High-transparency low-haze glass fiber reinforced polycarbonate composite material as well as preparation method and application thereof

Abstract

The invention provides a high-transparency low-haze glass fiber reinforced polycarbonate composite material as well as a preparation method and application thereof. The composite material comprises the following components in parts by weight: 39-90 parts of polycarbonate; 5 to 30 parts of glass fiber; 5 to 30 parts of PCCD resin; 0.1 to 0.2 part of an antioxidant; 0.1 to 0.3 part of a lubricant; and 0.05 to 0.15 part of a transesterification inhibitor. By introducing the high-refractive-index glass fibers, the PCCD resin and the ester exchange inhibitor, the light transmittance of the composite material can be effectively improved, and the haze can be reduced.

Description

Technical Field

[0001] This invention belongs to the field of polycarbonate material technology, specifically relating to a high-transparency, low-haze glass fiber reinforced polycarbonate composite material, its preparation method, and its application. Background Technology

[0002] Polycarbonate (PC), as one of the most common polyester materials, possesses characteristics such as high strength, high rigidity, and high toughness, and is widely used in engineering plastics applications. However, pure polycarbonate materials have inherent performance defects that limit their application in scenarios with higher performance requirements. Specifically, pure PC has low rigidity, poor processing flowability, is prone to stress cracking, and is quite sensitive to notches, making it difficult to meet the needs of applications subjected to complex mechanical loads or requiring precision molding. To overcome these defects and broaden the application boundaries of polycarbonate, the industry commonly adopts fiber reinforcement modification technology, which combines polycarbonate with high-performance fibers to improve the mechanical properties and dimensional stability of the material.

[0003] Among various reinforcing fibers, glass fiber has become one of the preferred materials for polycarbonate reinforcement modification due to its advantages such as low cost, high mechanical strength, excellent modulus, high temperature resistance, and corrosion resistance. The performance of glass fiber reinforced polycarbonate composites is significantly optimized compared to pure PC, specifically: rigidity, heat resistance, and dimensional stability are greatly improved, and the coefficient of thermal expansion of the material can be effectively reduced, stress cracking performance can be improved, and fatigue strength can be increased.

[0004] However, with the rapid development of new energy fields such as new energy vehicles, the industry's requirements for reinforced PC products are also getting higher and higher. In addition to requirements such as high strength and high modulus, they also need to have requirements such as high transparency and low haze. Summary of the Invention

[0005] In view of this, the purpose of this invention is to provide a high-transparency, low-haze glass fiber reinforced polycarbonate composite material, its preparation method, and its application. This composite material, while possessing comprehensive mechanical properties such as high rigidity, also exhibits excellent characteristics of high transparency and low haze, thus meeting application requirements.

[0006] To achieve this objective, the present invention adopts the following technical solution:

[0007] In a first aspect, the present invention provides a high-transparency, low-haze glass fiber reinforced polycarbonate composite material, comprising, by weight:

[0008] 39-90 parts polycarbonate;

[0009] 5-30 parts glass fiber;

[0010] 5-30 parts of PCCD resin;

[0011] Antioxidant 0.1~0.2 parts;

[0012] Lubricant 0.1~0.3 parts;

[0013] Transesterification inhibitor 0.05~0.15 parts.

[0014] In this invention, the high-transparency, low-haze glass fiber reinforced polycarbonate composite material comprises 39 to 90 parts of polycarbonate, specifically 39, 39.5, 49.5, 59.5, 69.5, 79.5, 89.5, or 90 parts.

[0015] In this invention, polycarbonate is used as a matrix material for automotive trim panels, medical stents, and electronic components. In some embodiments of this invention, the molecular weight of the polycarbonate is preferably 24,000 to 28,000.

[0016] In this invention, the high-transparency, low-haze glass fiber reinforced polycarbonate composite material further includes 5 to 30 parts of glass fiber, such as 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, or 30 parts.

[0017] In this invention, the glass fiber is preferably high-refractive-index glass fiber (also simply referred to as "high-refractive-index glass fiber"). The refractive index of this high-refractive-index glass fiber is preferably 1.580~1.590 (e.g., 1.580, 1.581, 1.582, 1.583, 1.584, 1.585, 1.586, 1.587, 1.588, 1.589, or 1.590, etc.). This range is controlled because the refractive index within this range is close to that of PC, both achieving the material performance objectives of this invention. In this invention, the aforementioned high-refractive-index glass fiber, as a reinforcing material for polycarbonate, can obtain a modified material with low haze, good visual light transmission, high rigidity, high heat resistance, and other excellent comprehensive mechanical properties without significantly reducing the light transmittance of PC.

[0018] The present invention does not impose any special restrictions on the source of the glass fiber mentioned above; any commercially available product is acceptable.

[0019] In this invention, the high-transparency, low-haze glass fiber reinforced polycarbonate composite material further includes 5 to 30 parts of poly(1,4-cyclohexanediethanol-1,4-cyclohexanedicarboxylate) (abbreviated as PCCD) resin, such as 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, or 30 parts, etc.

[0020] In this invention, the PCCD resin, as a modifier for polycarbonate, can reduce the haze of PC material, improve the processing flow properties of PC material, and improve stress cracking.

[0021] The PCCD resin mentioned above is preferably a product of Eastman Corporation.

[0022] In this invention, the high-transparency, low-haze glass fiber reinforced polycarbonate composite material further includes 0.05 to 0.15 parts of an ester exchange inhibitor, such as 0.05 parts, 0.06 parts, 0.07 parts, 0.08 parts, 0.09 parts, 0.1 parts, 0.11 parts, 0.12 parts, 0.13 parts, 0.14 parts, or 0.15 parts, etc.

[0023] In this invention, the transesterification inhibitor is used to inhibit the transesterification reaction between PC and PCCD. The transesterification inhibitor may be selected from any one or more of phosphoric acid, sodium dihydrogen phosphate, or zinc dihydrogen phosphate; specifically, the transesterification inhibitor is added in the form of an aqueous solution or a solid; the mass fraction of the solute in the aqueous solution is 30-70%, such as 30%, 40%, 50%, 60%, or 70%, etc.

[0024] In some specific embodiments of the present invention, the transesterification inhibitor may be selected from one or a mixture of several of the following: an aqueous solution of phosphoric acid (30% to 70% by mass), solid sodium dihydrogen phosphate, or solid zinc dihydrogen phosphate.

[0025] It should be noted that the glass fiber, PCCD resin and ester exchange inhibitor mentioned above have a synergistic effect, which can improve the light transmittance of glass fiber reinforced PC products, reduce haze, and maintain good mechanical properties such as high rigidity.

[0026] In this invention, the high-transparency, low-haze glass fiber reinforced polycarbonate composite material further includes 0.1 to 0.2 parts of antioxidant, such as 0.1, 0.12, 0.15, 0.18, or 0.2 parts. The addition of the antioxidant ensures that the modified reinforced material resists oxidative degradation during processing in a twin-screw extruder and subsequent applications.

[0027] In some embodiments of the present invention, the antioxidant is one or a mixture of several hindered phenols or phosphites. Specifically, it may be selected from one or more of antioxidant 1010, antioxidant 168, tetrakis(2,4-di-tert-butylphenyl-4,4'-biphenyl) bisphosphonate (PEPQ) or S-9228 antioxidant.

[0028] In this invention, the high-transparency, low-haze glass fiber reinforced polycarbonate composite material further includes 0.1 to 0.3 parts of lubricant, such as 0.1 parts, 0.12 parts, 0.15 parts, 0.18 parts, 0.2 parts, 0.25 parts, or 0.3 parts. The addition of the lubricant allows the modified reinforced material to maintain continuous and smooth production in subsequent injection molding processes.

[0029] In some embodiments of the present invention, the lubricant is a pentaerythritol stearate compound. Specifically, it may be selected from pentaerythritol stearate (abbreviated as PETS).

[0030] In summary, in some specific embodiments of the present invention, the high-transparency, low-haze glass fiber reinforced polycarbonate composite material, by weight, comprises:

[0031] 89.55 parts PC, 5 parts PCCD resin, 5 parts high refractive index glass fiber, 0.1 parts antioxidant, 0.3 parts lubricant, and 0.05 parts transesterification inhibitor;

[0032] or

[0033] 79.6 parts PC, 10 parts PCCD resin, 10 parts high refractive index glass fiber, 0.2 parts antioxidant, 0.1 parts lubricant, and 0.1 parts transesterification inhibitor;

[0034] or

[0035] 59.35 parts PC, 30 parts PCCD resin, 10 parts high refractive index glass fiber, 0.2 parts antioxidant, 0.3 parts lubricant, and 0.15 parts transesterification inhibitor;

[0036] or

[0037] 59.4 parts PC, 10 parts PCCD resin, 30 parts high refractive index glass fiber, 0.2 parts antioxidant, 0.3 parts lubricant, and 0.1 parts transesterification inhibitor;

[0038] or

[0039] 39.4 parts PC, 30 parts PCCD resin, 30 parts high refractive index glass fiber, 0.2 parts antioxidant, 0.3 parts lubricant, and 0.1 parts transesterification inhibitor.

[0040] The present invention also provides a method for preparing the above-mentioned high-transparency, low-haze glass fiber reinforced polycarbonate composite material, comprising the following steps:

[0041] Polycarbonate, PCCD resin, antioxidant, lubricant and transesterification inhibitor are added to an extruder for melt extrusion. Glass fiber is added to the extruder via side feeding. After cooling, the mixture is pelletized to obtain a high-transparency, low-haze glass fiber reinforced polycarbonate composite material.

[0042] As a preferred embodiment, the temperature of the extruder is set to 260~300℃, such as 260℃, 265℃, 270℃, 275℃, 280℃, 285℃, 290℃, 295℃, or 300℃; the screw speed is 400~700 rpm, such as 400 rpm, 450 rpm, 500 rpm, 550 rpm, 600 rpm, 650 rpm, or 700 rpm.

[0043] The present invention conducts performance tests on the above-mentioned high transparency and low haze glass fiber reinforced polycarbonate composite material, and the results show that the light transmittance of the composite material is ≥79% and the haze is <83%.

[0044] Finally, the present invention also provides an application of the above-mentioned high-transparency, low-haze glass fiber reinforced polycarbonate composite material in automotive trim panels, medical stents, and electronic and electrical components.

[0045] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0046] This invention provides a high-transparency, low-haze glass fiber reinforced polycarbonate composite material, comprising, by weight: 39-90 parts polycarbonate; 5-30 parts glass fiber; 5-30 parts PCCD resin; 0.1-0.2 parts antioxidant; 0.1-0.3 parts lubricant; and 0.05-0.15 parts transesterification inhibitor. This invention maximizes the light transmittance of PC by using high-refractive-index glass fiber, and further reduces the haze of the glass fiber reinforced PC material while maintaining high light transmittance. The necessary addition of transesterification inhibitors prevents transesterification and yellowing of the PC and PCCD, ultimately resulting in a modified glass fiber reinforced material with excellent mechanical properties such as high rigidity, high heat resistance, and high flowability, as well as high light transmittance and low haze. Detailed Implementation

[0047] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0048] To further illustrate the present invention, the following examples provide a detailed description. The raw materials used in the following examples are as follows: PC resin with a molecular weight of 24,000-28,000; PCCD resin is a product of Eastman Corporation; high-refractive-index glass fiber has a refractive index of 1.586; general-purpose glass fiber has a refractive index of 1.55; the antioxidant is tetrakis(2,4-di-tert-butylphenyl-4,4'-biphenyl) bisphosphonate PEPQ; the lubricant is pentaerythritol stearate PETS; and the transesterification inhibitor is a 50% aqueous solution of phosphoric acid.

[0049] Example 1

[0050] A high-transparency, low-haze glass fiber reinforced polycarbonate composite material, comprising, by weight:

[0051] 89.55 parts PC, 5 parts PCCD resin, 5 parts high refractive index glass fiber, 0.1 parts antioxidant, 0.3 parts lubricant, and 0.05 parts transesterification inhibitor;

[0052] The preparation method is as follows:

[0053] PC, PCCD, ester exchange inhibitor, antioxidant and lubricant are mixed evenly in a high-speed mixer and then added to an extruder for melt extrusion. Glass fiber is fed into the extruder through side feeding. The temperature is set to 270℃ and the screw speed is 450 rpm. After the extruded strip is cooled in a water tank, it is granulated to obtain the finished product.

[0054] Example 2

[0055] A high-transparency, low-haze glass fiber reinforced polycarbonate composite material, comprising, by weight:

[0056] 79.6 parts PC, 10 parts PCCD resin, 10 parts high refractive index glass fiber, 0.2 parts antioxidant, 0.1 parts lubricant, and 0.1 parts transesterification inhibitor;

[0057] The preparation method is the same as in Example 1.

[0058] Example 3

[0059] A high-transparency, low-haze glass fiber reinforced polycarbonate composite material, comprising, by weight:

[0060] 59.35 parts PC, 30 parts PCCD resin, 10 parts high refractive index glass fiber, 0.2 parts antioxidant, 0.3 parts lubricant, and 0.15 parts transesterification inhibitor;

[0061] The preparation method is the same as in Example 1.

[0062] Example 4

[0063] A high-transparency, low-haze glass fiber reinforced polycarbonate composite material, comprising, by weight:

[0064] 59.4 parts PC, 10 parts PCCD resin, 30 parts high refractive index glass fiber, 0.2 parts antioxidant, 0.3 parts lubricant, and 0.1 parts transesterification inhibitor;

[0065] The preparation method is the same as in Example 1.

[0066] Example 5

[0067] A high-transparency, low-haze glass fiber reinforced polycarbonate composite material, comprising, by weight:

[0068] PC 39.4 parts, PCCD resin 30 parts, high refractive index glass fiber 30 parts, antioxidant 0.2 parts, lubricant 0.3 parts, transesterification inhibitor 0.1 parts;

[0069] The preparation method is the same as in Example 1.

[0070] Comparative Example 1

[0071] A polycarbonate composite material, comprising, by weight:

[0072] PC 94.5 parts, high refractive index glass fiber 5 parts, antioxidant 0.2 parts, lubricant 0.3 parts.

[0073] The preparation method is the same as in Example 1.

[0074] Comparative Example 2

[0075] A polycarbonate composite material, comprising, by weight:

[0076] PC 89.5 parts, high refractive index glass fiber 10 parts, antioxidant 0.2 parts, lubricant 0.3 parts.

[0077] The preparation method is the same as in Example 1.

[0078] Comparative Example 3

[0079] A polycarbonate composite material, comprising, by weight:

[0080] PC 69.5 parts, high refractive index glass fiber 30 parts, antioxidant 0.2 parts, lubricant 0.3 parts.

[0081] The preparation method is the same as in Example 1.

[0082] Comparative Example 4

[0083] A polycarbonate composite material, comprising, by weight:

[0084] The composition is as follows: 89.5 parts PC, 5 parts PCCD, 5 parts high refractive index glass fiber, 0.2 parts antioxidant, and 0.3 parts lubricant.

[0085] The preparation method is the same as in Example 1.

[0086] Comparative Example 5

[0087] A polycarbonate composite material, comprising, by weight:

[0088] The composition is as follows: 94.5 parts PC, 5 parts general-purpose glass fiber, 0.2 parts antioxidant, and 0.3 parts lubricant.

[0089] The preparation method is the same as in Example 1.

[0090] Comparative Example 6

[0091] A polycarbonate composite material, comprising, by weight:

[0092] The composition is as follows: 89.5 parts PC, 10 parts general-purpose glass fiber, 0.2 parts antioxidant, and 0.3 parts lubricant.

[0093] The preparation method is the same as in Example 1.

[0094] Comparative Example 7

[0095] A polycarbonate composite material, comprising, by weight:

[0096] The composition is as follows: 69.5 parts PC, 30 parts general-purpose glass fiber, 0.2 parts antioxidant, and 0.3 parts lubricant.

[0097] The preparation method is the same as in Example 1.

[0098] Comparative Example 8

[0099] A polycarbonate composite material, comprising, by weight:

[0100] The composition is as follows: 89.4 parts PC, 10 parts general-purpose glass fiber, 5 parts PCCD, 0.2 parts antioxidant, 0.3 parts lubricant, and 0.1 parts transesterification inhibitor.

[0101] The preparation method is the same as in Example 1.

[0102] Performance testing

[0103] This invention tests light transmittance and haze according to ISO 13468-2 method, and tests melt index, tensile strength, heat distortion temperature and yellowness according to ISO standard.

[0104] The test results are shown in Table 1 (where melt index is in g / 10 min; tensile strength is in MPa; tensile modulus is in MPa; light transmittance is expressed as %; haze is in %; heat distortion temperature is in ℃; and yellowness b value is dimensionless).

[0105] Table 1

[0106]

[0107] The performance tests of the examples and comparative examples are shown in Table 1. Examples 1 to 5 use high refractive index glass fibers similar to PC materials, add PCCD resin components, and assist in the combination of ester exchange inhibitors to obtain glass fiber reinforced materials with high light transmittance (≥79%) and low haze (<83%). This trend is more obvious in the range of 5 to 30% high refractive index glass fiber addition.

[0108] Comparative Examples 1-3 added only high refractive index glass fiber to PC material. Although they also obtained reinforced materials with high light transmittance, the haze value was higher than that of the materials in Examples 1-5, and the overall transparency of the materials was not as good as that of Examples 1-5. This shows that adding PCCD and ester exchange inhibitor can improve the overall light transmittance of the material.

[0109] Comparative Example 4, based on high refractive index glass fiber reinforced PC material, added an additional amount of PCCD. However, compared with Example 1, no transesterification inhibitor was added. The light transmittance of the material was lower and the haze was higher than that of Example 1. This is because transesterification occurred between PC and PCCD, which changed the properties of PC and PCCD materials, resulting in a deterioration in the overall light transmittance of the material. At the same time, properties such as melt index, heat resistance, and yellow value b (the higher the value, the more yellow the color) also deteriorated.

[0110] Comparative Examples 5-7 filled PC material with type E general-purpose glass fiber material, with a refractive index of 1.55, which differs significantly from the PC refractive index of 1.586. Compared with Examples 1-5 and Comparative Examples 1-3, their light transmittance and haze performance were worse. This result indicates that using glass fiber with a high refractive index close to that of PC material has a significant effect on improving the overall light transmittance and haze of the material.

[0111] Comparative Example 8 used PC, E-type general-purpose glass fiber material with a refractive index of 1.55, and added PCCD and transesterification inhibitor. Although the overall melt index, heat resistance, and yellowing value (b-value) of the material were maintained well, the transmittance and haze were still not as good as those of Examples 1-5, but better than those of Comparative Example 5. This indicates that adding PCCD and transesterification inhibitor can improve the overall light transmittance of the material. This is because PCCD improves the light scattering of PC, thereby reducing haze, ultimately resulting in a high-transmittance, low-haze glass fiber reinforced material with better visual light transmission.

[0112] The above description of the disclosed embodiments enables those skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A high transparency and low haze glass fiber reinforced polycarbonate composite material, comprising, by weight parts: polycarbonate 39-90; glass fiber 5-30; PCCD resin 5-30; antioxidant 0.1-0.2; lubricant 0.1-0.3; transesterification inhibitor 0.05-0.

15. The refractive index of the glass fiber is 1.580-1.

590. The PCCD resin is a product of Eastman Company. The molecular weight of the polycarbonate is 24000-28000. The antioxidant is one or a mixture of several of hindered phenol or phosphite; The lubricant is a pentaerythritol stearate compound. The antioxidant is one or more of antioxidant 1010, antioxidant 168, PEPQ or S9228 antioxidant; 2. The high- transparency low-haze glass-fiber reinforced polycarbonate composite according to claim 1, characterized in that, The lubricant is pentaerythritol stearate pets.

3. The high- transparency low-haze glass-fiber reinforced polycarbonate composite according to claim 1 or 2, characterized in that The transesterification inhibitor is selected from any one or more of phosphoric acid, sodium dihydrogen phosphate or zinc dihydrogen phosphate; 4. The high- transparency low-haze glass-fiber reinforced polycarbonate composite according to any one of claims 1 to 3, characterized in that The transesterification inhibitor is added in the form of an aqueous solution or a solid; the mass fraction of solute in the aqueous solution is 30-70%.

5. The high- transparency low-haze glass-fiber reinforced polycarbonate composite according to any one of claims 1 to 4, characterized in that The composite material has a light transmittance ≥79% and a haze <83%. The method comprises the following steps:

6. The high- transparency low-haze glass-fiber reinforced polycarbonate composite according to any one of claims 1 to 5, characterized in that The polycarbonate, PCCD resin, antioxidant, lubricant and transesterification inhibitor are added to an extruder for melt extrusion, the glass fiber is added to the extruder through a side feeder, and after cooling, the high transparency and low haze glass fiber reinforced polycarbonate composite material is obtained by granulation.

10. Use of the high transparency and low haze glass fiber reinforced polycarbonate composite material of any one of claims 1-8 or the high transparency and low haze glass fiber reinforced polycarbonate composite material prepared according to the preparation method of claim 9 in an automobile trim panel, a medical stent or an electronic and electrical component product.

7. The high- transparency low-haze glass-fiber reinforced polycarbonate composite according to any one of claims 1 to 6, characterized in that ​ ​ 8. The high- transparency low-haze glass-fiber reinforced polycarbonate composite according to any one of claims 1 to 7, characterized in that ​ 9. A process for the production of a high transparent low haze glass fiber reinforced polycarbonate composite according to any one of claims 1 to 8, characterized in that, ​ ​ ​

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