A polyester nucleating agent composition and its preparation method and application

Abstract

The present invention relates to the field of polyester technology, and more particularly to a polyester nucleating agent composition, its preparation method, and application. The polyester nucleating agent composition comprises the following components in parts by weight: 100 parts of a complex of zinc phenylphosphonate, long-chain fatty acid calcium salt, and bifonazole, 11-18 parts of dimethyl terephthalate, 2-3 parts of triacetin, and 0.5-0.8 parts of glycol. The composition is primarily composed of a complex containing organic and inorganic groups, supplemented by raw materials for polyester production. The composition is uniformly dispersed in a polyester resin, effectively improving the crystallization rate and crystallinity of the polyester resin, and also exhibits good storage stability.

Description

Technical Field

[0001] The present invention relates to the technical field of polyesters, and more particularly to a polyester nucleating agent composition, a preparation method thereof and an application thereof. Background Art

[0002] Polyethylene terephthalate (PET) is a common thermoplastic polyester material. The C=O groups on its molecular chains reduce its symmetry, while the benzene rings on the main chain significantly increase its rigidity. This hinders the movement of molecular segments, resulting in a slow crystallization rate. Currently, the crystallization modification of polyester is primarily achieved by adding nucleating agents. Commonly used polyester nucleating agents include inorganic nucleating agents, organic nucleating agents, and polymer nucleating agents.

[0003] Among them, inorganic nucleating agents are mainly inorganic powders such as talc, calcium carbonate, and silica. Their nucleating effect is restricted by factors such as the particle size, dispersibility, and addition amount of the powder, so it is difficult to achieve ideal use effects. Moreover, this type of nucleating agent has poor compatibility with polyester matrix resins, and has a great impact on the transparency, glossiness, and strength of polyester products.

[0004] Organic nucleating agents are mainly Na, Li, Ba, Mg, and Ca salts of monocarboxylic acids, and Na, K, and Ca salts of benzoic acid. Although these overcome the problems of poor transparency and glossiness of inorganic nucleating agents, they are also prone to agglomeration in the PET resin system, which will cause the molecular weight of PET to decrease and damage the performance of polyester products.

[0005] Polymer nucleating agents are mainly Surlyn series ionomer sodium salts developed by DuPont in the United States. They can react with PET molecular chains at high temperatures to form PET-COONa, a product with ionic end groups, thereby promoting crystallization. However, this type of nucleating agent belongs to the category of chemical nucleating agents and will cause changes in the molecular weight of the polyester resin, making it difficult to control. Summary of the Invention

[0006] In order to solve the above problems, the present invention provides a polyester nucleating agent composition, a preparation method and application thereof. The polyester nucleating agent composition is mainly composed of a complex containing organic groups and inorganic groups, supplemented by raw materials for polyester production. It can not only be uniformly dispersed in the polyester resin, effectively improving the crystallization rate and crystallinity of the polyester resin, but also has good storage stability.

[0007] In a first aspect, the present invention provides a polyester nucleating agent composition comprising the following components in parts by weight: 100 parts of a complex of zinc phenylphosphonate-long-chain fatty acid calcium salt-bifonazole, 11-18 parts of dimethyl terephthalate, 2-3 parts of triacetin, and 0.5-0.8 parts of glycol.

[0008] The zinc phenylphosphonate-long-chain fatty acid calcium salt-bifonazole complex of the present invention has an organic group phenylphosphonate structure, an inorganic group calcium ion, a zinc ion, an imidazole ring and a rigid benzene ring. The phenylphosphonate structure is first used to promote the uniform dispersion of calcium ions in the polyester resin system, thereby reducing the interaction between the groups, thereby ensuring that the polyester is promoted to crystallize in the two stages of crystal nucleation and crystal growth, and having a high nucleation efficiency. Since the zinc phenylphosphonate and the long-chain fatty acid calcium salt have incompletely coordinated Zn during the replacement, the incompletely coordinated Zn 2+ The present invention further combines bifonazole with some of the excess Zn 2+ Complexation, the Zn 2+ The coordination structure with its imidazole ring can form a regular crystal surface, thereby promoting the orderly arrangement of polyester chain segments. The rigid benzene ring can also enhance the temperature of the complex and reduce structural collapse at high temperatures.

[0009] On this basis, the present invention further utilizes the good compatibility of dimethyl terephthalate with polyester resins to further accelerate the dispersion rate and effectiveness of the zinc phenylphosphonate-long-chain fatty acid calcium salt-bifonazole complex in the polyester resin system. The inventors discovered that although triacetin has poor compatibility with polyester resins, adding an appropriate amount of triacetin in the present invention actually facilitates nucleation. This may be due to the presence of a small amount of incompletely coordinated metal ions (such as Zn) on the surface of the zinc phenylphosphonate-long-chain fatty acid calcium salt-bifonazole complex. 2+ , Ca 2+ ), has an empty orbital, while the oxygen atom in the acetoxy group (-O-CO-CH3) of triacetin contains a lone pair of electrons, which can act as an electron donor to form a coordination bond with the metal ion. This allows triacetin to form an organic coating on the surface of the zinc phenylphosphonate-long-chain fatty acid calcium salt-bifonazole complex, enhancing the ability of the various groups in the complex to synergistically enhance nucleation. This also reduces surface energy and reduces interparticle agglomeration caused by van der Waals forces. By reducing surface activity and interparticle forces and enhancing the nucleation effect of the complex, dispersibility, storage stability, and nucleation efficiency are both improved. The co-addition of dimethyl terephthalate and triacetin promotes nucleation. Furthermore, a small amount of diol is added to the present invention. The zinc phenylphosphonate-long-chain fatty acid calcium salt-bifonazole complex in the composition also acts as a catalyst to promote the combination of diol and dimethyl terephthalate to form a polyester. This polyester can further improve the compatibility of the zinc phenylphosphonate-long-chain fatty acid calcium salt-bifonazole complex with polyester resins.

[0010] Therefore, the nucleating agent composition obtained by the present invention can be uniformly dispersed in the polyester resin, prompting the polyester resin to form more nucleation points during the crystallization process, effectively improving the crystallization rate and crystallinity of the polyester resin, while also having good storage stability and being easy to store and transport.

[0011] Preferably, the zinc phenylphosphonate-long-chain fatty acid calcium salt-bifonazole complex is prepared by compounding zinc phenylphosphonate, long-chain fatty acid calcium salt and bifonazole in a hot ethanol solution.

[0012] By adopting the above technical solution, zinc phenylphosphonate can increase the melt temperature of polyester resin, reduce melt viscosity and increase melt saturation, thereby promoting the formation and growth of polyester crystals and significantly improving the mechanical properties, thermal stability and heat resistance of polyester. Long-chain fatty acid calcium salt is a salt compound formed by long-chain fatty acids and calcium. The long-chain fatty acid part in its molecular structure can interact with the polyester molecular chain and guide the polyester molecular chain to the vicinity of zinc phenylphosphonate, forming an ordered crystal structure. Some of the Zn in bifonazole and zinc phenylphosphonate 2+ Complexation forms a regular crystal surface, thereby promoting the orderly arrangement of polyester chain segments. To achieve the three-way complexation, the present invention utilizes hot ethanol as a medium to promote full contact and reaction between zinc phenylphosphonate, long-chain fatty acid calcium salt, and bifonazole. The resulting zinc phenylphosphonate-long-chain fatty acid calcium salt-bifonazole complex has a more stable molecular structure. It not only combines the properties of zinc phenylphosphonate, long-chain fatty acid calcium salt, and bifonazole, but can also be effectively dispersed in the polyester resin. Compared with zinc phenylphosphonate-long-chain fatty acid calcium salt-bifonazole complexes obtained by complexation of other raw materials, it has a more excellent nucleating effect.

[0013] Preferably, the molar ratio of the zinc phenylphosphonate, the long-chain fatty acid calcium salt and the bifonazole is 0.7-0.9:1:0.1-0.2.

[0014] The above range is conducive to better formation of the coordination complex and can play a certain catalytic role in the reaction between dimethyl terephthalate and diol, thereby ensuring that the obtained polyester nucleating agent composition has good compatibility with the polyester resin.

[0015] Preferably, the preparation method of the zinc phenylphosphonate-long-chain fatty acid calcium salt-bifonazole complex comprises the following steps: taking an appropriate amount of ethanol and heating it to reflux temperature, first adding a set amount of long-chain fatty acid calcium salt and mixing evenly, then adding a set amount of zinc phenylphosphonate and mixing evenly, then keeping the mixture warm for 1-2 hours, then adding a set amount of bifonazole and keeping the mixture warm for 20-30 minutes, cooling to room temperature, filtering and drying to obtain the zinc phenylphosphonate-long-chain fatty acid calcium salt-bifonazole complex.

[0016] According to the technical solution, the present invention first adds a long-chain fatty acid calcium salt to hot ethanol to promote uniform dispersion and partial dissolution of the long-chain fatty acid calcium salt. Then, zinc phenylphosphonate is added to ensure that zinc phenylphosphonate is in partial contact with the long-chain fatty acid calcium salt. Finally, bifonazole is added to complex a portion of the zinc phenylphosphonate. The resulting zinc phenylphosphonate-long-chain fatty acid calcium salt-bifonazole complex has a more excellent nucleating effect.

[0017] Preferably, the long-chain fatty acid calcium salt is selected from one of calcium stearate and calcium palmitate.

[0018] Using the above technical solution, calcium stearate and calcium palmitate are both formed from long-chain fatty acids and calcium. The fatty acid in calcium stearate contains 18 carbon atoms, and the fatty acid in calcium palmitate contains 16 carbon atoms. The chain lengths of these two calcium salts are moderate. A chain length that is too short is not conducive to guiding the polyester molecular chain to nucleate around zinc phenylphosphonate, while a chain length that is too long is not conducive to the rapid dispersion of the nucleating agent. The zinc phenylphosphonate-long-chain fatty acid calcium salt-bifonazole complex prepared by selecting the above two calcium salts has a more excellent nucleating effect.

[0019] Preferably, the diol is selected from a mixture of one or more of ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, and 1,3-butylene glycol.

[0020] Preferably, the diol is a mixture of ethylene glycol and 1,3-propylene glycol in a weight ratio of 1:1.

[0021] By adopting the above technical solution, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol and 1,3-butylene glycol have small molecular weights and can be better polymerized with dimethyl terephthalate in the present invention. Among them, the present invention further prefers a diol formed by mixing ethylene glycol and 1,3-butanediol in a weight ratio of 1:1. This is based on the fact that ethylene glycol has a small molecular weight (62.07 g / mol), a short hydroxyl distance (C2 symmetrical structure), and high compatibility with the benzene ring structure of polyester (such as PET). In addition, its high polarity can promote the dispersion of the nucleating agent in the polyester, but it can easily lead to excessive local crystallization speed and the formation of small-sized grains. On the other hand, 1,3-propylene glycol has a larger molecular weight (76.09 g / mol) and an extended hydroxyl distance (C3 asymmetric structure), which is more compatible with the flexibility of the polyester chain. It can moderately reduce the crystallization rate and promote the stable growth of crystal nuclei, but excessive use may cause phase separation. Compounding the two in a 1:1 weight ratio can better balance the high dispersibility of ethylene glycol and the crystallization control ability of 1,3-propylene glycol, that is, ethylene glycol leads to rapid nucleation, and 1,3-propylene glycol controls grain growth, avoiding the defects of a single component, thereby optimizing the crystallinity and tensile strength of the polyester.

[0022] In a second aspect, the present invention provides a method for preparing a polyester nucleating agent composition, comprising the following steps:

[0023] An appropriate amount of ethanol is heated to reflux temperature, and a set amount of a complex of zinc phenylphosphonate-long-chain fatty acid calcium salt-bifonazole, dimethyl terephthalate, triacetin and glycol are sequentially added and mixed evenly. After heat treatment for 2-3 hours, the ethanol is evaporated and recovered, and the dried material is collected and pulverized to obtain the polyester nucleating agent composition.

[0024] By adopting the above technical solution, the present invention uses hot ethanol as a medium to promote the thorough mixing and compounding of the zinc phenylphosphonate-long-chain fatty acid calcium salt-bifonazole complex, dimethyl terephthalate, triacetin and glycol. The operation is simple and the reaction process is controllable. The ethanol can also be recycled, thereby achieving resource recycling and reducing production costs to a certain extent.

[0025] In a third aspect, the present invention provides a polyester material comprising the following components in parts by weight: 100 parts of a polyester resin and 0.5-0.8 parts of the polyester nucleating agent composition according to any one of claims 1-7.

[0026] In actual application, the amount of the polyester nucleating agent composition needs to be appropriate. When the crystallization modification is carried out in the above weight ratio, the obtained polyester material has a better nucleation effect, so it is further preferred.

[0027] In summary, the present invention has the following beneficial effects:

[0028] 1. The polyester nucleating agent composition of the present invention is mainly composed of a complex of zinc phenylphosphonate-long-chain fatty acid calcium salt-bifonazole, supplemented by dimethyl terephthalate, triacetin and glycol, so that it can be uniformly dispersed in the polyester resin to further increase the nucleation points, and can promote polyester crystallization in the two stages of crystal nucleation and crystal growth, effectively improving the crystallization rate and crystallinity of the polyester resin. At the same time, it also has good storage stability and is easy to store and transport.

[0029] 2. The zinc phenylphosphonate-long-chain fatty acid calcium salt-bifonazole complex of the present invention is prepared by compounding zinc phenylphosphonate, long-chain fatty acid calcium salt, and bifonazole in a specific ratio and then adding a diol with a relatively low molecular weight. This ensures that dimethyl terephthalate and the diol simultaneously complete the polymerization reaction to form polyester during the nucleation process, further improving the nucleation effect of the polyester material.

[0030] 3. The present invention uses hot ethanol as a medium when preparing the polyester nucleating agent composition. The operation is simple and the reaction process is controllable. The ethanol can also be recycled, thereby realizing the recycling of resources and reducing production costs to a certain extent. DETAILED DESCRIPTION

[0031] To make the above-mentioned objects, features, and advantages of the present invention more readily apparent, specific embodiments of the present invention are described in detail below. The following description sets forth numerous specific details to facilitate a full understanding of the present invention. However, the present invention can be implemented in many other ways than those described herein, and those skilled in the art may make similar modifications without departing from the scope of the present invention. Therefore, the present invention is not limited to the specific embodiments disclosed below.

[0032] The raw materials of the present invention are mainly commercially available products, which are as follows:

[0033] Phenylphosphonic acid: CAS number 1571-33-1, MacLean number P830253, purity 98%;

[0034] Zinc nitrate: CAS number 10198-18-6, Merck product number 96482, molecular formula Zn(NO3)2·6H2O, purity ≥99%;

[0035] Calcium stearate: CAS number 1592-23-0, purity ≥99%, concentration 6.6-7.4% Ca, heavy metal ≤0.004%, free acid ≤0.3%, molecular formula C 36 H 70 CaO4, molecular weight 607.02;

[0036] Calcium palmitate: CAS number 542-42-7, select Yongjian Pharmaceutical No. A12597 product, purity ≥ 98%, molecular formula C 32 H 62 CaO4, molecular weight 550.91;

[0037] Calcium montanate: CAS number is 52258-47-6, selected from Jinjinle Chemical products, purity ≥ 98%, molecular formula is C 56 H 110 CaO4, molecular weight 887.57;

[0038] Calcium propionate: CAS number 4075-81-4, Merck product number 21230, net dry matter content ≥ 97%, molecular formula C6H 10 CaO4, molecular weight 186.22;

[0039] Dimethyl terephthalate: CAS number 120-61-6, product with Maclean number 807069, purity ≥ 99%;

[0040] Triacetin: CAS number 102-76-1, product with Maclean number G810356, purity ≥ 98.5%;

[0041] Diol: can be selected from ethylene glycol, propylene glycol, butanediol, etc. In the present invention, a mixture of one or more of ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, and 1,3-butanediol is further preferred. The above diols are all common commercial products with a purity of ≥98%;

[0042] Polyester resin: DuPont Rynite PET FC01 is selected, with a relative density of 1.38, a light transmittance of 90%, and a water absorption rate of 0.6%.

[0043] Preparation example of zinc phenylphosphonate:

[0044] Weigh 19.0g of phenylphosphonic acid and dissolve it in 3L of deionized water; weigh 23.8g of zinc nitrate (Zn(NO3)2·6H2O) and dissolve it in 3L of dilute nitric acid with a concentration of 35mmol / L, that is, the concentration of phenylphosphonic acid is 40mmol / L, and the concentration of Zn(NO3)2·6H2O is 40mmol / L. 2+ The concentration of Zn is 40mmol / L, 2 + The molar ratio of zinc phenylphosphonate to phenylphosphonic acid is 1:1; the two solutions are mixed and stirred evenly, the pH is adjusted to 1.5 with a 1.5 mol / L sodium hydroxide solution, and magnetic stirring is performed for 30 minutes (30°C); the mixed solution is transferred to a 10L hydrothermal reactor and reacted at 120°C for 24 hours; after the reaction is completed, the reaction is cooled to room temperature, the reactor is opened, the reaction solution is transferred to a tray, and the reaction solution is placed in a constant temperature drying oven at 60°C and dried until the weight of the product no longer changes, and then ground into powder to obtain zinc phenylphosphonate.

[0045] Preparation Example of Complex of Zinc Phenylphosphonate-Long Chain Fatty Acid Calcium Salt-Bifonazole

[0046] Preparation Example 1

[0047] This preparation example discloses a method for preparing a complex of zinc phenylphosphonate-long-chain fatty acid calcium salt-bifonazole, comprising the following steps:

[0048] 50 mL of anhydrous ethanol (purity of 99.5%) was heated to a reflux temperature of 80°C, 9.11 g of calcium stearate was first added and mixed evenly, and then 2.68 g of the above-mentioned zinc phenylphosphonate was added and mixed evenly, followed by incubation for 1.5 hours, and then 0.70 g of bifonazole was added and incubated for 25 minutes, i.e., the molar ratio of zinc phenylphosphonate, calcium stearate, and bifonazole was 0.8:1:0.15. After cooling to room temperature, the mixture was filtered and dried, and the product was ground into powder after the weight no longer changed to obtain a complex a of zinc phenylphosphonate-long-chain fatty acid calcium salt-bifonazole.

[0049] Preparation Example 2

[0050] This preparation example discloses a method for preparing a complex of zinc phenylphosphonate-long-chain fatty acid calcium salt-bifonazole, comprising the following steps:

[0051] Take 50 mL of anhydrous ethanol (purity of 99.5%) and heat it to the reflux temperature of 80°C. First, add 9.11 g of calcium stearate and mix evenly. Then add 2.01 g of zinc phenylphosphonate and mix evenly. Then, keep the temperature for reaction for 1 hour. Then, add 0.23 g of bifonazole and keep the temperature for reaction for 20 minutes. That is, the molar ratio of zinc phenylphosphonate, calcium stearate and bifonazole is 0.6:1:0.05. After cooling to room temperature, filter and dry. After the weight of the product no longer changes, grind it into powder to obtain a complex b of zinc phenylphosphonate-long-chain fatty acid calcium salt-bifonazole.

[0052] Preparation Example 3

[0053] This preparation example discloses a method for preparing a complex of zinc phenylphosphonate-long-chain fatty acid calcium salt-bifonazole, comprising the following steps:

[0054] 50 mL of anhydrous ethanol (purity of 99.5%) was heated to a reflux temperature of 80°C, 9.11 g of calcium stearate was first added and mixed evenly, and then 2.35 g of zinc phenylphosphonate was added and mixed evenly, followed by incubation for 1 h, and then 0.47 g of bifonazole was added and incubated for 20 min, i.e., the molar ratio of zinc phenylphosphonate, calcium stearate, and bifonazole was 0.7:1:0.1. After cooling to room temperature, the mixture was filtered and dried, and the product was ground into powder after the weight no longer changed to obtain a complex c of zinc phenylphosphonate-long-chain fatty acid calcium salt-bifonazole.

[0055] Preparation Example 4

[0056] This preparation example discloses a method for preparing a complex of zinc phenylphosphonate-long-chain fatty acid calcium salt-bifonazole, comprising the following steps:

[0057] 50 mL of anhydrous ethanol (purity: 99.5%) was heated to a reflux temperature of 80°C, 9.11 g of calcium stearate was added and mixed evenly, and then 3.02 g of zinc phenylphosphonate was added and mixed evenly. The mixture was then kept warm for 2 h, and 0.93 g of bifonazole was added and kept warm for 30 min, i.e., the molar ratio of zinc phenylphosphonate, calcium stearate, and bifonazole was 0.9:1:0.2. The mixture was cooled to room temperature, filtered, and dried. After the weight of the product no longer changed, it was ground into powder to obtain a complex d of zinc phenylphosphonate-long-chain fatty acid calcium salt-bifonazole.

[0058] Preparation Example 5

[0059] This preparation example discloses a method for preparing a complex of zinc phenylphosphonate-long-chain fatty acid calcium salt-bifonazole, comprising the following steps:

[0060] Take 50 mL of anhydrous ethanol (purity of 99.5%) and heat it to the reflux temperature of 80°C. First, add 9.11 g of calcium stearate and mix evenly, then add 3.35 g of phenylphosphonic acid zinc and mix evenly, then keep warm for 2 hours, then add 1.16 g of bifonazole and keep warm for 30 minutes, that is, the molar ratio of phenylphosphonic acid zinc, calcium stearate and bifonazole is 1:1:0.25. After cooling to room temperature, filter and dry, and grind into powder after the weight of the product no longer changes to obtain a complex e of phenylphosphonic acid zinc-long-chain fatty acid calcium salt-bifonazole.

[0061] Preparation Example 6

[0062] This preparation example discloses a method for preparing a complex of zinc phenylphosphonate-long-chain fatty acid calcium salt-bifonazole, comprising the following steps:

[0063] 50 mL of anhydrous ethanol (purity: 99.5%) was heated to a reflux temperature of 80°C, 8.26 g of calcium palmitate was added and mixed evenly, and then 2.68 g of the above-mentioned zinc phenylphosphonate was added and mixed evenly. The mixture was then kept warm for 1.5 hours, and 0.70 g of bifonazole was added and kept warm for 25 minutes, i.e., the molar ratio of zinc phenylphosphonate, calcium palmitate, and bifonazole was 0.8:1:0.15. The mixture was cooled to room temperature, filtered, and dried. After the weight of the product no longer changed, it was ground into powder to obtain a complex f of zinc phenylphosphonate-long-chain fatty acid calcium salt-bifonazole.

[0064] Preparation Example 7

[0065] This preparation example discloses a method for preparing a complex of zinc phenylphosphonate-long-chain fatty acid calcium salt-bifonazole, comprising the following steps:

[0066] Take 50 mL of anhydrous ethanol (purity of 99.5%) and heat it to the reflux temperature of 80°C. First, add 13.31 g of calcium montanate and mix evenly. Then add 2.68 g of the above-mentioned zinc phenylphosphonate and mix evenly. Then, keep the reaction warm for 1.5 hours. Then, add 0.70 g of bifonazole and keep the reaction warm for 25 minutes, that is, the molar ratio of zinc phenylphosphonate, calcium montanate and bifonazole is 0.8:1:0.15. After cooling to room temperature, filter and dry. After the weight of the product no longer changes, grind it into powder to obtain a complex g of zinc phenylphosphonate-long-chain fatty acid calcium salt-bifonazole.

[0067] Preparation Example 8

[0068] This preparation example discloses a method for preparing a complex of zinc phenylphosphonate-long-chain fatty acid calcium salt-bifonazole, comprising the following steps:

[0069] Take 50 mL of anhydrous ethanol (purity of 99.5%) and heat it to the reflux temperature of 80°C. First, add 5.59 g of calcium propionate and mix evenly. Then add 5.36 g of the above-mentioned phenylphosphonate zinc and mix evenly. Then, keep the reaction warm for 1.5 hours. Then, add 1.40 g of bifonazole and keep the reaction warm for 25 minutes. That is, the molar ratio of phenylphosphonate zinc, calcium propionate and bifonazole is 0.8:1:0.15. After cooling to room temperature, filter and dry. After the weight of the product no longer changes, grind it into powder to obtain a complex h of phenylphosphonate zinc-long-chain fatty acid calcium salt-bifonazole.

[0070] Preparation Example 9

[0071] This preparation example discloses a method for preparing a complex of zinc phenylphosphonate-long-chain fatty acid calcium salt-bifonazole, comprising the following steps:

[0072] 9.11 g of calcium stearate, 2.68 g of the above-mentioned zinc phenylphosphonate, 0.70 g of bifonazole, and 50 mL of anhydrous ethanol (purity 99.5%) were mixed uniformly, then heated to a reflux temperature of 80°C and kept warm for 1.5 hours. The mixture was then cooled to room temperature, filtered, and dried. After the weight of the product no longer changed, it was ground into powder to obtain a complex i of zinc phenylphosphonate-long-chain fatty acid calcium salt-bifonazole.

[0073] The present invention is further described in detail below with reference to Examples and Comparative Examples.

[0074] Example

[0075] Example 1

[0076] This embodiment discloses a method for preparing a polyester nucleating agent composition, comprising the following steps:

[0077] 50 mL of ethanol was heated to a reflux temperature of 80°C, and 10.00 g of the complex a of zinc phenylphosphonate-long-chain fatty acid calcium salt-bifonazole prepared in Preparation Example 1, 1.32 g of dimethyl terephthalate, 0.24 g of triacetin and 0.06 g of diol (prepared by mixing ethylene glycol and 1,3-propylene glycol in a weight ratio of 1:1) were added in sequence and mixed evenly. After heat treatment for 2-3 h (specifically 2.5 h), the ethanol was evaporated and recovered, and the dried material was collected and pulverized to obtain a polyester nucleating agent composition.

[0078] Examples 2-4

[0079] Examples 2-4 are based on the method of Example 1, but the amounts of the components of the polyester nucleating agent composition are adjusted. For specific adjustments, please refer to Table 1 below.

[0080] Table 1 Component dosage of Examples 1-4 and Comparative Examples 1-3 (unit: g)

[0081] Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Complex of zinc phenylphosphonate-long chain fatty acid calcium salt-bifonazole a 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 Dimethyl terephthalate 1.32 1.10 1.54 1.80 / / 1.56 1.32 triacetin 0.24 0.20 0.24 0.30 / 1.56 / 0.24 diols 0.06 0.05 0.07 0.08 / 0.06 0.06 /

[0082] Examples 5-12

[0083] Examples 5-12 are based on the method of Example 1, except that the complex a of zinc phenylphosphonate-long-chain fatty acid calcium salt-bifonazole is replaced. Among them, in Example 5, the phenylphosphonic acid zinc-long-chain fatty acid calcium salt-bifonazole complex b prepared in Preparation Example 2 was used, in Example 6, the phenylphosphonic acid zinc-long-chain fatty acid calcium salt-bifonazole complex c prepared in Preparation Example 3 was used, in Example 7, the phenylphosphonic acid zinc-long-chain fatty acid calcium salt-bifonazole complex d prepared in Preparation Example 4 was used, in Example 8, the phenylphosphonic acid zinc-long-chain fatty acid calcium salt-bifonazole complex e prepared in Preparation Example 5 was used, in Example 9, the phenylphosphonic acid zinc-long-chain fatty acid calcium salt-bifonazole complex f prepared in Preparation Example 6 was used, in Example 10, the phenylphosphonic acid zinc-long-chain fatty acid calcium salt-bifonazole complex g prepared in Preparation Example 7 was used, in Example 11, the phenylphosphonic acid zinc-long-chain fatty acid calcium salt-bifonazole complex h prepared in Preparation Example 8 was used, and in Example 12, the phenylphosphonic acid zinc-long-chain fatty acid calcium salt-bifonazole complex i prepared in Preparation Example 9 was used.

[0084] Examples 13-16

[0085] Examples 13-16 are based on the method of Example 1, but the specific type of diol is adjusted. Specifically, the diol in Example 13 is ethylene glycol; the diol in Example 14 is 1,3-butanediol; the diol in Example 15 is a mixture of ethylene glycol and 1,2-butanediol in a weight ratio of 1:1; and the diol in Example 16 is a mixture of ethylene glycol and 1,3-butanediol in a weight ratio of 1:1.

[0086] Comparative Example

[0087] Comparative Example 1

[0088] The polyester nucleating agent of this comparative example is a single component, specifically the complex a of zinc phenylphosphonate-long-chain fatty acid calcium salt-bifonazole obtained in Preparation Example 1.

[0089] Comparative Examples 2-4

[0090] Comparative Examples 2-4 are based on the method of Example 1, with the components and amounts of the polyester nucleating agent composition adjusted. For specific adjustments, see Table 1 above.

[0091] Comparative Example 5

[0092] In this comparative example, based on the method of Example 1, the complex a of zinc phenylphosphonate-long-chain fatty acid calcium salt-bifonazole is replaced with an equal amount of a complex of zinc phenylphosphonate-long-chain fatty acid calcium salt. The preparation method of the complex of zinc phenylphosphonate-long-chain fatty acid calcium salt comprises the following steps:

[0093] Take 50 mL of anhydrous ethanol (purity of 99.5%) and heat it to the reflux temperature of 80°C. First, add 9.11 g of calcium stearate and mix evenly. Then add 2.68 g of the above-mentioned zinc phenylphosphonate and mix evenly. Then, keep the reaction warm for 1.5 hours, that is, the molar ratio of zinc phenylphosphonate to calcium stearate is 0.8:1. After cooling to room temperature, filter and dry. After the weight of the product no longer changes, grind it into powder to obtain a complex of zinc phenylphosphonate-long-chain fatty acid calcium salt.

[0094] Comparative Example 6

[0095] In this comparative example, based on the method of Example 1, the zinc phenylphosphonate-long-chain fatty acid calcium salt-bifonazole complex a is replaced with an equal amount of a zinc phenylphosphonate-bifonazole complex. The preparation method of the zinc phenylphosphonate-bifonazole complex comprises the following steps:

[0096] 50 mL of anhydrous ethanol (99.5% purity) was heated to a reflux temperature of 80°C, and 10.73 g of the above-mentioned zinc phenylphosphonate was added and mixed evenly. Then, 2.79 g of bifonazole was added and the mixture was kept warm for 25 minutes, i.e., the molar ratio of zinc phenylphosphonate, calcium stearate, and bifonazole was approximately 0.8:0.15. After cooling to room temperature, the mixture was filtered and dried. After the weight of the product no longer changed, it was ground into powder to obtain a zinc phenylphosphonate-bifonazole complex.

[0097] Performance testing

[0098] The polyester nucleating agent compositions prepared in Examples 1-16, the polyester nucleating agent of Comparative Example 1, and the polyester nucleating agent compositions prepared in Comparative Examples 2-6 were used as samples. 6 g of each sample was mixed uniformly with 1000 g of polyester resin. The resulting mixture was placed in an internal mixer and mixed at 260°C for 5 minutes before removal to obtain the corresponding polyester material. A separate group of polyester resins without the addition of the polyester nucleating agent served as a blank control group.

[0099] The polyester materials corresponding to Examples 1-16, Comparative Examples 1-6, and a blank control group were subjected to DSC testing, comprising the following steps: measuring the crystallization peak temperature of the polyester materials by DSC, with the temperature being raised from 25°C to 260°C at a heating rate of 20°C / min, followed by a 3-minute holding period to eliminate thermal history, and then cooling to 25°C at a cooling rate of 10°C / min. The test results are shown in Table 2 below, where the crystallization peak temperature is a parameter that measures the speed of polymer crystallization. A higher crystallization peak temperature indicates a faster crystallization rate, which is more conducive to shortening the polyester's processing cycle.

[0100] Table 2 Crystallization peak temperature of polyester materials

[0101] Nucleating agent Crystallization peak temperature (℃) Crystallization enthalpy (j / g) Crystallinity (%) Example 1 239.8 149.6 45.3 Example 2 232.1 144.5 40.0 Example 3 236.5 147.0 42.2 Example 4 235.3 146.1 41.5 Example 5 227.4 139.7 35.6 Example 6 234.0 145.5 40.1 Example 7 237.2 147.7 43.7 Example 8 231.1 143.4 39.2 Example 9 236.6 147.2 42.3 Example 10 229.5 141.8 37.1 Example 11 225.0 137.5 33.8 Example 12 237.7 148.5 44.2 Example 13 231.6 143.9 39.5 Example 14 232.4 144.5 40.0 Example 15 234.1 145.2 40.3 Example 16 236.1 147.0 42.1 Comparative Example 1 203.5 116.1 23.6 Comparative Example 2 207.2 118.8 24.7 Comparative Example 3 212.0 121.7 27.5 Comparative Example 4 223.1 135.4 35.7 Comparative Example 5 216.4 123.3 28.9 Comparative Example 6 201.2 110.8 23.0 Blank control group 123.6 117.2 21.8

[0102] In conjunction with Table 2 above, by comparing the test results of Examples 1-4 with Comparative Examples 1-6 and the blank control group, it can be seen that the complex of zinc phenylphosphonate-long-chain fatty acid calcium salt-bifonazole, dimethyl terephthalate, triacetin and glycol in the polyester nucleating agent composition of the present invention is compounded according to the set dosage to achieve a good nucleating effect.

[0103] Comparing the test results of Example 1 with those of Examples 5-12, it can be seen that the polyester nucleating agent composition of the present invention preferably uses a zinc phenylphosphonate-long-chain fatty acid calcium salt-bifonazole complex formed by complexing zinc phenylphosphonate and a long-chain fatty acid calcium salt. More preferably, the zinc phenylphosphonate-long-chain fatty acid calcium salt-bifonazole complex has a molar ratio of zinc phenylphosphonate:long-chain fatty acid calcium salt:bifonazole of 0.7-0.9:1:0.1-0.2. The resulting polyester nucleating agent composition has a higher crystallization peak temperature, crystallization enthalpy, and crystallinity for modifying the crystallization of the polyester resin, thereby exhibiting a good nucleating effect. The long-chain fatty acid calcium salt is preferably one of calcium stearate and calcium palmitate, with calcium stearate being more preferred.

[0104] By comparing the test results of Example 1 with those of Examples 13-16, it can be concluded that in the polyester nucleating agent composition of the present invention, the diol is preferably a mixture of one or more of ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, and 1,3-butanediol, and further preferably a diol mixed with ethylene glycol and 1,3-propylene glycol in a weight ratio of 1:1. The polyester nucleating agent composition obtained thereby can further improve the nucleating effect of the polyester.

[0105] Application Examples

[0106] Application Examples 1-5

[0107] In Application Examples 1-5, the polyester nucleating agent composition obtained in Example 1 was used to modify the crystallization of polyester resin. The modification steps were as follows: a predetermined amount of the polyester nucleating agent composition was mixed uniformly with 1000 g of polyester resin. The resulting mixture was placed in an internal mixer and mixed at 260°C for 5 minutes. The resulting polyester material was then removed and subjected to DSC testing. The dosages of the polyester nucleating agent composition used in these application examples and the test results for the corresponding polyester materials are shown in Table 3 below.

[0108] Table 3 Ingredients of Application Examples 1-5 and the corresponding crystallization peak temperature of polyester materials

[0109] Polyester nucleating agent composition (g) Polyester resin (g) Crystallization peak temperature (℃) Crystallization enthalpy (j / g) Crystallinity (%) Application Example 1 4 1000 224.7 133.5 34.8 Application Example 2 5 1000 228.5 139.4 38.1 Application Example 3 6 1000 239.8 149.6 45.3 Application Example 4 8 1000 231.2 140.9 40.5 Application Example 5 10 1000 226.5 137.0 36.9

[0110] Combined with the test results in Table 3 above, it can be seen that too much or too little use of the polyester nucleating agent composition of the present invention will affect its nucleating effect on the polyester resin, wherein 0.5-0.8 parts of the polyester nucleating agent composition is preferably used for 100 parts of polyester resin.

[0111] The specific embodiments are merely explanations of the present invention and are not limitations of the present invention. After reading this specification, those skilled in the art may make non-creative modifications to the embodiments as needed. However, as long as they are within the scope of the claims of the present invention, they are protected by patent law.

Claims

1. A polyester nucleating agent composition, characterized in that The invention comprises the following components in parts by weight: 100 parts of a complex of zinc phenylphosphonate-long-chain fatty acid calcium salt-bifonazole, 11-18 parts of dimethyl terephthalate, 2-3 parts of triacetin, and 0.5-0.8 parts of glycol; The zinc phenylphosphonate-long-chain fatty acid calcium salt-bifonazole complex is prepared by compounding zinc phenylphosphonate, long-chain fatty acid calcium salt and bifonazole in a hot ethanol solution, wherein the molar ratio of the zinc phenylphosphonate, long-chain fatty acid calcium salt and bifonazole is 0.7-0.9:1:0.1-0.2; The preparation method of the zinc phenylphosphonate-long-chain fatty acid calcium salt-bifonazole complex comprises the following steps: taking an appropriate amount of ethanol and heating it to reflux temperature, first adding a set amount of long-chain fatty acid calcium salt and mixing evenly, then adding a set amount of zinc phenylphosphonate and mixing evenly, then keeping the mixture warm for 1-2 hours, then adding a set amount of bifonazole and keeping the mixture warm for 20-30 minutes, cooling to room temperature, filtering and drying to obtain the zinc phenylphosphonate-long-chain fatty acid calcium salt-bifonazole complex.

2. The polyester nucleating agent composition according to claim 1, characterized in that The long-chain fatty acid calcium salt is selected from one of calcium stearate and calcium palmitate.

3. The polyester nucleating agent composition according to claim 1, characterized in that: The diol is selected from a mixture of one or more of ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, and 1,3-butylene glycol.

4. The polyester nucleating agent composition according to claim 3, characterized in that: The diol is prepared by mixing ethylene glycol and 1,3-propylene glycol in a weight ratio of 1:

1.

5. The method for preparing the polyester nucleating agent composition according to any one of claims 1 to 4, characterized in that: The following steps are involved: An appropriate amount of ethanol is heated to reflux temperature, and a set amount of a complex of zinc phenylphosphonate-long-chain fatty acid calcium salt-bifonazole, dimethyl terephthalate, triacetin and glycol are sequentially added and mixed evenly. After heat treatment for 2-3 hours, the ethanol is evaporated and recovered, and the dried material is collected and pulverized to obtain the polyester nucleating agent composition.

6. A polyester material, characterized in that: The invention comprises the following components in parts by weight: 100 parts of polyester resin and 0.5-0.8 parts of the polyester nucleating agent composition according to any one of claims 1 to 4.