Antistatic master batch and antistatic pp plate and preparation method thereof

Abstract

The application discloses an antistatic master batch and an antistatic PP plate and a preparation method thereof, and belongs to the field of high polymer materials. In the application, the surface of fullerene is treated by hydrogen peroxide to introduce -COOH and generate hydroxylated fullerene. Lysine diisocyanate (LDI) can react with the hydroxylated fullerene. The treated fullerene has similar polarity with a thermoplastic matrix PP, and the compatibility of the composite material is better, so that the mechanical properties of the PP plate are improved. In addition, the fullerene can also be used as a heterogeneous nucleating agent of the PP matrix to accelerate and improve the crystallization properties of the PP matrix and improve the mechanical properties of the PP plate.

Description

Technical Field

[0001] The present invention belongs to the field of polymer materials, and in particular relates to an antistatic masterbatch and a high-performance antistatic PP sheet used for preparing the same and a preparation method. Background Art

[0002] Polypropylene (PP) has the advantages of low density, good performance and low price, and is widely used in chemical, construction, light industry,

[0003] Polypropylene is widely used in the industrial fields of power supply, household appliances, packaging and automobiles. Since polypropylene is a highly insulating material with low mechanical properties, high surface resistivity and average toughness, its products are prone to static electricity accumulation or insufficient toughness during use, resulting in various defects and losses, thus limiting the application of polypropylene in corresponding fields.

[0004] In response to this situation, the present invention innovatively produces a PP sheet with excellent mechanical properties and antistatic properties. This material has not been reported so far, which has very important practical significance for expanding the application of PP sheets. Summary of the Invention

[0005] In view of this, the present invention innovatively synthesizes a high-performance antistatic PP sheet, which has excellent mechanical properties and antistatic properties, and solves the technical problem of limited mechanical properties and antistatic properties of PP sheets in the prior art.

[0006] In order to achieve the above objectives, the present invention adopts the following technical solutions.

[0007] One of the purposes of the present invention is to provide a method for preparing an antistatic masterbatch as follows:

[0008] (1.1) Weigh a certain amount of fullerene and the oxidant hydrogen peroxide, place them in a reaction vessel, react at 50-60°C for 6-8 hours, filter, wash, and dry to obtain hydroxylated fullerene.

[0009] The mass ratio of fullerene to oxidant hydrogen peroxide in step (1) is (30-40): (60-80).

[0010] (1.2) Weigh a certain amount of lysine diisocyanate (LDI), catalyst dibutyltin dilaurate, and hydroxylated fullerene into a reaction vessel and heat in an oil bath at 70-90°C for 6-10 hours. After filtering the product, the filter cake is extracted with acetone and dried in a vacuum drying oven at 80-100°C for 10-12 hours to obtain the modified fullerene.

[0011] In step (2), the mass ratio of lysine diisocyanate (LDI), catalyst dibutyltin dilaurate, and hydroxylated fullerene is (4-6): (0.2-0.4): (20-30).

[0012] (1.3) A certain amount of modified fullerene, polypropylene and antioxidant are weighed, mixed and stirred uniformly to obtain a mixture;

[0013] The mass ratio of the modified fullerene, polypropylene and antioxidant in step (3) is (10-12):(40-60):(0.1-0.3), and the antioxidant in step (3) is Irganox1010 produced by BASF Company in Germany.

[0014] (1.4) The mixture obtained in step (3) is extruded and granulated from the extruder to obtain the antistatic master batch.

[0015] The second object of the application is to provide a high-performance antistatic PP plate made from the following components by weight:

[0016] PP 50-70 parts,

[0017] The antistatic master batch prepared by the method of the application is 10-16 parts,

[0018] Basalt fiber 16-20 parts,

[0019] SEBS-g-MAH 0.2-0.4 parts

[0020] Antioxidant 0.1-0.5 parts.

[0021] The antioxidant is one or a mixture of several of the following: tris(2,4-di-tert-butyl) phenyl phosphite (Irganox168), tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid] pentaerythritol ester (Irganox1010) and 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxybenzyl) benzene (Irganox1330) produced by BASF Company.

[0022] The second object of the application is to provide a preparation method of the high-performance antistatic PP plate as described above, comprising the following steps:

[0023] (2.1) 50-70 parts by weight of PP, 10-16 parts by weight of antistatic master batch, 0.2-0.4 parts by weight of SEBS-g-MAH and 0.1-0.5 parts by weight of antioxidant are weighed, mixed and stirred uniformly to obtain a mixture;

[0024] (2.2) The mixture is added to the extruder and extruded by the screw to uniformly compound with 16-20 parts of basalt fiber into a prepreg tape;

[0025] (2.3) The prepreg tape is pressed into a structural plate by a hot pressing method.

[0026] The double screw extruder in the step (2.2) comprises six temperature zones arranged in sequence, the temperature of the first zone is 160-180 DEG C, the temperature of the second zone is 210-230 DEG C, the temperature of the third zone is 210-230 DEG C, the temperature of the fourth zone is 210-230 DEG C, the temperature of the fifth zone is 210-230 DEG C, the temperature of the sixth zone is 210-230 DEG C, and the temperature of the head is 210-230 DEG C; the screw rotation speed is 200-260 r / min.

[0027] In the step (2.3), the prepreg is pressed into a structural plate, and the laying mode and the laying layer of the prepreg are designed according to the actual use requirement; and the hot-pressing temperature is 210-230 DEG C.

[0028] Compared with the prior art, the present application has the following beneficial effects:

[0029] (1) The present application can introduce -COOH on the surface of fullerene by the hydrogen peroxide treatment of fullerene in the early stage, and generate hydroxylated fullerene. Lysine diisocyanate (LDI) can react with the hydroxylated fullerene, and the fullerene treated by LDI has similar polarity with the thermoplastic matrix PP, and the compatibility of the composite material is better, so that the mechanical properties of the PP plate are improved. In addition, the fullerene can also be used as a heterogeneous nucleating agent of the PP matrix, and the crystallization performance of the PP matrix is accelerated and improved, and the mechanical properties of the PP plate are improved.

[0030] (2) The addition of the antistatic master batch improves the antistatic properties of the PP plate. DETAILED DESCRIPTION

[0031] In order to facilitate the understanding of the present application, the present application will be described more fully below with reference to specific embodiments. However, the present application can be realized in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the disclosure of the present application more thorough and comprehensive.

[0032] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present application belongs. The terms used in the specification of the present application herein are only for the purpose of describing the specific embodiments and are not intended to limit the present application.

[0033] The raw materials used in the following examples are as follows:

[0034] PP (model Z30S), Sinopec Maoming; fullerene, Puyang Yongxin Fullerene Technology Co., Ltd.; hydrogen peroxide, Jinan Kunfeng Chemical Co., Ltd.; lysine diisocyanate, Hubei Keyijia Chemical Co., Ltd.; dibutyltin dilaurate, Shandong Hui'an Chemical Co., Ltd.; SEBS-g-MAH, Jiangsu Runfeng Synthetic Technology Co., Ltd.; basalt fiber, Taian Hongtuo New Material Co., Ltd.; antioxidants (models Irganox 168, Irganox 1010, Irganox 1330), BASF, Germany.

[0035] Preparation Example 1

[0036] (1) 300 g of fullerene and 600 g of oxidant hydrogen peroxide were weighed and placed in a reaction vessel, and reacted at 50°C for 6 h. After filtration, washing and drying, hydroxylated fullerene was obtained.

[0037] (2) 40 g of lysine diisocyanate (LDI), 2 g of catalyst dibutyltin dilaurate and 200 g of hydroxylated fullerene were weighed and placed in a reaction vessel, and heated in an oil bath at 70°C for 6 h. After the product was suction filtered, the filter cake was extracted with acetone, and then dried in a vacuum drying oven at 80°C for 10 h to obtain modified fullerene.

[0038] (3) 100 g of modified fullerene, 400 g of polypropylene and 0.1 g of antioxidant Irganox 1010 were weighed and mixed and stirred uniformly to obtain a mixture.

[0039] (4) The mixture obtained in step (3) was extruded and granulated from an extruder to obtain an antistatic master batch M1.

[0040] Example 1

[0041] A high-performance antistatic PP plate was prepared by the following method:

[0042] (1) 50 parts of PP, 10 parts of antistatic master batch M1, 0.2 parts of SEBS-g-MAH and 0.1 part of antioxidant Irganox 1010 were weighed and mixed and stirred uniformly to obtain a mixture.

[0043] (2) The mixture was added to an extruder and extruded with a screw to uniformly compound with 16 parts of basalt fiber to form a prepreg tape.

[0044] (3) The prepreg tape was pressed into a structural plate P1 by hot pressing.

[0045] The twin-screw extruder in step (2) includes six temperature zones arranged in sequence, with a temperature of 160°C in the first zone, 210°C in the second zone, 210°C in the third zone, 210°C in the fourth zone, 210°C in the fifth zone, 210°C in the sixth zone and 210°C in the die head; the screw rotation speed is 200 r / min.

[0046] In step (3), the prepreg is pressed into a structural plate, the laying method and the number of layers of the prepreg are designed according to the actual use requirement, and the hot-pressing temperature is 210℃.

[0047] Preparation Example 2

[0048] (1) 400 g of fullerene, 800 g of oxidant hydrogen peroxide were weighed and placed in a reaction vessel, and reacted at 60℃ for 8 h. After filtration, washing and drying, hydroxylated fullerene was obtained.

[0049] (2) 60 g of lysine diisocyanate (LDI), 4 g of catalyst dibutyltin dilaurate, and 300 g of hydroxylated fullerene were weighed and placed in a reaction vessel, and heated in an oil bath at 90℃ for 10 h. After the product was suction filtered, the filter cake was extracted with acetone, and then dried in a vacuum drying oven at 100℃ for 12 h to obtain modified fullerene.

[0050] (3) 120 g of modified fullerene, 600 g of polypropylene, and 3 g of antioxidant Irganox 1010 were mixed and stirred uniformly to obtain a mixture;

[0051] (4) The mixture obtained in step (3) was extruded and granulated from the extruder to obtain an antistatic masterbatch M2.

[0052] Example 2

[0053] (1) 70 parts of PP, 16 parts of antistatic masterbatch M2, 0.4 parts of SEBS-g-MAH, 0.1 parts of Irganox 1010, 0.2 parts of Irganox 168, and 0.2 parts of Irganox 1330 were mixed and stirred uniformly to obtain a mixture;

[0054] (2) The mixture was added to the extruder and extruded with a screw to uniformly compound with 20 parts of basalt fiber to form a prepreg;

[0055] (3) The prepreg was pressed into a structural plate P2 by hot-pressing.

[0056] The twin-screw extruder in step (2) includes six temperature zones arranged in sequence, with a first zone temperature of 180℃, a second zone temperature of 230℃, a third zone temperature of 230℃, a fourth zone temperature of 230℃, a fifth zone temperature of 230℃, and a sixth zone temperature of 230℃. The head temperature is 220℃, and the screw rotation speed is 260 r / min.

[0057] In step (3), the prepreg is pressed into a structural plate, the laying method and the number of layers of the prepreg are designed according to the actual use requirement, and the hot-pressing temperature is 230℃.

[0058] Preparation Example 3

[0059] (1) Take 350 g of fullerene, 700 g of oxidant hydrogen peroxide, and place them in a reaction vessel. React at 55℃ for 7h. Filter, wash, and dry to obtain hydroxylated fullerene.

[0060] (2) Take 50 g of lysine diisocyanate (LDI), 3 g of catalyst dibutyltin dilaurate, and 250 g of hydroxylated fullerene, and place them in a reaction vessel. Heat in an 80℃ oil bath for 8h. After the product is suction filtered, the filter cake is extracted with acetone, and then dried in a vacuum drying oven at 90℃ for 11h to obtain modified fullerene.

[0061] (3) Take 110 g of modified fullerene, 500 g of polypropylene, and 2 g of antioxidant Irganox 1010, mix and stir uniformly to obtain a mixture.

[0062] (4) Extrude the mixture obtained in step (3) from the extruder to obtain an antistatic masterbatch M3.

[0063] Example 3

[0064] (1) Take 60 parts of PP, 13 parts of antistatic masterbatch M3, 0.3 parts of SEBS-g-MAH, 0.1 parts of Irganox 1010, and 0.2 parts of Irganox 168, mix and stir uniformly to obtain a mixture.

[0065] (2) Add the mixture to the extruder and extrude with the screw to uniformly compound with 18 parts of basalt fiber into a prepreg tape.

[0066] (3) Use hot pressing method to press the prepreg tape into a structural panel.

[0067] The twin-screw extruder in step (2) includes six temperature zones arranged in sequence, with zone one temperature of 170℃, zone two temperature of 210℃, zone three temperature of 210℃, zone four temperature of 210℃, zone five temperature of 210℃, zone six temperature of 210℃, and die temperature of 210℃; screw rotation speed of 230r / min.

[0068] In step (3), when the prepreg tape is pressed into a structural panel, the laying method and the number of layers of the prepreg tape are designed according to the actual use requirements. The hot pressing temperature is 220℃.

[0069] Preparation Example 4

[0070] (1) Take 365 g of fullerene, 695 g of oxidant hydrogen peroxide, and place them in a reaction vessel. React at 55℃ for 7h. Filter, wash, and dry to obtain hydroxylated fullerene.

[0071] (2) Take 55 g of lysine diisocyanate (LDI), 3.5 g of catalyst dibutyltin dilaurate, 285 g of hydroxylated fullerene into a reaction vessel, heat in an oil bath at 75℃ for 7h, after the product is filtered, the filter cake is extracted with acetone, and then dried in a vacuum drying oven at 95℃ for 11h to obtain the modified fullerene.

[0072] (3) Take 105 g of modified fullerene, 425 g of polypropylene, 2.5 g of antioxidant Irganox1010, mix and stir uniformly to obtain a mixture;

[0073] (4) The mixture obtained in step (3) is extruded and granulated from the extruder to obtain the antistatic masterbatch M4.

[0074] Example 4

[0075] (1) Mix and stir 58 parts of PP, 14 parts of antistatic masterbatch M4, 0.2 parts of SEBS-g-MAH, 0.1 parts of Irganox1010, and 0.2 parts of Irganox1330 to obtain a mixture;

[0076] (2) The mixture is added to the extruder and extruded through the screw to uniformly compound with 17 parts of basalt fiber into a prepreg tape;

[0077] (3) The prepreg tape is pressed into a structural panel P4 by hot pressing.

[0078] The twin-screw extruder in step (2) includes six temperature zones arranged in sequence, with a first zone temperature of 165℃, a second zone temperature of 215℃, a third zone temperature of 215℃, a fourth zone temperature of 215℃, a fifth zone temperature of 215℃, a sixth zone temperature of 215℃, and a die temperature of 215℃; the screw rotation speed is 205r / min.

[0079] In step (3), when the prepreg tape is pressed into a structural panel, the laying method and the number of layers of the prepreg tape are designed according to the actual use requirements. The hot pressing temperature is 215℃.

[0080] Preparation Example 5

[0081] (1) Take 315 g of fullerene and 615 g of oxidant hydrogen peroxide, and place them in a reaction vessel, and react at 58℃ for 6h, filter, wash and dry to obtain hydroxylated fullerene.

[0082] (2) Take 45 g of lysine diisocyanate (LDI), 2.5 g of catalyst dibutyltin dilaurate, and 295 g of hydroxylated fullerene into a reaction vessel, heat in an oil bath at 85℃ for 8h, after the product is filtered, the filter cake is extracted with acetone, and then dried in a vacuum drying oven at 95℃ for 11h to obtain the modified fullerene.

[0083] (3) Weigh 105 g of modified fullerene, 515 g of polypropylene, and 2 g of antioxidant Irganox 1010, mix and stir evenly to obtain a mixture;

[0084] (4) The mixed material obtained in step (3) is extruded from an extruder and granulated to obtain antistatic masterbatch M5.

[0085] Example 5

[0086] (1) Weigh 59 parts of PP, 15 parts of antistatic masterbatch M5, 0.4 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;

[0087] (2) The mixed material is added into the extruder and extruded by screw to form a prepreg with 18 parts of basalt fiber;

[0088] (3) The prepreg tape is pressed into a structural plate P5 by hot pressing.

[0089] 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 225°C, the temperature of zone 3 being 225°C, the temperature of zone 4 being 225°C, the temperature of zone 5 being 225°C, the temperature of zone 6 being 225°C, and the temperature of die head being 225°C; the screw speed being 245 r / min.

[0090] 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 225°C.

[0091] Comparative Example 1

[0092] (1) Weigh 59 parts of PP, 0.4 parts of SEBS-g-MAH, 0.1 parts of Irganox 1010, and 0.1 parts of Irganox 168, mix and stir to obtain a mixture;

[0093] (2) The mixed material is added into the extruder and extruded by screw to form a prepreg with 18 parts of basalt fiber;

[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 225°C, the temperature of zone 3 being 225°C, the temperature of zone 4 being 225°C, the temperature of zone 5 being 225°C, the temperature of zone 6 being 225°C, and the temperature of die head being 195°C; and the screw speed being 245 r / min.

[0096] In the step (3), the prepreg is pressed into a structural plate according to the actual use requirements of the design of the prepreg laying mode and the laying layer number. The hot-pressing temperature is 225℃.

[0097] Comparative Example 2

[0098] (1) 59 parts of PP, 15 parts of fullerene, 0.4 parts of SEBS-g-MAH, 0.1 parts of Irganox1010, and 0.1 parts of Irganox168 were weighed and uniformly stirred to obtain a mixture;

[0099] (2) The mixture was added into an extruder to be uniformly compounded with 18 parts of basalt fiber into a prepreg through a screw extrusion;

[0100] (3) The prepreg was pressed into a structural plate P5 by a hot-pressing method.

[0101] The twin-screw extruder in the step (2) includes six temperature zones arranged in sequence, and the temperature of the first zone is 175℃, the temperature of the second zone is 225℃, the temperature of the third zone is 225℃, the temperature of the fourth zone is 225℃, the temperature of the fifth zone is 225℃, the temperature of the sixth zone is 225℃, and the temperature of the die head is 225℃. The screw rotation speed is 245r / min.

[0102] In the step (3), the prepreg is pressed into a structural plate according to the actual use requirements of the design of the prepreg laying mode and the laying layer number. The hot-pressing temperature is 225℃.

[0103] The performance data of the PP plates of the above-mentioned Examples 1-5 and Comparative Examples 1-2 are shown in the following table:

[0104]

[0105] As can be seen from the above table, the physical properties and antistatic properties of X1-5 are better than those of D1-D2, which shows that the PP plate prepared by the method provided by the present application has excellent physical properties and antistatic properties, and can expand the application field of the PP plate.

[0106] The technical features of the above-mentioned examples can be combined arbitrarily, and in order to make the description simple, all possible combinations of the technical features in the above-mentioned examples are not described, however, as long as the combination of the technical features does not exist contradictory, it should be considered as the scope of the present application.

[0107] The above embodiments only express several implementation manners of the present application, and the description is more specific and detailed, but it should not be understood as a limitation on the scope of the patent. It should be noted that for ordinary skilled persons in the art, without departing from the concept of the present application, several modifications and improvements can be made, which are within the scope of protection of the present application. Therefore, the protection scope of the patent of the present application should be subject to the appended claims.

Claims

1. A method for preparing an antistatic masterbatch, characterized in that: The preparation method comprises the following steps: (1.1) Weigh fullerene and hydrogen peroxide in a reaction vessel, react at 50-60°C for 6-8 h, filter, wash, and dry to obtain hydroxylated fullerene in a mass ratio of (30-40) fullerene to (60-80) hydrogen peroxide. (1.2) Weigh lysine diisocyanate, dibutyltin dilaurate, and hydroxylated fullerene into a reaction vessel and heat in an oil bath at 70-90°C for 6-10 h. Filter the product, extract the filter cake with acetone, and dry it in a vacuum oven at 80-100°C to obtain modified fullerene. The mass ratio of lysine diisocyanate, catalyst dibutyltin dilaurate, and hydroxylated fullerene is (4-6):(0.2-0.4):(20-30); (1.3) Weigh a certain amount of modified fullerene, polypropylene, and antioxidant, mix and stir evenly to obtain a mixture; The mass ratio of modified fullerene, polypropylene and antioxidant is (10-12): (40-60): (0.1-0.3); (1.4) The mixed material is extruded and granulated to obtain antistatic masterbatch.

2. An antistatic masterbatch, characterized in that: The antistatic masterbatch is prepared by the method according to claim 1.

3. A high-performance antistatic PP sheet, characterized in that: The PP sheet is made of the following components in parts by weight: PP 50-70 parts, 10-16 parts of the antistatic masterbatch prepared by the preparation method according to claim 1, 16-20 parts of basalt fiber, SEBS-g-MAH 0.2 parts to 0.4 parts, Antioxidant 0.1 part -0.5 part 4. The high-performance antistatic PP sheet according to claim 3, characterized in that: The antioxidant is one or more 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. The method for preparing a high-performance antistatic PP sheet according to claim 3 or 4, characterized in that: The preparation method comprises the following steps: (2.1) Weigh 50-70 parts by weight of PP, 10-16 parts by weight of antistatic masterbatch, 0.2-0.4 parts by weight of SEBS-g-MAH, and 0.1-0.5 parts by weight of antioxidant, mix and stir to obtain a mixture; (2.2) The mixed material is added to a twin-screw extruder and extruded by screw to form a prepreg tape uniformly with 16-20 parts of basalt fiber; the twin-screw extruder includes six temperature zones arranged in sequence, with the temperature of zone 1 being 160-180°C, the temperature of zone 2 being 210-230°C, the temperature of zone 3 being 210-230°C, the temperature of zone 4 being 210-230°C, the temperature of zone 5 being 210-230°C, the temperature of zone 6 being 210-230°C, the temperature of die head being 210-230°C, and the screw speed being 200-260 r / min; (2.3) The prepreg tape is pressed into a structural plate by hot pressing at a temperature of 210-230°C.

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