Thermally stable glass fiber reinforced polyketone composite and method of making

Abstract

The application discloses a heat-resistant and degradation-resistant glass fiber reinforced polyketone composite material and a preparation method thereof, and relates to the technical field of polymer composites. The heat-resistant and degradation-resistant glass fiber reinforced polyketone composite material comprises, by weight, 80-90 parts of polyketone, 10-20 parts of glass fiber, 0.5-1.5 parts of auxiliary antioxidant, 0.5-1.5 parts of main antioxidant, 0.5-1.5 parts of rare earth thermal stabilizer and 0.5-1.5 parts of lubricant. The heat-resistant and degradation-resistant glass fiber reinforced polyketone composite material comprises the main antioxidant, the auxiliary antioxidant and the rare earth thermal stabilizer, and the synergistic effect of the three can effectively solve the carbonolysis problem of the glass fiber reinforced polyketone composite material in the injection molding process, and is beneficial to improving the processing performance and heat resistance of the glass fiber reinforced polyketone composite material.

Description

Technical Field

[0001] This invention relates to the field of polymer composite materials technology, and more specifically, to heat-resistant and degradable glass fiber reinforced polyketone composite materials and their preparation methods. Background Technology

[0002] Polyketone (PK), a high-performance engineering plastic, is widely used in the automotive industry, electronic and electrical equipment, and machinery manufacturing due to its excellent wear resistance, chemical corrosion resistance, flame retardancy, and dimensional stability. To optimize the overall performance of PK materials, especially to improve its resistance to thermal degradation, researchers have conducted systematic modification studies.

[0003] In existing modification technologies, glass fiber reinforcement is a conventional method for improving the mechanical properties of polyketone. Chinese patent CN107793739A discloses a long glass fiber reinforced polyketone composite material. This technology uses continuous glass fibers to reinforce the polyketone resin, controlling the particle length to be 10-15 mm, causing the fibers to align along the particle direction, thereby endowing the material with excellent rigidity, impact toughness, and heat resistance. However, this composite material is prone to carbonization degradation during injection molding, which significantly limits its processing performance and service life.

[0004] Therefore, there is an urgent need to develop a new type of heat-resistant and degradable glass fiber reinforced polyketone composite material to overcome the carbonization problem in the injection molding process of composite materials, so as to meet the needs of high-end application fields.

[0005] In view of this, the present invention is proposed. Summary of the Invention

[0006] The purpose of this invention is to provide a heat-resistant and degradable glass fiber reinforced polyketone composite material and its preparation method, overcoming the problem of easy carbonization during the injection molding process of glass fiber reinforced polyketone composite materials.

[0007] This invention is implemented as follows: In a first aspect, the present invention provides a heat-resistant and degradable glass fiber reinforced polyketone composite material, comprising, by weight: 80-90 parts of polyketone, 10-20 parts of glass fiber, 0.5-1.5 parts of auxiliary antioxidant, 0.5-1.5 parts of primary antioxidant, 0.5-1.5 parts of rare earth heat stabilizer and 0.5-1.5 parts of lubricant.

[0008] In an optional embodiment, the auxiliary antioxidant is selected from one of tris(2,4-di-tert-butylphenyl) phosphite (AO-168), bis(2,4-dicumylphenyl) pentaerythritol-diphosphite (AO-686), and pentaerythritol tetra(3-lauryl thiopropionate) (AO-412S). And / or, the primary antioxidant is selected from pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (AO-1010) and 2,2"-oxamido-bis[ethyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)]propionate (MD-697).

[0009] In an optional embodiment, the auxiliary antioxidant is bis(2,4-dicumylphenyl)pentaerythritol-diphosphite (AO-686).

[0010] And / or, the primary antioxidant is 2,2"-oxamido-bis[ethyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)]propionate (MD-697).

[0011] In an optional embodiment, the rare earth heat stabilizer is selected from at least one of lanthanum trioxide, neodymium oxide, and dysprosium oxide.

[0012] And / or, the lubricant is polyethylene wax and / or calcium stearate.

[0013] In an optional embodiment, the mass ratio of lanthanum trioxide, neodymium oxide, and dysprosium oxide in the rare earth heat stabilizer is 1:1 to 2:1.

[0014] And / or, the mass ratio of the polyethylene wax to calcium stearate is 1:1.8 to 1:2.2.

[0015] In an optional embodiment, the number-average molecular weight of the polyketide is 10,000-100,000.

[0016] In an optional embodiment, the polyketide has a number-average molecular weight of 80,000-100,000.

[0017] In an optional embodiment, the average length of the glass fiber is 2.5-3.5 mm and the average diameter is 9-11 μm; And / or, the glass fiber is glass fiber treated with a silane coupling agent.

[0018] Secondly, the present invention provides a method for preparing the heat-resistant degradable glass fiber reinforced polyketone composite material according to any one of the foregoing embodiments, comprising: feeding a mixture of raw materials other than glass fiber through a main feed port, wherein the glass fiber is fed from the side, and melting and blending the mixture in a twin-screw extruder at 220-240°C to obtain the polyketone composite material.

[0019] In an optional embodiment, the temperature of zone 11 of the twin-screw extruder is set sequentially to 95-105℃, 215-225℃, 215-225℃, 215-225℃, 205-215℃, 205-215℃, 205-215℃, 195-205℃, 195-205℃, 195-205℃ and 215-225℃; And / or, the main motor speed of the twin-screw extruder is 200-300 rpm.

[0020] The present invention has the following beneficial effects: The synergistic effect among the components of the heat-degradable glass fiber reinforced polyketone composite material of this application is fully utilized, maximizing the antioxidant performance and effectively improving the overall performance of the glass fiber-filled polyketone composite material. In particular, the heat-degradable glass fiber reinforced polyketone composite material of this application includes a primary antioxidant, an auxiliary antioxidant, and a rare earth heat stabilizer. The synergistic effect of these three can effectively solve the carbonization problem of glass fiber reinforced polyketone composite material during injection molding, which is beneficial to improving the processing performance and heat resistance of glass fiber reinforced polyketone composite material. This allows the heat-degradable glass fiber reinforced polyketone composite material to maintain good processing performance after being held at 240°C for 60 minutes in an injection molding machine, extending the service life of the material. At the same time, it can still maintain good mechanical properties after being held at 150°C for 500 hours. In addition, it can also effectively improve the stability of antioxidants at high temperatures, reduce the consumption of antioxidants during injection molding, and achieve long-term anti-aging effect. Detailed Implementation

[0021] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially.

[0022] The present invention provides a heat-resistant and degradable glass fiber reinforced polyketone composite material, comprising, by weight: 80-90 parts of polyketone, 10-20 parts of glass fiber, 0.5-1.5 parts of auxiliary antioxidant, 0.5-1.5 parts of main antioxidant, 0.5-1.5 parts of rare earth heat stabilizer and 0.5-1.5 parts of lubricant.

[0023] The synergistic effect among the components of the heat-degradable glass fiber reinforced polyketone composite material of this application is fully utilized, maximizing the antioxidant performance and effectively improving the overall performance of the glass fiber-filled polyketone composite material. In particular, the heat-degradable glass fiber reinforced polyketone composite material of this application includes a primary antioxidant, an auxiliary antioxidant, and a rare earth heat stabilizer. The synergistic effect of these three can effectively solve the carbonization problem of glass fiber reinforced polyketone composite material during injection molding, which is beneficial to improving the processing performance and heat resistance of glass fiber reinforced polyketone composite material. This allows the heat-degradable glass fiber reinforced polyketone composite material to maintain good processing performance after being held at 240°C for 60 minutes in an injection molding machine, extending the service life of the material. At the same time, it can still maintain good mechanical properties after being held at 150°C for 500 hours. In addition, it can also effectively improve the stability of antioxidants at high temperatures, reduce the consumption of antioxidants during injection molding, and achieve long-term anti-aging effect.

[0024] In an optional embodiment, the auxiliary antioxidant is selected from one of tris(2,4-di-tert-butylphenyl) phosphite (AO-168), bis(2,4-dicumylphenyl) pentaerythritol-diphosphite (AO-686), and pentaerythritol tetra(3-lauryl thiopropionate) (AO-412S). And / or, the primary antioxidant is selected from pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (AO-1010) and 2,2"-oxamido-bis[ethyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)]propionate (MD-697).

[0025] The rational selection of auxiliary antioxidants and primary antioxidants can help avoid mutual interference between antioxidants in traditional antioxidant systems and can significantly improve the material's resistance to thermo-oxidative aging.

[0026] In an optional embodiment, the auxiliary antioxidant is bis(2,4-dicumylphenyl)pentaerythritol-diphosphite (AO-686).

[0027] And / or, the primary antioxidant is 2,2"-oxamido-bis[ethyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)]propionate (MD-697).

[0028] When AO-686 and MD-697 are used in combination with rare earth heat stabilizers, they are more effective in improving the heat resistance and processing performance of materials.

[0029] In an optional embodiment, the rare earth heat stabilizer is selected from at least one of lanthanum trioxide, neodymium oxide, and dysprosium oxide.

[0030] And / or, the lubricant is polyethylene wax and / or calcium stearate, and in some embodiments, the lubricant is a blend of polyethylene wax and calcium stearate.

[0031] In an optional embodiment, the mass ratio of lanthanum trioxide, neodymium oxide, and dysprosium oxide in the rare earth heat stabilizer is 1:1 to 2:1.

[0032] And / or, the mass ratio of the polyethylene wax to calcium stearate is 1:1.8 to 1:2.2.

[0033] Choosing a compound of rare earth heat stabilizers and lubricants is more conducive to improving the heat resistance and processing performance of heat-degradable glass fiber reinforced polyketone composites.

[0034] In an optional embodiment, the number-average molecular weight of the polyketide is 10,000-100,000.

[0035] In an optional embodiment, the polyketide has a number-average molecular weight of 80,000-100,000.

[0036] Appropriately increasing the number-average molecular weight of polyketone is beneficial to improving the heat resistance of heat-degradable glass fiber reinforced polyketone composites.

[0037] In an optional embodiment, the average length of the glass fiber is 2.5-3.5 mm and the average diameter is 9-11 μm; And / or, the glass fiber is glass fiber treated with a silane coupling agent, which can improve the bonding force between the glass fiber and the polyketone substrate. The coupling agent can be KH560.

[0038] Secondly, the present invention provides a method for preparing the heat-resistant degradable glass fiber reinforced polyketone composite material according to any one of the foregoing embodiments, comprising: feeding a mixture of raw materials other than glass fiber through a main feed port, wherein the glass fiber is fed from the side, and melting and blending the mixture in a twin-screw extruder at 220-240°C to obtain the polyketone composite material.

[0039] In an optional embodiment, the temperature of zone 11 of the twin-screw extruder is set sequentially to 95-105℃, 215-225℃, 215-225℃, 215-225℃, 205-215℃, 205-215℃, 205-215℃, 195-205℃, 195-205℃, 195-205℃ and 215-225℃; And / or, the main motor speed of the twin-screw extruder is 200-300 rpm.

[0040] The features and performance of the present invention will be further described in detail below with reference to embodiments.

[0041] Examples 1-7 and Comparative Examples 1-10 Examples 1-7 and Comparative Examples 1-10 of this application provide a heat-resistant and degradable glass fiber reinforced polyketone composite material, the raw material composition of which is shown in Table 1, and the specific preparation method includes the following steps: The raw materials, excluding glass fiber, are mixed evenly according to the proportions in Table 1 and fed through the main feed port. The glass fiber is fed from the side. The mixture is melt-blended in a twin-screw extruder to obtain a polyketide composite material. The temperatures of the 11 zones of the twin-screw extruder are set sequentially to 100℃, 220℃, 220℃, 220℃, 210℃, 210℃, 210℃, 200℃, 200℃, and 220℃, and the main engine speed of the twin-screw extruder is 250 rpm.

[0042] In Table 1, the polyketide model is M330A, which was provided by Hyosung Group of South Korea; The lubricant is a mixture of polyethylene wax and calcium stearate in a mass ratio of 1:2. The fiberglass is of type ECS301HP-3-H, with an average length of 3mm and an average diameter of 10μm; The rare earth heat stabilizer is obtained by mixing lanthanum trioxide, neodymium oxide and dysprosium oxide in a mass ratio of 1:1.5:1.

[0043] Table 1

[0044] Example 8 The only difference between this embodiment and Embodiment 1 is that the rare earth heat stabilizer is lanthanum trioxide.

[0045] Example 9 The only difference between this embodiment and Embodiment 1 is that the rare earth heat stabilizer is dysprosium oxide.

[0046] Example 10 The only difference between this embodiment and Embodiment 1 is that the rare earth heat stabilizer is neodymium oxide.

[0047] Example 11 The only difference between this embodiment and Example 1 is that the rare earth heat stabilizer is a mixture of lanthanum trioxide and neodymium oxide in a mass ratio of 1:1.5.

[0048] The properties of the composite materials of the above embodiments and comparative examples were tested, and the test results are shown in Table 2. The tensile strength test method refers to ISO 527. The method for testing elongation at break is based on ISO 527.

[0049] Table 2

[0050] Note: (1) No obvious change means no change observed by the naked eye before stopping at 240°C on the injection molding machine; Slight cross-linking refers to the appearance of yellow spots after the injection molding machine stops at 240°C, but the yellow spots are relatively scattered and the area is small; Partial cross-linking refers to the extruded sample becoming darker in color; Crosslinking refers to the extruded sample becoming darker in color and only a portion of the material being extruded, making it impossible to extrude a complete sample. Severe cross-linking means that the material cannot be extruded.

[0051] (2) 150℃, 500h aging refers to storing the heat-resistant degradable glass fiber reinforced polyketone composite material at 150℃ for 500h.

[0052] As can be seen from the data in Table 2 above: A comparison of Comparative Examples 1-10 with Example 1 shows that omitting any component of the auxiliary antioxidant, primary antioxidant, or rare earth heat stabilizer will result in poor performance in at least one of the following aspects of the heat resistance, oxidation resistance, and processing properties of the heat-degradable glass fiber reinforced polyketone composite material: heat resistance, oxidation resistance, and processing properties. A comparison of Comparative Examples 5-10 with Examples 1-2 shows that the addition of rare earth stabilizers can effectively improve the processing properties of polyketone fiber-reinforced materials, but it will sacrifice some mechanical properties. Therefore, adding too much rare earth stabilizer will result in insignificant improvement and excessive loss of mechanical properties. A comparison of Comparative Examples 1-4 with Examples 1-2 shows that selecting appropriate auxiliary antioxidants, primary antioxidants, and rare earth stabilizers for combined use can improve heat resistance, oxidation resistance, and processing properties.

[0053] A comparison of Examples 1 and 8-11 shows that the proportioned compounding of lubricants or rare earth heat stabilizers is more conducive to improving the heat resistance, oxidation resistance and processing performance of heat-resistant degradable glass fiber reinforced polyketone composites.

[0054] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A heat-degradable glass fiber reinforced polyketone composite material, characterized in that, By weight, it includes: 80-90 parts polyketone, 10-20 parts glass fiber, 0.5-1.5 parts auxiliary antioxidant, 0.5-1.5 parts main antioxidant, 0.5-1.5 parts rare earth heat stabilizer, and 0.5-1.5 parts lubricant; The auxiliary antioxidant is bis(2,4-dicumylphenyl) pentaerythritol-diphosphite; The primary antioxidant is 2,2'-oxamido-bis[ethyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)]propionate; The rare earth heat stabilizer is lanthanum trioxide, neodymium oxide, and dysprosium oxide, and the mass ratio of lanthanum trioxide, neodymium oxide, and dysprosium oxide in the rare earth heat stabilizer is 1:1-2:

1.

2. The heat-degradable glass fiber reinforced polyketone composite material according to claim 1, characterized in that, The lubricant is polyethylene wax and calcium stearate, and the mass ratio of polyethylene wax to calcium stearate is 1:1.8-1:2.

2.

3. The heat-degradable glass fiber reinforced polyketone composite material according to claim 1, characterized in that, The number-average molecular weight of the polyketone is 10,000-100,000; And / or, the polyketone is a polymer synthesized from carbon monoxide and olefins.

4. The heat-degradable glass fiber reinforced polyketone composite material according to claim 3, characterized in that, The number-average molecular weight of the polyketone is 80,000-100,000.

5. The heat-degradable glass fiber reinforced polyketone composite material according to claim 1, characterized in that, The glass fiber has an average length of 2.5-3.5 mm and an average diameter of 9-11 μm; And / or, the glass fiber is glass fiber treated with a silane coupling agent.

6. A method for preparing the heat-resistant degradable glass fiber reinforced polyketone composite material according to any one of claims 1-5, characterized in that, include: The mixture, which includes all raw materials except glass fiber, is fed through the main feed port. The glass fiber is fed from the side. The mixture is melt-blended in a twin-screw extruder at 220-240°C to obtain a polyketide composite material.

7. The method for preparing the heat-degradable glass fiber reinforced polyketone composite material according to claim 6, characterized in that, The temperatures of the 11 zones of the twin-screw extruder are set sequentially as follows: 95-105℃, 215-225℃, 215-225℃, 215-225℃, 205-215℃, 205-215℃, 205-215℃, 195-205℃, 195-205℃, 195-205℃, and 215-225℃. And / or, the main motor speed of the twin-screw extruder is 200-300 rpm.

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