A high-impact strength glass fiber reinforced PMMA / ABS resin and its preparation method and application

Abstract

The present invention discloses a high-impact glass fiber reinforced PMMA / ABS composite material and its preparation method and application. The high-impact glass fiber reinforced PMMA / ABS composite material comprises the following components by weight: 30 to 70 parts of polymethyl methacrylate PMMA; 10 to 40 parts of acrylonitrile-butadiene-styrene terpolymer ABS; 10 to 45 parts of toughening agent; 10 to 30 parts of glass fiber; 0.1 to 4.0 parts of lubricant; 0.1 to 0.5 parts of antioxidant; 1.0 to 5.0 parts of dispersant; the dispersant is ethylene-propylene copolymer and / or carboxyl-containing ethylene-propylene copolymer. The present invention improves the toughness of the glass fiber reinforced PMMA / ABS composite material by adding a specific dispersant and synergizing with the toughening agent. The toughness of the high-impact glass fiber reinforced PMMA / ABS composite material of the present invention is higher than the toughness of composite materials prepared by other toughening agent systems, and is more suitable for preparing home appliance housings and accessories.

Description

Technical Field

[0001] The invention relates to the technical field of polymer composite materials, and in particular to a high-impact strength glass fiber reinforced PMMA / ABS composite material and a preparation method and application thereof. Background Art

[0002] Since its birth, chemically synthesized polymer materials have greatly changed people's lives. Polymer materials have good physical properties, low density, easy molding, and most of them can be recycled and reused. Therefore, they are widely used in furniture, home appliances, stationery, automobiles, construction and other fields, which are closely related to our lives. At the same time, in order to make up for some performance shortcomings of polymer materials, composite materials came into being. The so-called composite material refers to a multi-component material that is formed by physically or chemically mixing two or more polymer materials, or polymer materials with metals and inorganic materials. Through the compounding of different materials, the defects of certain properties of the original materials can be made up and the material performance can be improved. Among the many research fields of composite materials, glass fiber reinforced modified plastics are an important direction. Glass fiber reinforced plastics have been widely used in many fields such as televisions, washing machines, power tools, and fan blades due to their good strength, low density, good dimensional stability and low cost. However, due to the high glass fiber content, the cantilever beam notched impact strength of glass fiber reinforced plastics is usually poor.

[0003] PMMA material has excellent weather resistance and light transmittance, and has excellent surface properties: high gloss and good scratch resistance. It is widely used in automotive accessories, home appliance accessories and other fields. ABS is a plastic that is easy to process. The product prepared by blending PMMA and ABS has good gloss and low production cost. However, the existing PMMA / ABS composite materials have the problem of insufficient toughness, which needs to be further improved. In the prior art, the toughness of PMMA / ABS composite materials is usually improved by glass fiber and toughening agent, but from the actual use, the existing scheme has improved the toughness of the material to a certain extent, but with the replacement and upgrading of products, the market has put forward higher requirements for the toughness of composite materials, and the toughness of PMMA / ABS composite materials needs to be further improved. Summary of the invention

[0004] In order to overcome the deficiencies of the prior art, the present invention provides a glass fiber reinforced PMMA / ABS composite material with better toughness and higher glossiness.

[0005] Another object of the present invention is to provide a method for preparing the glass fiber reinforced PMMA / ABS composite material.

[0006] Another object of the present invention is to provide an application of the glass fiber reinforced PMMA / ABS composite material.

[0007] The above-mentioned purpose of the present invention is achieved through the following technical solutions:

[0008] A high impact strength glass fiber reinforced PMMA / ABS composite material, comprising the following components by weight:

[0009]

[0010] The dispersant is an ethylene-propylene copolymer and / or a carboxyl-containing ethylene-propylene copolymer.

[0011] The inventor unexpectedly discovered that the use of a small amount of the above-mentioned ethylene-propylene copolymer as a dispersant added to glass fiber reinforced PMMA / ABS can better facilitate the dispersibility of glass fiber in PMMA / ABS composite materials, and further improve the toughness of PMMA / ABS composite materials. In particular, the functional groups on the surface of the carboxyl-containing ethylene-propylene copolymer can be combined with the hydroxyl groups on the surface of the glass fiber through van der Waals force, so that the dispersant can be well coated on the surface of the glass fiber, enhancing the bonding force between the glass fiber and the PMMA / ABS substrate, playing the role of an interfacial compatibilizer, greatly improving the impact strength of the composite material system, while the floating fiber situation on the surface of the composite material is improved, and the overall glossiness of the material is also improved.

[0012] Preferably, in the high impact strength glass fiber reinforced PMMA / ABS composite material, the amount of the dispersant is 3.0 to 4.5 parts.

[0013] Preferably, in the high impact strength glass fiber reinforced PMMA / ABS composite material, the amount of the toughening agent is 20 to 25 parts.

[0014] Preferably, the high impact strength glass fiber reinforced PMMA / ABS composite material comprises the following components in parts by weight:

[0015]

[0016] Preferably, the toughening agent is a methyl methacrylate toughening agent.

[0017] The inventors found that when the amount of PMMA is low, the toughness of the composite material is higher, but its gloss is lower. When the amount of PMMA is too high, although the gloss of the composite material becomes higher, its toughness will decrease significantly.

[0018] In the PMMA / ABS system, there are many optional toughening agents, and the inventors have found that using methyl methacrylate toughening agents in the system of the present invention has a better effect.

[0019] More preferably, the toughening agent is methyl methacrylate-butadiene-styrene (MBS) and / or methyl methacrylate-acrylonitrile-styrene terpolymer (MAS).

[0020] Most preferably, the toughening agent is most preferably methyl methacrylate-acrylonitrile-styrene terpolymer (MAS). When the toughening agent is methyl methacrylate-acrylonitrile-styrene terpolymer, the toughness of the obtained composite material is the best.

[0021] Preferably, the average diameter of the glass fiber is 10-30 μm. If the diameter of the glass fiber is too small, the reinforcing effect on the composite material is not obvious, and if the diameter of the glass fiber is too large, the bonding interface between the glass fiber and the composite material is not good.

[0022] Preferably, the melt mass flow rate of the ABS resin is 30-50 g / 10 min, the test standard is ISO1133-1-2011, and the test conditions are 220° C. and 10 kg. ABS within this melt mass flow rate range has better fluidity, which is conducive to better wrapping of the polymer with glass fibers.

[0023] Preferably, the melt mass flow rate of the PMMA resin is 15 to 30 g / 10 min, the test standard is ISO1133-1-2011, and the test conditions are 220° C. and 10 kg.

[0024] Preferably, the lubricant can be an amide lubricant, a stearate lubricant, a silicone lubricant or an ester lubricant. Preferably, the lubricant is an ester lubricant. Preferably, the ester lubricant is an aliphatic stearate, such as an oleic acid-based aliphatic polyester or an erucic acid-based aliphatic polyester.

[0025] The antioxidant is one of hindered amines, hindered phenols, phosphites or thioesters, or a mixture of several of them.

[0026] The hindered amine antioxidant can be UV-3808, LA-402XP, LA-402AF, etc.

[0027] The hindered phenol antioxidant can be N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxyphenylpropionamide (Irganox 1098), pentaerythritol tetrakis[1093,5-di-tert-butyl-4-hydroxyphenyl)propionate (Irganox 1010), triethylene glycol bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate (Iragnox 259), β-(4-hydroxy-3,5-di-tert-butylphenyl) propionate n-octadecyl (Iragno 1076) or spiroethylene glycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] (ADK AO-80), etc.

[0028] The phosphite antioxidant may be 2,4-di-tert-butylphenol (Irganox 168), bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol phosphite (PEP-36) or 627A.

[0029] The thioester antioxidant can be distearyl thiodipropionate, dilauryl thiodipropionate or pentaerythritol dodecapropylthioate.

[0030] The preparation method of the high impact strength glass fiber reinforced PMMA / ABS composite material comprises the following steps: uniformly mixing the components, melting and extruding at 160-240° C. through a twin-screw extruder, granulating, and drying to obtain the high impact strength glass fiber reinforced PMMA / ABS composite material.

[0031] The high impact strength glass fiber reinforced PMMA / ABS composite material is used in the preparation of home appliance housings and decorative parts. More specifically, the PMMA / ABS composite material itself has good gloss, and the shrinkage rate is lower after adding glass fiber, and is often used to prepare long strip decorative parts of home appliance housings, such as large-size (more than 50 inches) LED TV decorative strips.

[0032] Compared with the prior art, the present invention has the following beneficial effects:

[0033] The present invention further improves the toughness and glossiness of the glass fiber reinforced PMMA / ABS composite material by adding a specific dispersant to cooperate with the toughening agent under the premise of good other mechanical properties. The high impact strength glass fiber reinforced PMMA / ABS composite material of the present invention is more suitable for the application in the preparation of home appliance housings and accessories. DETAILED DESCRIPTION

[0034] The technical solutions in the embodiments of the present invention will be described clearly and completely below, but the implementation manner of the present invention is not limited thereto.

[0035] Unless otherwise specified, the reagents, methods and equipment used in the present invention are all commercially available conventional reagents, methods and equipment in the technical field.

[0036] The raw materials used in the following examples and comparative examples are as follows:

[0037] Polymethyl methacrylate PMMA LG Chemical Co., Ltd., brand PMMA LG2, melt flow rate 20g / min

[0038] Acrylonitrile-butadiene-styrene terpolymer ABS 1 BASF, brand ABS GP-35, melt flow rate 34g / 10min;

[0039] Acrylonitrile-butadiene-styrene terpolymer ABS 2LG Chemical Co., Ltd., brand ABS HP181, melt flow rate 43 g / min;

[0040] Toughener 1MBS LG Chemical Co., Ltd., EM500

[0041] Toughener 2MAS Anqiu Donghai Plastic Industry Co., Ltd., Q500

[0042] Toughener 3 High Rubber Powder Kumho Petrochemical Co., Ltd., HR181

[0043] Glass fiber Jushi Group Co., Ltd., ECS13-03-534C, average diameter 13μm

[0044] The lubricant is an ester lubricant, which is commercially available and the same one is used in all examples and comparative examples;

[0045] The antioxidants are antioxidant 1010 and antioxidant 168, the mass ratio of antioxidant 1010 to antioxidant 168 is 1:1, they are commercially available and the same antioxidant is used in all examples and comparative examples;

[0046] Dispersant 1 Ethylene-propylene copolymer Muye New Materials Technology (Shanghai) Co., Ltd., 9010-79-1

[0047] Dispersant 2 Carboxyl-containing ethylene-propylene copolymer Mitsui Chemicals, 1105A

[0048] Dispersant 3 Ethylene bis stearamide Hebei Tianyu Chemical Co., Ltd., EBS diffusion powder

[0049] The glass fiber reinforced PMMA / ABS composite materials of the embodiment and the comparative example were prepared by the following method:

[0050] The components were dried and mixed evenly according to the dosages in Table 1 and Table 2, and then put into a twin-screw extruder. The aspect ratio of the screw was 40:1, the diameter was 35 mm, the speed of the extruder was controlled to be 300 rpm, the processing temperature was 160-240°C, and the extruder was cooled and granulated to obtain a high impact strength glass fiber reinforced PMMA / ABS composite material.

[0051] Performance testing of composite materials:

[0052] Impact strength: The Izod notched impact strength test standard is ISO 180-2019, the test condition is room temperature, and the unit is KJ / m 2 ;

[0053] Gloss: The polypropylene composition was injection molded into a test sample, and the reflection data at an angle of 60° was tested using a gloss meter in accordance with GB / T8807-1988 “Test method for mirror gloss of plastics”.

[0054] Table 1

[0055]

[0056]

[0057] Table 2

[0058]

[0059] Table 3

[0060]

[0061]

[0062] From the comparison between Comparative Example 1 and Example 1, it can be seen that when no dispersant is added, even if a toughening agent is added, the notched impact strength of the composite material is only 4.6 KJ / m 2 From the comparison between Comparative Example 2 and Example 1, it can be seen that if a non-methyl methacrylate toughening agent is used, even if the dispersant of the present application is used, the notched impact strength of the composite material is only 4.9 KJ / m 2 From the comparison between Comparative Example 3 and Example 1, it can be seen that if other conventional dispersants are used, the notched impact strength of the composite material cannot reach the level of the present invention. Similarly, from the comparison between Comparative Example 4 and Example 6, it can be seen that if other conventional dispersants are used, the notched impact strength of the composite material cannot reach the level of the present invention.

[0063] From the comparison between Example 1 and Example 3, it can be seen that the toughening effect of using MAS as a toughening agent in the system of the present invention is better than that of MBS as a toughening agent. From the comparison between Example 1 and Example 4, it can be seen that the dispersing effect of the carboxyl-containing ethylene-propylene copolymer as a dispersant is worse than that of the ethylene-propylene copolymer dispersant, so the toughness of the obtained composite material is higher. From the comparison between Example 1 and Example 10, it can be seen that when the number of dispersants is small, the improvement in toughness is not as significant as the preferred solution (3 parts).

[0064] From the comparison between Example 1 and Example 6, it can be seen that as the PMMA content of the system increases, the glossiness improves, but the toughness of the material deteriorates, and the Izod notched impact strength decreases significantly.

[0065] From the comparison among Example 1, Example 12 and Example 17, it can be seen that when the glass fiber content is higher, the glossiness tends to decrease.

[0066] 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. A high impact strength glass fiber reinforced PMMA / ABS composite material, characterized in that: By weight, it includes the following components: The dispersant is an ethylene-propylene copolymer and / or a modified ethylene-propylene copolymer, and the modified ethylene-propylene copolymer is a carboxyl-containing ethylene-propylene copolymer; The melt mass flow rate of the ABS resin is 30 to 50 g / 10 min, the test standard is ISO 1133-1-2011, and the test conditions are 220° C. and 10 kg; The toughening agent is a methyl methacrylate toughening agent.

2. The high impact strength glass fiber reinforced PMMA / ABS composite material according to claim 1, characterized in that: By weight, it includes the following components:

3. The high impact strength glass fiber reinforced PMMA / ABS composite material according to claim 1 or 2, characterized in that: The toughening agent is MBS and / or MAS.

4. The high impact strength glass fiber reinforced PMMA / ABS composite material according to claim 1 or 2, characterized in that: The average diameter of the glass fiber is 10 to 30 μm.

5. The high impact strength glass fiber reinforced PMMA / ABS composite material according to claim 1 or 2, characterized in that: The melt mass flow rate of the PMMA resin is 15-30 g / 10 min, the test standard is ISO 1133-1-2011, and the test conditions are 220° C. and 10 kg.

6. The high impact strength glass fiber reinforced PMMA / ABS composite material according to claim 1 or 2, characterized in that: The lubricant is an ester lubricant; the antioxidant is one or a mixture of hindered amines, hindered phenols, phosphites or thioesters.

7. The method for preparing the high impact strength glass fiber reinforced PMMA / ABS composite material according to any one of claims 1 to 6, characterized in that: The components are mixed uniformly, melt-extruded and granulated at 160-240° C. by a twin-screw extruder, and dried to obtain the high-impact strength glass fiber reinforced PMMA / ABS composite material.

8. Use of the high impact strength glass fiber reinforced PMMA / ABS composite material according to any one of claims 1 to 6 in the preparation of housings and accessories of household appliances.

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