A pet nucleating agent composition and its use

Abstract

The application relates to the field of nucleating agents, and particularly discloses a PET nucleating agent composition and application thereof. The PET nucleating agent composition comprises the following components in a mass ratio: 50-70 parts of a nucleating component, and 30-50 parts of a plasticizing component; the nucleating component is a carboxylated cyclodextrin-whisker composite; the carboxylated cyclodextrin-whisker composite is obtained by grafting inorganic salt whiskers with hyperbranched polymers and then reacting with carboxylated cyclodextrin; and the plasticizing component comprises polyethylene glycol and phthalate ester in a mass ratio of (2-5):1. The PET nucleating agent composition has the advantages of fast crystallization rate and good crystallization effect.

Description

Technical Field

[0001] This application relates to the field of nucleating agents, and more specifically, to a PET nucleating agent composition and its application. Background Technology

[0002] Polyethylene terephthalate (PET) possesses excellent mechanical properties and electrical insulation, and is characterized by low production cost and high cost-effectiveness, making it widely used in fibers, films, polyester bottles, and other fields. However, due to the rigid benzene rings and the presence of only two methylene groups in the PET molecular chain, its molecular chain has low flexibility, high rigidity, and poor chain segment mobility, resulting in a slow crystallization rate. This is unfavorable for injection molding and greatly limits the application of PET in the field of engineering plastics.

[0003] To improve the crystallization rate of PET, nucleating agents are often added to modify the PET material. Commonly used nucleating agents for PET mainly include inorganic nucleating agents, small organic molecule nucleating agents, and high organic polymer nucleating agents. Among them, high molecular weight carboxylate nucleating agents are currently the most widely used and have the best performance in PET polyester nucleating agents. Their molecular chains contain a small number of ionic groups, which undergo transesterification with PET at high temperatures to form PET-COONa ion clusters, providing heterogeneous nucleation sites for PET and promoting crystallization. Furthermore, due to their high molecular weight, they act similarly to chain extenders, with minimal impact on the molecular weight of PET. However, at high temperatures, PET-COONa further reacts to form disodium terephthalate, which has no effect on crystallization, thus reducing the crystallization rate of carboxylate nucleating agents.

[0004] In view of the above, this application is hereby submitted. Summary of the Invention

[0005] In order to obtain a PET nucleating agent with fast crystallization rate and better crystallization performance, this application provides a PET nucleating agent composition and its application.

[0006] In a first aspect, this application provides a PET nucleating agent composition, which adopts the following technical solution:

[0007] A PET nucleating agent composition comprising the following components in weight percentages:

[0008] Nucleating components 50-70%, plasticizing components 30-50%;

[0009] The nucleating component is a carboxylated cyclodextrin-inorganic salt whisker complex; the preparation method of the carboxylated cyclodextrin-inorganic salt whisker includes: grafting inorganic salt whiskers with a hyperbranched polymer, and then reacting them with carboxylated cyclodextrin.

[0010] The plasticizing component comprises polyethylene glycol and phthalate in a mass ratio of (2-6):1.

[0011] Preferably, the hyperbranched polymer is at least one of hydroxyl-terminated hyperbranched polyester and amino-terminated hyperbranched polyamide.

[0012] Preferably, the inorganic salt whiskers are selected from at least one of calcium carbonate whiskers and calcium sulfate whiskers.

[0013] By adopting the above technical solution, inorganic salt whiskers, as heterogeneous nucleation sites, can promote the orderly arrangement and crystallization of PET molecular chains. The high aspect ratio and high strength of the whiskers enable them to play a role in reinforcing and toughening PET, and can also hinder the transfer of heat and stress, thereby improving the heat resistance of PET. At the same time, inorganic salt whiskers, as effective nucleating agents, can improve the crystallization rate.

[0014] Hyperbranched polymer grafts onto inorganic salt whiskers and then react with carboxylated cyclodextrin to form a "bridge" effect, enhancing the interfacial interaction between the inorganic salt whiskers and the PET matrix. This helps improve the crystallization properties of the composite material. Furthermore, the interaction between the grafted material with a supramolecular structure formed by the combination of hyperbranched polymer and carboxylated cyclodextrin and the PET molecular chains helps promote the orderly arrangement of PET molecular chains and improve the crystallization effect of PET. The introduction of hyperbranched polymers also improves the dispersibility and compatibility of inorganic salt whiskers in PET, reduces agglomeration, and more effectively promotes nucleation.

[0015] The molecular recognition between hyperbranched polymers and cyclodextrins, along with the high-density functionalization of hyperbranched polymers, can enhance the multifunctionality of the complex and provide more crystallization centers. After reacting with carboxylated cyclodextrins, it can provide more crystallization sites, further improving the crystallization behavior of PET and increasing nucleation efficiency and crystallization rate. The complex treated with carboxylated cyclodextrins can improve the crystallization perfection of PET crystals, increasing the proportion of crystals with complete spherulites, which helps to improve the overall performance of PET materials.

[0016] Preferably, the preparation method of the carboxylated cyclodextrin-whisker complex includes:

[0017] Inorganic salt whiskers were modified by coupling agent and then grafted with hyperbranched polymer to obtain hyperbranched polymer-grafted whiskers.

[0018] In the presence of a catalyst, carboxylated cyclodextrin is reacted with hyperbranched polymer-grafted whiskers to obtain a carboxylated cyclodextrin-whisker complex.

[0019] Preferably, the ratio of carboxylated cyclodextrin, hyperbranched polymer, and inorganic salt whiskers is (0.2-0.8):(1-1.2):1.

[0020] Preferably, the coupling agent is an epoxy silane coupling agent.

[0021] Preferably, the catalyst is selected from N,N'-dicyclohexylcarboimide and 4-dimethylaminopyridine.

[0022] Preferably, the carboxylated cyclodextrin is carboxymethyl-β-cyclodextrin.

[0023] By adopting the above technical solution, one end of the epoxy silane coupling agent is coupled with the active groups on the surface of the whisker, and the other end reacts with the terminal hydroxyl hyperbranched polyester or terminal amino hyperbranched polyamide through the epoxy group, so that the hyperbranched polymer is combined with the whisker surface; finally, under the action of a catalyst, the carboxylated cyclodextrin reacts with the terminal hydroxyl or terminal amino of the hyperbranched polymer to obtain the carboxylated cyclodextrin-whisker complex.

[0024] Preferably, the phthalate is selected from at least one of diisobutyl phthalate, diethyl phthalate, diisodecyl phthalate, and di-n-octyl phthalate.

[0025] Preferably, the molecular weight of the polyethylene glycol is 600-2000.

[0026] By adopting the above technical solution, the combination of polyethylene glycol and phthalate can improve the mobility and flexibility of PET molecular chains, which helps to improve the PET grain structure, crystallization effect and crystallization performance.

[0027] Secondly, this application provides an application of a PET nucleating agent composition, employing the following technical solution:

[0028] Application of a PET nucleating agent composition, wherein the PET nucleating agent composition is added to PET material at an amount of 0.5-2%.

[0029] In summary, this application has the following beneficial effects:

[0030] 1. This application uses a carboxylated cyclodextrin-whisker complex obtained by grafting inorganic salt whiskers with hyperbranched polymers and then reacting them with carboxylated cyclodextrin as a nucleating component, which provides abundant nucleation sites for PET, can effectively improve the nucleation efficiency of PET, and is conducive to refining grains and improving the nucleation effect;

[0031] 2. The reinforcing and toughening effects of inorganic salt whiskers and the highly branched structure of hyperbranched polymer-carboxylated cyclodextrin supramolecular complex can help improve the mechanical properties of PET materials and enhance their heat resistance, while having little impact on the molecular weight of PET.

[0032] 3. This application improves the grain structure and crystallization properties by adding plasticizing components to adjust the nucleation effect of PET, thereby enhancing the mobility and flexibility of PET molecular chains. Detailed Implementation

[0033] To further aid in understanding the technical solution of this invention, several specific implementation examples are provided below to describe the technical solution of this invention in more detail. All of these described embodiments are only some embodiments of this invention, and not all of them.

[0034] The following specific embodiments can be combined with each other, and the same or similar concepts or processes may not be described again in some embodiments; and the reaction apparatus, monomer compounds, etc. involved in the following embodiments are all commercially available. Specifically, calcium sulfate whiskers are commercially available products with CAS number: 7778-18-9; silane coupling agent KH560 is a commercially available product with CAS number: 2530-83-8; silane coupling agent KH550 is a commercially available product with CAS number: 919-30-2; hydroxyl-terminated hyperbranched polyester is a commercially available product with model number H201; amino-terminated hyperbranched polyamide is a commercially available product with model number N101; carboxylated cyclodextrin, CAS number: 218269-34-2; polyethylene glycol, CAS number: 25322-68-3; diisobutyl phthalate, CAS number: 84-69-5; diethyl phthalate, CAS number: 84-66-2.

[0035] The following specific embodiments can be combined with each other, and the same or similar concepts or processes may not be described again in some embodiments.

[0036] The following examples further illustrate the present invention, but the invention is not limited thereto. Unless otherwise specified in the examples, all percentages (%) are mass percentages.

[0037] Preparation Example

[0038] Preparation Example 1

[0039] This preparation example provides a carboxylated cyclodextrin-whisker complex, prepared by the following method:

[0040] Dissolve silane coupling agent KH560 in 90wt% ethanol solution to prepare a 10wt% coupling agent solution. Immerse calcium sulfate whiskers in the solution at a mass-volume ratio of 1:20. Stir at 70℃ for 30 min. After separation, wash and dry to obtain activated whiskers.

[0041] One part by mass of hydroxyl-terminated hyperbranched polyester and one part by mass of activated whiskers were added to 10 parts by mass of N,N-dimethylformamide, ultrasonically dispersed evenly, and then the pH value was adjusted to 10. The reaction was carried out at 135℃ for 4 hours, centrifuged, washed with acetone and deionized water respectively, and dried to obtain hyperbranched polyester grafted calcium sulfate whiskers.

[0042] The hyperbranched polyester-grafted calcium sulfate whiskers were added to 20 parts by mass of tetrahydrofuran along with 0.2 parts by mass of carboxylated cyclodextrin and 0.2 parts by mass of 4-dimethylaminopyridine. The mixture was ultrasonically dispersed and reacted at room temperature for 12 hours. After centrifugation, the mixture was washed with acetone and deionized water, respectively, and then dried to obtain the carboxylated cyclodextrin-whisker complex.

[0043] Preparation Example 2

[0044] The only difference between this preparation example and Preparation Example 1 is that the preparation method of the carboxylated cyclodextrin-whisker complex is as follows:

[0045] Dissolve silane coupling agent KH560 in 90wt% ethanol solution to prepare a 10wt% coupling agent solution. Immerse calcium sulfate whiskers in the solution at a mass-volume ratio of 1:20. Stir at 70℃ for 30 min. After separation, wash and dry to obtain activated whiskers.

[0046] One part by mass of hydroxyl-terminated hyperbranched polyester and one part by mass of activated whiskers were added to 10 parts by mass of N,N-dimethylformamide, ultrasonically dispersed evenly, the pH value was adjusted to 10, and the reaction was carried out at 135℃ for 4 hours. After centrifugation, the mixture was washed with acetone and deionized water respectively and dried to obtain hyperbranched polyester grafted calcium sulfate whiskers.

[0047] The hyperbranched polyester-grafted calcium sulfate whiskers were added to 20 parts by mass of tetrahydrofuran along with 0.4 parts by mass of carboxylated cyclodextrin and 0.4 parts by mass of 4-dimethylaminopyridine. The mixture was ultrasonically dispersed and reacted at room temperature for 12 hours. After centrifugation, the mixture was washed with acetone and deionized water, respectively, and then dried to obtain the carboxylated cyclodextrin-whisker complex.

[0048] Preparation Example 3

[0049] The only difference between this preparation example and Preparation Example 1 is that the preparation method of the carboxylated cyclodextrin-whisker complex is as follows:

[0050] Dissolve silane coupling agent KH560 in 90wt% ethanol solution to prepare a 10wt% coupling agent solution. Immerse calcium sulfate whiskers in the solution at a mass-volume ratio of 1:20. Stir at 70℃ for 30 min. After separation, wash and dry to obtain activated whiskers.

[0051] One part by mass of hydroxyl-terminated hyperbranched polyester and one part by mass of activated whiskers were added to 10 parts by mass of N,N-dimethylformamide, ultrasonically dispersed evenly, the pH value was adjusted to 10, and the reaction was carried out at 135℃ for 4 hours. After centrifugation, the mixture was washed with acetone and deionized water respectively and dried to obtain hyperbranched polyester grafted calcium sulfate whiskers.

[0052] The hyperbranched polyester-grafted calcium sulfate whiskers were added to 20 parts by mass of tetrahydrofuran along with 0.5 parts by mass of carboxylated cyclodextrin and 0.5 parts by mass of 4-dimethylaminopyridine. The mixture was ultrasonically dispersed and reacted at room temperature for 14 hours. After centrifugation, the mixture was washed with acetone and deionized water, respectively, and then dried to obtain the carboxylated cyclodextrin-whisker complex.

[0053] Preparation Example 4

[0054] The only difference between this preparation example and Preparation Example 1 is that the preparation method of the carboxylated cyclodextrin-whisker complex is as follows:

[0055] Dissolve silane coupling agent KH560 in 90wt% ethanol solution to prepare a 10wt% coupling agent solution. Immerse calcium sulfate whiskers in the solution at a mass-volume ratio of 1:20. Stir at 70℃ for 30 min. After separation, wash and dry to obtain activated whiskers.

[0056] One part by mass of hydroxyl-terminated hyperbranched polyester and one part by mass of activated whiskers were added to 10 parts by mass of N,N-dimethylformamide, ultrasonically dispersed evenly, the pH value was adjusted to 10, and the reaction was carried out at 135℃ for 4 hours. After centrifugation, the mixture was washed with acetone and deionized water respectively and dried to obtain hyperbranched polyester grafted calcium sulfate whiskers.

[0057] The hyperbranched polyester-grafted calcium sulfate whiskers were added to 20 parts by mass of tetrahydrofuran along with 0.8 parts by mass of carboxylated cyclodextrin and 0.8 parts by mass of 4-dimethylaminopyridine. The mixture was ultrasonically dispersed and reacted at room temperature for 16 hours. After centrifugation, the mixture was washed with acetone and deionized water, respectively, and then dried to obtain the carboxylated cyclodextrin-whisker complex.

[0058] Preparation Example 5

[0059] The only difference between this preparation example and Preparation Example 1 is that the preparation method of the carboxylated cyclodextrin-whisker complex is as follows:

[0060] Dissolve silane coupling agent KH560 in 90wt% ethanol solution to prepare a 10wt% coupling agent solution. Immerse calcium sulfate whiskers in the solution at a mass-volume ratio of 1:20. Stir at 70℃ for 30 min. After separation, wash and dry to obtain activated whiskers.

[0061] One part by mass of amino-terminated hyperbranched polyamide and one part by mass of activated whiskers were added to 10 parts by mass of N,N-dimethylformamide, ultrasonically dispersed evenly, the pH value was adjusted to 10, and the reaction was carried out at 145℃ for 5 hours. After centrifugation, the mixture was washed with acetone and deionized water respectively and then dried to obtain hyperbranched polyester-grafted calcium sulfate whiskers.

[0062] The hyperbranched polyester-grafted calcium sulfate whiskers were added to 20 parts by mass of tetrahydrofuran along with 0.2 parts by mass of carboxylated cyclodextrin and 0.2 parts by mass of 4-dimethylaminopyridine. The mixture was ultrasonically dispersed and reacted at room temperature for 12 hours. After centrifugation, the mixture was washed with acetone and deionized water, respectively, and then dried to obtain the carboxylated cyclodextrin-whisker complex.

[0063] Preparation Example 6

[0064] The only difference between this preparation example and Preparation Example 1 is that this preparation example provides a carboxylated cyclodextrin-hyperbranched polyester grafted whisker mixture, which is prepared by the following method:

[0065] Dissolve silane coupling agent KH560 in 90wt% ethanol solution to prepare a 10wt% coupling agent solution. Immerse calcium sulfate whiskers in the solution at a mass-volume ratio of 1:20. Stir at 70℃ for 30 min. After separation, wash and dry to obtain activated whiskers.

[0066] One part by mass of hydroxyl-terminated hyperbranched polyester and one part by mass of activated whiskers were added to 10 parts by mass of N,N-dimethylformamide, ultrasonically dispersed evenly, the pH value was adjusted to 10, and the reaction was carried out at 135℃ for 4 hours. After centrifugation, the mixture was washed with acetone and deionized water respectively and dried to obtain hyperbranched polyester grafted calcium sulfate whiskers.

[0067] The calcium sulfate whiskers grafted onto the hyperbranched polyester were mixed with 0.2 parts by mass of carboxylated cyclodextrin and 0.2 parts by mass of deionized water, ultrasonically dispersed, and dried to obtain a mixture of carboxylated cyclodextrin and hyperbranched polyester grafted whiskers.

[0068] Preparation Example 7

[0069] The only difference between this preparation example and Preparation Example 1 is that this example provides a hyperbranched polyester grafted whisker, which is prepared by the following method:

[0070] Dissolve silane coupling agent KH560 in 90wt% ethanol solution to prepare a 10wt% coupling agent solution. Immerse calcium sulfate whiskers in the solution at a mass-volume ratio of 1:20. Stir at 70℃ for 30 min. After separation, wash and dry to obtain activated whiskers.

[0071] One part by mass of terminal hydroxyl hyperbranched polyester and one part by mass of activated whiskers were added to 10 parts by mass of N,N-dimethylformamide, ultrasonically dispersed evenly, the pH value was adjusted to 10, and the reaction was carried out at 135℃ for 4 hours. After centrifugation, the mixture was washed with acetone and deionized water respectively and then dried to obtain hyperbranched polyester grafted calcium sulfate whiskers.

[0072] Preparation Example 8

[0073] The only difference between this preparation example and Preparation Example 1 is that the preparation method of the carboxylated cyclodextrin-whisker complex is as follows:

[0074] Dissolve silane coupling agent KH550 in 90wt% ethanol solution to prepare a 10wt% coupling agent solution. Immerse calcium sulfate whiskers in the solution at a mass-volume ratio of 1:20. Stir at 70℃ for 30 min. After separation, wash and dry to obtain activated whiskers.

[0075] One part by mass of activated whiskers, 0.5 parts by mass of carboxylated cyclodextrin, and 0.5 parts by mass of 4-dimethylaminopyridine were added to 20 parts by mass of tetrahydrofuran, and the mixture was ultrasonically dispersed and reacted at room temperature for 12 h. After centrifugation, the mixture was washed with acetone and deionized water, and then dried to obtain the carboxylated cyclodextrin-whisker complex.

[0076] Preparation Example 9

[0077] The only difference between this preparation example and Preparation Example 1 is that this preparation example provides a nucleating component, which is obtained by uniformly mixing 1 part calcium sulfate whiskers, 1 part terminal hydroxyl hyperbranched polyester, and 0.2 parts carboxylated cyclodextrin.

[0078] Example

[0079] Example 1

[0080] This embodiment provides a PET nucleating agent composition comprising 70 parts by weight of the carboxylated cyclodextrin-whisker complex prepared in Preparation Example 1, 20 parts by weight of polyethylene glycol PEG600, and 10 parts by weight of diisobutyl phthalate.

[0081] The components are mixed and highly dispersed according to the specified ratio to obtain a PET nucleating agent composition.

[0082] Example 2

[0083] The only difference between this embodiment and Example 1 is that the PET nucleating agent composition includes 70 parts by mass of the carboxylated cyclodextrin-whisker complex prepared in Example 1, 25 parts by mass of polyethylene glycol PEG600, and 5 parts by mass of diisobutyl phthalate.

[0084] The components are mixed and highly dispersed according to the specified ratio to obtain a PET nucleating agent composition.

[0085] Example 3

[0086] The only difference between this embodiment and Example 1 is that the PET nucleating agent composition includes 50 parts by mass of the carboxylated cyclodextrin-whisker complex prepared in Example 1, 40 parts by mass of polyethylene glycol PEG600, and 10 parts by mass of diisobutyl phthalate.

[0087] The components are mixed and highly dispersed according to the specified ratio to obtain a PET nucleating agent composition.

[0088] Examples 4-7

[0089] Examples 4-7 are basically the same as Example 1, except that the carboxylated cyclodextrin-whisker complexes were prepared sequentially from Preparation Examples 2-5.

[0090] Example 8

[0091] This embodiment provides a PET nucleating agent composition comprising 70 parts by weight of the carboxylated cyclodextrin-whisker complex prepared in Preparation Example 1, 20 parts by weight of polyethylene glycol PEG600, and 10 parts by weight of diethyl phthalate.

[0092] The components are mixed and highly dispersed according to the specified ratio to obtain a PET nucleating agent composition.

[0093] Example 9

[0094] This embodiment provides a PET nucleating agent composition comprising 70 parts by weight of the carboxylated cyclodextrin-whisker complex prepared in Preparation Example 1, 20 parts by weight of polyethylene glycol PEG2000, and 10 parts by weight of diisobutyl phthalate.

[0095] The components are mixed and highly dispersed according to the specified ratio to obtain a PET nucleating agent composition.

[0096] Example 10

[0097] This embodiment provides a PET nucleating agent composition comprising 70 parts by weight of the carboxylated cyclodextrin-whisker complex prepared in Preparation Example 1 and 30 parts by weight of polyethylene glycol PEG600.

[0098] The components are mixed and highly dispersed according to the specified ratio to obtain a PET nucleating agent composition.

[0099] Example 11

[0100] This embodiment provides a PET nucleating agent composition comprising 70 parts by weight of the carboxylated cyclodextrin-whisker complex prepared in Preparation Example 1 and 30 parts by weight of diisobutyl phthalate.

[0101] The components are mixed and highly dispersed according to the specified ratio to obtain a PET nucleating agent composition.

[0102] Comparative Example

[0103] Comparative Example 1

[0104] The only difference between this comparative example and Example 1 is that the PET nucleating agent composition includes 70 parts by weight of calcium sulfate whiskers, 20 parts by weight of polyethylene glycol PEG600, and 10 parts by weight of diisobutyl phthalate.

[0105] The components are mixed and highly dispersed according to the specified ratio to obtain a PET nucleating agent composition.

[0106] Comparative Example 2

[0107] The only difference between this comparative example and Example 1 is that the PET nucleating agent composition includes 70 parts by mass of the carboxylated cyclodextrin-whisker complex prepared in Preparation Example 6, 20 parts by mass of polyethylene glycol PEG600, and 10 parts by mass of diisobutyl phthalate.

[0108] The components are mixed and highly dispersed according to the specified ratio to obtain a PET nucleating agent composition.

[0109] Comparative Example 3

[0110] The only difference between this comparative example and Example 1 is that the PET nucleating agent composition includes 70 parts by mass of the carboxylated cyclodextrin-whisker complex prepared in Preparation Example 7, 20 parts by mass of polyethylene glycol PEG600, and 10 parts by mass of diisobutyl phthalate.

[0111] The components are mixed and highly dispersed according to the specified ratio to obtain a PET nucleating agent composition.

[0112] Comparative Example 4

[0113] The only difference between this comparative example and Example 1 is that the PET nucleating agent composition includes 70 parts by mass of the carboxylated cyclodextrin-whisker complex prepared in Preparation Example 8, 20 parts by mass of polyethylene glycol PEG600, and 10 parts by mass of diisobutyl phthalate.

[0114] The components are mixed and highly dispersed according to the specified ratio to obtain a PET nucleating agent composition.

[0115] Comparative Example 5

[0116] The only difference between this comparative example and Example 1 is that the PET nucleating agent composition includes 70 parts by mass of the nucleating component obtained in Preparation Example 9, 20 parts by mass of polyethylene glycol PEG600, and 10 parts by mass of diisobutyl phthalate.

[0117] The components are mixed and highly dispersed according to the specified ratio to obtain a PET nucleating agent composition.

[0118] Performance testing

[0119] The PET nucleating agent compositions obtained in each example and comparative example were blended with PET material, wherein the amount of PET nucleating agent composition added was 1%. Extrusion granulation was performed in an extruder at an extrusion temperature of 265-285℃ and an extrusion speed of 50-300 r / min to obtain PET material, which was then analyzed by DSC (differential scanning calorimetry).

[0120] Record the glass transition temperature T of PET material g The results, including thermal crystallization temperature, crystallinity, enthalpy of crystallization ΔHm, and crystallization rate, are summarized in Table 1.

[0121] Table 1

[0122]

[0123]

[0124] As can be seen from Examples 1-11, Comparative Example 1, and Table 1, the polyester nucleating agent composition prepared by the method disclosed in this application can effectively improve the crystallization rate of PET material and improve the crystallization performance of PET.

[0125] As can be seen from Example 1, Comparative Examples 1-5, and Table 1, the reaction of whiskers grafted with terminal hydroxyl hyperbranched polyester and then reacted with carboxylated cyclodextrin can promote the crystallization rate of PET material. This may be because the terminal hydroxyl or terminal amino hyperbranched polymer has a highly branched structure, which can provide more active end groups. These active end groups can form strong interactions with inorganic salt whiskers and carboxylated cyclodextrin to form grafts with supramolecular structures, providing more abundant nucleation centers and effectively promoting the increase in crystallization rate. Furthermore, the interaction between this structure and PET molecular chains helps to promote the orderly arrangement of PET molecular chains and improve the crystallization effect of PET.

[0126] As can be seen from Example 1, Comparative Example 2, and Table 1, compared with the preparation of nucleating agents by mixing hyperbranched polymer-grafted whiskers and carboxylated cyclodextrin, the present application obtains nucleating agent components by grafting hyperbranched polymer-grafted whiskers and then reacting them with carboxylated cyclodextrin. This results in a better nucleation and crystallization effect on PET. This may be because the grafting of carboxylated cyclodextrin with terminal hydroxyl hyperbranched polyester can obtain a more stable supramolecular structure, which is more likely to adsorb PET molecular chains, promote the arrangement and crystallization of PET molecular chains, and improve the crystallization rate and crystallinity.

[0127] As can be seen from Examples 1, 10-11 and Comparative Example 1, and Table 1, the combination of polyethylene glycol and phthalate helps to improve the crystallization properties of PET materials. This may be because polyethylene glycol and phthalate can improve the flexibility and flowability of PET molecules, which helps to refine the grains and regulate the crystallization effect.

[0128] This specific embodiment is merely an explanation of this application and is not intended to limit it. After reading this specification, those skilled in the art can make modifications to this embodiment without contributing any inventive step, but such modifications are protected by patent law as long as they fall within the scope of the claims of this application.

Claims

1. A PET nucleating agent composition, characterized in that, It includes the following components by weight percentage: nucleating components 50-70%, plasticizing components 30-50%; The nucleating component is a carboxylated cyclodextrin-whisker complex; The preparation method of the carboxylated cyclodextrin-whisker complex includes: grafting inorganic salt whiskers with hyperbranched polymers, and then reacting them with carboxylated cyclodextrin. The plasticizing component comprises polyethylene glycol and phthalate in a mass ratio of (2-5):

1.

2. The PET nucleating agent composition according to claim 1, characterized in that, The hyperbranched polymer is at least one of hydroxyl-terminated hyperbranched polyester and amino-terminated hyperbranched polyamide.

3. The PET nucleating agent composition according to claim 1, characterized in that, The inorganic salt whiskers are selected from at least one of calcium carbonate whiskers and calcium sulfate whiskers.

4. The PET nucleating agent composition according to claim 1, characterized in that, The preparation method of the carboxylated cyclodextrin-whisker complex includes: Inorganic salt whiskers were modified by coupling agent and then grafted with hyperbranched polymer to obtain hyperbranched polymer-grafted whiskers. In the presence of a catalyst, carboxylated cyclodextrin is reacted with hyperbranched polymer-grafted whiskers to obtain a carboxylated cyclodextrin-whisker complex.

5. The PET nucleating agent composition according to claim 4, characterized in that, The mass ratio of the carboxylated cyclodextrin, hyperbranched polymer, and inorganic salt whiskers is (0.2-0.8):(1-1.2):

1.

6. The PET nucleating agent composition according to claim 4, characterized in that, The coupling agent is an epoxy silane coupling agent.

7. The PET nucleating agent composition according to claim 4, characterized in that, The catalyst is selected from N,N'-dicyclohexylcarboimide and 4-dimethylaminopyridine.

8. The PET nucleating agent composition according to claim 1, characterized in that, The phthalate is selected from at least one of diisobutyl phthalate, diethyl phthalate, diisodecyl phthalate, and di-n-octyl phthalate.

9. The PET nucleating agent composition according to claim 1, characterized in that, The molecular weight of the polyethylene glycol is 600-2000.

10. The application of a PET nucleating agent composition according to any one of claims 1-9, characterized in that, The PET nucleating agent composition is added to the PET material at an amount of 0.5-2%.

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