Damping modifier, noise-reduction damping ABS material and preparation method of noise-reduction damping ABS material

Abstract

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

Description

Technical Field

[0001] The invention belongs to the field of polymer composite materials and relates to a damping modifier, a noise reduction and damping ABS material and a preparation method thereof. Background Art

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

[0003] Among them, the most common complaints from air conditioner users include noise. The traditional improvement method is to stick sponge or flannel on the surface of the product to reduce noise, but the improvement effect is poor. In addition, the noise factor needs to be considered during car driving. Generally, special sound-absorbing cotton is covered on the back of the dashboard, door trim and other parts to reduce noise. However, relying solely on the above solutions is far from satisfying consumers' pursuit of quality of life. If the air conditioner shell materials and the door panels on the car have good sound-absorbing properties, the noise control problem affecting consumers will be greatly improved.

[0004] The sound-absorbing performance of polymers and their modifications is determined by the damping factor tanθ, which represents the ratio of loss modulus to storage modulus. The larger the tanθ, the better the sound-absorbing effect. Patent CN103788629A discloses a high-wear-resistant, low-noise glass fiber reinforced nylon / ABS composite material composition and a preparation method. The damping factor of the composite material reaches about 0.04, which is still difficult to meet the needs of automobile noise reduction. Patent CN 111534038B 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 high damping, and the damping coefficient is greatly improved within -90°C to 30°C. The high damping temperature range with a damping coefficient greater than 0.05 is 92°C, but the maximum damping factor is still less than 0.1.

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

[0006] In order to solve the above problems, the present invention provides a damping modifier, and applies the damping modifier to ABS material, so that the prepared noise reduction and damping ABS material has excellent mechanical strength and good noise reduction and damping performance, and the preparation process is simple and easy.

[0007] In order to achieve the above invention object, the technical solution adopted by the present invention is as follows:

[0008] A noise reduction and damping ABS material is prepared from raw materials containing 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 reduction and damping ABS material of the present invention 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 processing aids, preferably 0.1-2 parts by weight.

[0016] In the noise reduction and damping ABS material of the present invention, the damping modifier is styrene-ethylene / butylene-styrene block copolymer grafted cage polysilsesquioxane (SEBS-POSS).

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

[0018] Preferably, the cage-type polysilsesquioxane is an amino-type cage-type polysilsesquioxane.

[0019] Specifically, the general structural formula of the amino cage-type polysilsesquioxane is R 1 a R 2 b (SiO 1.5 )n, where R 1 is selected from C1-C6 alkyl or substituted alkyl, R 2 The structure contains primary amino groups, 0≤a≤6, a+b=n, n=6, 8, 10 or 12.

[0020] Preferably, the aminated cage-type polysilsesquioxane is selected from one or more of octaaminopropyl octameric POSS, pentaisobutyltriaminopropyl octameric POSS, hexamethyldiaminopropyl octameric POSS and the like.

[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 invention, the damping modifier preparation method is: styrene-ethylene / butylene-styrene block copolymer and amino cage-type polysilsesquioxane are mixed and melt-blended for a certain period of time to obtain the damping modifier SEBS-POSS.

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

[0024] In the present invention, the temperature used for preparing the damping modifier is 180-220° C. and the time is 5-10 minutes.

[0025] In the noise reduction and damping ABS material of the present invention, the ABS is prepared by emulsion-bulk SAN blending or bulk method, preferably emulsion-bulk SAN blending method ABS;

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

[0027] In the noise reduction and damping ABS material of the present invention, the processing aid is selected from one or more of antioxidants, lubricants, ultraviolet absorbers, flame retardants, toughening agents, compatibilizers, light stabilizers, heat stabilizers, metal passivators, plasticizers, anti-adhesive agents, colorants, coupling agents, nucleating agents, foaming agents, antibacterial agents, mildew inhibitors, acid scavengers, hydrolysis resistant agents, chain extenders, flow modifiers, matting agents, antistatic agents, reinforcing agents, fillers, antifogging agents, light diffusers, infrared absorbers, fluorescent brighteners and laser marking agents.

[0028] Specifically, the antioxidant is one or a combination of two or more of hindered phenols, phosphites, thioesters, benzofurans, acryl-modified phenols, and hydroxylamine antioxidants, and one or more of antioxidants 1076, 1010, 168, and 618 are preferably used.

[0029] Specifically, the lubricant is one or more of fatty alcohols, metal soaps, fatty acids, fatty acid esters, montanic acid and its derivatives, amide waxes, saturated hydrocarbons, polyolefin waxes and its derivatives, silicones and silicone powders, organic fluorines, etc., and amide wax lubricants are preferably used.

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

[0031] The noise reduction and damping ABS material of the present invention can selectively use the above-mentioned additives according to the product performance characteristics.

[0032] On the other hand, the present invention also provides a method for preparing the above-mentioned noise reduction and damping ABS material, the method comprising the following steps:

[0033] (1) Premixing: ABS, a damping modifier and an optional processing aid are mixed according to a proportion to obtain a premix;

[0034] (2) Extrusion: The obtained premix is ​​melt-blended, granulated and dried by an extruder to obtain noise reduction and damping ABS material pellets.

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

[0036] The beneficial effects of the present invention are:

[0037] SEBS-g-MAH is a rubber-like elastomeric material, and its unique viscoelastic properties give it good damping performance, but the addition of SEBS-g-MAH will cause the decline of the mechanical properties of the polymer; while the unique hollow structure of amino polysilsesquioxane (POSS-NH2) can play a role in noise reduction, and its good lubricity will also reduce the friction coefficient of the material, thereby also playing a role in noise reduction, and the rigidity of POSS also improves the mechanical strength and modulus of the material. In addition, through the reaction of the maleic anhydride group on SEBS and the amino group on POSS-NH2, the two are more closely connected, so that when the material vibrates under the action of the outside world, SEBS propagates and dissipates energy through the motion friction of the molecular chain segments, and the adjacent POSS hollow rigid particles play a role in secondary energy dissipation, and the ABS material finally obtained shows excellent noise reduction and damping effects. DETAILED DESCRIPTION

[0038] For better understanding and implementation, the present invention is further described below in conjunction with embodiments, but the present invention is not limited to the listed embodiments, and should also include any other known changes within the scope of the rights claimed by the present invention.

[0039] Performance test 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 specimen at a test rate of 100 mm / min.

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

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

[0044] ABS-1: ABS produced by emulsion-bulk SAN blending method, with a melt flow index of 5g / 10min (220℃, 10kg), commercially available;

[0045] ABS-2: ABS produced by emulsion-bulk SAN blending method, with a melt flow index of 7g / 10min (220℃, 10kg), commercially available;

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

[0047] Amination polysilsesquioxane: cage polysilsesquioxane-octaammonium (amino) (octaamine POSS, cas: 150380-11-3), Xi'an Qiyue Biotechnology Co., Ltd.;

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

[0049] Lubricant: EBS, produced by CMS 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 added to the internal mixer at the same time. After heating and melt blending for 5 minutes, 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 added to the internal mixer at the same time. After heating and melt blending for 5 minutes, 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 added to the internal mixer at the same time. After heating and melt blending for 5 minutes, 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 mixer for mixing, added to a twin-screw extruder, extruded into granules, the processing temperature is 210°C, the screw speed is 400rpm, the vacuum degree of the vacuum device of the twin-screw metering section is -0.7bar, after granulation is completed, it is dried at 80°C for 4h to fully remove moisture, the injection mold temperature is controlled at 50°C, the barrel temperature is 210°C, the injection speed is 50mm / s, and the injection pressure is 60bar to obtain standard specimens and sample plates.

[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 mixer for mixing, added to a twin-screw extruder, extruded into granules, the processing temperature is 210°C, the screw speed is 400rpm, the vacuum degree of the vacuum device of the twin-screw metering section is -0.7bar, after granulation is completed, it is dried at 80°C for 4h to fully remove moisture, and the injection mold temperature is controlled at 50°C, the barrel temperature is 210°C, the injection speed is 50mm / s, and the injection pressure is 60bar to obtain standard specimens and sample plates.

[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 mixer for mixing, added to a twin-screw extruder, extruded into granules, the processing temperature is 210°C, the screw speed is 400rpm, the vacuum degree of the vacuum device of the twin-screw metering section is -0.7bar, after granulation is completed, it is dried at 80°C for 4h to fully remove moisture, the injection mold temperature is controlled at 50°C, the barrel temperature is 210°C, the injection speed is 50mm / s, and the injection pressure is 60bar to obtain standard specimens and sample plates.

[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 mixer for mixing, added to a twin-screw extruder, extruded into granules, the processing temperature is 210°C, the screw speed is 600rpm, the vacuum degree of the vacuum device of the twin-screw metering section is -0.7bar, after granulation is completed, it is dried at 80°C for 4h to fully remove moisture, the injection mold temperature is controlled at 50°C, the barrel temperature is 210°C, the injection speed is 50mm / s, and the injection pressure is 60bar to obtain standard specimens and samples.

[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 mixer for mixing, added to a twin-screw extruder, extruded into granules, the processing temperature is 220°C, the screw speed is 600rpm, the vacuum degree of the vacuum device of the twin-screw metering section is -0.7bar, after granulation is completed, it is dried at 80°C for 4h to fully remove moisture, the injection mold temperature is controlled at 50°C, the barrel temperature is 210°C, the injection speed is 50mm / s, and the injection pressure is 60bar to obtain standard specimens and samples.

[0063] Comparative Example 1

[0064] Raw material ABS: 100 parts, antioxidant 0.3 parts, lubricant 0.3 parts. Add the material composition to a high mixer for mixing, add it to a twin-screw extruder, extrude and granulate, the processing temperature is 210°C, the screw speed is 400rpm, the vacuum degree of the vacuum device of the twin-screw metering section is -0.7bar, after granulation, dry it at 80°C for 4h to fully remove moisture, control the injection mold temperature at 50°C, the barrel temperature at 210°C, the injection speed at 50mm / s, and the injection pressure at 60bar to obtain standard specimens and samples.

[0065] Comparative Example 2

[0066] Raw materials: ABS: 85 parts, SEBS-g-MAH: 15 parts, antioxidant: 0.3 parts, lubricant: 0.3 parts. The material composition was added to a high mixer for mixing, added to a twin-screw extruder, extruded for granulation, the processing temperature was 210°C, the screw speed was 400rpm, the vacuum degree of the vacuum device of the twin-screw metering section was -0.7bar, after granulation, it was dried at 80°C for 4h to fully remove moisture, the injection mold temperature was controlled at 50°C, the barrel temperature was 210°C, the injection speed was 50mm / s, and the injection pressure was 60bar, and standard specimens and samples were obtained.

[0067] Comparative Example 3

[0068] Raw materials: ABS: 80 parts, SEBS-g-MAH: 16 parts, POSS-NH2: 4 parts, antioxidant: 0.3 parts, lubricant: 0.3 parts. The material composition was added to a high mixer for mixing, added to a twin-screw extruder, extruded for granulation, the processing temperature was 210°C, the screw speed was 400rpm, the vacuum degree of the vacuum pumping device in the twin-screw metering section was -0.7bar, after granulation, it was dried at 80°C for 4h to fully remove moisture, the injection mold temperature was controlled at 50°C, the barrel temperature was 210°C, the injection speed was 50mm / s, and the injection pressure was 60bar, and standard specimens and samples were obtained.

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

[0070]

[0071] It can be seen from the embodiments and comparative examples that adding an appropriate amount of damping modifier SEBS-POSS to ABS can significantly reduce the surface friction coefficient and increase the damping factor, thereby greatly improving the noise reduction performance and greatly expanding the application range of ABS materials.

[0072] Those skilled in the art should understand that the present invention is not limited to the above-described embodiments, and that the present invention may be subject to various changes and modifications without departing from the spirit and scope of the present invention, and that these changes and modifications are all within the scope of the present invention to be protected.

Claims

1. A method for preparing a damping modifier, characterized in that: The preparation method is as follows: styrene-ethylene / butylene-styrene block copolymer grafted with maleic anhydride and amino-modified polysilsesquioxane are melt-blended to obtain a damping modifier.

2. The preparation method according to claim 1, characterized in that: The styrene content in the styrene-ethylene / butylene-styrene block copolymer is 20-35wt%; preferably, the grafting rate of maleic anhydride in the styrene-ethylene / butylene-styrene block copolymer grafted with maleic anhydride is 0.8-2%.

3. The preparation method according to claim 1, characterized in that: The polysilsesquioxane is an amino cage-type polysilsesquioxane.

4. The preparation method according to claim 1, characterized in that: The mass ratio of styrene-ethylene / butylene-styrene block copolymer grafted with maleic anhydride to amino-modified polysilsesquioxane is (80-95):(5-20).

5. The preparation method according to any one of claims 1 to 4, characterized in that: The melt blending temperature is 180-220°C and the time is 5-10 minutes.

6. A noise reduction and damping ABS material, characterized in that: It contains the following ingredients: 80-95 parts by weight of ABS; 5-20 parts by weight of a damping modifier, preferably 5-15 parts by weight; The damping modifier is a damping modifier prepared by the preparation method according to any one of claims 1 to 5.

7. The noise reduction and damping ABS material according to claim 6, characterized in that: ABS is prepared by emulsion-bulk SAN blending or bulk method, preferably prepared by emulsion-bulk SAN blending; preferably, when the test conditions are 220°C and 10kg, the melt flow index of ABS is 4-40g / 10min, preferably 4-20g / 10min, more preferably 4-10g / 10min.

8. The noise reduction and damping ABS material according to claim 6 or 7, characterized in that: The raw materials of the noise reduction and damping ABS material also include 0.1-3 parts by weight, preferably 0.1-2 parts by weight of a processing aid; the processing aid preferably includes one or more of an antioxidant, a lubricant and an ultraviolet absorber.

9. The method for preparing the noise reduction and damping ABS material according to any one of claims 6 to 8, characterized in that: The following steps are involved: (1) Premixing: ABS, a damping modifier and an optional processing aid are mixed according to a proportion to obtain a premix; (2) Extrusion: The premix is ​​melt-blended, granulated, and dried to obtain noise-reducing and damping ABS material pellets.

10. The preparation method according to claim 9, characterized in that: In step (2), a twin-screw extruder is used for melt blending, wherein the processing temperature of the twin-screw extruder is 200-220° C., the screw speed is 300-800 rpm, and the vacuum degree is -0.9 bar to -0.5 bar.

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