Piercing-resistant ABS composition, preparation method therefor, and use thereof

Abstract

Provided in the present invention is a piercing-resistant ABS composition. The piercing-resistant ABS composition comprises the following components in parts by weight: 50-70 parts of SAN resin, 2-12 parts of an ultra-high molecular weight polymer, 30-45 parts of a toughener, and 0.1-1 part of a processing aid. The ultra-high molecular weight polymer is at least one of an acrylate or a styrene-acrylonitrile copolymer, the toughener is an acrylonitrile-butadiene-styrene graft copolymer, and the mass percentage of acrylonitrile in the SAN resin is 26-36%. The styrene-acrylonitrile copolymer or acrylate polymer having an ultra-high molecular weight is added to serve as a piercing-resistance enhancing component and is cooperated with the toughener so as to balance the strength and toughness of the material, and therefore the ABS material exhibits excellent piercing resistance at both room temperature and low temperatures.

Description

A puncture-resistant ABS composition, its preparation method and application

[0001] Technical Field

[0002] This invention relates to the field of engineering plastics technology, and more specifically, to a puncture-resistant ABS composition, its preparation method, and its application. Background Technology

[0003] ABS, or acrylonitrile-butadiene-styrene copolymer, is widely used in industries such as electrical appliances, electronic components, and automobiles due to its excellent dimensional stability, high impact strength, and ease of processing. However, in some device housing applications, ABS requires good puncture resistance to prevent damage to internal items or personnel when the housing is struck by a sharp object, thus providing effective protection.

[0004] ABS resin has a two-phase structure, with polybutadiene rubber as the dispersed phase and SAN resin as the continuous matrix phase. The polybutadiene rubber phase is dispersed in the matrix resin in particulate form. The presence of rubber particles can improve the impact resistance of ABS resin, but the introduction of polybutadiene rubber also makes the material softer, thus reducing its resistance to puncture by sharp objects and making it difficult to meet the requirements of puncture-resistant applications. Especially in winter environments, the material becomes very brittle, which may cause it to break into small fragments when impacted by sharp objects.

[0005] Chinese patent CN114276645A discloses an antibacterial high-strength ABS sheet for helmet manufacturing and its preparation method. In this invention, continuous fibers are added to reinforce the ABS resin, thereby improving the material's puncture resistance. Summary of the Invention

[0006] The primary objective of this invention is to overcome the shortcomings of existing ABS materials in terms of insufficient puncture resistance at both room temperature and low temperature, and to provide a puncture-resistant ABS composition. This ABS composition balances the strength and toughness of the material by adding ultra-high molecular weight polymers as puncture-resistant reinforcing components and combining them with toughening agents, so that the ABS material has excellent puncture resistance at both room temperature and low temperature.

[0007] A second objective of this invention is to provide a method for preparing a puncture-resistant ABS composition.

[0008] A third objective of this invention is to provide an application of a puncture-resistant ABS composition.

[0009] The above-mentioned objective of this invention is achieved through the following technical solution:

[0010] A puncture-resistant ABS composition, comprising the following components by weight:

[0011] 50-70 parts of SAN resin

[0012] 2-12 parts of ultra-high molecular weight polymer,

[0013] 30-45 parts toughening agent

[0014] Processing aids: 0.1-1 part;

[0015] The ultra-high molecular weight polymer is at least one of ultra-high molecular weight acrylate or ultra-high molecular weight styrene-acrylonitrile copolymer, and the toughening agent is an acrylonitrile-butadiene-styrene graft copolymer; the acrylonitrile mass percentage of the SAN resin is 26-36%.

[0016] This invention selects SAN resin with high acrylonitrile content. SAN resin with high acrylonitrile content not only has high material strength, but can also be toughened more effectively by toughening agents, thereby reducing the amount of toughening agent used. While reducing the softening effect of polybutadiene rubber in the toughening agent on the material, it can maintain efficient absorption of puncture energy and reduce the destructive effect of sharp objects on the material.

[0017] This invention incorporates ultra-high molecular weight polymers (UHMWPAs) as puncture resistance reinforcing components. UHMWPAs have long molecular chains and high inherent strength; their addition to ABS compositions increases the material's hardness, making it better resistant to punctures from sharp objects. The UHMWPAs are selected from styrene-acrylonitrile copolymers or acrylate polymers. Styrene-acrylonitrile copolymers have the same composition as SAN resin, exhibiting good compatibility and allowing the UHMWPA material to be uniformly dispersed within the ABS material, thereby significantly improving the material's puncture resistance.

[0018] Preferably, the acrylonitrile content of the SAN resin is 28-34% by mass.

[0019] In this invention, the acrylonitrile content of the SAN resin can be determined by infrared spectroscopy.

[0020] Preferably, in this invention, the weight-average molecular weight of the SAN resin is 90,000 to 120,000 g / mol.

[0021] Preferably, the weight-average molecular weight of the ultra-high molecular weight polymer is 2.5 million to 8 million g / mol.

[0022] 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.

[0023] Preferably, the weight-average molecular weight of the ultra-high molecular weight polymer is 2.8 million to 7.5 million g / mol.

[0024] The weight-average molecular weight of the ultra-high molecular weight polymer of this invention can be measured by the following method:

[0025] Gel permeation chromatography (GPC) was used for the analysis. Tetrahydrofuran was used as the solvent, and polystyrene was used as the standard. The mobile phase was THF, and the flow rate was 0.35 mL / min. -1 Detector temperature: 40℃; Column: TSK gel Super Mutipore HZ-M*2; Column temperature: 40℃; Sample concentration: 1mg / mL; Injection volume: 20uL.

[0026] Preferably, the toughening agent is an acrylonitrile-butadiene-styrene graft copolymer.

[0027] Preferably, the toughening agent contains 50-70% butadiene by mass. Specifically, the toughening agent is, for example, ABS POW HR181, 60POWDER, etc.

[0028] In this invention, the butadiene content in the toughening agent is obtained by converting the C, H, and N element content in the toughening agent using a combustion method elemental analysis test.

[0029] More preferably, the butadiene content in the toughening agent is 55-65% by mass, and even more preferably 57-62%.

[0030] The toughening agent selected in this invention is an acrylonitrile-butadiene-styrene graft copolymer, which has good compatibility with both SAN resin and ultra-high molecular weight polymers. It can effectively improve the toughness of ABS materials, enabling the materials to achieve efficient absorption of puncture energy.

[0031] Preferably, the processing aid is at least one of hindered phenolic antioxidants and amide lubricants.

[0032] More preferably, the hindered phenolic antioxidant is at least one of alkyl monophenols, alkyl polyphenols, and thiobisphenols.

[0033] More specifically, the alkyl monophenol antioxidants may include grades such as SONOX 1010 and SONOX 1076.

[0034] More specifically, the optional grades of the alkyl polyphenol antioxidants include antioxidant SDT.1, etc.

[0035] More specifically, the thiobisphenol antioxidants may be categorized into grades such as RIANOX DSTDP and RIANOX 412S.

[0036] More preferably, the amide lubricant can be ethylene bis-stearamide. Specific options include EBS B50, EB-FF, EBSP400, EBS HI-LUBE, etc.

[0037] Preferably, the puncture-resistant ABS composition further includes 0-10 parts by weight of other additives.

[0038] More preferably, the other additives include at least one of weather-resistant agents, antistatic agents, or colorants.

[0039] The method for preparing the above-mentioned puncture-resistant ABS composition includes the following steps:

[0040] According to the above-mentioned parts by weight, SAN resin, ultra-high molecular weight polymer, toughening agent and other additives are mixed evenly, melted, extruded and granulated to prepare the puncture-resistant ABS composition.

[0041] Preferably, the melt extrusion is performed using a twin-screw extruder with a screw speed of 300~500 r / min.

[0042] Preferably, the temperature of the melt extrusion is 190~210℃.

[0043] Applications of the above-mentioned puncture-resistant ABS composition in security parts, electric vehicles, automobiles, and luggage products.

[0044] Compared with the prior art, the present invention has the following beneficial effects:

[0045] This invention adds ultra-high molecular weight styrene-acrylonitrile copolymer or ultra-high molecular weight acrylate polymer as puncture resistance reinforcing component, combined with toughening agent, to balance the strength and toughness of the material, so that ABS material has excellent puncture resistance at both room temperature and low temperature. Embodiments of the present invention

[0046] The present invention will be further illustrated below with reference to specific embodiments, but the embodiments do not limit the present invention in any way. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in this technical field.

[0047] Unless otherwise specified, all reagents and materials used in the following examples are commercially available.

[0048] SAN-1: KFA-130L, acrylonitrile content 28%, Liaoning Kingfa Science & Technology Co., Ltd.

[0049] SAN-2: SAN 350 N, acrylonitrile content 32%, Kumho Petrochemical Co., Ltd., South Korea;

[0050] SAN-3: SAN NX3400, acrylonitrile content 34%, Ningbo Taihua;

[0051] SAN-4: KFA-130, acrylonitrile content 25%, Liaoning Kingfa Science & Technology Co., Ltd.

[0052] Toughening agent: Acrylonitrile-butadiene-styrene graft copolymer HR181, with butadiene content of 60% by mass;

[0053] Ultra-high molecular weight polymer-1: styrene-acrylonitrile copolymer, HK-503, measured weight-average molecular weight of 7.5 million, Shandong Yuanbang New Material Co., Ltd.

[0054] Ultra-high molecular weight polymer-2: styrene-acrylonitrile copolymer, HK-507, measured weight-average molecular weight of 3.5 million, Shandong Yuanbang New Material Co., Ltd.

[0055] Ultra-high molecular weight polymer-3: acrylate, K-385, measured weight-average molecular weight is 2.8 million, Weihai Jinhesi Chemical Co., Ltd.

[0056] Ultra-high molecular weight polymer-4: acrylate, K418, measured weight-average molecular weight is 3.5 million, Weihai Jinhesi Chemical.

[0057] Ultra-high molecular weight polymer-5: styrene-acrylonitrile copolymer, HK-502, with a measured weight-average molecular weight of 8.5 million, Shandong Yuanbang New Material Co., Ltd.

[0058] Ultra-high molecular weight polymer-6: acrylate, K20P, weight average molecular weight approximately 1.5 million, Weihai Jinhesi Chemical.

[0059] Ultra-high molecular weight polymer-7: Polyethylene, L4000, weight average molecular weight approximately 3.5 million, Mitsui Chemicals, Japan;

[0060] Other additives: Antioxidant 1010 and EBS B50 are compounded in a weight ratio of 1:2 and are commercially available.

[0061] Unless otherwise specified, all components used in the parallel embodiments and comparative examples are the same commercially available products.

[0062] In the specific implementation method, the weight-average molecular weight of the ultra-high molecular weight polymer was determined by gel permeation chromatography (GPC), using polystyrene as the standard, tetrahydrofuran as the mobile phase, and a flow rate of 0.35 mL / min. -1Detector temperature: 40℃; Column: TSK gel Super Mutipore HZ-M*2; Column temperature: 40℃; Sample concentration: 1 mg / mL; Injection volume: 20 μL. The weight-average molecular weight of each grade of ultra-high molecular weight polymer in the specific implementation method was determined by the molecular weight of the standard polystyrene.

[0063] Example 1

[0064] A puncture-resistant ABS composition, wherein the weight parts of the raw materials used are shown in Table 1.

[0065] The method for preparing the above-mentioned puncture-resistant ABS composition includes the following steps:

[0066] According to the above-mentioned parts by weight, SAN resin, ultra-high molecular weight polymer, toughening agent and other additives are mixed evenly, melted, extruded and granulated to prepare the puncture-resistant ABS composition.

[0067] The melt extrusion process uses a twin-screw extruder. The screw temperatures of each section of the twin-screw extruder, from the feed port to the die head, are set as follows: Zone 1: 80-100℃; Zone 2: 190-200℃; Zone 3: 200-210℃; Zone 4: 200-210℃; Zone 5: 200-210℃; Zone 6: 200-210℃; Zone 7: 200-210℃; Zone 8: 200-210℃; Zone 9: 200-210℃; and Die head temperature: 210-220℃. The screw speed is 300-500 r / min.

[0068] Examples 2 to 13 and Comparative Examples 1 to 8

[0069] The weight proportions of the raw materials used in Examples 2 to 13 are shown in Table 1, and the weight proportions of the raw materials used in Comparative Examples 1 to 8 are shown in Table 2.

[0070] The preparation steps of Examples 2 to 13 and Comparative Examples 1 to 8 are the same as those of Example 1.

[0071] Table 1 Formulation components of Examples 1 to 13

[0072]

[0073] Table 2 Formulation components of Comparative Examples 1-8

[0074]

[0075] Performance testing

[0076] The properties of the ABS compositions obtained in the above embodiments and comparative examples were characterized. The specific test items, test methods, and results are as follows:

[0077] (1) Room temperature puncture height: The test was conducted on a drop hammer impact tester. The puncture head was a conical head with a 60° angle at the tip. The test sample was a 100mm×100mm square plate with a thickness of 3mm. Before the test, 10mm thick foam cotton was pasted on the back of the square plate. The square plate was fixed on the fixture, and a 3kg weight was applied to the puncture head. The height of the puncture head was continuously increased, and the puncture head was allowed to fall freely until the foam cotton on the back was punctured. The height of the puncture head from the sample was recorded. It is generally believed that a room temperature puncture height of 60cm or more is needed to better meet the puncture requirements of the application. The test results are shown in Table 3.

[0078] (2) Low-temperature puncture height: The test was conducted on a drop hammer impact tester. The puncture head was a conical head with a 60° angle at the tip. The test sample was a 100mm×100mm square plate with a thickness of 3mm. Before the test, the 3mm square plate was frozen at -20℃ for 4 hours. 10mm thick foam was pasted on the back of the square plate. The square plate was fixed on the fixture. A 3kg weight was applied to the puncture head, and the height of the puncture head was continuously increased, allowing the puncture head to fall freely until the foam on the back was punctured. The height of the puncture head from the sample was recorded. It is generally believed that a low-temperature puncture height of 45cm or more is needed to better meet the low-temperature puncture requirements of the application. The test results are shown in Table 3.

[0079] (3) Energy absorption at room temperature: The high-speed puncture impact test was conducted according to the standard "ISO6603-2-2000 Plastics - Determination of puncture properties of rigid plastics - Part 2 Instrumental impact test". The energy after puncture was recorded. The higher the absorbed energy, the better the toughness of the material. The test results are shown in Table 3.

[0080] (4) Low-temperature energy absorption: The square plate was first frozen at -20℃ for 4 hours, and then a high-speed puncture impact test was carried out. According to the standard "ISO6603-2-2000 Plastics - Determination of puncture properties of rigid plastics - Part 2 Instrumental impact test", the energy after puncture was recorded. The higher the absorbed energy, the better the toughness of the material at low temperature. The test results are shown in Table 3.

[0081] (5) Bending strength: Tested according to ISO 178-2010 "Determination of bending properties of plastics" at a test speed of 2 mm / min at room temperature. The test results are shown in Table 3.

[0082] Table 3 Performance test results of Examples 1-13 and Comparative Examples 1-8

[0083]

[0084] As shown in Table 3, the ABS compositions prepared in the embodiments of this application can achieve a puncture height of over 60cm at room temperature and over 45cm at low temperature, absorb energy of over 30J at room temperature and over 20J at low temperature, and have a flexural strength of over 60MPa, exhibiting excellent puncture resistance at both room temperature and low temperature.

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

[0086] The ABS compositions prepared in Examples 1 and 10, and Examples 11 and 12, wherein the higher the weight-average molecular weight of the ultra-high molecular weight polymer, the better the puncture resistance of the ABS composition at both room temperature and low temperature.

[0087] Comparative Example 1 had too little toughening agent added. Although the material had high flexural strength, its energy absorption at room temperature and low temperature was low, resulting in poor toughness and poor puncture resistance at both room temperature and low temperature.

[0088] Comparative Example 2 had too much toughening agent added. Although it had high energy absorption at room temperature and low temperature, the material had low flexural strength, resulting in low puncture height at room temperature and low temperature. The material had poor puncture resistance at both room temperature and low temperature.

[0089] In Comparative Example 3, when an equal amount of ultra-high molecular weight polymer was replaced with SAN-1, the flexural strength, room temperature puncture height, and low temperature puncture height of the material were lower, and the puncture resistance at both room temperature and low temperature was significantly worse.

[0090] In Comparative Example 4, the addition of excessive ultra-high molecular weight polymers resulted in high flexural strength, but the puncture resistance enhancer was difficult to disperse well in the ABS composition, easily leading to stress concentration, reducing the energy absorbed at room temperature and low temperature, and failing to achieve high puncture height at room temperature and low temperature.

[0091] In Comparative Example 5, when the SAN resin was replaced with SAN containing 25% AN, the flexural strength, room temperature energy absorption, and low temperature energy absorption of the material were all reduced, and the puncture resistance was decreased.

[0092] Comparative Example 6 was replaced with an acrylate-based ultra-high molecular weight polymer with a weight average molecular weight of 8.5 million. The excessively large molecular weight of the added ultra-high molecular weight polymer makes it difficult to disperse well in the ABS composition, which can easily cause stress concentration in the material, reduce the energy absorbed at room temperature and low temperature, and fail to obtain a high puncture height at room temperature and low temperature.

[0093] Comparative Example 7 was replaced with an acrylate-based ultra-high molecular weight polymer with a molecular weight of 1.5 million. The added ultra-high molecular weight polymer had a small molecular weight, which reduced the strength of the material. The energy absorbed at room temperature and at low temperature was also low, and a high puncture height at room temperature and at low temperature was not obtained.

[0094] In Comparative Example 8, the ultra-high molecular weight polymer was replaced with ultra-high molecular weight polyethylene. Due to the poor compatibility between ultra-high molecular weight polyethylene and ABS composition, the energy absorption of the material at room temperature and low temperature was severely affected, and the bending strength was also slightly reduced, resulting in a decrease in the puncture height at room temperature and the puncture height at low temperature.

[0095] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A puncture-resistant ABS composition, characterized in that, By weight, it includes the following components: 50-70 parts of SAN resin 2-12 parts of ultra-high molecular weight polymer, 30-45 parts toughening agent Processing aids: 0.1-1 part; 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 an acrylonitrile-butadiene-styrene graft copolymer, and the acrylonitrile mass percentage of 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 toughening agent contains 50-70% butadiene by mass.

4. The puncture-resistant ABS composition according to claim 1, characterized in that, The processing aid is at least one of hindered phenolic antioxidants and amide lubricants.

5. The puncture-resistant ABS composition according to claim 4, characterized in that, The hindered phenolic 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 bis-stearamide.

7. The puncture-resistant ABS composition according to claim 1, characterized in that, The puncture-resistant ABS composition also includes other additives in the form of 0-10 parts by weight.

8. A method for preparing the puncture-resistant ABS composition according to any one of claims 1 to 7, characterized in that, Includes the following steps: The puncture-resistant ABS composition is prepared by uniformly mixing SAN resin, ultra-high molecular weight polymer, toughening agent and other additives, melting, extruding and granulating.

9. The preparation method according to claim 8, characterized in that, The melting and extrusion temperature is 190~210℃.

10. The use of the puncture-resistant ABS composition according to any one of claims 1 to 7 in parts security, electric vehicles, automobiles, and luggage products.

Images