Glass fiber reinforced spraying-free aesthetic polycarbonate composition as well as preparation method and application thereof

Abstract

The invention discloses a glass fiber reinforced spraying-free aesthetic polycarbonate composition as well as a preparation method and application thereof, and belongs to the field of materials. The polycarbonate composition is prepared from the following raw materials in parts by weight: 50 to 78 parts of polycarbonate, 15 to 30 parts of glass fiber, 1 to 8 parts of spraying-free metal powder and 2 to 6 parts of styrene-glycidyl methacrylate copolymer, the preparation method of the styrene-glycidyl methacrylate copolymer comprises the following steps: mixing and stirring 40-80 parts of caprolactam, 20-59 parts of styrene and 0.1-1 part of glycidyl methacrylate; then adding 0.1 to 1 part of azodiisobutyronitrile, and reacting; crushing the reaction product, washing with deionized water to remove the water-soluble caprolactam solvent, washing with ethanol to remove an oily unconverted monomer, and drying to obtain a styrene-glycidyl methacrylate copolymer; the cantilever beam notch impact strength and glossiness of the polycarbonate composition material prepared by the invention are greatly improved.

Description

Technical Field

[0001] The invention relates to the field of materials, and in particular to a glass fiber reinforced spray-free aesthetic polycarbonate composition, a preparation method and application thereof. Background Art

[0002] With the rapid development of materials science, polymer materials are increasingly used in many fields. Spray-free metal / resin composite materials have a unique appearance and show broad application prospects in many fields. Especially in the automotive, consumer electronics, home appliances and other industries. However, how to achieve compatibility between two different materials, metal and resin, has always been the main technical difficulty in the in-depth development of metal / resin composite materials. Especially in terms of material toughness, structural rigidity and appearance quality, traditional material blending preparation technology can no longer meet the needs of modern industry. Summary of the invention

[0003] In view of the deficiencies in the prior art, the present invention provides a glass fiber reinforced spray-free aesthetic polycarbonate composition, a preparation method and application thereof.

[0004] This patent proposes a glass fiber reinforced spray-free aesthetic polycarbonate composition to solve the problem of low toughness and poor spray-free effect of existing glass fiber reinforced spray-free polycarbonate materials. It not only has excellent toughness and rigidity, but also can achieve the ideal appearance effect without spraying, and has a strong environmental advantage.

[0005] A glass fiber reinforced spray-free aesthetic polycarbonate composition comprises the following raw materials in parts by weight: 50-78 parts of polycarbonate, 15-30 parts of glass fiber, 1-8 parts of spray-free metal powder and 2-6 parts of styrene-glycidyl methacrylate copolymer; the preparation method of the styrene-glycidyl methacrylate copolymer comprises the following steps: mixing and stirring 40-80 parts of caprolactam, 20-59 parts of styrene and 0.1-1 part of glycidyl methacrylate; adding 0.1-1 part of azobisisobutyronitrile and reacting; crushing the reaction product, washing with deionized water to remove the water-soluble caprolactam solvent, washing with ethanol to remove the oily unconverted monomer, and drying to obtain the styrene-glycidyl methacrylate copolymer.

[0006] Preferably, the spray-free metal powder includes RK72008.

[0007] Preferably, the weight average molecular weight of the polycarbonate is 21,500.

[0008] Preferably, 4 parts by weight of a toughening agent is also included, wherein the toughening agent includes one or more of a maleic anhydride grafted polymer, a methyl methacrylate-butadiene-styrene copolymer, a methyl methacrylate-styrene-silicone copolymer, an acrylic polymer, an ethylene-butyl acrylate-glycidyl methacrylate copolymer, an ethylene-vinyl acetate copolymer, and a styrene-acrylonitrile-glycidyl methacrylate ternary random copolymer.

[0009] Preferably, the styrene-glycidyl methacrylate copolymer comprises the following raw materials in parts by weight: 40-80 parts of caprolactam, 20-59 parts of styrene, 0.1-1 part of glycidyl methacrylate and 0.1-1 part of azobisisobutyronitrile.

[0010] Preferably, the invention further comprises 0.3 parts by weight of an antioxidant, wherein the antioxidant comprises a combination of n-octadecylβ-(4-hydroxyphenyl-3,5-di-tert-butyl) propionate and tris(2,4-di-tert-butylphenyl) phosphite.

[0011] Preferably, the mass ratio of the β-(4-hydroxyphenyl-3,5-di-tert-butyl) propionate to tris(2,4-di-tert-butylphenyl) phosphite is 1:2.

[0012] Preferably, 0.7 parts by weight of a lubricant is further included, wherein the lubricant includes one or more of pentaerythritol stearate, N,N'-ethylene bisstearamide, oxidized polyethylene wax, polysiloxane, trihydroxymethylpropane and montanate metal soap.

[0013] A method for preparing a glass fiber reinforced spray-free aesthetic polycarbonate composition comprises the following steps:

[0014] 50-78 parts of polycarbonate, 1-8 parts of spray-free metal powder, 2-6 parts of styrene-glycidyl methacrylate copolymer, 4 parts of toughening agent, 0.3 parts of antioxidant and 0.7 parts of lubricant are mixed and stirred to obtain a mixture; 15-30 parts of glass fiber are added, melt-extruded and granulated to obtain a polycarbonate composition.

[0015] The glass fiber reinforced spray-free aesthetic polycarbonate composition or the glass fiber reinforced spray-free aesthetic polycarbonate composition prepared by the preparation method is used in the production of consumer electronics, home appliances and automobile products.

[0016] Compared with the prior art, the present invention has the following beneficial effects:

[0017] Therefore, this patent innovatively proposes a more efficient and simple capacity expansion strategy, that is, to select a linear molecule with reactive functional groups for melt blending, and to use the chemical reaction between functional groups to effectively reduce the interfacial tension, increase the interfacial adhesion, refine the phase region, and achieve efficient capacity expansion of the organic / inorganic blending system. At the same time, the glass fiber reinforced spray-free aesthetic polycarbonate composition has good impact strength, surface gloss, and good comprehensive performance, and can be used in the fields of automobiles, consumer electronics, and home appliances. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, for ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0019] Figure 1 It is a schematic diagram of the preparation method of the glass fiber reinforced spray-free aesthetic polycarbonate composition of the present invention. DETAILED DESCRIPTION

[0020] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0021] Unless otherwise specified, the components involved in the embodiments and comparative examples of the present invention are as follows:

[0022] Polycarbonate: 1000R, purchased from SABIC China Ltd.;

[0023] Glass fiber: 510, purchased from Jushi Group Co., Ltd.;

[0024] Spray-free metal powder: RK72008, particle size 10-50 μm, purchased from BASF AG;

[0025] Styrene: 99.5%, styrene (containing stabilizer p-tert-butylpyrocatechol), purchased from Anhui Zesheng Technology Co., Ltd.;

[0026] Caprolactam: industrial grade, Nanjing Dongfang Chemical Co., Ltd.;

[0027] Glycidyl methacrylate: 98%, purchased from Anhui Zesheng Technology Co., Ltd.;

[0028] Azobisisobutyronitrile: 99%, purchased from Sinopharm Chemical Reagent Co., Ltd.;

[0029] Ethanol: analytical grade, purchased from Sinopharm Chemical Reagent Co., Ltd.;

[0030] Antioxidant: β-(4-hydroxyphenyl-3,5-di-tert-butyl) propionate octadecyl alcohol ester and tris(2,4-di-tert-butylphenyl) phosphite were purchased from Ciba, Switzerland; in the following examples, β-(4-hydroxyphenyl-3,5-di-tert-butyl) propionate octadecyl alcohol ester and tris(2,4-di-tert-butylphenyl) phosphite were added at a mass ratio of 1:2;

[0031] Lubricant: Pentaerythritol stearate was purchased from LONZA Company, USA.

[0032] The following is the preparation method of the glass fiber reinforced spray-free aesthetic polycarbonate composition in the examples and comparative examples:

[0033] (1) adding the polycarbonate, the spray-free metal powder, the styrene-glycidyl methacrylate copolymer, the toughening agent, the antioxidant, and the lubricant into a mixer, mixing and stirring to obtain a mixture;

[0034] The obtained mixture is fed into a parallel twin-screw extruder from the main feeding port through a feeder, and the glass fiber is fed from the side feeding port alone for melt extrusion and granulation. The process parameters include: the temperature of zone 1 is 50°C, the temperature of zone 2 is 260°C, the temperature of zone 3 is 260°C, the temperature of zone 4 is 260°C, the temperature of zone 5 is 260°C, the temperature of zone 6 is 240°C, the temperature of zone 7 is 240°C, the temperature of zone 8 is 240°C, the temperature of die head is 240°C, and the screw speed is 400rpm; the screw shape of the parallel twin-screw extruder is single-thread; the ratio of screw length L to diameter D is 40:1;

[0035] For detailed implementation process, please refer to Figure 1 shown.

[0036] The following is the preparation method of the styrene-glycidyl methacrylate copolymer described in the examples and comparative examples:

[0037] 1. Add 60 parts of caprolactam, 39.76 parts of styrene and 0.24 parts of glycidyl methacrylate into a three-necked flask equipped with a mechanical stirrer;

[0038] 0.2 parts of azobisisobutyronitrile (AIBN) initiator was added, and the reaction system was kept at 80°C for 24 hours under a stirring speed of 200 r / min and a nitrogen atmosphere of 0.5 L / min;

[0039] The product is mechanically crushed and then washed with deionized water to remove the water-soluble caprolactam solvent;

[0040] Wash out the oily unconverted monomers with hot ethanol;

[0041] The above product was dried under vacuum at 95°C.

[0042] 2. Add 40 parts of caprolactam, 20 parts of styrene and 0.1 parts of glycidyl methacrylate into a three-necked flask equipped with a mechanical stirrer;

[0043] 0.1 parts of azobisisobutyronitrile (AIBN) initiator was added, and the reaction system was kept at 80°C for 24 hours under a stirring speed of 200 r / min and a nitrogen atmosphere of 0.5 L / min;

[0044] The product is mechanically crushed and then washed with deionized water to remove the water-soluble caprolactam solvent;

[0045] Wash out the oily unconverted monomers with hot ethanol;

[0046] The above product was dried under vacuum at 95°C.

[0047] 3. Add 80 parts of caprolactam, 59 parts of styrene and 1 part of glycidyl methacrylate into a three-necked flask equipped with a mechanical stirrer;

[0048] 1 part of azobisisobutyronitrile (AIBN) initiator was added, and the reaction system was kept at 80°C for 24 h under a stirring speed of 200 r / min and a nitrogen atmosphere of 0.5 L / min;

[0049] The product is mechanically crushed and then washed with deionized water to remove the water-soluble caprolactam solvent;

[0050] Wash out the oily unconverted monomers with hot ethanol;

[0051] The above product was dried under vacuum at 95°C.

[0052] In order to facilitate the understanding of the present invention, the present invention will be described more fully below with reference to the embodiments, and preferred embodiments of the present invention are given below. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. The purpose of providing these embodiments is to make the understanding of the disclosure of the present invention more thorough and comprehensive.

[0053] Embodiment 1:

[0054] The present embodiment provides a glass fiber reinforced spray-free aesthetic polycarbonate composition, which is prepared from raw materials including the following components in parts by weight:

[0055]

[0056] Embodiment 2:

[0057] The present embodiment provides a glass fiber reinforced spray-free aesthetic polycarbonate composition, which is prepared from raw materials including the following components in parts by weight:

[0058]

[0059]

[0060] Embodiment 3:

[0061] The present embodiment provides a glass fiber reinforced spray-free aesthetic polycarbonate composition, which is prepared from raw materials including the following components in parts by weight:

[0062]

[0063] Embodiment 4:

[0064] The present embodiment provides a glass fiber reinforced spray-free aesthetic polycarbonate composition, which is prepared from raw materials including the following components in parts by weight:

[0065]

[0066] Embodiment 5:

[0067] The present embodiment provides a glass fiber reinforced spray-free aesthetic polycarbonate composition, which is prepared from raw materials including the following components in parts by weight:

[0068]

[0069] Comparative Example 1:

[0070] The present embodiment provides a glass fiber reinforced spray-free aesthetic polycarbonate composition, which is prepared from raw materials including the following components in parts by weight:

[0071]

[0072] Comparative Example 2:

[0073] The present embodiment provides a glass fiber reinforced spray-free aesthetic polycarbonate composition, which is prepared from raw materials including the following components in parts by weight:

[0074]

[0075] Comparative Example 3:

[0076] The present embodiment provides a glass fiber reinforced spray-free aesthetic polycarbonate composition, which is prepared from raw materials including the following components in parts by weight:

[0077]

[0078] Comparative Example 4:

[0079] The present embodiment provides a glass fiber reinforced spray-free aesthetic polycarbonate composition, which is prepared from raw materials including the following components in parts by weight:

[0080]

[0081] Comparative Example 5

[0082] The present embodiment provides a glass fiber reinforced spray-free aesthetic polycarbonate composition, which is prepared from raw materials including the following components in parts by weight:

[0083]

[0084]

[0085] The raw material compositions of Examples 1-5 and Comparative Examples 1-5 are shown in Table 1 by weight:

[0086] Table 1

[0087]

[0088] Among them, the toughening agent added in the above embodiments and comparative examples is 4 parts, the antioxidant added is 0.3 parts, the mass ratio of β-(4-hydroxyphenyl-3,5-di-tert-butyl) propionate to tris(2,4-di-tert-butylphenyl) phosphite is 1:2, and the lubricant added is 0.7 parts.

[0089] The acrylonitrile-butadiene-styrene compositions obtained in the above Examples 1-5 and Comparative Examples 1-5 were baked at 120°C for 2 hours, and the injection molding temperatures were 275°C, 285°C, 295°C, and 285°C, the mold temperature was 100°C, and the injection molding speed was medium speed. The following test specimens were prepared and conditioned at 23°C and 50% RH for 24 hours, and then the corresponding performance tests were performed:

[0090] Izod notched impact strength: tested according to ASTM D251 standard, the specimen thickness is 3.2mm;

[0091] Gloss: tested according to ASTM D523 standard, the test angle is 60°;

[0092] The test results are shown in Table 2:

[0093] Table 2

[0094]

[0095] It can be seen from Examples 1-5 that under the action of styrene-methacrylate glycidyl copolymer, the toughness of the spray-free glass fiber reinforced polycarbonate material is significantly maintained, and the glossiness reaches more than 90°, with good comprehensive performance. Moreover, with the increase in the amount of styrene-methacrylate glycidyl copolymer added, the toughness and glossiness of the material both show an upward trend. This is because the polar groups of the copolymer can play a compatibilizing role, which can increase the compatibility of glass fiber and metal powder with the matrix resin, and at the same time, it also promotes the dispersion of glass fiber and metal powder, making its blending morphology more regular. Moreover, even if the glass fiber reaches 30 parts and the spray-free metal powder reaches 8 parts, the material can still maintain a high toughness and glossiness; by comparison, the comprehensive performance of Example 4 is the best.

[0096] Compared with Example 2, the toughness and surface gloss of the spray-free glass fiber reinforced polycarbonate composition without adding styrene-methacrylate glycidyl copolymer are very low. However, when styrene-methacrylate glycidyl copolymer is added excessively in Comparative Example 2, although the gloss reaches the highest, the toughness is low. This is because there is no elastic component in the molecular structure of styrene-methacrylate glycidyl copolymer, and when the copolymer is added excessively, a continuous phase will be formed, that is, a continuous brittle phase will be formed, which affects the overall toughness of the material; Compared with Example 1, the amount of styrene-methacrylate glycidyl copolymer added in Comparative Example 3 is also low, and the gloss and toughness of the material are still insufficient; Compared with Comparative Example 4 and Comparative Example 4 and Example 5, the inventor found that although the amount of styrene-methacrylate glycidyl copolymer added is within a reasonable range, due to the excessive use of spray-free metal powder and glass fiber, the toughness and gloss of A polycarbonate composition will be significantly reduced. By comparison, it can be found that the Izod notched impact strength and gloss performance of the polycarbonate composition material prepared by using the raw materials described in the present invention are greatly improved, and the obtained composition can be applied to automobiles, consumer electronics, home appliances and other fields.

[0097] In the description of this specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0098] The above shows and describes the basic principles, main features and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments, and the above embodiments and descriptions are only for explaining the principles of the present invention. Without departing from the spirit and scope of the present invention, the present invention may have various changes and improvements, and these changes and improvements all fall within the scope of the present invention to be protected.

Claims

1. A glass fiber reinforced spray-free aesthetic polycarbonate composition, characterized in that: The invention comprises the following raw materials in parts by weight: 50-78 parts of polycarbonate, 15-30 parts of glass fiber, 1-8 parts of spray-free metal powder and 2-6 parts of styrene-glycidyl methacrylate copolymer. The preparation method of the styrene-glycidyl methacrylate copolymer comprises the following steps: mixing and stirring 40-80 parts of caprolactam, 20-59 parts of styrene and 0.1-1 part of glycidyl methacrylate; adding 0.1-1 part of azobisisobutyronitrile and reacting; crushing the reaction product, washing with deionized water to remove the water-soluble caprolactam solvent, washing with ethanol to remove the oily unconverted monomer, and drying to obtain the styrene-glycidyl methacrylate copolymer.

2. The glass fiber reinforced spray-free aesthetic polycarbonate composition according to claim 1, characterized in that: The spray-free metal powder includes RK72008.

3. The glass fiber reinforced spray-free aesthetic polycarbonate composition according to claim 1, characterized in that: The weight average molecular weight of the polycarbonate is 21,500.

4. The glass fiber reinforced spray-free aesthetic polycarbonate composition according to claim 1, characterized in that: It also includes 4 parts by weight of a toughening agent, which includes one or more of a maleic anhydride grafted polymer, a methyl methacrylate-butadiene-styrene copolymer, a methyl methacrylate-styrene-silicone copolymer, an acrylic polymer, an ethylene-butyl acrylate-glycidyl methacrylate copolymer, an ethylene-vinyl acetate copolymer, and a styrene-acrylonitrile-glycidyl methacrylate ternary random copolymer.

5. The glass fiber reinforced spray-free aesthetic polycarbonate composition according to claim 1, characterized in that: The styrene-glycidyl methacrylate copolymer comprises the following raw materials in parts by weight: 40-80 parts of caprolactam, 20-59 parts of styrene, 0.1-1 part of glycidyl methacrylate and 0.1-1 part of azobisisobutyronitrile.

6. The glass fiber reinforced spray-free aesthetic polycarbonate composition according to claim 1, characterized in that: The invention also comprises 0.3 parts by weight of an antioxidant, wherein the antioxidant comprises a combination of n-octadecylβ-(4-hydroxyphenyl-3,5-di-tert-butyl) propionate and tris(2,4-di-tert-butylphenyl) phosphite.

7. The glass fiber reinforced spray-free aesthetic polycarbonate composition according to claim 6, characterized in that: The mass ratio of the β-(4-hydroxyphenyl-3,5-di-tert-butyl) propionate to tris(2,4-di-tert-butylphenyl) phosphite is 1:

2.

8. The glass fiber reinforced spray-free aesthetic polycarbonate composition according to claim 1, characterized in that: The invention also includes 0.7 parts by weight of a lubricant, which includes one or more of pentaerythritol stearate, N,N'-ethylene bisstearamide, oxidized polyethylene wax, polysiloxane, trihydroxymethylpropane and montanate metal soap.

9. A method for preparing a glass fiber reinforced spray-free aesthetic polycarbonate composition, characterized in that: The following steps are involved: 50-78 parts of polycarbonate, 1-8 parts of spray-free metal powder, 2-6 parts of styrene-glycidyl methacrylate copolymer, 4 parts of toughening agent, 0.3 parts of antioxidant and 0.7 parts of lubricant are mixed and stirred to obtain a mixture; 15-30 parts of glass fiber are added, melt-extruded and granulated to obtain a polycarbonate composition.

10. Use of the glass fiber reinforced spray-free aesthetic polycarbonate composition according to any one of claims 1 to 8 or the glass fiber reinforced spray-free aesthetic polycarbonate composition prepared by the preparation method according to claim 9 in the production of consumer electronics, home appliances and automobile products.

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