Flame-retardant PET composite material and preparation method thereof

Abstract

The invention belongs to the technical field of high polymer materials, and particularly relates to a flame-retardant PET (polyethylene terephthalate) composite material and a preparation method thereof, and the flame-retardant PET composite material comprises the following components in parts by weight: 90-100 parts of PET, 16-18 parts of decabromodiphenyl ethane, 3-5 parts of a synergistic flame retardant and 0.1-0.5 part of an antioxidant. The flame-retardant PET composite material prepared by the invention has excellent flame-retardant property, the flame-retardant property of the PET composite material can be well improved by using the specific synergistic flame retardant, and the flame-retardant PET composite material has great popularization value.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials, and particularly relates to a flame-retardant PET composite material and a preparation method thereof. Background Art

[0002] Polyethylene terephthalate (PET) is a widely used polymer polyester resin. PET has advantages such as good fatigue resistance, good heat resistance, and excellent dimensional stability. However, in some specific application fields, PET has high flame retardant properties. Ordinary PET materials can no longer meet this requirement, which limits the application of PET composite materials in some specific fields.

[0003] In response to this situation, the present invention innovatively produces a PET composite material with excellent flame retardant properties. This material has not been reported so far, which has very important practical significance for expanding the application of PET composite materials. Summary of the Invention

[0004] The object of the present invention is to provide a flame-retardant PET composite material and a preparation method thereof, which has excellent flame retardant properties and solves the problems existing in PET in the above-mentioned background technology.

[0005] To achieve the above objectives, this application is implemented through the following technical solutions:

[0006] A flame-retardant PET composite material is made from the following components in parts by weight:

[0007] PET 90-100 parts,

[0008] Decabromodiphenylethane 16-18 parts,

[0009] 3-5 parts of synergistic flame retardant,

[0010] Antioxidant 0.1 part -0.5 part

[0011] Furthermore, the synergistic flame retardant consists of ZnAl2O4, triphenyl phosphate and fluorinated silicon dioxide.

[0012] Furthermore, the weight ratio of ZnAl2O4, triphenyl phosphate and fluorinated silicon dioxide is 5:3:2.

[0013] Furthermore, the preparation method of the synergistic flame retardant adopts the following steps:

[0014] S1. Weigh a predetermined amount of zinc nitrate, aluminum nitrate, potassium acetate, anhydrous ethanol, and deionized water into a reaction vessel, pass ammonia gas through the vessel, and react in a water bath at 60-80°C for 8-16 hours to obtain solution A.

[0015] S2. Adding fluorinated silicon dioxide to solution A, mixing well, filtering, washing, and drying to obtain composition B;

[0016] S3. Add triphenyl phosphate to anhydrous ethanol to obtain solution C, add composition B to solution C, mix well, filter, wash, and dry to obtain a synergistic flame retardant.

[0017] Furthermore, the preparation method of the synergistic flame retardant adopts the following steps:

[0018] S4. Weigh a predetermined amount of zinc nitrate, aluminum nitrate, potassium acetate, anhydrous ethanol, and deionized water, place them in a reaction vessel, pass ammonia gas through the vessel, and react in a water bath at 60-80° C. for 8-16 hours to obtain solution A.

[0019] S5. Add fluorinated silicon dioxide and triphenyl phosphate to solution A, mix well, filter, wash, and dry to obtain a synergistic flame retardant.

[0020] Furthermore, in step S1 or step S4, the mass ratio of zinc nitrate, aluminum nitrate, potassium acetate, anhydrous ethanol, deionized water, and ammonia is (30-40): (30-36): (40-44): (60-66): (70-76): (28-32).

[0021] Furthermore, the antioxidant is one or a mixture of tris(2,4-di-tert-butyl)phenyl phosphite, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate or 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxybenzyl)benzene.

[0022] A method for preparing a flame-retardant PET composite material comprises the following steps:

[0023] (1) Weigh 90-100 parts of PET, 16-18 parts of decabromodiphenylethane, 3-5 parts of synergistic flame retardant, and 0.1-0.5 parts of antioxidant, mix and stir evenly to obtain a mixture;

[0024] (2) The mixed material obtained in step (1) is extruded from an extruder and granulated to obtain a PET composite material.

[0025] Furthermore, the step (2) is specifically as follows:

[0026] The mixed material obtained in step (1) is put into the hopper of a twin-screw extruder for extrusion and granulation to obtain a PET composite material, wherein the twin-screw extruder includes six temperature zones arranged in sequence, the temperature of zone 1 is 240-260°C, the temperature of zone 2 is 280-300°C, the temperature of zone 3 is 280-300°C, the temperature of zone 4 is 280-300°C, the temperature of zone 5 is 280-300°C, the temperature of zone 6 is 280-300°C, the head temperature is 280-300°C, and the screw speed is 200-280r / min.

[0027] The beneficial effects of the present invention are:

[0028] The flame retardant mechanism of ZnAl2O4 in the synergistic flame retardant of this invention is as follows: ZnAl2O4 absorbs a large amount of heat at high temperatures, lowering the surface temperature of the material, thereby slowing or preventing the spread of flames. The decomposition of ZnAl2O4 releases water vapor, which dilutes the concentration of combustible gases and oxygen, thus acting as a suffocating agent.

[0029] 2. When burning, fluorinated silicon dioxide combines with the residual carbon of the phosphorus and nitrogen flame retardant to form a dense carbon layer, isolating oxygen and preventing gas transfer.

[0030] 3. This application synthesizes a new type of synergistic flame retardant, which can greatly improve the flame retardant properties of PET composite materials and has great promotion value. DETAILED DESCRIPTION

[0031] The technical solution of the present invention is described in detail below with reference to the embodiments. The following embodiments are merely exemplary and can only be used to explain and illustrate the technical solution of the present invention, and cannot be interpreted as limiting the technical solution of the present invention.

[0032] In the following description, many specific details are set forth to facilitate a full understanding of the present invention. However, the present invention may also be implemented in other ways different from those described herein. Those skilled in the art may make similar generalizations without violating the connotation of the present invention. Therefore, the present invention is not limited to the specific embodiments disclosed below.

[0033] The raw materials and instruments used in the following examples of this application can be obtained through commercial channels, and the specific sources are not described here.

[0034] The preparation method of the fluorinated silica involved in the following examples of this application is to vacuum dry the nano-silica at 120°C for 6 hours, disperse it in anhydrous acetic acid, add perfluorooctyltriethoxysilane, reflux at 80°C for 6 hours, centrifuge, filter, wash until neutral, and dry at 80°C to obtain nano-fluorinated silica.

[0035] Specifically, the usage ratio of nano-silica, anhydrous acetic acid and perfluorooctyltriethoxysilane is 20g:200ml:1g.

[0036] During combustion, fluorinated silica combines with the polymer surface and the carbon residue of triphenyl phosphate, promoting the formation of a better and denser carbon layer on the polymer surface, further isolating oxygen and heat transfer.

[0037] Preparation Example 1

[0038] Preparation of synergistic flame retardant M1:

[0039] S1. Weigh 300 g of zinc nitrate, 300 g of aluminum nitrate, 400 g of potassium acetate, 600 g of anhydrous ethanol, and 700 g of deionized water, place them in a reaction vessel, pass 280 g of ammonia gas through them, and react in a 60°C water bath for 8 h to obtain solution A.

[0040] S2. Add 77 g of fluorinated silica to solution A, mix well, filter, wash, and dry to obtain composition B;

[0041] S3. Add 51 g of triphenyl phosphate to 400 g of anhydrous ethanol to obtain solution C, add composition B to solution C, mix well, filter, wash, and dry to obtain synergistic flame retardant M1.

[0042] Example 1

[0043] (1) Weigh 90 parts of PET, 16 parts of decabromodiphenylethane, 3 parts of synergistic flame retardant M1, and 0.1 parts of antioxidant Irganox 1010, mix and stir evenly to obtain a mixture;

[0044] (2) The mixed material obtained in step (1) is extruded from an extruder and granulated to obtain a PET composite material P1.

[0045] The temperature and screw speed of each zone of the twin-screw extruder are: zone 1 temperature 240℃, zone 2 temperature 280℃, zone 3 temperature 280℃, zone 4 temperature 280℃, zone 5 temperature 280℃, zone 6 temperature 280℃, die head temperature 280℃, screw speed 200r / min.

[0046] Preparation Example 2

[0047] S1. Weigh 400 g of zinc nitrate, 360 g of aluminum nitrate, 440 g of potassium acetate, 660 g of anhydrous ethanol, and 760 g of deionized water into a reaction vessel, pass 320 g of ammonia gas through the mixture, and react in an 80°C water bath for 16 h to obtain solution A.

[0048] S2. Add 93 g of fluorinated silica to solution A, mix well, filter, wash, and dry to obtain composition B;

[0049] S3. Add 62 g of triphenyl phosphate to 300 g of anhydrous ethanol to obtain solution C, add composition B to solution C, mix well, filter, wash, and dry to obtain synergistic flame retardant M2.

[0050] Example 2

[0051] (1) Weigh 100 parts of PET, 18 parts of decabromodiphenylethane, 5 parts of synergistic flame retardant M2, 0.1 parts of Irganox 1010, 0.2 parts of Irganox 168, and 0.2 parts of Irganox 1330, mix and stir evenly to obtain a mixture;

[0052] (2) The mixed material obtained in step (1) is extruded from an extruder and granulated to obtain a PET composite material P2.

[0053] The temperature and screw speed of each zone of the twin-screw extruder are: zone 1 temperature 260℃, zone 2 temperature 300℃, zone 3 temperature 300℃, zone 4 temperature 300℃, zone 5 temperature 300℃, zone 6 temperature 300℃, head temperature 300℃, screw speed 280r / min.

[0054] Preparation Example 3

[0055] S1. Weigh 350 g of zinc nitrate, 330 g of aluminum nitrate, 420 g of potassium acetate, 630 g of anhydrous ethanol, and 730 g of deionized water into a reaction vessel, pass 300 g of ammonia gas through the mixture, and react in an 80°C water bath for 12 h to obtain solution A.

[0056] S2. Add 84 g of fluorinated silica to solution A, mix well, filter, wash, and dry to obtain composition B;

[0057] S3. Add 56 g of triphenyl phosphate to 300 g of anhydrous ethanol to obtain solution C, add composition B to solution C, mix well, filter, wash, and dry to obtain synergistic flame retardant M3.

[0058] Example 3

[0059] (1) Weigh 95 parts of PET, 17 parts of decabromodiphenylethane, 4 parts of synergistic flame retardant M3, 0.1 parts of Irganox 168, and 0.2 parts of Irganox 1010, mix and stir to obtain a mixture;

[0060] (2) The mixed material obtained in step (1) is extruded from an extruder and granulated to obtain a PET composite material P3.

[0061] The temperatures and screw speeds of each zone of the twin-screw extruder are: zone 1 temperature 250°C, zone 2 temperature 290°C, zone 3 temperature 290°C, zone 4 temperature 290°C, zone 5 temperature 290°C, zone 6 temperature 290°C, die head temperature 290°C, and screw speed 240r / min.

[0062] Preparation Example 4

[0063] (1) Weigh 335 g of zinc nitrate, 358 g of aluminum nitrate, 435 g of potassium acetate, 655 g of anhydrous ethanol, and 745 g of deionized water into a reaction vessel, pass 315 g of ammonia gas through the vessel, and react in a 78 °C water bath for 13 h to obtain solution A.

[0064] (2) Add 92 g of fluorinated silica and 61 g of triphenyl phosphate to solution A, mix well, filter, wash, and dry to obtain synergistic flame retardant M4.

[0065] Example 4

[0066] (1) Weigh 98 parts of PET, 17.5 parts of decabromodiphenylethane, 4.5 parts of synergistic flame retardant M4, 0.1 parts of Irganox 1010, and 0.2 parts of Irganox 1330, mix and stir to obtain a mixture;

[0067] (2) The mixed material obtained in step (1) is extruded from an extruder and granulated to obtain a PET composite material P4.

[0068] The temperatures and screw speeds of each zone of the twin-screw extruder are: zone 1 temperature 245°C, zone 2 temperature 285°C, zone 3 temperature 285°C, zone 4 temperature 285°C, zone 5 temperature 285°C, zone 6 temperature 285°C, die head temperature 285°C, and screw speed 255r / min.

[0069] Preparation Example 5

[0070] (1) Weigh 368 g of zinc nitrate, 349 g of aluminum nitrate, 434 g of potassium acetate, 655 g of anhydrous ethanol, and 735 g of deionized water into a reaction vessel, pass 295 g of ammonia gas through the vessel, and react in a 67 °C water bath for 10 h to obtain solution A.

[0071] (2) Add 87 g of fluorinated silica and 5 g of triphenyl phosphate to solution A, mix well, filter, wash, and dry to obtain synergistic flame retardant M5.

[0072] Example 5

[0073] (1) Weigh 98 parts of PET, 16.5 parts of decabromodiphenylethane, 3.8 parts of synergistic flame retardant M5, 0.1 parts of Irganox 1010, and 0.1 parts of Irganox 168, mix and stir to obtain a mixture;

[0074] (2) The mixed material obtained in step (1) is extruded from an extruder and granulated to obtain a PET composite material P5.

[0075] The temperatures and screw speeds of each zone of the twin-screw extruder are: zone 1 temperature 250°C, zone 2 temperature 295°C, zone 3 temperature 295°C, zone 4 temperature 295°C, zone 5 temperature 295°C, zone 6 temperature 295°C, die head temperature 295°C, and screw speed 270r / min.

[0076] Comparative Example 1

[0077] (1) Weigh 98 parts of PET, 16.5 parts of decabromodiphenylethane, 3.8 parts of synergistic flame retardant antimony trioxide, 0.1 part of Irganox 1010, and 0.1 part of Irganox 168, mix and stir to obtain a mixture;

[0078] (2) The mixed material obtained in step (1) is extruded from an extruder and granulated to obtain a PET composite material D1.

[0079] The temperatures and screw speeds of each zone of the twin-screw extruder are: zone 1 temperature 250°C, zone 2 temperature 295°C, zone 3 temperature 295°C, zone 4 temperature 295°C, zone 5 temperature 295°C, zone 6 temperature 295°C, die head temperature 295°C, and screw speed 270r / min.

[0080] The PET composite materials prepared in Examples 1-5 and Comparative Example 1 were made into test strips using an injection molding machine. The test data are shown in the following table:

[0081]

[0082] It can also be seen from the table that the flame retardant properties of Examples 1-5 are better than that of Comparative Example 1. This greatly expands the application field of PET composite materials and is of great significance.

[0083] The above disclosures are only a few specific embodiments of the present application, but the present application is not limited thereto. Any changes that can be conceived by those skilled in the art should fall within the scope of protection of the present application.

Claims

1. A flame retardant PET composite material, characterized in that: Made from the following components in parts by weight: PET 90-100 parts, Decabromodiphenylethane 16-18 parts, 3-5 parts of synergistic flame retardant, Antioxidant 0.1 part -0.5 part 2. The flame retardant PET composite material according to claim 1, characterized in that The synergistic flame retardant consists of ZnAl2O4, triphenyl phosphate and fluorinated silicon dioxide.

3. The flame retardant PET composite material according to claim 2, characterized in that The weight ratio of ZnAl2O4, triphenyl phosphate and fluorinated silicon dioxide is 5:3:

2.

4. The flame retardant PET composite material according to claim 1, characterized in that The preparation method of the synergistic flame retardant comprises the following steps: S1. Weigh a predetermined amount of zinc nitrate, aluminum nitrate, potassium acetate, anhydrous ethanol, and deionized water into a reaction vessel, pass ammonia gas through the vessel, and react in a water bath at 60-80°C for 8-16 hours to obtain solution A. S2. Adding fluorinated silicon dioxide to solution A, mixing well, filtering, washing, and drying to obtain composition B; S3. Add triphenyl phosphate to anhydrous ethanol to obtain solution C, add composition B to solution C, mix well, filter, wash, and dry to obtain a synergistic flame retardant.

5. The flame retardant PET composite material according to claim 1, characterized in that The preparation method of the synergistic flame retardant comprises the following steps: S4. Weigh a predetermined amount of zinc nitrate, aluminum nitrate, potassium acetate, anhydrous ethanol, and deionized water, place them in a reaction vessel, pass ammonia gas through the vessel, and react in a water bath at 60-80° C. for 8-16 hours to obtain solution A. S5. Add fluorinated silicon dioxide and triphenyl phosphate to solution A, mix well, filter, wash, and dry to obtain a synergistic flame retardant.

6. The flame retardant PET composite material according to claim 4 or 5, characterized in that In step S1 or step S4, the mass ratio of zinc nitrate, aluminum nitrate, potassium acetate, anhydrous ethanol, deionized water, and ammonia is (30-40): (30-36): (40-44): (60-66): (70-76): (28-32).

7. The flame retardant PET composite material according to claim 1, characterized in that: The antioxidant is one or a mixture of tris(2,4-di-tert-butyl)phenyl phosphite, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate or 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxybenzyl)benzene.

8. A method for preparing a flame-retardant PET composite material, characterized in that: The following steps are involved: (1) Weigh 90-100 parts of PET, 16-18 parts of decabromodiphenylethane, 3-5 parts of synergistic flame retardant, and 0.1-0.5 parts of antioxidant, mix and stir evenly to obtain a mixture; (2) The mixed material obtained in step (1) is extruded from an extruder and granulated to obtain a PET composite material.

9. The method for preparing the flame-retardant PET composite material according to claim 8, wherein: The step (2) is specifically as follows: The mixed material obtained in step (1) is put into the hopper of a twin-screw extruder for extrusion and granulation to obtain a PET composite material, wherein the twin-screw extruder includes six temperature zones arranged in sequence, the temperature of zone 1 is 240-260°C, the temperature of zone 2 is 280-300°C, the temperature of zone 3 is 280-300°C, the temperature of zone 4 is 280-300°C, the temperature of zone 5 is 280-300°C, the temperature of zone 6 is 280-300°C, the head temperature is 280-300°C, and the screw speed is 200-280r / min.

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