[0035] According to one embodiment of this application, a high-gloss, hydrolysis-resistant reinforced polyamide composite may comprise, based on a total of 100 parts by weight, the following components in parts by weight:

[0036] 25-75 parts of polyamide

[0037] 30-70 parts chopped glass fiber

[0038] Antioxidant 0.1–0.6 parts

[0039] 0.1 to 0.5 parts of ultraviolet absorber

[0040] 0.1–0.5 parts of hindered amine light stabilizer

[0041] Dispersant 0.1 to 0.5 parts

[0042] 1-3 parts of color powder,

[0043] The pigments may include two or more selected from the following: pigment carbon black 7, pigment manganese iron black 26, pigment copper chromium black 28, and dye solvent black 5.

[0044] According to one embodiment of this application, the polyamide is preferably one or a mixture of two of PA6, PA66, PA610, PA6I / 6T, PA6T / 6I, PA9T, PA10T, and PA12, with an Ubbelohde relative viscosity of 2.0 to 3.0 (m-cresol is used as solvent).

[0045] According to one embodiment of this application, the polyamide may preferably be one or a mixture of two of PA6, PA66, PA6I / 6T, PA6T / 6I and PA12, with an Ubbelohde relative viscosity of 2.0 to 3.0 (m-cresol as solvent).

[0046] According to one embodiment of this application, the polyamide may further preferably include PA66 and PA6I / 6T.

[0047] According to one embodiment of this application, based on 100 parts by weight of the polyamide composite, the polyamide can be 25 to 75 parts. Furthermore, based on 100 parts by weight of the polyamide composite, the polyamide can be 30 to 70 parts, for example 40 to 70 parts, preferably 50 to 70 parts, more preferably 60 to 69 parts, even more preferably 65 to 68 parts, and even more preferably 66 to 68 parts.

[0048] According to one embodiment of this application, based on 100 parts by weight of the polyamide composite, the polyamide may include 15 to 55 parts of PA66 and 10 to 20 parts of PA6I / 6T, preferably 35 to 50 parts of PA66 and 15 to 20 parts of PA6I / 6T, more preferably 45 to 50 parts of PA66 and 15 to 18 parts of PA6I / 6T.

[0049] According to one embodiment of this application, the chopped glass fibers can be 3–4.5 mm in length and 7–15 μm in diameter. Preferably, the chopped glass fibers can be 3.5–4.5 mm in length and 8–15 μm in diameter.

[0050] According to one embodiment of this application, more preferably, the length of the chopped glass fiber can be 3 to 4.5 mm, the diameter can be 7 to 15 μm, and the cross-section can be circular and / or elliptical.

[0051] According to one embodiment of this application, more preferably, the length of the chopped glass fiber can be 3 to 4.5 mm, the diameter can be 8 to 15 μm, and the cross-section can be elliptical, with the ratio of the short and long diameters of the ellipse being 1:3 to 1:5.

[0052] According to one embodiment of this application, based on 100 parts by weight of the polyamide composite, the chopped glass fibers can be 30 to 70 parts. Furthermore, based on 100 parts by weight of the polyamide composite, the chopped glass fibers can be 30 to 65 parts, for example 30 to 60 parts, preferably 30 to 55 parts, more preferably 30 to 45 parts, even more preferably 30 to 40 parts, and even more preferably 30 to 35 parts.

[0053] According to one embodiment of this application, the antioxidant may include a primary antioxidant and a secondary antioxidant. Preferably, the weight ratio of the primary antioxidant to the secondary antioxidant may be 2:1. According to one embodiment of this application, the antioxidant may be a primary antioxidant and a secondary antioxidant compounded in a weight ratio of 2:1.

[0054] According to one embodiment of this application, the primary antioxidant preferably includes a hindered phenolic antioxidant. According to one embodiment of this application, the secondary antioxidant preferably includes a phosphite antioxidant. Preferably, the hindered phenolic antioxidant may include… 1098: N,N'-Hexamethylenebis(3,5-di-tert-butyl-4-hydroxyphenylpropionamide), 1010: Pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]. Preferably, the phosphite antioxidant may include... 686: Bis(2,4-dicumylphenyl)pentaerythritol diphosphite, 168: Tris(2,4-di-tert-butylphenyl) phosphite.

[0055] According to one embodiment of this application, the antioxidant can be 0.1 to 0.6 parts per 100 parts by weight of the polyamide composite. Furthermore, the antioxidant can be 0.15 to 0.5 parts per 100 parts by weight of the polyamide composite, for example, 0.2 to 0.4 parts, preferably 0.25 to 0.375 parts. (The last two sentences are repetitive and can be omitted.)

[0056] According to one embodiment of this application, based on 100 parts by weight of the polyamide composite, the main antioxidant can be 0.06 to 0.4 parts, for example 0.1 to 0.4 parts, preferably 0.15 to 0.3 parts, and more preferably 0.2 to 0.25 parts.

[0057] According to one embodiment of this application, based on 100 parts by weight of the polyamide composite, the auxiliary antioxidant can be 0.04 to 0.2 parts, for example 0.05 to 0.2 parts, preferably 0.075 to 0.15 parts, and more preferably 0.1 to 0.125 parts.

[0058] According to one embodiment of this application, the total amount of primary and secondary antioxidants per 100 parts by weight of the polyamide composite can be 0.1 to 0.6 parts. For example, the total amount of primary and secondary antioxidants per 100 parts by weight of the polyamide composite can be 0.15 to 0.5 parts, for example 0.2 to 0.4 parts, preferably 0.25 to 0.375 parts. Furthermore, the total amount of primary and secondary antioxidants per 100 parts by weight of the polyamide composite can be 0.1 to 0.5 parts, for example 0.15 to 0.4 parts, preferably 0.15 to 0.375 parts.

[0059] According to one embodiment of this application, the antioxidant may include hindered phenolic antioxidants and phosphite antioxidants, wherein based on 100 parts by weight of the polyamide composite, the hindered phenolic antioxidant may be 0.06 to 0.4 parts, the phosphite-assisted antioxidant may be 0.04 to 0.2 parts, preferably 0.1 to 0.4 parts, and the phosphite-assisted antioxidant may be 0.05 to 0.2 parts, more preferably the hindered phenolic antioxidant is... The amount of phosphite-assisted antioxidant is 0.15 to 0.3 parts, the amount of hindered phenolic antioxidant is 0.075 to 0.15 parts, particularly preferably the amount of hindered phenolic antioxidant is 0.2 to 0.25 parts, and the amount of phosphite-assisted antioxidant is 0.1 to 0.125 parts. The total amount of hindered phenolic antioxidant and phosphite antioxidant can be 0.1 to 0.6 parts, preferably 0.15 to 0.5 parts, more preferably 0.2 to 0.4 parts, and particularly preferably 0.3 to 0.375 parts.

[0060] According to one embodiment of this application, the preferred ultraviolet absorber includes 2-(2H-benzotriazole-2)-4,6-di(1-methyl-1-phenylethyl)-phenol, and more preferably 2-(2H-benzotriazole-2)-4,6-di(1-methyl-1-phenylethyl)-phenol.

[0061] According to one embodiment of this application, the ultraviolet absorber can be 0.1 to 0.5 parts based on 100 parts by weight of the polyamide composite. Furthermore, the ultraviolet absorber can be 0.1 to 0.45 parts based on 100 parts by weight of the polyamide composite, for example, 0.1 to 0.3 parts, preferably 0.1 to 0.25 parts, and more preferably 0.15 to 0.2 parts.

[0062] According to one embodiment of this application, the hindered amine light stabilizer preferably includes N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-N,N'-dialdehyde hexamethylenediamine, and more preferably N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-N,N'-dialdehyde hexamethylenediamine.

[0063] According to one embodiment of this application, the hindered amine light stabilizer can be 0.1 to 0.5 parts per 100 parts by weight of the polyamide composite. Furthermore, the hindered amine light stabilizer can be 0.1 to 0.45 parts per 100 parts by weight, for example, 0.1 to 0.3 parts, preferably 0.1 to 0.2 parts, and more preferably 0.1 to 0.15 parts.

[0064] According to one embodiment of this application, the dispersant may include stearates and / or vinyl bis-stearamide complexes. Preferably, the stearates may include magnesium stearate and / or zinc stearate, and preferably, the vinyl bis-stearamide complex may include a vinyl bis-stearamide (EBS) complex. The dispersant may also include magnesium stearate, zinc stearate, and / or a vinyl bis-stearamide (EBS) complex.

[0065] According to one embodiment of this application, the dispersant can be 0.1 to 0.5 parts per 100 parts by weight of the polyamide composite. Furthermore, the dispersant can be 0.1 to 0.45 parts per 100 parts by weight of the polyamide composite, preferably 0.15 to 0.3 parts, and more preferably 0.2 to 0.25 parts.

[0066] According to one embodiment of this application, the pigment may include two or more selected from the following: pigment carbon black 7, pigment manganese iron black 26, pigment copper chromium black 28, and dye solvent black 5.

[0067] According to one embodiment of this application, the colorant may include pigment carbon black 7 and dye solvent black 5.

[0068] According to one embodiment of this application, in addition to the aforementioned black pigment and / or dye, the color powder may also include one or more of the following: organic dye yellow 160:1, organic pigment blue 15:1, organic pigment blue 15:3, organic solvent blue 97, organic solvent red 52, organic solvent red 135, organic solvent red 179, organic solvent green 3, and organic solvent green 28.

[0069] According to one embodiment of this application, in addition to the aforementioned black pigment and / or dye, the color powder may also include one or more of the following: organic pigment blue 15:1, organic pigment blue 15:3, organic solvent blue 97, organic solvent red 52, organic solvent red 135, organic solvent red 179, organic solvent green 3, and organic solvent green 28.

[0070] According to one embodiment of this application, in addition to the aforementioned black pigment and / or dye, the color powder may also include one or more of the following: organic pigment blue 15:1, organic pigment blue 15:3, organic solvent blue 97, organic solvent red 52, organic solvent red 135, and organic solvent red 179.

[0071] According to one embodiment of this application, in addition to the aforementioned black pigment and / or dye, the color powder may also include organic pigment blue 15:3 and organic solvent red 135.

[0072] According to one embodiment of this application, the pigment may include two or more selected from the following: pigment carbon black 7, pigment manganese iron black 26, pigment copper chromium black 28, dye solvent black 5, organic dye yellow 160:1, organic pigment blue 15:1, organic pigment blue 15:3, organic solvent blue 97, organic solvent red 52, organic solvent red 135, organic solvent red 179, organic solvent green 3, and organic solvent green 28.

[0073] According to one embodiment of this application, the pigment may include three or more selected from the following: pigment carbon black 7, pigment manganese iron black 26, pigment copper chromium black 28, dye solvent black 5, organic dye yellow 160:1, organic pigment blue 15:1, organic pigment blue 15:3, organic solvent blue 97, organic solvent red 52, organic solvent red 135, organic solvent red 179, organic solvent green 3, and organic solvent green 28.

[0074] According to one embodiment of this application, the pigment may include four or more selected from the following: pigment carbon black 7, pigment manganese iron black 26, pigment copper chromium black 28, dye solvent black 5, organic dye yellow 160:1, organic pigment blue 15:1, organic pigment blue 15:3, organic solvent blue 97, organic solvent red 52, organic solvent red 135, organic solvent red 179, organic solvent green 3, and organic solvent green 28.

[0075] According to one embodiment of this application, the pigment may include five or more selected from the following: pigment carbon black 7, pigment manganese iron black 26, pigment copper chromium black 28, dye solvent black 5, organic dye yellow 160:1, organic pigment blue 15:1, organic pigment blue 15:3, organic solvent blue 97, organic solvent red 52, organic solvent red 135, organic solvent red 179, organic solvent green 3, and organic solvent green 28.

[0076] According to one embodiment of this application, the preferred colorant may include pigment carbon black 7, dye solvent black 5, organic pigment blue 15:1, organic solvent blue 97, organic solvent red 52 and organic solvent green 28.

[0077] According to one embodiment of this application, the pigment may include two or more selected from the following: pigment carbon black 7, pigment manganese iron black 26, pigment copper chromium black 28, dye solvent black 5, organic pigment blue 15:1, organic pigment blue 15:3, organic solvent blue 97, organic solvent red 52, organic solvent red 135, and organic solvent red 179.

[0078] According to one embodiment of this application, the pigment may include three or more selected from the following: pigment carbon black 7, pigment manganese iron black 26, pigment copper chromium black 28, dye solvent black 5, organic pigment blue 15:1, organic pigment blue 15:3, organic solvent blue 97, organic solvent red 52, organic solvent red 135, and organic solvent red 179.

[0079] According to one embodiment of this application, the pigment may include four or more selected from the following: pigment carbon black 7, pigment manganese iron black 26, pigment copper chromium black 28, dye solvent black 5, organic pigment blue 15:1, organic pigment blue 15:3, organic solvent blue 97, organic solvent red 52, organic solvent red 135, and organic solvent red 179.

[0080] According to one embodiment of this application, the pigment may include: pigment carbon black 7, dye solvent black 5, organic pigment blue 15:3 and organic solvent red 135.

[0081] As non-limiting examples, Pigment Black 7 can use MA-100; Dye Solvent Black 5 can use Ranbarblack P0085; Organic Pigment Blue 15:1 can use HOSTAPERM BLUE A2R; Organic Pigment Blue 15:3 can use HELIOGENBLUE K7090; Organic Solvent Blue 97 can use MACROLEX Blue RR; Organic Solvent Red 135 can use MACRO-ROT EG; Organic Solvent Red 52 can use MACROLEX RED 5B; Organic Solvent Green 28 can use Macrolex GREEN G.

[0082] According to one embodiment of this application, based on a total of 100% by weight of pigment powder, the pigment powder may include 35% to 75% of pigment carbon black 7, preferably 40% to 75% of pigment carbon black 7, more preferably 40% to 70% of pigment carbon black 7. For example, the pigment powder may include 70% of pigment carbon black 7, or 60% of pigment carbon black 7, or 50% of pigment carbon black 7, or 40% of pigment carbon black 7.

[0083] According to one embodiment of this application, based on a total of 100% by weight of pigment, the pigment may include 20% to 55% of dye solvent black 5, preferably 25% to 50% of dye solvent black 5. For example, the pigment may include 25% dye solvent black 5, or 35% dye solvent black 5, or 45% dye solvent black 5, or 50% dye solvent black 5.

[0084] According to one embodiment of this application, based on a total of 100% by weight of pigment powder, the pigment powder may include 1% to 5% organic pigment blue 15:3, preferably 1% to 4% organic pigment blue 15:3, more preferably 1% to 3% organic pigment blue 15:3, and even more preferably 1% to 2.5% organic pigment blue 15:3. For example, the pigment powder may include 2.5% organic pigment blue 15:3, or 1.5% organic pigment blue 15:3, or 1% organic pigment blue 15:3.

[0085] According to one embodiment of this application, based on a total of 100% by weight of pigment, the pigment may include 1% to 5% organic solvent red 135, preferably 1.5% to 4.5% organic solvent red 135, more preferably 2% to 4% organic solvent red 135, and even more preferably 2.5% to 4% organic solvent red 135. For example, the pigment may include 2.5% organic solvent red 135, or 3.5% organic solvent red 135, or 4% organic solvent red 135.

[0086] Besides the above-mentioned color powder combinations, there are no restrictions on the types and proportions of color powders added. For example, the types and proportions of color powders can be adjusted according to actual color requirements.

[0087] The high-gloss, hydrolysis-resistant reinforced polyamide composite of the present invention can be prepared by the following method, comprising the following steps:

[0088] Step 1: Prepare raw materials: including the aforementioned components and their weight proportions.

[0089] Step 2, Mixed Extrusion: Mix and extrude the prepared raw materials.

[0090] According to one embodiment of this application, in the above-mentioned mixed extrusion step, polyamide, antioxidant, ultraviolet absorber, hindered amine light stabilizer, dispersant, and colorant are mixed and stirred evenly, and then added to a twin-screw extruder; during the extrusion process of the above mixture, chopped glass fibers are added to the twin-screw extruder by side feeding and extruded together at high temperature, cooled, drawn and pelletized, with an extrusion temperature of 270℃~320℃, to obtain a high-gloss hydrolysis-resistant reinforced polyamide composite.

[0091] According to one embodiment of this application, in the above-mentioned mixing extrusion step, the extrusion temperature can be, for example, 270°C, 275°C, 280°C, 285°C, 290°C, 295°C, 300°C, 305°C, 310°C, 315°C, or 320°C.

[0092] The above description of the components (including content) in the high-gloss hydrolysis-resistant reinforced polyamide composite applies to the components (including content) in the preparation method.

[0093] The advantages of this invention are as follows: The high-gloss, hydrolysis-resistant reinforced polyamide composite of this invention, through the simultaneous use of multiple high-coloring-strength black pigments and organic pigments, reduces the severe surface roughness caused by poor dyeing effect of a single pigment. The multiple pigment blends also improve the adhesion between the resin and glass fiber, enhancing the hydrolysis and alcoholysis resistance of the polyamide. The optimized blended colorant combination, along with the following components—polyamide, antioxidant, UV absorber, hindered amine light stabilizer, dispersant, and colorant—and the rational selection of specific weights, enhances the material's resistance to cooling liquids. Under 135℃@2000 hours of operation, the mechanical property retention rate is 60%, and the surface finish is Ra<2μm, expanding the application range of hydrolysis-resistant polyamide materials and enabling their widespread use in the cooling systems of thermal management modules in new energy vehicles.

[0094] The high-gloss, hydrolysis-resistant reinforced polyamide composite of this invention can be applied to the thermal management system of new energy vehicles or the cooling piping system of fuel vehicles. Specifically, it can be used in thermal management modules such as water outlets, control valves, thermostats, and cooling water jackets in the cooling systems of new energy vehicles.

[0095] Example

[0096] The technical solution of the present invention will be described in more detail below with reference to specific comparative examples and embodiments. The above content can be better understood by referring to the following embodiments, but the embodiments are intended to be illustrative and not to limit the scope of the invention. In particular, the embodiments illustrate representative embodiments of the inherent principles of the invention, and these principles are not strictly limited to the specific conditions described in these embodiments. Therefore, it should be understood that the present invention covers various changes and modifications to the embodiments described herein, and such changes and modifications can be made without departing from the spirit and scope of the invention and without diminishing its intended advantages. Therefore, such changes and modifications are contemplated to be included in the appended claims.

[0097] Comparative Example 1

[0098] The ordinary hydrolysis-resistant polyamide composite 1 of this comparative example is composed of the following components in parts by weight: 50 parts polyamide PA66 (U4840NL NC01), 17.125 parts polyamide PA6I / 6T (TI1207), and 30 parts chopped glass fibers (…). 540H), 0.25 parts hindered phenolic antioxidant ( 1098), 0.125 parts of phosphite antioxidant ( 686), 0.15 parts UV absorber ( UV-234), 0.1 parts light stabilizer ( UV-944), 0.25 parts dispersant (CMS P-130), 2 parts color powder (90% pigment carbon black 7MA-100, 8% organic solvent blue 97 Macrolex Blue RR, 2% organic solvent green 28 Macrolex GREEN G).

[0099] The preparation method of the ordinary hydrolysis-resistant polyamide composite 1 of Comparative Example 1 includes the following steps:

[0100] Step 1: Mix polyamide PA66, polyamide PA6I / 6T, hindered phenolic antioxidant, phosphite antioxidant, UV absorber, light stabilizer, dispersant, and colorant until homogeneous.

[0101] Step 2: Add the mixture obtained in Step 1 into a twin-screw extruder. The twin-screw extruder has a total of 9 temperature sections. The temperature of the first and second sections is 270 degrees Celsius, and the temperature of the other three sections is 295 degrees Celsius. The main extruder speed is 800 rpm. Short glass fibers are added from the side feed during the extrusion process. Finally, after extrusion, cooling, traction, and pelletizing, a dark brown-black infrared-transmitting glass fiber reinforced polyamide material is obtained.

[0102] The obtained material was dried at 100 degrees Celsius for 4 hours in a dehumidifying dryer, and then injection molded into test samples.

[0103] Comparative Example 2

[0104] The ordinary hydrolysis-resistant polyamide composite 2 of this comparative example is composed of the following components in parts by weight: 50 parts polyamide PA66 (U4840NL NC01), 17.125 parts polyamide PA6I / 6T (TI1207), and 30 parts chopped glass fibers (…). 540H), 0.25 parts hindered phenolic antioxidant ( 1098), 0.125 parts of phosphite antioxidant ( 686), 0.15 parts UV absorber ( UV-234), 0.1 parts light stabilizer ( UV-944), 0.25 parts dispersant (CMS P-130), 2 parts pigment (90% dye solvent black 5 Ranbarblack P0085, 4% organic solvent red 135 MACRO-ROT EG, 6% organic pigment blue 15:3 HELIOGENBLUEK7090).

[0105] The preparation method of the ordinary hydrolysis-resistant polyamide composite 2 in this comparative example is the same as that in comparative example 1.

[0106] Example 1

[0107] The high-gloss, hydrolysis-resistant reinforced polyamide composite 1 of this embodiment is composed of the following components in parts by weight: 50 parts polyamide PA66 (U4840NL NC01), 17.125 parts polyamide PA6I / 6T (TI1207), and 30 parts chopped glass fiber (…). 540H), 0.25 parts hindered phenolic antioxidant ( 1098), 0.125 parts of phosphite antioxidant ( 686), 0.15 parts UV absorber ( UV-234), 0.1 parts light stabilizer ( UV-944), 0.25 parts dispersant (CMS P-130), 2 parts color powder (70% pigment carbon black 7MA-100, 25% dye solvent black 5 Ranbar black P0085, 2.5% organic solvent red 135 MACRO-ROT EG, 2.5% organic pigment blue 15:3 HELIOGENBLUE K7090).

[0108] The preparation method of the high-gloss hydrolysis-resistant reinforced polyamide composite 1 in this Example 1 is the same as that in Comparative Example 1.

[0109] Example 2

[0110] The high-gloss, hydrolysis-resistant reinforced polyamide composite 2 of this embodiment is composed of the following components in parts by weight: 50 parts polyamide PA66 (U4840NL NC01), 17.125 parts polyamide PA6I / 6T (TI1207), and 30 parts chopped glass fiber (…). 540H), 0.25 parts hindered phenolic antioxidant ( 1098), 0.125 parts of phosphite antioxidant ( 686), 0.15 parts UV absorber ( UV-234), 0.1 parts light stabilizer ( UV-944), 0.25 parts dispersant (CMS P-130), 2 parts color powder (60% pigment carbon black 7MA-100, 35% dye solvent black 5 Ranbar black P0085, 3.5% organic solvent red 135 MACRO-ROT EG, 1.5% organic pigment blue 15:3 HELIOGENBLUE K7090).

[0111] The preparation method of the high-gloss hydrolysis-resistant reinforced polyamide composite 2 in Example 2 is the same as that in Comparative Example 1.

[0112] Example 3

[0113] The high-gloss, hydrolysis-resistant reinforced polyamide composite 3 of this embodiment is composed of the following components in parts by weight: 50 parts polyamide PA66 (U4840NL NC01), 17.125 parts polyamide PA6I / 6T (TI1207), and 30 parts chopped glass fiber (…). 540H), 0.25 parts hindered phenolic antioxidant ( 1098), 0.125 parts of phosphite antioxidant ( 686), 0.15 parts UV absorber ( UV-234), 0.1 parts light stabilizer ( UV-944), 0.25 parts dispersant (CMS P-130), 2 parts color powder (50% pigment carbon black 7MA-100, 45% dye solvent black 5Ranbar black P0085, 4% organic solvent red 135MACRO-ROT EG, 1% organic pigment blue 15:3HELIOGENBLUE K7090).

[0114] The preparation method of the high-gloss hydrolysis-resistant reinforced polyamide composite 3 in Example 3 is the same as that in Comparative Example 1.

[0115] Example 4

[0116] The high-gloss, hydrolysis-resistant reinforced polyamide composite 4 of this embodiment is composed of the following components in parts by weight: 50 parts polyamide PA66 (U4840NL NC01), 17.125 parts polyamide PA6I / 6T (TI1207), and 30 parts chopped glass fiber (…). 540H), 0.25 parts hindered phenolic antioxidant ( 1098), 0.125 parts of phosphite antioxidant ( 686), 0.15 parts UV absorber ( UV-234), 0.1 parts light stabilizer ( UV-944), 0.25 parts dispersant (CMS P-130), 2 parts color powder (40% pigment carbon black 7MA-100, 50% dye solvent black 5 Ranbar black P0085, 4% organic solvent red 135 MACRO-ROT EG, 1% organic pigment blue 15:3 HELIOGENBLUE K7090).

[0117] The preparation method of the high-gloss hydrolysis-resistant reinforced polyamide composite 4 in Example 4 is the same as that in Comparative Example 1.

[0118] High gloss hydrolysis resistance test

[0119] The performance of the materials obtained in the comparative examples and embodiments was tested and evaluated using the following methods.

[0120] 1) Aging oven: Memmert

[0121] 2) Roughness testing equipment: JB-1C (Ra: 0.01-10μm)

[0122] 3) Universal tensile testing equipment: Z020

[0123] 4) Injection molded test specimen: 60x60x2mm template, ISO 527 1A strip.

[0124] 5) Coolant resistance (BASF G48) aging conditions include: Condition 1: 95℃, 2000 hours; Condition 2: 115℃, 2000 hours; Condition 3: 135℃, 2000 hours.

[0125] Time selection nodes: 50 hours, 500 hours, 750 hours, 1000 hours, 1500 hours, 2000 hours.

[0126] The formula for calculating the tensile strength retention rate is as follows: where the tensile strength refers to the breaking tensile strength.

[0127]

[0128] The table below shows the test results of the high-gloss hydrolysis resistance of the comparative and exemplary cases:

[0129] Table 1: Data after aging under condition 1: 95℃, 2000 hours

[0130]

[0131]

[0132] Table 2: Data after aging under condition 2: 115℃, 2000 hours

[0133]

[0134] Table 3: Data after aging under condition 3: 135℃, 2000 hours

[0135]

[0136] Based on the test results in the table above, it can be seen that the high-gloss hydrolysis-resistant reinforced polyamide composite of the present invention has excellent surface gloss and excellent resistance to coolant aging. The surface gloss can be as low as 1.8 μm, and the tensile strength at break can maintain about 60% of the initial properties.

[0137] The high-gloss, hydrolysis-resistant reinforced polyamide composite of this invention utilizes a combination of high-coloring-strength organic solvent black and organic pigments. This reduces the poor dyeing effect of single pigments, which can lead to severe surface roughness and poor product roughness. The multiple pigment combinations also improve the adhesion between the resin and glass fiber, enhancing the hydrolysis and alcoholysis resistance of the polyamide. The optimized compounded pigment combination, along with the following components—polyamide, antioxidant, UV absorber, hindered amine light stabilizer, dispersant, and pigment—and the appropriate selection of specific weights, enhances the material's resistance to cooling liquids. Under 135℃@2000 hours of operation, the mechanical property retention rate is 60%, and the surface finish is Ra<2μm. This expands the application range of hydrolysis-resistant polyamide materials, making them widely applicable in the cooling systems of thermal management modules in new energy vehicles.

[0138] Although the invention can be embodied in many different forms, specific preferred embodiments of the invention are described in detail herein. This disclosure is an example of the principles of the invention and is not intended to limit the invention to the specific embodiments described. Furthermore, the invention covers any possible combination of some or all of the various embodiments mentioned herein, described herein, and / or incorporated herein. In addition, the invention also specifically excludes any possible combination of any or some of the various embodiments mentioned herein, described herein, and / or incorporated herein.

[0139] The foregoing disclosure is intended to be illustrative and not exhaustive. Individual elements or features of a particular embodiment are generally not limited to that particular embodiment, but may be used in other embodiments and may be combined in other ways, even if not specifically shown or described. Such variations are included in this invention. Based on the description herein, many modifications and alternatives will be conceived by those skilled in the art. All such alternatives and modifications are intended to be included within the scope of the claims. Those skilled in the art will recognize other equivalents of the specific embodiments described herein, which are also intended to be covered by the claims.

Claims

1. A high-gloss, hydrolysis-resistant reinforced polyamide composite, comprising, based on 100 parts by weight, the following components in parts by weight: 25-75 parts of polyamide 30-70 parts chopped glass fiber Antioxidant 0.1–0.6 parts 0.1 to 0.5 parts of ultraviolet absorber 0.1–0.5 parts of hindered amine light stabilizer Dispersant 0.1-0.5 parts 1-3 parts of color powder, The pigments, based on a total weight of 100%, comprise 35% to 75% pigment carbon black 7, 20% to 55% dye solvent black 5, 1% to 5% organic solvent red 135, and 1% to 5% organic pigment blue 15:

3.

2. The polyamide composite according to claim 1, wherein the polyamide is one or a mixture of two of PA6, PA66, PA610, PA6I / 6T, PA6T / 6I, PA9T, PA10T, and PA12, and the Ubbelohde relative viscosity of the polyamide with m-cresol as solvent is 2.0 to 3.

0.

3. The polyamide composite according to claim 1, wherein the chopped glass fibers have a length of 3.5 to 4.5 mm and a diameter of 7 to 15 μm.

4. The polyamide composite according to claim 1, wherein the chopped glass fibers have a length of 3 to 4.5 mm, a diameter of 7 to 15 μm, and a circular and / or elliptical cross-section.

5. The polyamide composite according to claim 1, wherein the chopped glass fibers have a length of 3-4.5 mm, a diameter of 8-15 μm, and an elliptical cross-section, wherein the ratio of the short and long diameters of the ellipse is 1:3 to 1:

5.

6. The polyamide composite according to claim 1, wherein the antioxidant comprises a primary antioxidant and a secondary antioxidant in a weight ratio of 2:1, wherein the primary antioxidant comprises a hindered phenolic antioxidant, and the secondary antioxidant comprises a phosphite antioxidant.

7. The polyamide composite according to claim 6, wherein the hindered phenolic antioxidant comprises N,N'-hexamethylene bis(3,5-di-tert-butyl-4-hydroxyphenylpropionamide) and pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]; and the phosphite antioxidant comprises bis(2,4-dicumylphenyl)pentaerythritol diphosphite and tris(2,4-di-tert-butylphenyl) phosphite.

8. The polyamide composite according to claim 6, wherein the hindered phenolic antioxidant is 0.06 to 0.4 parts, the phosphite antioxidant is 0.04 to 0.2 parts, and the total amount of the hindered phenolic antioxidant and the phosphite antioxidant is 0.1 to 0.6 parts.

9. The polyamide composite according to claim 1, wherein the ultraviolet absorber comprises 2-(2H-benzotriazole-2)-4,6-di(1-methyl-1-phenylethyl)-phenol.

10. The polyamide composite according to claim 1, wherein the hindered amine light stabilizer comprises N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-N,N'-dialdehyde hexamethylenediamine.

11. The polyamide composite of claim 1, wherein the dispersant comprises stearates and / or vinyl bis-stearamide composites, wherein the stearates comprise magnesium stearate and / or zinc stearate, and the vinyl bis-stearamide composite comprises a vinyl bis-stearamide EBS composite.

12. A method for preparing a high-gloss, hydrolysis-resistant reinforced polyamide composite, comprising the following steps: Step 1, Prepare raw materials: The raw materials consist of the following components in parts by weight based on a total of 100 parts by weight: 25-75 parts of polyamide 30-70 parts chopped glass fiber Antioxidant 0.1–0.6 parts 0.1 to 0.5 parts of ultraviolet absorber 0.1–0.5 parts of hindered amine light stabilizer Dispersant 0.1-0.5 parts The pigment comprises 1 to 3 parts, wherein, based on a total weight of 100%, the pigment includes 35% to 75% pigment carbon black 7, 20% to 55% dye solvent black 5, 1% to 5% organic solvent red 135, and 1% to 5% organic pigment blue 15:

3. Step 2, Mixed Extrusion: Mix and extrude the prepared raw materials.

13. The method according to claim 12, wherein in the mixing extrusion step, the polyamide, the antioxidant, the UV absorber, the hindered amine light stabilizer, the dispersant and the colorant are mixed and stirred evenly, and then added to a twin-screw extruder; during the extrusion process of the mixture, the chopped glass fibers are added to the twin-screw extruder by side feeding and extruded together at high temperature, cooled, drawn and pelletized, with the extrusion temperature being 270℃~320℃, to obtain the high-gloss hydrolysis-resistant reinforced polyamide composite.

14. A high-gloss, hydrolysis-resistant reinforced polyamide composite prepared by the method according to claim 12 or 13.

15. The use of the high-gloss hydrolysis-resistant reinforced polyamide composite according to any one of claims 1 to 11 in the thermal management system of new energy vehicles or the cooling pipeline system of fuel vehicles.

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