Waterproof anti-aging carrier tape material and preparation method thereof
By introducing silicon-based modifiers and modified titanium dioxide into isosorbide-based polycarbonate, covalently linked polysiloxane segments and a hydrophobic protective layer are formed, solving the problems of thermal stability and water resistance of the carrier material and improving its waterproof and aging resistance properties.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- GUIXI RUOBANG ELECTRONICS SCI & TECH
- Filing Date
- 2026-02-02
- Publication Date
- 2026-05-12
AI Technical Summary
Existing polycarbonate carrier materials have shortcomings in terms of thermal stability and water resistance, which limits their application. In particular, isosorbide-based polycarbonates have high hydrophilicity, which makes the materials prone to aging.
Using isosorbide-containing polycarbonate as the matrix, a silicon-based modifier is introduced through melt transesterification-polymerization and modified titanium dioxide is added to form covalently linked polysiloxane segments. Combined with the UV shielding and surface modification of nano-titanium dioxide, a hydrophobic protective layer is constructed to improve waterproof and aging resistance.
It significantly improves the waterproof and aging resistance of carrier materials, while also possessing excellent mechanical properties and antistatic properties, solving the problems of thermal stability and water resistance of isosorbide-based polycarbonate.
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Abstract
Description
Technical Field
[0001] This invention relates to the field of polycarbonate technology, specifically to a waterproof and aging-resistant carrier tape material and its preparation method. Background Technology
[0002] Carrier tape is a key consumable in the automated packaging process of electronic components. It is mainly used to carry and transport small devices such as chips, resistors, and capacitors. Its surface has equally spaced holes to precisely house the components, and with the help of a cover tape, it achieves sealed protection. It needs to meet requirements such as anti-static, waterproof, moisture-proof, and high dimensional stability.
[0003] Polycarbonate (PC) is one of the most commonly used high-performance engineering plastics for carrier materials. It belongs to the non-metallic additive manufacturing polymer system. The PC molecule's main chain consists of alternating rigid benzene rings and flexible carbonate groups, exhibiting a high glass transition temperature, excellent impact resistance, and good transparency. Currently, bisphenol A polycarbonate (BPA-PC) is the most widely used in existing processes, offering balanced overall performance. However, its raw materials are non-renewable fossil resources, which does not align with the trend of green and sustainable development. Therefore, isosorbide-based polycarbonate (PIC) has gradually gained attention. Its raw material, isosorbide, can be prepared from glucose, making it a renewable source. However, due to its high hydrophilicity, PIC suffers from generally poor thermal stability, water resistance, and susceptibility to aging, limiting its application.
[0004] In conclusion, solving the above problems and preparing a waterproof and aging-resistant carrier material is of great significance. Summary of the Invention
[0005] The purpose of this invention is to provide a waterproof and aging-resistant carrier material and its preparation method to solve the problems mentioned in the background art.
[0006] To solve the above-mentioned technical problems, the present invention provides the following technical solution: A method for preparing a waterproof and aging-resistant carrier tape material includes the following steps: Polycarbonate, acrylonitrile-butadiene-styrene resin, methyl methacrylate-butadiene-styrene resin, modified titanium dioxide, and additives are blended and then melt-extruded and granulated to obtain a waterproof and aging-resistant carrier material. The polycarbonate includes a silicon-containing isosorbide-based polycarbonate, which is prepared by copolymerizing diphenyl carbonate, isosorbide, and 1,4-cyclohexanediethanol in a melt transesterification-condensation system with the addition of a silicon-based modifier.
[0007] Preferably, the waterproof and aging-resistant carrier material comprises the following raw materials in parts by weight: 100 parts polycarbonate, 20-25 parts acrylonitrile-butadiene-styrene resin, 3-5 parts methyl methacrylate-butadiene-styrene resin, 10-18 parts modified titanium dioxide, and 2-2.5 parts additives.
[0008] Preferredly, the preparation method of the silicon-containing isosorbide-based polycarbonate includes the following steps: under a nitrogen atmosphere, diphenyl carbonate, isosorbide, 1,4-cyclohexanediethanol, silicon-based modifier, and sodium hydroxide are mixed evenly, heated and stirred to react, and purified to obtain silicon-containing isosorbide-based polycarbonate.
[0009] Preferably, the raw materials for the silicon-containing isosorbide-based polycarbonate include diphenyl carbonate, isosorbide, and 1,4-cyclohexanediethanol in a mass ratio of 14.5~15.5:9~9.5:1; and the sodium hydroxide accounts for 2~3 ppm of the total diol mass.
[0010] Preferably, the silicon-based modifier accounts for 5-10 wt% of the total mass of the raw materials; The preparation method of the silicon-based modifier includes the following steps: (1) N-phenylmaleimide is added to anhydrous ethanol and stirred evenly, heated to 80~85℃, 4,4'-diaminodiphenylmethane-ethanol solution is added dropwise, the dropwise addition time is controlled to be 1~2h, the reaction is stirred for 12~18h, the precipitate is washed with ethanol, filtered, dried, and diamine is obtained; (2) Heat the epoxy-based double-terminated silicone oil to 190~200℃, add the diamine in batches and stir for 40~60min to obtain the silicon-based modifier.
[0011] Preferably, the raw materials for the diamine include N-phenylmaleimide and 4,4'-diaminodiphenylmethane in a mass ratio of 10:3.5~4; The raw materials for the silicon-based modifier include epoxy-based double-terminated silicone oil and diamine in a mass ratio of 4.5 to 5:1.
[0012] The preparation method of the silicon-based modifier is as follows: N-phenylmaleimide and 4,4'-diaminodiphenylmethane undergo a Michael addition reaction to obtain a diamine with a double-terminated phenyl-aminosuccinimide structure containing two secondary amino groups. Further, it undergoes a nucleophilic ring-opening reaction with a diepoxy-terminated silicone oil to obtain a silicon-based modifier containing multiple hydroxyl groups.
[0013] Preferably, the heating and stirring reaction process specifically includes the following steps: first, stirring the reaction at 160~170℃ for 30~40 min, then raising the temperature to 180~190℃ and stirring the reaction for 40~60 min, further raising the temperature to 230~240℃ and reducing the pressure to 12~16 kPa, stirring the reaction for 30~40 min, reducing the pressure to 4~8 kPa, stirring the reaction for 10~15 min, raising the temperature to 240~250℃ and reducing the pressure to 1~2 kPa, stirring the reaction for 5~10 min, and finally evacuating to 60~80 Pa and holding at that temperature for 5~10 min.
[0014] Preferred method for preparing modified titanium dioxide includes the following steps: (1) alkyl dimethyl tertiary amine and epichlorohydrin are mixed evenly under nitrogen atmosphere, stirred and reacted at 80~85℃ for 1~1.5h, and then distilled under reduced pressure to obtain alkyl quaternary ammonium salt; (2) Under a nitrogen atmosphere, epoxy-modified titanium dioxide and diamine were added to N,N-dimethylformamide and ultrasonically dispersed evenly. The mixture was stirred at 130~140℃ for 6~8h. Alkyl quaternary ammonium salt was added and the mixture was stirred for another 10~12h. The mixture was then filtered, washed, and dried to obtain modified titanium dioxide.
[0015] Preferably, the raw materials for the alkyl quaternary ammonium salt include alkyl dimethyl tertiary amine and epichlorohydrin in a molar ratio of 1:2.5~3; The epoxy-modified titanium dioxide is obtained by treating nano-titanium dioxide with 3-(2,3-epoxypropoxy)propyltrimethoxysilane; The raw materials for the modified titanium dioxide include epoxy-modified titanium dioxide, diamine, and alkyl quaternary ammonium salt in a mass ratio of 10:2.1~2.3:1.2~1.4.
[0016] The modified titanium dioxide is prepared by reacting the epoxy group of the epoxy-modified titanium dioxide with a secondary amine of a diamine, thereby grafting it onto the surface of titanium dioxide. Further addition of an alkyl quaternary ammonium salt and another secondary amine with a diamine structure yields the modified titanium dioxide.
[0017] Compared with the prior art, the beneficial effects achieved by the present invention are as follows: The present invention uses polycarbonate prepared by introducing silicon-based modifiers into the isosorbide-type polycarbonate melt transesterification-condensation system as the matrix, and by adding modified titanium dioxide, the waterproof and aging resistance of the carrier material is significantly improved, while also having excellent mechanical properties and antistatic properties.
[0018] To improve the hydrophobicity and processability of isosorbide-based polycarbonate, this application introduces hydrophobic polysiloxane segments into the polycarbonate backbone. These segments can increase the resin's toughness and enhance its mechanical properties. Compared to physical blending, the covalent bonding method used in this application can effectively prevent the accumulation of low surface energy polysiloxanes on the surface, which can lead to surface stickiness and decreased mechanical properties. At the same time, the siloxane segments are anchored to the backbone by N-phenylmaleimide. The rigid benzene ring and maleimide five-membered ring structure can generate a large steric hindrance, which can be used to limit the excessive movement of siloxane segments, improve the material's heat resistance and stability, and thus improve the long-term thermal oxidation resistance and anti-aging properties of polycarbonate.
[0019] The introduced nano-titanium dioxide itself is an effective UV shielding agent. This application significantly improves the dispersion stability of titanium dioxide by grafting a polycarbonate-compatible diamine onto its surface. Furthermore, the aromatic ring system in the diamine, after grafting onto the titanium dioxide surface, can synergistically interact with the titanium dioxide, reducing free radical generation by shielding and absorbing ultraviolet rays, thus significantly improving anti-aging performance. Further, a quaternary ammonium salt group is introduced through the epoxy reaction of the secondary amine at the other end of the diamine with an alkyl quaternary ammonium salt. This group can adsorb water and ionizable impurities from the air on the material surface, constructing a surface ionic conductive pathway, thereby increasing surface conductivity, effectively dissipating static charge, and improving antistatic performance. Simultaneously, the long-chain flexible aliphatic alkane introduced with the alkyl quaternary ammonium salt can improve processing performance and form a hydrophobic protective layer on the titanium dioxide surface, preventing water penetration and improving waterproof performance.
[0020] However, it is particularly important to emphasize that in the process of synthesizing silicon-based isosorbide polycarbonate, two gradient depressurization processes are required within the range of 230~240℃. This is because the silicon-based modifier has multiple hydroxyl structures, unlike traditional diols. If a conventional one-time depressurization process is used, the phenol removal rate will be too fast, the system viscosity will rise sharply, and the hydroxyl groups in the chain segments will not react sufficiently, ultimately resulting in a low molecular weight and a wide distribution. Through the gradient design of this application, the reaction efficiency can be significantly improved, and a polycarbonate matrix with controllable molecular weight, narrow distribution, and excellent performance can be obtained, thereby improving its overall performance. Detailed Implementation
[0021] The technical solutions in the embodiments of the present invention will be clearly and completely described below. 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 skilled in the art without creative effort are within the scope of protection of the present invention.
[0022] It should be noted that the following proportions are by weight. There are no special restrictions on the suppliers of any of the raw materials involved in this invention. Exemplary examples include: nano-titanium dioxide with a particle size of 20-50 nm; epoxy-terminated silicone oil with a molecular weight of 1300 and an epoxy content of 6.5 wt%; acrylonitrile-butadiene-styrene resin of grade PA-757-K; methyl methacrylate-butadiene-styrene resin of grade MBSTP-801; 3-(2,3-cyclohexane) CAS No.: 2530-83-8; CAS No.: 106-89-8; CAS No.: 941-69-5; CAS No.: 4,4'-diaminodiphenylmethane; CAS No.: 101-77-9; CAS No.: 102-09-0; CAS No.: 652-67-5; CAS No.: 105-08-8.
[0023] In the following examples, parts refer to parts by weight, and all raw materials mentioned above and others not mentioned are commercially available. In the following examples and comparative examples, the additives used include compatibilizer SAG-02, antioxidant AO300, and lubricant PETS in a mass ratio of 2:0.3:0.5; the alkyl dimethyl tertiary amine is hexadecyl dimethyl tertiary amine.
[0024] Pre-preparation: Preparation of modified titanium dioxide: (1) Nano titanium dioxide was ultrasonically dispersed in 80% ethanol aqueous solution, 3-(2,3-epoxypropoxy)propyltrimethoxysilane was added, and the mixture was stirred at 40℃ for 3h. After filtration, washing and drying, epoxy-modified titanium dioxide was obtained. The raw materials of epoxy-modified titanium dioxide included nano titanium dioxide and 3-(2,3-epoxypropoxy)propyltrimethoxysilane in a mass ratio of 1:0.15. (2) Under a nitrogen atmosphere, alkyl dimethyl tertiary amine and epichlorohydrin are mixed evenly and stirred at 80°C for 1 h. Excess epichlorohydrin is removed by vacuum distillation to obtain alkyl quaternary ammonium salt. The raw materials for alkyl quaternary ammonium salt include alkyl dimethyl tertiary amine and epichlorohydrin in a molar ratio of 1:2.5. (3) Under a nitrogen atmosphere, epoxy-modified titanium dioxide and diamine were added to N,N-dimethylformamide and ultrasonically dispersed evenly. The mixture was stirred at 135°C for 8 hours. Then, alkyl quaternary ammonium salt was added, and the mixture was stirred for another 12 hours. The mixture was then filtered, washed, and dried to obtain modified titanium dioxide. The raw materials for the modified titanium dioxide included epoxy-modified titanium dioxide, diamine, and alkyl quaternary ammonium salt in a mass ratio of 10:2.2:1.3.
[0025] Example 1: A method for preparing a waterproof and aging-resistant carrier tape material includes the following steps: Step 1: Preparation of silicon-based modifier: (1) Add N-phenylmaleimide to anhydrous ethanol and stir evenly, heat to 80°C, add 4,4'-diaminodiphenylmethane-ethanol solution dropwise, control the dropwise addition time to 1.5h, stir the reaction for 14h, wash the precipitate with ethanol, filter, dry, and obtain diamine; wherein, the raw materials of diamine include N-phenylmaleimide and 4,4'-diaminodiphenylmethane in a mass ratio of 10:3.7; (2) Heat the epoxy-based double-terminated silicone oil to 195°C, add diamine in batches and stir for 55 min to obtain a silicone-based modifier; wherein, the raw materials of the silicone-based modifier include epoxy-based double-terminated silicone oil and diamine in a mass ratio of 4.6:1; Step 2: Preparation of silicon-containing isosorbide-based polycarbonate: Under a nitrogen atmosphere, diphenyl carbonate, isosorbide, 1,4-cyclohexanediethanol, silicon-based modifier, and sodium hydroxide were mixed evenly. The mixture was stirred at 165°C for 35 min, then heated to 190°C and stirred for 50 min. The temperature was further increased to 230°C, and the pressure was reduced to 12 kPa. The mixture was stirred for 35 min, then the pressure was reduced to 4 kPa and stirred for 10 min. The temperature was then increased to 245°C and the pressure was reduced... The mixture was stirred at 2 kPa for 10 min, then evacuated to 60 Pa and held at that temperature for 10 min. It was then dissolved in chloroform, precipitated with anhydrous ethanol, washed, and dried to obtain a silicon-containing isosorbide-based polycarbonate. The raw materials for this polycarbonate included diphenyl carbonate, isosorbide, and 1,4-cyclohexanediol in a mass ratio of 15:9.2:1. The silicon-based modifier accounted for 8.4 wt% of the total raw material mass, and the sodium hydroxide accounted for 2 ppm of the total diol mass. Step 3: Preparation of waterproof and aging-resistant carrier material: 100 parts of siliceous isosorbide-based polycarbonate, 22 parts of acrylonitrile-butadiene-styrene resin, 4 parts of methyl methacrylate-butadiene-styrene resin, 14 parts of modified titanium dioxide, and 2.3 parts of additives are blended and then melt-extruded and granulated to obtain the waterproof and aging-resistant carrier material; wherein, the twin-screw extrusion temperature is 240~280℃, and the screw speed is 200r / min.
[0026] Example 2: A method for preparing a waterproof and aging-resistant carrier tape material includes the following steps: Step 1: Preparation of silicon-based modifier: (1) Add N-phenylmaleimide to anhydrous ethanol and stir evenly, heat to 80°C, add 4,4'-diaminodiphenylmethane-ethanol solution dropwise, control the dropwise addition time to 1.5h, stir the reaction for 14h, wash the precipitate with ethanol, filter, dry, and obtain diamine; wherein, the raw materials of diamine include N-phenylmaleimide and 4,4'-diaminodiphenylmethane in a mass ratio of 10:3.7; (2) Heat the epoxy-based double-terminated silicone oil to 195°C, add diamine in batches and stir for 55 min to obtain a silicone-based modifier; wherein, the raw materials of the silicone-based modifier include epoxy-based double-terminated silicone oil and diamine in a mass ratio of 4.6:1; Step 2: Preparation of silicon-containing isosorbide-based polycarbonate: Under a nitrogen atmosphere, diphenyl carbonate, isosorbide, 1,4-cyclohexanediethanol, silicon-based modifier, and sodium hydroxide were mixed evenly. The mixture was stirred at 165°C for 35 min, then heated to 190°C and stirred for 50 min. The temperature was further increased to 230°C, and the pressure was reduced to 12 kPa. The mixture was stirred for 35 min, then the pressure was reduced to 4 kPa and stirred for 10 min. The temperature was then increased to 245°C and the pressure was reduced... The mixture was stirred at 2 kPa for 10 min, then evacuated to 60 Pa and held at that temperature for 10 min. It was then dissolved in chloroform, precipitated with anhydrous ethanol, washed, and dried to obtain a silicon-containing isosorbide-based polycarbonate. The raw materials for this polycarbonate included diphenyl carbonate, isosorbide, and 1,4-cyclohexanediol in a mass ratio of 15:9.2:1. The silicon-based modifier accounted for 8.4 wt% of the total raw material mass, and the sodium hydroxide accounted for 2 ppm of the total diol mass. Step 3: Preparation of waterproof and aging-resistant carrier material: 100 parts of siliceous isosorbide-based polycarbonate, 20 parts of acrylonitrile-butadiene-styrene resin, 3 parts of methyl methacrylate-butadiene-styrene resin, 10 parts of modified titanium dioxide, and 2 parts of additives are blended and then melt-extruded and granulated to obtain the waterproof and aging-resistant carrier material; wherein, the twin-screw extrusion temperature is 240~280℃, and the screw speed is 200r / min.
[0027] Example 3: A method for preparing a waterproof and aging-resistant carrier tape material includes the following steps: Step 1: Preparation of silicon-based modifier: (1) Add N-phenylmaleimide to anhydrous ethanol and stir evenly, heat to 80°C, add 4,4'-diaminodiphenylmethane-ethanol solution dropwise, control the dropwise addition time to 1.5h, stir the reaction for 14h, wash the precipitate with ethanol, filter, dry, and obtain diamine; wherein, the raw materials of diamine include N-phenylmaleimide and 4,4'-diaminodiphenylmethane in a mass ratio of 10:3.7; (2) Heat the epoxy-based double-terminated silicone oil to 195°C, add diamine in batches and stir for 55 min to obtain a silicone-based modifier; wherein, the raw materials of the silicone-based modifier include epoxy-based double-terminated silicone oil and diamine in a mass ratio of 4.6:1; Step 2: Preparation of silicon-containing isosorbide-based polycarbonate: Under a nitrogen atmosphere, diphenyl carbonate, isosorbide, 1,4-cyclohexanediethanol, silicon-based modifier, and sodium hydroxide were mixed evenly. The mixture was stirred at 165°C for 35 min, then heated to 190°C and stirred for 50 min. The temperature was further increased to 230°C, and the pressure was reduced to 12 kPa. The mixture was stirred for 35 min, then the pressure was reduced to 4 kPa and stirred for 10 min. The temperature was then increased to 245°C and the pressure was reduced... The mixture was stirred at 2 kPa for 10 min, then evacuated to 60 Pa and held at that temperature for 10 min. It was then dissolved in chloroform, precipitated with anhydrous ethanol, washed, and dried to obtain a silicon-containing isosorbide-based polycarbonate. The raw materials for this polycarbonate included diphenyl carbonate, isosorbide, and 1,4-cyclohexanediol in a mass ratio of 15:9.2:1. The silicon-based modifier accounted for 8.4 wt% of the total raw material mass, and the sodium hydroxide accounted for 2 ppm of the total diol mass. Step 3: Preparation of waterproof and aging-resistant carrier material: 100 parts of siliceous isosorbide-based polycarbonate, 25 parts of acrylonitrile-butadiene-styrene resin, 5 parts of methyl methacrylate-butadiene-styrene resin, 18 parts of modified titanium dioxide, and 2.5 parts of additives are blended and then melt-extruded and granulated to obtain the waterproof and aging-resistant carrier material; wherein, the twin-screw extrusion temperature is 240~280℃, and the screw speed is 200r / min.
[0028] Comparative Example 1: Based on Example 1, a dihydroxy-terminated silicone oil was used to replace the silicone-based modifier (molecular weight 3000), with the remaining processes unchanged. Specifically, the following steps were included: Step 1: Preparation of isosorbide-containing polycarbonate: Under a nitrogen atmosphere, diphenyl carbonate, isosorbide, 1,4-cyclohexanediol, dihydroxy-terminated silicone oil, and sodium hydroxide were mixed evenly. The mixture was stirred at 165°C for 35 min, then heated to 190°C and stirred for 50 min. The temperature was further increased to 230°C, and the pressure was reduced to 12 kPa. The mixture was stirred for 35 min, then the pressure was reduced to 4 kPa and stirred for 10 min. The temperature was then increased to 245°C and the pressure was reduced... The mixture was stirred at 2 kPa for 10 min, then evacuated to 60 Pa and held at that temperature for 10 min. It was dissolved in chloroform, precipitated with anhydrous ethanol, washed, and dried to obtain a silicon-containing isosorbide-based polycarbonate. The raw materials for this silicon-containing isosorbide-based polycarbonate included diphenyl carbonate, isosorbide, and 1,4-cyclohexanediethanol in a mass ratio of 15:9.2:1. The dihydroxy-terminated silicone oil accounted for 8.4 wt% of the total raw material mass, and the sodium hydroxide accounted for 2 ppm of the total diol mass. Step 2: Preparation of waterproof and aging-resistant carrier material: 100 parts of siliceous isosorbide-based polycarbonate, 22 parts of acrylonitrile-butadiene-styrene resin, 4 parts of methyl methacrylate-butadiene-styrene resin, 14 parts of modified titanium dioxide, and 2.3 parts of additives are blended and then melt-extruded and granulated to obtain the waterproof and aging-resistant carrier material; wherein, the twin-screw extrusion temperature is 240~280℃, and the screw speed is 200r / min.
[0029] Comparative Example 2: Based on Example 1, the modified titanium dioxide was modified only using 3-(2,3-epoxypropoxy)propyltrimethoxysilane, with the remaining processes unchanged, specifically including the following steps: Step 1: Preparation of silicon-based modifier: (1) Add N-phenylmaleimide to anhydrous ethanol and stir evenly, heat to 80°C, add 4,4'-diaminodiphenylmethane-ethanol solution dropwise, control the dropwise addition time to 1.5h, stir the reaction for 14h, wash the precipitate with ethanol, filter, dry, and obtain diamine; wherein, the raw materials of diamine include N-phenylmaleimide and 4,4'-diaminodiphenylmethane in a mass ratio of 10:3.7; (2) Heat the epoxy-based double-terminated silicone oil to 195°C, add diamine in batches and stir for 55 min to obtain a silicone-based modifier; wherein, the raw materials of the silicone-based modifier include epoxy-based double-terminated silicone oil and diamine in a mass ratio of 4.6:1; Step 2: Preparation of silicon-containing isosorbide-based polycarbonate: Under a nitrogen atmosphere, diphenyl carbonate, isosorbide, 1,4-cyclohexanediethanol, silicon-based modifier, and sodium hydroxide were mixed evenly. The mixture was stirred at 165°C for 35 min, then heated to 190°C and stirred for 50 min. The temperature was further increased to 230°C, and the pressure was reduced to 12 kPa. The mixture was stirred for 35 min, then the pressure was reduced to 4 kPa and stirred for 10 min. The temperature was then increased to 245°C and the pressure was reduced... The mixture was stirred at 2 kPa for 10 min, then evacuated to 60 Pa and held at that temperature for 10 min. It was then dissolved in chloroform, precipitated with anhydrous ethanol, washed, and dried to obtain a silicon-containing isosorbide-based polycarbonate. The raw materials for this polycarbonate included diphenyl carbonate, isosorbide, and 1,4-cyclohexanediol in a mass ratio of 15:9.2:1. The silicon-based modifier accounted for 8.4 wt% of the total raw material mass, and the sodium hydroxide accounted for 2 ppm of the total diol mass. Step 3: Preparation of waterproof and aging-resistant carrier material: 100 parts of siliceous isosorbide-based polycarbonate, 22 parts of acrylonitrile-butadiene-styrene resin, 4 parts of methyl methacrylate-butadiene-styrene resin, 14 parts of modified titanium dioxide, and 2.3 parts of additives are blended and then melt-extruded and granulated to obtain the waterproof and aging-resistant carrier material; wherein, the twin-screw extrusion temperature is 240~280℃, and the screw speed is 200r / min.
[0030] The preparation method of modified titanium dioxide includes the following steps: ultrasonically dispersing nano-titanium dioxide in an 80% ethanol aqueous solution, adding 3-(2,3-epoxypropoxy)propyltrimethoxysilane, stirring at 40°C for 3 hours, filtering, washing, and drying to obtain modified titanium dioxide; wherein, the raw materials for modified titanium dioxide include nano-titanium dioxide and 3-(2,3-epoxypropoxy)propyltrimethoxysilane in a mass ratio of 1:0.15; Comparative Example 3: Based on Example 1, an alkyl quaternary ammonium salt with 8 carbon atoms was used, with the remaining processes unchanged. The specific steps included were as follows: Step 1: Preparation of silicon-based modifier: (1) Add N-phenylmaleimide to anhydrous ethanol and stir evenly, heat to 80°C, add 4,4'-diaminodiphenylmethane-ethanol solution dropwise, control the dropwise addition time to 1.5h, stir the reaction for 14h, wash the precipitate with ethanol, filter, dry, and obtain diamine; wherein, the raw materials of diamine include N-phenylmaleimide and 4,4'-diaminodiphenylmethane in a mass ratio of 10:3.7; (2) Heat the epoxy-based double-terminated silicone oil to 195°C, add diamine in batches and stir for 55 min to obtain a silicone-based modifier; wherein, the raw materials of the silicone-based modifier include epoxy-based double-terminated silicone oil and diamine in a mass ratio of 4.6:1; Step 2: Preparation of silicon-containing isosorbide-based polycarbonate: Under a nitrogen atmosphere, diphenyl carbonate, isosorbide, 1,4-cyclohexanediethanol, silicon-based modifier, and sodium hydroxide were mixed evenly. The mixture was stirred at 165°C for 35 min, then heated to 190°C and stirred for 50 min. The temperature was further increased to 230°C, and the pressure was reduced to 12 kPa. The mixture was stirred for 35 min, then the pressure was reduced to 4 kPa and stirred for 10 min. The temperature was then increased to 245°C and the pressure was reduced... The mixture was stirred at 2 kPa for 10 min, then evacuated to 60 Pa and held at that temperature for 10 min. It was then dissolved in chloroform, precipitated with anhydrous ethanol, washed, and dried to obtain a silicon-containing isosorbide-based polycarbonate. The raw materials for this polycarbonate included diphenyl carbonate, isosorbide, and 1,4-cyclohexanediol in a mass ratio of 15:9.2:1. The silicon-based modifier accounted for 8.4 wt% of the total raw material mass, and the sodium hydroxide accounted for 2 ppm of the total diol mass. Step 3: Preparation of waterproof and aging-resistant carrier material: 100 parts of siliceous isosorbide-based polycarbonate, 22 parts of acrylonitrile-butadiene-styrene resin, 4 parts of methyl methacrylate-butadiene-styrene resin, 14 parts of modified titanium dioxide, and 2.3 parts of additives are blended and then melt-extruded and granulated to obtain the waterproof and aging-resistant carrier material; wherein, the twin-screw extrusion temperature is 240~280℃, and the screw speed is 200r / min.
[0031] The preparation method of modified titanium dioxide includes the following steps: (1) ultrasonically disperse nano-titanium dioxide in 80% ethanol aqueous solution, add 3-(2,3-epoxypropoxy)propyltrimethoxysilane, stir at 40°C for 3h, filter, wash, and dry to obtain epoxy-modified titanium dioxide; wherein, the raw materials of epoxy-modified titanium dioxide include nano-titanium dioxide and 3-(2,3-epoxypropoxy)propyltrimethoxysilane in a mass ratio of 1:0.15; (2) Under a nitrogen atmosphere, alkyl dimethyl tertiary amine (octyl dimethyl tertiary amine) and epichlorohydrin are mixed evenly and stirred at 80°C for 1 h. Excess epichlorohydrin is removed by vacuum distillation to obtain alkyl quaternary ammonium salt. The raw materials for alkyl quaternary ammonium salt include alkyl dimethyl tertiary amine and epichlorohydrin in a molar ratio of 1:2.5. (3) Under a nitrogen atmosphere, epoxy-modified titanium dioxide and diamine were added to N,N-dimethylformamide and ultrasonically dispersed evenly. The mixture was stirred at 135°C for 8 hours. Then, alkyl quaternary ammonium salt was added, and the mixture was stirred for another 12 hours. The mixture was then filtered, washed, and dried to obtain modified titanium dioxide. The raw materials for the modified titanium dioxide included epoxy-modified titanium dioxide, diamine, and alkyl quaternary ammonium salt in a mass ratio of 10:2.2:1.3.
[0032] Comparative Example 4: Based on Example 1, the preparation process of silicon-containing isosorbide-based polycarbonate involved a single pressure reduction method at 230°C, with the remaining processes unchanged. Specifically, the process included the following steps: Step 1: Preparation of silicon-based modifier: (1) Add N-phenylmaleimide to anhydrous ethanol and stir evenly, heat to 80°C, add 4,4'-diaminodiphenylmethane-ethanol solution dropwise, control the dropwise addition time to 1.5h, stir the reaction for 14h, wash the precipitate with ethanol, filter, dry, and obtain diamine; wherein, the raw materials of diamine include N-phenylmaleimide and 4,4'-diaminodiphenylmethane in a mass ratio of 10:3.7; (2) Heat the epoxy-based double-terminated silicone oil to 195°C, add diamine in batches and stir for 55 min to obtain a silicone-based modifier; wherein, the raw materials of the silicone-based modifier include epoxy-based double-terminated silicone oil and diamine in a mass ratio of 4.6:1; Step 2: Preparation of silicon-containing isosorbide-based polycarbonate: Under a nitrogen atmosphere, diphenyl carbonate, isosorbide, 1,4-cyclohexanediethanol, a silicon-based modifier, and sodium hydroxide were mixed evenly and stirred at 165°C for 35 min. The temperature was then increased to 190°C and stirred for 50 min. The temperature was further increased to 230°C, and the pressure was reduced to 4 kPa. The mixture was stirred for 45 min, then increased to 245°C, and the pressure was reduced to 2 kPa. The mixture was stirred for 10 min, and finally, a vacuum was applied to 60 Pa and held for 10 min. The mixture was dissolved in chloroform, precipitated with anhydrous ethanol, washed, and dried to obtain silicon-containing isosorbide-based polycarbonate. The raw materials for the silicon-containing isosorbide-based polycarbonate included diphenyl carbonate, isosorbide, and 1,4-cyclohexanediethanol in a mass ratio of 15:9.2:1. The silicon-based modifier accounted for 8.4 wt% of the total raw material mass, and the sodium hydroxide accounted for 2 ppm of the total diol mass. Step 3: Preparation of waterproof and aging-resistant carrier material: 100 parts of siliceous isosorbide-based polycarbonate, 22 parts of acrylonitrile-butadiene-styrene resin, 4 parts of methyl methacrylate-butadiene-styrene resin, 14 parts of modified titanium dioxide, and 2.3 parts of additives are blended and then melt-extruded and granulated to obtain the waterproof and aging-resistant carrier material; wherein, the twin-screw extrusion temperature is 240~280℃, and the screw speed is 200r / min.
[0033] Performance testing: (1) The yield strength of each example and comparative sample was tested using a universal testing machine. The sample size was 80mm×8mm×0.08mm and the tensile rate was 10mm / min. (2) The notched impact strength of each example and comparative sample was measured according to GB / T1843-2008. (3) The samples of each example and comparative sample were subjected to ultraviolet aging treatment according to ISO 4892.2 for 2000h. The notched impact strength was measured and the impact strength retention rate was calculated. (4) The samples of each example and comparative sample were subjected to moisture aging treatment at a relative humidity of 95% and a temperature of 75℃ for 2000h. After recovery at room temperature, the notched impact strength was measured and the impact strength retention rate was calculated. (5) The surface resistivity of each example and comparative sample was measured according to ASTM D257. The experimental data are shown in the table below.
[0034] Conclusion: As shown in the table above, Comparative Example 1, which uses dihydroxy-terminated silicone oil to replace the silicone-based modifier, suffers from reduced rigidity and significantly decreased thermal stability due to the lack of a rigid benzene ring and five-membered ring structure provided by N-phenylmaleimide. Its performance deteriorates severely under long-term humid and hot conditions. Comparative Example 2, which modifies titanium dioxide using only 3-(2,3-epoxypropoxy)propyltrimethoxysilane without grafting an aromatic ring-containing diamine, exhibits reduced dispersibility and lacks a synergistic UV-resistant structure, resulting in decreased UV aging resistance. Furthermore, the absence of a quaternary ammonium salt structure prevents the construction of a quaternary ammonium salt structure. The surface ion-conducting pathways increase surface resistivity. In Comparative Example 3, a short-chain alkyl quaternary ammonium salt with 6 carbon atoms was used, which reduced the barrier performance against moisture. Due to the short chain segments, it was difficult to form ion-conducting pathways on the surface, resulting in increased surface resistivity and reduced antistatic performance. In Comparative Example 4, a single pressure reduction method was used at 230~240℃. The phenol was removed too aggressively, and the viscosity of the system increased sharply. This resulted in uneven and incomplete hydroxyl reaction, leading to a lower molecular weight and a wider molecular weight distribution of the synthesized polycarbonate. The yield strength was greatly reduced, and the impact resistance was significantly decreased.
[0035] In summary, this invention uses polycarbonate prepared by introducing a silicon-based modifier into the isosorbide-based polycarbonate melt transesterification-condensation system as the matrix. By adding modified titanium dioxide, the waterproof and aging-resistant properties of the carrier material are significantly improved, while also exhibiting excellent mechanical properties and antistatic properties.
[0036] Finally, it should be noted that the above descriptions are merely preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.
Claims
1. A method for preparing a waterproof and aging-resistant carrier tape material, characterized in that: Includes the following steps: Polycarbonate, acrylonitrile-butadiene-styrene resin, methyl methacrylate-butadiene-styrene resin, modified titanium dioxide, and additives are blended and then melt-extruded and granulated to obtain a waterproof and aging-resistant carrier material. The polycarbonate includes a silicon-containing isosorbide-based polycarbonate, which is prepared by copolymerizing diphenyl carbonate, isosorbide, and 1,4-cyclohexanediethanol in a melt transesterification-condensation system with the addition of a silicon-based modifier.
2. The method for preparing a waterproof and aging-resistant carrier tape material according to claim 1, characterized in that: The waterproof and aging-resistant carrier material comprises the following raw materials, by weight: 100 parts polycarbonate, 20-25 parts acrylonitrile-butadiene-styrene resin, 3-5 parts methyl methacrylate-butadiene-styrene resin, 10-18 parts modified titanium dioxide, and 2-2.5 parts additives.
3. The method for preparing a waterproof and aging-resistant carrier tape material according to claim 1, characterized in that: The preparation method of the silicon-containing isosorbide-based polycarbonate includes the following steps: under a nitrogen atmosphere, diphenyl carbonate, isosorbide, 1,4-cyclohexanediethanol, silicon-based modifier, and sodium hydroxide are mixed evenly, heated and stirred to react, and purified to obtain silicon-containing isosorbide-based polycarbonate.
4. The method for preparing a waterproof and aging-resistant carrier tape material according to claim 3, characterized in that: The raw materials for the silicon-containing isosorbide-based polycarbonate include diphenyl carbonate, isosorbide, and 1,4-cyclohexanediethanol in a mass ratio of 14.5~15.5:9~9.5:1; the sodium hydroxide accounts for 2~3 ppm of the total diol mass.
5. The method for preparing a waterproof and aging-resistant carrier tape material according to claim 3, characterized in that: The silicon-based modifier accounts for 5-10 wt% of the total mass of the raw materials; The preparation method of the silicon-based modifier includes the following steps: (1) N-phenylmaleimide is added to anhydrous ethanol and stirred evenly, heated to 80~85℃, 4,4'-diaminodiphenylmethane-ethanol solution is added dropwise, the dropwise addition time is controlled to be 1~2h, the reaction is stirred for 12~18h, the precipitate is washed with ethanol, filtered, dried, and diamine is obtained; (2) Heat the epoxy-based double-terminated silicone oil to 190~200℃, add diamine in batches and stir for 40~60 min to obtain a silicon-based modifier.
6. The method for preparing a waterproof and aging-resistant carrier tape material according to claim 5, characterized in that: The raw materials for the diamine include N-phenylmaleimide and 4,4'-diaminodiphenylmethane in a mass ratio of 10:3.5~4. The raw materials for the silicon-based modifier include epoxy-based double-terminated silicone oil and diamine in a mass ratio of 4.5 to 5:
1.
7. The method for preparing a waterproof and aging-resistant carrier tape material according to claim 3, characterized in that: The heating and stirring reaction process specifically includes the following steps: first, stirring the reaction at 160~170℃ for 30~40 minutes, then raising the temperature to 180~190℃ and stirring the reaction for 40~60 minutes, then further raising the temperature to 230~240℃ and reducing the pressure to 12~16 kPa, stirring the reaction for 30~40 minutes, then reducing the pressure to 4~8 kPa, stirring the reaction for 10~15 minutes, then raising the temperature to 240~250℃ and reducing the pressure to 1~2 kPa, stirring the reaction for 5~10 minutes, and finally evacuating to 60~80 Pa and holding at that temperature for 5~10 minutes.
8. The method for preparing a waterproof and aging-resistant carrier tape material according to claim 1, characterized in that: The preparation method of the modified titanium dioxide includes the following steps: (1) alkyl dimethyl tertiary amine and epichlorohydrin are mixed evenly under a nitrogen atmosphere, stirred and reacted at 80~85℃ for 1~1.5h, and then distilled under reduced pressure to obtain alkyl quaternary ammonium salt; (2) Under a nitrogen atmosphere, epoxy-modified titanium dioxide and diamine were added to N,N-dimethylformamide and ultrasonically dispersed evenly. The mixture was stirred at 130~140℃ for 6~8h. Alkyl quaternary ammonium salt was added and the mixture was stirred for another 10~12h. The mixture was then filtered, washed, and dried to obtain modified titanium dioxide.
9. The method for preparing a waterproof and aging-resistant carrier tape material according to claim 8, characterized in that: The raw materials for the alkyl quaternary ammonium salt include alkyl dimethyl tertiary amine and epichlorohydrin in a molar ratio of 1:2.5~3; The epoxy-modified titanium dioxide is obtained by treating nano-titanium dioxide with 3-(2,3-epoxypropoxy)propyltrimethoxysilane; The raw materials for the modified titanium dioxide include epoxy-modified titanium dioxide, diamine, and alkyl quaternary ammonium salt in a mass ratio of 10:2.1~2.3:1.2~1.
4.
10. The waterproof and aging-resistant carrier material prepared by the method for preparing a waterproof and aging-resistant carrier material according to any one of claims 1 to 9.