ABS composite material as well as preparation method and application thereof

Abstract

The invention relates to an ABS composite material as well as a preparation method and application thereof. The anti-dripping ABS composite material is prepared from the following components in parts by weight: 54 to 85 parts of ABS resin, 11 to 21 parts of brominated flame retardant and 5 to 11 parts of anti-dripping agent, the anti-dripping agent is an ultra-high molecular weight acrylate polymer, and the weight-average molecular weight of the anti-dripping agent is greater than or equal to 1.2 * 10 < 6 > g / mol. The ABS composite material disclosed by the invention has good flame retardant property, good anti-dripping property and high melt strength.

Description

Technical Field

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

[0002] ABS is a terpolymer of acrylonitrile (A)-butadiene (B)-styrene (S). It combines the properties of the three components, of which acrylonitrile has high hardness and strength, heat resistance and corrosion resistance; butadiene has impact resistance and toughness; and styrene has high surface gloss, easy coloring and easy processing. ABS has been widely used in manufacturing industries such as machinery, electrical, textile, automobile, aircraft, and shipbuilding, as well as in the chemical industry.

[0003] The polar oxygen index of ABS is only 18-20, and it is a flammable polymer material. When ABS is used in the housing of electrical equipment that requires electrical insulation and flame retardancy, it needs to be flame retardant and anti-dripping modified. Adding flame retardants is a simple and efficient way to achieve flame retardant modification of ABS. The commonly used flame retardants in ABS are brominated flame retardants. However, the flame retardant performance of ABS with only brominated flame retardants is limited, and the anti-dripping performance is poor.

[0004] At present, the main method is to add polytetrafluoroethylene to further improve the flame retardant properties and achieve anti-dripping, such as the Chinese patent named a heat-resistant flame-retardant ABS resin. However, polytetrafluoroethylene has been gradually restricted in production and use due to environmental issues. Therefore, it is necessary to develop other synergistic flame retardant and anti-dripping technologies for ABS materials that replace polytetrafluoroethylene.

[0005] In addition, when the material is injection molded into the housing of large electrical equipment, the material needs to have high melt strength to ensure that the melt is stable during the extrusion process, thereby ensuring the size and appearance of the housing are good. However, the current ABS material has the problem of low melt strength when made into the housing of large electrical equipment. Summary of the invention

[0006] The primary purpose of the present invention is to overcome the problem that there is a lack of technology to replace the addition of polytetrafluoroethylene to improve the synergistic flame retardant technology and anti-dripping performance of ABS resin materials, or the melt strength of ABS materials is not good, and to provide an ABS composite material.

[0007] A further object of the present invention is to provide a method for preparing the above ABS composite material.

[0008] A further object of the present invention is to provide the use of the above ABS composite material in the preparation of household appliance control boxes, electronic appliance racks or building decoration materials.

[0009] The above-mentioned object of the present invention is achieved by the following technical solutions:

[0010] An ABS composite material comprises the following components in parts by weight:

[0011] ABS resin 54-85 parts,

[0012] 11 to 21 parts of brominated flame retardant,

[0013] 5-11 parts of anti-dripping agent;

[0014] The anti-dripping agent is an ultra-high molecular weight acrylic polymer, and the weight average molecular weight of the anti-dripping agent is ≥1.2×10 6 g / mol.

[0015] The inventors of the present invention have found through research that the use of ultra-high molecular weight (≥1.2×10 6 The acrylate polymer with an acrylate group of 100 g / mol is used as an anti-dripping agent. Since the polarity of the acrylate group is close to that of the SAN component in the ABS resin, it has good compatibility with the ABS resin. In addition, its molecular chain is very long, and it is easy to be oriented by shearing and stretching during injection molding, and it is easy to overlap each other to form a network structure, and cooperate with the brominated flame retardant to improve the anti-dripping performance of the ABS composite material. At the same time, the addition of the ultra-high molecular weight acrylate polymer is also conducive to improving the flame retardant performance of the ABS composite material.

[0016] In addition, the inventors have also found that since the molecular chains of ultra-high molecular weight acrylic polymers are very long and the entanglement of the molecular chains is strong, it provides support for the melt, thereby improving the melt strength of the ABS composite material.

[0017] In the present invention, the weight average molecular weight of the ultra-high molecular weight acrylic ester polymer can be measured by gel permeation chromatography. The weight average molecular weight of the acrylic ester polymer can be specifically 1.2×10 6 , 1.5×10 6 , 2.0×10 6 , 2.5×10 6 , 3.0×10 6 , 3.3×10 6 , 3.3×10 6 , 3.8×10 6 4.0×10 6 , 4.5×10 6 4.8×10 6 , 5.0×10 6 , 5.5×10 6 , 5.8×10 6 , 6.0×10 6 , 6.5×10 6 , 7.0×10 6, 7.5×10 6 , 8.0×10 6 or 8.2×10 6 g / mol or 9.0×10 6 The amount of the anti-dripping agent added can be 5, 6, 7, 8, 9 or 10 parts by weight or the range between any of the above values.

[0018] The weight average molecular weight of ultra-high molecular weight acrylic polymers is determined by gel permeation chromatography. The specific process is as follows: Pretreatment: Take a small amount of acrylic polymer and dissolve it in tetrahydrofuran, and use microporous filtration to inject it into the injection bottle; the mobile phase is tetrahydrofuran, the test temperature is 40°C, the flow rate is 0.35mL / min, the standard sample is polystyrene, and the chromatographic column model is: TSK gel Super Mutipore HZ-M*2.

[0019] In the present invention, ABS resin is used as the main resin, which accounts for more than 50wt% of the ABS composite material.

[0020] Preferably, the ABS composite material comprises the following components in parts by weight:

[0021] ABS resin 55-71 parts,

[0022] 15-20 parts of brominated flame retardant,

[0023] 8 to 10 parts of anti-dripping agent.

[0024] By regulating the amounts of the components of the ABS composite material within this range, the obtained ABS composite material has higher anti-drip performance and higher melt strength.

[0025] Preferably, the weight average molecular weight of the anti-dripping agent is ≥1.5×10 6 g / mol.

[0026] More preferably, the weight average molecular weight of the anti-dripping agent is 3.5×10 6 g / mol~9.0×10 6 g / mol.

[0027] More preferably, the weight average molecular weight of the anti-dripping agent is 5.0×10 6 g / mol~8.0×10 6 g / mol.

[0028] By regulating the weight average molecular weight of the anti-drip agent within this range, the obtained ABS composite material has higher anti-drip performance and higher melt strength.

[0029] Preferably, the melt flow rate of the ABS resin at 220° C. and 10 kg load is 10 to 25 g / 10 min. The melt flow rate of the ABS resin is measured according to ISO1133-1-2011 standard.

[0030] Preferably, the average particle size of the rubber phase of the ABS resin is 200-1000 nm. The average particle size of the rubber phase can be obtained by transmission electron microscopy and statistics.

[0031] Preferably, the ABS resin has a butadiene content of 10 to 30 wt%, an acrylonitrile content of 15 to 30 wt%, and a styrene content of 40 to 75 wt%.

[0032] In the present invention, the butadiene content, acrylonitrile content and styrene content of the ABS resin can be obtained by testing the carbon, hydrogen and nitrogen content in the ABS resin by combustion element analysis and converting them.

[0033] Preferably, the acrylic polymer is at least one of a butyl acrylate polymer and a copolymer of butyl acrylate and methyl methacrylate.

[0034] Preferably, the brominated flame retardant is at least one of tetrabromobisphenol A, tris(tribromophenoxy)cyanurate, brominated epoxy oligomer or decabromodiphenylethane.

[0035] More preferably, the brominated flame retardant is tetrabromobisphenol A. By selecting the brominated flame retardant, the obtained ABS composite material has better anti-dripping performance and higher melt strength.

[0036] Preferably, the ABS composite material further comprises 2 to 5 parts of a flame retardant synergist.

[0037] More preferably, the flame retardant synergist is an antimony-containing compound.

[0038] More preferably, the antimony-containing compound is at least one of antimony trioxide, antimony pentoxide or antimonate.

[0039] In order to improve the toughness of the ABS composite material, a toughening agent may also be added in the present invention.

[0040] Preferably, the ABS composite material further comprises 2 to 10 parts of a toughening agent.

[0041] More preferably, the toughening agent is at least one of a linear structure toughening agent or a core-shell structure toughening agent.

[0042] Further preferably, the linear structural toughening agent includes but is not limited to at least one of chlorinated polyethylene, styrene-butadiene-styrene block copolymer, hydrogenated styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer or styrene-butadiene random copolymer.

[0043] Further preferably, the core-shell structure toughening agent includes but is not limited to styrene-butadiene-acrylonitrile graft copolymer.

[0044] Preferably, the ABS composite material further comprises 0.1 to 1 part of other additives.

[0045] More preferably, the other auxiliary agent is at least one of an antioxidant, a lubricant or a weathering agent.

[0046] More preferably, the antioxidant is at least one of a hindered phenol antioxidant or a phosphate antioxidant.

[0047] Further preferably, the hindered phenol antioxidant is at least one of an alkyl monophenol antioxidant, an alkyl polyphenol antioxidant or a thiobisphenol antioxidant.

[0048] More preferably, the phosphate antioxidant is at least one of 2,4-di-tert-butylphenol (Irganox 168), bis(2,6-di-tert-butyl-4-tolyl) pentaerythritol phosphite (PEP-36) or 627A.

[0049] Further preferably, the lubricant includes but is not limited to amide lubricants.

[0050] Further preferably, the stearamide lubricant is at least one of EBS B50 (ethylene bisstearamide), EB-FF (ethylene bisstearamide), EBS P400 (ethylene bisstearamide) or WK1890 (erucic acid amide).

[0051] More preferably, the weathering agent is at least one of a benzophenone ultraviolet absorber, a benzotriazole ultraviolet absorber, a triazine ultraviolet absorber or a hindered amine light stabilizer.

[0052] The preparation method of the above ABS composite material comprises the following steps:

[0053] The components are mixed uniformly, melted, extruded and granulated to obtain the ABS composite material.

[0054] The application of the above ABS composite material in the preparation of household appliances, electronic appliances or office supplies also falls within the protection scope of the present invention.

[0055] Compared with the prior art, the present invention has the following beneficial effects:

[0056] The ABS composite material of the present invention has good flame retardancy, good anti-dripping performance and high melt strength. Specifically, the continuous burning dripping time of the ABS composite material of the present invention is more than 35 seconds, the flame retardancy level is more than V-0, and the melt strength test is 230-450mN. DETAILED DESCRIPTION

[0057] 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.

[0058] Some of the reagents selected in the embodiments and comparative examples of the present invention are described as follows:

[0059] ABS resin 1#: KF-730, melt flow rate at 220°C and 10kg load is 22g / 10min, produced by Liaoning Kingfa Technology Co., Ltd.;

[0060] ABS resin 2#: brand ABS 8434, melt flow rate at 220°C and 10kg load is 16g / 10min, produced by Shanghai Gaoqiao Co., Ltd.;

[0061] ABS resin 3#: brand name is ABS KF-718, melt flow rate at 220℃ and 10kg load is 12g / 10min, manufacturer is Liaoning Jinfa Technology Co., Ltd.;

[0062] Brominated flame retardant 1#: tris(tribromophenyl)cyanurate, commercially available;

[0063] Brominated flame retardant 2#: brominated epoxy oligomer, brand CXB-714C, manufactured by Korea Yujin Company;

[0064] Brominated flame retardant 3#: tetrabromobisphenol A, commercially available;

[0065] Flame retardant synergist: antimony trioxide, commercially available;

[0066] Anti-drip agent 1#: copolymer of butyl acrylate and methyl methacrylate, brand K-700, weight average molecular weight is about 7.0×10 6 g / mol, the manufacturer is Weihai Jinhesi Chemical;

[0067] Anti-drip agent 2#: polybutyl acrylate (butyl acrylate polymer), brand K-418, weight average molecular weight is about 3.5×10 6 g / mol, the manufacturer is Weihai Jinhesi Chemical;

[0068] Anti-drip agent 3#: polybutyl acrylate (butyl acrylate polymer), brand K-618, weight average molecular weight is about 5.0×10 6 g / mol, the manufacturer is Weihai Jinhesi Chemical;

[0069] Anti-drip agent 4#: copolymer of butyl acrylate and methyl methacrylate, brand HK-90, weight average molecular weight is about 8.0×10 6 g / mol, the manufacturer is Shandong Yuanbang New Materials Co., Ltd.;

[0070] Anti-drip agent 5#: copolymer of butyl acrylate and methyl methacrylate, brand K-20P, weight average molecular weight is about 1.5×10 6 g / mol, the manufacturer is Weihai Jinhesi Chemical;

[0071] Anti-drip agent 6#: copolymer of butyl acrylate and methyl methacrylate, brand HK-901, weight average molecular weight is about 9.0×10 6 g / mol, the manufacturer is Shandong Yuanbang New Materials Co., Ltd.;

[0072] Conventional acrylic polymer: copolymer of methyl methacrylate and butyl acrylate, brand name BA141, manufacturer LG Chemical Co., Ltd., weight average molecular weight 1.0×10 5 g / mol.

[0073] The weight average molecular weight of the above-mentioned acrylic ester polymer is determined by gel permeation chromatography, and the specific process is as follows: pretreatment: take a small amount of acrylic ester polymer and dissolve it in tetrahydrofuran, and use microporous filtration to inject into the injection bottle; the mobile phase is tetrahydrofuran, the test temperature is 40°C, the flow rate is 0.35mL / min, the standard sample is polystyrene, and the chromatographic column model is: TSK gelSuper Mutipore HZ-M*2.

[0074] Polyethylene: Brand name L4000, weight average molecular weight about 3.5 million, manufactured by Japan Mitsui Chemicals;

[0075] Polytetrafluoroethylene: brand name is X-010, produced by Shandong Dongyue Polymer Materials Co., Ltd.;

[0076] Toughening agent: Chlorinated polyethylene, IM500, Weifang Shandao Chemical Co., Ltd.;

[0077] Other additives 1#: The weight ratio of antioxidant to lubricant is 1:2. The antioxidant is pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, commercially available; the lubricant is vinyl bisstearamide, commercially available;

[0078] Unless otherwise specified, the components (such as other auxiliary agent 1#) selected in each parallel example and comparative example are the same commercially available products.

[0079] The properties of the ABS composite materials provided in the embodiments and comparative examples of the present invention were measured according to the following test methods:

[0080] Continuous burning dripping time: According to the vertical burning test in standard UL94-□2018; the material is injection molded into a standard specimen (length 125mm, width 12.7mm, thickness 1.5mm) at 220℃. After being placed at room temperature for 24 hours, the standard specimen is continuously subjected to vertical burning until dripping occurs in the specimen, and the time from the application of flame to dripping is recorded.

[0081] Flame retardant grade: According to the UL94-2018 standard, vertical combustion test, 1.5mm specimens should meet the V-0 grade requirements;

[0082] Melt strength: measured using a melt strength tester. The tester stretches the ABS composite material melt uniaxially. First, the melt is extruded downward from the extruder die and pulled by two sticks with opposite movement directions installed on the balance beam. The force on the melt bundle when stretched is the roller uniformly accelerated until the melt bundle breaks. The force on the melt bundle when it breaks is used to characterize the melt strength. The larger the value, the greater the melt strength.

[0083] The preparation process of the ABS composite material of each embodiment of the present invention and each comparative example is as follows: weigh each component according to the formula, put it into a high-speed mixer and mix it evenly, and then melt-extrude and granulate it through a twin-screw extruder to obtain an ABS composite material. Wherein, the screw speed is 400rpm, and the screw temperature of each section of the twin-screw extruder is set to 90°C for zone 1, 180°C for zone 2, 190°C for zone 3, 190°C for zone 4, 190°C for zone 5, 200°C for zone 6, 200°C for zone 7, 200°C for zone 8, 200°C for zone 9, and 210°C for zone 9 from the feed port to the die.

[0084] Examples 1 to 12

[0085] Examples 1 to 12 provide a series of ABS composite materials, whose formulations are shown in Tables 1 and 2.

[0086] Table 1 Formulas of Examples 1 to 7 (parts by weight)

[0087]

[0088] Table 2 Formulas of Examples 8 to 12 (parts by weight)

[0089]

[0090] Comparative Examples 1 to 5

[0091] Comparative Examples 1 to 5 provide a series of ABS composite materials, whose formulas are shown in Table 3.

[0092] Table 3 Formulas of Comparative Examples 1 to 5 (parts by weight)

[0093]

[0094] The properties of the ABS composite materials of the embodiments and comparative examples were measured according to the above-mentioned test methods. The test results are shown in Table 4.

[0095] Table 4 Performance test results of liquid crystal polymer materials of various embodiments and comparative examples

[0096]

[0097]

[0098] It can be seen from Table 4 that the continuous burning dripping time of the ABS composite materials of Examples 1 to 12 is all above 35 seconds, the flame retardant grades are all above V-0, and the melt strength tests are all between 230 and 450 mN, indicating that the ABS composite materials of the present invention have good flame retardant properties, good anti-dripping properties, and high melt strength.

[0099] Comparative Example 1 adds a conventional molecular weight acrylic polymer, and the continuous burning dripping time of the ABS composite material is short, the flame retardant grade is poor, and the melt strength is low. Comparative Example 2 adds high molecular weight polyethylene, and the various properties of the ABS composite material are poor. Comparative Example 3 adds a small amount of polytetrafluoroethylene to make the flame retardant and anti-dripping properties of the ABS composite material equivalent to those of Example 1, but the selection of polytetrafluoroethylene has environmental issues. Comparative Example 4 adds too little high molecular weight acrylic polymer, and the continuous burning dripping time of the ABS composite material is short, the flame retardant grade is poor, and the melt strength is low. Comparative Example 5 adds too much high molecular weight acrylic polymer, resulting in excessive melt strength of the ABS composite material, affecting the dispersion of the flame retardant, prolonging the flame retardant time, and reducing the flame retardant grade.

[0100] 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. An anti-drip ABS composite material, characterized in that: The composition comprises the following components in parts by weight: ABS resin 54-85 parts, 11 to 21 parts of brominated flame retardant, 5-11 parts of anti-dripping agent; The anti-dripping agent is an ultra-high molecular weight acrylic polymer, and the weight average molecular weight of the anti-dripping agent is ≥1.2×10 6 g / mol.

2. The ABS composite material according to claim 1, characterized in that: The melt flow rate of the ABS resin at 220° C. and a load of 10 kg is 10 to 25 g / 10 min.

3. The ABS composite material according to claim 1, characterized in that: The brominated flame retardant is at least one of tetrabromobisphenol A, tris(tribromophenoxy)cyanurate, brominated epoxy oligomer or decabromodiphenylethane.

4. The ABS composite material according to claim 1, characterized in that: The ABS composite material also includes 2 to 5 parts of a flame retardant synergist.

5. The ABS composite material according to claim 1, characterized in that: The ABS composite material also includes 2 to 10 parts of toughening agent.

6. The ABS composite material according to claim 1, characterized in that: The weight average molecular weight of the anti-dripping agent is ≥1.5×10 6 g / mol; preferably 3.5×10 6 g / mol~9.0×10 6 g / mol; more preferably 5.0×10 6 g / mol~8.0×10 6 g / mol.

7. The ABS composite material according to claim 1, characterized in that: The acrylic polymer is at least one of a butyl acrylate polymer and a copolymer of butyl acrylate and methyl methacrylate.

8. The ABS composite material according to claim 1, characterized in that: The ABS composite material also includes 0.1 to 1 part of other additives.

9. The method for preparing the ABS composite material according to any one of claims 1 to 8, characterized in that: The steps include: The components are mixed uniformly, melted, extruded and granulated to obtain the ABS composite material.

10. Use of the ABS composite material according to any one of claims 1 to 8 in the preparation of household appliances, electronic appliances or office supplies.

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