A damping modifier, a noise-reducing damping ABS material, and a method for preparing the same

Abstract

The application discloses a damping modifier, a noise-reducing damping ABS material and a preparation method thereof, and comprises the following components: 80-95 parts by weight of ABS, 5-20 parts by weight of a damping modifier and 0-3 parts by weight of a processing aid. The material has excellent mechanical properties, a high damping coefficient and excellent noise reduction effect.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of high polymer composite materials, and relates to a damping modifier, a noise-reducing damping ABS material and a preparation method thereof. BACKGROUND

[0002] ABS is a general-purpose engineering plastic with balanced performance in all aspects, and is widely used in the automobile and home appliance industries due to its high mechanical strength, good impact resistance, dimensional stability and good electrical insulation.

[0003] Among them, the noise problem is included in the common complaints of air conditioner users. The traditional improvement method is to paste cotton or cloth on the surface of the product to reduce noise, but the improvement effect is poor. In addition, noise needs to be considered during driving. Generally, special sound-absorbing cotton is covered on the back of the instrument panel, door trim and other parts to reduce noise. However, only relying on the above solutions cannot meet the pursuit of consumers for the quality of life. If the air conditioner shell material and the door plate material on the car have good noise reduction performance, the noise control problem affecting consumers will be greatly improved.

[0004] The noise reduction performance of the polymer and its modified material is determined by the damping factor tan θ, which represents the ratio of loss modulus to storage modulus. The larger the tan θ, the better the noise reduction effect. Patent CN103788629A discloses a high-wear-resistant and low-noise glass fiber reinforced nylon / ABS composite composition and a preparation method. The damping factor of the composite material is about 0.04, which still cannot meet the demand of automobile noise reduction. Patent CN111534038B discloses a self-lubricating wide-temperature-range high-damping ABS material and a preparation method thereof. The self-lubricating wide-temperature-range high-damping ABS material prepared by the invention has a wide temperature range and high damping. The damping coefficient is greatly improved within-90℃ to 30℃. The high-damping temperature range with a damping coefficient greater than 0.05 is 92℃, but the maximum damping factor is still less than 0.1.

[0005] Therefore, it is necessary to develop a new noise-reducing damping ABS composition, which has very important value and significance for the current consumer market. SUMMARY

[0006] To solve the above problems, the present application provides a damping modifier, and applies the damping modifier to ABS material, so that the prepared noise-reducing damping ABS material has excellent mechanical strength and good noise-reducing damping performance, and the preparation process is simple and easy to implement.

[0007] In order to achieve the above application purposes, the technical solutions adopted by the present application are as follows:

[0008] A noise-reducing damping ABS material is prepared from raw materials comprising the following components:

[0009] 80-95 parts by weight of ABS;

[0010] 5-20 parts by weight of a damping modifier;

[0011] and 0-3 parts by weight of a processing aid.

[0012] Preferably, the noise-reducing damping ABS material of the present application comprises:

[0013] 80-95 parts by weight of ABS;

[0014] 5-15 parts by weight of a damping modifier;

[0015] 0.1-3 parts by weight of a processing aid, preferably 0.1-2 parts by weight.

[0016] In the noise-reducing damping ABS material of the present application, the damping modifier is styrene-ethylene / butylene-styrene block copolymer grafted cage polyhedral oligomeric silsesquioxane (SEBS-POSS).

[0017] Preferably, the proportion of styrene in SEBS is 20-35 wt%;

[0018] Preferably, the cage polyhedral oligomeric silsesquioxane is an aminated cage polyhedral oligomeric silsesquioxane.

[0019] Specifically, the structure of the aminated cage polyhedral oligomeric silsesquioxane is R 1 a R 2 b (SiO 1.5 )n, wherein R 1 is selected from C1-C6 alkyl or substituted alkyl, R 2 contains a primary amino group in the structure, 0≤a≤6, a+b=n, n=6, 8, 10 or 12.

[0020] Preferably, the aminated cage polyhedral oligomeric silsesquioxane is selected from one or more of octylaminopropyl octa-POSS, penta-isobutyl-triaminopropyl octa-POSS, hexamethyl-diaminopropyl octa-POSS, etc.

[0021] Preferably, the styrene-ethylene / butylene-styrene block copolymer is preferably maleic anhydride grafted SEBS (SEBS-g-MAH), and the maleic anhydride grafting rate is preferably 0.8-2%.

[0022] In the present application, the damping modifier is prepared by mixing styrene-ethylene / butylene-styrene block copolymer and aminated cage polyhedral oligomeric silsesquioxane and melt blending for a certain time to obtain the product damping modifier SEBS-POSS.

[0023] In the present application, the mass ratio of styrene-ethylene / butylene-styrene block copolymer to aminated polysilsesquioxane is (80-95):(5-20).

[0024] In the present application, the temperature for preparing the damping modifier is 180-220 DEG C, and the time is 5-10 min.

[0025] In the present application, the ABS is prepared by emulsion-body SAN blending or body method, preferably emulsion-body SAN blending method;

[0026] Preferably, the melt flow index of the ABS is 4-40 g / 10 min, preferably 4-20 g / 10 min, and more preferably 4-10 g / 10 min under the test condition of 220 DEG C and 10 kg.

[0027] In the present application, the processing aid is selected from one or more of antioxidant, lubricant, ultraviolet absorber, flame retardant, toughening agent, compatibilizer, light stabilizer, thermal stabilizer, metal deactivator, plasticizer, anti-sticking agent, colorant, coupling agent, nucleating agent, foaming agent, antibacterial agent, mildew-proof agent, acid-removing agent, hydrolysis-resistant agent, chain extender, flow modifier, matting agent, antistatic agent, reinforcing agent, filler, anti-fog agent, light diffusing agent, infrared absorber, optical brightener and laser marking agent.

[0028] Specifically, the antioxidant is one or a combination of two or more of hindered phenol, phosphite, thioester, benzofuran, acryl-modified phenol and hydroxylamine antioxidant, and preferably one or more of antioxidant 1076, 1010, 168 and 618.

[0029] Specifically, the lubricant is one or more of fatty alcohol, metal soap, fatty acid, fatty acid ester, montanic acid and its derivatives, amide wax, saturated hydrocarbon, polyolefin wax and its derivatives, organic silicon and silicone powder, organic fluorine and the like, and preferably amide wax.

[0030] Specifically, the ultraviolet absorber is one or more of benzophenone, benzotriazole, triazine, benzoate, cyanoacrylate and phenylimidazole, and preferably benzotriazole and triazine, such as Tinuvin 234, Tinuvin 360 and Tinuvin 1577 of BASF.

[0031] The noise-reducing damping ABS material of the present application can selectively use the above-mentioned aids according to the performance characteristics of the product.

[0032] In another aspect, the present application also provides a preparation method of the noise-reducing damping ABS material, which comprises the following steps:

[0033] (1) Premixing: mixing ABS, damping modifier and optional processing aids in proportion to obtain a premix;

[0034] (2) Extrusion: melt blending-pelletizing-drying the obtained premix by an extruder to obtain noise-reducing damping ABS material pellets.

[0035] Preferably, the extruder in step (2) is preferably a twin-screw extruder, the twin-screw extruder has a processing temperature zone temperature of 200-220℃, a screw rotation speed of 300-800 rpm and a vacuum degree of -0.9 bar to -0.5 bar.

[0036] The present application has the following beneficial effects:

[0037] SEBS-g-MAH as a rubber-based elastomer material has unique viscoelastic properties, which endows it with good damping performance, but the addition of SEBS-g-MAH will cause the mechanical properties of the polymer to decrease; and aminopolyhedral oligomeric silsesquioxane (POSS-NH2) has a unique hollow structure that can reduce noise, and its good lubricity also reduces the friction coefficient of the material, thereby also reducing noise, and the rigidity of POSS also improves the mechanical strength and modulus of the material. In addition, the maleic anhydride groups on SEBS and the amino groups on POSS-NH2 react, and the two are more closely connected, so that when the material vibrates under external action, SEBS causes energy to spread and dissipate through the movement of molecular segments, and the adjacent hollow rigid particles of POSS dissipate energy again, and the finally obtained ABS material exhibits excellent noise-reducing damping effect. DETAILED DESCRIPTION

[0038] For better understanding and implementation, the present application will be further described below in conjunction with examples, but the present application is not limited to the listed examples, and any other known changes within the scope of the claimed rights of the present application should also be included.

[0039] Performance tests such as

[0040] Tensile properties were tested according to ASTM D638.

[0041] Surface friction coefficient test: the friction coefficient tester Zwick-Roell Z0.5 tests the static / dynamic friction coefficient of the sample at a test rate of 100 mm / min.

[0042] Dynamic mechanical property test: Q800, TA Instruments, USA.

[0043] The raw materials of the comparative examples and the examples are as follows:

[0044] ABS-1: ABS produced by emulsion-mass SAN blending method, melt flow index 5 g / 10 min (220°C, 10 kg), commercially available;

[0045] ABS-2: ABS produced by emulsion-mass SAN blending method, melt flow index 7 g / 10 min (220°C, 10 kg), commercially available;

[0046] Maleic anhydride grafted styrene-ethylene / butylene-styrene block copolymer (SEBS-g-MAH): Kraton FG1901, Kraton RP6670, Asahi M1943;

[0047] Aminated polysilsesquioxane: cage-type polysilsesquioxane-octylammonium (amino) (octylamine POSS, cas: 150380-11-3), Xi'an Qiyue Biological Technology Co., Ltd.;

[0048] Antioxidant: Irganox B900, produced by BASF Company;

[0049] Lubricant: EBS, produced by CMS Company in Indonesia.

[0050] Preparation of damping modifier SEBS-POSS-1: after the temperature of the internal mixer rises to 210°C, 95 parts of SEBS-g-MAH (FG1901) and 5 parts of POSS-NH2 are simultaneously added to the internal mixer, and after heating and melting blending for 5 min, the product modified toughening agent SEBS-POSS-1 is obtained.

[0051] Preparation of damping modifier SEBS-POSS-2: after the temperature of the internal mixer rises to 200°C, 90 parts of SEBS-g-MAH (RP6670) and 10 parts of POSS-NH2 are simultaneously added to the internal mixer, and after heating and melting blending for 5 min, the product modified toughening agent SEBS-POSS-2 is obtained.

[0052] Preparation of damping modifier SEBS-POSS-3: after the temperature of the internal mixer rises to 210°C, 80 parts of SEBS-g-MAH (M1943) and 20 parts of POSS-NH2 are simultaneously added to the internal mixer, and after heating and melting blending for 5 min, the product modified toughening agent SEBS-POSS-3 is obtained.

[0053] Example 1

[0054] Raw materials: ABS: 90 parts, SEBS-POSS-1: 10 parts, antioxidant 0.3 parts, lubricant 0.3 parts. The material composition is added to a high-speed mixer for mixing, added to a twin-screw extruder for extrusion and granulation, the processing temperature is 210°C, the screw rotation speed is 400 rpm, the vacuum degree of the vacuum device in the metering section of the twin-screw is -0.7 bar, after the granulation is completed, the granulation is dried at 80°C for 4 h to sufficiently remove the moisture, the injection mold temperature is controlled at 50°C, the cylinder temperature is 210°C, the injection speed is 50 mm / s, the injection pressure is 60 bar, and standard samples and sample plates are obtained.

[0055] Example 2

[0056] Raw materials: ABS: 85 parts, SEBS-POSS-1: 15 parts, antioxidant 0.3 parts, lubricant 0.3 parts. The material composition is added to a high-speed mixer for mixing, added to a twin-screw extruder for extrusion and granulation, the processing temperature is 210°C, the screw rotation speed is 400 rpm, the vacuum degree of the vacuum device in the metering section of the twin-screw is -0.7 bar, after the granulation is completed, the granulation is dried at 80°C for 4 h to sufficiently remove the moisture, the injection mold temperature is controlled at 50°C, the cylinder temperature is 210°C, the injection speed is 50 mm / s, the injection pressure is 60 bar, and standard samples and sample plates are obtained.

[0057] Example 3

[0058] Raw materials: ABS: 80 parts, SEBS-POSS-1: 20 parts, antioxidant 0.3 parts, lubricant 0.3 parts. The material composition is added to a high-speed mixer for mixing, added to a twin-screw extruder for extrusion and granulation, the processing temperature is 210°C, the screw rotation speed is 400 rpm, the vacuum degree of the vacuum device in the metering section of the twin-screw is -0.7 bar, after the granulation is completed, the granulation is dried at 80°C for 4 h to sufficiently remove the moisture, the injection mold temperature is controlled at 50°C, the cylinder temperature is 210°C, the injection speed is 50 mm / s, the injection pressure is 60 bar, and standard samples and sample plates are obtained.

[0059] Example 4

[0060] Raw materials: ABS: 80 parts, SEBS-POSS-2: 10 parts, antioxidant 0.3 parts, lubricant 0.3 parts. The material composition is added to a high-speed mixer for mixing, added to a twin-screw extruder for extrusion and granulation, the processing temperature is 210°C, the screw rotation speed is 600 rpm, the vacuum degree of the vacuum device in the metering section of the twin-screw is -0.7 bar, after the granulation is completed, the granulation is dried at 80°C for 4 h to sufficiently remove the moisture, the injection mold temperature is controlled at 50°C, the cylinder temperature is 210°C, the injection speed is 50 mm / s, the injection pressure is 60 bar, and standard samples and sample plates are obtained.

[0061] Example 5

[0062] Raw materials: ABS: 80 parts, SEBS-POSS-3: 15 parts, antioxidant 0.3 parts, lubricant 0.3 parts. The material composition is added to a high-speed mixer for mixing, added to a twin-screw extruder for extrusion and granulation, the processing temperature is 220°C, the screw rotation speed is 600 rpm, the vacuum degree of the vacuum device in the metering section of the twin-screw is -0.7 bar, after the granulation is completed, drying at 80°C for 4 h is performed to sufficiently remove moisture, the injection mold temperature is controlled to be 50°C, the cylinder temperature is 210°C, the injection speed is 50 mm / s, the injection pressure is 60 bar, and standard samples and sample plates are obtained.

[0063] Comparative Example 1

[0064] Raw materials: ABS: 100 parts, antioxidant 0.3 parts, lubricant 0.3 parts. The material composition is added to a high-speed mixer for mixing, added to a twin-screw extruder for extrusion and granulation, the processing temperature is 210°C, the screw rotation speed is 400 rpm, the vacuum degree of the vacuum device in the metering section of the twin-screw is -0.7 bar, after the granulation is completed, drying at 80°C for 4 h is performed to sufficiently remove moisture, the injection mold temperature is controlled to be 50°C, the cylinder temperature is 210°C, the injection speed is 50 mm / s, the injection pressure is 60 bar, and standard samples and sample plates are obtained.

[0065] Comparative Example 2

[0066] Raw materials: ABS: 85 parts, 15 parts of SEBS-g-MAH, antioxidant 0.3 parts, lubricant 0.3 parts. The material composition is added to a high-speed mixer for mixing, added to a twin-screw extruder for extrusion and granulation, the processing temperature is 210°C, the screw rotation speed is 400 rpm, the vacuum degree of the vacuum device in the metering section of the twin-screw is -0.7 bar, after the granulation is completed, drying at 80°C for 4 h is performed to sufficiently remove moisture, the injection mold temperature is controlled to be 50°C, the cylinder temperature is 210°C, the injection speed is 50 mm / s, the injection pressure is 60 bar, and standard samples and sample plates are obtained.

[0067] Comparative Example 3

[0068] Raw materials: ABS: 80 parts, 16 parts of SEBS-g-MAH, 4 parts of POSS-NH2, antioxidant 0.3 parts, lubricant 0.3 parts. The material composition is added to a high-speed mixer for mixing, added to a twin-screw extruder for extrusion and granulation, the processing temperature is 210°C, the screw rotation speed is 400 rpm, the vacuum degree of the vacuum device in the metering section of the twin-screw is -0.7 bar, after the granulation is completed, drying at 80°C for 4 h is performed to sufficiently remove moisture, the injection mold temperature is controlled to be 50°C, the cylinder temperature is 210°C, the injection speed is 50 mm / s, the injection pressure is 60 bar, and standard samples and sample plates are obtained.

[0069] The material performance comparison of the examples and comparative examples is shown in the following table:

[0070]

[0071] As can be seen from the examples and comparative examples, the addition of the appropriate amount of damping modifier SEBS-POSS in ABS can significantly reduce the surface friction coefficient and improve the damping factor, so that the noise reduction performance is greatly improved, and the application range of ABS material is greatly expanded.

[0072] Those skilled in the art should understand that the present application is not limited to the above examples, and various changes and improvements can be made without departing from the spirit and scope of the present application, and these changes and improvements all fall within the scope of the claimed present application.

Claims

1. A process for the preparation of a damping modifier, characterized in that, The preparation method is as follows: melt blending styrene-ethylene / butylene-styrene block copolymer grafted maleic anhydride and aminosilicone to obtain a damping modifier; the mass ratio of styrene-ethylene / butylene-styrene block copolymer grafted maleic anhydride to aminosilicone is (80-95):(5-20).

2. The production method according to claim 1, characterized by, The content of styrene in the styrene-ethylene / butylene-styrene block copolymer is 20-35 wt%.

3. The production method according to claim 2, characterized by, The grafting rate of maleic anhydride in the styrene-ethylene / butylene-styrene block copolymer grafted maleic anhydride is 0.8-2%.

4. The production method according to any one of claims 1 to 3, characterized by, The melt blending temperature is 180-220℃, and the time is 5-10 min.

5. A noise reducing damping ABS material characterized by, It comprises the following raw materials: 80-95 parts by weight of ABS; 5-20 parts by weight of a damping modifier; The damping modifier is prepared by the preparation method of any one of claims 1-4.

6. The noise reducing damping ABS material of claim 5, wherein, The damping modifier is 5-15 parts by weight.

7. The noise reducing damping ABS material of claim 5, wherein, The ABS is prepared by emulsion-body SAN blending or body method.

8. The noise reducing damping ABS material of claim 7, wherein, The melt flow index of the ABS is 4-40 g / 10 min under the test conditions of 220℃, 10 kg.

9. The noise reducing damping ABS material of claim 8, wherein, The melt flow index of the ABS is 4-20 g / 10 min under the test conditions of 220℃, 10 kg.

10. The noise reducing damping ABS material of claim 5 or 6, wherein, The raw materials of the noise reduction damping ABS material further comprise 0.1-3 parts by weight of a processing aid, and the processing aid comprises one or more of an antioxidant, a lubricant, and an ultraviolet absorber.

11. The noise reducing damping ABS material of claim 10, wherein, The processing aid is 0.1-2 parts by weight.

12. The method of claim 5-11, wherein the method further comprises the step of: It comprises the following steps: (1) Pre-mixing: mixing ABS, a damping modifier, and optionally a processing aid in a certain proportion to obtain a pre-mix; (2) Extrusion: melt blending-pelletizing-drying the pre-mix to obtain noise reduction damping ABS material granules.

13. The method of claim 12, wherein, In step (2), melt blending is performed using a twin-screw extruder, and the twin-screw extruder has a processing temperature zone temperature of 200-220℃, a screw rotation speed of 300-800 rpm, and a vacuum degree of -0.9 bar to -0.5 bar.

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