PBT / PET material, its preparation method and application

Abstract

The application discloses a PBT / PET material which comprises the following components in parts by weight: 40-50 parts of PBT resin; 5-30 parts of PET; 15-35 parts of glass fiber; 10-18 parts of bromine flame retardant; 1-3 parts of poly-pentabromobenzyl acrylate; 3-5 parts of sodium antimonate; and 0.1-0.2 parts of monovalent or divalent metal phosphate. The PBT / PET material has the advantages of good formability, good laser marking performance and good heat resistance.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, and in particular to a PBT / PET material, its preparation method, and its applications. Background Technology

[0002] As one of the five major engineering plastics, polybutylene terephthalate (PBT) is widely used in various fields, such as electronics, lighting, home appliances, and automobiles, due to its excellent processing performance, solvent resistance, electrical properties, and heat resistance. With increasing environmental awareness, more and more brands are requiring the addition of recycled plastics to their materials to reduce plastic pollution and achieve high-value utilization of waste plastics. Recycled PET is widely available and of stable quality, with properties similar to PBT, making it ideal for recycling in PBT materials. However, the addition of recycled PET and flame retardants degrades the molding performance and reduces the heat resistance of PBT / PET alloy materials, leading to issues such as film sticking and shrinkage during molding, and heat deformation during use. Summary of the Invention

[0003] The purpose of this invention is to overcome the above-mentioned technical defects and provide a PBT / PET material with good formability, good laser marking performance, and good heat resistance.

[0004] This invention is achieved through the following technical solution: A PBT / PET material, by weight, comprises the following components: 40-50 parts of PBT resin; PET 5-30 portions; 15-35 parts glass fiber; 10-18 parts of brominated flame retardant; 3-5 parts sodium antimonate; 1-3 parts of pentabromobenzyl polyacrylate; 0.1-0.2 parts of monovalent or divalent metal phosphates.

[0005] Preferably, the composition includes 3.5-4.5 parts sodium antimonate and 1.8-2.5 parts pentabromobenzyl polyacrylate. The average diameter of the glass fiber is ≤13μm.

[0006] The brominated flame retardant is selected from at least one of brominated epoxy, brominated polystyrene, polybrominated styrene, brominated polycarbonate, decabromodiphenyl ethane, and bromotriazine; brominated polystyrene is preferred.

[0007] The monovalent or divalent metal phosphate is selected from at least one of sodium dihydrogen phosphate, disodium dihydrogen pyrophosphate, tricalcium phosphate, and zinc dihydrogen phosphate. Preferably, the monovalent or divalent metal phosphate is selected from zinc dihydrogen phosphate.

[0008] The PET can be recycled material and / or virgin material. Recycled PET can be derived from PET-containing components such as mineral water bottles and purified water bottles, with an intrinsic viscosity of 0.65-0.78 dL / g (25℃), and the solvent is phenol / tetrachloroethane (mass ratio 1:1). The testing method is in accordance with GB / T 14190-2017.

[0009] Whether to add 0-1% additives can be selected based on actual conditions; the additives are selected from at least one of antioxidants and lubricants. The lubricant is one or more of aliphatic carboxylic acid esters, erucamide, ethylene bis-stearamide, montan esters, polyethylene wax, and oxidized polyethylene wax. The antioxidant is a composite antioxidant system composed of one or more of hindered phenolic antioxidants, phosphite antioxidants, and organosulfur antioxidants.

[0010] The method for preparing PBT / PET material of the present invention includes the following steps: mixing the components evenly according to the formula, and granulating by extrusion through a twin-screw extruder (screw temperature range is 230-260℃, rotation speed range is 200-500 rpm) to obtain PBT / PET material.

[0011] The present invention relates to the application of PBT / PET materials in the preparation of electrical components.

[0012] The present invention has the following beneficial effects: This invention inhibits the transesterification reaction between PBT and PET by using sodium antimonate and monovalent or divalent metal phosphates, thereby increasing the crystallization temperature of the PBT / PET material and improving its crystallization properties, thus enhancing its processing performance and heat resistance. Simultaneously, in the field of electrical components, materials are often required to have laser marking capabilities. Adding laser marking agents is a common solution; however, laser marking agents are expensive. This invention improves laser marking performance while achieving flame retardancy by adding a small amount of sodium antimonate and pentabromobenzyl polyacrylate. Detailed Implementation

[0013] The present invention will now be described in detail with reference to specific embodiments. These embodiments will help those skilled in the art to further understand the present invention, but do not limit the invention in any way. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention. These all fall within the scope of protection of the present invention.

[0014] The raw materials used in this invention are sourced from the following sources: PBT Resin 1: Changchun PBT 1200-211M; PBT resin 2: Yizheng PBT GX112; Recycled PET resin: recycled material, Yonghong PET-YH002, intrinsic viscosity 0.73 dL / g (25℃); New PET resin: New material, Yizheng PET BG80, intrinsic viscosity 0.79 dL / g (25℃).

[0015] Brominated polystyrene: SAYTEX 621, Albemarle; Brominated polycarbonate: FG-8500, Teijin; Brominated epoxy: F-2100, Israel Chemicals; Poly(pentabromobenzyl) acrylate: Israel Chemicals FR-1025; Sodium antimonate: SA-F, Chengdu launch; Fiberglass: Jushi Fiberglass ECS11-4.5-534A, diameter 11 micrometers; Disodium dihydrogen pyrophosphate: Nagase Co., Ltd., DHPP; Sodium dihydrogen phosphate: Lianyungang Xidu, MSP2040; Tricalcium phosphate: Budenheim, C13-09; Zinc dihydrogen phosphate: Budenheim, BUDIT T21; Antioxidant: Antioxidant 1010 and Antioxidant 168 were mixed in a ratio of 1:3, commercially available, and the same antioxidants were used in the examples and comparative examples; Lubricant: PETs, aliphatic carboxylic acid esters, commercially available, and the same lubricant was used in the examples and comparative examples.

[0016] The preparation method of PBT / PET materials in the examples and comparative examples includes the following steps: according to the formula, the components are mixed evenly, and granulated by extrusion through a twin-screw extruder (the screw temperatures of each section of the twin-screw extruder from the feed port to the die head are 230℃, 240℃, 240℃, 250℃, 260℃, 250℃, 240℃, 230℃, and 230℃ respectively; the screw speed is 400 rpm) to obtain PBT / PET materials.

[0017] Test methods: (1) Molding evaluation: The demolding force was measured with reference to Chinese patent CN202020371834.4, in bar. The lower the demolding force, the better.

[0018] (2) Heat resistance evaluation: Deformation test. The obtained PBT / PET material granules were baked in an oven at 120℃ for 4 hours, and then injection molded into a 125×13.0×1.0mm sample. A 10g weight was added to the middle of the sample, and it was placed in an oven with a span of 7cm and a temperature of 85℃ for 40 minutes. After cooling, the height from the top of the sample to the horizontal plane was measured as the deformation degree, in mm. The lower the deformation degree, the better the heat resistance.

[0019] (3) Laser marking test: The square plate was laser marked with a laser marking machine, and the color difference ΔE of the square plate before and after laser marking was measured with a spectrophotometer. The laser marking machine used was a TFL-M20 (Shenzhen Taide Laser Technology Co., Ltd.), and the marking parameters were: power of 60% of rated power, frequency of 20KHz, and speed of 1500mm / s.

[0020] Table 1: Weight contents and test results of each component in PBT / PET materials of Examples 1-4 PBT resin 1 50 40 PBT resin 2 40 40 Recycled PET resin 5 30 30 New PET resin 30 Fiberglass 15 15 15 15 Brominated polystyrene 10 10 10 10 Polypentabromobenzyl acrylate 1 1 1 1 Sodium antimonate 3 3 3 3 Sodium dihydrogen pyrophosphate 0.1 0.1 0.1 0.1 antioxidants 0.1 0.1 0.1 0.1 lubricant 0.3 0.3 0.3 0.3 Demolding force, bar 121 150 152 147 Deformation, mm 0.9 3.0 3.1 2.9 Color difference △E 16.2 16.3 16.3 16.5 As can be seen from Examples 3 and 4, the present invention is applicable to recycled PET and virgin PET.

[0021] Table 2: Weight contents and test results of each component in PBT / PET materials of Examples 5-10 PBT resin 2 40 40 40 40 40 40 Recycled PET resin 30 30 30 30 30 30 Fiberglass 15 15 15 15 15 35 Brominated polystyrene 10 10 10 18 Brominated polycarbonate 10 Brominated epoxy 10 Polypentabromobenzyl acrylate 1 1 1 1 1 1 Sodium antimonate 3 3 3 3 3 3 Sodium dihydrogen pyrophosphate 0.1 0.1 0.2 Sodium dihydrogen phosphate 0.1 Tricalcium phosphate 0.1 Zinc dihydrogen phosphate 0.1 antioxidants 0.1 0.1 0.1 0.1 0.1 0.1 lubricant 0.3 0.3 0.3 0.3 0.3 0.3 Demolding force, bar 169 171 166 164 161 143 Deformation, mm 4.2 4.3 4.2 4.2 3.8 2.2 Color difference △E 16.4 16.3 16.3 16.4 16.3 16.8 As can be seen from Examples 3 / 5 / 6, brominated polystyrene is preferred as the flame retardant, resulting in lower demolding force and smaller deformation.

[0022] As can be seen from Examples 3 / 7-9, monovalent or divalent metal phosphates are preferred, especially zinc dihydrogen phosphate, which has a lower release force, indicating that it has a stronger ability to inhibit transesterification.

[0023] When Example 10 contains more glass fiber and is within the scope of the present invention, its deformation and demolding force are less than those of other examples.

[0024] Table 3: Weight Parts of Each Component and Test Results of PBT / PET Materials Implemented in 11-13 PBT resin 1 40 40 40 Recycled PET resin 30 30 30 Fiberglass 15 15 15 Brominated polystyrene 10 10 10 Polypentabromobenzyl acrylate 1.9 2.4 3 Sodium antimonate 4.4 3.6 3 Sodium dihydrogen pyrophosphate 0.1 0.1 0.1 antioxidants 0.1 0.1 0.1 lubricant 0.3 0.3 0.3 Demolding force, bar 151 153 153 Deformation, mm 3.0 3.0 3.1 Color difference △E 17.7 18.8 18.0 As can be seen from Examples 2 / 11-13, the overall performance is better when the content of pentabromobenzyl polyacrylate and sodium antimonate is optimal.

[0025] Table 4: Weight Parts of Each Component and Test Results of Comparative PBT / PET Materials PBT resin 2 40 40 40 40 Recycled PET resin 30 30 30 30 Fiberglass 15 15 15 15 Brominated polystyrene 10 10 10 10 Polypentabromobenzyl acrylate 5 1 1 Sodium antimonate 3 3 0 3 Sodium dihydrogen pyrophosphate 0.1 0.1 0.1 antioxidants 0.1 0.1 0.1 0.1 lubricant 0.3 0.3 0.3 0.3 Demolding force, bar 150 155 152 179 Deformation, mm 3.0 3.1 3.1 5.1 Color difference △E 11.2 15.8 15.3 16.1 As shown in Comparative Example 1, an appropriate amount of pentabromobenzyl polyacrylate can improve the color difference after laser marking, indicating that the laser marking performance has been improved.

[0026] As shown in Comparative Example 2, if the content of pentabromobenzyl bromide in brominated polyacrylate is too high, the color difference will actually decrease.

[0027] As shown in Comparative Example 3, the ability of polypentabromobenzyl acrylate to improve laser marking performance is limited if it does not contain sodium antimonate.

[0028] As shown in Comparative Example 4, the absence of disodium dihydrogen pyrophosphate significantly degrades various performance characteristics.

Claims

1. A PBT / PET material, characterized in that, By weight, it includes the following components: 40-50 parts of PBT resin; PET 5-30 portions; 15-35 parts glass fiber; 10-18 parts of brominated flame retardant; 3.5-4.5 parts sodium antimonate; 1.8-2.5 parts of pentabromobenzyl polyacrylate; 0.1-0.2 parts of monovalent or divalent metal phosphates; The monovalent or divalent metal phosphate is selected from disodium dihydrogen pyrophosphate.

2. The PBT / PET material according to claim 1, characterized in that, The average diameter of the glass fiber is ≤13μm.

3. The PBT / PET material according to claim 1, characterized in that, The brominated flame retardant is selected from at least one of brominated epoxy, brominated polystyrene, polybrominated styrene, brominated polycarbonate, decabromodiphenyl ethane, and bromotriazine.

4. The PBT / PET material according to claim 3, characterized in that, The brominated flame retardant is selected from brominated polystyrene.

5. The PBT / PET material according to claim 1, characterized in that, The PET mentioned is recycled material and / or virgin material.

6. The PBT / PET material according to claim 1, characterized in that, The product also includes 0-1 parts by weight of additives; the additives are selected from at least one of antioxidants and lubricants.

7. A method for preparing the PBT / PET material according to any one of claims 1-6, characterized in that, The process includes the following steps: mixing the components evenly according to the formula, and granulating them by extrusion through a twin-screw extruder to obtain the PBT / PET composite material.

8. The application of the PBT / PET material according to any one of claims 1-6, characterized in that, Manufacturing electrical components.