PC composite material and preparation method and application thereof

Abstract

The application discloses a PC composite material and a preparation method and application thereof, and belongs to the technical field of high polymer materials. The application adds a specific amount of hydrogenated petroleum resin into PC, and limits the hydrogenated petroleum resin to contain first hydrogenated petroleum resin and second hydrogenated petroleum resin in a specific ratio, so as to improve the water vapor barrier property, water vapor durability and heat resistance of the material by using the two kinds of hydrogenated petroleum resins in cooperation, so that the obtained material has good water vapor barrier property, water vapor durability and heat resistance at the same time, and is suitable for preparing a head-up display or a radar cover plastic part.

Description

Technical Field

[0001] This application relates to the field of polymer materials technology, specifically to a PC composite material and its preparation method and application. Background Technology

[0002] Polycarbonate (PC) is an amorphous, tasteless, odorless, non-toxic, and transparent thermoplastic polymer with excellent impact toughness, transparency, dimensional stability, creep resistance, weather resistance, and electrical insulation. However, due to the large number of ester groups in the PC backbone, it is highly polar and has a strong affinity for water, resulting in high water vapor permeability. Under humid and hot conditions, it is prone to hydrolysis, causing molecular chain breakage or the formation of small molecules, resulting in surface micropores or precipitation. When used in HUDs (Head-Up Displays) and radomes, this affects the image clarity and quality of the camera. Therefore, improving the water vapor barrier properties of PC and reducing its water vapor permeability is of great significance. Furthermore, HUD and radar applications also require components with good durability.

[0003] Currently, adding layered fillers such as mica, montmorillonite, attapulgite, and organic clay can improve water vapor barrier properties by increasing the diffusion path and time of water molecules when they diffuse through the planar oriented layered channels, bypassing the layers. However, the appearance is poor, the specimens are opaque, and due to interfacial bonding and contact surface issues, there are minor defects inside the specimens, resulting in poor dimensional stability.

[0004] Therefore, it is necessary to develop a technology that enables transparent PC materials to simultaneously possess good water vapor barrier properties and dimensional stability. Summary of the Invention

[0005] Based on the deficiencies of the existing technology, the purpose of this application is to provide a PC composite material, its preparation method and application, which aims to enable the PC composite material to have good water vapor barrier and dimensional stability, as well as a transparent appearance and a wide range of applications.

[0006] To achieve the above objectives, in a first aspect, this application provides a PC composite material comprising the following components in parts by weight: 100 parts PC, 0.4 to 6 parts hydrogenated petroleum resin, wherein the hydrogenated petroleum resin comprises a first hydrogenated petroleum resin and a second hydrogenated petroleum resin, the first hydrogenated petroleum resin being a C5 hydrogenated petroleum resin, and the second hydrogenated petroleum resin being at least one of a C9 hydrogenated petroleum resin and a DCPD hydrogenated petroleum resin, wherein the weight ratio of the first hydrogenated petroleum resin to the second hydrogenated petroleum resin is 1:(1.25 to 2).

[0007] The water vapor permeation process in PC involves water molecules first adsorbing onto the PC surface, then attacking the surface and slowly penetrating into its internal structure, thereby reducing the hydrophilicity of functional groups and altering the physicochemical structure. Adding a specific amount of hydrogenated petroleum resin to PC, specifically containing a first and second hydrogenated petroleum resin in a defined ratio, demonstrates the superior compatibility of these two resins with PC. These resins bind to the PC carbon chains via van der Waals forces, forming a barrier film on the material surface and improving the material's water vapor barrier properties. Furthermore, their chemical stability and heat resistance are better than PC, enhancing the PC's water vapor durability and heat resistance. The second hydrogenated petroleum resin shows a significantly stronger effect in improving the water vapor barrier properties, water vapor durability, and heat resistance of PC. However, adding only the second hydrogenated petroleum resin can lead to material flowability deviations, hindering processing and affecting the effectiveness of the second hydrogenated petroleum resin. The addition of the first hydrogenated petroleum resin increases the material's flowability. With the combined action of these two hydrogenated petroleum resins, the material achieves even better water vapor barrier properties, water vapor durability, and heat resistance.

[0008] The weight ratio of the first hydrogenated petroleum resin to the second hydrogenated petroleum resin is 1:(1.25~2), such as 1:1.25, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9 or 1:2.

[0009] The amount of hydrogenated petroleum resin added affects the material's water vapor barrier properties, water vapor durability, and heat resistance. Too little addition results in minimal improvement in these properties; too much addition leads to the hydrogenated petroleum resin dispersing between PC molecular chains, reducing steric hindrance and negatively impacting their performance. Therefore, this application controls the amount of hydrogenated petroleum resin to be between 0.4 and 6 parts by weight, such as 0.4, 0.5, 0.7, 0.9, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, or 6 parts by weight. Preferably, the amount of hydrogenated petroleum resin is 1.5 to 3.5 parts by weight to improve the material's water vapor barrier properties, water vapor durability, and heat resistance.

[0010] Preferably, the softening points of the first hydrogenated petroleum resin and the second hydrogenated petroleum resin are each independently between 80°C and 150°C. More preferably, the softening points of the first hydrogenated petroleum resin and the second hydrogenated petroleum resin are each independently between 95°C and 135°C.

[0011] Controlling the softening points of the first and second hydrogenated petroleum resins independently to 80℃~150℃, especially to 95℃~135℃, not only improves their chemical stability and heat resistance, but also prevents surface delamination, ensuring better uniformity and moisture barrier properties of the barrier layer formed on the material surface. The softening point of the first hydrogenated petroleum resin can be selected from 80℃, 85℃, 89℃, 90℃, 95℃, 100℃, 105℃, 110℃, 115℃, 120℃, 125℃, 130℃, 135℃, 140℃, 145℃, or 150℃, etc. The softening point of the second hydrogenated petroleum resin can be selected as 80℃, 85℃, 89℃, 90℃, 95℃, 100℃, 105℃, 110℃, 115℃, 120℃, 125℃, 130℃, 135℃, 140℃, 145℃ or 150℃, etc.

[0012] The softening points of the first hydrogenated petroleum resin and the second hydrogenated petroleum resin can be determined by the following method: GB / T 24138-2022 Petroleum Resins.

[0013] Preferably, the PC has a melt flow rate of 10-30 g / 10 min at 300°C and 1.2 kg.

[0014] Preferably, the PC is bisphenol A type polycarbonate.

[0015] When the melt flow rate of the PC at 300℃ and 1.2kg is within the range of 10-30 g / 10min, the material exhibits better overall performance in terms of water vapor barrier properties, water vapor durability, and heat resistance. The melt flow rate of the PC at 300℃ and 1.2kg can be selected from 10 g / 10min, 12 g / 10min, 14 g / 10min, 16 g / 10min, 18 g / 10min, 20 g / 10min, 22 g / 10min, 24 g / 10min, 26 g / 10min, 28 g / 10min, or 30 g / 10min, etc.

[0016] The melt flow rate of the PC can be measured according to ISO 1133-2005.

[0017] Preferably, the PC composite material further includes the following components in parts by weight: 0.01 to 2 parts of additives.

[0018] Preferably, the additives include at least one of flame retardants, antioxidants, fillers, antibacterial agents, and toughening agents.

[0019] For example, the flame retardant includes at least one of phosphorus-based flame retardants, silicone-based flame retardants, sulfur-based flame retardants, and inorganic flame retardants; the antioxidant includes at least one of hindered phenolic antioxidants (such as antioxidant 1076, antioxidant 1010, etc.), phosphite antioxidants (such as antioxidant 168, etc.), and aromatic amine antioxidants (such as antioxidant HP-136, etc.); the filler includes at least one of talc, mica, kaolin, barium sulfate, and wollastonite; the antibacterial agent includes at least one of silver ion antibacterial agents and vanillin antibacterial agents; and the toughening agent includes at least one of methyl methacrylate-butadiene-styrene terpolymer toughening agent MBS, ethylene (E) and methyl acrylate (MA) binary copolymer toughening agent EMA, acrylonitrile-butadiene-styrene copolymer toughening agent SMA, organosilicon toughening agents, and core-shell structure acrylate copolymer toughening agents ACR.

[0020] Preferably, the PC composite material contains 92.6% or more PC by weight. For example, 92.6%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, or 99.6%.

[0021] Secondly, this application also provides a method for preparing the PC composite material, comprising the following steps: mixing and dispersing all component raw materials, melt extrusion, granulation, and obtaining the PC composite material.

[0022] Preferably, the temperature of the melt extrusion is 250–280°C.

[0023] Thirdly, this application also provides the application of the PC composite material in head-up displays or radome plastic parts. Specifically, the PC composite material can be used to manufacture the housing of a head-up display.

[0024] Compared with the prior art, the beneficial effects of this application are as follows: This application adds a specific amount of hydrogenated petroleum resin to PC, and limits the hydrogenated petroleum resin to include a first hydrogenated petroleum resin and a second hydrogenated petroleum resin in a specific ratio, so as to utilize the two hydrogenated petroleum resins to synergistically improve the water vapor barrier properties, water vapor durability and heat resistance of the material, so that the resulting material has good water vapor barrier properties, water vapor durability and heat resistance at the same time, and is suitable for manufacturing head-up displays or radar dome plastic parts. Detailed Implementation

[0025] To better illustrate the purpose, technical solutions, and advantages of this application, the following description, in conjunction with specific embodiments and comparative examples, aims to provide a detailed understanding of the content of this application, rather than limiting it. All other embodiments obtained by those skilled in the art without inventive effort are within the protection scope of this application. Unless otherwise specified, the experimental reagents and instruments involved in the implementation of this application are commonly used reagents and instruments. In this application, the technical features described in an open-ended manner include both closed-ended technical solutions composed of the listed features and open-ended technical solutions that include the listed features.

[0026] The raw materials used in the following embodiments and comparative examples are shown in Table 1, and unless otherwise specified, all raw materials are commercially available. Furthermore, the same raw materials were used in each parallel experiment.

[0027] Table 1

[0028]

[0029] The following examples and comparative examples all provide a PC composite material, comprising the following steps: mixing and dispersing all component raw materials, feeding them into a twin-screw extruder, melt extruding, granulating, and obtaining the PC composite material. The melt extrusion temperature is 250–280°C. The formulations of these PC composite materials in the examples and comparative examples are shown in Tables 2 and 3.

[0030] Table 2

[0031]

[0032] Table 3

[0033]

[0034] The PC composite materials of the above embodiments and comparative examples were subjected to the following performance tests, and the test results are shown in Table 4.

[0035] (1) Water vapor barrier performance test method

[0036] PC composite material particles are added to an injection molding machine and melted at temperatures of 280°C in the first stage, 270°C in the second stage, 270°C in the third stage, 260°C in the fourth stage, and 250°C in the fifth stage to form a sample strip with a thickness of 125mm×13.0mm×1mm.

[0037] The instrument used was an Illinois Instruments-7002 water vapor permeation analyzer, and the reference standards were GB / T 21529-2008 Determination of water vapor transmission rate of plastic films and sheets - Electrolytic sensor method, and ISO 15106-3: Plastics - Film and sheeting - Determination of water vapor transmission rate - Part 3: Electrolytic detection sensor method. The temperature during the test was 38℃ and the humidity was 90%.

[0038] (2) Dimensional stability performance

[0039] PC composite material particles were added to an injection molding machine and melted at five different temperatures: 280℃ in the first stage, 270℃ in the second stage, 270℃ in the third stage, 260℃ in the fourth stage, and 250℃ in the fifth stage. A 100mm*100mm*2mm sample was prepared and its length was recorded as L0. The sample was then baked at 80℃ for 24 hours. The length of the sample after baking was measured and recorded as L1. The dimensional change rate was calculated as (L1-L0) / L0*100%.

[0040] (3) Durability test

[0041] PC composite material particles were added to an injection molding machine and melted at a temperature of 270℃~290℃ to form a standard color plate with dimensions of 54mm*84mm*2mm (length*width*thickness). The haze was measured, and then the plate was placed in a PCT high-pressure cooker for testing at 0.17MPa, 120℃, and saturated humidity (100%RH) for 1000 hours. The haze was then measured again, and the haze change rate was calculated. The haze test was performed using a WGT-S transmittance / haze meter from Shanghai Jingke.

[0042] Table 4

[0043]

[0044]

[0045] As can be seen from the above data, the PC composite materials in each embodiment simultaneously possess good water vapor barrier properties, water vapor durability, and heat resistance. For example, the water vapor barrier property is 0.5 g / (m²). 2 *day) and below, the dimensional change rate after baking at 80℃ for 24 hours is less than 1.2%, and the haze change rate after being placed at 0.17MPa, 120℃ and 100%RH for 1000h is less than 15%.

[0046] Comparative Example 1 only added C5 hydrogenated petroleum resin, without adding C9 hydrogenated petroleum resin and DCPD hydrogenated petroleum resin. The water vapor barrier properties, water vapor durability and heat resistance of the material were all poor.

[0047] Comparative Examples 2 and 3 only added DCPD hydrogenated petroleum resin or C9 hydrogenated petroleum resin, without adding C5 hydrogenated petroleum resin. The material processing performance was deviated, resulting in deviations in its water vapor barrier properties, water vapor durability, and heat resistance.

[0048] In Comparative Examples 4-5, silicone oil or white oil was added. Silicone oil and white oil have poor compatibility with PC and are prone to precipitation, resulting in an unstable surface barrier layer and poor performance, which in turn causes deviations in the material's water vapor barrier properties, water vapor durability, and other properties.

[0049] As can be seen from the comparison of Examples 1 to 4, the amount of hydrogenated petroleum resin added affects the water vapor barrier properties, water vapor durability, and heat resistance of the material. In order to improve the water vapor barrier properties, water vapor durability, and heat resistance of the material, it is preferable that when the amount of PC is 100 parts by weight, the amount of hydrogenated petroleum resin added is 1.5 to 3.5 parts by weight.

[0050] A comparison of Examples 3 and 7-10 shows that the softening point of the first hydrogenated petroleum resin affects the material's water vapor barrier properties, water vapor durability, and heat resistance. Preferably, its softening point is 95℃ to 135℃ to improve the overall performance of the obtained material in terms of water vapor barrier properties, water vapor durability, and heat resistance.

[0051] As can be seen from the comparison of Examples 3 and 11-14, the softening point of the second hydrogenated petroleum resin affects the water vapor barrier properties, water vapor durability, and heat resistance of the material. It is preferable that its softening point is 95℃ to 135℃ so that the overall performance of the obtained material in terms of water vapor barrier properties, water vapor durability, and heat resistance is better.

[0052] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of this application and are not intended to limit the scope of protection of this application. Although this application has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of this application without departing from the substance and scope of the technical solutions of this application.

Claims

1. A PC composite material, characterized in that, The product comprises the following components in parts by weight: 100 parts PC and 0.4 to 6 parts hydrogenated petroleum resin, wherein the hydrogenated petroleum resin includes a first hydrogenated petroleum resin and a second hydrogenated petroleum resin, the first hydrogenated petroleum resin being a C5 hydrogenated petroleum resin and the second hydrogenated petroleum resin being at least one of a C9 hydrogenated petroleum resin and a DCPD hydrogenated petroleum resin, the weight ratio of the first hydrogenated petroleum resin to the second hydrogenated petroleum resin being 1:(1.25 to 2); the softening point of the first hydrogenated petroleum resin and the second hydrogenated petroleum resin are each independently 85°C to 150°C.

2. The PC composite material as described in claim 1, characterized in that, The hydrogenated petroleum resin is 1.5 to 3.5 parts.

3. The PC composite material as described in claim 1, characterized in that, The softening points of the first hydrogenated petroleum resin and the second hydrogenated petroleum resin are each independently 95℃~135℃.

4. The PC composite material as described in claim 1, characterized in that, The PC has a melt flow rate of 10-30 g / 10 min at 300℃ and 1.2 kg.

5. The PC composite material as described in claim 1, characterized in that, It also includes the following components by weight: 0.01 to 2 parts of additives.

6. The PC composite material as described in claim 5, characterized in that, The additives include at least one of flame retardants, antioxidants, fillers, antibacterial agents, and toughening agents.

7. A method for preparing a PC composite material as described in any one of claims 1 to 6, characterized in that, The process includes the following steps: mixing and dispersing all component raw materials, melt extrusion, granulation, and obtaining PC composite material.

8. The method for preparing the PC composite material as described in claim 7, characterized in that, The temperature of the melt extrusion is 250~280℃.

9. The use of the PC composite material as described in any one of claims 1 to 6 in head-up displays or radome plastic parts.

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