Polyester nucleating agent composition as well as preparation method and application thereof

Abstract

The invention relates to the technical field of polyester, in particular to a polyester nucleating agent composition as well as a preparation method and application thereof. The polyester nucleating agent composition disclosed by the invention is prepared from the following components in parts by weight: 100 parts of a compound of zinc phenylphosphonate-long-chain fatty acid calcium salt-bifonazole, 11 to 18 parts of dimethyl terephthalate, 2 to 3 parts of glyceryl triacetate and 0.5 to 0.8 part of diol, by taking a complex containing an organic group and an inorganic group as a main component and taking a raw material generated by polyester as an auxiliary component, the polyester dispersing agent not only can be uniformly dispersed in polyester resin and effectively improves the crystallization rate and crystallinity of the polyester resin, but also has good storage stability.

Description

Technical Field

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

[0002] Polyethylene terephthalate (PET) is one of the common thermoplastic polyester materials. The C=O groups on its molecular chain reduce the symmetry of the molecular chain, and the benzene rings on the main chain greatly increase its rigidity, which makes the movement of molecular segments difficult, resulting in a slow crystallization rate of PET. At present, the crystallization modification of polyesters is mainly solved by adding nucleating agents. The common types of polyester nucleating agents mainly include inorganic nucleating agents, organic nucleating agents, polymer nucleating agents, etc.

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

[0004] Organic nucleating agents are mainly salts of Na, Li, Ba, Mg, Ca of monocarboxylic acids, salts of Na, K, Ca of benzoic acid, etc. Although this type overcomes the problems of poor transparency and gloss of inorganic nucleating agents, it is also easy to agglomerate in the PET resin system, which will cause a decrease in the molecular weight of PET and damage the performance of polyester products.

[0005] Polymer nucleating agents mainly include Surlyn series ionomer sodium salts developed by DuPont Company in the United States. It can react with the PET molecular chain at high temperature to form a product PET-COONa with ionic end groups, thereby playing a role in promoting crystallization. However, this type of nucleating agent belongs to the scope of chemical nucleating agents, which will change the molecular weight of polyester resin and is 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 thereof, and an application thereof. The polyester nucleating agent composition is mainly composed of a complex containing organic groups and inorganic groups, supplemented by the raw materials for generating polyesters. It can not only be evenly dispersed in the polyester resin, effectively improve the crystallization rate and crystallinity of the polyester resin, but also has good storage stability.

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

[0008] The phenylphosphonic acid zinc-calcium long-chain fatty acid salt-bifonazole complex of the present invention has both an organic group phenylphosphonic acid structure, inorganic groups calcium ions, zinc ions, imidazole rings, and rigid benzene rings. First, the phenylphosphonic acid structure is used to promote the uniform dispersion of calcium ions in the polyester resin system, thereby reducing the interaction between groups, and then ensuring that polyester crystallization is promoted respectively in the two stages from crystal nucleus formation to crystal growth, with a high nucleation efficiency. Since there will be incompletely coordinated Zn when phenylphosphonic acid zinc and calcium long-chain fatty acid salt are displaced 2+ , the present invention further complexes with part of the excess Zn through bifonazole 2+ . The coordination structure of this Zn 2+ with its imidazole ring can form a regular crystal surface, thereby promoting the orderly arrangement of polyester segments. The rigid benzene ring therein can also enhance the temperature of the complex and reduce the structural collapse at high temperatures.

[0009] On this basis, the present invention also utilizes the good compatibility of dimethyl terephthalate with polyester resin to accelerate the further dispersion rate and dispersion effect of the phenylphosphonic acid zinc-calcium long-chain fatty acid salt-bifonazole complex in the polyester resin system. The inventor found that although triacetin has poor compatibility with polyester resin, adding an appropriate amount of triacetin in the present invention is beneficial to nucleation. This may be because there are still a small amount of incompletely coordinated metal ions (such as Zn 2+ , Ca 2+ ) on the surface of the phenylphosphonic acid zinc-calcium long-chain fatty acid salt-bifonazole complex, which have empty orbitals, and the oxygen atom in the acetoxy group (-O-CO-CH3) of triacetin contains lone pair electrons and can act as an electron donor to form a coordination bond with metal ions, so that triacetin forms an organic coating layer on the surface of the phenylphosphonic acid zinc-calcium long-chain fatty acid salt-bifonazole complex to enhance the ability of each group of the complex to synergistically improve the nucleation effect, while reducing the surface energy and reducing the aggregation caused by the van der Waals force between particles; by reducing the surface activity and the force between particles and improving the nucleation effect of the complex, the dual improvement of dispersibility and storage stability and nucleation ability is achieved. The co-addition of dimethyl terephthalate and triacetin promotes nucleation. In addition, a small amount of diol is added in the present invention, and the phenylphosphonic acid zinc-calcium long-chain fatty acid salt-bifonazole complex in the composition can also act as a catalyst to promote the combination of diol and dimethyl terephthalate to generate polyester, and this polyester can further improve the compatibility of the phenylphosphonic acid zinc-calcium long-chain fatty acid salt-bifonazole complex with polyester resin.

[0010] Thus, the nucleating agent composition obtained by the present invention can be uniformly dispersed in the polyester resin, promote the formation of more nucleation points during the crystallization process of the polyester resin, effectively improve the crystallization rate and crystallinity of the polyester resin, and at the same time has good storage stability, which is convenient for storage and transportation.

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

[0012] With the above technical solution, zinc phenylphosphonate can increase the melt temperature of the polyester resin, reduce the melt viscosity and increase the melt saturation, thereby promoting the formation and growth of polyester crystals and significantly improving the mechanical properties, thermal stability and heat resistance of the polyester. Calcium long-chain fatty acid salt is a salt compound formed by a long-chain fatty acid and calcium. The long-chain fatty acid part in its molecular structure can interact with the polyester molecular chain and then guide the polyester molecular chain around zinc phenylphosphonate to form an ordered crystal structure. Bifonazole and part of Zn in zinc phenylphosphonate 2+ Complex to form a regular crystal surface, thereby promoting the ordered arrangement of polyester segments. To achieve the complexation of the three, the present invention uses hot ethanol as a medium to promote the full contact and reaction of zinc phenylphosphonate, calcium long-chain fatty acid salt and bifonazole. As a result, the molecular structure of the complex of zinc phenylphosphonate-calcium long-chain fatty acid-bifonazole obtained is more stable. It not only has the characteristics of zinc phenylphosphonate, calcium long-chain fatty acid salt and bifonazole, but also can be effectively dispersed in the polyester resin. Compared with the complex of zinc phenylphosphonate-calcium long-chain fatty acid-bifonazole obtained by complexing with other raw materials, it has a more excellent nucleating effect.

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

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

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

[0016] With the above technical solution, in the present invention, calcium long-chain fatty acid salt is first added to hot ethanol to promote the uniform dispersion and partial dissolution of the calcium long-chain fatty acid salt. At this time, adding zinc phenylphosphonate can ensure its full contact with the calcium long-chain fatty acid salt. Finally, bifonazole is added to complex a part of the zinc phenylphosphonate. The obtained zinc phenylphosphonate-calcium long-chain fatty acid salt-bifonazole complex has a more excellent nucleation effect.

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

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

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

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

[0021] With the above technical solution, the molecular weights of ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, and 1,3-butanediol are small, and they can better polymerize with dimethyl terephthalate in the present invention. Among them, the present invention further preferably uses a diol composed of ethylene glycol and 1,3-butanediol mixed in a weight ratio of 1:1. This is because ethylene glycol has a small molecular weight (62.07 g / mol), a short hydroxyl spacing (C2 symmetric structure), and a 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 polyester, but it is easy to cause too fast local crystallization rate and form small-sized grains; while 1,3-propanediol has a larger molecular weight (76.09 g / mol), an extended hydroxyl spacing (C3 asymmetric structure), and a higher flexibility matching degree with 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 weight ratio of 1:1 can better balance the high dispersibility of ethylene glycol and the crystallization regulation ability of 1,3-propanediol, that is, ethylene glycol dominates rapid nucleation, and 1,3-propanediol regulates the growth of crystal grains, avoiding the defects of single components, and thus optimizing the crystallinity and tensile strength of polyester.

[0022] Second aspect, the present invention provides a preparation method of a polyester nucleating agent composition, comprising the following steps: Take an appropriate amount of ethanol and heat it to the reflux temperature. Then, sequentially add a set amount of the complex of zinc phenylphosphonate-calcium long-chain fatty acid salt-bifonazole, dimethyl terephthalate, glycerol triacetate, and diol, and mix them evenly. After heat preservation treatment for 2 - 3 h, evaporate and recover the ethanol, collect the dried material, and pulverize and grind it to obtain the polyester nucleating agent composition.

[0023] Adopting the above technical solution, the present invention uses hot ethanol as a medium to promote the full mixing and compounding of the complex of zinc phenylphosphonate-calcium long-chain fatty acid salt-bifonazole, dimethyl terephthalate, glycerol triacetate, and diol. Its operation is simple and the reaction process is controllable. Moreover, the ethanol can be recycled, thereby realizing the recycling of resources and reducing the production cost to a certain extent.

[0024] Third aspect, the present invention provides a polyester material, comprising the following components in parts by weight: 100 parts of polyester resin, and 0.5 - 0.8 part of the polyester nucleating agent composition according to any one of claims 1 - 7.

[0025] In the actual application process, the dosage of the polyester nucleating agent composition needs to be appropriate. When performing crystallization modification with the above weight ratio, the obtained polyester material has a more excellent nucleation effect, so it is further preferred.

[0026] In summary, the present invention has the following beneficial effects: 1. In the polyester nucleating agent composition of the present invention, the complex of zinc phenylphosphonate-calcium long-chain fatty acid salt-bifonazole is the main component, and dimethyl terephthalate, glycerol triacetate, and diol are the auxiliary components, enabling it to be uniformly dispersed in the polyester resin to further increase the nucleation sites, and promoting the crystallization of the polyester in two stages from crystal nucleus formation to crystal growth, effectively improving the crystallization rate and crystallinity of the polyester resin. At the same time, it also has good storage stability, facilitating storage and transportation.

[0027] 2. The complex of zinc phenylphosphonate-calcium long-chain fatty acid salt-bifonazole of the present invention is compounded from zinc phenylphosphonate, calcium long-chain fatty acid salt, and bifonazole according to a specific ratio, and then cooperated with diol having a relatively small molecular weight, thereby ensuring that dimethyl terephthalate and diol simultaneously complete the polymerization reaction to form polyester during the nucleation process, further improving the nucleation effect of the polyester material.

[0028] 3. When preparing the polyester nucleating agent composition of the present invention, hot ethanol is used as a medium. Its operation is simple and the reaction process is controllable. Moreover, the ethanol can be recycled, thereby realizing the recycling of resources and reducing the production cost to a certain extent. Specific embodiments

[0029] To make the above objects, features, and advantages of the present invention more apparent and understandable, the following provides a detailed description of the specific embodiments of the present invention. Many specific details are set forth in the following description to facilitate a full understanding of the present invention. However, the present invention can be implemented in many other ways different from those described herein, and those skilled in the art can make similar improvements without departing from the spirit of the present invention. Therefore, the present invention is not limited by the specific embodiments disclosed below.

[0030] The raw materials of the present invention are mainly commercially available products, specifically as follows: Phenylphosphonic acid: CAS No. is 1571-33-1, and the product with Macklin number P830253 is selected, with a purity of 98%; Zinc nitrate: CAS No. is 10198-18-6, and the product with Merck number 96482 is selected, with a molecular formula of Zn(NO3)2·6H2O and a purity ≥ 99%; Calcium stearate: CAS No. is 1592-23-0, with a purity ≥ 99%, a concentration of 6.6 - 7.4% Ca, heavy metals ≤ 0.004%, free acid ≤ 0.3%, and a molecular formula of C 36 H 70 CaO4, with a molecular weight of 607.02; Calcium palmitate: CAS No. is 542-42-7, and the product with Yongjian Medicine number A12597 is selected, with a purity ≥ 98% and a molecular formula of C 32 H 62 CaO4, with a molecular weight of 550.91; Calcium montanate: CAS No. is 52258-47-6, and the product of Jinjinle Chemical is selected, with a purity ≥ 98% and a molecular formula of C 56 H 110 CaO4, with a molecular weight of 887.57; Calcium propionate: CAS No. is 4075-81-4, and the product with Merck number 21230 is selected, with a dry matter net content ≥ 97% and a molecular formula of C6H 10 CaO4, with a molecular weight of 186.22; Dimethyl terephthalate: CAS No. is 120-61-6, and the product with Macklin number 807069 is selected, with a purity ≥ 99%; Glycerol triacetate: CAS No. is 102-76-1, and the product with Macklin number G810356 is selected, with a purity ≥ 98.5%; Diol: It can be selected from ethylene glycol, propylene glycol, butylene glycol, etc. In the present invention, 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 is further preferred. The above diols are all ordinary commercially available products, and the purity of each is ≥ 98%; 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%.

[0031] Preparation example of zinc phenylphosphonate:

[0032] Weigh 19.0 g of phenylphosphonic acid and dissolve it in 3 L of deionized water; weigh 23.8 g of zinc nitrate (Zn(NO3)2·6H2O) and dissolve it in 3 L of dilute nitric acid with a concentration of 35 mmol / L. That is, the concentration of phenylphosphonic acid is 40 mmol / L, and the concentration of Zn 2+ is 40 mmol / L, and the molar ratio of Zn 2 + to phenylphosphonic acid is 1:1; mix the two solutions and stir evenly, adjust its pH = 1.5 with 1.5 mol / L sodium hydroxide solution, and stir magnetically for 30 min (30 °C); transfer the mixed solution to a 10 L hydrothermal reaction kettle and react at 120 °C for 24 h; after the reaction is completed, cool to room temperature, open the kettle, transfer the reaction solution to a tray, and place it in a constant temperature drying oven at 60 °C to dry until the weight of the product no longer changes, and then grind it into powder to obtain zinc phenylphosphonate.

[0033] Preparation example of the complex of zinc phenylphosphonate - calcium long-chain fatty acid salt - bifonazole

[0034] Preparation example 1 This preparation example discloses a preparation method of the complex of zinc phenylphosphonate - calcium long-chain fatty acid salt - bifonazole, which includes the following steps: Take 50 mL of absolute ethanol (purity 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 zinc phenylphosphonate and mix evenly. Subsequently, keep the temperature for reaction for 1.5 h, and then add 0.70 g of bifonazole and keep the temperature for reaction for 25 min. That is, the molar ratio of zinc phenylphosphonate, calcium stearate, and bifonazole is 0.8:1:0.15. After cooling to room temperature, filter and dry it. After the weight of the product no longer changes, grind it into powder to obtain the complex a of zinc phenylphosphonate - calcium long-chain fatty acid salt - bifonazole.

[0035] Preparation example 2 This preparation example discloses a preparation method of the complex of zinc phenylphosphonate - calcium long-chain fatty acid salt - bifonazole, which includes the following steps: Take 50 mL of absolute ethanol (purity 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. Subsequently, keep the temperature for reaction for 1 h, then add 0.23 g of bifonazole and keep the temperature for reaction for 20 min. 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 the complex b of zinc phenylphosphonate-calcium long-chain fatty acid salt-bifonazole.

[0036] Preparation Example 3 This preparation example discloses a preparation method of a complex of zinc phenylphosphonate-calcium long-chain fatty acid salt-bifonazole, comprising the following steps: Take 50 mL of absolute ethanol (purity 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 2.35 g of zinc phenylphosphonate and mix evenly. Subsequently, keep the temperature for reaction for 1 h, then add 0.47 g of bifonazole and keep the temperature for reaction for 20 min. That is, the molar ratio of zinc phenylphosphonate, calcium stearate, and bifonazole is 0.7:1:0.1. After cooling to room temperature, filter and dry. After the weight of the product no longer changes, grind it into powder to obtain the complex c of zinc phenylphosphonate-calcium long-chain fatty acid salt-bifonazole.

[0037] Preparation Example 4 This preparation example discloses a preparation method of a complex of zinc phenylphosphonate-calcium long-chain fatty acid salt-bifonazole, comprising the following steps: Take 50 mL of absolute ethanol (purity 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 3.02 g of zinc phenylphosphonate and mix evenly. Subsequently, keep the temperature for reaction for 2 h, then add 0.93 g of bifonazole and keep the temperature for reaction for 30 min. That is, the molar ratio of zinc phenylphosphonate, calcium stearate, and bifonazole is 0.9:1:0.2. After cooling to room temperature, filter and dry. After the weight of the product no longer changes, grind it into powder to obtain the complex d of zinc phenylphosphonate-calcium long-chain fatty acid salt-bifonazole.

[0038] Preparation Example 5 This preparation example discloses a preparation method of a complex of zinc phenylphosphonate-calcium long-chain fatty acid salt-bifonazole, comprising the following steps: Take 50 mL of absolute ethanol (purity 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 zinc phenylphosphonate and mix evenly. Subsequently, keep the temperature for reaction for 2 h, then add 1.16 g of bifonazole and keep the temperature for reaction for 30 min. That is, the molar ratio of zinc phenylphosphonate, calcium stearate and bifonazole is 1:1:0.25. After cooling to room temperature, filter and dry. After the weight of the product no longer changes, grind it into powder to obtain the complex e of zinc phenylphosphonate-calcium long-chain fatty acid salt-bifonazole.

[0039] Preparation Example 6 This preparation example discloses a preparation method of a complex of zinc phenylphosphonate-calcium long-chain fatty acid salt-bifonazole, including the following steps: Take 50 mL of absolute ethanol (purity 99.5%) and heat it to the reflux temperature of 80 °C. First, add 8.26 g of calcium palmitate and mix evenly, then add 2.68 g of the above-mentioned zinc phenylphosphonate and mix evenly. Subsequently, keep the temperature for reaction for 1.5 h, then add 0.70 g of bifonazole and keep the temperature for reaction for 25 min. That is, the molar ratio of zinc phenylphosphonate, calcium palmitate 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 the complex f of zinc phenylphosphonate-calcium long-chain fatty acid salt-bifonazole.

[0040] Preparation Example 7 This preparation example discloses a preparation method of a complex of zinc phenylphosphonate-calcium long-chain fatty acid salt-bifonazole, including the following steps: Take 50 mL of absolute ethanol (purity 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. Subsequently, keep the temperature for reaction for 1.5 h, then add 0.70 g of bifonazole and keep the temperature for reaction for 25 min. 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 the complex g of zinc phenylphosphonate-calcium long-chain fatty acid salt-bifonazole.

[0041] Preparation Example 8 This preparation example discloses a preparation method of a complex of zinc phenylphosphonate-calcium long-chain fatty acid salt-bifonazole, including the following steps: Take 50 mL of absolute ethanol (purity 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 zinc phenylphosphonate and mix evenly. Subsequently, keep the temperature for reaction for 1.5 h, then add 1.40 g of bifonazole and keep the temperature for reaction for 25 min. That is, the molar ratio of zinc phenylphosphonate, 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 the complex h of zinc phenylphosphonate - calcium long-chain fatty acid salt - bifonazole.

[0042] Preparation Example 9 This preparation example discloses a method for preparing a complex of zinc phenylphosphonate - calcium long-chain fatty acid salt - bifonazole, including the following steps: Take 9.11 g of calcium stearate, 2.68 g of the above-mentioned zinc phenylphosphonate, 0.70 g of bifonazole, and 50 mL of absolute ethanol (purity 99.5%). First, mix them evenly, then heat to the reflux temperature of 80 °C and keep the temperature for reaction for 1.5 h. Subsequently, cool to room temperature, filter and dry. After the weight of the product no longer changes, grind it into powder to obtain the complex i of zinc phenylphosphonate - calcium long-chain fatty acid salt - bifonazole.

[0043] The present invention will be further described in detail below with reference to examples and comparative examples.

[0044] Examples Example 1

[0045] This example discloses a method for preparing a polyester nucleating agent composition, including the following steps: Take 50 mL of ethanol and heat it to the reflux temperature of 80 °C. Sequentially add 10.00 g of the complex a of zinc phenylphosphonate - calcium long-chain fatty acid salt - bifonazole prepared in Preparation Example 1, 1.32 g of dimethyl terephthalate, 0.24 g of glycerol triacetate, and 0.06 g of diol (formed by mixing ethylene glycol and 1,3-propanediol in a weight ratio of 1:1) and mix evenly. After heat preservation treatment for 2 - 3 h (specifically 2.5 h), evaporate and recover the ethanol, collect the dried material, and perform pulverization and grinding to obtain the polyester nucleating agent composition.

[0046] Examples 2 - 4

[0047] Examples 2 - 4 are based on the method of Example 1, and the component dosages of the polyester nucleating agent composition are adjusted. For the specific adjustment situation, refer to Table 1 below.

[0048] Table 1 Component Dosage Table of Examples 1 - 4 and Comparative Examples 1 - 3 (unit: g) Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Complex a of zinc phenylphosphonate - calcium long-chain fatty acid salt - bifonazole 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 Glycerol triacetate 0.24 0.20 0.24 0.30 / 1.56 / 0.24 Glycol 0.06 0.05 0.07 0.08 / 0.06 0.06 / Examples 5 - 12

[0049] Examples 5 - 12 are based on the method of Example 1, with the complex a of zinc phenylphosphonate - calcium long - chain fatty acid salt - bifonazole replaced. Among them, in Example 5, the complex b of zinc phenylphosphonate - calcium long - chain fatty acid salt - bifonazole prepared in Preparation Example 2 is used; in Example 6, the complex c of zinc phenylphosphonate - calcium long - chain fatty acid salt - bifonazole prepared in Preparation Example 3 is used; in Example 7, the complex d of zinc phenylphosphonate - calcium long - chain fatty acid salt - bifonazole prepared in Preparation Example 4 is used; in Example 8, the complex e of zinc phenylphosphonate - calcium long - chain fatty acid salt - bifonazole prepared in Preparation Example 5 is used; in Example 9, the complex f of zinc phenylphosphonate - calcium long - chain fatty acid salt - bifonazole prepared in Preparation Example 6 is used; in Example 10, the complex g of zinc phenylphosphonate - calcium long - chain fatty acid salt - bifonazole prepared in Preparation Example 7 is used; in Example 11, the complex h of zinc phenylphosphonate - calcium long - chain fatty acid salt - bifonazole prepared in Preparation Example 8 is used; in Example 12, the complex i of zinc phenylphosphonate - calcium long - chain fatty acid salt - bifonazole prepared in Preparation Example 9 is used.

[0050] Examples 13 - 16

[0051] Examples 13 - 16 are based on the method of Example 1, with the specific variety of diol adjusted. Among them, 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; the diol in Example 16 is a mixture of ethylene glycol and 1,3 - butanediol in a weight ratio of 1:1.

[0052] Comparative Example Comparative Example 1

[0053] The polyester nucleating agent in this comparative example is a single component, specifically the complex a of zinc phenylphosphonate - calcium long - chain fatty acid salt - bifonazole obtained in Preparation Example 1.

[0054] Comparative Examples 2 - 4

[0055] Comparative Examples 2 - 4 are based on the method of Example 1, with the components and dosages of the polyester nucleating agent composition adjusted. For the specific adjustment situation, see Table 1 above.

[0056] Comparative Example 5 Based on the method of Example 1, in this comparative example, the complex a of zinc phenylphosphonate - calcium long - chain fatty acid salt - bifonazole is replaced with an equal amount of the complex of zinc phenylphosphonate - calcium long - chain fatty acid salt. The preparation method of the complex of zinc phenylphosphonate - calcium long - chain fatty acid salt includes the following steps: Take 50 mL of absolute ethanol (purity 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. Subsequently, carry out a heat preservation reaction for 1.5 h, 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 the complex of zinc phenylphosphonate - calcium long-chain fatty acid salt.

[0057] Comparative Example 6 Based on the method of Example 1, in this comparative example, the complex a of zinc phenylphosphonate - calcium long-chain fatty acid salt - bifonazole is replaced with an equal amount of the complex of zinc phenylphosphonate - bifonazole. The preparation method of the complex of zinc phenylphosphonate - bifonazole includes the following steps: Take 50 mL of absolute ethanol (purity 99.5%) and heat it to the reflux temperature of 80 °C. First, add 10.73 g of the above-mentioned zinc phenylphosphonate and mix evenly, then add 2.79 g of bifonazole and carry out a heat preservation reaction for 25 min, that is, the molar ratio of zinc phenylphosphonate, calcium stearate and bifonazole is approximately 0.8:0.15. After cooling to room temperature, filter and dry. After the weight of the product no longer changes, grind it into powder to obtain the complex of zinc phenylphosphonate - bifonazole.

[0058] Performance detection test

[0059] Take the polyester nucleating agent compositions prepared in Examples 1 - 16 above, the polyester nucleating agent of Comparative Example 1, and the polyester nucleating agent compositions prepared in Comparative Examples 2 - 6 as samples. For each example / comparative example, take 6 g of the sample and mix it evenly with 1000 g of polyester resin. The obtained mixture is put into a mixer and taken out after mixing at 260 °C for 5 min to obtain the corresponding polyester materials. Another group of polyester resins without adding polyester nucleating agent is set as the blank control group.

[0060] The present invention carried out DSC tests on the polyester materials corresponding to Examples 1 - 16, Comparative Examples 1 - 6 and the blank control group, including the following steps: Measure the crystallization peak temperature of the above-mentioned polyester materials through DSC. The specific temperature control process is as follows: Heat from 25 °C to 260 °C at a heating rate of 20 °C / min, then keep warm for 3 min to eliminate the thermal history, and then cool to 25 °C at a cooling rate of 10 °C / min. The test results are shown in Table 2 below. Among them, the crystallization peak temperature is a parameter to measure the crystallization speed of the polymer. The higher the crystallization peak temperature, the faster the crystallization speed, and it is more beneficial to shorten the processing and molding cycle of polyester.

[0061] Table 2 Crystallization peak temperature of polyester materials Nucleating agent Crystallization peak temperature (°C) 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 Combined with Table 2 above, by comparing the test results of Examples 1-4, Comparative Examples 1-6 and the blank control group, it can be obtained that the complex of zinc phenylphosphonate - calcium long-chain fatty acid salt - bifonazole, dimethyl terephthalate, glycerol triacetate and diol in the polyester nucleating agent composition of the present invention are compounded in set dosages, and the nucleating effect is well exerted.

[0062] By comparing the test results of Example 1 with those of Examples 5-12, it can be obtained that in the polyester nucleating agent composition of the present invention, it is preferably to use the complex of zinc phenylphosphonate - calcium long-chain fatty acid salt - bifonazole formed by complexing zinc phenylphosphonate and calcium long-chain fatty acid salt. Further preferably, the molar ratio of zinc phenylphosphonate, calcium long-chain fatty acid salt and bifonazole is 0.7-0.9:1:0.1-0.2 for the complex of zinc phenylphosphonate - calcium long-chain fatty acid salt - bifonazole. The polyester nucleating agent composition obtained thereby has higher crystallization peak temperature, crystallization heat enthalpy and crystallinity for the crystallization modification of polyester resin, and thus has a good nucleating effect. The calcium long-chain fatty acid salt therein is preferably one of calcium stearate and calcium palmitate, and further preferably calcium stearate.

[0063] By comparing the test results of Example 1 with those of Examples 13-16, it can be obtained that in the polyester nucleating agent composition of the present invention, the diol is preferably one or a mixture of ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol. Further preferably, the diol is a mixture of ethylene glycol and 1,3-propanediol mixed in a weight ratio of 1:1. The polyester nucleating agent composition obtained thereby can further improve the nucleating effect of polyester.

[0064] Application Examples Application Examples 1-5

[0065] In Application Examples 1-5, the polyester resin was subjected to crystallization modification with the polyester nucleating agent composition obtained in Example 1, and the modification steps were as follows: A set amount of the polyester nucleating agent composition was mixed evenly with 1000 g of polyester resin, and the obtained mixture was put into a mixer and taken out after mixing at 260°C for 5 minutes to obtain the corresponding polyester material, and DSC testing was also carried out. The dosages of the polyester nucleating agent composition in the above application examples and the test results of the corresponding polyester materials are shown in Table 3 below.

[0066] Table 3 Formulation table of Application Examples 1-5 and crystallization peak temperature of the corresponding polyester materials Polyester nucleating agent composition (g) Polyester resin (g) Crystallization peak temperature (°C) 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 It can be seen from the test results in Table 3 above that too much or too little dosage of the polyester nucleating agent composition of the present invention will affect its nucleating effect on polyester resin, and it is appropriate to use 0.5-0.8 parts of the polyester nucleating agent composition per 100 parts of polyester resin.

[0067] The specific embodiments are only explanations of the present invention and do not limit the present invention. After reading this specification, those skilled in the art can make modifications to these embodiments that do not contribute creatively as needed, but as long as they are within the scope of the claims of the present invention, they are protected by the 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.

2. The polyester nucleating agent composition according to claim 1, characterized in that: 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.

3. The polyester nucleating agent composition according to claim 2, characterized in that, The molar ratio of the zinc phenylphosphonate, the long-chain fatty acid calcium salt and bifonazole is 0.7-0.9:1:0.1-0.

2.

4. The polyester nucleating agent composition according to claim 2, characterized in that: 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 the 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 temperature for reaction for 1-2 hours, then adding a set amount of bifonazole and keeping the temperature for reaction for 20-30 minutes, cooling to room temperature and filtering and drying, so as to obtain the zinc phenylphosphonate-long-chain fatty acid calcium salt-bifonazole complex.

5. 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.

6. The polyester nucleating agent composition according to claim 1, wherein: 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.

7. The polyester nucleating agent composition according to claim 6, characterized in that: The diol is prepared by mixing ethylene glycol and 1,3-propylene glycol in a weight ratio of 1:

1.

8. A method for preparing the polyester nucleating agent composition according to any one of claims 1-7, characterized in that, The following steps are involved: Take an appropriate amount of ethanol and heat it to the reflux temperature, add a set amount of phenylphosphonic acid zinc-long chain fatty acid calcium salt-bifonazole complex, dimethyl terephthalate, triacetin and glycol in sequence and mix them evenly, after heat preservation for 2-3 hours, evaporate and recover the ethanol, collect the dried material and grind it to obtain the polyester nucleating agent composition.

9. 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 described in any one of claims 1-7.