Halogen-free flame-retardant ABS material, preparation method and application thereof

Abstract

A halogen-free flame-retardant ABS material comprises the following components in parts by weight: ABS resin and PBT resin, glass fiber, toughening agent, compatibilizer, aluminum phosphonate flame retardant, nitrogen-based flame retardant. The present application can utilize the more easily carbonized characteristics of PBT resin relative to ABS resin by using a specific weight ratio of ABS resin and PBT resin, improve the flame resistance of the resin matrix, the condensed phase flame-retardant effect of aluminum phosphonate, and the gas phase flame-retardant effect of melamine, to achieve the V-0 flame-retardant grade of the ABS material in a flame-retardant mode in which the three work together. At the same time, the compatibilizer can significantly improve the mechanical properties of the halogen-free flame-retardant ABS material.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, and in particular to a method for preparing and applying a halogen-free flame-retardant ABS material. Background Technology

[0002] ABS resin contains butadiene rubber and has a low oxygen index, making it a flammable material. To expand its applications, its fire resistance must be improved through flame-retardant modification. Currently, mature reinforced flame-retardant ABS on the market belongs to the bromine-based flame-retardant system, which is a halogenated flame-retardant system. During material processing, it is prone to degradation, producing small-molecule hydrogen halide gas that corrodes molds. Therefore, from the perspective of flame-retardant material technology development trends, the future focus will be on halogen-free flame retardants, and the research and development of new halogen-free flame-retardant ABS has become a hot research direction.

[0003] The paper, "Study on the GWIT Flame Retardant Properties of ABS Polyester Alloy," authored by Du Ronghua and Tang Lei, discloses an ABS / PBT alloy. The alloy, described as ABS / PBT (0.75:0.25), utilizes a bromine-antimony flame retardant system, exhibiting good flame retardancy and GWIT performance. However, experiments revealed that the SMA compatibilizer used in this design insufficiently improves the mechanical properties of the phosphorus-based flame retardant system. Summary of the Invention

[0004] The purpose of this invention is to provide a V-0 flame-retardant ABS material with good mechanical properties, as well as its preparation method and application.

[0005] This invention is achieved through the following technical solution:

[0006] A halogen-free flame-retardant ABS material, comprising the following components by weight:

[0007] 35-46 parts of ABS resin;

[0008] 14-21 parts of PBT resin;

[0009] 20-30 parts glass fiber;

[0010] 2-5 parts toughening agent;

[0011] 3-7 parts compatibilizer;

[0012] 15-20 parts of aluminum phosphonate flame retardant;

[0013] 2-6 parts of nitrogen-based flame retardant.

[0014] The ABS resin in which the rubber content is required to achieve the purpose of the present invention is in the range of 9-35 wt%, preferably in the range of 18-26 wt%.

[0015] Rubber content test method: Weigh a certain mass (m1) of ABS granules and put them into a centrifuge tube (m2). Dissolve them in acetone by sonication for ≥4 hours, then centrifuge them in a high-speed centrifuge for more than 40 minutes at a speed of 15000~17500 r / min. Remove the supernatant. Wash the rubber at the bottom of the centrifuge tube with acetone solvent 3 times. Dry the insoluble matter and centrifuge tube in an oven at 80℃ for 4 hours. Then place them in a vacuum drying oven at 65℃ for 12 hours and weigh them. The rubber mass fraction is equal to m3-m2 / m1.

[0016] The weight ratio of ABS resin to PBT resin is (2-3):1; preferably, the weight ratio of ABS resin to PBT resin is (2.2-2.8):1.

[0017] Preferably, in the halogen-free flame-retardant ABS material of the present invention, the sum of the contents of PBT and ABS accounts for not less than 40 wt% of the total weight of the halogen-free flame-retardant ABS material.

[0018] The technical solution of this invention does not have any particular limitations on PBT. Preferably, the flow rate is 20-34 g / 10 min as measured by the ISO1133-1:2022 method, and the test conditions are 1.2 kg / temperature 235℃.

[0019] The compatibilizer is selected from at least one of PMMA, PC, PETG, and ethylene-acrylate copolymer; preferably, the compatibilizer is ethylene-acrylate copolymer. These substances all contain ester structures, which have good compatibility with ABS. They can act as a compatibilizer and bridge between the PBT phase and the ABS phase, improving the compatibility between the two phases and achieving excellent mechanical properties.

[0020] Specifically, the melt flow rate range of PMMA is: 15-25 g / 10 min, 230℃, 3.8 kg;

[0021] The melt flow rate range of PC is: 10-25 g / 10 min, 300℃, 1.2 kg;

[0022] The melt flow rate range for PETG is: 15-30 g / 10 min, 220 °C, 10 kg;

[0023] The melt flow rate range of the ethylene-acrylate copolymer is: 1-10 g / 10 min, 190 °C, 2.16 kg;

[0024] PMMA is polymethyl methacrylate;

[0025] PC stands for polycarbonate.

[0026] PETG stands for polyethylene terephthalate-1,4-cyclohexanediethanol ester.

[0027] PMMA can be purchased from: PMMA LG2, Sumitomo Chemical Co., Ltd., Japan; PMMA CM-211, Chi Mei Corporation, Taiwan, China.

[0028] The ethylene-acrylate copolymer can be an ethylene-butyl acrylate copolymer, which can be purchased from: A560, DuPont, USA; 17BA 04, Arkema, France;

[0029] The PC can be purchased from: PC H-2000F, Mitsubishi Corporation, Japan; POLYCARBONATE RESIN TARFLONFN2200, Idemitsu Corporation, Japan.

[0030] PETG can be purchased from: PETG GN071, Eastman Chemical Company, USA; CR-5511, China Resources Chemical.

[0031] The toughening agent is selected from at least one of high-resin powder, SBS, and SEBS. These toughening agents are all commonly used elastomers in ABS and PBT, and have good toughening effects.

[0032] The nitrogen-based flame retardant is selected from melamine, melamine cyanurate, and melamine polyphosphate; preferably, the nitrogen-based flame retardant is selected from melamine polyphosphate, which has good compatibility and flame retardant efficiency.

[0033] The structure of the aluminum phosphonate flame retardant is as follows:

[0034]

[0035] Among them, R1, R2, R3, R4, R5, and R6 are independently selected from -OH, -C2H5, and -C6H, respectively. 13 -C8H 17 Any one of them;

[0036] In the aforementioned aluminum phosphonate flame retardant, R1, R2, R3, R4, R5, and R6 are all -OH; or R1, R2, R3, R4, R5, and R6 are all -C2H5; or R1, R2, R3, R4, R5, and R6 are all -C6H 13 ; or R1, R2, R3, R4, R5, and R6 are all -C8H 17 .

[0037] Preferably, in the aluminum phosphonate flame retardant, R1, R2, R3, R4, R5, and R6 are all -C2H5.

[0038] Specifically, the aluminum phosphonate flame retardant can be selected from aluminum diethylphosphite, aluminum dihydrogen phosphate, etc.

[0039] The mass ratio of aluminum phosphonate flame retardant to nitrogen-based flame retardant is 2.5-10, preferably 3.5-8, which has high flame retardant efficiency and achieves a V-0 flame retardant effect.

[0040] Diethylphosphonic acid aluminum flame retardant is available from Clariant's EXOLIT OP 1230.

[0041] Those skilled in the art can add antioxidants and lubricants to the halogen-free flame-retardant ABS material of the present invention as needed.

[0042] Antioxidants can be: 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene; 3,5-di-tert-butyl-4-hydroxybenzyl dimethylamine; diethyl-3,5-di-tert-butyl-4-hydroxybenzyl phosphate; stearyl-3,5-di-tert-butyl-4-hydroxybenzyl phosphate; 3,5-di-tert-butyl-4-hydroxyphenyl-3,5-distearate-thiotriazolylamine; 2,6-di-tert-butyl-4-hydroxymethylphenol; 2,4-di-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylglycerol allyl ether)-1,3 ,5-Triazine; N,N'-Hexamethylene di(3,5-di-tert-butyl-4-hydroxy-hydrogenated cinnamamide); N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexamethylenediamine; Octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate; Pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]; Di(triethylene glycol) bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate]; 2,2'-Thiodiethyl-di[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, etc.

[0043] The lubricant may be at least one of the following: stearate lubricant, fatty acid lubricant, and stearate ester lubricant; wherein the stearate lubricant is selected from at least one of calcium stearate, magnesium stearate, and zinc stearate; wherein the fatty acid lubricant is selected from at least one of fatty acids, fatty acid derivatives, and fatty acid esters; and wherein the stearate ester lubricant is selected from at least one of pentaerythritol stearate.

[0044] The preparation method of halogen-free flame-retardant ABS material includes the following steps: according to the formula, the components are mixed evenly, and granulated by extrusion through a twin-screw extruder at a speed of 300-500 rpm and a barrel temperature of 200-220℃ to obtain halogen-free flame-retardant ABS material.

[0045] Halogen-free flame-retardant ABS materials are used in household appliance parts and office supplies.

[0046] The present invention has the following beneficial effects:

[0047] This invention utilizes a specific weight ratio of ABS resin and PBT resin. By leveraging the fact that PBT resin is more prone to charring than ABS resin, the flame retardancy of the resin matrix is ​​improved. The condensed-phase flame retardant effect of aluminum phosphonate flame retardant and the gas-phase flame retardant effect of melamine work synergistically to achieve a V-0 flame retardant rating for ABS materials. Simultaneously, a compatibilizer enhances the compatibility of ABS with PBT and aluminum phosphate flame retardants, significantly improving the mechanical properties of the halogen-free flame-retardant ABS material of this invention. Detailed Implementation

[0048] 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.

[0049] The raw materials used in this invention are sourced from the following sources:

[0050] PBT: PBT 1084HQ, Nantong Xingchen Company, melt flow rate 22g / 10min, test conditions 1.2kg / temperature 235℃.

[0051] ABS-A: Rubber content 9.8% by weight, Gaoqiao Petrochemical, ABS 275;

[0052] ABS-B: Rubber content 11.7% by weight, Gaoqiao Petrochemical, ABS 8434;

[0053] ABS-C: Rubber content 18.5% by weight, Guoqiao Petrochemical, ABS D-670;

[0054] ABS-D: Rubber content 25% by weight, Guoqiao Petrochemical, ABS D-100;

[0055] ABS-E: Rubber content 35% by weight, Chi Mei Corporation, Taiwan, PA-757;

[0056] Rubber content test method: Weigh a certain mass (m1) of ABS granules, put them into a centrifuge tube (m2), dissolve them in acetone by ultrasonication for ≥4 hours, then centrifuge them in a high-speed centrifuge for more than 40 minutes at a speed of 15000~17500 r / min, remove the supernatant, wash the rubber at the bottom of the centrifuge tube with acetone solvent 3 times, dry the insoluble matter and centrifuge tube in an oven at 80℃ for 4 hours, and then place them in a vacuum drying oven at 65℃ for 12 hours, weigh m3, and the rubber mass fraction is equal to m3-m2 / m1;

[0057] Fiberglass: ECS13-4.5-534A, China Jushi Co., Ltd.;

[0058] Toughening agent: High-polymer powder, ABS HR POWER 181, Kumho Corporation, South Korea;

[0059] Compatibilizer A: PMMA, PMMA LG2, Sumitomo Chemical Co., Ltd., Japan;

[0060] Compatibilizer B: Ethylene-butyl acrylate copolymer, A560, DuPont, USA;

[0061] Compatibilizer C: PC, PC H-2000F, Mitsubishi Corporation, Japan;

[0062] Compatibilizer D: PETG, PETG GN071, Eastman Chemical Company, USA;

[0063] SMA: SMA 700, Jiaxing Huawen Chemical Co., Ltd.;

[0064] Aluminum phosphonate flame retardant A: Aluminum diethylphosphonate flame retardant, Clariant Corporation;

[0065] Aluminum phosphonate flame retardant B: Aluminum dihydrogen phosphate, Hubei Zhonglong Kangcheng Company;

[0066] Melamine polyphosphate: FR-NP, Shouguang Weidong Company;

[0067] Melamine cyanurate: MCA-01, Shouguang Weidong Company;

[0068] Melamine: Shandong Aojin Chemical Co., Ltd.

[0069] Antioxidant: RIANOX 1010, Tianjin Lianlong New Material Co., Ltd.;

[0070] Preparation method of halogen-free flame-retardant ABS material in the examples and comparative examples: According to the formula, the components are mixed evenly and extruded and granulated by a twin-screw extruder at a speed of 300-500 rpm and a barrel temperature of 200-220℃ to obtain halogen-free flame-retardant ABS material.

[0071] Test methods:

[0072] (1) Vertical burning: UL94 standard, test conditions: sample thickness 1.5mm;

[0073] (2) Notched impact strength of cantilever beam: ISO 180 / 1A standard, temperature 23℃, spline thickness 4mm;

[0074] (3) Heat distortion temperature: ISO 75-1:2020 standard, test conditions 1.8MPa load, flat.

[0075] Table 1: Weight parts and test results of each component in the halogen-free flame-retardant ABS materials of Examples 1-6

[0076] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 ABS-D 40 41.2 44.2 45 40 36.7 PBT 20 18.8 15.8 15 20 18.3 Fiberglass 25 25 25 25 30 20 toughening agent 3 3 3 3 5 5 Compatibilizer A 5 5 5 5 7 3 Aluminum phosphonate flame retardant A 18 18 18 18 15 20 melamine polyphosphate 4 4 4 4 2 6 antioxidants 0.5 0.5 Vertical combustion V-0 V-0 V-0 V-0 V-0 V-0 <![CDATA[Notch impact strength, kJ / m 2 > 5.5 5.6 5.8 5.9 5.4 5.2 Heat distortion temperature, °C 102 105 103 100 108 100

[0077] As can be seen from Examples 1-4, the optimal ABS / PBT ratio results in a better heat distortion temperature and moderate notched impact strength.

[0078] Table 2: Weight parts of each component and test results of halogen-free flame-retardant ABS materials in Examples 7-10

[0079] Example 7 Example 8 Example 9 Example 10 ABS-A 40 ABS-B 40 ABS-C 40 ABS-E 40 PBT 20 20 20 20 Fiberglass 25 25 25 25 toughening agent 3 3 3 3 Compatibilizer A 5 5 5 5 Aluminum phosphonate flame retardant A 18 18 18 18 melamine polyphosphate 4 4 4 4 Vertical combustion V-0 V-0 V-0 V-0 <![CDATA[Notched impact strength, kJ / m 2 > 3.7 4.4 5.2 5.9 Heat distortion temperature, °C 105 103 103 100

[0080] As can be seen from Examples 1 / 7-10, the higher the weight content of rubber in ABS resin, the better the notched impact strength and the slower the heat distortion temperature decreases. Preferably, when the weight content of rubber in ABS resin is 18-26 wt%, the overall performance of notched impact strength and heat distortion temperature is better.

[0081] Table 3: Weight parts of each component and test results of halogen-free flame-retardant ABS materials in Examples 11-14

[0082] Example 11 Example 12 Example 13 Example 14 ABS-D 40 40 40 40 PBT 20 20 20 20 Fiberglass 25 25 25 25 toughening agent 3 3 3 3 Compatibilizer A 5 Compatibilizer B 5 Compatibilizer C 5 Compatibilizer D 5 Aluminum phosphonate flame retardant A 18 18 18 Aluminum phosphonate flame retardant B 18 melamine polyphosphate 4 4 4 4 Vertical combustion V-0 V-0 V-0 V-0 <![CDATA[Izod impact strength, kJ / m 2 > 7.8 5.8 6.3 4.5 Heat distortion temperature, °C 103 101 102 100

[0083] As can be seen from Examples 1 / 11-13, the compatibilizer is preferably an ethylene-butyl acrylate copolymer.

[0084] As can be seen from Examples 1 / 14, the preferred flame retardant is aluminum diethylphosphite.

[0085] Table 4: Weight parts of each component and test results of comparative halogen-free flame-retardant ABS materials

[0086] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 ABS-D 30 48 40 40 40 PBT 30 12 20 20 20 Fiberglass 25 25 25 25 25 toughening agent 3 3 3 3 3 Compatibilizer A 5 5 5 5 SMA 5 Aluminum phosphonate flame retardant A 18 18 14 21 18 melamine polyphosphate 4 4 8 1 4 Vertical combustion V-0 V-2 V-2 V-1 V-0 <![CDATA[Izod impact strength, kJ / m 2 > 4.1 6.1 5.7 5.6 2.6 Heat distortion temperature, °C 95 97 103 102 98

[0087] As shown in Comparative Example 1 / 2, if the ABS content is too low, the notched impact strength and heat distortion temperature will not meet the requirements; if the ABS content is too high, the flame retardancy will not reach V-0, and the heat distortion temperature will not meet the requirements.

[0088] As can be seen from Comparative Example 3 / 4, when the ratio of flame retardant is outside the range of the present invention, the flame retardancy cannot reach V-0.

[0089] As shown in Comparative Example 5, the notched impact strength is insufficient when SMA is used as a compatibilizer.

Claims

1. A halogen-free flame-retardant ABS material, characterized in that, By weight, it includes the following components: 35-46 parts of ABS resin; 14-21 parts of PBT resin; 20-30 parts glass fiber; 2-5 parts toughening agent; 3-7 parts compatibilizer; 15-20 parts of aluminum phosphonate flame retardant; 2-6 parts of nitrogen-based flame retardant; The compatibilizer is selected from at least one of PMMA, PC, PETG, and ethylene-butyl acrylate copolymer; The weight content of rubber in the ABS resin ranges from 18 to 26 wt%.

2. The halogen-free flame-retardant ABS material according to claim 1, characterized in that, The weight ratio of ABS resin to PBT resin is (2-3):

1.

3. The halogen-free flame-retardant ABS material according to claim 2, characterized in that, The weight ratio of ABS resin to PBT resin is (2.2-2.8):

1.

4. The halogen-free flame-retardant ABS material according to claim 1, characterized in that, The compatibilizer is an ethylene-butyl acrylate copolymer.

5. The halogen-free flame-retardant ABS material according to claim 1, characterized in that, The toughening agent is selected from at least one of high-rubber powder, SBS, and SEBS.

6. The halogen-free flame-retardant ABS material according to claim 1, characterized in that, The nitrogen-based flame retardant is selected from melamine, melamine cyanurate, and melamine polyphosphate.

7. The halogen-free flame-retardant ABS material according to claim 6, characterized in that, The nitrogen-based flame retardant is selected from melamine polyphosphate.

8. The halogen-free flame-retardant ABS material according to claim 1, characterized in that, The structure of the aluminum phosphonate flame retardant is as follows: ， Among them, R1, R2, R3, R4, R5, and R6 are independently selected from -OH, -C2H5, and -C6H, respectively. 13 -C8H 17 Any one of them.

9. The halogen-free flame-retardant ABS material according to claim 8, characterized in that, In the aforementioned aluminum phosphonate flame retardant, R1, R2, R3, R4, R5, and R6 are all -OH; or R1, R2, R3, R4, R5, and R6 are all -C2H5; or R1, R2, R3, R4, R5, and R6 are all -C6H 13 ; or R1, R2, R3, R4, R5, and R6 are all -C8H 17 .

10. The halogen-free flame-retardant ABS material according to claim 9, characterized in that, In the aluminum phosphonate flame retardant, R1, R2, R3, R4, R5, and R6 are all -C2H5.

11. The halogen-free flame-retardant ABS material according to claim 1, characterized in that, By weight, it also includes antioxidants and lubricants.

12. A method for preparing the halogen-free flame-retardant ABS material according to any one of claims 1-11, characterized in that, The process includes the following steps: mixing the components evenly according to the formula, granulating them by extrusion through a twin-screw extruder at a speed of 300-500 rpm and a barrel temperature of 200-220℃ to obtain halogen-free flame-retardant ABS material.

13. The application of the halogen-free flame-retardant ABS material according to any one of claims 1-11, characterized in that, Used in household appliance parts and office supplies.

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