PC / PCTG composite material and preparation method and application thereof

Abstract

The application discloses a PC / PCTG composite material and a preparation method and application thereof, relates to the technical field of modified PC / PCTG composite materials, and provides a PC / PCTG composite material, which comprises the following components in parts by weight: PC resin 55-75 parts, PCTG resin 20-35 parts, SMA resin 1-5 parts, organic phosphorus flame retardant 3-7 parts, and titanate 0.1-0.5 parts; the mass percentage content of maleic anhydride in the SMA resin is greater than or equal to 13%. Through the cooperation of the SMA resin, the organic phosphorus flame retardant and the titanate with specific parts by weight and specific components, the heat resistance, the solvent resistance and the flame retardance of the polycarbonate composite material can be simultaneously improved under the condition that good light transmittance is ensured.

Description

Technical Field

[0001] This invention relates to the field of modified PC / PCTG composite materials technology, and in particular to a PC / PCTG composite material, its preparation method and application. Background Technology

[0002] Polycarbonate (PC) is an engineering plastic with excellent overall performance, possessing superior toughness, good dimensional stability, high light transmittance, and flame retardancy. It has wide applications in electronic products such as printers, monitors, computers, game consoles, and electronic pens. However, polycarbonate also has problems such as poor solvent resistance and decreased transparency after achieving a V0 flame retardant rating. This limits its application in some scenarios where solvent resistance, flame retardancy, and heat resistance are crucial, such as transparent windows in kitchen appliances and transparent lighting fixtures. Improving the solvent resistance of polycarbonate usually involves adding a second component with good solvent resistance, such as polybutylene terephthalate (PET) or polyethylene terephthalate (PET). However, these components have a high limiting oxygen index, which deteriorates the flame retardancy of PC after addition. Furthermore, conventional techniques for improving flame retardancy often lead to a decrease in the light transmittance of polycarbonate. Therefore, as the application fields of polycarbonate expand, the requirements for material performance are constantly increasing.

[0003] To address the aforementioned technical challenges, existing technologies have developed PC / PCTG composite materials, which combine the advantages of both PC and PCTG, exhibiting characteristics such as high light transmittance and good solvent resistance. However, in practical applications, PC / PCTG composite systems still suffer from issues such as loss of light transmittance when using conventional flame-retardant methods, and the inability to significantly improve heat resistance and solvent resistance. Therefore, a PC / PCTG composite material with excellent light transmittance, heat resistance, solvent resistance, and flame retardancy, meeting the requirements of specific application scenarios, holds broad application prospects. Summary of the Invention

[0004] Based on this, the purpose of the present invention is to overcome the shortcomings of the prior art and provide a PC / PCTG composite material with good light transmittance, heat resistance, solvent resistance and flame retardancy.

[0005] To achieve the above objectives, the technical solution adopted by the present invention is as follows: a PC / PCTG composite material, comprising the following components in parts by weight: 55-75 parts of PC resin, 20-35 parts of polyethylene terephthalate-1,4-cyclohexanediol ester (PCTG resin), 1-5 parts of maleic anhydride-styrene random copolymer (SMA resin), 3-7 parts of organophosphorus flame retardant, and 0.1-0.5 parts of titanate; wherein the SMA resin contains ≥13% maleic anhydride by mass.

[0006] In the PC / PCTG system, this invention, through the synergistic effect of specific weight parts and specific components of SMA resin, organophosphorus flame retardant, and titanate, can ensure good light transmittance while simultaneously improving the solvent resistance, flame retardancy, and heat resistance of polycarbonate composite materials.

[0007] This invention improves the interfacial bonding between PC and PCTG by selecting a specific weight percentage of SMA resin, enabling the establishment of bonds between molecular chains. Insufficient SMA resin addition fails to effectively establish bonds between molecular chains; excessive addition leads to a decrease in the overall flame retardant properties of the PC / PCTG composite material. This invention, through the use of SMA resin with a specific mass percentage of maleic anhydride, better improves the interfacial bonding between PC and PCTG, enabling the establishment of bonds between molecular chains, resisting deformation, and increasing heat resistance.

[0008] This invention, through the selection of specific weight parts of organophosphorus flame retardants, titanates, and SMA resins, achieves the following: on the one hand, the titanates and organophosphorus flame retardants work synergistically to improve the flame retardant properties of the PC / PCTG composite material system; on the other hand, the titanates can combine with specific SMA resins, promoting the breaking of PC and PCTG molecular chains while allowing PC and PCTG to bind tightly together, further affecting the light transmittance and improving the solvent resistance and heat resistance of the PC / PCTG composite material.

[0009] Preferably, the maleic anhydride grafting rate of the present invention can be determined by infrared spectroscopy: Fourier transform infrared spectrometer is used to test a sample of fixed thickness to obtain characteristic absorption peaks in the infrared spectrum, and the grafting rate of maleic anhydride can be calculated by comparing the ratio of the absorption intensity of carbonyl and methylene groups.

[0010] Preferably, the PC resin accounts for no less than 50% by weight in the PC / PCTG composite material.

[0011] Preferably, the PC / PCTG composite material comprises the following components in parts by weight: 60-70 parts PC resin, 25-30 parts PCTG resin, 1.5-3 parts SMA resin, 4-5 parts organophosphorus flame retardant, and 0.3-0.4 parts titanate.

[0012] During actual experiments, the inventors discovered that the weight proportions of PC resin, PCTG resin, SMA resin, organophosphorus flame retardant, and titanate further affect the overall light transmittance, heat resistance, solvent resistance, and flame retardancy of the PC / PCTG composite material system. When the weight proportions of PC resin, PCTG resin, SMA resin, organophosphorus flame retardant, and titanate are within the above-mentioned range, the overall light transmittance, heat resistance, solvent resistance, and flame retardancy of the PC / PCTG composite material system are better.

[0013] Preferably, the SMA resin contains 13-27% maleic anhydride by mass.

[0014] Preferably, the number-average molecular weight of the PC resin is 18,000-30,000; and the intrinsic viscosity of the PCTG resin is 0.58-0.92 dl / g.

[0015] Optionally, the PC resin is in the range of 55 parts, 58 parts, 60 parts, 61 parts, 63 parts, 65 parts, 68 parts, 70 parts, 71 parts, 73 parts, and 75 parts by weight, or any two of these values; the PCTG resin is in the range of 20 parts, 21 parts, 23 parts, 25 parts, 28 parts, 30 parts, 32 parts, and 35 parts by weight, or any two of these values; the SMA resin is in the range of 1 part, 1.5 parts, 2 parts, 2.3 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, and 5 parts by weight, or any two of these values; the organophosphorus flame retardant is in the range of 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 6 parts, 6.5 parts, and 7 parts by weight, or any two of these values; and the titanate is in the range of 0.1 parts, 0.3 parts, and 0.5 parts by weight, or any two of these values.

[0016] Optionally, the SMA resin contains maleic anhydride at a mass percentage of 13%, 15%, 18%, 19%, 22%, 23%, 25%, and 27%, or any combination thereof. The PC resin has a number-average molecular weight of 18,000, 20,000, 25,000, 26,000, 28,000, and 30,000, or any combination thereof. The PCTG has an intrinsic viscosity of 0.58 dl / g, 0.60 dl / g, 0.62 dl / g, 0.65 dl / g, 0.7 dl / g, 0.79 dl / g, 0.82 dl / g, 0.87 dl / g, 0.89 dl / g, and 0.92 dl / g, or any combination thereof.

[0017] Preferably, the organophosphorus flame retardant is at least one of phosphate esters and phosphazenes, and the titanate is at least one of tetrabutyl titanate, isopropyl titanate, propyl dioleoyloxy (dioctyl phosphoyloxy) titanate, propyl dioleoyloxy (dioctyl phosphoyloxy) titanate, isopropyl tris (dioctyl phosphoyloxy) titanate, isopropyl trioleoyloxy titanate, isopropyl tris (dodecylbenzene sulfonic acid) titanate, isopropyl tris (dioctyl pyrophosphoyloxy) titanate, isopropyl tris (dioctyl pyrophosphoyloxy) ethylene titanate, and tetraisopropyl di (dioctyl phosphite) titanate.

[0018] Preferably, the PC / PCTG composite material further includes 0.1-1 parts of processing aid, wherein the processing aid is at least one of lubricant and antioxidant.

[0019] Optionally, the antioxidant is 0.1-0.5 parts by weight, and the antioxidant is at least one of hindered phenolic antioxidants and phosphite antioxidants, such as antioxidant 168 (tris[2,4-di-tert-butylphenyl] phosphite) and antioxidant 1010 (pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]).

[0020] Optionally, the lubricant is 0.1-0.5 parts by weight, and the lubricant is at least one of stearates, stearates, and ethylene bis-stearamides, such as pentaerythritol stearate, zinc stearate, etc.

[0021] Furthermore, the present invention provides a method for preparing the PC / PCTG composite material, comprising the following steps: mixing the components in proportion, performing melt extrusion, and granulation to obtain the PC / PCTG composite material.

[0022] Preferably, the temperature of the melt extrusion is 210-260°C.

[0023] Furthermore, this invention provides applications of the aforementioned PC / PCTG composite material in the fields of electronic appliances or household appliances. The PC / PCTG composite material can be applied to transparent windows and transparent lighting components in household appliances. Specifically, the PC / PCTG composite material can be applied to transparent windows in washing machines, rice cookers, microwave ovens, etc., as well as transparent windows in electronic cigarettes, electronic pens, etc.

[0024] Compared to existing technologies, the beneficial effects of this invention are as follows: By selecting a specific weight percentage of SMA resin, this invention improves the interfacial bonding force between the PC and PCTG system phases, enabling the establishment of connections between molecular chains. Insufficient SMA resin addition fails to effectively establish connections between molecular chains; excessive addition leads to a decrease in the overall flame retardant performance of the PC / PCTG composite material. This invention, through a specific mass percentage of maleic anhydride in SMA resin, better improves the interfacial bonding force between PC and PCTG, enabling the establishment of connections between molecular chains, resisting deformation, and increasing heat resistance. Too low a mass percentage of maleic anhydride results in weak connections between molecular chains; too high a mass percentage of maleic anhydride easily leads to micelle formation, resulting in decreased light transmittance.

[0025] This invention, through the selection of specific weight parts of organophosphorus flame retardants, titanates, and SMA resins, achieves the following: on the one hand, the titanates and organophosphorus flame retardants work synergistically to improve the flame retardant properties of the PC / PCTG composite material system; on the other hand, the titanates can combine with specific SMA resins, promoting the breaking of PC and PCTG molecular chains while allowing PC and PCTG to bind tightly together, further affecting the light transmittance and improving the solvent resistance and heat resistance of the polycarbonate composite material. Detailed Implementation

[0026] To better illustrate the purpose, technical solution, and advantages of this invention, the invention will be further described below with reference to specific embodiments. The purpose is to provide a detailed understanding of the invention, not to limit it. All other embodiments obtained by those skilled in the art without inventive effort are within the scope of protection of this invention. Unless otherwise specified, the experimental reagents and instruments designed in the embodiments and comparative examples of this invention are commonly used reagents and instruments, all of which are commercially available. Unless otherwise specified, the experimental methods used in the embodiments and comparative examples are conventional methods; and unless otherwise specified, the raw materials used in parallel experiments are from the same batch.

[0027] The raw materials used in the embodiments and comparative examples are described below, but are not limited to these materials:

[0028] PC Resin-1: Number average molecular weight of 20,000, H-3000F, Mitsubishi, Japan.

[0029] PC Resin-2: Number average molecular weight is 28,000, S-2000F, Mitsubishi, Japan.

[0030] PCTG Resin-1: TX1501HF, Eastman Chemical, wherein the intrinsic viscosity of the PCTG resin is 0.58 dl / g.

[0031] PCTG Resin-2: DN-011, Eastman Chemical, wherein the intrinsic viscosity of the PCTG resin is 0.7 dl / g.

[0032] PCTG Resin-3: Z6018, Eastman Chemical, wherein the intrinsic viscosity of the PCTG resin is 0.92 dl / g.

[0033] SMA Resin-1: Maleic anhydride-styrene random copolymer, SMA-700, wherein the mass percentage of maleic anhydride in the SMA resin is 18%, Hua Wen.

[0034] SMA Resin-2: Maleic anhydride-styrene random copolymer, SZ23110, wherein the mass percentage of maleic anhydride in the SMA resin is 23%, POLYSCOPE.

[0035] SMA Resin-3: Maleic anhydride-styrene random copolymer, SZ15170, wherein the mass percentage of maleic anhydride in the SMA resin is 15%, POLYSCOPE.

[0036] SMA Resin-4: Maleic anhydride-styrene random copolymer, SMA-725K, wherein the mass percentage of maleic anhydride in the SMA resin is 25%, Hua Wen.

[0037] SMA Resin-5: Maleic anhydride-styrene random copolymer, SMA EF80, wherein the mass percentage of maleic anhydride in the SMA resin is 10%, POLYSCOPE.

[0038] Organophosphorus flame retardant-1: Bisphenol A bis(diphenyl phosphate) BDP, commercially available.

[0039] Organophosphorus flame retardant-2: Phosphazene, commercially available.

[0040] Titanate-1: Tetrabutyl titanate, commercially available.

[0041] Titanate-2: Tetraisopropyl di(dioctylphosphite)titanate, commercially available.

[0042] The antioxidant is a compound of commercially available hindered phenolic antioxidant 1010 and commercially available phosphite antioxidant 168 in a mass ratio of 1:1.

[0043] Examples 1-12 and Comparative Examples 1-5

[0044] The components and weight parts of the PC / PCTG composite material described in the embodiments and comparative examples of the present invention are shown in Tables 1-2. The preparation method of the PC / PCTG composite material includes the following steps: mixing the components in proportion, performing melt extrusion, and granulation to obtain the PC / PCTG composite material. The melt extrusion conditions are 210-260℃.

[0045] Performance testing

[0046] Heat resistance test: According to the test standard ASTM D648-2016, the heat distortion temperature (HDT) was measured by placing a 6.4 mm thick rod flat under a load of 1.82 MPa, and the results were recorded in °C.

[0047] Flame retardancy test: According to UL-94-2018; standard test pieces with injection molded specifications of 125*13*3.0mm were tested using a vertical burning tester; according to the standard, the test results include V-0, V-1, V-2, and V-2 not met, etc.

[0048] Light transmittance test: Tested according to ASTM D1003-2013 standard;

[0049] Solvent resistance test: According to ASTM D543-2014, peanut oil was applied to the tensile strength test specimen (3.2 mm thick) with a 1.0% strain fixture, and the appearance changes were observed. The specimens were divided into four grades according to the severity of cracking: A (no crack), B (minor crack), C (severe crack) and D (fracture).

[0050] The results of the performance tests are shown in the table below.

[0051] Table 1

[0052]

[0053]

[0054] Table 2

[0055] Components (parts by weight) Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 PC Resin-1 66 66 66 66 66 PCTG Resin-1 26 26 26 15 45 SMA resin-1 0 2.4 0 2.4 2.4 SMA Resin-5 2.4 0 0 0 0 Organophosphorus flame retardant-1 4.5 4.5 4.5 4.5 4.5 Titanate-1 0.3 0 0.3 0.3 0.3 antioxidants 0.1 0.1 0.1 0.1 0.1 Heat distortion temperature (°C) 86 89 85 102 77 Flame retardant properties V1 V1 V2 V0 V2 Light transmittance (%) 88 88 89 88 88 Solvent resistance A A A C A

[0056] As shown in the table above, the PC / PCTG composite materials prepared in the embodiments of the present invention can all meet the requirements of solvent resistance A, light transmittance ≥85%, flame retardancy V0, and heat distortion temperature ≥80℃. They also have good light transmittance, heat resistance, solvent resistance and flame retardancy, which meet the application requirements of specific scenarios.

[0057] As can be seen from the comparison of Examples 1-4, when the mass percentage of maleic anhydride in the SMA resin is 13-27%, it has good light transmittance, heat resistance, solvent resistance and flame retardancy, which meets the application requirements of specific scenarios.

[0058] As can be seen from the comparison of Examples 1 and 9-12, when the PC resin is 60-70 parts, the PCTG resin is 25-30 parts, the SMA resin is 1.5-3 parts, the organophosphorus flame retardant is 4-5 parts, and the titanate is 0.3-0.4 parts, the prepared PC / PCTG composite material has better light transmittance, heat resistance, solvent resistance and flame retardancy.

[0059] As can be seen from the comparison of Example 1 and Comparative Examples 1-3, when titanate, SMA resin, and organophosphorus flame retardant work synergistically, they exhibit good light transmittance, heat resistance, solvent resistance, and flame retardancy, meeting the application requirements of specific scenarios.

[0060] As can be seen from the comparison of Example 1 and Comparative Examples 4-5, if the amount of PCTG added is too low, the solvent resistance test result is C; if the amount of PCTG added is too high, the flame retardant performance is V2 and the heat resistance is poor, neither of which meets the requirements.

[0061] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention 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 the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A PC / PCTG composite material, characterized in that, It comprises the following components in parts by weight: 55-75 parts PC resin, 20-35 parts PCTG resin, 1-5 parts SMA resin, 3-7 parts organophosphorus flame retardant, and 0.1-0.5 parts titanate; wherein the SMA resin contains 13-27% maleic anhydride by mass.

2. The PC / PCTG composite material as described in claim 1, characterized in that, It includes the following components in parts by weight: 60-70 parts PC resin, 25-30 parts PCTG resin, 1.5-3 parts SMA resin, 4-5 parts organophosphorus flame retardant, and 0.3-0.4 parts titanate.

3. The PC / PCTG composite material as described in claim 1, characterized in that, The organophosphorus flame retardant is at least one of phosphate esters and phosphazenes; the titanate is at least one of tetrabutyl titanate, isopropyl titanate, propyl dioleoyloxy (dioctylphosphoyloxy) titanate, isopropyl tris (dioctylphosphoyloxy) titanate, isopropyl trioleoyloxy titanate, isopropyl tris (dodecylbenzenesulfonic acid) titanate, isopropyl tris (dioctylpyrophosphoyloxy) titanate, isopropyl tris (dioctylpyrophosphoyloxy) ethylene titanate, and tetraisopropyl di (dioctylphosphite) titanate.

4. The PC / PCTG composite material as described in claim 1, characterized in that, The number average molecular weight of the PC resin is 18,000-30,000; the intrinsic viscosity of the PCTG is 0.58-0.92 dl / g.

5. The PC / PCTG composite material as described in claim 1, characterized in that, The PC / PCTG composite material also includes 0.1-1 parts of processing aid, wherein the processing aid is at least one of lubricant and antioxidant.

6. A method for preparing the PC / PCTG composite material as described in any one of claims 1-5, characterized in that, Includes the following steps: The components are mixed in proportion, melt extruded, and granulated to obtain the PC / PCTG composite material.

7. The application of the PC / PCTG composite material as described in any one of claims 1-5 in the field of electronic appliances or household appliances.

8. The application of the PC / PCTG composite material as described in any one of claims 1-5 in a transparent window of electronic or household appliances.

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