A transparent IC tube with permanent protective plastic material and its preparation method

Abstract

This invention relates to the field of polymer materials technology, and discloses a transparent IC tube permanent antistatic plastic material and its preparation method. The plastic material is made from the following components in parts by weight: 10-16 parts of polyether-grafted antistatic masterbatch, 66-80 parts of general-purpose polystyrene resin, and 10-18 parts of styrene-butadiene block copolymer. The polyether-grafted antistatic masterbatch is prepared from a styrene-maleic anhydride random copolymer, an amino-terminated polyether, a polyether ester amide block copolymer, and a composite thermal stability inhibitor. In preparation, the above components are premixed, melt-extruded, formed through a die, cooled and shaped, and then traction-cut to obtain the finished product. This invention improves the dispersion of the antistatic phase in the polystyrene matrix by forming a polyether-grafted styrene copolymer through a ring-opening amidation reaction, forming a bulk electrostatic dissipation structure; and improves low-temperature impact resistance through the styrene-butadiene block copolymer.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, specifically to a transparent IC tube permanent plastic material and its preparation method. Background Technology

[0002] Integrated circuits are highly sensitive to electrostatic discharge (ESD) during production, transportation, and storage. Therefore, the IC tubes used in their outer packaging need to have stable anti-ESD properties to prevent ESD from damaging the internal electronic components. At the same time, to facilitate automated identification on the production line and manual visual inspection, the IC tube material is typically required to maintain high optical transparency and a certain level of physical impact resistance.

[0003] Conventional transparent IC tubes typically achieve their antistatic effect by coating or impregnating the surface of a low-molecular-weight antistatic agent after molding a base resin such as polystyrene. While this surface treatment process is simple, the antistatic layer adhering to the material surface gradually peels off and is lost during use due to friction between tubes, collisions during handling, alcohol wiping, or routine cleaning. As the surface antistatic agent is consumed, its antistatic effectiveness decreases, making it difficult to maintain stable electrostatic protection over a long service life. Furthermore, the low-molecular-weight antistatic agent may migrate or precipitate on the material surface, affecting the surface cleanliness of the IC tube and its stability during subsequent packaging and use.

[0004] To overcome the issue of easy failure in surface coating methods, the industry has attempted to use an internal blending approach, directly adding polyether, amide, or polyether ester amide polymeric antistatic components to a transparent matrix resin. These antistatic components can provide electrostatic dissipation within the bulk phase of the material, exhibiting better abrasion resistance compared to surface-coated antistatic agents. However, general-purpose polystyrene resin is a hydrophobic, non-polar resin, while polyether antistatic components typically have strong polarity. During melt blending, insufficient interfacial compatibility between the two leads to phase separation and localized enrichment. Increased antistatic phase dispersion size increases the interfacial refractive index difference within the material, causing light scattering and resulting in increased haze and decreased light transmittance in the pipe.

[0005] Meanwhile, when the antistatic component is unevenly dispersed in the polystyrene matrix, localized enrichment areas are prone to forming structural defects or stress concentration points. Under low-temperature impact conditions, this may promote crack propagation, reducing the low-temperature impact resistance of the transparent IC tube. On the other hand, if a low-molecular-weight hygroscopic antistatic agent is used, its antistatic effect is easily affected by ambient humidity. In low-humidity environments, its static dissipation capacity is reduced, and low-molecular-weight components still have the problem of migration, precipitation, or removal by wiping during long-term use.

[0006] Therefore, this invention proposes a transparent IC tube with a permanent plastic material and its preparation method to overcome the shortcomings of the prior art. Summary of the Invention

[0007] To address the shortcomings of existing technologies, this invention provides a transparent IC tube with a permanent antistatic plastic material and its preparation method. This solves the problems of existing transparent IC tubes where the surface coating with antistatic agent is prone to peeling and failure, and where direct blending of water-based conductive polymers is prone to agglomeration due to poor compatibility and moisture evaporation, resulting in processing defects and a decrease in material transparency and mechanical properties.

[0008] Firstly, to achieve the above objectives; This invention is achieved through the following technical solution: a transparent IC tube with a permanently protective plastic material, wherein the plastic material is made of components comprising the following parts by weight: 10-16 parts of polyether-grafted antistatic masterbatch; 66-80 parts of general-purpose polystyrene resin; 10-18 parts of styrene-butadiene block copolymer; The polyether-grafted antistatic masterbatch is prepared from raw materials comprising the following parts by weight: 60-85 parts of styrene-maleic anhydride random copolymer; 15-35 parts of amino-terminated polyether; 20-45 parts of polyether ester amide block copolymer; 1.0 to 2.0 parts of compound heat stability inhibitor.

[0009] General-purpose polystyrene resin serves as the transparent continuous phase, polyether-grafted antistatic masterbatch as the internally added electrostatic dissipative component, and styrene-butadiene block copolymer as the low-temperature toughening component. During melt blending, these three components form a composite system with polystyrene as the main body and the antistatic and elastic phases synergistically dispersed, which helps to improve antistatic stability and low-temperature impact resistance while maintaining transparency.

[0010] In the polyether-grafted antistatic masterbatch, the styrene-maleic anhydride random copolymer contains both styrene and maleic anhydride structural units. The styrene structural units have a similar molecular structure to general-purpose polystyrene resin, which facilitates the integration of the masterbatch into the continuous polystyrene phase during subsequent blending. The maleic anhydride structural units can undergo ring-opening amidation with terminal amino polyethers, allowing polyether segments to be grafted onto the styrene-maleic anhydride random copolymer molecular chains. This grafted product contains both styrene and polyether segments, with the styrene segments leaning towards the polystyrene phase and the polyether segments leaning towards the polyether ester amide block copolymer phase. This acts as an interfacial transition between the two phase regions, reducing the coarsening tendency of the antistatic phase in the polystyrene matrix.

[0011] Polyether-grafted styrene copolymers can also improve the dispersion of polyether ester amide block copolymers in a polystyrene matrix, reducing light scattering caused by increased phase size and interfacial refractive index differences, allowing the material to maintain high transmittance and low haze even after the introduction of antistatic components. In styrene-butadiene block copolymers, the styrene segments are compatible with the polystyrene matrix, and the butadiene segments form an elastic dispersed phase. Under low-temperature impact conditions, the elastic dispersed phase can induce crazes and shear bands in the matrix, absorbing some of the impact energy, thereby reducing the risk of brittle fracture of the pipe during low-temperature transportation and use.

[0012] Therefore, this invention, through the combination of polyether-grafted antistatic masterbatch, general-purpose polystyrene resin and styrene-butadiene block copolymer, enables transparent IC tube materials to form a bulk electrostatic dissipation structure without surface antistatic liquid immersion or coating treatment, while taking into account transparency and low-temperature impact resistance.

[0013] The terminal amino polyether has a number average molecular weight of 1000-2000 g / mol, each molecule contains at least one terminal amino group, and the water content is ≤0.2 wt%.

[0014] The terminal amino groups in amino-terminated polyethers provide reaction sites for ring-opening amidation reactions, while the polyether segments provide polar segmental structures for subsequent electrostatic dissipation microregions. With a number-average molecular weight of 1000–2000 g / mol, amino-terminated polyethers possess suitable segment lengths, allowing them to participate in grafting reactions without compromising compatibility with the antistatic phase due to excessively short segments, nor increasing the system's phase separation tendency due to excessively long segments. A moisture content ≤0.2 wt% helps reduce moisture evaporation during melt reactions and subsequent extrusion processing, lowering the likelihood of defects such as bubbles and micropores.

[0015] The polyether ester amide block copolymer is a block copolymer containing polyether segments and amide segments, wherein the mass fraction of the polyether segments is 40wt% to 60wt%.

[0016] Polyether segments provide a polar electrostatic dissipation structure for the material, while amide segments enhance the interaction between polymer segments and improve thermal stability. When the polyether segment mass fraction is 40wt%–60wt%, the polyether ester amide block copolymer achieves a suitable balance between antistatic properties and processing compatibility. When the polyether segment content is too low, bulk electrostatic dissipation pathways are difficult to form; when the polyether segment content is too high, the compatibility between the antistatic phase and the polystyrene matrix decreases, and the material's haze may increase. Adopting the above range is beneficial for obtaining stable antistatic properties while maintaining transparency.

[0017] The composite heat stability inhibitor is composed of antioxidant 626 and antioxidant DLTP in a mass ratio of 1:1.

[0018] Antioxidant 626 can decompose peroxides during the melt processing stage, reducing the risk of thermo-oxidative degradation of the polystyrene matrix and styrene-butadiene block copolymer; antioxidant DLTP can continue to inhibit oxidation reactions during subsequent processing and hot air aging. When the two are compounded in a 1:1 mass ratio, the yellowing tendency of the material during extrusion molding and thermal aging can be reduced, which is beneficial to maintaining the optical stability of transparent IC tube materials.

[0019] Secondly, this invention provides a method for preparing a transparent IC tube with a permanently resistant plastic material, comprising the following steps: S1. Premixing: High-concentration antistatic masterbatch, general-purpose polystyrene resin and styrene-butadiene block copolymer are added to a high-speed mixer and mixed to obtain a premix; S2. Melt extrusion: The premixed material is fed into a co-rotating twin-screw extruder for melt extrusion, and the material is extruded through a die to form a melt. S3. Cooling and Shaping: The melt is placed in a shaping water tank for cooling and shaping. After being pulled and cut, the transparent IC tube permanent plastic material is obtained.

[0020] Polyether-grafted antistatic masterbatch, general-purpose polystyrene resin, and styrene-butadiene block copolymer are first mixed at high speed to ensure macroscopic distribution of the different particulate materials before entering the extruder. In a co-rotating twin-screw extruder, the materials undergo heating, plasticizing, shearing, mixing, and conveying extrusion processes, gradually dispersing the polyether-grafted antistatic masterbatch into the continuous polystyrene phase. The polyether ester amide block copolymer is distributed within the matrix under the interfacial compatibility of the graft copolymer, forming bulk electrostatic dissipation micro-regions. The styrene-butadiene block copolymer forms an elastic dispersed phase within the polystyrene matrix, improving the material's energy dissipation capacity under low-temperature impact conditions. After extrusion through a die, the melt enters a cooling bath. The cooling process restricts the continued migration and coarsening of the antistatic and elastic phases in a highly elastic state, maintaining a relatively stable internal phase structure in the extruded pipe, thus balancing antistatic stability, transparency, and low-temperature mechanical properties.

[0021] In step S2, the length-to-diameter ratio of the co-rotating twin-screw extruder is 36:1 to 40:1; the temperature of each zone of the twin-screw extruder is set as follows: zone 1 165 to 175°C, zone 2 185 to 195°C, zone 3 200 to 210°C, and die 195 to 205°C; the screw speed is set to 150 to 250 rpm.

[0022] Co-rotating twin-screw extruders with aspect ratios of 36:1 to 40:1 provide relatively sufficient melting, mixing, and dispersion distances for materials. Maintaining a zone temperature of 165–175°C in the first zone helps reduce bridging or feeding fluctuations caused by premature melting of materials in the feeding section. The temperatures in zones two and three gradually increase, allowing general-purpose polystyrene resin, polyether-grafted antistatic masterbatch, and styrene-butadiene block copolymers to gradually plasticize and form a homogeneous melt. Maintaining a die temperature of 195–205°C helps maintain melt flowability and extrusion stability. At screw speeds of 150–250 rpm, the system achieves moderate shear, further dispersing the antistatic and elastic phases while reducing the risk of chain segment degradation and yellowing caused by excessive shear.

[0023] In step S1, the mixing time at room temperature is 5 to 10 minutes; in step S3, the shaping water tank is a vacuum shaping water tank.

[0024] Mixing at room temperature for 5–10 minutes allows the polyether-grafted antistatic masterbatch, general-purpose polystyrene resin, and styrene-butadiene block copolymer to form a more uniform macroscopic distribution before entering the extruder, reducing component fluctuations during extrusion. The vacuum setting water bath allows the extruded melt to adhere to the shaped structure and cool under negative pressure, which helps improve the dimensional stability of the pipe and reduces defects such as surface air bubbles, collapse, and uneven shrinkage. For transparent IC tube materials, this setting method also helps maintain the smoothness and gloss of the tube wall surface.

[0025] The high-concentration antistatic reaction masterbatch is prepared in advance through the following steps: Styrene-maleic anhydride random copolymer, polyethylene glycol and xylene were added to a nitrogen-purified reactor, and the mixture was heated and stirred at a constant temperature to form a homogeneous solution. After adding anhydrous zinc acetate and stirring at a constant temperature, the system temperature is maintained and poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid aqueous dispersion is added dropwise to the reactor. During the dropwise addition, the water in the system forms an azeotrope with xylene and evaporates to the water separator for liquid-liquid separation. The bottom aqueous phase is drained and the upper xylene phase is completely refluxed back into the reactor until no water phase is separated out. Close the xylene reflux line, heat the reactor and remove most of the xylene solvent by atmospheric distillation, then turn on the vacuum preparation to reduce the pressure inside the reactor to negative pressure, and maintain the temperature and pressure at this temperature and pressure for the reaction. The vacuum was broken and nitrogen gas was introduced to restore normal pressure. After the reactor was cooled, a composite thermal stability inhibitor was added, and the mixture was stirred and mixed. The melt was then extruded, granulated, and dried.

[0026] The polyether-grafted antistatic masterbatch is not obtained by simple physical mixing of the components. Instead, it first forms a polyether-grafted styrene copolymer in the molten state, and then uses this grafting product to pre-disperse the polyether ester amide block copolymer. This process completes the graft compatibility and antistatic phase dispersion at the masterbatch stage, which reduces the large-scale phase separation caused by the direct entry of the polyether ester amide block copolymer into the non-polar matrix when blended with polystyrene resin in the later stage.

[0027] When the amino group in the amino-terminated polyether comes into contact with the maleic anhydride structural unit, the amino group undergoes nucleophilic attack on the carbonyl group of the anhydride, opening the anhydride ring and generating a grafted structure containing amide bonds and carboxyl groups. In the resulting polyether-grafted styrene copolymer, the styrene segments are biased towards the polystyrene phase, while the polyether segments are biased towards the polyether ester amide phase. After the addition of the polyether ester amide block copolymer, the graft copolymer can be distributed at the interface between different phase regions, reducing interfacial incompatibility between phase regions and allowing the antistatic phase to form a finer dispersion structure in the masterbatch. When this masterbatch is subsequently blended with general-purpose polystyrene resin, the antistatic phase can disperse into the polystyrene matrix along with the masterbatch, providing a basis for the formation of bulk electrostatic dissipation pathways.

[0028] Preferably, the styrene-maleic anhydride random copolymer and the amino-terminated polyether are mixed in the molten state for 20-60 min; after adding the polyether ester amide block copolymer, the mixture is further molten and mixed for 10-30 min.

[0029] Mixing the styrene-maleic anhydride random copolymer with the amino-terminated polyether in the molten state for 20–60 min allows the anhydride groups to fully contact the amino-terminated polyether and undergo a ring-opening amidation reaction. If the mixing time is too short, the grafting reaction is insufficient, weakening the subsequent compatibility with the polyether ester amide block copolymer; if the mixing time is too long, the system's residence time at high temperatures increases, potentially raising the risk of thermo-oxidative degradation and color changes. Continuing to mix for 10–30 min after adding the polyether ester amide block copolymer further disperses the antistatic component in the graft copolymer, reducing the possibility of localized enrichment.

[0030] Preferably, during the vacuum devolatilization process, the pressure inside the internal mixer is reduced to -0.08 to -0.095 MPa, and the vacuum devolatilization time is 20 to 60 minutes; the composite heat stability inhibitor is added after the temperature inside the internal mixer drops to 135 to 145°C, and then stirred for 10 to 20 minutes after addition.

[0031] Vacuum devolatilization under gauge pressure of -0.08 to -0.095 MPa allows low-molecular-weight volatiles and trace byproducts to be removed from the system, reducing bubbles, fogging, and surface defects during subsequent extrusion molding. The vacuum devolatilization time is controlled between 20 and 60 minutes to meet the devolatilization requirements while preventing the material from remaining under high temperature and negative pressure for too long. The composite heat stability inhibitor is added at 135–145°C to reduce its loss during the high-temperature vacuum stage and ensure its effectiveness in masterbatch discharge, granulation, and subsequent secondary melting processing. Stirring and mixing for 10–20 minutes after addition ensures uniform distribution of the antioxidant in the masterbatch system, contributing to improved color stability during material processing and aging.

[0032] This invention provides a transparent IC tube with a permanently protective plastic material and its preparation method. It has the following beneficial effects: 1. This invention utilizes a compounding process of polyether-grafted antistatic masterbatch, general-purpose polystyrene resin, and styrene-butadiene block copolymer to form a bulk electrostatic dissipation structure within the polystyrene matrix. This structure does not rely on surface coating or immersion to form an antistatic layer, and maintains a relatively stable surface resistivity after friction or alcohol wiping, thereby improving the problem of easy detachment and failure of surface-type antistatic agents. Simultaneously, the styrene-butadiene block copolymer forms an elastic dispersed phase within the matrix, which is beneficial for improving the low-temperature impact resistance of transparent IC tube materials. 2. In the preparation stage of the polyether-grafted antistatic masterbatch, this invention involves a ring-opening amidation reaction between a styrene-maleic anhydride random copolymer and an amino-terminated polyether to form a grafted copolymer containing styrene segments and polyether segments. This grafted structure improves the compatibility between the polyether ester amide block copolymer and the polystyrene matrix, reduces large-scale phase separation of the antistatic phase, lowers material haze, and facilitates the formation of continuous or semi-continuous bulk electrostatic dissipation pathways. 3. This invention reduces the risk of thermo-oxidative degradation and yellowing of materials during melt processing and hot air aging by compounding antioxidant 626 and antioxidant DLTP in equal proportions. Combined with a vacuum forming water bath for cooling and shaping, it helps control the dimensional stability of the tube, reduces surface defects such as air bubbles, collapse, and uneven shrinkage, and maintains the appearance quality and optical stability of the transparent IC tube material. Attached Figure Description

[0033] Figure 1 The Fourier transform infrared spectrum curves of each test sample of the present invention are shown below. Figure 2 This is a comparison diagram of the shift and shape changes of the characteristic Raman spectra of the present invention; Figure 3 The above is a comparison chart of thermogravimetric analysis and differential thermogravimetric analysis of the present invention, wherein (a) is a thermogravimetric curve during the heating process, and (b) is a differential thermogravimetric curve corresponding to the thermogravimetric curve. Figure 4 The optical performance distribution comparison diagram of the present invention is shown in (a) and (b) is the scatter plot of transmittance test data of each sample. Figure 5 This is a comparison chart of surface resistivity tests according to the present invention; Figure 6 This is a colorimetric comparison diagram of the thermo-oxidative aging resistance of various test samples in this invention. Detailed Implementation

[0034] The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. 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.

[0035] The main raw materials and reagents used in the following examples and comparative examples have the following sources and specifications. Reagents not specifically mentioned are all commercially available analytical grade or higher grade products.

[0036] The main raw materials and reagents used in the following examples and comparative examples have the following sources and specifications. Unless otherwise specified, all raw materials are commercially available industrial grade or higher products.

[0037] Styrene-maleic anhydride random copolymer, CAS number 9011-16-9, wherein the mass fraction of maleic anhydride monomer unit is 15wt% and the weight average molecular weight Mw is 100000g / mol.

[0038] Amino-terminated polyethers with a number average molecular weight of 1000–2000 g / mol, each molecule containing at least one amino terminus, and a water content ≤0.2 wt%.

[0039] The polyether ester amide copolymer antistatic agent is a block copolymer containing polyether and amide segments, wherein the mass fraction of the polyether segments is 40wt% to 60wt%, the melt flow rate is 5.0 g / 10 min to 15.0 g / 10 min, and the volume resistivity is 10 Ω·cm. 7 Ω·cm~10 9 Ω·cm.

[0040] Bis(2,4-di-tert-butylphenyl) pentaerythritol diester, commonly known as antioxidant 626, has the CAS number 26741-53-7.

[0041] Dilaurate thiodipropionate, commonly known as antioxidant DLTP, has the CAS number 123-28-4.

[0042] General-purpose polystyrene resin, CAS No. 9003-53-6, with a light transmittance ≥90%, and a melt mass flow rate of 2.5 g / 10 min to 5.0 g / 10 min under 200℃ and 5 kg load conditions.

[0043] Styrene-butadiene block copolymer, CAS No. 9003-55-8, wherein the mass fraction of butadiene block is 25wt% to 30wt%, and the light transmittance is ≥88%.

[0044] Preparation Example 1: This preparation example provides a method for preparing a polyether-grafted antistatic masterbatch, comprising the following steps: The internal mixer, after being purged with nitrogen, is heated to 160°C. 75 parts by weight of styrene-maleic anhydride random copolymer and 25 parts by weight of terminal amino polyether are added to the internal mixer. Stirring is started, and the materials are mixed in a molten state for 40 minutes. This allows the anhydride groups in the styrene-maleic anhydride random copolymer to undergo a ring-opening amidation reaction with the amino groups in the terminal amino polyether, forming a polyether-grafted styrene copolymer.

[0045] Subsequently, 30 parts by weight of polyether ester amide block copolymer were added to the internal mixer and the mixture was melt-mixed for 20 minutes to uniformly disperse the polyether ester amide block copolymer in the polyether grafted styrene copolymer and form stable bulk electrostatic dissipation micro-regions through the polar interaction and chain entanglement between polyether segments.

[0046] Turn on the vacuum equipment and reduce the pressure inside the internal mixer to -0.09 MPa (gauge pressure). Vacuum de-devour at 160°C for 40 minutes to remove low-molecular-weight volatiles and trace byproducts generated during the reaction.

[0047] The vacuum was removed and nitrogen was introduced to restore normal pressure. The temperature inside the internal mixer was lowered to 140°C. 1.5 parts by weight of a composite heat stability inhibitor (composed of antioxidant 626 and antioxidant DLTP in a 1:1 mass ratio) was added, and the mixture was stirred for 15 minutes. The melt was extruded, cooled, pelletized, and dried to obtain polyether-grafted antistatic masterbatch.

[0048] Preparation Example 2: This preparation example provides a method for preparing a polyether-grafted permanent antistatic masterbatch, comprising the following steps: The internal mixer, after being purged with nitrogen, is heated to 150°C. 60 parts by weight of styrene-maleic anhydride random copolymer and 15 parts by weight of terminal amino polyether are added to the internal mixer. Stirring is started, and the materials are mixed in a molten state for 20 minutes. This allows the anhydride groups in the styrene-maleic anhydride random copolymer to undergo a ring-opening amidation reaction with the amino groups in the terminal amino polyether, forming a polyether-grafted styrene copolymer.

[0049] Subsequently, 20 parts by weight of polyether ester amide block copolymer were added to the internal mixer and melt-mixed for 10 minutes to disperse the polyether ester amide block copolymer in the polyether grafted styrene copolymer and form an internal electrostatic dissipative structure in the subsequent polystyrene matrix.

[0050] Turn on the vacuum equipment and reduce the pressure inside the internal mixer to -0.08 MPa (gauge pressure). Vacuum de-devour at 150°C for 20 minutes to remove low-molecular-weight volatiles from the system.

[0051] The vacuum was removed and nitrogen gas was introduced to restore normal pressure. The temperature inside the internal mixer was lowered to 135°C. 1.0 part by weight of a composite heat stability inhibitor (composed of antioxidant 626 and antioxidant DLTP in a 1:1 mass ratio) was added, and the mixture was stirred for 10 minutes. The melt was extruded, cooled, pelletized, and dried to obtain polyether-grafted antistatic masterbatch.

[0052] Preparation Example 3: This preparation example provides a method for preparing a polyether-grafted antistatic masterbatch, including the following steps: The internal mixer, after being purged with nitrogen, is heated to 175°C. 85 parts by weight of styrene-maleic anhydride random copolymer and 35 parts by weight of terminal amino polyether are added to the internal mixer. Stirring is started, and the materials are mixed in a molten state for 60 minutes. This allows the anhydride groups in the styrene-maleic anhydride random copolymer to undergo a ring-opening amidation reaction with the amino groups in the terminal amino polyether, forming a polyether-grafted styrene copolymer.

[0053] Subsequently, 45 parts by weight of polyether ester amide block copolymer were added to the internal mixer and the mixture was melt-mixed for 30 minutes to fully disperse the polyether ester amide block copolymer in the polyether grafted styrene copolymer and form a stable polymeric antistatic phase.

[0054] Vacuum preparation was initiated, and the pressure inside the internal mixer was reduced to the gauge pressure of -0.095 MPa. Vacuum de-devouring was carried out at 175°C for 60 minutes to remove low-molecular-weight volatiles from the system and improve the processing stability of the masterbatch.

[0055] The vacuum was removed and nitrogen was introduced to restore normal pressure. The temperature inside the internal mixer was lowered to 145°C. 2.0 parts by weight of a composite heat stability inhibitor (composed of antioxidant 626 and antioxidant DLTP in a 1:1 mass ratio) were added, and the mixture was stirred for 20 minutes. The melt was extruded, cooled, pelletized, and dried to obtain polyether-grafted antistatic masterbatch.

[0056] Example 1: This example provides a method for preparing a transparent IC tube with a permanently resistant plastic material, including the following steps: 15 parts by weight of the polyether-grafted antistatic masterbatch prepared in Preparation Example 1, 70 parts by weight of general-purpose polystyrene resin and 15 parts by weight of styrene-butadiene block copolymer were added to a high-speed mixer and mixed at room temperature for 8 minutes to obtain a premix.

[0057] The premixed material is fed into a co-rotating twin-screw extruder with a length-to-diameter ratio of 40:1 for melt extrusion. The temperature of each zone of the extruder is set as follows: Zone 1 170℃, Zone 2 190℃, Zone 3 205℃, Die 200℃, and the screw speed is set to 200 rpm.

[0058] After the melt is extruded through a die, it enters a vacuum shaping water bath for cooling and shaping. After being pulled and cut, a transparent IC tube permanent plastic material is obtained.

[0059] Example 2: This example provides a method for preparing a transparent IC tube with a permanently resistant plastic material, including the following steps: Ten parts by weight of the polyether-grafted antistatic masterbatch prepared in Preparation Example 2, 80 parts by weight of general-purpose polystyrene resin, and 10 parts by weight of styrene-butadiene block copolymer were added to a high-speed mixer and mixed at room temperature for 5 minutes to obtain a premix.

[0060] The premixed material is fed into a co-rotating twin-screw extruder with a length-to-diameter ratio of 36:1 for melt extrusion. The temperature of each zone of the extruder is set as follows: Zone 1 165℃, Zone 2 185℃, Zone 3 200℃, Die 195℃, and the screw speed is set to 150 rpm.

[0061] After the melt is extruded through a die, it enters a vacuum shaping water bath for cooling and shaping. After being pulled and cut, a transparent IC tube permanent plastic material is obtained.

[0062] Example 3: This example provides a method for preparing a transparent IC tube with a permanently resistant plastic material, including the following steps: 16 parts by weight of the polyether-grafted antistatic masterbatch prepared in Preparation Example 3, 66 parts by weight of general-purpose polystyrene resin, and 18 parts by weight of styrene-butadiene block copolymer were added to a high-speed mixer and mixed at room temperature for 10 minutes to obtain a premix.

[0063] The premixed material is fed into a co-rotating twin-screw extruder with a length-to-diameter ratio of 40:1 for melt extrusion. The temperature of each zone of the extruder is set as follows: Zone 1 175℃, Zone 2 195℃, Zone 3 210℃, Die 205℃, and the screw speed is set to 250 rpm.

[0064] After the melt is extruded through a die, it enters a vacuum shaping water bath for cooling and shaping. After being pulled and cut, a transparent IC tube permanent plastic material is obtained.

[0065] Comparative Example 1: Compared with Example 1, the difference is that in the preparation process of the polyether grafted antistatic masterbatch, no terminal amino polyether is added, the amount of styrene-maleic anhydride random copolymer is adjusted to 100 parts by weight, and then 30 parts by weight of polyether ester amide block copolymer is added for melt mixing. The remaining masterbatch preparation conditions, raw material amounts and subsequent extrusion molding processes are the same as in Example 1.

[0066] Comparative Example 2: Compared with Example 1, the difference is that instead of preparing polyether-grafted antistatic masterbatch, the styrene-maleic anhydride random copolymer, amino-terminated polyether, polyether ester amide block copolymer and composite heat stability inhibitor in the application amount of Preparation Example 1 are directly added to a high-speed mixer for premixing with general-purpose polystyrene resin and styrene-butadiene block copolymer, and then directly melt extruded. All other process conditions are the same as in Example 1.

[0067] Comparative Example 3: Compared with Example 1, the difference is that no polyether ester amide block copolymer is added during the preparation of the polyether grafted antistatic masterbatch, while the other masterbatch preparation conditions and subsequent extrusion molding process are the same as in Example 1.

[0068] Comparative Example 4: Compared with Example 1, the difference is that styrene-butadiene block copolymer is not added in the premixing stage, and the amount of general-purpose polystyrene resin added is adjusted to 85 parts by weight, while the rest are the same.

[0069] Comparative Example 5: Compared with Example 1, the difference is that polyether-grafted antistatic masterbatch is not used. Instead, an equal amount of low-molecular-weight surface-type antistatic agent is used to replace the polyether-grafted antistatic masterbatch. It is then directly added to a high-speed mixer for premixing with general-purpose polystyrene resin and styrene-butadiene block copolymer, followed by melt extrusion. The remaining raw material amounts and process conditions are the same as in Example 1.

[0070] Test Example 1: This test example aims to verify the ring-opening amidation grafting reaction between the styrene-maleic anhydride random copolymer and the terminal amino polyether in this invention by Fourier transform infrared spectroscopy.

[0071] The experimental steps are as follows: The following samples were used as test samples: pure styrene-maleic anhydride random copolymer raw material, pure amino-terminated polyether raw material, polyether-grafted styrene copolymer intermediate prepared in Example 1 before the addition of polyether ester amide block copolymer, and control sample obtained by mechanically mixing styrene-maleic anhydride random copolymer and amino-terminated polyether at room temperature for 5 min in the same proportion as in Example 1.

[0072] Solid test samples are made into thin films with a thickness of about 10 to 20 micrometers using a hot pressing method, while liquid or semi-solid test samples are directly coated onto the surface of potassium bromide salt sheets.

[0073] Turn on the Fourier transform infrared spectrometer and perform optical path calibration. Before testing, collect the air background spectrum and perform baseline subtraction.

[0074] The prepared test sample is fixed on the optical path of the spectrometer.

[0075] The spectrometer's test parameters were set to a scanning range of 4000 cm⁻¹. -1 Up to 400cm -1 Resolution set to 4cm -1 The cumulative number of scans for a single sample is set to 32.

[0076] After the test run is completed, the infrared spectral data of each sample are recorded and output. The characteristic absorption peak of the benzene ring of the styrene structural unit is used as the internal standard peak. After normalizing the characteristic absorption peak of the target region, the corresponding absorbance data is extracted.

[0077] The experimental data are shown in Table 1: .

[0078] in conclusion: According to Table 1 and Figure 1 Data shows that the random copolymer of pure styrene-maleic anhydride is at 1851 cm⁻¹. -1 and 1779cm -1 The characteristic absorption peaks of asymmetric and symmetric carbonyl stretching vibrations of the anhydride group are observed at 3351 cm⁻¹; pure amino-terminated polyethers exhibit characteristic absorption peaks of terminal amino groups or associated NH groups at 3351 cm⁻¹. In the infrared spectrum of the grafting intermediate in Example 1, the characteristic absorption peak at 1849 cm⁻¹ is observed. -1 1 and 1778cm -1 The absorbance of the characteristic peaks of the anhydride at 1658 cm⁻¹ decreased to 0.071 and 0.163, respectively, while at 1658 cm⁻¹... -1 and 1543cm -1 Characteristic absorption peaks of amide I and amide II bands with absorbances of 0.826 and 0.563, respectively, appear at 3347 cm⁻¹. -1 The absorbance of the NH absorption peak at that point decreased to 0.216.

[0079] In contrast, the control sample had a 1850cm diameter. -1 and 1779cm -1 The characteristic peak of the anhydride at 1659 cm⁻¹ still maintains a high absorbance, and at 1659 cm⁻¹ -1 and 1544cm -1Only a weak absorption peak was observed. These results indicate that, under the melt reaction conditions of this invention, the maleic anhydride groups on the main chain of the styrene-maleic anhydride random copolymer underwent a significant ring-opening amidation reaction with the amino groups in the terminal amino polyether, forming a polyether-grafted styrene copolymer; while room-temperature mechanical mixing only exhibited simple physical blending and failed to form a significant chemical grafting structure. This grafting structure is beneficial for the stable dispersion of the subsequent polyether ester amide block copolymer in the polystyrene matrix, thereby improving the bulk antistatic properties and transparency of the material.

[0080] Test Example 2: This test example aims to verify the changes in the local microenvironment of the polyether chain segments and the improvement in the uniformity of antistatic phase dispersion in this invention through Raman spectroscopy, and to analyze its influence on the formation of bulk electrostatic dissipation pathways in combination with the surface resistivity test results.

[0081] The experimental steps are as follows: Pure polyether ester amide block copolymer, the polyether grafted antistatic masterbatch used in Example 1, and the antistatic masterbatch prepared in Comparative Example 1 were used as test objects.

[0082] The pure polyether ester amide block copolymer was calendered into a sheet with a thickness of about 0.5 mm in a flat press; the solid antistatic masterbatches of Example 1 and Comparative Example 1 were calendered into sheets with a thickness of about 0.5 mm in a flat press and fixed onto a glass slide.

[0083] Turn on the Raman spectrometer and preheat it. Select a 785nm wavelength laser to reduce fluorescence background interference during the polymer material testing process.

[0084] Place the glass slide containing the sample on the microscope stage, adjust the focus until the sample surface is clearly imaged, and select a flat area without obvious impurities as the laser application point.

[0085] The spectrometer's test parameters were set to a scanning range of 4000 cm⁻¹. -1 Up to 400cm -1 Resolution set to 4cm -1 The cumulative number of scans for a single sample is set to 32.

[0086] After the test run is completed, the infrared spectral data of each sample are recorded and output. The characteristic absorption peak of the benzene ring of the styrene structural unit is used as the internal standard peak. After normalizing the characteristic absorption peak of the target region, the corresponding absorbance data is extracted.

[0087] The experimental data are shown in Table 2: .

[0088] in conclusion: According to Table 2 and Figure 2According to the data, in the Raman spectrum of the pure polyether ester amide block copolymer, the characteristic peak center position corresponding to the C–O–C symmetric stretching vibration in the polyether segment is located at 1129.4 cm⁻¹. -1 Its half-peak width is 31.6cm. -1 The antistatic masterbatch of Comparative Example 1, without the addition of terminal amino polyethers, has a characteristic peak centered at 1127.8 cm⁻¹. -1 The full width of the half-peak is 28.9cm. -1 The data fluctuations were relatively small. In Example 1, the center position of the corresponding characteristic peak of the antistatic masterbatch shifted to 1121.6 cm⁻¹. -1 Meanwhile, its full width at half maximum (FWHM) decreased to 19.8 cm. -1。

[0089] The shift of the characteristic peak of the C–O–C symmetric stretching vibration of the polyether segments in the Raman spectrum to the lower wavenumber region indicates a change in the local microenvironment of the polyether segments and enhanced inter-segment interactions. The reduction in the full width at half maximum (FWHM) reflects a more concentrated local structural distribution of the polyether phase in the system, indicating a more homogeneous microenvironment. Compared with Comparative Example 1, the polyether-grafted styrene copolymer formed by reacting the styrene-maleic anhydride random copolymer with terminal amino polyether in Example 1 can improve the dispersion uniformity of the polyether ester amide block copolymer in the masterbatch and enhance its interfacial compatibility with the styrene matrix. Combined with the subsequent surface resistivity test results, it can be inferred that this improvement in dispersion uniformity is conducive to the formation of continuous or semi-continuous bulk electrostatic dissipation pathways of the polyether-type electrostatic dissipative phase in the matrix, thereby achieving a stable antistatic effect at a lower addition amount.

[0090] Test Example 3: This test example aims to verify, through thermogravimetric analysis, the role of end-amino polyether grafting compatibility and uniform dispersion of the antistatic phase in improving the thermal oxidation stability of the antistatic masterbatch in the process of this invention.

[0091] The experimental steps are as follows: The polyether-grafted antistatic masterbatch used in Example 1 and the antistatic masterbatch prepared in Comparative Example 1 were taken as test samples, respectively.

[0092] The solid test sample was frozen and embrittled in a liquid nitrogen environment, then crushed and sieved using a mortar and pestle to collect sample powder with uniform particle size.

[0093] Turn on the thermogravimetric analyzer system and stabilize the high-precision microbalance to perform baseline and temperature calibration.

[0094] Weigh out 5.2 to 5.6 mg of each sample powder, spread them evenly at the bottom of the alumina crucible, and transfer them into the heating furnace of the thermogravimetric analyzer.

[0095] The test gas atmosphere inside the heating furnace was set to dry synthetic air to simulate the oxygen-rich environment in thermal processing and actual use, and the gas flow rate was set to 50 mL / min.

[0096] Set the equipment's heating program. The initial test temperature is 30℃. After holding the temperature for 5 minutes, heat it continuously to 600℃ at a constant heating rate of 10℃ / min.

[0097] After the test procedure is completed, the continuous data of the sample mass change with temperature is recorded, the thermogravimetric (TG) curve is output, and its first derivative is calculated to obtain the derivative thermogravimetric (DTG) curve. The corresponding temperature when the mass loss is 5% and the temperature corresponding to the maximum thermal weight loss rate are extracted.

[0098] The experimental data are shown in Table 3: .

[0099] in conclusion: According to Table 3 and Figure 3 The data shows that, compared to Example 1, the antistatic masterbatch experienced a 5% mass loss at 268.7°C, its mass retention decreased to 95.34% at 250°C, and it reached its maximum thermal weight loss rate at 401.2°C. In contrast, the antistatic masterbatch of Example 1 experienced a 5% mass loss at a later temperature of 319.8°C, maintained a mass retention rate of 98.92% at 250°C, and its maximum thermal weight loss rate corresponded to a higher temperature of 423.6°C. This indicates that the antistatic masterbatch of Example 1 has higher thermal stability under thermo-oxidative conditions.

[0100] In Comparative Example 1, due to the absence of terminal amino polyether, there was a lack of effective chemical grafting and interfacial compatibility between the styrene-maleic anhydride random copolymer and the polyether ester amide block copolymer. This resulted in uneven dispersion of the polar phase within the system, numerous local interfacial defects, and increased susceptibility to low-molecular-weight volatilization and segmental thermo-oxidative degradation under heating conditions. Consequently, significant mass loss occurred even at lower temperature ranges. In Example 1, the styrene-maleic anhydride random copolymer underwent a ring-opening amidation reaction with the terminal amino polyether to form a polyether-grafted styrene copolymer. This grafted structure enhanced the interfacial bonding between the polyether ester amide block copolymer and the styrene matrix, and improved the uniformity of the antistatic phase dispersion in the system. This reduced structurally weak areas in the initial stage of thermo-oxidative aging, delayed the thermal decomposition process of the material, and improved the structural stability of the antistatic masterbatch during high-temperature processing and use.

[0101] Test Example 4: This test example aims to verify the effect of the process of the present invention on maintaining the transparency of polystyrene-based internally added antistatic composite materials through optical performance testing.

[0102] The experimental steps are as follows: Transparent IC tube materials prepared by the extrusion molding process corresponding to Examples 1 to 3 and Comparative Examples 1 to 5 were used as test objects.

[0103] To eliminate the interference of the pipe's curved surface on the optical path test, a pipe wall sample of a certain length was placed in a flat vulcanizing machine and hot-pressed for 2 minutes at 190℃ and 5MPa to produce a flat test sample with a thickness of 1.0mm.

[0104] Turn on the haze transmittance tester and preheat it. Perform blank calibration of the instrument against an air background.

[0105] Clean the surface of the test sample with a lint-free cloth and isopropyl alcohol to ensure that there are no fingerprints or dust adhering to it.

[0106] According to the ASTM D1003 standard for testing the transparency of plastics, the sample is fixed vertically in the test window so that the incident light passes perpendicularly through the center of the sample.

[0107] The test program is started, and the instrument automatically integrates and records the total transmitted light flux and scattered light flux through the sample, and extracts the transmittance and haze values ​​of the sample.

[0108] Five different samples were taken from each group of materials for repeated testing, and the average value was calculated as the final optical performance data of that group of materials.

[0109] The experimental data are shown in Table 4: .

[0110] in conclusion: According to Table 4 and Figure 4 The data shows that the light transmittance of Examples 1 to 3 is 88.8% to 90.2% and the haze is 1.9% to 2.5%, indicating that the present invention can still maintain good transparency after introducing an internally added antistatic component.

[0111] Comparative Example 1, without the addition of terminal amino polyether, showed a decrease in transmittance to 83.6% and an increase in haze to 5.8%, indicating that the lack of grafted compatibility structure leads to uneven dispersion of the antistatic phase and increased light scattering. Comparative Example 2, without pre-preparing polyether-grafted antistatic masterbatch, directly physical blended the components, resulting in a decrease in transmittance to 78.4% and an increase in haze to 11.6%, indicating that masterbatch processing is beneficial for improving the uniformity of antistatic phase dispersion in the polystyrene matrix.

[0112] Comparative Example 3, without the addition of polyether ester amide block copolymer, had a transmittance of 91.1% and a haze of 1.6%, but it lacked bulk electrostatic dissipative components. Comparative Example 4, without the addition of styrene-butadiene block copolymer, had a transmittance of 90.4% and a haze of 2.0%, indicating that the toughening component had little impact on transparency. Comparative Example 5, using a low-molecular-weight surface-type antistatic agent instead of polyether-grafted antistatic masterbatch, had a transmittance of 86.7% and a haze of 4.9%, indicating that the low-molecular-weight component was prone to migration or local enrichment, increasing scattering defects in the material.

[0113] In Examples 1 to 3, the styrene-maleic anhydride random copolymer reacts with the amino-terminated polyether to form a polyether-grafted styrene copolymer, which improves the compatibility of the polyether ester amide block copolymer with the polystyrene matrix, keeping the antistatic phase in a finely dispersed state, thereby achieving the internal antistatic function while maintaining high light transmittance and low haze.

[0114] Test Example 5: This test example aims to verify the continuity of the bulk electrostatic dissipation pathway and the long-term stability of the antistatic properties of the composite material system of the present invention through the attenuation test of surface resistivity.

[0115] The experimental steps are as follows: Transparent IC tubing extruded under the process conditions of Examples 1 to 3 and Comparative Examples 1 to 5 was used as the test object.

[0116] The pipe is cut along the axial direction and a 100mm long pipe wall strip is cut. The strip is placed in a flat vulcanizing machine and hot-pressed at 190℃ to obtain a rectangular test sample with uniform thickness.

[0117] The test sample was placed in a standard environmental test chamber with a temperature of 23±2℃ and a relative humidity of 50±5% and allowed to stand for 48 hours to eliminate residual processing stress and allow the material surface to absorb moisture to reach equilibrium.

[0118] Turn on the weighted surface resistivity tester and set the test voltage to 100V. Place the sample flat on the insulating pad, press the two parallel electrode weights of the instrument onto the sample surface, apply the voltage and hold for 60 seconds, then read the stable display value of the instrument and record the initial surface resistivity.

[0119] Remove the sample and fix it on the worktable of the abrasion tester. Wrap the friction head with a standard lint-free cloth and add 2.0 mL of anhydrous ethanol to wet it.

[0120] Adjust the load weight of the testing machine to apply a vertical pressure of 10N to the sample surface with the friction head, set the reciprocating friction frequency to 60 times / min, and continuously wipe and rub the same surface area of ​​the sample 100 times.

[0121] After the wiping process is completed, the sample is removed and placed back in the above-mentioned standard environmental test chamber for 24 hours to allow residual solvent on the surface to evaporate.

[0122] Following the operating procedure in step 4, test again on the area of ​​the sample that has been wiped and rubbed, and record the surface resistivity after wiping. Perform 5 tests on each group of samples and take the logarithmic average.

[0123] The experimental data are shown in Table 5: .

[0124] in conclusion: According to Table 5 and Figure 5 According to the data, the initial surface resistivity of Examples 1 to 3 is 10. 7 With a resistivity on the order of Ω / sq, after 100 cycles of mechanical reciprocating friction with anhydrous ethanol, its surface resistivity remains at 10. 7 The value is on the order of Ω / sq, with no increase across orders of magnitude, indicating that the material of this invention has stable antistatic properties.

[0125] Comparative Example 1, which did not add terminal amino polyethers during the preparation of antistatic masterbatch, showed an initial surface resistivity that increased to 1.62 × 10⁻⁶. 9 Ω / sq, which further increased to 4.83×10 after wiping. 9 The Ω / sq indicates that without a grafted compatible structure, the polyether ester amide block copolymer struggles to form a continuous and effective bulk electrostatic dissipation pathway within the polystyrene matrix. Comparative Example 2 did not pre-prepare a polyether-grafted antistatic masterbatch; instead, it employed a direct physical blending method, achieving an initial surface resistivity of 3.95 × 10⁻⁶. 10 Ω / sq, increased to 7.21×10 after wiping. 10 The value of Ω / sq indicates that it is difficult to achieve uniform dispersion and effective connectivity of the antistatic phase by simply relying on physical blending.

[0126] Comparative Example 3, without the addition of polyether ester amide block copolymer, had an initial surface resistivity of 8.65 × 10⁻⁶. 11 Ω / sq, increased to 1.94×10 after wiping. 12 The Ω / sq indicates that the material essentially lacks antistatic capability when the key electrostatic dissipation component is missing. Comparative Example 4, without the addition of styrene-butadiene block copolymer, has an initial and post-wiping surface resistivity of 2.36 × 10⁻⁶ Ω / sq, respectively. 7 Ω / sq and 3.08×10 7 The Ω / sq value is close to that of Example 1, indicating that the toughening component has little impact on antistatic properties. Comparative Example 5 uses a low-molecular-weight surface-type antistatic agent instead of the polyether-grafted antistatic masterbatch, and its initial surface resistivity is 4.12 × 10⁻⁶. 8 Ω / sq, increased to 2.76×10 after wiping.11 The value of Ω / sq indicates that the low-molecular-weight antistatic components are prone to migration or loss under the action of alcohol wiping and mechanical friction, resulting in poor stability of antistatic performance.

[0127] In Examples 1 to 3, the styrene-maleic anhydride random copolymer reacts with amino-terminated polyether to form a polyether-grafted styrene copolymer, which improves the interfacial compatibility between the polyether ester amide block copolymer and the polystyrene matrix, and allows the electrostatic dissipative phase to form a more continuous bulk conduction path within the material. This structure does not rely on a single antistatic layer on the material surface, and therefore maintains stable antistatic properties after being wiped with alcohol and subjected to mechanical friction.

[0128] Test Example 6: This test case aims to verify the effect of the polyether-grafted antistatic masterbatch of the present invention on the thermo-oxidative aging resistance and color stability of polystyrene-based composite materials through hot air aging experiments and colorimetric tests.

[0129] The experimental steps are as follows: Transparent IC tubes prepared under the extrusion molding process corresponding to Examples 1 to 3 and Comparative Examples 1 to 5 were obtained as test samples.

[0130] The pipe was cut and placed in a flat vulcanizing machine, and rolled for 2 minutes at a set pressure of 190℃ and 5MPa to produce a rectangular test sample with a thickness of 2.0mm and a smooth surface.

[0131] Turn on the colorimeter, set the light source to D65 standard light source, set the field of view to 10°, and use a standard white board and black box to perform black and white calibration of the instrument.

[0132] Fix the test sample onto the test hole of the colorimeter, start the test to obtain the initial tristimulus values ​​of the sample, and the instrument's built-in software calculates and outputs the initial yellowing index of the sample according to the ASTM E313 standard.

[0133] The samples that have completed the initial test are suspended in a forced convection hot air aging oven, with the internal temperature of the oven set at 85°C, and the aging process is carried out for 168 hours.

[0134] After the aging process is completed, the sample is removed and placed in a standard laboratory environment with a temperature of 23±2℃ and a relative humidity of 50±5% to cool and condition for 24 hours.

[0135] Using the same colorimeter and test parameters, measurements were taken in the original test area of ​​the sample to obtain the yellowing index after aging.

[0136] Based on the test values ​​of each sample before and after aging, the change in yellowing index was calculated. Three parallel samples were taken from each material group, and the average value was calculated.

[0137] The experimental data are shown in Table 6: .

[0138] in conclusion: According to Table 6 and Figure 6 Data, based on Table 6 and Figure 6 According to the data, the initial yellowing index of Examples 1 to 3 ranged from 2.24 to 2.81, and the yellowing index after 168 hours of thermal aging remained between 0.91 and 1.11, indicating that the material maintained a stable optical color under high-temperature processing and long-term thermo-oxidative environment.

[0139] Comparative Example 1, without the addition of terminal amino polyether, had an initial yellowing index of 5.86, which increased to 9.74 after aging. Comparative Example 2, without pre-prepared polyether-grafted antistatic masterbatch, was directly physically blended, and its initial yellowing index was 7.92, which increased to 13.85 after aging. These results indicate that without a grafted compatible structure or a masterbatch dispersion process, polyether ester amide block copolymers are prone to local phase separation and micro-region enrichment in the polystyrene matrix, leading to increased interfacial defects and thus accelerating color degradation during thermo-oxidative aging.

[0140] Comparative Example 3, without the addition of polyether ester amide block copolymer, showed a yellowing index change of 0.98, indicating good color stability after removing the antistatic phase, but lacking bulk electrostatic dissipative components. Comparative Example 4, without the addition of styrene-butadiene block copolymer, showed a yellowing index change of 0.83, indicating that the toughening component had little impact on color stability. Comparative Example 5, using a low-molecular-weight surface-type antistatic agent instead of polyether-grafted antistatic masterbatch, had an initial yellowing index of 8.68, which increased to 15.46 after aging, indicating that the low-molecular-weight antistatic component easily migrates, accumulates, or undergoes oxidative degradation in a thermo-oxidative environment, leading to increased yellowing.

[0141] In Examples 1 to 3, the styrene-maleic anhydride random copolymer reacts with amino-terminated polyether to form a polyether-grafted styrene copolymer, which improves the compatibility between the polyether ester amide block copolymer and the polystyrene matrix. Furthermore, the use of a composite thermal stability inhibitor reduces the risk of thermo-oxidative degradation during processing and aging. Therefore, the material of this invention maintains its antistatic function while exhibiting good anti-yellowing properties and optical stability.

[0142] Test Example 7: This test case aims to evaluate the styrene-butadiene block copolymer toughening component in the formulation system through impact testing under low-temperature conditions.

[0143] The experimental steps are as follows: Transparent IC tubing prepared under the extrusion molding process corresponding to Examples 1 to 3 and Comparative Examples 1 to 5 was used as test material.

[0144] Cut pipe sections to a length of 150 mm, and prepare 50 pipe section samples for each material group for drop hammer impact testing. Place a portion of the pipe in a flat vulcanizing machine and roll it under a pressure of 190℃ and 5MPa, and then machine it into standard strips with dimensions of 63.5 mm × 12.7 mm × 3.2 mm. A V-shaped notch is machined in the middle of the strip for cantilever beam notched impact testing.

[0145] All prepared pipe section samples and notched strips were moved into a low-temperature environment test chamber. The internal temperature of the test chamber was set to -20℃ and kept constant for 24 hours to ensure uniform temperature distribution inside the material.

[0146] Turn on the drop hammer impact testing machine and adjust the spacing of the V-shaped support frame. Take out the pipe section samples one by one from the low-temperature test chamber and place them on the support frame. Set the drop hammer mass to 1.0 kg and the drop hammer height to 0.5 m. Release the drop hammer to impact the middle of the sample and record the number of samples that cracked or broke after the impact. Calculate the breakage rate of each group of 50 samples.

[0147] Turn on the cantilever beam impact testing machine and perform zero-point calibration. Remove notched specimens one by one from the low-temperature chamber and fix them to the fixture. Impact the specimens using a pendulum. Read the impact absorbed energy recorded on the instrument dial and calculate the notched impact strength based on the cross-sectional area at the notch of the specimen. Test 5 specimens for each material group and calculate the average value. The time from removing the specimen to completing the impact test should be controlled within 5 seconds.

[0148] The experimental data are shown in Table 7: Table 7: Low-Temperature Mechanical Properties Test Data of Materials in Each Example and Comparative Example .

[0149] in conclusion: According to the data in Table 7, in a low-temperature test environment of -20℃, the notched impact strength of the cantilever beams in Examples 1 to 3 ranged from 94 to 4.21 kJ / m. 2 Between these values, the drop hammer impact failure rate remained in the low range of 2.0% to 8.0%, indicating that the material of this invention has good low-temperature impact resistance.

[0150] Comparative Example 4, which did not contain styrene-butadiene block copolymer, showed a decrease in cantilever beam notched impact strength to 1.12 kJ / m², and a corresponding increase in drop hammer impact failure rate to 84.0%, indicating that styrene-butadiene block copolymer is a key component for improving the low-temperature toughness of the material.

[0151] General-purpose polystyrene is an amorphous rigid polymer with large benzene ring side groups on its main molecular chain, which restricts the internal rotation and slippage of the chain segments. At a low temperature of -20°C, the molecular chain segments of the polystyrene matrix are frozen, and the material is prone to brittle fracture. When subjected to impact loads, it is difficult to absorb energy through plastic deformation, thus triggering rapid crack propagation and macroscopic damage.

[0152] The premixed formulation of this embodiment incorporates a styrene-butadiene block copolymer. The polybutadiene rubber phase in this copolymer has a low glass transition temperature and retains some elasticity even at -20°C. During the blending extrusion process, the styrene-butadiene block copolymer is uniformly dispersed within the continuous polystyrene phase, forming a microphase structure. When the material is subjected to low-temperature impact, the dispersed rubber phase can induce the formation of crazes and shear bands in the matrix, absorbing and dissipating impact energy, thereby delaying crack propagation and improving the material's low-temperature impact toughness.

Claims

1. A transparent IC tube with a permanently resistant plastic material, characterized in that, The plastic material is made of components comprising the following parts by weight: 10-16 parts of polyether-grafted antistatic masterbatch; 66-80 parts of general-purpose polystyrene resin; 10-18 parts of styrene-butadiene block copolymer; The polyether-grafted antistatic masterbatch is prepared from raw materials comprising the following parts by weight: 60-85 parts of styrene-maleic anhydride random copolymer; 15-35 parts of amino-terminated polyether; 20-45 parts of polyether ester amide block copolymer; 1.0 to 2.0 parts of compound heat stability inhibitor.

2. The transparent IC tube waterproof plastic material according to claim 1, characterized in that, The terminal amino polyether has a number average molecular weight of 1000-2000 g / mol, each molecule contains at least one terminal amino group, and the water content is ≤0.2 wt%.

3. The transparent IC tube waterproof plastic material according to claim 1, characterized in that, The polyether ester amide block copolymer is a block copolymer containing polyether segments and amide segments, wherein the mass fraction of the polyether segments is 40wt% to 60wt%.

4. The transparent IC tube waterproof plastic material according to claim 1, characterized in that, The composite heat stability inhibitor is composed of antioxidant 626 and antioxidant DLTP in a mass ratio of 1:

1.

5. A method for preparing a transparent IC tube with a permanent plastic material according to any one of claims 1-4, characterized in that, Includes the following steps: S1. Premixing: High-concentration antistatic masterbatch, general-purpose polystyrene resin and styrene-butadiene block copolymer are added to a high-speed mixer and mixed to obtain a premix; S2. Melt extrusion: The premixed material is fed into a co-rotating twin-screw extruder for melt extrusion, and the material is extruded through a die to form a melt. S3. Cooling and Shaping: The melt is placed in a shaping water tank for cooling and shaping. After being pulled and cut, the transparent IC tube permanent plastic material is obtained.

6. The method for preparing the transparent IC tube permanent plastic material according to claim 5, characterized in that, In step S2, the length-to-diameter ratio of the co-rotating twin-screw extruder is 36:1 to 40:1; the temperature of each zone of the twin-screw extruder is set as follows: zone 1 165 to 175°C, zone 2 185 to 195°C, zone 3 200 to 210°C, and die 195 to 205°C; the screw speed is set to 150 to 250 rpm.

7. The method for preparing the transparent IC tube permanent plastic material according to claim 5, characterized in that, In step S1, the mixing time at room temperature is 5 to 10 minutes; in step S3, the shaping water tank is a vacuum shaping water tank.

8. The method for preparing the transparent IC tube permanent plastic material according to claim 5, characterized in that, The high-concentration antistatic reaction masterbatch is prepared in advance through the following steps: Styrene-maleic anhydride random copolymer, polyethylene glycol and xylene were added to a nitrogen-purified reactor, and the mixture was heated and stirred at a constant temperature to form a homogeneous solution. After adding anhydrous zinc acetate and stirring at a constant temperature, the system temperature is maintained and poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid aqueous dispersion is added dropwise to the reactor. During the dropwise addition, the water in the system forms an azeotrope with xylene and evaporates to the water separator for liquid-liquid separation. The bottom aqueous phase is drained and the upper xylene phase is completely refluxed back into the reactor until no water phase is separated out. Close the xylene reflux line, heat the reactor and remove most of the xylene solvent by atmospheric distillation, then turn on the vacuum preparation to reduce the pressure inside the reactor to negative pressure, and maintain the temperature and pressure at this temperature and pressure for the reaction. The vacuum was broken and nitrogen gas was introduced to restore normal pressure. After the reactor was cooled, a composite thermal stability inhibitor was added, and the mixture was stirred and mixed. The melt was then extruded, granulated, and dried.

9. The method for preparing the transparent IC tube permanent plastic material according to claim 8, characterized in that, The styrene-maleic anhydride random copolymer and the amino-terminated polyether are mixed in the melt state for 20-60 min; after adding the polyether ester amide block copolymer, the mixture is continued to melt mix for 10-30 min.

10. The method for preparing the transparent IC tube permanent plastic material according to claim 8, characterized in that, In the step of reducing the pressure inside the reactor to negative pressure and maintaining the temperature and pressure for the reaction, the pressure inside the reactor is reduced to -0.08 to -0.095 MPa, and the temperature and pressure maintaining reaction time is 20 to 60 minutes; the composite thermal stability inhibitor is added after the temperature inside the reactor drops to 135 to 145°C, and then stirred and mixed for 10 to 20 minutes.

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