Composition of a granulated masterbatch

Abstract

The application discloses a granulation masterbatch composition, which comprises liquid crystal polyester, a modifier and a flow improver. The modifier comprises oxidized polyethylene wax, hyperbranched carboxyl polymer, polyimide compound or a combination thereof. The flow improver comprises pentaerythritol oleate. Through the synergistic effect of the modifier and the flow improver, the entanglement of the molecular chains of the liquid crystal polyester can be effectively solved, and the molecular chains are arranged in the same direction, so that the flowability and granulation processing stability of the material as a whole are improved.

Description

Technical Field

[0001] The present invention relates to a composition, and more particularly to a composition of a granulation masterbatch. Background Technology

[0002] For the granulation application of liquid crystal polyester materials in the textile industry, the highly ordered and entangled molecular chains of liquid crystal polyester often lead to insufficient flowability during granulation due to its high viscosity in the molten state. This results in problems such as unstable processing, uneven melting, or breakage. Existing technologies lack targeted methods to address the stability issues in the granulation process of liquid crystal polyester, failing to effectively improve granulation processability and maintain masterbatch quality. This limits the application of liquid crystal polyester in the textile industry to some extent. Summary of the Invention

[0003] According to one or more embodiments of the present invention, a granulation masterbatch comprises a liquid crystal polyester, a modifier, and a flow promoter. The modifier includes oxidized polyethylene wax, hyperbranched carboxylated polymers, polyimide compounds, or combinations thereof. The flow promoter includes pentaerythritol oleate.

[0004] In one or more embodiments of the present invention, the modifier is an oxidized polyethylene wax, and the weight average molecular weight of the modifier is 2,000 to 4,000 Daltons.

[0005] In one or more embodiments of the present invention, the modifier is an oxidized polyethylene wax, and the acid value of the modifier is from 1 mg KOH / g to 20 mg KOH / g.

[0006] In one or more embodiments of the present invention, the modifier is an oxidized polyethylene wax, and the crystallinity of the modifier is 47% to 80%.

[0007] In one or more embodiments of the present invention, the modifier comprises a polyimide compound, and the intrinsic viscosity of the polyimide compound dissolved in N-methylpyrrolidone to form a 15% by weight solution at a temperature of 20°C to 50°C is 100 to 190 centipoise.

[0008] In one or more embodiments of the present invention, the modifier comprises a polyimide compound having repeating units as shown in formula (1):

[0009]

[0010] In one or more embodiments of the present invention, the modifier comprises a hyperbranched carboxyl polymer, and the degree of branching of the hyperbranched carboxyl polymer is 0.4% to 0.7%.

[0011] In one or more embodiments of the present invention, the modifier comprises a hyperbranched carboxyl polymer, and the preparation method of the hyperbranched carboxyl polymer comprises: performing a condensation reaction between a core molecule and a plurality of branching monomers to form a hyperbranched carboxyl polymer, wherein the core molecule is a tricarboxylic acid or a triol, and the branching monomers are a dicarboxylic acid or a diol.

[0012] In one or more embodiments of the present invention, the tricarboxylic acid is citric acid, the triol is trimethylolpropane, the dicarboxylic acid is phthalic acid, adipic acid or a combination thereof, and the diol is 1,4-butanediol, ethylene glycol or a combination thereof.

[0013] In one or more embodiments of the present invention, the liquid crystal polyester has monomer units as shown in formulas (2) and (3):

[0014]

[0015] According to the above embodiments of the present invention, the synergistic effect of the modifier and the flow promoter can effectively untangle the molecular chains of the liquid crystal polyester and promote the oriented alignment of the molecular chains, thereby improving the overall flowability and processing stability of the material. Specifically, the modifier can reduce the interaction forces between molecular chains, while the flow promoter can further enhance the ordered arrangement of the molecular chains, thereby improving the efficiency and quality of the granulation process, effectively reducing the processing temperature required for granulation, and improving the subsequent processability of the liquid crystal polyester material. Detailed Implementation

[0016] Several embodiments will be disclosed below, and for clarity, many practical details will be described in the following description. It should be understood that these practical details are not intended to limit the invention. That is, in some embodiments of the invention, these practical details are not essential and therefore should not be used to limit the invention.

[0017] In this article, the structure of polymers or groups is sometimes represented by a skeleton formula. This representation may omit carbon atoms, hydrogen atoms, and carbon-hydrogen bonds. Of course, if the structural formula explicitly shows atoms or atomic groups, the representation shown by the artist shall prevail.

[0018] This invention provides a composition of a granulation masterbatch, comprising liquid crystal polyester, a modifier, and a flow promoter. By adding the modifier and flow promoter to the liquid crystal polyester, it is possible to achieve high-quality granulation at lower processing temperatures, reduce energy consumption and equipment heat load, while maintaining the mechanical properties and chemical stability of the liquid crystal polyester during high-temperature processing, thereby enhancing the application potential of liquid crystal polyester in the textile field. The liquid crystal polyester, modifier, and flow promoter will be described in sequence below.

[0019] [Liquid Crystal Polyester]

[0020] In some embodiments, the liquid crystal polyester is a polyarylate. Polyarylates possess a highly ordered liquid crystal arrangement and a rigid backbone, giving them advantages in mechanical properties, heat resistance, dimensional stability, and chemical resistance. The rigid structure of polyarylates not only imparts good tensile strength and modulus to the material but also maintains stable physical properties in high-temperature environments. The liquid crystal polyester can complement modifiers and flow promoters. The liquid crystal polyester provides high structural strength and thermal stability, while the modifiers and flow promoters improve flowability by reducing chain entanglement in the molten state and increasing the oriented alignment of the liquid crystal polyester, thereby improving granulation efficiency. This combination effectively alleviates the problem of poor processability of liquid crystal polyester; that is, the composition of the granulation masterbatch of the present invention enables a stable and efficient granulation process.

[0021] Furthermore, the polyarylate and the modifier selected in this invention (described later) can have high compatibility. For example, the intermolecular forces between the two can reduce phase separation, thereby promoting uniform mixing and ensuring the stability of the overall material properties. This good compatibility helps to form a consistent dispersed phase structure during processing, allowing the modifier to penetrate more effectively into the molecular chain gaps of the polyarylate, further reducing viscosity and improving the flowability of granulation processing. At the same time, good compatibility can also help to improve the homogeneity of the final molded material, ensuring that it can maintain excellent structural and functional properties under high temperature or stress. In some embodiments, the weight average molecular weight of the liquid crystal polyester can be from 40,000 Daltons to 200,000 Daltons, and the liquid crystal polyester can have monomer units as shown in formulas (2) and (3):

[0022]

[0023] [Modifier]

[0024] Modifiers can regulate the molecular chain structure of liquid crystal polyesters. More specifically, modifiers can untangle the molecular chains, reducing the intermolecular forces in the molten state and thus improving the flowability of the material during granulation. Through the action of the modifier, the molecular chains of the liquid crystal polyester can move more freely during processing, reducing processing difficulties caused by chain entanglement and further improving the stability and efficiency of the material during high-temperature processing. This, in turn, helps the flow promoter to further act on the untangled molecular chains of the liquid crystal polyester, aligning the molecular chains in the processing direction (this will be explained later), thereby improving the problem of insufficient granulation properties of liquid crystal polyesters.

[0025] In some embodiments, the modifier may include, for example, oxidized polyethylene wax. Oxidized polyethylene wax has the characteristic of introducing oxygen functional groups (e.g., carboxyl, hydroxyl, ester groups). These polar groups readily interact with the molecular chains of the liquid crystal polyester, reducing molecular chain entanglement and thus improving the flowability of the liquid crystal polyester. This makes the liquid crystal polyester easier to melt during processing, ultimately improving the smoothness of the granulation process. It should be noted that in this document, "oxidized" in the term "oxidized polyethylene wax" refers to polyethylene wax that has undergone oxidation treatment during preparation, resulting in the introduction of oxygen functional groups (e.g., carboxyl, hydroxyl, ester groups) into the molecular structure of the polyethylene wax.

[0026] In some embodiments, the weight-average molecular weight of the oxidized polyethylene wax can be between 2000 Daltons and 4000 Daltons (e.g., 2200 Daltons, 2400 Daltons, 2600 Daltons, 2800 Daltons, 3000 Daltons, 3200 Daltons, 3400 Daltons, 3600 Daltons, 3800 Daltons). When the weight-average molecular weight of the oxidized polyethylene wax falls within the above range, it can more effectively enter the molecular structure of the liquid crystal polyester, further improving the arrangement of molecular chains, thereby enhancing the fluidity of the liquid crystal polyester and promoting the stability and uniformity of the granulation process. In contrast, if the weight-average molecular weight of the oxidized polyethylene wax is too low, its molecular structure may be too simple, easily leading to cracking problems during high-temperature processes, resulting in a less than expected improvement in granulation performance; while if the weight-average molecular weight of the oxidized polyethylene wax is too high, the high molecular weight oxidized polyethylene wax may not be able to effectively enter the molecular structure during melting, thus reducing its interaction with the liquid crystal polyester and reducing the chance of molecular chain entanglement. However, even if the weight average molecular weight of oxidized polyethylene wax falls outside the above range, oxidized polyethylene wax can still provide a certain degree of granulation effect, although it may not achieve optimal performance.

[0027] In some embodiments, the acid value of the oxidized polyethylene wax can be from 1 mg KOH / g to 20 mg KOH / g (e.g., 2 mg KOH / g, 4 mg KOH / g, 6 mg KOH / g, 8 mg KOH / g, 10 mg KOH / g, 12 mg KOH / g, 14 mg KOH / g, 16 mg KOH / g, 18 mg KOH / g). When the acid value of the oxidized polyethylene wax falls within the above range, good flowability modification can be achieved without excessively introducing polar groups, thereby helping to stabilize granulation performance and improve granulation uniformity. If the acid value of the oxidized polyethylene wax is too high, the excessive number of polar groups in the wax may enhance intermolecular interactions, limiting the flexibility of the liquid crystal polyester molecular chains to rearrange, resulting in a slight decrease in material flowability and an increased likelihood of agglomeration during granulation. Conversely, if the acid value of the oxidized polyethylene wax is too low, the content of polar groups may be insufficient, weakening the interaction between the oxidized polyethylene wax and the liquid crystal polyester molecular chains. This makes the liquid crystal polyester molecular chains more prone to entanglement, potentially reducing the expected improvement in flowability. However, even if the acid value of the oxidized polyethylene wax falls outside the aforementioned range, it can still provide a certain degree of modification effect, although it may not achieve optimal performance.

[0028] In some embodiments, the crystallinity of the oxidized polyethylene wax can be from 47% to 80% (e.g., 50%, 55%, 60%, 65%, 70%, or 75%). When the crystallinity of the oxidized polyethylene wax falls within the above range, its internal structure has a moderate degree of order, achieving a good balance between physical properties and processability. This provides sufficient crystallinity to maintain appropriate structural strength while avoiding viscosity increases due to over-crystallization, thus contributing to improved stability of the granulation process and uniformity of the masterbatch. If the crystallinity of oxidized polyethylene wax is too low, although it can still provide some modification effect on liquid crystal polyester materials, its internal structure may be too disordered, leading to a decrease in physical strength. This may result in a negligible improvement in processing stability and granulation quality. Furthermore, excessively low crystallinity may affect the compatibility between the oxidized polyethylene wax and the liquid crystal polyester, reducing the detangling effect of molecular chains. Conversely, if the crystallinity of the oxidized polyethylene wax is too high, its structure may be overly ordered, reducing fluidity and further affecting its dispersion performance in the liquid crystal polyester. This could result in a modification effect slightly below the optimal level. However, even if the crystallinity of the oxidized polyethylene wax falls outside the aforementioned range, it can still provide a certain degree of modification effect, although it may not achieve optimal performance.

[0029] In some embodiments, the modifier may include, for example, a hyperbranched carboxyl polymer. A hyperbranched carboxyl polymer is a polymer with a highly branched structure, possessing a three-dimensional network structure and multiple terminal carboxyl groups. Due to the large number of terminal carboxyl groups in the structure of the hyperbranched carboxyl polymer, these carboxyl groups have polar properties and can form intermolecular interactions (e.g., hydrogen bonds or other weak interactions) with the molecular chains of the liquid crystal polyester. This interaction effectively disrupts the original tight entanglement between the molecular chains of the liquid crystal polyester. As the entanglement of the molecular chains is gradually untied, the molecular chains of the liquid crystal polyester have more space to move, allowing them to rearrange and exhibit better fluidity in the molten state, reducing the melt viscosity of the material, promoting the uniformity and stability of the material during granulation, and contributing to improved overall processing performance. Furthermore, the hyperbranched carboxyl polymer can also provide a significant steric hindrance effect, effectively preventing the molecular chains of the liquid crystal polyester from entangleing again. Simultaneously, the low hydrodynamic volume of the hyperbranched carboxyl polymer gives it higher flow properties, exhibiting good dispersibility and uniformity during granulation, ensuring the stability of the modification effect. Overall, hyperbranched carboxyl polymers can effectively improve the granulation stability of liquid crystal polyesters in this invention.

[0030] In some embodiments, the hyperbranched carboxyl polymer has a multilayered dendritic structure with a central unit as the core and extending outwards, wherein multiple branch units are covalently bonded to the central unit to form a highly branched three-dimensional network. This three-dimensional network structure not only provides a high density of functional terminal groups (i.e., terminal carboxyl groups), but also enables the molecule to have good dispersibility and tunable physicochemical properties. In some embodiments, the preparation method of the hyperbranched carboxyl polymer includes a condensation polymerization reaction of a core molecule with multiple branch-forming monomers, wherein the core molecule forms the central unit of the hyperbranched carboxyl polymer after the reaction, and the branch-forming monomers form the branch units of the hyperbranched carboxyl polymer after the reaction.

[0031] In some embodiments, the core molecule is a tricarboxylic acid (e.g., a tricarboxylic acid) or a triol. For the core molecule, a ternary molecule can guide the formation of more branches, thereby increasing the branching degree of the polymer. Furthermore, the simple structure and high reactivity of the tricarboxylic acid or triol contribute to the formation of a stable and highly branched polymer structure. In some embodiments, the tricarboxylic acid is citric acid, and the triol is trimethylolpropane. In some embodiments, the branching monomer is a diacarboxylic acid or a diol. For the branching monomer, the diacarboxylic acid or diol has two reactive functional groups, which can provide precise and balanced crosslinking points in the polymerization reaction, thereby promoting the formation of a stable and controllable three-dimensional network structure. The selective reactivity of the diacarboxylic acid also facilitates the regular growth of the dendritic structure, ensuring that the final product has a relatively uniform molecular weight distribution. On the other hand, the condensation reaction has high controllability, and the reaction conditions can be precisely adjusted according to actual needs, thereby controlling the structural characteristics of the hyperbranched carboxylic polymer.

[0032] In some embodiments, the dicarboxylic acid may be phthalic acid, adipic acid, or a combination thereof. Phthalic acid and adipic acid each have their own mechanisms in the de-entanglement process. The rigid benzene ring in phthalic acid can interfere with the arrangement of molecular chains, disrupting the overly regular entangled structure and thus promoting the loosening of entanglement. Furthermore, the benzene ring provides a significant spatial barrier effect, helping to reduce the forces between molecular chains, making the molecular chains of the liquid crystal polyester easier to move and rearrange. On the other hand, the flexible segments of adipic acid can penetrate into the entangled regions between the liquid crystal polyester molecular chains, gradually opening up the overly entangled molecular chains through the compliant segment characteristics without causing excessive internal stress. Overall, phthalic acid and adipic acid affect the entanglement of liquid crystal polyester molecular chains through rigid interference and flexible penetration, respectively, and the combination of the two helps to effectively improve entanglement and optimize the flow properties of the material.

[0033] In some embodiments, the diol may be 1,4-butanediol, ethylene glycol, or a combination thereof. Similarly, 1,4-butanediol and ethylene glycol each have their own mechanisms in the de-entanglement process. 1,4-Butanediol has a relatively long carbon chain structure, which helps the molecular chain to more easily pass through the entanglement regions between liquid crystal polyester molecular chains, further improving the flowability and de-entanglement effect of the liquid crystal polyester molecular chains. In contrast, ethylene glycol has a shorter molecular structure, is a more rigid molecule, and has strong hydrophilicity. This allows ethylene glycol to generate a strong affinity for the liquid crystal polyester molecular chains, thereby helping to break the entanglement structure of the liquid crystal polyester molecular chains. Overall, 1,4-butanediol and ethylene glycol affect the entanglement of liquid crystal polyester molecular chains through flexible penetration and rigid interference, respectively, and the combination of the two helps to effectively improve entanglement and optimize the flow properties of the material.

[0034] In some embodiments, the degree of branching (DB) of the hyperbranched carboxyl polymer can be from 0.40% to 0.70% (e.g., 0.45%, 0.50%, 0.55%, 0.60%, 0.65%). When the degree of branching of the hyperbranched carboxyl polymer falls within the above range, its molecular structure can achieve a balance between the degree of branching and molecular arrangement. Specifically, an appropriate degree of branching provides sufficient intermolecular voids, which facilitates the interaction between the hyperbranched carboxyl polymer and the liquid crystal polyester molecular chains, thereby promoting the deentanglement of molecular chains and improving the processing stability of the granulation masterbatch. On the other hand, an appropriate degree of branching can avoid the structural loosening problems that may result from excessive branching, thereby maintaining the necessary structural strength and uniformity. If the branching degree of the hyperbranched carboxyl polymer is too low, although it can still provide a certain degree of detangling effect on the liquid crystal polyester, the relatively small intermolecular gaps may limit its interaction with the liquid crystal polyester molecular chains, reducing the detangling efficiency and resulting in a slightly insufficient modification effect. Conversely, if the branching degree of the hyperbranched carboxyl polymer is too high, the overly complex branched structure may weaken its molecular arrangement ability, thereby affecting its dispersibility and stability in the liquid crystal polyester. However, even if the branching degree of the hyperbranched carboxyl polymer falls outside the above range, it can still exert a certain modification effect, although it may not achieve optimal performance.

[0035] In some embodiments, the modifier may, for example, comprise a polyimide compound. In some embodiments, the polyimide compound has repeating units as shown in formula (1):

[0036]

[0037] In some embodiments, m-phenylenediamine can be placed in N-methylpyrrolidone and stirred for about 25 to 35 minutes (e.g., 30 minutes) until completely dissolved. Then, 2,2-bis[4-dicarboxylic acid phenoxyphenyl]propane dianhydride is added in portions to control the total solid content at 25 wt% to 35 wt% (e.g., 30 wt%), and a condensation polymerization reaction is carried out to generate polyamic acid. After the polymerization reaction is completed, an appropriate amount of catalyst (pyridine) and acetic anhydride are added, and the temperature is raised to 115 to 125 degrees Celsius (e.g., 120 degrees Celsius) and reacted for 2.5 to 3.5 hours (e.g., 3 hours) to allow the polyamic acid to cyclize into a polyimide compound.

[0038] Polyimide compounds, through their chemical structure design, can effectively reduce the processing viscosity of liquid crystal polyesters and improve their flowability, thereby enhancing the stability and efficiency of thermal processing. Specifically, 2,2-bis[4-dicarboxylic acid phenoxyphenyl]propane dianhydride contains ether bonds and alkyl structures. Introducing these flexible groups into the polyimide backbone reduces the rigidity of the polyimide molecular chain, increases the rotational freedom of the molecular chain, and makes it easier for the material to undergo intermolecular slip at high temperatures, thus entering the molecular chains of the liquid crystal polyester and improving the overall material flowability. Furthermore, the meta-structure of m-phenylenediamine can disrupt the linearity of the polyimide backbone, reduce π-π stacking between molecular chains, and weaken intermolecular interactions, making it easier for the liquid crystal polyester to melt and flow during thermal processing. Additionally, the propane group in 2,2-bis[4-dicarboxylic acid phenoxyphenyl]propane dianhydride can further prevent regular stacking of molecular chains, reduce the crystallinity of the material, and thus contribute to improving intermolecular flowability.

[0039] On the other hand, this invention ensures that the resulting polyimide compound has a small molecular structure by designing the molar ratio between 2,2-bis[4-dicarboxylic acid phenoxyphenyl]propane dianhydride and m-phenylenediamine. The small molecular structure of the polyimide compound results in a lower molecular weight and relatively lower melt viscosity, making it easier to flow under external force during processing, thereby reducing energy consumption during processing. Furthermore, the small molecular structure of the polyimide compound exhibits lower entanglement of molecular chains in the molten state, significantly reducing intermolecular sliding resistance and resulting in better processing performance. Additionally, the small molecular structure of the polyimide compound can suppress the rigidity and stacking regularity of molecular chains, thereby increasing its molecular freedom in the molten state, enabling it to form a more uniform mixed phase with the liquid crystal polyester, reducing phase separation, and further promoting its overall flowability. Moreover, the low molecular weight and high molecular mobility of the small molecular structure of the polyimide compound allow it to more easily enter the molecular chains of the liquid crystal polyester, thereby forming a more uniform mixture and further improving the overall flowability of the liquid crystal polyester.

[0040] Specifically, to form polyimide compounds with small molecular structures, the present invention controls the molar ratio of 2,2-bis[4-dicarboxylic acid phenoxyphenyl]propane dianhydride to m-phenylenediamine to be between 2:1 and 4:3 (e.g., 3:2). More specifically, when the molar ratio is less than 2:1 (e.g., 1:1), the proportion of dianhydride is insufficient, which may cause the resulting polyimide compound to tend to form a high molecular weight linear polymer. Furthermore, due to the excess of amino groups in m-phenylenediamine, unreacted amino group ends may remain in the structure, leading to enhanced interchain forces and making the molecular chains prone to entanglement. This results in a material exhibiting high viscosity, which is detrimental to flowability during thermal processing. Conversely, when the molar ratio is greater than 4:3 (e.g., 5:4), the proportion of dianhydride is too high. The excess anhydride functional groups tend to participate in cross-linking reactions, generating network or highly cross-linked and high molecular weight polymer structures. This increases the entanglement and stacking of molecular chains, making intermolecular sliding difficult and also detrimental to flowability during thermal processing.

[0041] In some embodiments, the intrinsic viscosity of the small-molecule polyimide compound can be characterized by its viscosity. More specifically, at temperatures between 20°C and 50°C, the intrinsic viscosity of a 15% (w / w) solution of the polyimide compound dissolved in N-methylpyrrolidone is between 100 and 190 centipoise (e.g., 110, 120, 130, 140, 150, 160, 170, and 180 centipoise). When the intrinsic viscosity of the polyimide compound falls within this range, it indicates that the polyimide compound has a suitable molecular weight and low intermolecular forces, thereby ensuring good flowability in the molten state. Furthermore, this characteristic viscosity range also indirectly reflects the balanced characteristics of the polyimide compound in its structural design. That is, by adjusting the molar ratio of 2,2-bis[4-dicarboxylic acid phenoxyphenyl]propane dianhydride to m-phenylenediamine, it is neither too linearized, resulting in high viscosity, nor too cross-linked, leading to processing difficulties.

[0042] Overall, the modifiers of the present invention may include the aforementioned oxidized polyethylene wax, the aforementioned hyperbranched carboxylated polymer, the aforementioned polyimide compound, or a combination thereof.

[0043] [Flow Improver]

[0044] Flow promoters can further act on the liquid crystal polyester molecular chains that have been untangled by the modifier, causing the molecular chains to align in the processing direction. Specifically, when the molecular chains of the liquid crystal polyester are less entangled due to the action of the modifier, the flow promoter can provide a directional flow driving force by reducing the internal friction between the molecular chains, arranging the molecular chains into a more ordered structure. This aligning characteristic not only helps to improve the flowability of the liquid crystal polyester, but also improves its uniformity and stability during processing. As the degree of aligning of the molecular chains increases, the liquid crystal polyester can more effectively disperse stress during processing, ultimately significantly improving the granulation performance and granulation quality of the material.

[0045] In some embodiments, the flow promoter may include pentaerythritol oleate. The molecular structure of pentaerythritol oleate has multiple branches and polar groups. These branches provide good flexibility, allowing it to freely shuttle between liquid crystal polyester molecules, reducing friction between molecular chains and lowering resistance to molecular motion. On the other hand, the polar groups can interact moderately with the molecular chains of the liquid crystal polyester, forming transient bonds or coordination, thereby providing directional alignment drive for the molecular chains. Through these properties, pentaerythritol oleate can effectively promote the oriented alignment of liquid crystal polyester molecular chains along the processing direction, improving the flowability and uniformity of the material during granulation, and further improving the physical properties and quality of the masterbatch.

[0046] In some embodiments, the liquid crystal polyester content is 100 parts by weight, the modifier content can be greater than or equal to 1 part by weight and less than or equal to 3 parts by weight (e.g., 1.5 parts by weight, 2 parts by weight, or 2.5 parts by weight), and the flow promoter content can be greater than or equal to 0.1 parts by weight and less than or equal to 2 parts by weight (e.g., 0.2 parts by weight, 0.4 parts by weight, 0.6 parts by weight, 0.8 parts by weight, 1 part by weight, 1.2 parts by weight, 1.4 parts by weight, 1.6 parts by weight, or 1.8 parts by weight). The ratio of modifier to flow promoter can balance the effects of untangling and oriented molecular chain alignment. If the modifier content is too high, it may lead to excessive untangling of molecular chains, destroying the ordered structure of the liquid crystal polyester, thereby affecting the mechanical properties and stability of the material; while if the flow promoter content is too high, it may cause excessive lubrication, resulting in insufficient interaction force between molecular chains, affecting the ordered alignment of molecular chains, and may also lead to a decrease in the uniformity of the internal structure of the material, thereby affecting the physical properties and quality of the final masterbatch. Therefore, adjusting the ratio within this range can not only fully leverage the synergistic effect of the modifier and flow promoter, but also ensure the stability of the liquid crystal polyester during processing and the uniformity of granulation quality.

[0047] In the following description, several embodiments will be listed to demonstrate the effectiveness of the invention. It should be understood that the invention should not be interpreted as limiting by the embodiments described below.

[0048] In this experimental example, the thermal properties, injection molded specimen properties, flowability, and granulation properties of the granulation masterbatch composition of each embodiment were evaluated. The thermal property tests include melting point testing (using differential scanning calorimetry) and 5% thermal decomposition temperature testing (using thermogravimetric analysis); the physical property evaluation of injection molded specimens includes tensile strength and elongation testing (using standard method ASTM D638), flexural strength and flexural modulus testing (using standard method ASTM D790), and impact strength testing (using standard method ASTM D256); the flowability evaluation includes melt index testing (using standard method ASTM D1238); the mixing parameters for granulation evaluation are: mixing temperature of 310–335 degrees Celsius (lower than commonly used mixing temperatures), screw speed of 600–900 rpm, pelletizing speed of 500–800 rpm, current of 16–20 amperes, pressure of 10–24 bar, and material temperature of 320–330 degrees Celsius.

[0049] Table 1 provides a detailed description of the composition of the granulation masterbatch in each embodiment, while Table 2 presents a detailed evaluation result of the composition of the granulation masterbatch in each embodiment.

[0050] Table 1

[0051]

[0052] Note 1: The model number of polyarylate is... A6000, industrial and plastic grade.

[0053] Note 2: The grade of oxidized polyethylene wax is Hi- 405MP.

[0054] Note 3: The model number of the hyperbranched carboxyl polymer is... C100.

[0055] Note 4: The structure of the polyimide compound is formula (1).

[0056] Note 5: The model number for pentaerythritol oleate is... 900P.

[0057] Table 2

[0058]

[0059] Note 6: Polyarylate The A6000 was tested (the test methods correspond to the test methods of each item in each embodiment) and has a melting point of 329 degrees Celsius, a 5% thermal decomposition temperature of 502 degrees Celsius, a tensile strength of 181 MPa, a flexural strength of 176 MPa, and an impact strength of 14.40 J.

[0060] As shown in Table 2, the melt flow index (MI) of each embodiment was generally improved, which is beneficial for granulation processing. All embodiments passed the granulation test without any breakage or melt instability, demonstrating excellent processing stability. Furthermore, the melting point, thermal decomposition temperature, tensile strength, flexural strength, and impact strength of each embodiment were very similar to those of the unmodified liquid crystal polyester, indicating that the modifiers and flow promoters added in this invention effectively improve the material's processing performance while having almost no impact on the original physical properties of the liquid crystal polyester. It is worth mentioning that all embodiments were processed at temperatures lower than commonly used mixing temperatures (approximately 340–350 degrees Celsius), proving that the composition of the granulation masterbatch of this invention can achieve stable and efficient granulation at lower mixing temperatures, helping to reduce energy consumption and improve processing efficiency.

[0061] According to the above embodiments of the present invention, the synergistic effect of the modifier and the flow promoter can effectively untangle the molecular chains of liquid crystal polyester and promote the oriented alignment of the molecular chains, thereby improving the overall flowability and processing stability of the material. Specifically, the modifier can reduce the interaction forces between molecular chains, while the flow promoter can further enhance the ordered arrangement of the molecular chains, thereby improving the efficiency and quality of the granulation process and effectively reducing the processing temperature required for granulation, thus solving the problem of poor granulation properties of liquid crystal polyester materials.

[0062] Although the present invention has been disclosed above by way of embodiments, it is not intended to limit the present invention. Any person skilled in the art can make various modifications and refinements without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention shall be determined by the scope defined in the appended claims.

Claims

1. A composition of a granulation masterbatch, characterized in that, include: One liquid crystal polyester; A modifier, comprising an oxidized polyethylene wax, a hyperbranched carboxyl polymer, a polyimide compound, or a combination thereof; and One flow promoter, including pentaerythritol oleate.

2. The composition of the granulation masterbatch according to claim 1, characterized in that, The modifier is the oxidized polyethylene wax, and the weight average molecular weight of the modifier is 2000 Daltons to 4000 Daltons.

3. The composition of the granulation masterbatch according to claim 1, characterized in that, The modifier is the oxidized polyethylene wax, and the acid value of the modifier is from 1 mg KOH / g to 20 mg KOH / g.

4. The composition of the granulation masterbatch according to claim 1, characterized in that, The modifier is the oxidized polyethylene wax, and the crystallinity of the modifier is 47% to 80%.

5. The composition of the granulation masterbatch according to claim 1, characterized in that, The modifier contains the polyimide compound, and at a temperature of 20°C to 50°C, the polyimide compound dissolves in N-methylpyrrolidone to form a solution with a weight percentage concentration of 15% and an intrinsic viscosity of 100 centipoise to 190 centipoise.

6. The composition of the granulation masterbatch according to claim 1, characterized in that, The modifier comprises the polyimide compound having repeating units as shown in formula (1):

7. The composition of the granulation masterbatch according to claim 1, characterized in that, The modifier contains the hyperbranched carboxyl polymer, and the degree of branching of the hyperbranched carboxyl polymer is 0.4% to 0.7%.

8. The composition of the granulation masterbatch according to claim 1, characterized in that, The modifier comprises the hyperbranched carboxyl polymer, and the preparation method of the hyperbranched carboxyl polymer comprises: The hyperbranched carboxyl polymer is formed by condensing a core molecule with multiple branched monomers, wherein the core molecule is a tricarboxylic acid or a triol, and the branched monomers are dicarboxylic acids or diols.

9. The composition of the granulation masterbatch according to claim 8, characterized in that, The tricarboxylic acid is citric acid, the triol is trimethylolpropane, the dicarboxylic acid is phthalic acid, adipic acid or a combination thereof, and the diol is 1,4-butanediol, ethylene glycol or a combination thereof.

10. The composition of the granulation masterbatch according to claim 1, characterized in that, The liquid crystal polyester has monomer units as shown in formulas (2) and (3):

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