Hydrolysis-resistant reinforced nylon / polyphenyl ether alloy material and preparation method thereof

Abstract

The invention discloses a hydrolysis-resistant reinforced nylon / polyphenyl ether alloy material and a preparation method thereof, and belongs to the technical field of polymer composites.The hydrolysis-resistant reinforced nylon / polyphenyl ether alloy material is prepared from, by weight, 20-55 parts of nylon resin, 10-20 parts of polyphenyl ether resin, 3-5 parts of compatilizer and 0.5-0.7 part of hydrolysis-resistant agent, the glass fiber reinforced plastic is prepared from the following components in parts by weight: 0.1-0.5 part of a heat stabilizer, 0.2-0.5 part of a lubricant, 0.05-0.2 part of a nucleating agent, 0.2-0.6 part of an antioxidant, 0.5-2 parts of black masterbatch and 27-33 parts of alcoholysis glass fiber. An active functional group of polyphenyl ether grafted maleic anhydride reacts with a functional group at the tail end of a nylon molecular chain to form a micro-crosslinking structure, the surface of selected alcoholysis glass fiber is infiltrated by an ethylene and maleic anhydride copolymer, and lignite acid partially esterified by butanediol is selected, so that the surface of the alcoholysis glass fiber is modified. According to the present invention, the glass fiber and the nylon material are mixed with the ester wax saponified by using calcium hydroxide to serve as the lubricant, and the P22 nucleating agent is compounded, such that the glass fiber and nylon material interface bonding strength is enhanced, and the excellent hydrolysis resistance is provided.

Description

Technical Field

[0001] This invention belongs to the field of polymer composite materials technology, specifically relating to a hydrolysis-resistant reinforced nylon / polyphenylene ether alloy material and its preparation method. Background Technology

[0002] With the rapid development of the automotive industry, lightweighting and the replacement of steel with plastics have become the development direction of automotive materials, and more and more automotive parts are using plastics instead of metals. As an important component of the cooling system, the automotive water chamber needs to meet multiple performance requirements: on the one hand, in order to adapt to the complex injection molding process, the material must have excellent fluidity; on the other hand, the water chamber is in direct contact with antifreeze containing alcohol solvents for a long time, and the working environment is often accompanied by temperature fluctuations. Therefore, the material must have outstanding resistance to hydrolysis and alcohol solvent corrosion, while maintaining stable mechanical strength to avoid safety hazards such as cracking and leakage after long-term use.

[0003] Traditional automotive water chamber materials use polyhexamethylene adipamide (PA66) as the base material. PA66 has good mechanical strength, heat resistance, and processing fluidity, which can meet the basic requirements for water chamber molding. However, it has significant performance shortcomings: the amide bond density in the PA66 molecular chain is high, and the amide bonds are prone to hydrolysis reaction with water molecules, leading to molecular chain breakage. This results in a significant decrease in the tensile strength, impact strength, and other mechanical properties of the material. At the same time, the surface is prone to powdering and cracking, which greatly shortens the service life of the water chamber. In severe cases, it may cause antifreeze leakage, affecting the normal operation of the automotive cooling system, and even causing safety risks such as engine overheating.

[0004] Therefore, this invention proposes a hydrolysis-resistant reinforced nylon / polyphenylene ether alloy material and its preparation method. Summary of the Invention

[0005] The purpose of this section is to outline some aspects of embodiments of the present invention and to briefly describe some preferred embodiments. Simplifications or omissions may be made in this section, as well as in the abstract and title of this application, to avoid obscuring the purpose of these documents; however, such simplifications or omissions should not be construed as limiting the scope of the invention.

[0006] In view of the problems existing in the above and / or prior art, the present invention is proposed.

[0007] Therefore, the purpose of this invention is to overcome the shortcomings of the prior art and provide a hydrolysis-resistant reinforced nylon / polyphenylene ether alloy material.

[0008] To solve the above-mentioned technical problems, the present invention provides the following technical solution: the raw materials are composed of the following parts by weight: The composition includes 20-55 parts nylon resin, 10-20 parts polyphenylene ether resin, 3-5 parts compatibilizer, 0.5-0.7 parts anti-hydrolysis agent, 0.1-0.5 parts heat stabilizer, 0.2-0.5 parts lubricant, 0.05-0.2 parts nucleating agent, 0.2-0.6 parts antioxidant, 0.5-2 parts black masterbatch, and 27-33 parts alcoholyzed glass fiber. The mass ratio of nylon resin to polyphenylene ether resin is 1~5:1.

[0009] As a preferred embodiment of the hydrolysis-resistant reinforced nylon / polyphenylene ether alloy material of the present invention, wherein the nylon resin is at least one of PAMXD6 and PA610.

[0010] As a preferred embodiment of the hydrolysis-resistant reinforced nylon / polyphenylene ether alloy material of the present invention, the lubricant is a mixture of silicone powder and lignite wax in a mass ratio of 1:1~2.

[0011] As a preferred embodiment of the hydrolysis-resistant reinforced nylon / polyphenylene ether alloy material of the present invention, the nucleating agent is P22 nucleating agent.

[0012] As a preferred embodiment of the hydrolysis-resistant reinforced nylon / polyphenylene ether alloy material of the present invention, the heat stabilizer is an organic copper salt complex, wherein the organic copper salt is a product of cuprous ions and organic phosphonate ions bonded by ionic bonds.

[0013] As a preferred embodiment of the hydrolysis-resistant reinforced nylon / polyphenylene ether alloy material of the present invention, the antioxidant is a mixture of hindered phenolic antioxidant and phosphite antioxidant in a mass ratio of 1:1 to 2.

[0014] As a preferred embodiment of the hydrolysis-resistant reinforced nylon / polyphenylene oxide alloy material of the present invention, the compatibilizer is at least one of maleic anhydride-grafted PPE and maleic anhydride-grafted SEBS.

[0015] As a preferred embodiment of the hydrolysis-resistant reinforced nylon / polyphenylene ether alloy material of the present invention, the maleic anhydride grafting rate in the compatibilizer is 1.0%~2%.

[0016] This invention also proposes a method for producing hydrolysis-resistant reinforced nylon / polyphenylene ether alloy materials, comprising the following steps: S1: Add compatibilizer, anti-hydrolysis agent, heat stabilizer, lubricant, antioxidant, and black masterbatch to a mixer and mix evenly to obtain mixture A; S2: Dry the nylon resin at 90~110℃ for 4~6 hours, mix it evenly with the polyphenylene ether resin, and then add it to the mixer with mixture A and mix evenly to obtain mixture B; S3: Mixture B is added to a twin-screw extruder through the main feed port and glass fiber is added through the side feed port. After melt extrusion, it is cooled, dried, and pelletized to obtain hydrolysis-resistant reinforced nylon / polyphenylene ether alloy material.

[0017] In a preferred embodiment of the preparation method of the hydrolysis-resistant reinforced nylon / polyphenylene ether alloy material of the present invention, the extruder barrel temperature is 180-280℃ and the screw speed is 300~500r / min.

[0018] Beneficial effects of this invention: This invention utilizes a preferred mass ratio of nylon resin to polyphenylene ether resin of 1-5:1. The active functional groups of the polyphenylene ether grafted with maleic anhydride react with the functional groups at the ends of the nylon molecular chains to form a micro-crosslinked structure, thereby protecting the molecular chains. The selected alcoholyzed glass fiber surface is impregnated with an ethylene and maleic anhydride copolymer. A mixture of partially esterified lignite acid (butanediol-based) and saponified ester wax (calcium hydroxide-based) is used as a lubricant, along with a P22 nucleating agent, to enhance the interfacial bonding strength between the glass fiber and nylon materials and impart excellent hydrolysis resistance. The heat stabilizer reacts and chelates with the amide groups in the nylon molecular chains during processing, protecting the amide groups from attack by thermo-oxidative groups and other active groups in long-term UV and thermo-oxidative environments, preventing molecular chain breakage and degradation, and thus improving the material's hydrolysis resistance under long-term high-temperature conditions. Detailed Implementation

[0019] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, the specific embodiments of the present invention will be described in detail below with reference to the examples in the specification.

[0020] Many specific details are set forth in the following description in order to provide a full understanding of the invention. However, the invention may also be practiced in other ways different from those described herein, and those skilled in the art can make similar extensions without departing from the spirit of the invention. Therefore, the invention is not limited to the specific embodiments disclosed below.

[0021] Secondly, the term "one embodiment" or "embodiment" as used herein refers to a specific feature, structure, or characteristic that may be included in at least one implementation of the present invention. The phrase "in one embodiment" appearing in different places in this specification does not necessarily refer to the same embodiment, nor is it a single or selective embodiment that is mutually exclusive with other embodiments.

[0022] In this invention, PAMXD6 was purchased from Shanghai Yinggu Chemical Co., Ltd., brand name AP250; PA610 was purchased from Shandong Guangyin New Materials Co., Ltd., grade F150. PA66 was purchased from Pingdingshan Shenma Engineering Plastics Co., Ltd., grade EPR27; The polyphenylene oxide resin was purchased from Bluestar Company, brand name LXR035; The compatibilizer selected was maleic anhydride-grafted polyphenylene ether (PPE-MAH), purchased from Jia Yi Rong Polymer (Shanghai) Co., Ltd., brand name FB820, with a maleic anhydride grafting rate of 1.0%. The alcoholyzed glass fiber was purchased from Shandong Taishan Glass Fiber, with the grade HMG-10-435TM and a diameter of 10μm. The ordinary fiberglass was also purchased from Shandong Taishan Fiberglass, with the grade ECS-10-T435N; The hydrolysis inhibitor was purchased from Bruggolite GmbH, Germany, brand name H3337; The heat stabilizer was purchased from Bruggolite GmbH, Germany, brand name H3336. The lubricant is a 1:1 mixture of silicone powder and lignite wax, wherein the silicone powder was purchased from Chengdu Silike Technology, brand name LYSI-300C, and the lignite wax was purchased from Clariant Chemical, brand name WAX ​​OP; The nucleating agent was purchased from Bruggolite GmbH, Germany, brand name P22; The antioxidant is a mixture of hindered phenolic antioxidant and phosphite antioxidant in a weight ratio of 1:2; wherein the hindered phenolic antioxidant is BASF's 1098 and the phosphite antioxidant is DOVEN's high-temperature auxiliary antioxidant S9228. The black masterbatch is an oil-soluble aniline black masterbatch, purchased from Gao Lai, grade N54 / 1033.

[0023] Example This embodiment provides a method for preparing a hydrolysis-resistant reinforced nylon / polyphenylene ether alloy material, including the following steps: 1) Add compatibilizer, anti-hydrolysis agent, heat stabilizer, lubricant, nucleating agent, antioxidant, and black masterbatch to a mixer and mix evenly to obtain mixture A; 2) Dry the nylon resin at 90~110℃ for 4~6 hours, mix it evenly with the polyphenylene ether resin, and then add it to the mixer with mixture A and mix evenly to obtain mixture B; 3) Mixture B is added to the twin-screw extruder through the main feed port and hydrolyzed glass fiber is added through the side feed port. After melt extrusion, it is cooled, dried, and pelletized to obtain hydrolysis-resistant reinforced nylon / polyphenylene ether alloy material. The extruder barrel temperature is 180-280℃ and the screw speed is 300-500r / min. The composition of each component of the alloy materials obtained in Examples 1-5 and Comparative Examples 1-4 is shown in Table 1.

[0024] Table 1

[0025] The alloy materials obtained in Examples 1-5 and Comparative Examples 1-4 were dried in a vacuum drum drying oven at 110°C for 8 hours to reduce the moisture content to between 500 and 800 ppm. Then, they were injection molded into standard mechanical property test specimens at 270°C. The injection-molded specimens were placed in a standard laboratory environment (23°C, 50%RH) for 24 hours. Tensile strength and elongation at break were tested according to ISO 527-2; flexural strength and modulus were tested according to ISO 178-1; the specimens were then placed in a forced-air-ventilation oven at 150°C for 1000 hours. Afterward, the specimens were removed, and the tensile strength after thermal aging was tested according to ISO 527-2. Test hydrolysis resistance using the following steps: 1) Place the sample in a reaction vessel containing ethylene glycol, lined with polytetrafluoroethylene digestion and with a 304 stainless steel body. Then place the reaction vessel in an oven at 135°C for 48 hours. After that, take out the sample and observe whether cracks appear on the surface of the sample. 2) Place the sample in a reactor equipped with a polytetrafluoroethylene digestion vessel liner and a 304 stainless steel tank, pour in a long-lasting coolant prepared by ethylene glycol and water in a mass ratio of 1:1, and then place the reactor in an oven at 135~150℃ for 1000h. After that, take out the sample and test the tensile strength of the material after hydrolysis according to ISO527-2 method.

[0026] The performance test results are shown in Table 2.

[0027] Table 2

[0028] As shown in Table 2, compared with the composite materials modified by mixing single nylon resin and polyphenylene ether resin prepared in Examples 1-2, the composite material prepared in Example 3, which is jointly modified by mixed nylon resin and polyphenylene ether resin, has a lower water absorption rate and a significantly improved tensile strength after being immersed in a long-lasting coolant at 135°C for 1000 hours to resist hydrolytic aging. This is because the concentration of amide groups in the mixed nylon resin and polyphenylene ether resin is reduced, thereby reducing hydrophilic sites and lowering the water absorption rate. Compared with Example 3, the content of polyphenylene ether in Example 4 was doubled. Compared with Example 3, the content of anti-hydrolysis agent in Example 5 was increased. The composite materials prepared in Examples 4 and 5 had better water absorption, hydrolysis resistance and heat aging resistance than those in Example 3, but the tensile strength and flexural modulus were reduced to varying degrees. Comparative Example 1 is a traditional automotive water chamber material, using PA66 as the base resin. However, due to the high density of amide bonds in PA66, it is a material that easily absorbs water. In contrast, this invention selects long-chain nylon PA610 or semi-aromatic nylon PAMXD6 with low water absorption rate and blends them with polyphenylene ether, which has almost no water absorption rate, to form an alloy. This can greatly reduce the water absorption of the material. It can be seen that the composite material prepared by this invention has a lower water absorption rate and better hydrolysis resistance compared with Comparative Example 1. Comparative Example 2, without the addition of polyphenylene ether and compatibilizer, had a significantly higher water absorption rate and decreased hydrolysis resistance. Comparative Example 3, without the addition of anti-hydrolysis agent, and Comparative Example 4, using ordinary glass fiber, showed that the composite materials prepared by Comparative Examples 3 to 4 cracked after 48 hours of hydrolysis at 135℃, indicating poor hydrolysis resistance and failing to meet the requirements for use in automotive cooling systems and water chambers.

[0029] The nylon / polyphenylene ether alloy material prepared by this invention has excellent dimensional stability, hydrolysis resistance, heat aging resistance, and excellent antifreeze resistance, which can meet its application requirements in automotive cooling systems and water chambers.

[0030] It should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all such modifications or substitutions should be covered within the scope of the claims of the present invention.

Claims

1. A hydrolysis-resistant reinforced nylon / polyphenylene oxide alloy material, characterized in that: It consists of the following raw materials in parts by weight: The composition includes 20-55 parts nylon resin, 10-20 parts polyphenylene ether resin, 3-5 parts compatibilizer, 0.5-0.7 parts anti-hydrolysis agent, 0.1-0.5 parts heat stabilizer, 0.2-0.5 parts lubricant, 0.05-0.2 parts nucleating agent, 0.2-0.6 parts antioxidant, 0.5-2 parts black masterbatch, and 27-33 parts alcoholyzed glass fiber. The mass ratio of nylon resin to polyphenylene ether resin is 1~5:

1.

2. The hydrolysis-resistant reinforced nylon / polyphenylene oxide alloy material as described in claim 1, characterized in that: The nylon resin is at least one of PAMXD6 and PA610.

3. The hydrolysis-resistant reinforced nylon / polyphenylene oxide alloy material as described in claim 1, characterized in that: The lubricant is a mixture of silicone powder and lignite wax in a mass ratio of 1:1 to 2.

4. The hydrolysis-resistant reinforced nylon / polyphenylene oxide alloy material as described in claim 3, characterized in that: The nucleating agent is P22 nucleating agent.

5. The hydrolysis-resistant reinforced nylon / polyphenylene oxide alloy material as described in claim 1, characterized in that: The heat stabilizer is an organic copper salt complex, wherein the organic copper salt is a product of cuprous ions and organic phosphonate ions bonded by ionic bonds.

6. The hydrolysis-resistant reinforced nylon / polyphenylene oxide alloy material as described in claim 1, characterized in that: The antioxidant is a mixture of hindered phenolic antioxidants and phosphite antioxidants in a mass ratio of 1:1 to 2.

7. The hydrolysis-resistant reinforced nylon / polyphenylene oxide alloy material as described in claim 1, characterized in that: The compatibilizer is at least one of maleic anhydride-grafted PPE and maleic anhydride-grafted SEBS.

8. The hydrolysis-resistant reinforced nylon / polyphenylene oxide alloy material as described in claim 7, characterized in that: The maleic anhydride grafting rate in the compatibilizer is 1.0%~2%.

9. A method for preparing the hydrolysis-resistant reinforced nylon / polyphenylene ether alloy material as described in any one of claims 1 to 7, characterized in that, Includes the following steps: S1: Add compatibilizer, anti-hydrolysis agent, heat stabilizer, lubricant, antioxidant, and black masterbatch to a mixer and mix evenly to obtain mixture A; S2: Dry the nylon resin at 90~110℃ for 4~6 hours, mix it evenly with the polyphenylene ether resin, and then add it to the mixer with mixture A and mix evenly to obtain mixture B; S3: Mixture B is added to a twin-screw extruder through the main feed port and glass fiber is added through the side feed port. After melt extrusion, it is cooled, dried, and pelletized to obtain hydrolysis-resistant reinforced nylon / polyphenylene ether alloy material.

10. The method for preparing hydrolysis-resistant reinforced nylon / polyphenylene ether alloy material as described in claim 9, characterized in that: The extruder barrel temperature is 180-280℃ and the screw speed is 300~500r / min.

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