Polyester alloy material and method for producing the same

Abstract

This invention relates to the field of polymer materials technology, specifically to a polyester alloy material and its preparation method. The polyester alloy material provided by this invention, by weight, comprises the following raw materials: 45-50 parts polycarbonate; 28-32 parts polybutylene terephthalate; 18-22 parts glass fiber; 0.1-5 parts compatibilizer; 0.1-1 part anti-hydrolysis agent; 0.1-1 part transesterification inhibitor; 0.1-0.5 parts antioxidant; and 0.1-1 part lubricant. For the anti-hydrolysis agent of the polyester alloy formed by polycarbonate and polybutylene terephthalate, the addition of glass fiber significantly improves its mechanical properties. The addition of the anti-hydrolysis agent, without affecting the mechanical properties, significantly improves the light transmittance of the polyester alloy material.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, specifically to a polyester alloy material and its preparation method. Background Technology

[0002] Polycarbonate (PC) and polybutylene terephthalate (PBT) are two commonly used engineering plastics. PC has high impact resistance, heat resistance, dimensional stability, and good light transmittance, while PBT has excellent chemical resistance and processing flowability. Blending PC and PBT to prepare alloy materials can combine the advantages of both, resulting in a material system with superior overall performance.

[0003] However, PC / PBT alloys have relatively low strength in practical applications. While adding reinforcing phases can improve the material's mechanical properties, it reduces light transmittance, thus limiting its application in transparent or translucent products. There is an urgent need for a polyester alloy material that can combine good mechanical properties with high light transmittance. Summary of the Invention

[0004] Therefore, the technical problem to be solved by the present invention is to overcome the lack of a polyester alloy material with both good mechanical properties and high light transmittance in the prior art, thereby providing a polyester alloy material and its preparation method.

[0005] In a first aspect, the present invention provides a polyester alloy material, comprising, by weight, 45-50 parts of polycarbonate; 28-32 parts of polybutylene terephthalate; 18-22 parts of glass fiber; 0.1-5 parts of compatibilizer; 0.1-1 part of anti-hydrolysis agent; 0.1-1 part of transesterification inhibitor; 0.1-0.5 parts of antioxidant; and 0.1-1 part of lubricant. Among them, polybutylene terephthalate includes hydrolysis-resistant polybutylene terephthalate and laser-transparent polybutylene terephthalate resin.

[0006] Hydrolysis-resistant grade polybutylene terephthalate refers to polybutylene terephthalate that retains ≥60% of its tensile strength after 1000 hours of accelerated damp heat aging at 85℃ / 85%RH (e.g., greater than 60, 65, 70, 80, 90, or within any range of the above values).

[0007] Laser-transparent polybutylene terephthalate resin refers to the laser transmittance of a 1mm sample measured with LPKF TMG3. High transmittance is usually ≥50% (e.g., greater than 50, 55, 60, 65, 70, 80, 90, or within any range of the above values).

[0008] This invention provides a polyester alloy material, comprising, by weight, 45-50 parts of polycarbonate (e.g., 45, 46, 47, 48, 49, or 50 parts, or within any range of the above values); 28-32 parts of polybutylene terephthalate (e.g., 28, 28.5, 29, 29.5, 30, 30.5, 31, 31.5, or 32 parts, or within any range of the above values); 18-22 parts of glass fiber (e.g., 18, 18.5, 19, 19.5, 20, 21.5, or 22 parts, or within any range of the above values); and 0.1-5 parts of compatibilizer (e.g., 0.1, 0.2, 0.5, 0.8, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, or 5 parts, or within any range of the above values). Within the range of values); anti-hydrolysis agent 0.1-1 part (e.g., 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 or 1, or within any range of values ​​above); transesterification inhibitor 0.1-1 part (e.g., 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 or 1, or within any range of values ​​above); antioxidant 0.1-0.5 part (e.g., 0.1, 0.2, 0.3, 0.4 or 0.5, or within any range of values ​​above); lubricant 0.1-1 part (0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 or 1, or within any range of values ​​above).

[0009] Preferably, the polycarbonate has a melt flow rate of 15-40 g / 10min at 300℃ and 1.2kg load, a refractive index of 1.58-1.59, a laser transmittance of >90% and a haze of <1% at a thickness of 1mm. Preferably, the intrinsic viscosity of the hydrolysis-resistant grade polybutylene terephthalate is 1.28 ± 0.03 dL / g; Preferably, the hydrolysis-resistant grade polybutylene terephthalate has a terminal carboxyl group content ≤25mol / t; Preferably, the laser-transparent polybutylene terephthalate resin has a refractive index of 1.57-1.58, a melt viscosity of 5000-7000 poise, and a melt index of 10-20 g / 10 min at 250℃ and 2.16 kg.

[0010] Understandably, in this application, the laser used in the laser transmittance test refers to a laser with a wavelength of 980 nm.

[0011] Preferably, the mass ratio of hydrolysis-resistant polybutylene terephthalate to laser-transparent polybutylene terephthalate resin is (0.8-1.2):(0.8-1.2).

[0012] Preferably, the transesterification inhibitor includes at least one of phosphate transesterification inhibitors and phosphate transesterification inhibitors.

[0013] Preferably, the glass fiber is selected from alkali-free glass fiber whose surface has been modified with a silane coupling agent; Preferably, the alkali coupling agent used in the silane coupling agent modified alkali-free glass fiber is selected from aminosilane or epoxysilane.

[0014] Preferably, the glass fiber has an average length of 50-300 μm and an average diameter of 5-25 μm; Preferably, the aspect ratio of the glass fiber is 10-30; Preferably, the glass fiber has a refractive index of 1.57-1.59.

[0015] Preferably, the compatibilizer comprises an ethylene-acrylate-glycidyl methacrylate copolymer; Preferably, the ethylene-acrylate-glycidyl methacrylate copolymer is a random terpolymer; Preferably, the ethylene-methyl acrylate-glycidyl methacrylate random terpolymer has a glycidyl methacrylate content of 7-9% by mass and a melt flow rate of 4-8 g / 10min at 190°C and 2.16kg load.

[0016] Preferably, the anti-hydrolysis agent is selected from carbodiimide anti-hydrolysis agents; Preferably, the carbodiimide anti-hydrolysis agent includes monocarbodiimide anti-hydrolysis agent and polycarbodiimide anti-hydrolysis agent; Preferably, the monocarbodiimide antihydrolysis agent comprises monomeric aromatic carbodiimide; Preferably, the monocarbodiimide antihydrolysis agent comprises N,N'-bis(2,6-diisopropylphenyl)carbodiimide; Preferably, the polycarbodiimide anti-hydrolysis agent is an aromatic polycarbodiimide or an aliphatic polycarbodiimide; Preferably, the polycarbodiimide anti-hydrolysis agent comprises poly(4,4'-diphenylmethane)carbodiimide with a number average molecular weight of 1000-5000 and a softening point ≥70℃.

[0017] Secondly, the present invention also provides a method for preparing the above-mentioned polyester alloy material, comprising the following steps: (1) The polycarbonate, polybutylene terephthalate, compatibilizer, anti-hydrolysis agent, transesterification inhibitor, antioxidant and lubricant in the raw materials are mixed to obtain a premix; (2) The premixed material and the glass fiber in the raw material are melt-extruded and granulated to obtain the polyester alloy material.

[0018] Preferably, the process of drying polycarbonate and polybutylene terephthalate separately is included before mixing in step (1).

[0019] Preferably, the temperature for drying polycarbonate is 100-120℃ and the time is 4-6 hours; Preferably, the temperature for drying polybutylene terephthalate is 100-120°C and the time is 4-6 hours.

[0020] Preferably, melt extrusion is performed using a twin-screw extruder; Preferably, during the melt extrusion process, the temperature of each zone of the twin-screw extruder is 230℃~260℃, and the screw speed is 300~400rpm / min.

[0021] Preferably, the process of melt extruding the premix and the glass fiber in the raw material involves adding the premix into the twin-screw extruder through the main feed port and adding the glass fiber into the twin-screw extruder through the side feed port.

[0022] The technical solution of this invention has the following advantages: The present invention provides a polyester alloy material, which, by weight, comprises 45-50 parts of polycarbonate; 28-32 parts of polybutylene terephthalate; 18-22 parts of glass fiber; 0.1-5 parts of compatibilizer; 0.1-1 parts of anti-hydrolysis agent; 0.1-1 parts of transesterification inhibitor; 0.1-0.5 parts of antioxidant; and 0.1-1 parts of lubricant. The addition of glass fiber significantly improves the mechanical properties of the polyester alloy formed by polycarbonate and polybutylene terephthalate, and the addition of the anti-hydrolysis agent significantly enhances the light transmittance of the polyester alloy material without affecting its mechanical properties. Detailed Implementation

[0023] The following embodiments are provided to better understand the present invention and are not limited to the preferred embodiments described. They do not constitute a limitation on the content and scope of protection of the present invention. Any product that is the same as or similar to the present invention, derived by any person under the guidance of the present invention or by combining the features of the present invention with other prior art, falls within the protection scope of the present invention.

[0024] For experiments not specifically described in the examples, the procedures or conditions should be followed according to the conventional experimental procedures described in the literature in this field. Reagents or instruments whose manufacturers are not specified are all commercially available conventional reagent products.

[0025] The polycarbonate used in the embodiments and comparative examples of this application is a bisphenol A type polycarbonate with a melt mass flow rate of 15-25 g / 10min at 300°C and 1.2 kg load, a refractive index of 1.58-1.59, a laser transmittance of >90% and a haze of <1% at a thickness of 1 mm; it was purchased from Covestro, model Makrolon® 2405.

[0026] The polybutylene terephthalate (PBT) used in the embodiments and comparative examples of this application includes the following types: Hydrolysis-resistant grade polybutylene terephthalate (PBT): intrinsic viscosity 1.28±0.03dL / g, terminal carboxyl group content ≤25mol / t, purchased from Yizheng Chemical Fiber, model GL236; Laser-transparent polybutylene terephthalate resin (transparent PBT): refractive index 1.57-1.58, melt viscosity 5000-7000 poise, melt index 10-20 g / 10 min at 250℃ and 2.16 kg. Purchased from BASF, model Ultradur LUX.

[0027] The alkali-free glass fibers used in the embodiments and comparative examples of this application, which have been modified with silane coupling agent, have a refractive index of 1.58, an average length of 300 μm, and an average diameter of 10 μm. They were purchased from Jushi Group and are model ECS10-03-534H.

[0028] The ordinary glass fiber used in the comparative example of this application has a refractive index of 1.58, an average length of 300 μm, and an average diameter of 10 μm.

[0029] The compatibilizer used in the embodiments and comparative examples of this application is a random terpolymer of ethylene-methyl acrylate-glycidyl methacrylate, wherein the mass percentage of glycidyl methacrylate is 7-9%, and the melt mass flow rate at 190°C and 2.16 kg load is 4-8 g / 10 min. It was purchased from Arkema, model AX8900.

[0030] The anti-hydrolysis agents used in the embodiments and comparative examples of this application include: Monomer-type hydrolysis inhibitor: N,N'-bis(2,6-diisopropylphenyl)carbodiimide, CAS No. 2162-74-5, melting point 50-55℃, purity ≥99%, purchased from Rhein Chemicals, model Stabaxol I; Polymerized anti-hydrolysis agent: poly(4,4'-diphenylmethane)carbodiimide, number average molecular weight 1000-5000, softening point ≥70℃, purchased from Rhein Chemicals, model Stabaxol P.

[0031] The transesterification inhibitor used in the examples and comparative examples of this application is sodium dihydrogen phosphate, CAS number 7558-80-7, purchased from Sinopharm Group.

[0032] The antioxidants used in the embodiments and comparative examples of this application are a mixture of hindered phenolic antioxidants (such as Irganox 1010) and phosphite antioxidants (such as Irgafos 168) in a mass ratio of 1:1, purchased from BASF.

[0033] The lubricant used in the embodiments and comparative examples of this application is pentaerythritol stearate (PETS), CAS number 115-83-3, purchased from Lonza. The epoxy resin used in the comparative examples of this application is KH-560 (γ-glycidoxypropyltrimethoxysilane).

[0034] The maleic anhydride-grafted POE used in the comparative example of this application is Shandong Dawn: POE-g-MAH DWB-200.

[0035] Example 1 This embodiment provides a polyester alloy material, the preparation method of which includes the following steps (raw materials are in parts by weight): (1) 48 parts of polycarbonate and 30 parts of polybutylene terephthalate (including 15 parts of hydrolysis-resistant polybutylene terephthalate and 15 parts of laser-transparent polybutylene terephthalate resin) were dried at 110°C for 5 hours. Then, the dried polycarbonate, polybutylene terephthalate, 2 parts of compatibilizer (8900 compatibilizer), 0.5 parts of hydrolysis inhibitor (polymerization-type hydrolysis-resistant agent), 0.3 parts of transesterification inhibitor, 0.2 parts of antioxidant and 0.3 parts of lubricant were mixed evenly to obtain a premix. (2) The premix obtained in step (1) is added to a twin-screw extruder through the main feed port (the temperature of each zone of the screw of the twin-screw extruder is 230 ~ 260 ℃ and the screw speed is 300 ~ 400 rpm / min). 20 parts of glass fiber (silane coupling agent modified alkali-free glass fiber) are added to the twin-screw extruder through the side feed port and melt-extruded. After that, the polyester alloy material is obtained by stretching, cooling and pelletizing.

[0036] Examples 2-5 each provide a polyester alloy material, with a preparation process similar to that of Example 1, the difference being the raw materials; the specific composition is shown in Table 1; Comparative Examples 1-7 each provide a polyester alloy material, with a preparation process similar to that of Example 1, except that the raw materials are different. The specific composition is shown in Table 2.

[0037] Table 1

[0038] Table 2

[0039] " / " indicates that the substance was not added. Test case The polyester alloy materials prepared in the examples and comparative examples were injection molded and then subjected to performance testing. Some test items and test standards are as follows: Density: ISO 1183-1 Tensile modulus: ISO 527 Tensile strength: ISO 527 Elongation at break: ISO 527 Flexural modulus: ISO 178 Bending strength: ISO 178 Notched impact strength of simply supported beam: ISO 179-1 / 1eA Unnotched impact strength of simply supported beam: ISO 179-1 / 1eU Laser transmittance test: The laser transmittance of the sample was tested by LPKF's TMG3 with a sample size of 60 (length) × 60 (width) × 1.5 (thickness) mm.

[0040] Hydrolysis resistance test: The standard specimens prepared according to ISO standards were placed in a high temperature and high humidity chamber at 85℃ and 85% humidity for 1000 hours, and then equilibrated in a 23℃ and 50% humidity chamber for 24 hours before testing.

[0041] The results are shown in Table 3. Table 3

[0042] Density: g / cm3; Tensile modulus: MPa; Tensile strength: MPa; Flexural modulus: MPa; Flexural strength: MPa; Notched impact strength: kJ / m2; Unnotched impact strength: kJ / m2; Tensile strength after hydrolysis and aging: MPa.

[0043] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. A polyester alloy material, characterized in that, By weight, the raw materials include 45-50 parts polycarbonate; 28-32 parts polybutylene terephthalate; 18-22 parts glass fiber; 0.1-5 parts compatibilizer; 0.1-1 part anti-hydrolysis agent; 0.1-1 part transesterification inhibitor; 0.1-0.5 parts antioxidant; and 0.1-1 part lubricant. Among them, polybutylene terephthalate includes hydrolysis-resistant polybutylene terephthalate and laser-transparent polybutylene terephthalate resin.

2. The polyester alloy material according to claim 1, characterized in that, The polycarbonate has a melt flow rate of 15-40 g / 10 min at 300°C and 1.2 kg load, and a refractive index of 1.58-1.

59. Preferably, the polycarbonate has a laser transmittance of >90% and a haze of <1% when the thickness is 1mm. Preferably, the intrinsic viscosity of the hydrolysis-resistant grade polybutylene terephthalate is 1.28 ± 0.03 dL / g; Preferably, the laser-transparent polybutylene terephthalate resin has a refractive index of 1.57-1.58, a melt viscosity of 5000-7000 poise, and a melt index of 10-20 g / 10 min at 250℃ and 2.16 kg. Preferably, the mass ratio of hydrolysis-resistant grade polybutylene terephthalate to laser-transparent polybutylene terephthalate resin is (0.8-1.2):(0.8-1.2). Preferably, the transesterification inhibitor includes at least one of phosphate transesterification inhibitors and phosphate transesterification inhibitors.

3. The polyester alloy material according to claim 1 or 2, characterized in that, The glass fiber is selected from alkali-free glass fiber whose surface has been modified with a silane coupling agent; Preferably, the glass fiber has an average length of 50-300 μm, an average diameter of 5-25 μm, and an aspect ratio of 10-30; Preferably, the glass fiber has a refractive index of 1.57-1.

59.

4. The polyester alloy material according to any one of claims 1-3, characterized in that, The compatibilizer includes an ethylene-acrylate-glycidyl methacrylate copolymer; Preferably, the ethylene-acrylate-glycidyl methacrylate copolymer is a random terpolymer; Preferably, the ethylene-methyl acrylate-glycidyl methacrylate random terpolymer has a glycidyl methacrylate content of 7-9% by mass and a melt flow rate of 4-8 g / 10min at 190°C and 2.16kg load.

5. The polyester alloy material according to any one of claims 1-4, characterized in that, The anti-hydrolysis agent is selected from carbodiimide-based anti-hydrolysis agents; Preferably, the carbodiimide anti-hydrolysis agent includes monocarbodiimide anti-hydrolysis agent and polycarbodiimide anti-hydrolysis agent; Preferably, the monocarbodiimide antihydrolysis agent comprises monomeric aromatic carbodiimide; Preferably, the monocarbodiimide antihydrolysis agent comprises N,N'-bis(2,6-diisopropylphenyl)carbodiimide; Preferably, the polycarbodiimide anti-hydrolysis agent is an aromatic polycarbodiimide or an aliphatic polycarbodiimide; Preferably, the polycarbodiimide anti-hydrolysis agent comprises poly(4,4'-diphenylmethane)carbodiimide with a number average molecular weight of 1000-5000 and a softening point ≥70℃.

6. A method for preparing the polyester alloy material according to any one of claims 1-5, characterized in that, Includes the following steps: (1) The polycarbonate, polybutylene terephthalate, compatibilizer, anti-hydrolysis agent, transesterification inhibitor, antioxidant and lubricant in the raw materials are mixed to obtain a premix; (2) The premixed material and the glass fiber in the raw material are melt-extruded and granulated to obtain the polyester alloy material.

7. The preparation method according to claim 6, characterized in that, The process of drying polycarbonate and polybutylene terephthalate separately before mixing in step (1) also includes the process of drying polycarbonate and polybutylene terephthalate separately.

8. The preparation method according to claim 6 or 7, characterized in that, The temperature for drying polycarbonate is 100-120℃, and the time is 4-6 hours. Preferably, the temperature for drying polybutylene terephthalate is 100-120°C and the time is 4-6 hours.

9. The preparation method according to any one of claims 6-8, characterized in that, Melt extrusion is performed using a twin-screw extruder; Preferably, during the melt extrusion process, the temperature of each zone of the twin-screw extruder is 230℃~260℃, and the screw speed is 300~400rpm / min.

10. The preparation method according to any one of claims 6-9, characterized in that, The process of melt extruding the premix and glass fiber in the raw material involves feeding the premix into the twin-screw extruder through the main feed port and feeding the glass fiber into the twin-screw extruder through the side feed port.

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