A high-performance wear-resistant POM plate and its preparation method

Abstract

A high-performance, wear-resistant POM sheet and its preparation method, comprising 80-100 parts of POM, 10-16 parts of modified titanium boride whiskers, 0.2-0.4 parts of SEBS-g-MAH, and 0.1-0.5 parts of an antioxidant, have excellent mechanical properties and wear resistance, which are of great practical significance for expanding the application of POM sheets.

Description

Technical Field

[0001] The invention belongs to the field of polymer materials, and particularly relates to a high-performance wear-resistant POM plate and a preparation method thereof. Background Art

[0002] Polyoxymethylene (POM) is a widely used polymer polyester resin. POM has the advantages of good fatigue resistance, good heat resistance, excellent dimensional stability, etc. However, in some specific application fields, POM has very high requirements for mechanical properties and wear resistance, which limits the application of POM sheets in some specific fields.

[0003] To address these shortcomings, the present invention innovatively synthesizes a new type of high-performance wear-resistant POM sheet with excellent mechanical and wear resistance. This POM sheet has not been reported before, which has very important practical significance for expanding the application field of POM sheet. Summary of the Invention

[0004] In view of this, the present invention innovatively synthesizes a high-performance wear-resistant POM plate, which has excellent mechanical properties and wear resistance, and solves the technical problem of limited mechanical properties and wear resistance of POM in the prior art.

[0005] The object of the present invention is achieved through the following technical solutions:

[0006] A high-performance wear-resistant POM plate, composed of the following components in parts by weight:

[0007] POM 80-100 copies,

[0008] 10-16 parts of modified titanium boride whiskers,

[0009] SEBS-g-MAH 0.2-0.4 parts,

[0010] Antioxidant 0.1-0.5 parts,

[0011] The preparation method of the modified titanium boride whisker comprises the following steps:

[0012] (1) Weigh a certain amount of magnesium nitrate, ammonium fluoride, and deionized water, add them to a reaction vessel, react at 30-50°C for 6-8 hours, and cool to room temperature to obtain solution A.

[0013] (2) Filter solution A, wash it, and dry it at 40-60°C for 6-10 hours to obtain magnesium fluoride.

[0014] (3) Weigh a certain amount of magnesium fluoride, cerium nitrate, anhydrous ethanol, and deionized water, add them to a reaction vessel, react at 70-90°C for 8-10 hours, filter, wash, and dry at 70-90°C for 6-8 hours to obtain solid B.

[0015] (4) Solid B is placed in a muffle furnace and calcined at 680-720 °C for 10-12 h to obtain MgF2@CeO2 with MgF2 as the core and CeO2 as the shell.

[0016] (5) Weigh a certain amount of MgF2@CeO2, titanium boride whiskers, and anhydrous ethanol, add them to a ball mill, fill the ball mill with nitrogen, and ball mill for 10-16 hours. After the mill is finished, sinter it in a vacuum hot pressing furnace at 320-360℃ for 12-16 hours, and pass it through a 500-mesh sieve to obtain modified titanium boride whiskers.

[0017] Preferably, the mass ratio of magnesium nitrate, ammonium fluoride and deionized water in step (1) is (30-40): (50-60): (70-90).

[0018] Preferably, the mass ratio of magnesium fluoride, cerium nitrate, anhydrous ethanol and deionized water in step (3) is (30-40): (40-50): (40-60): (80-90).

[0019] Preferably, the mass ratio of MgF2@CeO2, titanium boride whiskers and anhydrous ethanol in step (5) is (30-50): (40-60): (60-80).

[0020] The antioxidant is one or a mixture of BASF's tris(2,4-di-tert-butyl)phenyl phosphite (abbreviated as Irganox168), pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (abbreviated as Irganox1010) and 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxybenzyl)benzene (abbreviated as Irganox1330).

[0021] The high-performance wear-resistant POM plate and its preparation method include the following steps:

[0022] (1) Weigh 80-100 parts of POM, 0.2-0.4 parts of SEBS-g-MAH, and 0.1-0.5 parts of antioxidant, mix and stir evenly to obtain a mixture;

[0023] (2) adding the mixed material into an extruder and extruding it through a screw to uniformly compound it with 10-16 parts of modified titanium boride whiskers into a prepreg;

[0024] (3) The prepreg tape is pressed into a structural plate by hot pressing.

[0025] The twin-screw extruder in step (2) includes six temperature zones arranged in sequence, with the temperature of zone 1 being 160-180°C, the temperature of zone 2 being 200-220°C, the temperature of zone 3 being 200-220°C, the temperature of zone 4 being 200-220°C, the temperature of zone 5 being 200-220°C, the temperature of zone 6 being 200-220°C, the temperature of die head being 200-220°C, and the screw speed being 200-280 r / min.

[0026] When the prepreg tape is pressed into a structural plate in step (3), the laying method and number of layers of the prepreg tape are designed according to actual use requirements. The hot pressing temperature is 200-220°C.

[0027] Compared with the prior art, the present invention has the following beneficial effects:

[0028] (1) The reaction equation of magnesium fluoride is as follows:

[0029] Mg(NO3)2+2NH4F→MgF2+2NH4NO3

[0030] (2) The MgF2@CeO2 coated particles adhere to the surface of the TiB2 whiskers. During the sintering process, the MgF2@CeO2 coated particles become liquid due to the lower melting point of their coating layer, which drives the MgF2 to be more evenly distributed in the POM matrix material, thereby enhancing the interfacial bonding strength between MgF2 and TiB2 whiskers. In addition, the presence of the MgF2@CeO2 coated particles also inhibits the growth of the POM matrix grains, plays a role in refining the POM grains, and thus enhances the mechanical properties of the POM material.

[0031] (3) TiB2 whiskers have a hexagonal crystal structure and high wear resistance. Their addition improves the wear resistance of POM sheets.

[0032] (4) During the friction process of the POM sheet, MgF2 in the MgF2@CeO2 coated particles precipitates, forming a uniform and continuous lubricating film on the surface of the POM sheet, thereby reducing the friction force during the friction process. The reduction in friction force also effectively reduces the friction coefficient of the POM sheet and enhances the wear resistance of the POM material. DETAILED DESCRIPTION

[0033] To facilitate understanding of the present invention, the present invention will be described more fully below in conjunction with specific embodiments. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to provide a more thorough and comprehensive understanding of the disclosure of the present invention.

[0034] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art of the present invention. The terms used in the specification of the present invention herein are only for the purpose of describing specific embodiments and are not intended to limit the present invention.

[0035] The raw materials used in the following examples are as follows:

[0036] POM, Shanghai Yunmo Plastics Co., Ltd.; SEBS-g-MAH, Nanjing Deba Polymer Materials Co., Ltd.; magnesium nitrate, Shanxi Dongxing Chemical Co., Ltd.; ammonium fluoride, Shandong Duoju Chemical Co., Ltd.; deionized water, Xiamen Aoquan Environmental Protection Technology Co., Ltd.; cerium nitrate, Shandong Changyao New Materials Co., Ltd.; anhydrous ethanol, Shanghai Fangye Chemical Co., Ltd.; titanium boride whiskers, Hubei Xingyan New Materials Technology Co., Ltd.; antioxidants (models Irganox168, Irganox1010, Irganox1330), BASF.

[0037] Preparation Example 1

[0038] (1) Weigh 300 g of magnesium nitrate, 500 g of ammonium fluoride, and 700 g of deionized water, add them to a reaction vessel, react at 30 °C for 6 h, and cool to room temperature to obtain solution A.

[0039] (2) Solution A was filtered, washed, and dried at 40°C for 6 h to obtain magnesium fluoride.

[0040] (3) Weigh 300 g of magnesium fluoride, 400 g of cerium nitrate, 400 g of anhydrous ethanol, and 800 g of deionized water, add them to a reaction vessel, react at 70°C for 8 h, filter, wash, and dry at 70°C for 6 h to obtain solid B.

[0041] (4) Solid B was placed in a muffle furnace and calcined at 680 °C for 10 h to obtain MgF2@CeO2 with MgF2 as the core and CeO2 as the shell.

[0042] (5) Weigh 300 g of MgF2@CeO2, 400 g of titanium boride whiskers, and 600 g of anhydrous ethanol, add them to a ball mill, fill the ball mill with nitrogen, and ball mill for 10 h. After the mill is finished, sinter it in a vacuum hot pressing furnace at 320 °C for 12 h, and pass it through a 500-mesh sieve to obtain modified titanium boride whiskers M1.

[0043] Example 1

[0044] (1) Weigh 80 parts of POM, 0.2 parts of SEBS-g-MAH, and 0.1 parts of Irganox 1010, mix and stir evenly to obtain a mixture;

[0045] (2) The mixed material is added into the extruder and extruded by screw to form a prepreg with 10 parts of modified titanium boride whiskers M1;

[0046] (3) The prepreg tape is pressed into a structural plate P1 by hot pressing.

[0047] The twin-screw extruder in step (2) includes six temperature zones arranged in sequence, with the temperature of zone 1 being 160°C, the temperature of zone 2 being 200°C, the temperature of zone 3 being 200°C, the temperature of zone 4 being 200°C, the temperature of zone 5 being 200°C, the temperature of zone 6 being 200°C, the head temperature being 200°C, and the screw speed being 200 r / min.

[0048] When the prepreg tape is pressed into a structural plate in step (3), the laying method and number of layers of the prepreg tape are designed according to actual use requirements. The hot pressing temperature is 200°C.

[0049] Preparation Example 2

[0050] (1) Weigh 400 g of magnesium nitrate, 600 g of ammonium fluoride, and 900 g of deionized water, add them to a reaction vessel, react at 50 °C for 8 h, and cool to room temperature to obtain solution A.

[0051] (2) Solution A was filtered, washed, and dried at 60°C for 10 h to obtain magnesium fluoride.

[0052] (3) Weigh 400 g of magnesium fluoride, 500 g of cerium nitrate, 600 g of anhydrous ethanol, and 900 g of deionized water, add them to a reaction vessel, react at 90°C for 10 h, filter, wash, and dry at 90°C for 8 h to obtain solid B.

[0053] (4) Solid B was placed in a muffle furnace and calcined at 720 °C for 12 h to obtain MgF2@CeO2 with MgF2 as the core and CeO2 as the shell.

[0054] (5) Weigh 500 g of MgF2@CeO2, 600 g of titanium boride whiskers, and 800 g of anhydrous ethanol, add them to a ball mill, fill the ball mill with nitrogen, and ball mill for 16 h. After the mill is finished, sinter it in a vacuum hot pressing furnace at 360 °C for 16 h, and pass it through a 500-mesh sieve to obtain modified titanium boride whiskers M2.

[0055] Example 2

[0056] (1) Weigh 100 parts of POM, 0.4 parts of SEBS-g-MAH, 0.1 parts of antioxidant Irganox 1010, 0.2 parts of antioxidant Irganox 168, and 0.2 parts of antioxidant Irganox 1330, mix and stir evenly to obtain a mixture;

[0057] (2) The mixed material is added into the extruder and extruded by screw to uniformly compound with 16 parts of modified titanium boride whiskers M2 into a prepreg;

[0058] (3) The prepreg is pressed into a structural plate P2 by hot pressing.

[0059] The twin-screw extruder in step (2) includes six temperature zones arranged in sequence, with the temperature of zone 1 being 180°C, the temperature of zone 2 being 220°C, the temperature of zone 3 being 220°C, the temperature of zone 4 being 220°C, the temperature of zone 5 being 220°C, the temperature of zone 6 being 220°C, the head temperature being 220°C, and the screw speed being 280 r / min.

[0060] When the prepreg tape is pressed into a structural plate in step (3), the laying method and number of layers of the prepreg tape are designed according to actual use requirements. The hot pressing temperature is 220°C.

[0061] Preparation Example 3

[0062] (1) Weigh 350 g of magnesium nitrate, 550 g of ammonium fluoride, and 800 g of deionized water, add them to a reaction vessel, react at 40 °C for 7 h, and cool to room temperature to obtain solution A.

[0063] (2) Solution A was filtered, washed, and dried at 50°C for 8 h to obtain magnesium fluoride.

[0064] (3) Weigh 350 g of magnesium fluoride, 450 g of cerium nitrate, 500 g of anhydrous ethanol, and 850 g of deionized water, add them to a reaction vessel, react at 80°C for 9 h, filter, wash, and dry at 80°C for 7 h to obtain solid B.

[0065] (4) Solid B was placed in a muffle furnace and calcined at 700 °C for 11 h to obtain MgF2@CeO2 with MgF2 as the core and CeO2 as the shell.

[0066] (5) Weigh 400 g of MgF2@CeO2, 500 g of titanium boride whiskers, and 700 g of anhydrous ethanol, add them to a ball mill, fill the ball mill with nitrogen, and ball mill for 13 h. After the mill is finished, sinter it in a vacuum hot pressing furnace at 340 °C for 14 h, and pass it through a 500-mesh sieve to obtain modified titanium boride whiskers M3.

[0067] Example 3

[0068] (1) Weigh 90 parts of POM, 0.3 parts of SEBS-g-MAH, 0.1 parts of antioxidant Irganox 168, and 0.2 parts of antioxidant Irganox 1010, mix and stir evenly to obtain a mixture;

[0069] (2) The mixed material is added into the extruder and extruded by screw to uniformly compound with 13 parts of modified titanium boride whiskers M3 into a prepreg;

[0070] (3) The prepreg tape is pressed into a structural plate P3 by hot pressing.

[0071] The twin-screw extruder in step (2) includes six temperature zones arranged in sequence, with the temperature of zone 1 being 170°C, the temperature of zone 2 being 210°C, the temperature of zone 3 being 210°C, the temperature of zone 4 being 210°C, the temperature of zone 5 being 210°C, the temperature of zone 6 being 210°C, the head temperature being 210°C, and the screw speed being 240 r / min.

[0072] When the prepreg tape is pressed into a structural plate in step (3), the laying method and number of layers of the prepreg tape are designed according to actual use requirements. The hot pressing temperature is 210°C.

[0073] Preparation Example 4

[0074] (1) Weigh 355 g of magnesium nitrate, 555 g of ammonium fluoride, and 725 g of deionized water, add them to a reaction vessel, react at 45 °C for 8 h, and cool to room temperature to obtain solution A.

[0075] (2) Solution A was filtered, washed, and dried at 60°C for 6 h to obtain magnesium fluoride.

[0076] (3) Weigh 325 g of magnesium fluoride, 435 g of cerium nitrate, 525 g of anhydrous ethanol, and 895 g of deionized water, add them to a reaction vessel, react at 85 °C for 10 h, filter, wash, and dry at 75 °C for 8 h to obtain solid B.

[0077] (4) Solid B was placed in a muffle furnace and calcined at 705 °C for 12 h to obtain MgF2@CeO2 with MgF2 as the core and CeO2 as the shell.

[0078] (5) Weigh 385 g of MgF2@CeO2, 415 g of titanium boride whiskers, and 755 g of anhydrous ethanol, add them to a ball mill, fill the ball mill with nitrogen, and ball mill for 15 h. After the mill is finished, sinter it in a vacuum hot pressing furnace at 345 °C for 15 h, and pass it through a 500 mesh sieve to obtain modified titanium boride whiskers M4.

[0079] Example 4

[0080] (1) Weigh 95 parts of POM, 0.2 parts of SEBS-g-MAH, 0.1 parts of antioxidant Irganox 1010, and 0.2 parts of antioxidant Irganox 1330, mix and stir evenly to obtain a mixture;

[0081] (2) The mixed material is added into the extruder and extruded by screw to form a prepreg with 15 parts of modified titanium boride whiskers M4;

[0082] (3) The prepreg tape is pressed into a structural plate P4 by hot pressing.

[0083] The twin-screw extruder in step (2) includes six temperature zones arranged in sequence, with the temperature of zone 1 being 175°C, the temperature of zone 2 being 215°C, the temperature of zone 3 being 215°C, the temperature of zone 4 being 215°C, the temperature of zone 5 being 215°C, the temperature of zone 6 being 215°C, the head temperature being 215°C, and the screw speed being 255 r / min.

[0084] When the prepreg tape is pressed into a structural plate in step (3), the laying method and number of layers of the prepreg tape are designed according to actual use requirements. The hot pressing temperature is 215°C.

[0085] Preparation Example 5

[0086] (1) Weigh 385 g of magnesium nitrate, 575 g of ammonium fluoride, and 885 g of deionized water, add them to a reaction vessel, react at 35 °C for 8 h, and cool to room temperature to obtain solution A.

[0087] (2) Solution A was filtered, washed, and dried at 55°C for 9 hours to obtain magnesium fluoride.

[0088] (3) Weigh 315 g of magnesium fluoride, 425 g of cerium nitrate, 535 g of anhydrous ethanol, and 885 g of deionized water, add them to a reaction vessel, react at 85 °C for 10 h, filter, wash, and dry at 80 °C for 8 h to obtain solid B.

[0089] (4) Solid B was placed in a muffle furnace and calcined at 715 °C for 12 h to obtain MgF2@CeO2 with MgF2 as the core and CeO2 as the shell.

[0090] (5) Weigh 455 g of MgF2@CeO2, 585 g of titanium boride whiskers, and 735 g of anhydrous ethanol, add them to a ball mill, fill the ball mill with nitrogen, and ball mill for 16 h. After the mill is finished, sinter it in a vacuum hot pressing furnace at 335 °C for 15 h, and pass it through a 500 mesh sieve to obtain modified titanium boride whiskers M5.

[0091] Example 5

[0092] (1) Weigh 95 parts of POM, 0.3 parts of SEBS-g-MAH, 0.1 parts of antioxidant Irganox 1010, and 0.1 parts of antioxidant Irganox 168, mix and stir evenly to obtain a mixture;

[0093] (2) The mixed material is added into the extruder and extruded by screw to form a prepreg with 13 parts of modified titanium boride whiskers M5;

[0094] (3) The prepreg tape is pressed into a structural plate P5 by hot pressing.

[0095] The twin-screw extruder in step (2) includes six temperature zones arranged in sequence, with the temperature of zone 1 being 175°C, the temperature of zone 2 being 205°C, the temperature of zone 3 being 205°C, the temperature of zone 4 being 205°C, the temperature of zone 5 being 205°C, the temperature of zone 6 being 205°C, the head temperature being 205°C, and the screw speed being 255 r / min.

[0096] When the prepreg tape is pressed into a structural plate in step (3), the laying method and number of layers of the prepreg tape are designed according to actual use requirements. The hot pressing temperature is 205°C.

[0097] Comparative Example 1

[0098] (1) Weigh 95 parts of POM, 0.3 parts of SEBS-g-MAH, 0.1 parts of antioxidant Irganox 1010, and 0.1 parts of antioxidant Irganox 168, mix and stir evenly to obtain a mixture;

[0099] (2) The mixed material is added to the extruder and extruded by screw to form a prepreg with 13 parts of titanium boride whiskers;

[0100] (3) The prepreg tape is pressed into a structural plate by hot pressing.

[0101] The twin-screw extruder in step (2) includes six temperature zones arranged in sequence, with the temperature of zone 1 being 175°C, the temperature of zone 2 being 205°C, the temperature of zone 3 being 205°C, the temperature of zone 4 being 205°C, the temperature of zone 5 being 205°C, the temperature of zone 6 being 205°C, the head temperature being 205°C, and the screw speed being 255 r / min.

[0102] When the prepreg tape is pressed into a structural plate in step (3), the laying method and number of layers of the prepreg tape are designed according to actual use requirements. The hot pressing temperature is 205°C.

[0103] The POM sheets prepared in Examples 1-5 and Comparative Example 1 were made into strips using an injection molding machine for testing. The test data are shown in the following table:

[0104] Test items Test standards unit P1 P2 P3 P4 P5 D1 Coefficient of friction (dry grinding) ASTM D1894 0.13 0.14 0.14 0.13 0.14 0.18 tensile strength ASTM D638 MPa 46.4 47.3 45.8 46.7 45.2 37.1 Bending strength ASTM D790 MPa 3580 3420 3610 3490 3560 2810 Izod notched impact strength ASTM D256 <![CDATA[kJ / m 2 ]]> 4.8 5.1 4.9 5.2 4.4 3.1

[0105] As can be seen from the above table, the mechanical properties and wear resistance of Examples 1-5 are better than those of Comparative Example 5. This shows that the POM board prepared by the method provided by the present invention has excellent mechanical properties and wear resistance, and can expand the application field of POM board.

[0106] The technical features of the above-mentioned embodiments can be combined arbitrarily. In order to make the description concise, not all possible combinations of the technical features in the above-mentioned embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0107] The above-described embodiments merely illustrate several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention. It should be noted that a person skilled in the art would be able to make numerous modifications and improvements without departing from the spirit of the present invention, all of which fall within the scope of protection of the present invention. Therefore, the scope of protection of the present invention shall be determined by the appended claims.

Claims

1. A high performance wear-resistant POM plate, characterized in that: The board is composed of the following components by weight: POM 80-100 parts, 10-16 parts of modified titanium boride whiskers, SEBS-g-MAH 0.2-0.4 parts, 0.1-0.5 parts of antioxidant, The modified titanium boride whiskers are prepared by the following method: (1) Weigh magnesium nitrate, ammonium fluoride, and deionized water in a mass ratio of (30-40): (50-60): (70-90), add them to a reaction vessel, react at 30-50°C for 6-8 hours, and cool to room temperature to obtain solution A; (2) Filtering, washing, and drying solution A at 40-60°C for 6-10 hours to obtain magnesium fluoride; (3) Weigh magnesium fluoride, cerium nitrate, anhydrous ethanol, and deionized water in a mass ratio of (30-40): (40-50): (40-60): (80-90), add them to a reaction vessel, react at 70-90°C for 8-10 hours, filter, wash, and dry at 70-90°C for 6-8 hours to obtain solid B; (4) Solid B is placed in a muffle furnace and calcined at 680-720°C for 10-12 hours to obtain MgF2@CeO2 with MgF2 as the core and CeO2 as the shell; (5) Weigh MgF2@CeO2, titanium boride whiskers, and anhydrous ethanol in a mass ratio of (30-50): (40-60): (60-80), add them to a ball mill, fill the ball mill with nitrogen, and ball mill for 10-16 hours. After the mill is finished, sinter it in a vacuum hot pressing furnace at 320-360℃ for 12-16 hours, and pass it through a 500-mesh sieve to obtain modified titanium boride whiskers.

2. The high performance wear-resistant POM plate according to claim 1, characterized in that: The antioxidant is tris(2,4-di-tert-butyl)phenyl phosphite, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and / or 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxybenzyl)benzene.

3. A method for preparing a high-performance wear-resistant POM plate according to claim 1 or 2, characterized in that: The preparation method comprises the following steps: (1) Weigh 80-100 parts of POM, 0.2-0.4 parts of SEBS-g-MAH, and 0.1-0.5 parts of antioxidant, mix and stir evenly to obtain a mixture; (2) Adding the mixed material into the extruder and extruding it into a prepreg by screw extrusion with 10-16 parts of modified titanium boride whiskers; the twin-screw extruder includes six temperature zones arranged in sequence, the temperature of zone 1 is 160-180°C, the temperature of zone 2 is 200-220°C, the temperature of zone 3 is 200-220°C, the temperature of zone 4 is 200-220°C, the temperature of zone 5 is 200-220°C, the temperature of zone 6 is 200-220°C, the head temperature is 200-220°C, and the screw speed is 200-280r / min; (3) The prepreg tape is pressed into a structural plate by hot pressing at a temperature of 200-220°C.

4. The method for preparing a high-performance wear-resistant POM plate according to claim 3, wherein: When the prepreg tape is pressed into a structural plate in step (3), the laying method and number of layers of the prepreg tape are designed according to actual use requirements.