CN115260729A - Polycarbonate composite material, preparation method and application thereof - Google Patents

Abstract

The invention discloses a polycarbonate composite material which comprises the following components in parts by weight: 60-85 parts of polycarbonate; 5-20 parts of acrylonitrile-styrene copolymer; 5-10 parts of a toughening agent; 4-8 parts of a compatilizer; 0.2-1 part of lubricant; 0.2-1 part of antioxidant, and the total weight of the components in the polycarbonate composite material is 100 parts. The invention also discloses a preparation method of the high-gloss high-hardness polycarbonate material. The product of the invention has the characteristics of high gloss, high hardness and the like, and the surface hardness can reach 2H level. The excellent performance of the polycarbonate is maintained, the glossiness and the surface hardness of the product are increased, and the application range of the product is expanded.

Description

Polycarbonate composite material and its preparation method and application

technical field

The invention belongs to the field of polymer composite materials, and relates to a high-gloss and high-hardness polycarbonate composite material and a preparation method thereof.

Background technique

Polycarbonate refers to a type of polymer whose macromolecular chain is composed of carbonate-type repeating structural units. The English name Polycarbonate, referred to as PC, has excellent impact resistance and transparency, excellent mechanical properties and electrical insulation. It is used Wide temperature range (-100°C-130°C), high dimensional stability and high creep resistance, it is a typical plastic representative integrating rigidity, hardness and toughness. Due to these advantages, polycarbonate is widely used in many fields such as electronic appliances, office supplies, precision machinery, medical treatment, labor insurance, household goods and automobiles. Polycarbonate is also an optical plastic with excellent performance, and its light transmittance can reach as much as 89%. However, due to the poor wear resistance, low hardness and low gloss of polycarbonate, the application range of polycarbonate is greatly limited. If its hardness and gloss are improved in some way, its application range will be greatly expanded.

At present, the commonly used method to improve the surface gloss of polycarbonate materials is mainly to carry out blending modification with acrylonitrile-butadiene-styrene copolymer or acrylate-styrene-acrylonitrile copolymer. Diene-styrene copolymer modification can improve gloss, but the light resistance and weather resistance of the material are poor; modified with acrylate-styrene-acrylonitrile copolymer, the alloy toughness is low, and the material cost is high .

At present, the most commonly used method to improve the surface hardness of polycarbonate materials is to coat the polycarbonate with a high-hardness coating after molding. This process has low production efficiency, high production input costs and complicated processes. In addition, the surface hardness of polycarbonate material is improved by adding PMMA material. Due to the poor impact performance of PMMA material itself, the notched impact performance of PC/PMMA alloy is low, which limits its application.

Contents of the invention

The purpose of the present invention is to provide a high-gloss high-hardness polycarbonate material and a preparation method thereof in order to overcome the defects in the prior art. The high-gloss and high-hardness polycarbonate material has the advantages of short molding cycle, low processing cost, high gloss, high surface hardness, good fluidity of the alloy material, and strength and toughness close to that of PC material.

The invention provides a kind of polycarbonate composite material, and described polycarbonate composite material comprises following component:

The total weight of each component in the polycarbonate composite material is 100 parts.

According to an embodiment of the present invention, the polycarbonate is one or more of aromatic, aliphatic, and aliphatic-aromatic.

According to another embodiment of the present invention, the MI of the polycarbonate is 10-30 g/10 min.

According to another embodiment of the present invention, the toughening agent is an ether ester thermoplastic elastomer, and its Shore hardness is 60A-95A.

According to another embodiment of the present invention, the MI of the styrene-acrylonitrile copolymer is 10-60 g/10 min.

According to another embodiment of the present invention, the compatibilizer is one or more of ABS-g-MAH and styrene block copolymer.

According to another embodiment of the present invention, the antioxidant is one or more of 1076, 168, 1010, and CA.

According to another embodiment of the present invention, the lubricant is one or more of polyethylene wax, polypropylene wax, zinc stearate, and N,N-ethylene bisstearamide.

According to another embodiment of the present invention, one or more additives selected from the group consisting of release agents, pigments, antistatic agents, antimicrobial agents, processing aids and anti-friction/wear agents are also included.

The present invention also provides a method for preparing the above-mentioned polycarbonate composite material, comprising: S1, weighing polycarbonate resin, styrene-acrylonitrile copolymer, toughening agent, compatibilizer, antioxidant, Lubricant, and mix evenly; S2, send the mixed material into the twin-screw extruder, extrude after the shearing and mixing of the screws, and water-cooled strands, pelletizing; wherein, the twin-screw extruder The working temperature range is 220-280°C, and the vacuum exhaust is 0.6-0.8Kpa.

The product of the invention has the characteristics of high gloss and high hardness, and the surface hardness can reach 2H level. While maintaining the performance of polycarbonate, the gloss and surface hardness of the material are improved, and the application range of the product is expanded.

Detailed ways

The present invention will be described in detail below in combination with specific embodiments.

The polycarbonate used in the polycarbonate composite material of the present invention has a melt index (MI) of 10-30 g/10 min (300° C., 1.2 kg). Preferably the melt index is 15-25 g/10 min. The melt index of polycarbonate affects the processing performance of the material. The processing performance of polycarbonate with low melt index is poor, which is not conducive to injection molding, while the impact performance and tensile performance of polycarbonate with high melt index decrease significantly. Based on 100 parts by total weight of the high-gloss and high-hardness polycarbonate material, polycarbonate is used in an amount of 60-85 parts, preferably 70-80 parts. If the content is less than 60 parts, the toughness of the high-gloss and high-hardness polycarbonate material will decrease significantly; if the content is higher than 85 parts, the effect of improving the surface gloss and hardness of the high-gloss and high-hardness polycarbonate material will be poor.

The styrene-acrylonitrile copolymer used in the polycarbonate composite material of the present invention improves the hardness of the material and is beneficial to improving the surface gloss of the material. The melt index (MI) of the styrene-acrylonitrile copolymer used is 10-60g/10min (220°C, 10kg), preferably the melt index is 30-50g/10min. If the melt index of styrene-acrylonitrile copolymer is lower than 10g/10min, the fluidity of the polycarbonate composite will be affected, and if the melt index is higher than 60g/10min, the polycarbonate composite will have obvious compatibility problems. Based on 100 parts of the total weight of the high-gloss and high-hardness polycarbonate composite material, the amount of the styrene-acrylonitrile copolymer is 5-20 parts, preferably 10-15 parts. If the content is less than 5 parts, the surface hardness of the polycarbonate composite material will not be improved. If the content is greater than 20 parts, the impact resistance of the polycarbonate composite material will decrease significantly.

The ether ester type thermoplastic elastomer is used in the polycarbonate composite material of the present invention to improve the impact resistance of the high-gloss and high-hardness polycarbonate composite material. Ether ester thermoplastic elastomer is a block copolymer of phenyl ester hard segment and polyether glycol soft segment. It has excellent elasticity and easy processability of thermoplastics, good creep resistance, excellent toughness and rebound, and hardness Wide range (Shore hardness 60A-50D). Compared with ordinary PC tougheners, it has better weather resistance, low temperature resistance and impact resistance. The Shore hardness of the ether-ester thermoplastic elastomer is low, and the toughening effect is more obvious, and the surface hardness of the composite material is also reduced. Based on 100 parts of the total weight of the high-gloss and high-hardness polycarbonate composite material, it is used in an amount of 5-10 parts, preferably 6-8 parts.

The compatibilizer ABS-g-MAH, styrene block copolymer and the like used in the high-gloss high-hardness polycarbonate material in the present invention are preferably ABS-g-MAH.

The antioxidant used in the high-gloss and high-hardness polycarbonate material in the present invention is one or more of 1076, 168, 1010, and CA, preferably a mixture of 1076 and antioxidant 168.

Among the present invention, the lubricant used in the high-gloss high-hardness polycarbonate material is one or more of polyethylene wax, polypropylene wax, zinc stearate, N,N-ethylene bisstearic acid amide, preferably N , N-ethylene bis stearic acid amide.

According to requirements, in addition to the above components, a release agent, pigment, antistatic agent, etc. can also be appropriately added in the present invention.

The preparation method of the above-mentioned polycarbonate composite material comprises: S1, weigh polycarbonate resin, styrene-acrylonitrile copolymer, toughening agent, compatibilizer, antioxidant, lubricant by weight ratio, and mix uniformly ; S2, feed the mixed material into the twin-screw extruder, extrude after the shearing and mixing of the screw, and then water-cooled, stretch and pelletize; the working temperature range of the twin-screw extrusion is 220-280°C , the vacuum degree is 0.6-0.8Kpa. Working temperature lower than 220°C will affect the gloss of the material, and higher than 280°C will cause yellowing of the material. A vacuum lower than 0.6Kpa will result in high moisture content of the polycarbonate composite material and low surface gloss in subsequent processing; a vacuum higher than 0.8Kpa will take away some additives (antioxidants and lubricants) and affect the polycarbonate composite material. Processing performance. The aspect ratio of the twin-screw extruder can be 44:1, which is beneficial to improve the mixing and plasticizing effect. The screw diameter may be 55-75 mm.

The present invention is further described below by specific examples. However, these examples are only exemplary and do not constitute any limitation to the protection scope of the present invention.

In the following examples and comparative examples, the reagents, materials and instruments used are commercially available unless otherwise specified.

Carry out the physical characteristic evaluation of following embodiment and comparative example according to following test method:

Melt flow index (MI): evaluated based on ISO 1133 (300°C, 1.2kg);

Tensile strength: evaluated based on ISO 527-2/50;

Bending strength: evaluated based on ISO 178;

Impact strength: evaluated based on ISO 179;

Rockwell hardness: evaluated based on ISO 2039;

Surface Gloss: Evaluation based on ASTM D2457 (using 20°)

Specific examples are as follows:

According to demand, embodiment and comparative example adopt following raw material model:

1. Polycarbonate (PC): Jiaxing Teijin PC-1225L, its MI is 21g/10min

2. Styrene-acrylonitrile (SAN): Zhenjiang Chimei PN-108L125, its MI is 50g/10min

3. Toughening agent (ether ester thermoplastic elastomer): Mitsubishi Chemical 1706C, its Shore hardness is 70A

4. Compatibilizer (ABS-g-MAH): Keaisi ABS KS-05, which is ABS-g-MAH type

5. Lubricant: Japan Kao, model EB-FF

Weigh polycarbonate resin, styrene-acrylonitrile copolymer, toughening agent, compatibilizer, antioxidant, lubricant according to the weight ratio, add to the high-speed mixer and mix well; then send the mixed material into In the twin-screw extruder, it is extruded after shearing and kneading by the screw, and is water-cooled and pelletized.

Each embodiment and comparative example were injection molded respectively, and samples were made into standard test strips. Then test the main performance parameters of each test piece by the aforementioned test method.

A. Performance test of polycarbonate composite materials with different component contents:

Table 1 Polycarbonate composites with different component contents

Example 1 Example 2 Example 3 Example 4 Comparative example 1 Comparative example 2 polycarbonate 65 75 80 85 100 / Styrene-acrylonitrile copolymer 20 12 10 5 / 100 Toughener 8 6 5 5 / / Compatibilizer 6 6 4 4 / / antioxidant 0.3 0.3 0.3 0.3 / / lubricant 0.7 0.7 0.7 0.7 / / total 100 100 100 100 100 100

The performance parameter contrast of table 2 embodiment and comparative example

Main performance parameters Example 1 Example 2 Example 3 Example 4 Comparative example 1 Comparative example 2 Melt index (g/10min) 42 30 28 25 twenty one 5 Tensile strength (MPa) 65 56 51 53 61 67 Bending strength (MPa) 97 95 93 92 93 101 Notched Impact Strength (KJ/m²) 46 58 62 64 67 3.8 Rockwell hardness (R) 99 92 85 79 72 104 surface gloss 152 138 126 110 98 145

As can be seen in Examples 1-4 and Comparative Example 1 in Table 2, after the polycarbonate material is added with styrene-acrylonitrile copolymer, the melt index, Rockwell hardness and surface gloss of the material increase with the increase of styrene-acrylonitrile copolymer. The content of acrylonitrile copolymer increases and increases; the tensile strength and bending strength change little; the impact strength decreases gradually with the content increasing. Comprehensive various performance parameters, wherein the scheme of embodiment 2 and embodiment 3 is better.

B. the present invention adopts styrene-acrylonitrile copolymer to improve the hardness and the glossiness of PC material, compare with the performance of PC-PMMA alloy commonly used now:

This time, the PC-PMMA alloy adopts the scratch-resistant KH3260UR and KH3360UR of Mitsubishi Engineering in Japan.

Table 3 Embodiment 2 and 3 compare with the performance parameters of Mitsubishi scratch-resistant PC-PMMA alloy

Main performance parameters Example 2 Example 3 KH3260UR KH3360UR Melt index (g/10min) 30 28 25 26 Tensile strength (MPa) 56 51 68 73 Bending strength (MPa) 95 93 109 110 Notched Impact Strength (KJ/m²) 58 62 3 3 Rockwell hardness (R) 92 85 96 98 surface gloss 138 126 125 129

It can be seen in Table 3 that the tensile strength, bending strength and Rockwell hardness of the PC-PMMA alloy material of Mitsubishi Engineering are better than those of Examples 2 and 3. The notched impact properties of Examples 2 and 3 are obviously better than PC-PMMA alloy materials.

C. The present invention adopts ether ester type thermoplastic elastomer as a toughening agent, which has better toughness and gloss than the commonly used PC toughening agent (styrene-acrylate).

Table 4 Polycarbonate composites with different tougheners and contents

Table 5 Example 2 and 3 are compared with the performance parameters of commonly used PC tougheners

Main performance parameters Example 2 Example 3 Comparative example 3 Comparative example 4 Melt index (g/10min) 30 28 29 27 Tensile strength (MPa) 56 51 52 49 Bending strength (MPa) 95 93 88 87 Notched Impact Strength (KJ/m²) 58 62 52 52 Rockwell hardness (R) 92 85 89 82 surface gloss 138 126 126 116

As shown in Table 5, the polycarbonate composite material has better notched impact strength, surface hardness and surface gloss when ether ester thermoplastic elastomer is used as the toughening agent.

As described above, the high-gloss high-hardness polycarbonate material according to the present invention provides excellent surface hardness and gloss while maintaining excellent mechanical properties. It can be used for products requiring high hardness and high gloss.

Although the exemplary embodiments of the present invention have been described in detail, the protection scope of the present invention is not limited to the aforementioned embodiments, and those skilled in the art can understand that various modifications and changes made using the basic concept of the present invention defined in the claims Also included in the protection scope of the present invention.

Claims (10)

1. a polycarbonate composite material, is characterized in that, described polycarbonate composite material comprises following component:

The total weight of each component in the polycarbonate composite material is 100 parts. 2. The polycarbonate composite material according to claim 1, wherein the polycarbonate is one or more of aromatic, aliphatic, and aliphatic-aromatic. 3. The polycarbonate composite material according to claim 1, characterized in that, the MI of the polycarbonate is 10-30g/10min. 4. The polycarbonate composite material according to claim 1, characterized in that, the toughening agent is an ether ester type thermoplastic elastomer, and its Shore hardness is 60A-95A. 5. The polycarbonate composite material according to claim 1, characterized in that, the MI of the styrene-acrylonitrile copolymer is 10-60g/10min. 6. The polycarbonate composite material according to claim 1, wherein the compatibilizer is one or more of ABS-g-MAH and styrene block copolymer. 7. The polycarbonate composite material according to claim 1, wherein the antioxidant is one or more of 1076, 168, 1010, CA. 8. polycarbonate composite material according to claim 1, is characterized in that, described lubricant is polyethylene wax, polypropylene wax, zinc stearate, N,N-ethylene bis stearic acid amide one or more. 9. The polycarbonate composite material according to any one of claims 1-8, further comprising one selected from the group consisting of release agent, pigment, antistatic agent, antimicrobial agent, processing aid and anti-friction/wear agent or various additives. 10. A preparation method of the polycarbonate composite material according to any one of claims 1-9, characterized in that, comprising: S1, take polycarbonate resin, styrene-acrylonitrile copolymer, toughening agent, compatibilizer, antioxidant, lubricant by weight ratio, and mix uniformly; S2, feeding the mixed material into a twin-screw extruder, extruding after shearing and kneading by the screws, drawing strands by water cooling, and pelletizing; Wherein, the working temperature range of the twin-screw extrusion is 220-280° C., and the vacuum degree is 0.6-0.8 Kpa.