Puncture-resistant ABS (Acrylonitrile Butadiene Styrene) composition and preparation method and application thereof

Abstract

The invention provides a puncture-resistant ABS (Acrylonitrile Butadiene Styrene) composition. The puncture-resistant ABS composition is prepared from the following components in parts by weight: 50 to 70 parts of SAN (Styrene Acrylonitrile Butadiene Styrene) resin, 2 to 12 parts of ultra-high molecular weight polymer, 30 to 45 parts of flexibilizer and 0.1 to 1 part of processing aid, the ultra-high molecular weight polymer is at least one of acrylate or a styrene-acrylonitrile copolymer, the flexibilizer is an acrylonitrile-butadiene-styrene graft copolymer, and the mass percentage of acrylonitrile in the SAN resin is 26-36%. According to the present invention, the styrene-acrylonitrile copolymer or the acrylate polymer with the ultra-high molecular weight is added as the puncture resistance reinforcing component, and is matched with the toughening agent to balance the strength and the toughness of the material, such that the ABS material has excellent normal-temperature and low-temperature puncture resistance.

Description

Technical Field

[0001] The present invention relates to the technical field of engineering plastics, and more specifically to a puncture-resistant ABS composition, a preparation method thereof and an application thereof. Background Art

[0002] ABS is a copolymer of acrylonitrile-butadiene-styrene. It is widely used in electrical appliances, electronic components, automobiles and other industrial fields due to its excellent dimensional stability, high impact strength and easy processing. However, in the shell application of some devices, ABS needs to have good puncture resistance to prevent the items or people inside from being damaged when the shell is hit by a sharp object, thus playing a good protective role.

[0003] ABS resin has a two-phase structure, with polybutadiene rubber as the dispersed phase and SAN resin as the matrix continuous phase. The polybutadiene rubber phase is dispersed in the matrix resin in the form of particles. Due to the presence of rubber particles, the impact resistance of ABS resin can be improved, but the introduction of polybutadiene rubber will also make the material softer, thereby reducing the ability to resist puncture from sharp objects, making it difficult to meet the application requirements of puncture resistance. Especially in winter environments, the material will become very brittle, resulting in small fragments that may fly out directly when impacted by sharp objects.

[0004] Chinese patent CN114276645A discloses an antibacterial high-strength ABS sheet for helmet manufacturing and a preparation method thereof. In the invention, continuous fibers are added to reinforce the ABS resin, thereby improving the material's puncture resistance. Summary of the invention

[0005] The primary purpose of the present invention is to overcome the defect of the existing ABS material having insufficient puncture resistance at room temperature and low temperature, and to provide a puncture-resistant ABS composition. The ABS composition balances the strength and toughness of the material by adding an ultra-high molecular weight polymer as a puncture-resistant reinforcing component and combining a toughening agent, so that the ABS material has excellent puncture resistance at room temperature and low temperature.

[0006] The second object of the present invention is to provide a method for preparing a puncture-resistant ABS composition.

[0007] The third object of the present invention is to provide an application of a puncture-resistant ABS composition

[0008] The above-mentioned object of the present invention is achieved by the following technical solutions:

[0009] A puncture-resistant ABS composition comprises the following components in parts by weight:

[0010] SAN resin 50-70 parts,

[0011] Ultra-high molecular weight polymer 2-12 parts,

[0012] 30-45 parts of toughening agent,

[0013] Processing aid 0.1-1 part;

[0014] The ultra-high molecular weight polymer is at least one of ultra-high molecular weight acrylate or ultra-high molecular weight styrene-acrylonitrile copolymer; the toughening agent is acrylonitrile-butadiene-styrene graft copolymer; and the mass percentage of acrylonitrile in the SAN resin is 26-36%.

[0015] The present invention selects SAN resin with high acrylonitrile content. The SAN resin with high acrylonitrile content not only has high material strength itself, but can also be toughened by a toughening agent more effectively, thereby reducing the amount of the toughening agent used, while reducing the softening effect of the polybutadiene rubber in the toughening agent on the material, while maintaining efficient absorption of puncture energy, thereby reducing the destructive effect of sharp objects on the material.

[0016] The present invention adds an ultra-high molecular weight polymer as an anti-puncture enhancement component. The ultra-high molecular weight polymer has a long molecular chain and high strength. When added to the ABS composition, the hardness of the material can be increased, making it better resistant to puncture by sharp objects. The ultra-high molecular weight polymer is selected from styrene-acrylonitrile copolymer or acrylic ester polymer. The styrene-acrylonitrile copolymer is consistent with the SAN resin component and has good compatibility. The ultra-high molecular weight substance can be evenly dispersed in the ABS material, thereby significantly improving the puncture resistance of the material.

[0017] Preferably, the mass percentage of acrylonitrile in the SAN resin is 28-34%.

[0018] In the present invention, the acrylonitrile content of the SAN resin can be determined by infrared spectroscopy.

[0019] Preferably, in the present invention, the weight average molecular weight of the SAN resin is 90,000 to 120,000 g / mol.

[0020] Preferably, the weight average molecular weight of the ultrahigh molecular weight polymer is 2.5 million to 8 million g / mol.

[0021] Those skilled in the art can select parameters within the above range according to actual needs. The weight average molecular weight of the ultra-high molecular weight polymer can also be 2.5 million g / mol, 3 million g / mol, 3.5 million g / mol, 4 million g / mol, 4.5 million g / mol, 5 million g / mol or any value within the above range.

[0022] Preferably, the weight average molecular weight of the ultrahigh molecular weight polymer is 2.8 to 7.5 million g / mol.

[0023] The weight average molecular weight of the ultra-high molecular weight polymer of the present invention can be measured by the following method:

[0024] Gel permeation chromatography (GPC) was used for testing. The solvent was tetrahydrofuran, polystyrene was used as the standard, and the mobile phase was THF. The flow rate was 0.35 mL min -1 ; Detector temperature: 40℃; Chromatographic column: TSK gel Super Mutipore HZ-M*2; Column temperature: 40℃; Sample concentration: 1mg / mL; Injection volume 20uL.

[0025] Preferably, the toughening agent is acrylonitrile-butadiene-styrene graft copolymer.

[0026] Preferably, the mass percentage of butadiene in the toughening agent is 50-70%. Specifically, the brand of the toughening agent is, for example, ABS POW HR181, 60POWDER, etc.

[0027] In the present invention, the content of butadiene in the toughening agent is calculated by testing the content of C, H and N elements in the toughening agent through elemental analysis using a combustion method.

[0028] More preferably, the mass percentage of butadiene in the toughening agent is 55-65%, more preferably 57-62%.

[0029] The toughening agent selected in the present invention is acrylonitrile-butadiene-styrene graft copolymer, which has good compatibility with SAN resin and ultra-high molecular weight polymer, can well improve the toughness of ABS material, and enable the material to achieve the effect of efficiently absorbing puncture energy.

[0030] Preferably, the processing aid is at least one of a hindered phenol antioxidant and an amide lubricant.

[0031] More preferably, the hindered phenol antioxidant is at least one of alkyl monophenols, alkyl polyphenols and thiobisphenols.

[0032] More specifically, the optional brands of the alkyl monophenol antioxidant include SONOX 1010, SONOX 1076 and the like.

[0033] More specifically, the optional grades of the alkyl polyphenol antioxidant include antioxidant SDT.1 and the like.

[0034] More specifically, the optional brands of the thiobisphenol antioxidant include RIANOX DSTDP, RIANOX 412S, etc. More preferably, the amide lubricant can be ethylene bisstearamide. Specific optional brands include EBSB50, EB-FF, EBSP400, EBS HI-LUBE, etc.

[0035] Preferably, the puncture-resistant ABS composition further comprises 0-10 parts by weight of other additives.

[0036] More preferably, the other auxiliary agents include at least one of a weathering agent, an antistatic agent or a colorant.

[0037] The preparation method of the puncture-resistant ABS composition comprises the following steps:

[0038] According to the above weight parts, the SAN resin, the ultra-high molecular weight polymer, the toughening agent and other additives are uniformly mixed, melted, extruded and granulated to prepare the puncture-resistant ABS composition.

[0039] Preferably, the melt extrusion is performed using a twin-screw extruder with a screw speed of 300 to 500 r / min.

[0040] Preferably, the temperature of the melt extrusion is 190-210°C.

[0041] The puncture-resistant ABS composition is used in security products, electric vehicles, automobiles, and luggage products.

[0042] Compared with the prior art, the present invention has the following beneficial effects:

[0043] The present invention adds ultra-high molecular weight styrene-acrylonitrile copolymer or ultra-high molecular weight acrylic polymer as a puncture resistance enhancing component and combines it with a toughening agent to balance the strength and toughness of the material, so that the ABS material has excellent room temperature and low temperature puncture resistance. DETAILED DESCRIPTION

[0044] In order to more clearly and completely describe the technical solution of the present invention, the present invention is further described in detail through specific embodiments below. It should be understood that the specific embodiments described herein are only used to explain the present invention, and are not used to limit the present invention. Various changes can be made within the scope of the rights of the present invention.

[0045] In the following examples, unless otherwise stated, the raw materials and reagents used in the examples of the present invention are conventionally purchased raw materials and reagents:

[0046] SAN-1: KFA-130L, acrylonitrile content 28%, Liaoning Jinfa Technology Co., Ltd.;

[0047] SAN-2: SAN 350N, acrylonitrile content 32%, Kumho Petrochemical Co., Ltd., South Korea;

[0048] SAN-3: SAN NX3400, acrylonitrile content 34%, Ningbo Formosa Chemical Co., Ltd.

[0049] SAN-4: KFA-130, acrylonitrile content 25%, Liaoning Jinfa Technology Co., Ltd.;

[0050] Toughening agent: acrylonitrile-butadiene-styrene graft copolymer HR181, butadiene mass percentage is 60%;

[0051] Ultra-high molecular weight polymer-1: styrene-acrylonitrile copolymer, HK-503, the measured weight average molecular weight is 7.5 million, Shandong Yuanbang New Materials Co., Ltd.;

[0052] Ultra-high molecular weight polymer-2: styrene-acrylonitrile copolymer, HK-507, weight average molecular weight measured value is 3.5 million, Shandong Yuanbang New Materials Co., Ltd.;

[0053] Ultra-high molecular weight polymer-3: Acrylate, K-385, the measured weight average molecular weight is 2.8 million, Weihai Jinhesi Chemical;

[0054] Ultra-high molecular weight polymer-4: acrylic ester, K418, the measured weight average molecular weight is 3.5 million, Weihai Jinhesi Chemical;

[0055] Ultra-high molecular weight polymer-5: styrene-acrylonitrile copolymer, HK-502, weight average molecular weight measured value is 8.5 million, Shandong Yuanbang New Materials Co., Ltd.;

[0056] Ultra-high molecular weight polymer-6: acrylic esters, K20P, weight average molecular weight of about 1.5 million, Weihai Jinhesi Chemical;

[0057] Ultra-high molecular weight polymer-7: polyethylene, L4000, weight average molecular weight of about 3.5 million, Mitsui Chemicals, Japan;

[0058] Other additives: Antioxidant 1010 and EBS B50 are mixed in a weight ratio of 1:2 and are commercially available.

[0059] Unless otherwise specified, the components used in the parallel embodiments and comparative examples are all the same commercially available products.

[0060] In a specific embodiment, the weight average molecular weight of the ultrahigh molecular weight polymer is measured by gel permeation chromatography (GPC), using polystyrene as a standard, tetrahydrofuran as a mobile phase, and a flow rate of 0.35 mL min -1 ; Detector temperature: 40°C; Chromatographic column: TSK gel Super Mutipore HZ-M*2; Column temperature: 40°C; Sample concentration: 1 mg / mL; Injection volume: 20 uL. The weight average molecular weight of each brand of ultra-high molecular weight polymer in the specific implementation method is determined by the molecular weight of standard polystyrene.

[0061] Example 1

[0062] A puncture-resistant ABS composition, the weight proportions of raw materials used are shown in Table 1.

[0063] The preparation method of the puncture-resistant ABS composition comprises the following steps:

[0064] According to the above weight parts, the SAN resin, the ultra-high molecular weight polymer, the toughening agent and other additives are uniformly mixed, melted, extruded and granulated to prepare the puncture-resistant ABS composition.

[0065] Among them, a twin-screw extruder is used for melt extrusion, and the temperatures of each section of the screw of the twin-screw extruder are set to 80-100°C for zone 1, 190-200°C for zone 2, 200-210°C for zone 3, 200-210°C for zone 4, 200-210°C for zone 5, 200-210°C for zone 6, 200-210°C for zone 7, 200-210°C for zone 8, 200-210°C for zone 9, and 210-220°C for zone head from the feeding port to the die, and the screw speed is 300-500r / min.

[0066] Examples 2 to 13 and Comparative Examples 1 to 8

[0067] The weight portions of the raw materials used in Examples 2 to 13 are shown in Table 1, and the weight portions of the raw materials used in Comparative Examples 1 to 8 are shown in Table 2.

[0068] The preparation steps of Examples 2 to 13 and Comparative Examples 1 to 8 are the same as those of Example 1.

[0069] Table 1 Formula components of Examples 1 to 13

[0070]

[0071]

[0072] Table 2 Formula components of comparative examples 1 to 8

[0073] Comparative Example 1 2 3 4 5 6 7 8 SAN resin-1 60 60 65 60 / 60 60 60 SAN resin-4 / / / / 60 / / / Toughening agent 25 55 35 35 35 35 35 35 Ultra high molecular weight polymer-1 5 5 / 15 5 / / / Ultra High Molecular Weight Polymer-5 / / / / / 5 / / Ultra high molecular weight polymer-6 / / / / / / 5 / Ultra high molecular weight polymer-7 / / / / / / / 5 Processing Aids 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8

[0074] Performance Testing

[0075] The properties of the ABS compositions obtained in the above examples and comparative examples were characterized, and the specific test items, test methods and results are as follows:

[0076] (1) Puncture height at room temperature: The test is carried out on a drop hammer impact tester. The puncture head is a conical head with a tip angle of 60°. The test sample is a 100mm×100mm square plate with a thickness of 3mm. Before the test, a 10mm thick foam cotton is pasted on the back of the square plate, and the square plate is fixed on the fixture. A 3kg weight is applied to the puncture head, and the height of the puncture head is continuously increased. The puncture head is allowed to fall freely until the foam cotton on the back is punctured. The height of the puncture head from the sample is recorded. It is generally believed that the puncture height at room temperature must reach more than 60cm to better meet the puncture requirements of the application. The test results are shown in Table 3;

[0077] (2) Low-temperature puncture height: The test is carried out on a drop hammer impact tester. The puncture head is a conical head with a tip at an angle of 60°. The test sample is a 100mm×100mm square plate with a thickness of 3mm. Before the test, the 3mm square plate is frozen at -20℃ for 4h, and a 10mm thick foam cotton is pasted on the back of the square plate. The square plate is fixed on the fixture, and a 3kg weight is applied to the puncture head. The height of the puncture head is continuously increased, and the puncture head is allowed to fall freely until the foam cotton on the back is punctured. The height of the puncture head from the sample is recorded. It is generally believed that the low-temperature puncture height must reach more than 45cm to better meet the low-temperature puncture requirements of the application. The test results are shown in Table 3;

[0078] (3) Absorbed energy at room temperature: The high-speed puncture impact test is carried out in accordance with the standard "ISO6603-2-2000 Plastics. Determination of puncture properties of rigid plastics Part 2 Instrumented impact test", and the energy after puncture is recorded. The higher the absorbed energy, the better the toughness of the material. The test results are shown in Table 3;

[0079] (4) Low-temperature energy absorption: First, freeze the square plate at -20°C for 4 hours, and then conduct a high-speed puncture impact test. According to the standard "ISO6603-2-2000 Plastics. Determination of puncture properties of rigid plastics Part 2 Instrumented impact test", record the energy after puncture. The higher the absorbed energy, the better the toughness of the material at low temperature. The test results are shown in Table 3;

[0080] (5) Flexural strength: tested in accordance with ISO 178-2010 “Determination of flexural properties of plastics”, with a test speed of 2 mm / min and tested at room temperature. The test results are shown in Table 3.

[0081] Table 3 Performance test results of Examples 1 to 13 and Comparative Examples 1 to 8

[0082]

[0083]

[0084] It can be seen from the data in Table 3 that the ABS compositions prepared in the examples of the present application have a room temperature puncture height of more than 60 cm, a low temperature puncture height of more than 45 cm, a high temperature absorption energy of more than 30 J, a low temperature absorption energy of more than 20 J, and a bending strength of more than 60 MPa, and have excellent room temperature and low temperature puncture resistance.

[0085] In the ABS compositions prepared in Examples 1 to 3, the higher the acrylonitrile content of the SAN resin, the better the room temperature and low temperature puncture resistance of the ABS composition.

[0086] In the ABS compositions prepared in Examples 1 and 10, and Examples 11 and 12, the larger the weight average molecular weight of the ultrahigh molecular weight polymer is, the better the room temperature and low temperature puncture resistance of the ABS composition is.

[0087] In Comparative Example 1, too little toughening agent is added. Although the bending strength of the material is high, the energy absorption at room temperature and low temperature is low, the toughness of the material is poor, and the puncture resistance at room temperature and low temperature is poor.

[0088] In Comparative Example 2, too much toughening agent was added. Although the material had higher room-temperature absorption energy and low-temperature absorption energy, the bending strength of the material was low, resulting in lower room-temperature puncture height and low-temperature puncture height, and the material's room-temperature and low-temperature puncture resistance was poor.

[0089] In Comparative Example 3, an equal amount of ultrahigh molecular weight polymer was replaced with SAN-1. The bending strength, room temperature puncture height and low temperature puncture height of the material were lower, and the room temperature and low temperature puncture resistance performance deteriorated significantly.

[0090] In Comparative Example 4, too much ultra-high molecular weight polymer is added. Although the bending strength is high, the anti-puncture enhancer is difficult to disperse well in the ABS composition, which easily causes stress concentration, reduces the room temperature absorption energy and low temperature absorption energy, and fails to obtain a higher room temperature puncture height and low temperature puncture height.

[0091] In Comparative Example 5, the SAN resin was replaced with SAN with an AN content of 25%. The bending strength, room temperature absorption energy and low temperature absorption energy of the material were reduced, and the puncture resistance performance decreased.

[0092] Comparative Example 6 was replaced with an acrylic ultra-high molecular weight polymer with a weight-average molecular weight of 8.5 million. The ultra-high molecular weight of the added polymer was too large, which would make it difficult to disperse well in the ABS composition, and would easily cause stress concentration in the material, reduce the room-temperature absorption energy and the low-temperature absorption energy, and fail to obtain a higher room-temperature puncture height and a lower-temperature puncture height.

[0093] Comparative Example 7 was replaced with an acrylic ultra-high molecular weight polymer with a molecular weight of 1.5 million. The added ultra-high molecular weight polymer had too small a molecular weight, so the strength of the material was reduced, and the room temperature absorption energy and low temperature absorption energy were also low, so a higher room temperature puncture height and low temperature puncture height were not obtained.

[0094] In Comparative Example 8, the ultrahigh molecular weight polymer is replaced with ultrahigh molecular weight polyethylene. Since the compatibility of ultrahigh molecular weight polyethylene with the ABS composition is very poor, the room temperature and low temperature energy absorption of the material is seriously affected, and the bending strength is also slightly reduced, resulting in a decrease in the room temperature puncture height and the low temperature puncture height.

[0095] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the embodiments here. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the claims of the present invention.

Claims

1. A puncture-resistant ABS composition, characterized in that: By weight, it includes the following components: The ultra-high molecular weight polymer is at least one of ultra-high molecular weight acrylate or ultra-high molecular weight styrene-acrylonitrile copolymer, the toughening agent is acrylonitrile-butadiene-styrene graft copolymer, and the mass percentage of acrylonitrile in the SAN resin is 26-36%.

2. The puncture-resistant ABS composition according to claim 1, characterized in that: The weight average molecular weight of the ultra-high molecular weight polymer is 2.5 million to 8 million g / mol.

3. The puncture-resistant ABS composition according to claim 1, characterized in that: The mass percentage of butadiene in the toughening agent is 50-70%.

4. The puncture-resistant ABS composition according to claim 1, characterized in that: The processing aid is at least one of a hindered phenol antioxidant and an amide lubricant.

5. The puncture-resistant ABS composition according to claim 4, characterized in that: The hindered phenol antioxidant is at least one of alkyl monophenols, alkyl polyphenols and thiobisphenols.

6. The puncture-resistant ABS composition according to claim 4, characterized in that: The amide lubricant is ethylene bisstearamide.

7. The puncture-resistant ABS composition according to claim 1, characterized in that: The puncture-resistant ABS composition further comprises other auxiliary agents in 0-10 parts by weight.

8. The method for preparing the puncture-resistant ABS composition according to any one of claims 1 to 7, characterized in that: The steps include: The SAN resin, ultra-high molecular weight polymer, toughening agent and other additives are uniformly mixed, melted, extruded and granulated to prepare the puncture-resistant ABS composition.

9. The preparation method according to claim 8, characterized in that: The temperature of the melting and extrusion is 190-210°C.

10. Use of the puncture-resistant ABS composition according to any one of claims 1 to 7 in products such as security products, electric vehicles, automobiles, and luggage boxes.

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