Polycarbonate alloy material, its preparation method and use

Abstract

The present invention discloses a polycarbonate alloy material, which comprises, by weight, 40-70 parts of polycarbonate, 20-40 parts of polyethylene terephthalate and 0.1-2 parts of a metal compound, the metal compound being selected from any one of metal oxides, metal bases or metal salts, the metal being selected from any one of copper, iron, magnesium, calcium, titanium, antimony, sodium or potassium. In the present invention, the polycarbonate alloy material obtained by adding a certain amount of polyethylene terephthalate and a specific metal compound to polycarbonate not only has excellent chemical resistance, but also has high melt strength and low melt cooling rate, and is suitable for extrusion blow molding of thick and large packaging container products, providing the packaging field with new material and molding method options, especially to meet the requirements of pharmaceutical packaging containers, and further expanding the application of polycarbonate materials.

Description

Technical Field

[0001] The present invention relates to the technical field of engineering plastics, and particularly to polycarbonate alloy materials, their preparation methods and uses.

Background Art

[0002] Extrusion blow molding is the largest category of blow molding methods used in the manufacture of hollow thermoplastic parts. Its molding process mainly involves extruding a molten tubular material through an extruder, placing it in the center of an open hot blow mold, closing the mold to clamp the material, and then introducing compressed air in a timely manner to expand it and bring it close to the inner wall of the mold cavity to form the part. After cooling and solidifying, the mold is opened to take out the part. The most important blow molded products in extrusion blow molding are packaging containers for containing liquids and solid powders such as food, cosmetics, pharmaceuticals, and chemicals. In recent years, their applications in automotive parts and household items have also increased. Currently, many packaging container products made by extrusion blow molding use conventional plastics such as HDPE and PP, but there are problems such as inferior mechanical properties.

[0003] Engineering plastic polycarbonate (PC) has excellent comprehensive properties, high mechanical strength and toughness, but has low chemical resistance and requires advanced process requirements during extrusion blow molding. Therefore, its application in extrusion blow molding packaging containers (especially pharmaceutical packaging containers) is limited. Currently, there are related technologies for using PC materials in extrusion blow molding. Chinese Patent Application CN106589778A discloses a polymer suitable for blow molding, and by blending PC and ABS to form an alloy, the strength and toughness of the material are improved. Chinese Patent Application CN108164960A discloses a blow molded PC / ABS composite material, and by adding a styrene-acrylonitrile copolymer, which is a melting promoter, to the material, the melting strength of the material is increased and the extrusion blow molding performance is improved. However, the above-mentioned conventional PC materials are mainly used for small supporting parts and automotive tail fins, etc., and their chemical resistance has not been improved, and they are not particularly suitable for packaging containers for containing pharmaceuticals.

[0004] Therefore, the present invention mainly studies a PC material suitable for extrusion blow molding, which can meet the usage requirements of pharmaceutical packaging containers and is very important for expanding the application of PC materials.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0006] In order to overcome the deficiencies of the above prior art, the object of the present invention is to provide a polycarbonate alloy material that not only has excellent chemical resistance, but also has high melt strength and low melt cooling rate, is suitable for manufacturing packaging containers by extrusion blow molding, and can also be used for pharmaceutical packaging.

[0007] Another object of the present invention is to provide a method for preparing the above polycarbonate alloy material.

[0008] Another object of the present invention is to provide the use of the above polycarbonate alloy material.

Means for Solving the Problems

[0009] The present invention is realized by the following technical solutions.

[0010] A polycarbonate alloy material, by weight parts, 40 to 70 parts of polycarbonate, 20 to 40 parts of polyethylene terephthalate, and 0.1 to 2 parts of a metal compound, The above metal compound is selected from any one or more of metal oxides, metal bases or metal salts, and the above metal is selected from any one or more of copper, iron, magnesium, calcium, titanium, antimony, sodium or potassium.

[0011] Preferably, the above polycarbonate alloy material is, by weight parts, 50 to 65 parts of polycarbonate, 25 to 35 parts of polyethylene terephthalate, and 0.3 to 1.2 parts of a metal compound.

[0012] As can be seen from the research of the present invention, when a certain amount of polyethylene terephthalate PET and a specific metal compound are added to polycarbonate, the metal compound promotes the reaction between PC and PET to a certain extent to form a block copolymer, effectively improving the melt strength of the material. At the same time, it delays the crystallization of the PET resin and reduces the melt cooling rate of the material. Therefore, the molten tubular material extruded from the material in the extrusion blow molding process has high stability, can maintain the molten state even in the deflection process, and the upper and lower diameters are close without breaking. As a result, it is possible to manufacture thick-walled and large-sized packaging container products by blow molding. Furthermore, crystalline PET effectively improves the chemical resistance of the material and can ensure the resistance of the material to chemical substances such as drugs.

[0013] Preferably, the above metal compound is selected from any one or more of titanium metal oxides or antimony metal oxides, and more preferably, the above metal compound is selected from any one or more of antimony metal oxides.

[0014] Preferably, the above titanium metal oxide can be selected from one or more of TiO, TiO2 or Ti2O3, and the above antimony metal oxide can be selected from one or more of Sb2O3, Sb2O4, Sb2O5, Sb6O 13 and SbO.

[0015] Preferably, the viscosity-average molecular weight of the polycarbonate is 10,000 to 40,000. If the molecular weight of the polycarbonate is too low, the neck becomes thin during the extrusion process, the material is likely to be damaged, and the material has poor corrosion resistance. On the other hand, if the molecular weight is too high, the rotation of the screw of the extruder is restricted and the extrusion process becomes difficult. More preferably, the viscosity-average molecular weight of the polycarbonate is 18,000 to 35,000, and even more preferably, the viscosity-average molecular weight of the polycarbonate is 25,000 to 33,000.

[0016] The polycarbonate can be selected from any one or more of aromatic polycarbonates, and the aromatic polycarbonate can be selected from bisphenol A polycarbonate.

[0017] The intrinsic viscosity of the polyethylene terephthalate is 0.65 to 0.88 dl / g. If the viscosity of the PET is too low, its chemical resistance is poor, and if the viscosity is too high, the extrusion process becomes difficult. Preferably, the intrinsic viscosity of the polyethylene terephthalate is 0.7 to 0.88 dl / g. The intrinsic viscosity of the polyethylene terephthalate is measured with reference to the standard GT / T1632.5-08. The time taken for a PET solution with a solvent at 25°C and a concentration of 0.005 g / mL to flow out of the capillary is measured, and its intrinsic viscosity is calculated based on the measurement time and the solution concentration of the sample.

[0018] The polycarbonate alloy material described in the present invention may further contain 2 to 10 parts by weight of an antistatic agent. The antistatic agent is selected from any one or more of carbon nanotubes. Preferably, the antistatic agent is selected from any one or more of multi-walled carbon nanotubes with a diameter of 1.0 to 80 nm and a length of 2 to 70 μm. More preferably, the antistatic agent is selected from any one or more of multi-walled carbon nanotubes with a diameter of 20 to 60 nm and a length of 10 to 25 μm.

[0019] In the present invention, by adding a certain amount of carbon nanotubes, the melt strength of the material can be further improved, and the stability of the molten tubular material extruded during the extrusion blow molding process can be improved. As a result, the extrusion blow molding process performance of the material can be effectively improved, and at the same time, excellent antistatic properties can be imparted to the material.

[0020] The polycarbonate alloy material described in the present invention may further contain 4 to 8 parts by weight of a reinforcing agent. The reinforcing agent is selected from one or more of ethylene-butyl acrylate-glycidyl methacrylate copolymer, ethylene-octene-glycidyl methacrylate copolymer, methyl methacrylate-butadiene-styrene copolymer, methyl methacrylate-acrylic acid copolymer, ethylene-methyl acrylate copolymer, or methyl methacrylate-acrylic ester-silicone copolymer.

[0021] By adding a certain amount of the reinforcing agent, the present invention can effectively improve the low-temperature toughness of the material and further improve the chemical resistance of the material. Preferably, the reinforcing agent is obtained by blending an ethylene-butyl acrylate-glycidyl methacrylate copolymer and a methyl methacrylate-butadiene-styrene copolymer in a weight ratio of 1:2 to 2:1.

[0022] According to the performance requirements of the materials, the polycarbonate alloy materials described in the present invention further contain 0.01 to 1 part by weight of an antioxidant. The above antioxidant is selected from any one or more of octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, tris(nonylphenyl)phosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, β-(3,5-di-tert-butyl-4-hydroxyphenyl)n-octadecanol propionate, distearyl pentaerythritol diphosphite, tetrakis[methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]methane, distearyl thiodipropionate, dilauryl thiodipropionate, tridecyl thiodipropionate, pentaerythritol-tetrakis[3-(3,5-di-tert-butyl 4-hydroxyphenyl)propionate] or β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid amide.

[0023] The present invention further provides a method for preparing the above polycarbonate alloy material. The method includes the steps of putting each component into a mixer according to the blending ratio and blending until uniform to obtain a premix, and then putting the premix into a twin-screw extruder for melt mixing and extrusion granulation to prepare a polycarbonate alloy material. The ratio of the screw length to the diameter of the twin-screw extruder is 40:1 to 50:1, the screw barrel temperature is 240 to 260 °C, and the screw rotation speed is 400 to 500 rpm.

[0024] The present invention further provides the use of the above polycarbonate alloy material in the field of pharmaceutical packaging. Specifically, an extrusion blow molding can be used to manufacture a pharmaceutical packaging container.

Advantages of the Invention

[0025] Compared with the prior art, the present invention has the following effects.

[0026] In the present invention, a polycarbonate alloy material obtained by adding a certain amount of polyethylene terephthalate and a specific metal compound to polycarbonate not only has excellent chemical resistance, but also has high melt strength and a low melt cooling rate, and is suitable for the extrusion blow molding of thick-walled and large-sized packaging container products. In particular, in order to meet the usage requirements of pharmaceutical packaging containers, it provides new material and molding method options in the packaging field, and further expands the application of polycarbonate materials.

Mode for Carrying Out the Invention

[0027] Hereinafter, the present invention will be described in detail with reference to specific examples. The following examples are helpful for those skilled in the art to further understand the present invention, but do not limit the present invention in any form. It should be pointed out that those skilled in the art can make some modifications and improvements without departing from the concept of the present invention. All of them belong to the protection scope of the present invention.

[0028] Hereinafter, the raw materials used in the examples and comparative examples of the present invention are shown, but are not limited thereto. Polycarbonate 1: Viscosity average molecular weight 28000, PC E-2000F, Mitsubishi, Japan Polycarbonate 2: Viscosity average molecular weight 23000, PC S-3000F, Mitsubishi, Japan Polycarbonate 3: Viscosity average molecular weight 16000, PC H-4000F, Mitsubishi, Japan Polycarbonate 4: Viscosity average molecular weight 35000, PC E-1000F, Mitsubishi, Japan Polycarbonate 5: Viscosity average molecular weight 40000, PC K-1000F, Mitsubishi, Japan Polyethylene terephthalate 1: Intrinsic viscosity 0.8 dl / g, PET BG80, Yizheng Chemical Fiber Polyethylene terephthalate 1: Intrinsic viscosity 0.65 dl / g, PET FG600, Yizheng Chemical Fiber Polybutylene terephthalate: PBT GX112, Yizheng Chemical Acrylonitrile-butadiene-styrene copolymer: ABS PA-757, Chi Mei Antimony metal oxide 1: Sb2O3, Sb2O3 - 99.8, Hunan Huaxing, Antimony metal oxide 2: Sb2O4, Sigma - Aldrich, Antimony metal oxide 3: Sb2O5, Sigma - Aldrich, Titanium metal oxide: TiO2, Sigma - Aldrich, Copper metal oxide: CuO, WSD - T201, Wujiang Weishida Copper Industry, Iron metal oxide: Fe2O3, Hongwu New Materials, Antimony metal base: Sb(OH)3, Sigma - Aldrich, Antimony metal salt: SbCl3, Sigma - Aldrich, Sodium metal salt: NaCl, Hefei Yingheng Chemical, Calcium metal salt: CaCl2, 94% anhydrous powder, Dongxin New Materials, Magnesium metal base: Mg(OH)2, Shanghai Juna, Potassium metal base: KOH, Shandong Feishuo Chemical Industry, Antistatic agent 1: Multi - walled carbon nanotubes, diameter 30 - 50 nm, length 10 - 20 μm, CNT106, Beijing Deke Daojin Technology, Antistatic agent 2: Multi - walled carbon nanotubes, diameter 1.4 - 8 nm, length 10 - 30 μm, CNT102, Beijing Deke Daojin Technology, Antistatic agent 3: Single - walled carbon nanotubes, diameter 1.4 - 2.2 nm, length 5 - 30 μm, OCSIAL, Antistatic agent 4: Carbon black, 250G, Imerys, Reinforcing agent 1: Ethylene - butyl acrylate - glycidyl methacrylate copolymer, commercially available, Reinforcing agent 2: Methyl methacrylate - butadiene - styrene copolymer, commercially available, Antioxidant: β-(3,5 - di - tert - butyl - 4 - hydroxyphenyl) n - octadecanol propionate, commercially available.

[0029] Preparation methods of examples and comparative examples According to the compounding ratio, put each component into a mixer and blend until uniform to obtain a premix. Next, put the premix into a twin-screw extruder for melt mixing and extrusion granulation to prepare a polycarbonate alloy material. The ratio of the screw length to the diameter of the twin-screw extruder is 45:1, the screw barrel temperature is 240 - 260 °C, and the screw rotation speed is 500 rpm.

[0030] Related performance test methods (1) Extrusion blow molding performance test: Huatai Machinery's extrusion molding machine, HT-110, screw diameter 110 mm, ratio of screw length to diameter 25 / 1, motor output 4.5 KW, maximum motor speed 1500 m. The extrusion temperature in all five stages is 280 °C, and the screw rotation speed is set at 80 r / min. The blow molded product is a drum with a wall thickness of 4 mm, a diameter of 300 mm, and a height of 500 mm. The air source pressure is 0.7 MPa, and the clamping force is 500 kn.

[0031] A. Melt temperature: When the material extrusion is stable, test the surface temperature (infrared thermometer) of the material 400 m below the die head. The higher the test temperature, the higher the relative yield of blow molding.

[0032] B. Stability of sagging material: When the material sags by 500 mm visually, the whole material is in a sagging state. The closer the diameters of the upper and lower parts of the whole tubular material are, the higher the melt strength and the easier the blow molding. The thinner the neck above the tubular material, the lower the melt strength and the more difficult the blow molding. "*" indicates the sagging state of the material. The fewer the number of "*", the closer the diameters of the upper and lower parts of the whole tubular material are. The more the number of "*", the thinner the upper neck. Here, "*****" means that the neck is so thin that it breaks and falls to the ground.

[0033] (2) Chemical resistance test: After conditioning a molded square plate with a thickness of 3 mm at 23 °C and a humidity of 50% for 24 hours, drop 2 ml of toluene on its surface, let it stand for 10 minutes, observe the occurrence of surface cracks, and evaluate according to the following criteria. ◎: There is no change in the surface appearance. ○: Slight cracks can be seen on the surface. △: Many cracks can be seen on the surface. ×: Severe cracks or through-cracks exist on the surface.

[0034] (3) Antistatic performance test: Using the surface resistivity, the antistatic properties of the material were characterized. After conditioning a 3-mm thick molded square plate at 23°C and 50% humidity for 24 hours, the surface resistivity of the square plate was tested according to ASTM D257-93. When the surface resistivity of the material is in the range of 10 6 ohm / sq to 10 9 ohm / sq, the material exhibits better antistatic properties.

[0035] (4) Low-temperature toughness test: After leaving the drum obtained by blow molding for 24 hours, 11 kg of gravel was put into it, and it was left in an environment of -30°C for 24 hours, then freely dropped from a height of 1 m, and this was repeated 3 times, and the cracks on the bottom surface were observed.

[0036] It is evaluated based on the following criteria. ◎: There is no change in the appearance of the bottom surface. ○: Slight cracks can be seen on the bottom surface. △: Many cracks can be seen on the bottom surface. ×: Severe cracks or through-cracks exist on the bottom surface.

[0037]

Table 1

[0038] As can be seen from the above examples and comparative examples, in the present invention, since a certain amount of polyethylene terephthalate and a specific metal compound are added to the polycarbonate, the material not only has excellent chemical resistance, but also has high melt strength and low melt cooling rate, and the stability of the melted and deflected material extruded during the extrusion blow molding process is increased, which is useful for blow molding.

[0039] In Comparative Examples 1 / 2, since no metal compound is added or the added amount is too small, the cooling rate of the melt of the material is fast, the strength is low, and the stability of the flexible material is low.

[0040] In Comparative Example 3, when the added amount of the metal compound is too large, the cooling rate of the melt becomes fast, the strength of the melt is low, and the chemical resistance of the material also becomes low.

[0041]

Table 2

[0042] When comparing Examples 9 to 17 with Example 1, preferably, the metal compound is a titanium metal oxide or an antimony metal oxide.

[0043]

Table 3

[0044] In Comparative Example 4, when polybutylene terephthalate PBT is added, the cooling rate of the melt of the material is fast, the strength is low, and the stability of the flexible material is low.

[0045] In Comparative Example 5, when acrylonitrile-butadiene-styrene copolymer ABS is added, the chemical resistance of the material is low, the cooling rate of the melt becomes fast, the strength of the melt is low, and the stability of the flexible material is also low.

[0046]

Table 4

[0047] As can be seen from Examples 23 to 28, in the present invention, a certain amount of antistatic agent carbon nanotubes and a reinforcing agent can be added, effectively improving the antistatic properties and low-temperature toughness of the material, and at the same time, ensuring the chemical resistance of the material. Therefore, the material has a low melt cooling rate and high melt strength, and as a result, blow extrusion molding can be effectively realized, meeting the usage requirements of pharmaceutical packaging containers.

[0048] In Comparative Example 6, the use of carbon black was not very effective in improving the antistatic properties of the material, the melt strength of the material was low, the stability of the deflected material was low, and the low-temperature toughness of the material was also poor.

Claims

1. A polycarbonate alloy material, based on parts by weight based on 100 parts by weight of the polycarbonate alloy material, 59 to 70 parts of polycarbonate, 20 to 40 parts of polyethylene terephthalate, 0.1 to 2 parts of a metal compound, and 2 to 10 parts of an antistatic agent are included, the antistatic agent is selected from any one or more of carbon nanotubes, the metal compound is selected from any one or more of metal oxides, metal bases or metal salts, and the metal is selected from any one or more of copper, iron, magnesium, calcium, titanium, antimony, sodium or potassium. A polycarbonate alloy material characterized by that.

2. Based on parts by weight based on 100 parts by weight of the polycarbonate alloy material, 59 to 65 parts of polycarbonate, 25 to 35 parts of polyethylene terephthalate, 0.3 to 1.2 parts of a metal compound, and 2 to 10 parts of an antistatic agent are included, and the polycarbonate alloy material according to claim 1 is characterized by that.

3. The polycarbonate alloy material according to claim 1, wherein the metal compound is selected from any one or more of titanium metal oxide or antimony metal oxide.

4. The titanium metal oxide is selected from one or more of TiO, TiO ２ or Ti ２ O ３ and the antimony metal oxide is selected from one or more of Sb ２ O ３ , Sb ２ O ４ , Sb ２ O ５ , Sb ６ O １３ and SbO. The polycarbonate alloy material according to claim 3, characterized in that it is selected from one or more of them.

5. The polycarbonate alloy material according to claim 1, wherein the viscosity average molecular weight of the polycarbonate is 10,000 to 40,000, and the intrinsic viscosity of the polyethylene terephthalate is 0.65 to 0.9 dl / g.

6. The polycarbonate alloy material according to claim 1, wherein the antistatic agent is selected from any one or more of multi-walled carbon nanotubes having a diameter of 1.0 to 80 nm and a length of 2 to 70 μm.

7. Based on parts by weight based on 100 parts by weight of the polycarbonate alloy material, 4 to 8 parts of a reinforcing agent are further included, and the reinforcing agent is ethylene-butyl acrylate-glycidyl methacrylate copolymer, ethylene-octene-glycidyl methacrylate copolymer, methyl methacrylate-butadiene-styrene copolymer, methyl methacrylate-acrylic acid copolymer, ethylene-methyl acrylate copolymer or methyl methacrylate-acrylic ester-silicone copolymer. The polycarbonate alloy material according to claim 1, which is obtained by being selected from one or more of them.

8. Based on 100 parts by weight of the polycarbonate alloy material, it further contains 0.01 to 1 part by weight of an antioxidant, and the antioxidant is octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, tris(nonylphenyl)phosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, β-(3,5-di-tert-butyl-4-hydroxyphenyl)n-octadecanol propionate, distearyl pentaerythritol diphosphite, tetrakis[methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]methane, distearyl thiodipropionate, dilauryl thiodipropionate, tridecyl thiodipropionate, pentaerythritol-tetrakis[3-(3,5-di-tert-butyl 4-hydroxyphenyl)propionate] or β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid amide, and is characterized in that it is selected from any one or more of them. The polycarbonate alloy material according to claim 1.

9. According to the blending ratio, each component is put into a mixer and blended until uniform to obtain a premix. Next, the premix is put into a twin-screw extruder for melt mixing and extrusion granulation to prepare a polycarbonate alloy material. The ratio of the screw length to the diameter of the twin-screw extruder is 40:1 to 50:1, the screw barrel temperature is 240 to 260 °C, and the screw rotation speed is 400 to 500 rpm. The method for preparing a polycarbonate alloy material according to any one of claims 1 to 8.

10. Use of the polycarbonate alloy material according to any one of claims 1 to 8 in the field of pharmaceutical packaging.

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