An ABS composition resistant to low-temperature abnormal noise, its preparation method and application

Abstract

The present invention discloses an anti-low-temperature abnormal noise ABS composition, a preparation method thereof and an application. The anti-low-temperature abnormal noise ABS composition of the present invention uses coated boron nitride as an anti-low-temperature abnormal noise agent. The anti-low-temperature abnormal noise agent is coated boron nitride, and the surface of the coated boron nitride is coated with polyolefin. The mass ratio of polyolefin to boron nitride is 10:1 to 10:4. The ABS composition prepared by the present invention has lower noise, better toughness and scratch resistance. The noise does not exceed 25 dB under the condition of -30 °C, and the impact performance at -30 °C is not lower than 15 KJ / m 2 , and the color difference of the scratch resistance performance is not higher than 1.0.

Description

Technical Field

[0001] The present invention belongs to the technical field of general plastics, and more specifically, relates to an anti-low-temperature abnormal sound ABS and its preparation method and application. Background Art

[0002] Acrylonitrile-butadiene-styrene copolymer (ABS resin) is widely used in household appliances due to its excellent balance of rigidity and toughness, dimensional stability and easy processability. For example, in air-conditioning products, it is used in appearance and structural components such as panels, volute casings, bases, etc. However, with the improvement of living standards, consumers' requirements for the comfort of air conditioners are also increasing day by day. People expect to work, study and live in a comfortable and quiet environment, but the abnormal sound of air conditioners will affect the user experience. This kind of noise is random and irregular, and due to its irregularity, it is quite difficult to rectify.

[0003] Traditional methods usually involve sticking flannelette or sponge on the contact surfaces of air-conditioning parts to reduce abnormal sounds, but these are all external means to reduce the abnormal sound problem of materials and do not solve the problem from the source; moreover, when the temperature is relatively low, the abnormal sound during the operation of the air conditioner will be louder, and at the same time, the material is required to have a certain toughness and scratch resistance. Therefore, there is an urgent need in this field to develop an ABS material with low noise under low-temperature conditions and at the same time having good toughness and scratch resistance. Summary of the Invention

[0004] The purpose of the present invention is to overcome the problem of abnormal sound in the low-temperature environment in the existing ABS composition, and to provide an anti-low-temperature abnormal sound ABS composition.

[0005] Another purpose of the present invention is to provide a preparation method of the anti-low-temperature abnormal sound ABS composition.

[0006] Another purpose of the present invention is to provide an application of the anti-low-temperature abnormal sound ABS composition.

[0007] To achieve the above purposes, the present invention is realized through the following technical solutions:

[0008] An anti-low-temperature abnormal sound ABS composition, comprising the following components calculated by weight:

[0009]

[0010]

[0011] Among them, the anti-low-temperature abnormal sound agent is coated boron nitride, and the coated boron nitride is that boron nitride is coated with polyolefin on the surface, and the mass ratio of polyolefin to boron nitride is 10:1 to 10:4.

[0012] The present invention provides an anti-low-temperature abnormal noise ABS composition. By using an ABS resin as the matrix resin and coating boron nitride as the anti-low-temperature abnormal noise agent, the problem of low-temperature abnormal noise can be effectively improved. The inventor guesses that it may be because boron nitride in the coated boron nitride has good thermal conductivity, which can greatly reduce the temperature difference of the material, reduce the thermal expansion and cold shrinkage coefficients of the material, reduce the friction coefficient, and reduce the generation of abnormal noise. Moreover, there are certain differences in solubility parameters between the polyolefin material and the ABS resin. During the processing process, it is easy to migrate to the surface of the material. At the same time, due to its good ductility, the static friction force is relatively small during vibration, which can reduce frictional abnormal noise. And the boron nitride coated with polyolefin migrates to the surface of the material together with the polyolefin, which can better conduct heat, reduce the friction coefficient, and reduce the generation of abnormal noise. At the same time, the composition has good scratch resistance.

[0013] Moreover, it is necessary to strictly control the mass ratio of polyolefin and boron nitride in the coated boron nitride. If the mass ratio of polyolefin and boron nitride is too small, good coating may not be achieved, and part of the boron nitride may agglomerate, affecting its performance. If the mass ratio of polyolefin and boron nitride is too large, the coating layer of the coated boron nitride may be too thick, affecting the thermal conductivity of boron nitride, and thus the effect of better reducing low-temperature abnormal noise cannot be achieved.

[0014] It should be noted that the mass ratio of polyolefin and boron nitride in the present invention is 10:1 to 10:4, such as but not limited to 10:1, 10:1.5, 10:2, 10:2.5, 10:3, 10:3.5 or 10:4, etc., as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the range.

[0015] Furthermore, the mass ratio of polyolefin and boron nitride is 10:1.5 to 10:3.5.

[0016] Furthermore, the average particle size of the boron nitride is 1 μm to 45 μm.

[0017] Furthermore, the polyolefin is polyethylene and / or polypropylene.

[0018] In some specific embodiments, the melt flow rate of the polyethylene at 190 °C under a load of 2.16 kg is 0.2 to 3 g / 10 min; the melt flow rate of the polypropylene at 230 °C under a load of 2.16 kg is 3 to 15 g / 10 min.

[0019] It should be noted that there are no special requirements for the preparation method of the coated boron nitride in the present invention. For example, the coated boron nitride can be prepared by the following method:

[0020] The product is obtained by polymerization reaction of boron nitride and olefin monomers under transition metal catalyst conditions.

[0021] In a specific embodiment, the preparation method of the coated boron nitride is:

[0022] Boron nitride is dispersed in an inert solvent, a transition metal catalyst is added, the reaction is controlled at 80-90° C. under stirring for 3-6 hours, an inert hydrocarbon diluent and an olefin monomer are added, and the reaction is carried out at 30-40 MPa for 2-4 hours to obtain coated boron nitride.

[0023] Specifically, the inert solvent is one or more of gasoline, kerosene or petroleum ether.

[0024] Specifically, the transition metal catalyst is a transition metal halide and / or a transition metal oxyhalide, the transition metal halide is for example but not limited to one or more of titanium chloride, tantalum chloride, niobium chloride, titanium bromide, tantalum bromide or niobium bromide; the transition metal oxyhalide is for example but not limited to one or more of tungsten oxychloride, titanium oxychloride or vanadium trichloride.

[0025] Specifically, the inert hydrocarbon diluent is one or more of hexane, heptane or octane.

[0026] It should be noted that, in the low-temperature noise-proof ABS composition of the present invention, the content of ABS resin is not less than 55wt%.

[0027] Furthermore, the low-temperature noise-proof ABS composition comprises the following components calculated in parts by weight:

[0028]

[0029] In the present invention, the ABS resin is a general-purpose ABS resin, which may be a bulk ABS resin and / or an emulsion ABS resin.

[0030] In a specific implementation, the melt flow rate of the ABS resin at 220° C. and a load of 10 kg is 10 to 50 g / 10 min.

[0031] Specifically, the melt flow rate of the ABS resin is determined according to ISO 1133-1-2011.

[0032] Furthermore, the reinforcing agent is one or more of calcium carbonate, talc or barium sulfate.

[0033] Specifically, the average particle size of the reinforcing agent is 1 μm to 10 μm.

[0034] Furthermore, the toughening agent is ABS high rubber powder and / or MBS impact modifier.

[0035] Furthermore, the lubricant includes one or more of polyethylene wax, stearate or EBS.

[0036] Furthermore, the auxiliary agent includes antioxidant and / or weathering agent.

[0037] Specifically, the antioxidant can be a commonly used antioxidant selected according to the prior art, such as but not limited to one or more of hindered phenol antioxidants, phosphite antioxidants or thioester antioxidants.

[0038] Specifically, the hindered phenol antioxidant is one or more of N, N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxyhydrocinnamide) (Irganox 1098), pentaerythritol tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (Irganox1010), 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (Irganox 259), n-octadecyl β-(4-hydroxy-3,5-di-tert-butylphenyl)propionate (Irganox 1076) or 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)acrylic acid]-1,1-dimethyl}-2,4,8,10-tetraoxaspiro[5.5]undecane (ADK AO-80).

[0039] The phosphite antioxidant is one or more of tris(2,4-di-tert-butylphenyl) phosphite (Irganox 168), bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite (PEP-36) or 627A.

[0040] The thioester antioxidant is one or more of distearyl thiodipropionate, dilauryl thiodipropionate or pentaerythritol lauryl thiodipropionate.

[0041] In the present invention, a commonly used weathering agent can be selected according to the prior art, such as but not limited to ultraviolet absorber and / or light stabilizer.

[0042] The present invention also protects a preparation method of the above low-temperature abnormal noise-proof ABS composition, comprising the following steps:

[0043] S1. Mix the ABS resin, the low-temperature abnormal noise-proof agent and the auxiliary agent evenly to obtain a premix;

[0044] S2. Feed the premix obtained in S1 into an extruder through a main feed port, and feed a toughening agent and a reinforcing agent into the extruder through a side feed port, and then mix, melt and extrude and pelletize to obtain the low-temperature abnormal noise-proof ABS composition.

[0045] Furthermore, in step S2, the length-diameter ratio of the screw of the extruder is 36-48:1.

[0046] The present invention also protects the application of the above-mentioned low-temperature noise-proof ABS composition in the preparation of air-conditioning component materials.

[0047] Compared with the prior art, the present invention has the following beneficial effects:

[0048] The present invention provides a low-temperature noise-proof ABS composition, which uses coated boron nitride as a low-temperature noise-proof agent and controls the mass ratio of polyolefin and boron nitride; it can effectively reduce the noise under low-temperature conditions, and the noise of the obtained ABS composition does not exceed 25 dB at -30°C, and the impact performance at -30°C is not less than 15 KJ / m 2 , and the color difference of the scratch resistance performance is not higher than 1.0. Detailed implementation manners

[0049] The following further elaborates the present invention in detail with reference to specific embodiments. The embodiments are only used to explain the present invention and are not used to limit the scope of the present invention. The test methods used in the following embodiments are all conventional methods unless otherwise specified; the materials, reagents, etc. used are commercially available reagents and materials unless otherwise specified.

[0050] Raw materials used in each embodiment and comparative example:

[0051] ABS resin: ABS KF-730, melt flow rate at 220°C under 10 kg load is 22 g / 10 min, purchased from Liaoning Kingfa Technology Co., Ltd.;

[0052] Toughening agent: ABS POW HR181, purchased from Shanghai Kumho Asahi Plastics Co., Ltd.;

[0053] Reinforcing agent: calcium carbonate, commercially available;

[0054] Olefin monomer:

[0055] Olefin monomer 1: ethylene, commercially available;

[0056] Olefin monomer 2: propylene, commercially available;

[0057] Non-olefin monomer: styrene, commercially available;

[0058] Boron nitride:

[0059] Boron nitride 1: average particle size is 10 μm, purchased from Aladdin Chemical Reagent Co., Ltd.;

[0060] Boron nitride 2: average particle size is 1 μm, purchased from Aladdin Chemical Reagent Co., Ltd.;

[0061] Boron nitride 3: average particle size is 45 μm, purchased from Aladdin Chemical Reagent Co., Ltd.;

[0062] Lubricant: polyethylene wax;

[0063] Auxiliary agents:

[0064] Antioxidant: a mixture of antioxidant SONOX 168 and antioxidant SONOX 1076 with a mass ratio of 1:2;

[0065] Weathering agent: UV-234; The auxiliary agents are all commercially available, and the same auxiliary agents are used in the parallel experiments of the examples and comparative examples in the present invention.

[0066] The anti-low-temperature abnormal noise agent (coated boron nitride) used in the examples and comparative examples is prepared according to the formula in Table 1 by the following method, including the following steps:

[0067] Disperse boron nitride in petroleum ether, add titanium chloride in a nitrogen atmosphere, control the stirring reaction at 80-90 °C for 4 h, add hexane and olefin monomer, and react under the condition of 30-40 MPa for 3 h to obtain coated boron nitride.

[0068] Table 1 Formulation of Coated Boron Nitride (unit: parts by weight)

[0069]

[0070] Coated boron nitride 10 is obtained by heating and melting and coating 10 parts by weight of polyethylene (synthesized from ethylene monomer by the method of coated boron nitride 1) and 3 parts by weight of boron nitride 1;

[0071] Examples 1-9 and Comparative Examples 1-4

[0072] The ABS compositions in Examples 1-9 and Comparative Examples 1-4 are prepared according to the formula in Table 2 by the following preparation method:

[0073] S1. Mix the ABS resin, anti-low-temperature abnormal noise agent and auxiliary agents evenly to obtain a premix;

[0074] S2. Feed the premix obtained in S1 into the extruder through the main feed port, feed the toughening agent and reinforcing agent into the extruder through the side feed port, and obtain the anti-low-temperature abnormal noise ABS composition through mixing, melting and extrusion granulation; the temperature of the extruder is 80-120 °C in zone 1, 180-200 °C in zones 2-5, and 200-230 °C in other zones; the length-diameter ratio of the screw of the twin-screw extruder is (36-48):1.

[0075] Table 2 Dosages of each component in the anti-low-temperature abnormal noise ABS composition in Examples 1-9 (unit: parts by weight)

[0076]

[0077] Table 3 Dosages of each component in the ABS compositions of Comparative Examples 1 to 4 (unit: parts by weight)

[0078]

[0079]

[0080] It should be noted that the polyethylene used in Comparative Example 1 was synthesized from an equal amount of ethylene monomers according to the method in Coated Boron Nitride 1, with the only difference being that Boron Nitride 1 was not added.

[0081] Performance test:

[0082] The performances of the ABS compositions prepared in the above Examples 1 to 9 and Comparative Examples 1 to 4 were tested. The specific test items and test methods are as follows:

[0083] 1. Test method:

[0084] (1) Low-temperature notched impact performance test: Place the ABS compositions prepared in the Examples and Comparative Examples in a low-temperature chamber at -30°C and freeze for 4 hours. Take out the test samples and complete the test according to the standard ISO 180-2018 within 10 s, with a Type A notch;

[0085] (2) Scratch resistance test: Test the ABS compositions prepared in the Examples and Comparative Examples according to the Volkswagen PV3852-2002 standard. The specific test conditions are a test load F = 10 N, a cutting speed V = 1000 mm / min, a scraper diameter of 1 mm, and 20*20 grid cutting times;

[0086] (3) Low-temperature abnormal noise performance test: Inject the polypropylene compositions prepared in the above Examples and Comparative Examples into an upper plate and a lower plate. The specifications of the upper plate are 45 mm × 25 mm × 2 mm, and the specifications of the lower plate are 200 mm × 50 mm × 2 mm. Use a sealing strip wear-resistant test machine and a Delixi electronic DSM D2 decibel meter for testing. The specific test steps are as follows:

[0087] a. Fix the lower plate on the loading platform of the test machine, with the 200 mm × 50 mm surface facing up as the contact surface with the upper plate; fix the upper plate on the fixture of the test machine, with the 25 mm × 2 mm surface facing down as the contact surface with the lower plate;

[0088] b. In an environment without external noise interference, fix the decibel meter at a position 3 cm away from the two contact surfaces; fix a 2500 g weight on the fixture and use it to apply a load to the upper plate;

[0089] c. Place the experimental device in a low-temperature environmental chamber at -30 °C. After freezing for 4 hours, start the testing machine to make the upper and lower plates slide relative to each other at a constant rate, and test and record the frictional noise through a decibel meter.

[0090] 2. Test Results

[0091] The measurement results of each example and comparative example are shown in Table 4.

[0092] Table 4 Test Results of Each Example and Comparative Example

[0093] Test Items <![CDATA[Low-temperature impact performance (KJ / m 2 )]]> Noise Value (dB) Scratch Resistance (Color Difference) Example 1 21 15 0.6 Example 2 19 23 0.8 Example 3 16 25 0.9 Example 4 17 17 0.8 Example 5 19 19 0.9 Example 6 17 20 0.8 Example 7 18 25 0.9 Example 8 20 23 1.0 Example 9 16 25 1.0 Comparative Example 1 14 65 1.6 Comparative Example 2 11 78 1.7 Comparative Example 3 15 79 1.5 Comparative Example 4 10 76 1.3

[0094] It can be seen from Table 4 that the low-temperature noise-proof ABS composition prepared by the present invention has a good low-temperature noise-proof effect, good low-temperature toughness, and good scratch resistance. Specifically: at -30 °C, the noise does not exceed 25 dB, the impact performance at -30 °C is not less than 15 KJ / m 2 , and the color difference of the scratch resistance performance is not higher than 1.0.

[0095] It can be seen from Examples 2 to 3 that as the mass ratio of polyolefin to boron nitride in the coated boron nitride increases, the low-temperature impact strength of the prepared ABS composition first increases and then decreases, and its noise first decreases and then increases.

[0096] It can be seen from Examples 1 and 4 to 5 that as the size of boron nitride increases, its low-temperature toughness first increases and then decreases, and its noise value first decreases and then increases.

[0097] It can be seen from Examples 1 and 6 that using polyethylene-coated boron nitride as a low-temperature noise-proof agent, the prepared ABS composition has better comprehensive performance.

[0098] It can be seen from Comparative Example 1 that if polyethylene and boron nitride are directly added to the ABS resin system, the prepared ABS composition has a low low-temperature impact strength and a high noise value. It is speculated that directly adding boron nitride may cause it to agglomerate in the system and cannot migrate to the surface of the composition with the polyolefin, resulting in poor performance.

[0099] It can be seen from Comparative Example 2 that if the boron nitride coated with polystyrene instead of polyolefin is used as a low-temperature noise-proof agent to prepare the noise-proof material, the low-temperature toughness is poor and the noise value is high.

[0100] It can be seen from Comparative Examples 3 and 4 that when the mass ratio of polyolefin to boron nitride is too low or too high, the prepared noise-proof material has poor low-temperature toughness and a high noise value.

[0101] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, rather than limitations on the implementation manners of the present invention. For those of ordinary skill 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 enumerate all implementation manners here. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the claims of the present invention.

Claims

1. An anti-low-temperature abnormal noise ABS composition, characterized in that, It comprises the following components calculated by weight: Among them, the low-temperature abnormal noise inhibitor is coated boron nitride, and the coated boron nitride is that polyolefin is coated on the surface of boron nitride, and the mass ratio of polyolefin to boron nitride is 10:1 to 10:4; the average particle size of the boron nitride is 1 μm to 45 μm; the polyolefin is polyethylene and / or polypropylene.

2. The low-temperature anti-abnormal-noise ABS composition according to claim 1, wherein The mass ratio of the polyolefin to the boron nitride is 10:1.5 to 10:3.

5.

3. The anti-low-temperature abnormal noise ABS composition according to claim 1, wherein The toughening agent is ABS high rubber powder and / or MBS impact modifier.

4. The anti-low-temperature abnormal noise ABS composition according to claim 1, wherein The melt flow rate of the ABS resin at 220 °C under a load of 10 kg is 10 to 50 g / 10 min.

5. The anti-low-temperature abnormal noise ABS composition according to claim 1, wherein The coated boron nitride is prepared by the following method: It is obtained by carrying out a polymerization reaction between boron nitride and an olefin monomer under the condition of a transition metal catalyst.

6. The anti-low-temperature abnormal noise ABS composition according to claim 1, wherein The reinforcing agent is one or more of calcium carbonate, talcum powder or barium sulfate.

7. A method for preparing the low-temperature noise-proof ABS composition according to any one of claims 1 to 6, characterized in that, It comprises the following steps: S1. Mix the ABS resin, the low-temperature abnormal noise inhibitor and the additives evenly to obtain a premix; S2. Feed the premix obtained in S1 into an extruder through the main feed port, feed the toughening agent and the reinforcing agent into the extruder through the side feed port, and carry out mixing, melting and extrusion granulation to obtain a low-temperature abnormal noise-proof ABS composition.

8. Use of the low-temperature abnormal noise-proof ABS composition according to any one of claims 1 to 6 in the preparation of air-conditioning component materials.

Images