A PPS composite material and preparation method thereof

Abstract

The application discloses a PPS composite material and a preparation method thereof. The PPS composite material is prepared from the following components in parts by weight: PPS 80-100 parts, dielectric filler 10-16 parts, basalt fiber 8-12 parts, SEBS-g-MAH 0.2-0.4 parts and antioxidant 0.1-0.5 parts. The dielectric filler is composed of Mg@ZrO2@PDA nanoparticles, which are formed by sequentially coating PDA and Mg nanoparticles on the surface of the nanoparticle ZrO2. The dielectric performance and mechanical performance of the PPS composite material are improved by adding the dielectric filler and the basalt fiber in the PPS resin matrix, so that the application of the PPS composite material is expanded.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials, and in particular relates to a PPS composite material and a preparation method thereof. Background Art

[0002] Polyphenylene sulfide (PPS), a high-performance thermoplastic, boasts advantages such as high-temperature and chemical resistance, flame retardancy, low water absorption, and a small linear expansion coefficient. It is widely used in the electronics, automotive, machinery, and chemical industries, and is an excellent raw material for high-voltage computer components, relays, contact switches, light reflectors, bearings, and corrosion-resistant pipes. PPS exhibits excellent thermal stability, dimensional stability, and moldability. Further improvements to its mechanical and dielectric properties could allow its use in specialized components in the communications industry, such as antenna arrays.

[0003] The present invention is devoted to explaining a PPS composite material with excellent dielectric and mechanical properties and a preparation method thereof. Summary of the Invention

[0004] In view of this, it is necessary to provide a PPS composite material in the present invention, in which dielectric fillers and basalt fibers are added to a PPS resin matrix to improve the dielectric properties and mechanical properties of the PPS composite material, thereby expanding the application of the PPS composite material.

[0005] In order to achieve the above object, the present invention adopts the following technical solutions:

[0006] The present invention first provides a PPS composite material, which is prepared from the following components in parts by weight:

[0007] PPS 80-100 copies,

[0008] Dielectric filler 10-16 parts,

[0009] 8-12 parts of basalt fiber,

[0010] SEBS-g-MAH 0.2 parts to 0.4 parts,

[0011] 0.1-0.5 parts of antioxidant;

[0012] The dielectric filler is composed of Mg@ZrO2@PDA nanoparticles, which are formed by sequentially coating PDA and Mg nanoparticles on the surface of the ZrO2 nanoparticles.

[0013] In a further embodiment, the preparation of the dielectric filler comprises the following steps:

[0014] S1. Weigh ZrO2, Tris-HCl aqueous solution, and dopamine hydrochloride, mix, and react at room temperature for 10-12 hours to obtain solution A;

[0015] S2, filtering, washing, and drying the solution A to obtain ZrO2@PDA;

[0016] S3. Weigh ZrO2@PDA, magnesium nitrate, sodium borohydride, and deionized water, mix them, and react them at room temperature for 10-16 hours to obtain solution B;

[0017] S4. Filtering, washing, and drying the solution B to obtain Mg@ZrO2@PDA, which is a dielectric filler.

[0018] In a further embodiment, in step S1, the mass ratio of ZrO2, Tris-HCl aqueous solution, and dopamine hydrochloride is (40-50):(160-200):(20-30).

[0019] In a further embodiment, in step S3, the mass ratio of the ZrO2@PDA, magnesium nitrate, sodium borohydride, and deionized water is (30-40): (16-20): (1-3): (120-160).

[0020] In a further embodiment, the antioxidant is selected from at least one of tris(2,4-di-tert-butyl)phenyl phosphite, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxybenzyl)benzene.

[0021] The present invention further provides a method for preparing the PPS composite material as described in any of the above, comprising the following steps:

[0022] Weigh 80-100 parts of PPS, 10-16 parts of dielectric filler, 8-12 parts of basalt fiber, 0.2-0.4 parts of SEBS-g-MAH, and 0.1-0.5 parts of antioxidant according to the weight ratio, and mix thoroughly to obtain a uniform mixture;

[0023] The mixed material is added into a twin-screw extruder for extrusion and granulation to prepare a PPS composite material.

[0024] In a further embodiment, the twin-screw extruder includes six temperature zones arranged in sequence, and the temperatures are: zone 1 temperature 260-280°C, zone 2 temperature 320-360°C, zone 3 temperature 320-360°C, zone 4 temperature 320-360°C, zone 5 temperature 320-360°C, and zone 6 temperature 320-360°C.

[0025] In a further embodiment, the head temperature of the twin-screw extruder is 320-360° C., and the screw speed is 200-280 r / min.

[0026] Compared with the prior art, the present invention has the following beneficial effects:

[0027] The present invention provides a PPS composite material with high dielectric properties and low dielectric loss by adding a dielectric filler. Specifically, the coating of PDA in the dielectric filler significantly improves the dispersibility of the dielectric filler and the interfacial compatibility between the dielectric filler and the PPS matrix. Compared with unmodified nano-ZrO2, the dielectric properties of the PPS composite material with the addition of ZrO2@PDA are improved to a certain extent. Furthermore, after coating Mg nanoparticles on ZrO2@PDA, the Coulomb blockade effect is successfully introduced into the PPS composite material, which significantly reduces the dielectric loss of the composite material with the addition of Mg@ZrO2@PDA nanoparticles, which is of great significance.

[0028] Furthermore, in the present invention, the mechanical properties of the PPS composite material are significantly improved by adding basalt fibers.

[0029] The PPS composite material of the present invention has very good high dielectric properties, low dielectric loss and excellent mechanical properties, and can be used as an antenna array material. DETAILED DESCRIPTION

[0030] The present invention is described below by means of specific examples. It should be noted that the following specific examples are only for illustrative purposes and do not limit the scope of the present invention in any way. In addition, unless otherwise specified, methods without specific conditions or steps are conventional methods, and the reagents and materials used are commercially available. "Parts" and "number of parts" involved, unless otherwise specified, refer to parts by weight.

[0031] The raw material information used in the following examples and comparative examples is as follows:

[0032] PPS 1301-8349, Lehman Foss, Germany; nano-ZrO2, Beijing Dekedaojin Technology Co., Ltd.; Tris-HCl aqueous solution, Jinan Xinwang Chemical Co., Ltd.; dopamine hydrochloride, Hubei Yuancheng Saichuang Technology Co., Ltd.; magnesium nitrate, Jinan Junteng Chemical Co., Ltd.; sodium borohydride, Henan Jiawang Chemical Products Co., Ltd.; deionized water, Shanghai Jingchun Water Treatment Technology Co., Ltd.; basalt fiber, Shandong Senhong Engineering Materials Co., Ltd.; SEBS-g-MAH, Nanjing Deba Polymer Materials Co., Ltd.; antioxidants (models Irganox 168, Irganox 1010, and Irganox 1330), BASF, Germany.

[0033] Example 1

[0034] Preparation of dielectric fillers

[0035] Weigh 400 g of nano-ZrO2, 1.6 kg of Tris-HCl aqueous solution, and 200 g of dopamine hydrochloride, place them in a reaction vessel, and react at room temperature for 10 h to obtain solution A;

[0036] Solution A was filtered, washed, and dried to obtain ZrO2@PDA;

[0037] Weigh 300 g ZrO2@PDA, 160 g magnesium nitrate, 10 g sodium borohydride, and 1.2 kg deionized water, place them in a reaction vessel, and react at room temperature for 10 h to obtain solution B;

[0038] Solution B is filtered, washed, and dried to obtain a dielectric filler, which is recorded as X1.

[0039] Preparation of PPS composite materials

[0040] Weigh 80 parts of PPS, 10 parts of dielectric filler X1, 8 parts of basalt fiber, 0.2 parts of SEBS-g-MAH, and 0.1 parts of Irganox 1010, mix and stir evenly to obtain a mixture;

[0041] The obtained mixture was added to a twin-screw extruder for extrusion and granulation to obtain a PPS composite material, which was recorded as P1; wherein the twin-screw extruder includes six temperature zones arranged in sequence, and the temperatures are: zone 1 temperature 260°C, zone 2 temperature 320°C, zone 3 temperature 320°C, zone 4 temperature 320°C, zone 5 temperature 320°C, zone 6 temperature 320°C; the head temperature is 320°C, and the screw speed is 200 r / min.

[0042] Example 2

[0043] Preparation of dielectric fillers

[0044] Weigh 500g of nano-ZrO2, 2.0kg of Tris-HCl aqueous solution, and 300g of dopamine hydrochloride, place them in a reaction vessel, and react at room temperature for 12h to obtain solution A;

[0045] Solution A was filtered, washed, and dried to obtain ZrO2@PDA;

[0046] Weigh 400 g of ZrO2@PDA, 200 g of magnesium nitrate, 30 g of sodium borohydride, and 1.6 kg of deionized water, place them in a reaction vessel, and react at room temperature for 16 h to obtain solution B;

[0047] Solution B is filtered, washed, and dried to obtain a dielectric filler, which is recorded as X2.

[0048] Preparation of PPS composite materials

[0049] Weigh 100 parts of PPS, 16 parts of dielectric filler X2, 12 parts of basalt fiber, 0.4 parts of SEBS-g-MAH, 0.2 parts of Irganox 1330, 0.1 parts of Irganox 168, and 0.2 parts of Irganox 1010, mix and stir uniformly to obtain a mixture;

[0050] The obtained mixture was added to a twin-screw extruder for extrusion and granulation to obtain a PPS composite material, which was recorded as P2; wherein the twin-screw extruder includes six temperature zones arranged in sequence, and the temperatures are: zone 1 temperature 280°C, zone 2 temperature 360°C, zone 3 temperature 360°C, zone 4 temperature 360°C, zone 5 temperature 360°C, zone 6 temperature 360°C; the head temperature is 360°C, and the screw speed is 280 r / min.

[0051] Example 3

[0052] Preparation of dielectric fillers

[0053] Weigh 450 g of nano-ZrO2, 1.8 kg of Tris-HCl aqueous solution, and 250 g of dopamine hydrochloride, place them in a reaction vessel, and react at room temperature for 11 h to obtain solution A;

[0054] Solution A was filtered, washed, and dried to obtain ZrO2@PDA;

[0055] Weigh 350 g ZrO2@PDA, 180 g magnesium nitrate, 20 g sodium borohydride, and 1.4 kg deionized water into a reaction vessel and react at room temperature for 13 h to obtain solution B.

[0056] Solution B was filtered, washed, and dried to obtain dielectric filler X3.

[0057] Preparation of PPS composite materials

[0058] Weigh 90 parts of PPS, 13 parts of dielectric filler X3, 10 parts of basalt fiber, 0.3 parts of SEBS-g-MAH, 0.1 parts of Irganox 1010, and 0.2 parts of Irganox 168, mix and stir evenly to obtain a mixture;

[0059] The obtained mixture was added to a twin-screw extruder for extrusion and granulation to obtain a PPS composite material, which was recorded as P3; wherein the twin-screw extruder includes six temperature zones arranged in sequence, and the temperatures are: zone 1 temperature 270°C, zone 2 temperature 340°C, zone 3 temperature 340°C, zone 4 temperature 340°C, zone 5 temperature 340°C, zone 6 temperature 340°C; the head temperature is 340°C, and the screw speed is 240 r / min.

[0060] Example 4

[0061] Preparation of dielectric fillers

[0062] Weigh 480 g of nano-ZrO2, 1.85 kg of Tris-HCl aqueous solution, and 255 g of dopamine hydrochloride, place them in a reaction vessel, and react at room temperature for 10 h to obtain solution A;

[0063] Solution A was filtered, washed, and dried to obtain ZrO2@PDA;

[0064] Weigh 385 g ZrO2@PDA, 185 g magnesium nitrate, 28 g sodium borohydride, and 1.35 kg deionized water into a reaction vessel and react at room temperature for 12 h to obtain solution B.

[0065] Solution B is filtered, washed, and dried to obtain a dielectric filler, which is designated as X4.

[0066] Preparation of PPS composite materials

[0067] Weigh 95 parts of PPS, 14 parts of low dielectric filler X4, 11 parts of basalt fiber, 0.2 parts of SEBS-g-MAH, 0.1 parts of Irganox 1010, and 0.1 parts of Irganox 168, mix and stir evenly to obtain a mixture;

[0068] The obtained mixture was added to a twin-screw extruder for extrusion and granulation to obtain a PPS composite material, which was recorded as P4; wherein the twin-screw extruder includes six temperature zones arranged in sequence, and the temperatures are: zone 1 temperature 275°C, zone 2 temperature 335°C, zone 3 temperature 335°C, zone 4 temperature 335°C, zone 5 temperature 335°C, zone 6 temperature 335°C; the head temperature is 335°C, and the screw speed is 275r / min.

[0069] Example 5

[0070] Preparation of dielectric fillers

[0071] Weigh 495g of nano-ZrO2, 1.55kg of Tris-HCl aqueous solution, and 265g of dopamine hydrochloride, place them in a reaction vessel, and react at room temperature for 11h to obtain solution A;

[0072] Solution A was filtered, washed, and dried to obtain ZrO2@PDA;

[0073] Weigh 380 g ZrO2@PDA, 185 g magnesium nitrate, 28 g sodium borohydride, and 1.35 kg deionized water into a reaction vessel and react at room temperature for 14 h to obtain solution B.

[0074] Solution B is filtered, washed, and dried to obtain a dielectric filler, which is designated as X5.

[0075] Preparation of PPS composite materials

[0076] Weigh 85 parts of PPS, 12 parts of dielectric filler X5, 9 parts of basalt fiber, 0.3 parts of SEBS-g-MAH, and 0.1 parts of Irganox 1010, mix and stir evenly to obtain a mixture;

[0077] The obtained mixture was fed into a twin-screw extruder for extrusion and granulation to obtain a PPS composite material, which was recorded as P5; wherein the twin-screw extruder includes six temperature zones arranged in sequence, and the temperatures are: zone 1 temperature 265°C, zone 2 temperature 345°C, zone 3 temperature 345°C, zone 4 temperature 345°C, zone 5 temperature 345°C, zone 6 temperature 345°C; the head temperature is 345°C, and the screw speed is 245 r / min.

[0078] Comparative Example 1

[0079] Preparation of PPS composite materials

[0080] Weigh 85 parts of PPS, 0.3 parts of SEBS-g-MAH, and 0.1 parts of Irganox 1010, mix and stir evenly to obtain a mixture;

[0081] The obtained mixture was added to a twin-screw extruder for extrusion and granulation to obtain a PPS composite material, which was recorded as D1; ​​wherein the twin-screw extruder includes six temperature zones arranged in sequence, and the temperatures are: zone 1 temperature 265°C, zone 2 temperature 345°C, zone 3 temperature 345°C, zone 4 temperature 345°C, zone 5 temperature 345°C, zone 6 temperature 345°C; the head temperature is 345°C, and the screw speed is 245 r / min.

[0082] Comparative Example 2

[0083] Preparation of PPS composite materials

[0084] Weigh 85 parts of PPS, 12 parts of nano-ZrO2, 0.3 parts of SEBS-g-MAH and 0.1 parts of Irganox1010, mix and stir evenly to obtain a mixture;

[0085] The obtained mixture was added into a twin-screw extruder for extrusion and granulation to obtain a PPS composite material, which was recorded as D2; wherein, the twin-screw extruder included six temperature zones arranged in sequence, and the temperatures were: zone 1 temperature 265°C, zone 2 temperature 345°C, zone 3 temperature 345°C, zone 4 temperature 345°C, zone 5 temperature 345°C, zone 6 temperature 345°C; the head temperature was 345°C, and the screw speed was 245 r / min.

[0086] Test Case

[0087] The PPS composite materials prepared in the examples and comparative examples were made into strips using an injection molding machine and tested for relevant properties, as follows:

[0088] The tensile strength is in accordance with GB / T 1040.1 / 2. The tensile specimen used is (170.0±5.0) mm×(10.0±0.5) mm×(4.0±0.2) mm, and the tensile rate is 5 mm / min.

[0089] The bending modulus refers to GB / T 9341. The bending spline used is (80.0±5.0)mm×(10.0±0.5)mm×(4.0±0.2)mm, and the bending rate is 2mm / min.

[0090] The Izod impact strength is determined according to GB / T 1843. The notched Izod impact strength specimen is (80.0±5.0)mm×(10.0±0.5)mm×(4.0±0.2)mm. The notch is machined and has a depth of (2.0±0.2)mm.

[0091] The dielectric properties refer to IEC 60250-69. The specifications of the dielectric properties test board are: (120.0±5.0)mm×(120.0±5.0)mm×(3.0±0.2)mm, and the test frequency is 1.1MHz.

[0092] The test results are shown in Table 1.

[0093] Table 1 PPS composite material performance test results

[0094] Test items unit P1 P2 P3 P4 P5 D1 D2 flexural modulus MPa 8850 9020 9120 9270 9040 3880 4070 Izod impact strength <![CDATA[kJ / m 2 ]]> 8.5 8.3 7.7 8.4 8.5 4.4 4.9 tensile strength MPa 124.4 125.6 127.2 126.4 125.4 100.6 107.7 Dielectric constant / 12.52 13.24 12.84 12.11 12.56 4.88 8.56 Dielectric loss / 0.0021 0.0028 0.0025 0.0026 0.0027 0.0051 0.0036

[0095] The test results in Table 1 show that the physical properties, dielectric constant, dielectric loss, and mechanical properties of Examples 1-5 are all better than those of Comparative Examples 1-2. This indicates that the PPS composite material of the present invention has superior dielectric and mechanical properties and is considered suitable for use in antenna array materials.

[0096] 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.

[0097] The above-described embodiments merely illustrate several implementations of the present invention, and while their descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the patent. It should be noted that a person skilled in the art would be able to make numerous variations 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 patent for this invention shall be determined by the appended claims.

Claims

1. A PPS composite material, characterized in that: The invention is prepared from the following components in parts by weight: 80-100 parts of PPS, 10-16 parts of dielectric filler, 8-12 parts of basalt fiber, 0.2-0.4 parts of SEBS-g-MAH, and 0.1-0.5 parts of antioxidant; The dielectric filler is composed of Mg@ZrO2@PDA nanoparticles, which are formed by sequentially coating PDA and Mg nanoparticles on the surface of ZrO2 nanoparticles. The preparation of the dielectric filler includes the following steps: S1. Weigh ZrO2, Tris-HCl aqueous solution, and dopamine hydrochloride, mix, and react at room temperature for 10-12 hours to obtain solution A; S2, filtering, washing, and drying the solution A to obtain ZrO2@PDA; S3. Weigh ZrO2@PDA, magnesium nitrate, sodium borohydride, and deionized water, mix them, and react them at room temperature for 10-16 hours to obtain solution B; S4. Filtering, washing, and drying the solution B to obtain Mg@ZrO2@PDA, which is a dielectric filler.

2. The PPS composite material according to claim 1, wherein In step S1, the mass ratio of ZrO2, Tris-HCl aqueous solution, and dopamine hydrochloride is (40-50): (160-200): (20-30).

3. The PPS composite material according to claim 1, wherein In step S3, the mass ratio of the ZrO2@PDA, magnesium nitrate, sodium borohydride, and deionized water is (30-40): (16-20): (1-3): (120-160).

4. The PPS composite material according to claim 1, wherein The antioxidant is selected from at least one of tris(2,4-di-tert-butyl)phenyl phosphite, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxybenzyl)benzene.

5. A method for preparing a PPS composite material according to any one of claims 1 to 4, characterized in that: The following steps are involved: Weigh 80-100 parts of PPS, 10-16 parts of dielectric filler, 8-12 parts of basalt fiber, 0.2-0.4 parts of SEBS-g-MAH, and 0.1-0.5 parts of antioxidant according to the weight ratio, and mix thoroughly to obtain a uniform mixture; The mixed material is added into a twin-screw extruder for extrusion and granulation to prepare a PPS composite material.

6. The preparation method according to claim 5, wherein The twin-screw extruder includes six temperature zones arranged in sequence, with the temperatures being: zone one temperature 260-280°C, zone two temperature 320-360°C, zone three temperature 320-360°C, zone four temperature 320-360°C, zone five temperature 320-360°C, and zone six temperature 320-360°C.

7. The preparation method according to claim 5, wherein The head temperature of the twin-screw extruder is 320-360° C., and the screw speed is 200-280 r / min.