A pom composition, its preparation and use

Abstract

The present application provides a POM composition, a preparation method and application thereof. The POM composition comprises the following components in parts by weight: 100 parts of polyoxymethylene resin; 2-6 parts of EVA resin grafted maleic anhydride; 1-3 parts of hydroxyl silicone oil; and 20-30 parts of glass fiber. The present application can effectively improve the wear resistance of the POM composition by adding EVA grafted maleic anhydride and hydroxyl silicone oil in the glass fiber reinforced POM composition, and meanwhile, the POM composition has better strength and modulus, and is especially suitable for application in materials such as automobile sunroof slide rails and automobile seat slide rails.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of high molecular materials, and more particularly, to a POM composition, a preparation method and application thereof. BACKGROUND

[0002] Polyoxymethylene resin (POM resin) has good lubricity and wear resistance, and is widely used in industrial equipment, office equipment, automobiles and other fields. With the complication and diversification of various parts, higher requirements are put forward for the performance of parts. Not only good wear resistance is required, but also high strength and modulus are required, such as materials for automobile sunroof slide rails and automobile seat slide rails.

[0003] Adding glass fibers to POM resin can effectively improve the strength and modulus of POM, but will significantly reduce the wear resistance of POM, which cannot meet the higher performance requirements. Therefore, there is a need in the art to develop a POM composition with good mechanical properties and good wear resistance. SUMMARY

[0004] The present application aims to overcome the defects or deficiencies in the prior art that POM materials cannot have both mechanical properties and wear resistance, and to provide a POM composition.

[0005] Another object of the present application is to provide a preparation method of the POM composition.

[0006] Another object of the present application is to provide an application of the POM composition.

[0007] To achieve the above object, the present application adopts the following technical solutions:

[0008] A POM composition comprises the following components calculated by weight parts:

[0009]

[0010] The present application provides a POM composition, which uses POM composition as base resin, adds glass fibers to enhance mechanical properties, and adds EVA grafted maleic anhydride and hydroxyl silicone oil, so that the glass fiber reinforced POM composition has good wear resistance, lower friction coefficient, and higher mechanical properties. Specifically, the maleic anhydride groups in the EVA grafted maleic anhydride can react with the hydroxyl groups of the hydroxyl silicone oil to graft, and at the same time, the compatibility of the hydroxyl silicone oil and the POM resin can be increased, thereby improving the wear resistance and friction coefficient, and the mechanical properties are good.

[0011] It should be noted that the content of polyoxymethylene resin in the POM composition of the present application is preferably not less than 70wt%.

[0012] It should be noted that the EVA grafted maleic anhydride in the present application is 2-6 parts, which can be 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts or 6 parts, etc., and specific point values between the above point values, limited to the length and for the sake of simplicity, the specific point values included in the range are not listed in the present application.

[0013] The hydroxyl silicone oil is 1-3 parts, which can be 1 part, 1.2 parts, 1.5 parts, 1.8 parts, 2 parts, 2.2 parts, 2.5 parts, 2.8 parts or 3 parts, etc., and specific point values between the above point values, limited to the length and for the sake of simplicity, the specific point values included in the range are not listed in the present application.

[0014] Further, the POM composition comprises the following components calculated by weight parts:

[0015]

[0016] Further, the mass ratio of the EVA grafted maleic anhydride and the hydroxyl silicone oil is (1.5-3):1, such as but not limited to 1.5:1, 1.8:1, 2:1, 2.2:1, 2.5:1, 2.8:1 or 3:1, etc.

[0017] Further, the mass ratio of the EVA grafted maleic anhydride and the hydroxyl silicone oil is (1.8-2.5):1. Adjusting the mass ratio of the two can further improve the wear resistance and reduce the friction coefficient.

[0018] Further, the content of maleic anhydride in the EVA grafted maleic anhydride is not less than 0.5wt%.

[0019] Further, the content of maleic anhydride in the EVA grafted maleic anhydride is preferably not higher than 2wt%.

[0020] Further, the melt flow rate of the EVA grafted maleic anhydride is 1-20 g / 10 min under the condition of 190℃ and 2.16 kg load according to the ISO 1133-2022 standard.

[0021] Specifically, the content of vinyl acetate in the EVA resin in the EVA grafted maleic anhydride is 20-30wt%.

[0022] Specifically, the measurement standard of the content of vinyl acetate is ASTM E168-2023.

[0023] Further, the hydroxyl content of the hydroxyl silicone oil is 0.5-3.0wt%.

[0024] Specifically, the measurement standard of the hydroxyl content is GB / T 7383-2020.

[0025] Further, the viscosity of the hydroxyl silicone oil is 30-110 mm 2 / s.

[0026] Specifically, the viscosity measurement standard is GB / T 10247-1988.

[0027] Further, the melt flow rate of the polyformaldehyde resin is 5-30 g / 10 min under the test of ISO 1133-2022 standard at 190℃, 2.16 kg load.

[0028] Further, the average diameter of the glass fiber is 9-12 μm.

[0029] Further, the wear-resistant and mute POM composition further comprises 0.1-5 parts of an auxiliary agent.

[0030] Specifically, the auxiliary agent includes but is not limited to one or more of an antioxidant, a formaldehyde absorber, a weathering agent, or a toner.

[0031] The present application can select a commonly used antioxidant according to the prior art, for example but not limited to one or more of the antioxidant is a hindered phenol antioxidant, a phosphite antioxidant, or a thioester antioxidant.

[0032] Specifically, the hindered phenol antioxidant is one or more of N,N'-hexamethylene bis(3,5-di-tert-butyl-4-hydroxyphenylpropionamide) (Irganox 1098), tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid] pentaerythritol ester (Irganox 1010), 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (Irganox 259), n-octadecyl β-(4-hydroxy-3,5-di-tert-butylphenyl)propionate (Irganox 1076), or 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)acrylic acid]-1,1-dimethyl}-2,4,8,10-tetraoxaspiroundecane (ADK AO-80).

[0033] The phosphite antioxidant is one or more of tris(2,4-di-tert-butylphenyl) phosphite (Irganox 168), bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol phosphite (PEP-36), or 627A.

[0034] The thioether antioxidant is one or more of distearyl thiodipropionate, dilauryl thiodipropionate, or dodecylthiopropionate.

[0035] The formaldehyde absorbent can be selected according to the prior art, for example, but not limited to, the formaldehyde absorbent is one or more of allantoin, dicyandiamide or melamine.

[0036] The weathering agent can be selected according to the prior art, for example, but not limited to, the weathering agent is an ultraviolet absorber and / or a light stabilizer.

[0037] The application further provides a preparation method of the POM composition, comprising the following steps:

[0038] The components are mixed uniformly in proportion, and then melt-extruded, cooled and granulated to obtain the POM composition.

[0039] Specifically, the melt-extrusion is performed by using a twin-screw extruder.

[0040] Specifically, the temperature of the first zone of the twin-screw extruder is 130-170℃, the temperature of the second zone is 190-210℃, the temperature of the third zone is 190-220℃, the temperature of the fourth zone is 200-220℃, the temperature of the fifth zone to the ninth zone is 190-220℃, and the temperature of the tenth zone is 180-200℃; the rotation speed of the screw of the twin-screw extruder is 250-350rpm.

[0041] The application further protects the use of the POM composition in preparing automobile accessories, such as automobile sunroof slide rails, automobile seat slide rails and the like.

[0042] Compared with the prior art, the application has the following beneficial effects:

[0043] The application provides a POM composition, in which EVA grafted maleic anhydride and hydroxyl silicone oil are added into a glass fiber reinforced POM resin system, so that the wear resistance and friction coefficient of the POM composition can be effectively improved, and the POM composition has good mechanical properties. DETAILED DESCRIPTION

[0044] The technical solutions in the embodiments of the application will be clearly and completely described below, but the embodiments of the application are not limited thereto.

[0045] The reagents, methods and devices used in the application are conventional reagents, methods and devices in the technical field, unless otherwise specified.

[0046] 1. The raw materials used in the following examples and comparative examples are as follows:

[0047] Polyformaldehyde resin:

[0048] POM resin 1: M90-44, purchased from Borealis AG;

[0049] POM resin 2: M270-44, purchased from Borealis AG;

[0050] EVA grafted with maleic anhydride:

[0051] EVA grafted with maleic anhydride 1:C250, with a melt flow rate of 1.5 g / 10 min at 190 °C and a load of 2.16 kg, was purchased from Dow Chemical.

[0052] EVA grafted with maleic anhydride 2:C190, with a melt flow rate of 16 g / 10 min at 190 °C and a load of 2.16 kg, was purchased from Dow Chemical.

[0053] EVA grafted with maleic anhydride 3:39E660, with a melt flow rate of 2.5 g / 10 min at 190 °C and a load of 2.16 kg, was purchased from Dow Chemical.

[0054] SEBS grafted maleic anhydride: SEBS-g-MAH 7126, purchased from TSRC Corporation;

[0055] EVA resin: ELVAX 265, with a melt flow rate of 3 g / 10 min at 190°C and a load of 2.16 kg, purchased from Dow Chemical.

[0056] Hydroxy silicone oil:

[0057] Hydroxy silicone oil 1: QLS-203M-A, with a hydroxyl content of 1.2wt% and a viscosity of 60mm / s, was purchased from Wuxi Quanli Technology Co., Ltd.

[0058] Hydroxy silicone oil 2: QLS-203M-B, with a hydroxyl content of 0.8wt% and a viscosity of 100mm / s, was purchased from Wuxi Quanli Technology Co., Ltd.

[0059] Amino silicone oil: Cheersil 8120, amino content 1.0%, viscosity 35 mm / s, purchased from Suzhou Qitian New Materials Co., Ltd.;

[0060] Fiberglass: ECS10-3.0-T445, purchased from Taishan Fiberglass;

[0061] Additives:

[0062] Antioxidant: Irganox 168; commercially available;

[0063] Formaldehyde absorbent: allantoin, commercially available; it should be noted that the same raw materials were used in the parallel experiments of each example and comparative example.

[0064] 2. The POM compositions described in the examples and comparative examples were prepared according to the formulations in Tables 1-2 by the following preparation methods:

[0065] The components are put into a high-speed mixer in proportion, mixed uniformly, melt-extruded by a twin-screw extruder, and cooled and granulated to obtain a POM composition; the temperature of the first zone of the twin-screw extruder is 150℃, the temperature of the second zone is 200℃, the temperature of the third zone is 205℃, the temperature of the fourth zone is 210℃, the temperature of the fifth zone to the ninth zone is 205℃, and the temperature of the tenth zone is 190℃; the screw rotation speed of the twin-screw extruder is 300rpm.

[0066] 3. Performance test

[0067] (1) Specific wear and friction coefficient test: the POM composition prepared from each example and comparative example is tested according to JIS K7218-1986, the rotation speed is 0.8m / s, the load is 10N, the rotation distance is 3km, each sample is measured twice, and the average value is taken;

[0068] (2) Mechanical property test: the tensile strength of the POM composition prepared from each example and comparative example is tested according to ISO-527-2-2012; the bending modulus and bending strength are tested according to ISO 178-2019.

[0069] Examples 1-9 and Comparative Examples 1-5

[0070] Table 1 Formulation (unit: weight parts) and performance of POM composition in Examples 1-9

[0071]

[0072]

[0073] Table 2 Formulation (unit: weight parts) and performance of POM composition in Comparative Examples 1-5

[0074] Comparative Example 1 2 3 4 5 POM Resin 1 100 100 100 100 100 EVA Grafted Maleic Anhydride 1 / 4 4 / / SEBS Grafted Maleic Anhydride / / / 4 / EVA Resin / / / / 4 Hydroxyl Silicone Oil 1 2 / / 2 2 Amino Silicone Oil / / 2 / / Glass Fiber 25 25 25 25 25 Antioxidant 1 1 1 1 1 Formaldehyde Absorbent 1 1 1 1 1 Specific wear amount (10 -3 mm 3 / N·km)]]> 1438 1266 1157 1002 1364 Friction Coefficient 0.234 0.353 0.298 0.224 0.216 Tensile Strength (MPa) 132 126 127 122 128 Flexural Strength (MPa) 183 174 178 163 176 Flexural Modulus (MPa) 7645 7552 7532 7210 7432

[0075] The POM composition prepared by the application has good wear resistance and good mechanical properties, specifically: the specific wear is not higher than 700 10 -3 mm 3 / N·km, the friction coefficient is not higher than 0.2, the tensile strength is not lower than 120MPa, the bending strength is not lower than 170MPa, and the bending modulus is not lower than 7250MPa.

[0076] As can be seen from Comparative Examples 1 or 2, if only EVA grafted maleic anhydride or hydroxyl silicone oil is added, the wear resistance cannot be effectively improved, and the friction coefficient is significantly higher than that of the examples.

[0077] As can be seen from Comparative Example 3, using other silicone oils to replace the hydroxyl silicone oil in the application cannot well play a synergistic effect, and the comprehensive performance of the prepared POM composition does not improve significantly.

[0078] As can be seen from Comparative Examples 4 and 5, if other resins grafted with maleic anhydride or EVA resins are used to replace the EVA grafted with maleic anhydride in the present application, the wear resistance of the POM composition prepared is poor and the friction coefficient is higher than that of the Examples.

[0079] Obviously, the above-mentioned embodiments of the present application are merely examples for clearly illustrating the present application, and are not intended to limit the embodiments of the present application. Based on the above description, other different forms of changes or variations can be made by those skilled in the art. Here, it is not necessary and also impossible to enumerate all the embodiments. Any modification, equivalent replacement and improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the claims of the present application.

Claims

1. A POM composition characterized in that, It comprises the following components by weight parts:

2. The POM composition according to claim 1, characterized in that, It comprises the following components by weight parts:

3. The POM composition according to claim 1, characterized in that, The melt flow rate of the EVA grafted maleic anhydride is 1-20 g / 10 min at 190℃, 2.16 kg load according to ISO 1133-2022 standard test.

4. The POM composition according to claim 1, characterized in that, The content of vinyl acetate in the EVA resin of the EVA grafted maleic anhydride is 20-30 wt%.

5. The POM composition according to claim 1, characterized in that, The content of hydroxyl group in the hydroxyl silicone oil is 0.5-3.0 wt%.

6. The POM composition according to claim 1, characterized in that, The melt flow rate of the polyoxymethylene resin is 5-30 g / 10 min at 190℃, 2.16 kg load according to ISO 1133-2022 standard test.

7. The POM composition according to claim 1, wherein The average diameter of the glass fiber is 9-12 μm.

8. The POM composition according to claim 1, characterized in that, It further comprises 0.1-5 parts of an auxiliary.

9. A process for the preparation of the POM composition according to any one of claims 1 to 8, characterized in that, It comprises the following steps: The components are mixed uniformly in proportion, and then melt-extruded, cooled and granulated to obtain the POM composition.

10. Use of the POM composition according to any one of claims 1-8 in the preparation of automobile parts.

Images