Low-carbon 5VA flame-retardant ABS material, preparation method and application thereof

Abstract

The application belongs to the technical field of high polymer materials, and discloses a low-carbon 5VA flame-retardant ABS material, a preparation method and application thereof.The low-carbon 5VA flame-retardant ABS material comprises the following components in parts by weight: ABS resin 55-65 parts, AS resin 6-14 parts, cellulose 5-9 parts, a compatilizer 2-6 parts, a flame retardant 12-18 parts and an auxiliary agent 0.2-1 part; the compatilizer is a stearic acid alcohol ester compatilizer; the rubber content of the ABS resin ranges from 32 w.t.% to 39 w.t.%; and the average fiber length of the cellulose ranges from 200 mu m to 500 mu m.The ABS material has both 5VA flame-retardant performance and toughness, can be directly injection molded, is easy to process, reduces carbon emission of the material, and realizes low carbonization of material preparation.The ABS material is suitable for thin-walled products or office supplies in the fields of bathroom, household appliances and automobile.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, in particular to the technical field of modified plastics, and in particular to a low-carbon 5VA flame-retardant ABS material and a preparation method and application thereof. Background Art

[0002] ABS resin boasts a balanced mechanical property of stiffness and toughness, a good appearance, and excellent processing properties, making it widely used in home appliances, office supplies, automobiles, and electronic and electrical applications. With an oxygen index of only 18, ABS resin is a flammable material. Prior art has modified ABS resin into a flame-retardant material by adding flame retardants, achieving a V-0 vertical flammability rating and meeting general product fire protection requirements. Currently, thin-walled products are becoming a trend in many finished products, leading to increasingly stringent flame retardancy requirements. The V-0 vertical flammability rating is no longer sufficient for thin-walled ABS resin. Therefore, 5VA flame retardancy, which surpasses the V-0 vertical flammability rating, has become an important development direction for flame-retardant ABS.

[0003] However, conventional bromine-antimony synergistic flame retardant solutions or simply increasing the flame retardant dosage cannot achieve a 5VA flame retardant rating at the same thickness. For example, Chinese invention patent document CN 109111677 A discloses a low-smoke density UL94-5VA flame-retardant ABS material. Using magnesium salt whiskers and washed montmorillonite as bromine-antimony synergistic flame retardants can achieve a 5VA flame retardant rating. However, the addition of these two minerals increases the material's water absorption, making it difficult to dry, leading to cosmetic defects such as material smear and silver streaks during injection molding. Chinese invention patent document CN 109679271 A discloses a glass fiber-reinforced flame-retardant ABS 5VA material for wind blades. By utilizing the melt strength of the glass fiber-reinforced material, it achieves a stable 2.0mm 5VA flame retardant. However, the composite material has poor toughness and low impact strength, making it difficult to achieve a good balance of rigidity and toughness. Moreover, the presence of glass fiber makes it unsuitable for products requiring aesthetically pleasing appearance. Chinese invention patent CN 110483941B discloses a low-smoke, environmentally friendly 5VA flame-retardant ABS material that incorporates a large amount of CPE to enhance its flame retardancy and toughness. This allows for both thin-walled 5VA flame retardancy and high toughness. However, the addition of large amounts of CPE results in poor thermal stability, and the HCl produced by decomposition during injection molding can corrode the mold surface. Furthermore, the ABS resin in flame-retardant ABS is a post-processing product derived from petroleum, which increases carbon emissions during production.

[0004] Therefore, there is an urgent need to develop an ABS resin that can take into account multiple properties such as 5VA flame retardancy, rigidity and toughness balance and is easy to process. Summary of the Invention

[0005] The purpose of the present invention is to overcome the shortcomings of the prior art and provide a low-carbon 5VA flame-retardant ABS material and its preparation method and application, in order to overcome the technical problem in the prior art that it is difficult to strike a balance between the flame retardant properties and the toughness and toughness of ABS resin 5VA.

[0006] To achieve the above object, the technical solution adopted by the present invention is as follows:

[0007] In a first aspect, the present invention provides a low-carbon 5VA flame-retardant ABS material, comprising the following components, calculated by weight: 55-65 parts of ABS resin, 6-14 parts of AS resin, 5-9 parts of cellulose, 2-6 parts of compatibilizer, 12-18 parts of flame retardant, and 0.2-1 part of additive;

[0008] The compatibilizer is a stearic acid alcohol ester compatibilizer;

[0009] The rubber content of the ABS resin ranges from 32wt% to 39wt%; and the average fiber length of the cellulose ranges from 200μm to 500μm.

[0010] In the low-carbon 5VA flame-retardant ABS material of the present invention, the use of a specific number of compatibilizers, stearyl alcohol esters, can effectively enhance the compatibility between cellulose and ABS, improving the material's toughness and melt strength. This is because the hydroxyl functional groups of stearyl alcohol esters can interact with the hydroxyl groups of cellulose, while the alkyl and ester groups of stearyl alcohol esters have good compatibility with the ABS resin matrix. Thus, stearyl alcohol esters act as a bridge between cellulose and ABS resin, enhancing their interaction and improving the material's melt strength and toughness. Other compatibilizers (stearamide, stearates, paraffin, etc.) are not as effective as the stearyl alcohol ester compatibilizer. Using cellulose with a specific average fiber length can enhance the material's 5VA flame retardancy (the material square plate will not burn through and can pass the 5VA test). Considering the inherent properties of cellulose, within the average length range of this application, it can be assumed that its average fiber length does not change before and after processing. Using an ABS resin with a rubber content of 32% to 39% by weight is more conducive to synergizing with other components to achieve excellent overall performance. When the rubber content is less than 32% by weight, the melt strength of the substrate is low, which is not conducive to achieving 5VA flame retardancy, and the toughness is poor.

[0011] That is, by adding cellulose with a specific average fiber length, a stearic acid alcohol ester compatibilizer, and an ABS resin with a specific rubber content to the flame-retardant ABS, the present invention can significantly improve the melt strength of the material, thereby achieving 5VA flame retardancy while maintaining good toughness, meeting the flame retardancy and toughness requirements of thin-walled products.

[0012] Wherein, the stearic acid alcohol ester compatibilizer includes pentaerythritol monostearate, pentaerythritol tetrastearate or dipentaerythritol stearate.

[0013] As a preferred embodiment of the low-carbon 5VA flame-retardant ABS material of the present invention, the flame retardant comprises a brominated flame retardant and an antimony flame retardant in a mass ratio of (2-4):1. The brominated flame retardant and antimony flame retardant exhibit a synergistic flame retardant effect, achieving a V-0 flame retardancy rating.

[0014] As a preferred embodiment of the low-carbon 5VA flame-retardant ABS material described in the present invention, the brominated flame retardant is at least one of bromotriazine, tetrabromobisphenol A, and brominated epoxy; the antimony flame retardant is antimony trioxide and / or antimony pentoxide.

[0015] As a preferred embodiment of the low-carbon 5VA flame-retardant ABS material of the present invention, the auxiliary agent includes an antioxidant and a lubricant; in parts by weight, the antioxidant is 0.2 to 0.4 parts, and the lubricant is 0.4 to 0.6 parts.

[0016] As a preferred embodiment of the low-carbon 5VA flame-retardant ABS material of the present invention, the antioxidant is a hindered phenol antioxidant or a phosphite antioxidant.

[0017] As a preferred embodiment of the low-carbon 5VA flame-retardant ABS material of the present invention, the lubricant is at least one of a silicone lubricant and an amide lubricant.

[0018] In a second aspect, the present invention provides a method for preparing the above-mentioned low-carbon 5VA flame-retardant ABS material, comprising the following steps:

[0019] The components are taken according to the weight parts, mixed, kneaded, extruded and post-processed to obtain the product.

[0020] As a preferred embodiment of the preparation method of the present invention, the extrusion temperature is 190° C. to 210° C. and the screw speed is 250 r / min to 300 r / min.

[0021] In a third aspect, the present invention applies the low-carbon 5VA flame-retardant ABS material to thin-walled products or office supplies in the fields of home appliances, sanitary ware, and automobiles.

[0022] Compared with the prior art, the present invention has the following beneficial effects:

[0023] The present invention uses a specific number of compatibilizers, stearic acid alcohol ester, to effectively improve the compatibility of cellulose and ABS, improve the toughness and melt strength of the material, and use cellulose with a specific average fiber length to improve the melt strength of the material; by adding cellulose with a specific average fiber length, stearic acid alcohol ester compatibilizer, and ABS resin with a specific rubber content to flame-retardant ABS, the melt strength of the material can be greatly improved, thereby achieving 5VA flame retardancy while maintaining good toughness, meeting the flame retardancy and toughness requirements of thin-walled products. The present invention prepares a low-carbon 5VA flame-retardant ABS material that takes into account 5VA flame retardancy, toughness, and easy processing, and its cantilever beam notched impact strength is ≥16.0kJ / m 2 , can be directly injection molded and easily processed. It is suitable for thin-walled products or office supplies in the bathroom, home appliance, and automotive sectors. Furthermore, the low-carbon 5VA flame-retardant ABS material of this invention uses renewable cellulose, reducing carbon emissions and achieving a low-carbon material preparation. DETAILED DESCRIPTION

[0024] To better illustrate the purpose, technical solutions and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments. Those skilled in the art should understand that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0025] In the following examples and comparative examples, unless otherwise specified, brominated flame retardants, antimony flame retardants, antioxidants and lubricants were all commercially available, and the same brominated flame retardants, antimony flame retardants, antioxidants and lubricants were used in parallel experiments.

[0026] The raw materials used in the following examples and comparative examples are described below, but are not limited to these materials:

[0027] ABS resin 1: ABS AE8000-H, rubber (butadiene) content 38.5 wt%, Taiwan Formosa Plastics Corporation;

[0028] ABS resin 2: ABS PA-747S, rubber (butadiene) content 32.1 wt%, Chi Mei Chemical Products Co., Ltd., Taiwan;

[0029] ABS resin 3: ABS HS3302, rubber (butadiene) content 28.2 wt%, Mitsubishi Rayon Co., Ltd., Japan;

[0030] ABS resin 4: ABSD-120, rubber (butadiene) content 40.2 wt%, Guoqiao Chemical Co., Ltd.

[0031] The rubber (butadiene) content in the aforementioned ABS resins was determined using the dissolution precipitation method. Specifically, the dissolution precipitation method involves dissolving the styrene and styrene phases in an organic solvent (such as dichloromethane). However, the butadiene phase, being insoluble in the organic solvent, undergoes phase separation, and the butadiene content is determined after drying.

[0032] AS resin: DG-AS106, Tianjin Dagu Chemical Co., Ltd.;

[0033] Cellulose 1: TW200, average fiber length 200 μm, Huzhou Linghu Xinwang Chemical Co., Ltd.

[0034] Cellulose 2: TD250, average fiber length 250 μm, Huzhou Linghu Xinwang Chemical Co., Ltd.

[0035] Cellulose 3: TW500, average fiber length 500 μm, Huzhou Linghu Xinwang Chemical Co., Ltd.

[0036] Cellulose 4: TB120, average fiber length 120 μm, Huzhou Linghu Xinwang Chemical Co., Ltd.

[0037] Cellulose 5: TC1000, average fiber length 1000 μm, Huzhou Linghu Xinwang Chemical Co., Ltd.

[0038] Brominated flame retardant: brominated triazine, commercially available;

[0039] Antimony flame retardant: antimony trioxide, commercially available;

[0040] Compatibilizer 1: PEMS, pentaerythritol monostearate, Jiaxing Zhongcheng Environmental Protection Technology Co., Ltd.

[0041] Compatibilizer 2: PETS-AP, pentaerythritol tetrastearate, Jiaxing Zhongcheng Environmental Protection Technology Co., Ltd.

[0042] Compatibilizer 3: DIPE-1, dipentaerythritol stearate, Ruijie Chemical Co., Ltd.

[0043] Compatibilizer 4: KT-2, maleic anhydride grafted ABS, Shenyang Ketong Plastic Technology Co., Ltd.

[0044] Compatibilizer 5: FG1901 GT, maleic anhydride grafted SEBS, Kraton, USA;

[0045] Compatibilizer 6: SMA-800, styrene-maleic anhydride copolymer, Shanghai Huawen Electronic New Materials Co., Ltd.

[0046] Antioxidant: phosphite antioxidant tris(2,4-di-tert-butylphenyl) phosphite, commercially available;

[0047] Lubricant: Amide lubricant EBS B50, commercially available.

[0048] The components of the low-carbon 5VA flame-retardant ABS materials of Examples 1 to 14 and Comparative Examples 1 to 12 are shown in Tables 1 and 2.

[0049] In the low-carbon 5VA flame-retardant ABS material, the content of ABS resin is not less than 55%.

[0050] The preparation method of the low-carbon 5VA flame-retardant ABS material of Examples 1 to 14 and Comparative Examples 1 to 12 comprises the following steps:

[0051] (1) Weighing ABS resin, AS resin, cellulose, brominated flame retardant, antimony flame retardant, compatibilizer, antioxidant and lubricant, adding them into a high-speed mixer and mixing them evenly to obtain a premix;

[0052] (2) The prepared premix is ​​fed into an extruder for mixing, extrusion, and post-processing, wherein the extrusion temperature is 190° C. to 210° C. and the screw speed is 250 r / min to 300 r / min.

[0053] Table 1 Composition of low carbon 5VA flame retardant ABS material (parts by weight)

[0054]

[0055] Table 2 Comparative Example of low carbon 5VA flame retardant ABS material components (parts by weight)

[0056]

[0057] The low-carbon 5VA flame-retardant ABS materials of Examples 1 to 14 and Comparative Examples 1 to 12 were prepared into sample specimens, and their relevant properties were tested using ISO standards. The specific performance testing method is as follows:

[0058] (1) Flame retardant test standard: The test standard refers to "UL 94-2018 Tests for Flammability of Materials for Equipment and Appliance Components", and the specimen thickness is 2.0 mm;

[0059] (2) Izod notched impact strength: The test standard refers to ISO 180-2000 Plastics - Determination of Izod impact strength;

[0060] (3) Flexural modulus: The test standard refers to ISO 178-2010 Plastics - Determination of flexural properties;

[0061] The test results are shown in Table 3:

[0062] Table 3 Performance test results of low-carbon 5VA flame retardant ABS materials of the embodiment and comparative example

[0063]

[0064]

[0065] Examples 1-14 utilize specific raw materials such as ABS resin, AS resin, cellulose, brominated flame retardants, antimony flame retardants, compatibilizers, lubricants, and antioxidants to prepare low-carbon 5VA flame-retardant ABS materials. Samples are prepared that combine 5VA flame retardancy with toughness and are easy to process. Cellulose, as a renewable material, can replace ABS resin, a post-processing product of petroleum, reducing carbon emissions. The notched Izod impact strength reaches 16.0 kJ / m². 2 ~19.5kJ / m 2 (Preferably 18.1 kJ / m 2 ~19.5kJ / m 2 ), the flexural modulus reaches 2004MPa~2178MPa (preferably 2091MPa~2178MPa), and the flame retardancy reaches 5VA level.

[0066] Compared with Example 3, in the sample of Comparative Example 1, 2 parts of AS resin are used, that is, the amount of AS resin added is small, and the amount of AS resin with high modulus added is small, resulting in a low flexural modulus of the sample and a flame retardancy of only 5VB level; in the sample of Comparative Example 2, 50 parts of ABS resin and 20 parts of AS resin are used. The amount of ABS resin added is small, and the amount of AS resin added is large. The ABS resin content is low, resulting in a low rubber content and low material melt strength, resulting in a low Izod notched impact strength of the sample and a flame retardancy of only 5VB level.

[0067] Compared with Example 2, in the sample of Comparative Example 3, the rubber content in the ABS resin used is 28.2wt% and 25.3wt% respectively, the rubber content is low, the melt strength of the material is low, so the Izod notched impact strength of the sample is low, and the flame retardancy only reaches 5VB level; in the sample of Comparative Example 4, the average fiber length of cellulose used is 120μm, the fiber length is short, and the improvement of melt strength is limited, so the flame retardancy of the sample only reaches 5VB level; in the sample of Comparative Example 5, the average fiber length of cellulose used is 1000μm, the fiber length is long, resulting in large defects in the material, so that the Izod notched impact strength of the sample is low, and the fiber length is long, and the material appearance has defects; in the sample of Comparative Example 6, cellulose is not added, the melt strength is not improved, and the sample The flexural modulus is low, and the flame retardancy only reaches the 5VB level; in the samples of Comparative Examples 7, 8 and 9, the compatibilizers used are maleic anhydride grafted ABS, maleic anhydride grafted SEBS and styrene-maleic anhydride copolymer, respectively, which cannot effectively improve the compatibility of ABS resin and cellulose, and cannot improve the toughness and melt strength, so that the Izod notched impact strength of the sample is low, and the flame retardancy only reaches the 5VB level; in the sample of Comparative Example 10, no compatibilizer is added, the compatibility of ABS resin and cellulose is poor, and the melt strength is limitedly improved, so that the Izod notched impact strength of the sample is low, and the flame retardancy only reaches the 5VB level; in the sample of Comparative Example 11, the rubber content in the ABS resin used is 40.2%, the rubber content is too high, the material is soft, the modulus of the sample is low, and the rigidity is insufficient.

[0068] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that the technical solutions of the present invention may be modified or replaced by equivalents without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A low-carbon 5VA flame-retardant ABS material, characterized in that: The composition comprises the following components by weight: 55-65 parts of ABS resin, 6-14 parts of AS resin, 5-9 parts of cellulose, 2-6 parts of compatibilizer, 12-18 parts of flame retardant and 0.2-1 part of auxiliary agent; The compatibilizer is a stearic acid alcohol ester compatibilizer, and the stearic acid alcohol ester compatibilizer is pentaerythritol monostearate, pentaerythritol tetrastearate or dipentaerythritol stearate; The rubber content of the ABS resin is in the range of 32wt% to 39wt%; The average fiber length of the cellulose is 200 μm to 500 μm; The flame retardant comprises a brominated flame retardant and an antimony flame retardant in a mass ratio of (2-4):

1.

2. The low-carbon 5VA flame-retardant ABS material according to claim 1, characterized in that: The brominated flame retardant is at least one of brominated triazine, tetrabromobisphenol A, and brominated epoxy.

3. The low-carbon 5VA flame-retardant ABS material according to claim 1, characterized in that: The antimony-based flame retardant is antimony trioxide and / or antimony pentoxide.

4. The low-carbon 5VA flame-retardant ABS material according to claim 1, characterized in that: The auxiliary agent comprises an antioxidant and a lubricant; by weight, the antioxidant comprises 0.2 to 0.4 parts, and the lubricant comprises 0.4 to 0.6 parts.

5. The low-carbon 5VA flame-retardant ABS material according to claim 4, characterized in that: The antioxidant is a hindered phenol antioxidant or a phosphite antioxidant.

6. The low-carbon 5VA flame-retardant ABS material according to claim 4, characterized in that: The lubricant is at least one of a silicone lubricant and an amide lubricant.

7. The method for preparing the low-carbon 5VA flame-retardant ABS material according to any one of claims 1 to 6, characterized in that: The following steps are involved: The components are taken according to the weight parts, mixed, kneaded, extruded and post-processed to obtain the product.

8. The preparation method according to claim 7, characterized in that The extrusion temperature is 190° C. to 210° C., and the screw speed is 250 r / min to 300 r / min.

9. Use of the low-carbon 5VA flame-retardant ABS material according to any one of claims 1 to 6 in thin-walled products or office supplies in the fields of home appliances, sanitary ware, and automobiles.

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