Polyester composite material as well as preparation method and application thereof

Abstract

The invention provides a polyester composite material as well as a preparation method and application thereof. The polyester composite material comprises polybutylene terephthalate, polycarbonate, a bromine-containing flame retardant, a synergistic flame retardant and a toughening agent in specific parts, the bromine-containing flame retardant comprises a combination of at least two of brominated epoxy resin, brominated polycarbonate or brominated polystyrene; polybutylene terephthalate and polycarbonate are selected to be matched, and at least two specific bromine-containing flame retardants and synergistic flame retardants are added for flame retardant modification, so that the obtained polyester composite material not only has excellent flame retardant property, but also has lower amount of precipitation in a mouth mold when being extruded by a mold head of an extruder; further, the problem that die precipitates are carbonized at high temperature and then flow into a product to pollute the product can be effectively avoided, and the product quality of the finally obtained polyester composite material is effectively improved.

Description

Technical Field

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

[0002] Polybutylene terephthalate (PBT) is an engineering plastic of the polyester series. It has high mechanical strength, toughness, fatigue resistance, self-lubrication, outstanding chemical resistance, heat resistance and excellent electrical properties, but its disadvantages are low notch impact strength and large molding shrinkage. Polycarbonate resin (PC) is one of the five major engineering plastics and is an excellent thermoplastic engineering plastic. It is widely used in electronics, automotive industry, medical equipment, aerospace and other fields, but its melt viscosity is high and its processing performance is poor. Therefore, blending and modifying PC and PBT can not only make up for the shortcomings of PC such as high melt viscosity, poor fluidity and poor solvent resistance, but also improve the defects of PBT such as low impact resistance, achieving synergistic synergy.

[0003] However, the flame retardant properties of PC / PBT composite materials are poor, so it is usually necessary to add flame retardants to improve the flame retardant properties of the materials, and the mechanical properties of the materials should not be affected. For example, CN110885545A discloses a weather-resistant flame-retardant PC / PBT alloy and a preparation method thereof, comprising 50-60 parts of PC resin; 10-30 parts of PBT resin; 10-13 parts of BDP flame retardant; 1-5 parts of compatibilizer; 1-3 parts of MBS toughening agent; 0.3-0.8 parts of polytetrafluoroethylene; 0.2-0.4 parts of antioxidant; 0.3-0.5 parts of lubricant; PC resin, PBT resin, compatibilizer, MBS toughening agent, polytetrafluoroethylene, antioxidant, lubricant, ultraviolet absorber are dried and then mixed with BDP flame retardant, and then melted, extruded, cooled, air-dried and granulated to obtain PC / PBT alloy, so that the PC / PBT alloy has good flame retardant properties and weather resistance.

[0004] However, in actual production, during the alloying production process of PC and PBT, the mixed material will precipitate out of the die at the die head of the extruder. As time goes by, the precipitate precipitated out of the die will carbonize at high temperature. The carbonized precipitate will flow into the product, thereby contaminating the product, causing the product to be contaminated with colored particles and deteriorating its quality.

[0005] Therefore, developing a polyester composite material with low die precipitates and excellent flame retardant properties is still a technical problem that needs to be urgently solved in the field. Summary of the invention

[0006] In view of the deficiencies in the prior art, the object of the present invention is to provide a polyester composite material and a preparation method and application thereof. The polyester composite material has excellent flame retardant properties, and at the same time, the amount of precipitation at the die of the extruder die is low, and the precipitate carbonization time is long, thereby effectively reducing the probability of the die precipitate flowing into the product after carbonization and causing contamination to the product.

[0007] To achieve this object, the present invention adopts the following technical solutions:

[0008] In a first aspect, the present invention provides a polyester composite material, wherein the polyester composite material comprises the following components in parts by weight:

[0009]

[0010] The bromine-containing flame retardant comprises a combination of at least two of brominated epoxy resin, brominated polycarbonate or brominated polystyrene.

[0011] The polyester composite material provided by the present invention comprises specific portions of polybutylene terephthalate, polycarbonate, a bromine-containing flame retardant, a synergistic flame retardant and a toughening agent, and the bromine-containing flame retardant comprises a combination of at least two of brominated epoxy resin, brominated polycarbonate or brominated polystyrene; on the one hand, synergistic synergy is achieved by selecting polybutylene terephthalate and polycarbonate for combination; on the other hand, flame retardant modification is performed by adding a bromine-containing flame retardant and a synergistic flame retardant, and the bromine-containing flame retardant is limited to a combination of at least two of brominated epoxy resin, brominated polycarbonate or brominated polystyrene, so that the obtained polyester composite material not only has excellent flame retardant properties, but also has a lower die precipitation amount. When extruding at the extruder die head, there are less die precipitations, and the precipitates change color for a longer time, thereby effectively avoiding the problem that the die precipitations are carbonized at high temperature and flow into the product to pollute the product, and effectively improving the quality of the finally obtained polyester composite material.

[0012] Wherein, the content of the polybutylene terephthalate can be 20 parts by weight, 22 parts by weight, 24 parts by weight, 26 parts by weight, 28 parts by weight, 30 parts by weight, 32 parts by weight, 34 parts by weight, 36 parts by weight, 38 parts by weight, 40 parts by weight, 42 parts by weight, 44 parts by weight, 46 parts by weight, 48 parts by weight or 50 parts by weight, etc., and the mass percentage of polybutylene terephthalate in the polyester composite material provided by the present invention is ≥20%.

[0013] The content of the polycarbonate can be 20 parts by weight, 22 parts by weight, 24 parts by weight, 26 parts by weight, 28 parts by weight, 30 parts by weight, 32 parts by weight, 34 parts by weight, 36 parts by weight, 38 parts by weight, 40 parts by weight, 42 parts by weight, 44 parts by weight, 46 parts by weight, 48 parts by weight or 50 parts by weight, etc.

[0014] The content of the bromine-containing flame retardant may be 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, 16 parts by weight, etc.

[0015] The content of the synergistic flame retardant can be 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight or 5 parts by weight, etc.

[0016] The content of the toughening agent can be 0.5 parts by weight, 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight or 4 parts by weight, etc.

[0017] Preferably, the melt index of the polybutylene terephthalate is ≥5g / 10min, for example, 6g / 10min, 7g / 10min, 8g / 10min, 10g / 10min, 20g / 10min, 30g / 10min, 40g / 10min, 50g / 10min, 60g / 10min, 70g / 10min, 80g / 10min, 90g / 10min or 100g / 10min, and more preferably 5-100g / 10min, and the test temperature of the melt index is 250°C and the test load is 2.16kg.

[0018] Preferably, the intrinsic viscosity of the polybutylene terephthalate is ≥0.5dl / g, for example, 0.6dl / g, 0.7dl / g, 0.8dl / g, 0.9dl / g, 1dl / g, 1.1dl / g, 1.2dl / g, 1.3dl / g, 1.4dl / g, 1.5dl / g, 2dl / g, 3dl / g, 4dl / g, 5dl / g, 6dl / g, 7dl / g, 8dl / g, 9dl / g or 10dl / g, etc., more preferably 0.5-10dl / g, and the testing temperature of the intrinsic viscosity is 25°C.

[0019] Preferably, the melt index of the polycarbonate is ≤15g / 10min, for example, 14g / 10min, 13g / 10min, 12g / 10min, 10g / 10min, 9g / 10min, 8g / 10min, 7g / 10min, 6g / 10min, 5g / 10min, 4g / 10min, 3g / 10min, 2g / 10min or 1g / 10min, and the test temperature of the melt index is 300°C and the test load is 1.2kg.

[0020] In the present invention, the melt index of the polybutylene terephthalate and the polycarbonate can be tested according to the method provided in ISO1133-1:2022.

[0021] In the present invention, the intrinsic viscosity of the polybutylene terephthalate is tested by the capillary viscometer method in accordance with the GB / T 14190-2008 standard.

[0022] Preferably, the bromine-containing flame retardant is a combination of brominated epoxy resin and brominated polycarbonate, and the mass ratio of the brominated epoxy resin to the brominated polycarbonate is 1:(0.05-20), for example, 1:0.05, 1:0.1, 1:0.5, 1:1, 1:2, 1:4, 1:6, 1:8, 1:10, 1:12, 1:14, 1:16, 1:18, 1 or 20, etc., and more preferably 1:(0.1-10).

[0023] Preferably, the bromine-containing flame retardant is a combination of brominated epoxy resin and brominated polystyrene, and the mass ratio of the brominated epoxy resin to the brominated polystyrene ester is 1:(0.05-20), for example, 1:0.05, 1:0.1, 1:0.5, 1:1, 1:2, 1:4, 1:6, 1:8, 1:10, 1:12, 1:14, 1:16, 1:18, 1 or 20, etc., and more preferably 1:(0.1-10).

[0024] Preferably, the bromine-containing flame retardant is a combination of brominated polycarbonate and brominated polystyrene, and the mass ratio of the brominated polycarbonate to the brominated polystyrene is 1:(0.05-20), for example, 1:0.05, 1:0.1, 1:0.5, 1:1, 1:2, 1:4, 1:6, 1:8, 1:10, 1:12, 1:14, 1:16, 1:18, 1 or 20, etc., and more preferably 1:(0.1-10).

[0025] The present invention further limits the mass ratio of any two bromine-containing flame retardants in the bromine-containing flame retardants to the above-mentioned specific range, which can further reduce the amount of die precipitation of the final polyester composite material, prolong the time for the precipitate to change color, and further reduce the problem of carbonization of the die precipitate flowing into the product and contaminating the product, thereby improving the quality of the final polyester composite material.

[0026] Preferably, the bromine-containing flame retardant comprises a combination of brominated epoxy resin, brominated polycarbonate and brominated polystyrene, and the mass ratio of any two of the brominated epoxy resin, brominated polycarbonate and brominated polystyrene is 1:(0.05-20), more preferably 1:(0.1-10);

[0027] The mass ratio of the brominated epoxy resin to the brominated polycarbonate may be 1:0.05, 1:0.1, 1:0.5, 1:1, 1:2, 1:4, 1:6, 1:8, 1:10, 1:12, 1:14, 1:16, 1:18 or 1:20, and the mass ratio of the brominated epoxy resin to the brominated polystyrene may be 1:0.05, 1:0.1, 1:0.5, 1:1, 1:2, 1:4, 1:6, 1:8, 1:10, 1:12, 1:14, 1:16, 1:18 or 1:20, etc., and the mass ratio of the brominated polystyrene to the brominated polycarbonate can be 1:0.05, 1:0.1, 1:0.5, 1:1, 1:2, 1:4, 1:6, 1:8, 1:10, 1:12, 1:14, 1:16, 1:18 or 1:20, etc.

[0028] The present invention further selects the above three different types of bromine-containing flame retardants for compounding, and the three synergistically enhance the effect, which can further improve the flame retardant properties of the obtained polyester composite material, further reduce the amount of precipitation at the die of the extruder die head, and further improve the quality of the product.

[0029] Preferably, the weight average molecular weight of the brominated epoxy resin is ≥5000, for example, 5000, 6000, 7000, 8000, 9000, 10000, 12000, 14000, 15000, 16000, 17000, 18000, 19000, 20000, 21000, 22000, 23000, 24000 or 25000, more preferably ≥6000, and even more preferably 6000-30000.

[0030] Preferably, the weight average molecular weight of the brominated polycarbonate is ≥3000, for example, 3000, 4000, 4100, 4200, 4300, 4400, 4500, 4600, 4700, 4800, 4900, 5000, 5200, 5400, 5600, 5800 or 6000, more preferably ≥4000, and even more preferably 4000-8000.

[0031] Preferably, the weight average molecular weight of the brominated polystyrene is ≥5000, for example, 5000, 5500, 6000, 6500, 7000, 9000, 10000, 50000, 100000, 200000, 400000 or 600000, more preferably ≥7000, and even more preferably 7000-700000.

[0032] In the present invention, the weight average molecular weights of the brominated epoxy resin, brominated polycarbonate and brominated polystyrene are all measured by gel chromatography.

[0033] Preferably, the synergistic flame retardant comprises antimony trioxide.

[0034] Preferably, the toughening agent includes any one of ethylene-acrylate-glycidyl methacrylate copolymer, ethylene-acrylate copolymer, ethylene-vinyl acetate copolymer, methacrylate-styrene-silicone copolymer or methacrylate-styrene-butadiene copolymer, or a combination of at least two thereof.

[0035] In a second aspect, the present invention provides a method for preparing the polyester composite material as described in the first aspect, the preparation method comprising: mixing polybutylene terephthalate, polycarbonate, a bromine-containing flame retardant, a synergistic flame retardant and a toughening agent, extruding and granulating in an extruder to obtain the polyester composite material.

[0036] Preferably, the bromine-containing flame retardant is obtained by mixing brominated epoxy resin, brominated polycarbonate and brominated polystyrene.

[0037] Preferably, the mixing time is 2 to 5 min, for example, 2 min, 2.5 min, 3 min, 3.5 min, 4 min, 4.5 min or 5 min.

[0038] Preferably, the extruder is a single screw extruder.

[0039] Preferably, the extrusion temperature of the single screw extruder is 200-300°C, for example, 200°C, 220°C, 240°C, 260°C, 270°C, 280°C, 290°C or 300°C.

[0040] In a third aspect, the present invention provides an application of the polyester composite material as described in the first aspect in electronic and electrical, automotive industry, medical equipment or aerospace.

[0041] Compared with the prior art, the present invention has the following beneficial effects:

[0042] (1) The polyester composite material provided by the present invention comprises specific proportions of polybutylene terephthalate, polycarbonate, a bromine-containing flame retardant, a synergistic flame retardant and a toughening agent, and the bromine-containing flame retardant comprises a combination of at least two of brominated epoxy resin, brominated polycarbonate or brominated polystyrene; by selecting polybutylene terephthalate and polycarbonate for combination, and adding at least two specific bromine-containing flame retardants and synergistic flame retardants for flame retardant modification, the obtained polyester composite material not only has excellent mechanical properties and flame retardant properties, but also has a low amount of die precipitation at the extruder die head, thereby effectively avoiding the problem of die precipitation being carbonized at high temperature and flowing into the product to contaminate the product, thereby effectively improving the quality of the finally obtained polyester composite material;

[0043] (2) Specifically, the weight of the die precipitate of the polyester composite material provided by the present invention at the die head of the extruder is only 0.125 to 0.230 g, the time for the precipitate to change color is as long as 10 to 17 minutes, and the flame retardant grade can reach V-0 level. DETAILED DESCRIPTION

[0044] The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only used to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0045] Some of the raw material information involved in the following examples and comparative examples are as follows:

[0046] (1) Polybutylene terephthalate (PBT)

[0047] PBT-1: melt index is 8g / 10min, purchased from Sinopec Yizheng Chemical Fiber Co., Ltd., brand GL236;

[0048] PBT-2: melt index is 30g / 10min, purchased from Sinopec Yizheng Chemical Fiber Co., Ltd., brand name PBT-GX121;

[0049] PBT-3: The melt index is 65 g / 10 min, purchased from Sinopec Yizheng Chemical Fiber Co., Ltd., with the brand name PBT-GX112.

[0050] (2) Polycarbonate (PC)

[0051] PC-1: melt index is 3.9 g / 10 min, purchased from Mitsubishi Engineering-Plastics Co., Ltd. (Mitsubishi Chemical), brand name is PC7030PJ;

[0052] PC-1: melt index is 10 g / 10 min, purchased from LG Chemical, brand name is PC 1300-10NP.

[0053] (3) Brominated flame retardants

[0054] (A) Brominated Epoxy Resin

[0055] A1: weight average molecular weight 24000, purchased from Shandong Tianyi Chemical Co., Ltd., brand Z-52;

[0056] A2: weight average molecular weight is 20,000, purchased from the Dead Sea in Israel, brand name powder F-2100;

[0057] A3: weight average molecular weight is 15000, purchased from Changchun Man-Made Resin Factory Co., Ltd., brand number is BEB-6000.

[0058] A4: weight average molecular weight is 5500, purchased from Suzhou Borida, brand name is CR-100K.

[0059] (B) Brominated polycarbonate

[0060] B1: weight average molecular weight is 4500, purchased from Teijin, Japan, brand FG8500;

[0061] B2: weight average molecular weight is 4000, purchased from Teijin, Japan, brand FG7500;

[0062] B3: weight average molecular weight is 3500, purchased from LANXESS, brand name powder BC-58.

[0063] (C) Brominated polystyrene

[0064] C1: weight average molecular weight is 600000, purchased from Shandong Brothers, brand number is BPS-3010.

[0065] C2: weight average molecular weight is 200000, purchased from Shandong Brothers, brand number is XZ-6700;

[0066] C3: weight average molecular weight 13500, purchased from Albemarle, USA, brand HP-3010PST;

[0067] C4: weight average molecular weight is 6000, purchased from Albemarle, USA, brand number HP-5010PST.

[0068] (5) Synergistic flame retardants

[0069] Antimony trioxide: purchased from Yiyang Shengli Materials, brand name S-04N.

[0070] (6) Toughening agent

[0071] Ethylene-acrylate copolymer, available from DuPont, brand name Elvaloy resins PTW.

[0072] Examples 1 to 19 and Comparative Examples 1 to 9

[0073] Examples 1 to 19 and Comparative Examples 1 to 9 respectively provide a polyester composite material, and the components and amounts thereof are shown in Tables 1 to 3;

[0074] In Tables 1 to 3, the dosage ranges of each component are all "parts by weight";

[0075] Table 1

[0076]

[0077] Table 2

[0078]

[0079]

[0080] Table 3

[0081]

[0082] The preparation method of the polyester composite material provided in Examples 1 to 19 and Comparative Examples 1 to 9 includes: mixing polybutylene terephthalate, polycarbonate, a bromine-containing flame retardant (obtained by mixing brominated epoxy resin, brominated polycarbonate and brominated polystyrene), a synergistic flame retardant and a toughening agent for 3 minutes, extruding in a single-screw extruder at an extrusion temperature of 270°C and an extrusion frequency of 40 Hz, and obtaining the polyester material through granulation and drying.

[0083] Performance Test:

[0084] (1) Die precipitation: A single screw extruder was used for extrusion, the extrusion temperature was 270°C, the experimental weight was 10 kg, the extrusion frequency was 40 Hz, the time for the die precipitate to change color (carbonization) was recorded, and the precipitate was collected and weighed.

[0085] (3) Flame retardant performance: tested in accordance with UL94 standard.

[0086] The polyester composite materials provided by Examples 1 to 19 and Comparative Examples 1 to 9 were tested according to the above test method. The test results are shown in Table 4:

[0087] Table 4

[0088]

[0089]

[0090] From the data in Table 4, we can see that:

[0091] The polyester composite material provided by the present invention has a lower die precipitation amount and excellent flame retardant properties, and the specific analysis is as follows:

[0092] (1) The weight of the die precipitate of the polyester composite material obtained in Examples 1 to 19 is 0.125 to 0.230 g, the time for the precipitate to change color is 10 to 17 minutes, and the flame retardant grade can reach V-0 level;

[0093] Among them, the weight of the precipitate of the polyester composite materials provided by Examples 1 to 5, Examples 12 to 13, Examples 15 and Examples 17 to 18 is only 0.125 to 0.156 g, the time for the precipitate to change color is as long as 14 to 17 minutes, and the flame retardant grade can reach the V-0 level, and the die precipitation and flame retardancy are both optimal.

[0094] (2) Compared with Example 1, the relative amount of polybutylene terephthalate in the polyester composite material provided in Comparative Examples 1 to 2 is too low or too high, which will lead to an increase in die precipitates and a shortened time for the precipitates to change color, which will cause the carbonized precipitates to easily flow into the product, affecting the product quality.

[0095] (3) Compared with Example 1, the total amount of bromine-containing flame retardant added in the polyester composite material provided in Comparative Example 3 is relatively low, which not only leads to an increase in die precipitates, but also leads to a significant decrease in flame retardant properties; while the total amount of bromine-containing flame retardant added in the polyester composite provided in Comparative Example 4 is too much, which does not further improve the flame retardant properties, but instead leads to an increase in die precipitates, affecting product quality.

[0096] (4) Compared with Example 1, the polyester composite materials provided in Comparative Examples 5 to 7 all use a single type of bromine-containing flame retardant, which has little effect on the flame retardant properties, but will lead to a significant increase in die precipitates and a significantly shortened time for the precipitates to change color, seriously affecting product quality.

[0097] (5) Compared with Example 1, the polyester composite materials provided in Comparative Examples 8 to 9 do not contain any bromine-containing flame retardant or synergistic flame retardant, resulting in flame retardancy levels of only HB and V-2, which are poor in flame retardancy.

[0098] The applicant declares that the present invention illustrates a polyester composite material and its preparation method and application through the above embodiments, but the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must rely on the above embodiments to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of various raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A polyester composite material, characterized in that: The polyester composite material comprises the following components in parts by weight: The bromine-containing flame retardant comprises a combination of at least two of brominated epoxy resin, brominated polycarbonate or brominated polystyrene.

2. The polyester composite material according to claim 1, characterized in that: The melt index of the polybutylene terephthalate is ≥5g / 10min; Preferably, the melt index of the polycarbonate is ≤15 g / 10 min.

3. The polyester composite material according to claim 1 or 2, characterized in that: The bromine-containing flame retardant is a combination of brominated epoxy resin and brominated polycarbonate, and the mass ratio of the brominated epoxy resin to the brominated polycarbonate is 1:(0.05-20), preferably 1:(0.1-10); Or, the bromine-containing flame retardant is a combination of brominated epoxy resin and brominated polystyrene, and the mass ratio of the brominated epoxy resin to the brominated polystyrene ester is 1:(0.05-20), and more preferably 1:(0.1-10); Alternatively, the bromine-containing flame retardant is a combination of brominated polycarbonate and brominated polystyrene, and the mass ratio of the brominated polycarbonate to the brominated polystyrene is 1:(0.05-20), and more preferably 1:(0.1-10).

4. The polyester composite material according to claim 1, characterized in that: The bromine-containing flame retardant is a combination of brominated epoxy resin, brominated polycarbonate and brominated polystyrene; The mass ratio of any two of the brominated epoxy resin, brominated polycarbonate and brominated polystyrene is 1:(0.05-20), and more preferably 1:(0.1-10).

5. The polyester composite material according to claim 1, characterized in that: The weight average molecular weight of the brominated epoxy resin is ≥5000, preferably ≥6000; Preferably, the weight average molecular weight of the brominated polycarbonate is ≥3000, more preferably ≥4000; Preferably, the weight average molecular weight of the brominated polystyrene is ≥5000, more preferably ≥7000.

6. The polyester composite material according to claim 1 or 2, characterized in that: The synergistic flame retardant includes antimony trioxide.

7. The polyester composite material according to claim 1 or 2, characterized in that: The toughening agent includes any one of ethylene-acrylate-glycidyl methacrylate copolymer, ethylene-acrylate copolymer, ethylene-vinyl acetate copolymer, methacrylate-styrene-silicone copolymer or methacrylate-styrene-butadiene copolymer, or a combination of at least two thereof.

8. A method for preparing the polyester composite material according to any one of claims 1 to 7, characterized in that: The preparation method comprises: mixing polybutylene terephthalate, polycarbonate, a bromine-containing flame retardant, a synergistic flame retardant and a toughening agent, and performing extrusion and granulation in an extruder to obtain the polyester composite material.

9. The preparation method according to claim 8, characterized in that: The mixing time is 2 to 5 minutes; Preferably, the extruder is a single screw extruder; Preferably, the extrusion temperature of the single screw extruder is 200-300°C.

10. Use of the polyester composite material as described in any one of claims 1 to 7 in electronic and electrical, automotive industry, medical equipment or aerospace.

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