Stress-cracking-resistant, high-heat-resistant and flame-retardant ABS composite material as well as preparation method and application thereof

Abstract

The invention discloses a stress-cracking-resistant, high-heat-resistant and flame-retardant ABS composite material and a preparation method thereof. The stress-cracking-resistant, high-heat-resistant and flame-retardant ABS composite material is prepared from the following components in parts by weight: 30 to 60 parts of ABS, 30 to 50 parts of heat-resistant master batch, 12 to 20 parts of brominated flame retardant, 5 to 8 parts of flame-retardant master batch, 3 to 10 parts of flexibilizer, 0.3 to 1.5 parts of antioxidant and 0.2 to 3 parts of lubricant. The invention also discloses application of the stress-cracking-resistant, high-heat-resistant and flame-retardant ABS composite material in manufacturing of automobile storage batteries. The heat-resistant master batch and the ABS composite material are prepared step by step, and the heat-resistant master batch, the brominated flame retardant and the flame-retardant master batch cooperate with one another, so that the heat resistance, the flame retardance and the stress cracking resistance of the ABS composite material are improved, and the problem that heat resistance, flame retardance and toughness are difficult to consider at the same time is effectively solved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of high polymer composite materials, and in particular to a stress-cracking-resistant high-heat-resistant flame-retardant ABS composite material, a preparation method thereof and an application thereof. BACKGROUND

[0002] With the popularization of start-stop systems (Start-Stop) and intelligent micro-hybrid (MHEV) technologies, lead-acid storage batteries are developing in the direction of high rate and high power. Such batteries generate a lot of heat during the process of high-current charging and discharging, and the working temperature of the shell can reach 50-75℃. The traditional ABS (heat distortion temperature HDT ≈ 80℃) is prone to softening and deformation. At the same time, the battery shell needs to withstand the corrosion of electrolyte, assembly stress and transportation vibration for a long time, and the environmental stress cracking (ESCR) performance is crucial.

[0003] Currently, commercially available flame-retardant ABS adopts the following schemes: heat-resistant modification by adding N-phenyl maleimide graft copolymer or alpha-methyl styrene oligomer (AMS), but the melting point of N-phenyl maleimide graft copolymer, such as styrene-N-phenyl maleimide-maleic anhydride copolymer, is very high (>130℃), which requires a processing temperature ≥240℃; the flame-retardant performance is improved by adding a combination of a bromine-based flame retardant (such as decabromodiphenyl ethane) and antimony trioxide (Sb2O3), but there are certain defects in the above two performance improvement processes: the bromine-based flame retardant is prone to decomposition at >230℃, which conflicts with the high temperature requirement of N-phenyl maleimide graft copolymer; Sb2O3 is a rigid inorganic particle that significantly reduces the elongation at break of ABS (from 30% to <15%), which aggravates the risk of stress cracking, and direct blending leads to uneven dispersion of N-phenyl maleimide graft copolymer, and overheating of the extrusion temperature causes decomposition of the bromine-based flame retardant, which reduces the mechanical properties of the material.

[0004] Therefore, it is necessary to provide a technical scheme to overcome the shortcomings of the prior art. SUMMARY

[0005] The present application overcomes the shortcomings of the prior art and provides a stress-cracking-resistant high-heat-resistant flame-retardant ABS composite material, a preparation method thereof and an application thereof, which effectively solves the problem that heat resistance, flame retardancy and toughness are difficult to be considered simultaneously, and in particular improves the environmental stress cracking resistance of the ABS composite material.

[0006] The present application is implemented by the following technical scheme: a stress-cracking-resistant high-heat-resistant flame-retardant ABS composite material, comprising the following components in parts by weight: ABS 30-60 parts, heat-resistant masterbatch 30-50 parts, bromine-based flame retardant 12-20 parts, flame-retardant masterbatch 5-8 parts, toughening agent 3-10 parts, antioxidant 0.3-1.5 parts, and lubricant 0.2-3 parts.

[0007] Preferably, the heat-resistant master batch comprises the following components by weight parts: ABS 40~60 parts, heat-resistant agent 30~60 parts, antioxidant 0.3~1.5 parts, lubricant 0.2~3 parts.

[0008] Preferably, the heat-resistant agent is N-phenyl maleimide graft copolymer.

[0009] Preferably, the bromine-based flame retardant is one of decabromodiphenyl ethane and brominated triazine.

[0010] Preferably, the toughening agent is one of ABS high glue powder, MBS, and silicon-based toughening agent.

[0011] Preferably, the flame retardant master batch is nitrogen-containing phosphorus heterocyclic compound.

[0012] The second object of the present application is to provide a preparation method of the stress cracking resistant high heat-resistant flame retardant ABS composite material, comprising the following steps: After the ABS, heat-resistant agent, antioxidant and lubricant are mixed uniformly according to the weight parts, they are melt-extruded and granulated by a double screw extruder to prepare the heat-resistant master batch; After the ABS, heat-resistant master batch, antioxidant and lubricant are mixed uniformly according to the weight parts, they are added from the main feeding port of the double screw extruder, and after the bromine-based flame retardant, flame retardant master batch and toughening agent are mixed uniformly according to the weight parts, they are added from the middle segment side feeding port of the double screw extruder, they are melt-extruded and granulated by a double screw extruder to prepare the stress cracking resistant high heat-resistant flame retardant ABS composite material.

[0013] Preferably, the extrusion temperature of the corresponding double screw extruder in the preparation process of the heat-resistant master batch is set to 200~250℃.

[0014] Preferably, the extrusion temperature of the corresponding double screw extruder in the preparation process of the stress cracking resistant high heat-resistant flame retardant ABS composite material is set to 180~210℃.

[0015] The third object of the present application is to provide the use of the above-mentioned stress cracking resistant high heat-resistant flame retardant ABS composite material for manufacturing automobile storage batteries.

[0016] The present application improves the heat resistance, flame retardance and stress cracking resistance of the ABS composite material by preparing the heat-resistant master batch and the ABS composite material in steps and by the synergy of the heat-resistant master batch, bromine-based flame retardant and flame retardant master batch, effectively solving the problem that heat resistance, flame retardance and toughness are difficult to be considered together. DETAILED DESCRIPTION

[0017] In order to have a clearer understanding of the technical features, objects and effects of the present application, the specific embodiments of the present application will be described in detail.

[0018] The technical solutions in the embodiments of the present application will be clearly and completely described below in conjunction with the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments of the present application, all other embodiments obtained by a person of ordinary skill in the art without creative work fall within the protection scope of the present application.

[0019] Embodiment 1

[0020] The heat-resistant master batch provided in the embodiment includes the following components by weight: ABS 40-60 parts, heat-resistant agent 30-60 parts, antioxidant 0.3-1.5 parts, and lubricant 0.2-3 parts.

[0021] The heat-resistant agent is an N-phenyl maleimide graft copolymer, the antioxidant is a compound mixture of one or more of antioxidant 1076, antioxidant 168 and antioxidant 1010, in the embodiment, the antioxidant is a compound mixture of antioxidant 1076, antioxidant 168 and antioxidant 1010 in a weight ratio of 1:1:1, the lubricant is EB-FF, and the heat-resistant agent is a styrene-N-phenyl maleimide-maleic anhydride copolymer.

[0022] After the ABS, the heat-resistant agent, the antioxidant and the lubricant are uniformly mixed by weight, they are melt-extruded and granulated by a twin-screw extruder to obtain the heat-resistant master batch. The extrusion temperature of the twin-screw is set to 200-250℃, the main machine speed is 450-550 r / min, specifically, the die temperature is 220℃, the temperature of the first zone is 200℃, the temperature of the second zone is 220℃, the temperature of the third zone is 235℃, the temperature of the fourth to sixth zones is 240℃, the temperature of the seventh and eighth zones is 235℃, the main machine speed is 520 r / min, and the vacuum degree is-0.06 MPa.

[0023] By the above preparation method, the 1# and 2# heat-resistant master batches are obtained in the embodiment. The specific components and corresponding weights are shown in the following table: Heat-resistant master batch formula table Component 1# 2# ABS 60 40 Heat Stabilizer 40 60 Antioxidant 1076 0.2 0.2 Antioxidant 168 0.2 0.2 Antioxidant 1010 0.2 0.2 Lubricant EB-FF 1 0.2 Embodiment 2

[0024] The stress-cracking-resistant high-heat-resistant flame-retardant ABS composite material includes the following components by weight: ABS 30-60 parts, heat-resistant master batch 30-50 parts, bromine-based flame retardant 12-20 parts, flame-retardant master batch 5-8 parts, toughening agent 3-10 parts, antioxidant 0.3-1.5 parts, and lubricant 0.2-3 parts.

[0025] The bromine flame retardant is one of decabromodiphenyl ethane and bromine triazine, the toughening agent is one of ABS high glue powder, MBS and silicon toughening agent, the flame retardant master batch is a nitrogen-containing phosphorus heterocyclic compound, and the flame retardant master batch in this embodiment is PolyFR provided by Ningbo Haikai Chemical Co., Ltd. @ T6550, the PolyFR @ T6550 is a nitrogen-containing phosphorus heterocyclic compound prepared by adding an antimony trioxide additive, a carrier resin and mixing and granulating at low temperature, and has the advantages of low-temperature processing, improved material flowability, improved impact strength and good carrier compatibility.

[0026] The ABS, the heat-resistant master batch, the antioxidant and the lubricant are uniformly mixed according to the weight parts, and then added from the main feeding port of the twin-screw extruder. The bromine flame retardant, the flame retardant master batch and the toughening agent are uniformly mixed according to the weight parts, and then added from the middle segment side feeding port of the twin-screw extruder. The twin-screw extruder is melt-extruded and granulated to prepare the stress cracking resistant high heat resistant flame retardant ABS composite material. The extrusion temperature of the twin-screw extruder is set to 180-210 DEG C to prevent the bromine flame retardant from decomposing. The main machine speed is 450-550 r / min. Specifically, the head temperature is 190 DEG C, the first zone temperature is 180 DEG C, the second zone temperature is 190 DEG C, the third zone to the sixth zone temperature is all 200 DEG C, the seventh zone temperature is 195 DEG C, the eighth zone temperature is 190 DEG C, the main machine speed is 500 r / min, and the vacuum degree is-0.06 MPa. The mixed bromine flame retardant, the flame retardant master batch and the toughening agent are added into the twin-screw extruder from the feeding port corresponding to the fifth zone. Example 3

[0027] The embodiment also provides that the stress cracking resistant high heat resistant flame retardant ABS composite material prepared in Example 2 is used to manufacture an automobile storage battery.

[0028] Comparative Example 1 The difference between the comparative example and Example 2 is that the ABS, the heat-resistant agent, the antioxidant and the lubricant are uniformly mixed according to the weight parts, and then added from the main feeding port of the twin-screw extruder. The bromine flame retardant, the antimony trioxide and the toughening agent are uniformly mixed according to the weight parts, and then added from the middle segment side feeding port of the twin-screw extruder. The twin-screw extruder is melt-extruded and granulated.

[0029] Comparative Example 2 The difference between the comparative example and Example 2 is that the ABS, the 1# heat-resistant master batch, the antioxidant and the lubricant are uniformly mixed according to the weight parts, and then added from the main feeding port of the twin-screw extruder. The bromine flame retardant, the antimony trioxide and the toughening agent are uniformly mixed according to the weight parts, and then added from the middle segment side feeding port of the twin-screw extruder. The twin-screw extruder is melt-extruded and granulated.

[0030] Comparative Example 3 The difference between the comparative example and Example 2 is that the ABS, heat-resistant masterbatch, antioxidant and lubricant are mixed uniformly according to the weight parts, and then added from the main feeding port of the twin-screw extruder, the bromine-based flame retardant, antimony trioxide and toughening agent are mixed uniformly according to the weight parts, and then added from the middle segment side feeding port of the twin-screw extruder, and then melt-extruded and granulated by the twin-screw extruder.

[0031] Comparative Example 4 The difference between the comparative example and Example 2 is that the ABS, heat-resistant masterbatch, antioxidant and lubricant are mixed uniformly according to the weight parts, and then added from the main feeding port of the twin-screw extruder, the bromine-based flame retardant, antimony trioxide and toughening agent are mixed uniformly according to the weight parts, and then added from the middle segment side feeding port of the twin-screw extruder, and then melt-extruded and granulated by the twin-screw extruder.

[0032] The products obtained after granulation in Examples 2 and Comparative Examples 1-4 were prepared into test samples for testing, and the following performance comparison table was obtained: Performance Comparison Table Name Model Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 A B C D Heat Stabilizer Masterbatch 1# --- 30 --- --- 30 40 --- --- Heat Stabilizer Masterbatch 2# --- --- 30 --- --- --- 30 30 ABS 72 40 40 72 40 30 40 50 Heat Stabilizer 12 --- --- 12 --- --- --- --- Sb203 4 4 4 --- --- --- --- --- Flame Retardant Masterbatch PolyFR @ T6550]]> --- --- --- 5 5 5 5 5 Bromine Flame Retardant FR-245 18 18 18 18 18 18 18 18 Antioxidant 1010 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Antioxidant 168 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Antioxidant 1076 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Lubricant EB-FF 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Flame Retardancy V-1 V-0 V-0 V-0 V-0 V-0 V-0 V-0 Tensile Strength MPa 38.5 39 39.2 38.5 39.5 40.2 40.3 40 Elongation at Break (%) 9 9.5 10 14 18 16.5 17.5 16 Izod impact strength (KJ / m 2 ) 14.5 15.6 16.1 14.8 17.3 17 16.5 16 Heat Distortion Temperature (°C) 87 94 94.5 93.4 95 97.5 95.3 98.2 ESCR Test (Vinegar Immersion) Cracking Cracked Cracked Slightly Cracked No Cracking No Cracking No Cracking No Cracking The four groups of ABS composites A, B, C and D prepared in Example 2 were prepared by preparing heat-resistant masterbatch and ABS composite at different temperatures, which solved the conflict between the easy decomposition of bromine-based flame retardant at greater than or equal to 230°C and the processing temperature of greater than or equal to 240°C required by heat-resistant agent, and the four groups of ABS composites in Example 2 were all free of antimony trioxide, which reduced the pollution risk of heavy metals, met the RoHS exemption provisions applicable to batteries, made the prepared automobile storage battery environmentally compliant, and the flame retardant performance of the test samples prepared from the four groups of ABS composites in Example 2 reached UL94 V-0 under the condition of a front width of 1.5 mm, without halogen migration risk, and the heat distortion temperature HDT obtained by testing under the condition of 0.45 MPa was greater than or equal to 95°C, meeting the high-rate battery temperature rise requirement, and the tensile elongation at break was more than 16%, which was at least 60% higher than Comparative Examples 1-3 and at least 10% higher than Comparative Example 4, and could meet the ESCR test under glacial acetic acid immersion, and the processing temperature window of the ABS composite was wide, from 180°C to 210°C, and under this span, the test sample had no yellowing and no precipitation, and the ABS composite prepared in Example 2 effectively solved the problem that heat resistance, flame retardance and toughness were difficult to be considered together.

[0033] This invention has been illustrated through several specific embodiments. Those skilled in the art will understand that various modifications and equivalent substitutions can be made to this invention without departing from its scope. Furthermore, various modifications can be made to this invention for specific situations or circumstances without departing from its scope. Therefore, this invention is not limited to the specific embodiments disclosed, but should include all embodiments falling within the scope of the claims.

Claims

1. A stress-cracking resistant, heat-resistant, and flame-retardant ABS composite material, characterized in that, It includes the following components by weight: 30-60 parts ABS, 30-50 parts heat-resistant masterbatch, 12-20 parts bromine-based flame retardant, 5-8 parts flame retardant masterbatch, 3-10 parts toughening agent, 0.3-1.5 parts antioxidant, and 0.2-3 parts lubricant.

2. The stress-cracking resistant, heat-resistant, and flame-retardant ABS composite material as described in claim 1, characterized in that, The heat-resistant masterbatch comprises the following components in parts by weight: 40-70 parts ABS, 30-60 parts heat resistant agent, 0.3-1.5 parts antioxidant, and 0.2-3 parts lubricant.

3. The stress-cracking resistant, heat-resistant, and flame-retardant ABS composite material as described in claim 2, characterized in that, The heat-resistant agent is an N-phenylmaleimide graft copolymer.

4. The stress-cracking resistant, heat-resistant, and flame-retardant ABS composite material as described in claim 1, characterized in that, The bromine-based flame retardant is one of decabromodiphenyl ethane and bromotriazine.

5. The stress-cracking resistant, heat-resistant, and flame-retardant ABS composite material as described in claim 1, characterized in that, The toughening agent is one of ABS high-resin powder, MBS, or silicone-based toughening agents.

6. The stress-cracking resistant, heat-resistant, and flame-retardant ABS composite material as described in claim 1, characterized in that, The flame retardant masterbatch is a nitrogen- and phosphorus-containing heterocyclic compound.

7. A method for preparing a stress-cracking resistant, heat-resistant, and flame-retardant ABS composite material as described in any one of claims 1 to 6, characterized in that, Includes the following steps: The heat-resistant masterbatch is prepared by uniformly mixing ABS, heat resistant agent, antioxidant and lubricant according to the weight parts, and then melt extruding and granulating it through a twin-screw extruder. ABS, heat-resistant masterbatch, antioxidant, and lubricant are mixed evenly according to their weight proportions and then fed into the main feed port of a twin-screw extruder. Brominated flame retardant, flame retardant masterbatch, and toughening agent are mixed evenly according to their weight proportions and then fed into the middle side feed port of the twin-screw extruder. The mixture is then melt-extruded and granulated by the twin-screw extruder to obtain the stress-cracking resistant, heat-resistant, and flame-retardant ABS composite material.

8. The method for preparing the stress-cracking resistant, heat-resistant, and flame-retardant ABS composite material as described in claim 7, characterized in that, The extrusion temperature of the twin-screw extruder used in the preparation of the heat-resistant masterbatch is set to 200℃~250℃.

9. The method for preparing the stress-cracking resistant, heat-resistant, and flame-retardant ABS composite material as described in claim 7, characterized in that, In the preparation process of the stress crack resistant, heat resistant, and flame retardant ABS composite material, the extrusion temperature of the corresponding twin-screw extruder is set to 180℃~210℃.

10. The use of the stress-cracking resistant, heat-resistant, and flame-retardant ABS composite material according to any one of claims 1 to 6 in the manufacture of automotive batteries.