Heat stabilizer for PVC and preparation method, modifier, and use

Abstract

The present invention provides a heat stabilizer for PVC and a preparation method, a modifier, and a use, and provides a tung oil-derived nitrogen-containing zirconium carboxylate heat stabilizer and a tung oil-derived calcium / zinc imidazole carboxylate heat stabilizer, and preparation methods therefor. The tung oil-derived nitrogen-containing zirconium carboxylate and the tung oil-derived calcium / zinc imidazole carboxylate are used as a composite heat stabilizer which is then compounded with an antioxidant 1010, an antioxidant 168, and stearic acid to prepare a modifier containing the tung oil-derived nitrogen-containing zirconium carboxylate composite heat stabilizer. The composite heat stabilizer and the modifier prepared by the present invention have the characteristics of no toxicity, no heavy metal, environmental friendliness and the like, and endow the PVC with excellent initial and long-term thermal stability. The preparation methods of the present invention involve a simple processing and manufacturing process and have low processing costs, exhibit environmental friendliness and no toxicity, and are suitable for industrial mass production and promotion.

Description

A heat stabilizer for PVC, preparation method, modifier and application thereof Technical Field

[0001] The present invention belongs to the field of plastic additives, and in particular relates to a heat stabilizer for PVC, a preparation method thereof, a modifier and applications thereof. Background Art

[0002] Thermal stabilizers are essential additives for the processing of polyvinyl chloride (PVC) resins, and their research has become increasingly in-depth with the widespread use of PVC. The main types of thermal stabilizers currently available are: lead salts, organotin, metal soaps, and organic nitrogen. Lead salts and organotin thermal stabilizers have good long-term thermal stability, but are gradually being phased out of the market due to their toxicity. Pure organic thermal stabilizers have relatively poor thermal stabilization effects and are usually used as auxiliary thermal stabilizers, so heavy metal-free metal soap thermal stabilizers have become a hot topic of research. Heavy metal-free metal soap thermal stabilizers are mainly commercially available calcium stearate zinc soap thermal stabilizers, which are environmentally friendly and low-cost. Calcium stearate soap or zinc stearate soap alone cannot be used directly as a thermal stabilizer. Using a combination of the two as a PVC thermal stabilizer is prone to cause a "zinc burn" reaction, so a variety of other auxiliary thermal stabilizers are needed to compensate for the shortcomings of the calcium stearate zinc composite thermal stabilizer in stabilizing PVC.

[0003] Therefore, a new type of metal soap derived from tung oil and containing special heat-stabilizing functional groups was developed to make up for the shortcomings of calcium zinc heat stabilizer in heat-stabilizing PVC.

[0004] Summary of the Invention

[0005] In view of the shortcomings of the existing technology, the present invention provides a tung oil-derived nitrogen-containing zirconium carboxylate heat stabilizer for PVC, a tung oil-derived imidazole carboxylate calcium / zinc heat stabilizer and a preparation method thereof, as well as a composite heat stabilizer formed by compounding the tung oil-derived nitrogen-containing zirconium carboxylate heat stabilizer and the tung oil-derived imidazole carboxylate calcium / zinc, and a modifier for PVC; thus, a green composite heat stabilizer with excellent initial and long-term thermal stability is obtained.

[0006] The present invention achieves the above technical objectives through the following technical means.

[0007] A tung oil-derived nitrogen-containing zirconium carboxylate heat stabilizer for PVC, characterized in that the tung oil-derived zirconium amic acid has the structural formula:

[0008] The preparation method of the tung oil-derived nitrogen-containing zirconium carboxylate heat stabilizer for PVC is characterized by being prepared by the following steps:

[0009] Step 1: Add 90-100g of tung oil anhydride to the reactor 50 mL of acetone was added with 20 g of p-aminobenzoic acid under nitrogen atmosphere and reacted at 50-60°C for 3-4 hours. After the reaction, the mixture was rotary evaporated and dried to obtain a light yellow solid, which was tung oil-based amic acid.

[0010] Step 2: Tung oil-based amic acid and isopropyl alcohol are added to a reactor in a mass ratio of 1:(1-2). When the temperature is raised to 65°C, a zirconium acetate solution with a zirconium content of 15wt.%-16wt.% is added in a mass ratio of (3.0-5.0) to tung oil-based amic acid:1, and then stirring is continued at 75-80°C for 30 minutes. After the reaction is completed, the mixture is filtered and dried to obtain a beige solid powder, which is tung oil-based zirconium amic acid.

[0011] Furthermore, the mass ratio of the zirconium acetate solution to the tung oil-based amic acid is (3.20-4.80):1.

[0012] A tung oil-derived imidazole carboxylate calcium / zinc heat stabilizer for PVC, characterized in that the molecular structural formulas of the tung oil-derived imidazole carboxylate calcium and the tung oil-derived imidazole carboxylate zinc are:

[0013] Wherein, R1 is Ca or Zn, and R2 is any one selected from the following

[0014] The preparation method of the tung oil-derived imidazole carboxylate calcium / zinc heat stabilizer for PVC is characterized by being prepared by the following steps:

[0015] Step 1: Add tung oil anhydride and N,N-dimethylformamide in a mass ratio of 1:(1-2) into a reactor, heat to 45-60°C under a nitrogen atmosphere, add compound A in a molar ratio of (1-1.1):1 to tung oil anhydride, and react at 45-60°C for 3-5 hours; filter and rotary evaporate to obtain a light yellow liquid, which is tung oil-based oxadiazole acid;

[0016] The second step is to add tung oil-based imidazole acid and anhydrous ethanol in a mass ratio of 1:2 into a reaction vessel, add sodium hydroxide in a molar ratio of (0.45-0.50) to tung oil-based imidazole acid in multiple batches at 60-70° C., and continue stirring at 70° C. for 1 hour; then, completely dissolve calcium chloride or zinc sulfate heptahydrate in anhydrous ethanol in a molar ratio of (0.45-0.50) to tung oil-based imidazole acid in 1 and add them to the reactor in batches; after the reaction, filter, wash with deionized water, and vacuum dry to obtain tung oil-derived imidazole carboxylate calcium or tung oil-derived imidazole carboxylate zinc.

[0017] Furthermore, the compound A is at least one of 5-amino-1H-tetrazole, 3-amino-1,2,4-triazole, and 4-amino-4H-1,2,4-triazole.

[0018] A composite heat stabilizer containing tung oil-derived nitrogen-containing zirconium carboxylate for PVC is characterized by comprising the following components in parts by weight: 0.67-2 parts of tung oil-derived zirconium amic acid, 0-1.33 parts of tung oil-derived imidazole carboxylate calcium, or 0-1.33 parts of tung oil-derived imidazole carboxylate zinc.

[0019] Furthermore, the mass ratio of the tung oil-derived zirconium amidate to the tung oil-derived imidazole carboxylate calcium is 1:1.

[0020] 9. A PVC modifier containing a tung oil-derived nitrogen-containing zirconium carboxylate composite heat stabilizer, characterized in that it is composed of the following components in parts by weight: 2 parts of tung oil-derived nitrogen-containing zirconium carboxylate / calcium / zinc heat stabilizer, 0.25 parts of antioxidant 1010, 0.25 parts of antioxidant 168, and 0.5 parts of stearic acid.

[0021] The application of the PVC modifier is characterized in that it is used to prepare PVC products and improve the thermal stability of PVC products.

[0022] The tung oil-derived nitrogen-containing zirconium carboxylate and tung oil-derived imidazole carboxylate calcium / zinc of the present invention both use tung oil-derived anhydride as raw material, have abundant raw material sources, are inexpensive, and are free from dependence on petrochemical resources.

[0023] Compared with metal composite heat stabilizers based on common fatty acids as a basic skeleton, the tung oil-derived nitrogen-containing zirconium carboxylate composite heat stabilizer prepared in the present invention has the following advantages: tung oil-derived zirconium amidate soap can both neutralize HCl and replace unstable chlorine atoms with carboxylate radicals, and its conversion product, zirconium chloride, has no catalytic effect, thereby inhibiting initial coloration and slowing down the HCl removal rate of PVC; and the heat-stabilizing functional group imidazole contained in tung oil-derived imidazole calcium carboxylate and tung oil-derived imidazole zinc carboxylate can rapidly absorb hydrogen chloride and chlorine free radicals, and exhibits excellent initial and long-term heat stability when used in conjunction with zirconium soap. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] FIG1 is an infrared spectrum of tung oil-derived zirconium amidate, tung oil-derived anhydride, tung oil-derived anhydride-p-aminobenzoic acid adduct;

[0025] FIG2 is an infrared spectrum of tung oil-derived imidazole carboxylic acid anhydride, tung oil-derived imidazole carboxylic acid anhydride-imidazole adduct, tung oil-derived imidazole carboxylic acid calcium, and tung oil-derived imidazole carboxylic acid zinc. DETAILED DESCRIPTION

[0026] The present invention will be further described below with reference to the accompanying drawings and specific embodiments. The following are preferred embodiments of the present invention, but the protection scope of the present invention is not limited thereto.

[0027] Example 1:

[0028] (1) Add 95 g of tung oil anhydride and 50 mL of acetone to a reactor, then add 20 g of p-aminobenzoic acid under a nitrogen atmosphere, and react at 55° C. for 4 h. After the reaction, evaporate and dry to obtain a light yellow solid, which is tung oil-based amic acid.

[0029] (2) Tung oil-based amic acid and isopropyl alcohol are added to a reactor in a mass ratio of 1:2. When the temperature is raised to 65°C, a zirconium acetate solution having a zirconium content of 15wt.%-16wt.% is added in a mass ratio of 4.2:1 to oleyl amic acid, and then stirring is continued at 75-80°C for 30 minutes. After the reaction is completed, the mixture is filtered and dried to obtain a beige solid powder, which is tung oil-based amic acid zirconium.

[0030] (3) Add tung oil anhydride and N,N-dimethylformamide into the reactor at a mass ratio of 1:2, heat to 60°C under nitrogen atmosphere, add 5-amino-1H-tetrazole at a molar ratio of 1.05:1 to tung oil anhydride, and react at 45-60°C for 3 hours; filter and rotary evaporate to obtain a light yellow liquid, which is tung oil-based azole acid;

[0031] (4) Tung oil-based imidazole acid and anhydrous ethanol are added to a reaction vessel in a mass ratio of 1:2, and sodium hydroxide with a molar ratio of 0.48:1 to tung oil-based imidazole acid is added in multiple batches at 60-70°C, and stirring is continued at 70°C for 1 hour; then calcium chloride with a molar ratio of 0.48:1 to tung oil-based imidazole acid is completely dissolved in anhydrous ethanol and added to the reactor in batches; after the reaction is completed, the mixture is filtered, washed with deionized water, and vacuum dried to obtain tung oil-based imidazole carboxylate calcium.

[0032] (5) One part of tung oil-derived zirconium amide acid and one part of tung oil-derived imidazole carboxylate calcium are compounded into a composite heat stabilizer, which is then compounded with 0.25 parts of antioxidant 1010, 0.25 parts of antioxidant 168, and 0.5 parts of stearic acid to obtain a modifier for PVC, which is used to improve the thermal stability of PVC.

[0033] It should be noted that when preparing the PVC modifier, 1 part of tung oil-derived zirconium amide, 1 part of tung oil-derived calcium imidazole carboxylate, 0.25 parts of antioxidant 1010, 0.25 parts of antioxidant 168, and 0.5 parts of stearic acid can also be directly mixed.

[0034] The infrared spectrum of the tung oil-derived zirconium amic acid prepared in this example is shown in Figure 1. The infrared spectra of tung oil anhydride and tung oil anhydride-p-aminobenzoic acid adduct are compared. The infrared spectra of tung oil anhydride-p-aminobenzoic acid adduct contain 1870 and 1792 cm -1 The characteristic absorption peaks of anhydride disappeared; 2925 and 2856 cm -1 The characteristic peaks of CH antisymmetric stretching vibration and CH symmetric stretching vibration of alkanes in tungaronic anhydride are retained; 3026, 1605 and 853 cm -1The characteristic absorption peaks of benzene ring appear at 3341 and 3255 cm -1 (NH stretching vibration), 1289cm -1 (CN stretching vibration) and 1532cm -1 (NH bending vibration) shows characteristic absorption peaks of amide structure; 2679 and 2533 cm -1 Carboxylic acid OH stretching vibration appears; 1742 cm -1 The C=O stretching vibration characteristic peak of the ester group in the tung oil anhydride was retained, which shows that the tung oil anhydride-p-aminobenzoic acid adduct was successfully synthesized. From the infrared spectrum of the tung oil-derived amic acid zirconium salt in Figure 1, it can be seen that the peaks at 2679 and 2533 cm -1 There is no characteristic absorption peak of carboxylic acid OH stretching vibration at 3341 and 3255 cm -1 Shift to 3435 and 3337 cm -1 ; 1176cm -1 The characteristic peak at 1560cm is due to the stretching vibration of CN in amide; -1 and 1441cm -1 The characteristic absorption peaks of symmetric and asymmetric stretching vibrations of carboxylate appeared at the positions of the 5′-1′′-HEXANOIN. Thus, the adduct of tungsten anhydride and p-aminobenzoic acid was successfully converted into the corresponding zirconium soap.

[0035] The infrared spectrum of the tung oil-derived imidazole carboxylic acid calcium salt prepared in this example is shown in Figure 2. The infrared spectra of tung oil anhydride and tung oil anhydride-imidazole adduct are compared. The infrared spectra of tung oil anhydride-imidazole adduct have the following peaks: 1865 and 1784 cm -1 The characteristic absorption peaks of anhydride disappeared; 2863 and 2933 cm -1 The characteristic peaks of CH symmetric stretching vibration and antisymmetric stretching vibration of alkanes in tungaronic anhydride are retained; ~3026cm -1 (NH stretching vibration), 1251cm -1 (CN stretching vibration) and 737cm -1 (NH out-of-plane bending vibration) shows a characteristic absorption peak of amide structure; 2554cm -1 Carboxylic acid OH stretching vibration appears; 1742 cm -1 The characteristic peak of C=O stretching vibration of ester group in tung-malic anhydride is retained. From the infrared spectrum of calcium salt in Figure 2, we can see that 2554cm -1 There is no characteristic absorption peak of carboxylic acid OH stretching vibration at 3267 cm -1 Offset to 3415cm -1 The characteristic peak of CN stretching vibration in amide is from 1110cm -1Offset to 1116cm -1 ; 1440 and 1574cm at the same time -1 The characteristic absorption peaks of symmetric and asymmetric stretching vibrations of carboxylate appeared at , respectively. Thus, the tungsten anhydride-imidazole adduct was successfully converted into the corresponding calcium salt.

[0036] Example 2

[0037] (1) Add 95 g of tung oil anhydride and 50 mL of acetone to a reactor, then add 20 g of p-aminobenzoic acid under a nitrogen atmosphere, and react at 55° C. for 4 h. After the reaction, evaporate and dry to obtain a light yellow solid, which is tung oil-based amic acid.

[0038] (2) Tung oil-based amic acid and isopropyl alcohol are added to a reactor in a mass ratio of 1:2. When the temperature is raised to 65°C, a zirconium acetate solution with a zirconium content of 15wt.%-16wt.% is added in a mass ratio of 3.2:1 to oleyl amic acid, and then stirring is continued at 75°C for 30 minutes. After the reaction is completed, the mixture is filtered and dried to obtain a beige solid powder, which is tung oil-based amic acid zirconium.

[0039] (3) Add tung oil-based anhydride and N,N-dimethylformamide into the reactor at a mass ratio of 1:2. Under nitrogen atmosphere, heat to 60°C. Add 3-amino-1,2,4-triazole at a molar ratio of 1.1:1 to tung oil-based anhydride. React at 60°C for 4 hours. After filtration and rotary evaporation, a light yellow liquid is obtained, which is tung oil-based triazole acid.

[0040] (4) Tung oil-based imidazole acid and anhydrous ethanol are added to a reaction vessel in a mass ratio of 1:2, and sodium hydroxide with a molar ratio of 0.48:1 to tung oil-based imidazole acid is added in multiple batches at 60-70°C, and stirring is continued at 70°C for 1 hour; then calcium chloride with a molar ratio of 0.48:1 to tung oil-based imidazole acid is completely dissolved in anhydrous ethanol and added to the reactor in batches; after the reaction is completed, the mixture is filtered, washed with deionized water, and vacuum dried to obtain tung oil-based imidazole carboxylate calcium.

[0041] (5) 0.67 parts of tung oil-derived zirconium amide acid and 1.33 parts of tung oil-derived imidazole carboxylate calcium were compounded into a composite heat stabilizer, which was then compounded with 0.25 parts of antioxidant 1010, 0.25 parts of antioxidant 168, and 0.5 parts of stearic acid to obtain a PVC modifier containing a tung oil-derived nitrogen-containing zirconium carboxylate composite heat stabilizer.

[0042] Example 3

[0043] (1) Add 95 g of tung oil anhydride and 50 mL of acetone to a reactor, then add 20 g of p-aminobenzoic acid under a nitrogen atmosphere, and react at 55° C. for 3 h. After the reaction, evaporate and dry to obtain a light yellow solid, which is tung oil-based amic acid.

[0044] (2) Tung oil-based amic acid and isopropyl alcohol are added to a reactor in a mass ratio of 1:2. When the temperature is raised to 65°C, a zirconium acetate solution having a zirconium content of 15wt.%-16wt.% is added in a mass ratio of 4.8:1 to oleyl amic acid, and then stirring is continued at 75°C for 30 minutes. After the reaction is completed, the mixture is filtered and dried to obtain a beige solid powder, which is tung oil-based amic acid zirconium.

[0045] (3) Add tung oil-based anhydride and N,N-dimethylformamide into the reactor at a mass ratio of 1:2. Under nitrogen atmosphere, heat to 50°C. Add 4-amino-4H-1,2,4-triazole at a molar ratio of 1.1:1 to tung oil-based anhydride. React at 50°C for 5 hours. Filter and evaporate to obtain a light yellow liquid, which is tung oil-based triazole acid.

[0046] (4) Tung oil-based imidazole acid and anhydrous ethanol are added to a reaction vessel in a mass ratio of 1:2, and sodium hydroxide with a molar ratio of 0.48:1 to tung oil-based imidazole acid is added in multiple batches at 60-70°C, and stirring is continued at 70°C for 1 hour; then calcium chloride with a molar ratio of 0.48:1 to tung oil-based imidazole acid is completely dissolved in anhydrous ethanol and added to the reactor in batches; after the reaction is completed, the mixture is filtered, washed with deionized water, and vacuum dried to obtain tung oil-based imidazole carboxylate calcium.

[0047] (5) 1.33 parts of tung oil-derived zirconium amide acid, 0.67 parts of tung oil-derived imidazole carboxylate calcium, 0.25 parts of antioxidant 1010, 0.25 parts of antioxidant 168, and 0.5 parts of stearic acid were compounded to obtain a PVC modifier containing a tung oil-derived nitrogen-containing zirconium carboxylate composite heat stabilizer.

[0048] Example 4

[0049] (1) Add 95 g of tung oil anhydride and 50 mL of acetone to a reactor, then add 20 g of p-aminobenzoic acid under a nitrogen atmosphere, and react at 60° C. for 4 h. After the reaction, evaporate and dry to obtain a light yellow solid, which is tung oil-based amic acid.

[0050] (2) Tung oil-based amic acid and isopropyl alcohol are added to a reactor in a mass ratio of 1:2. When the temperature is raised to 65°C, a zirconium acetate solution having a zirconium content of 15wt.%-16wt.% is added in a mass ratio of 3.2:1 to oleyl amic acid, and then stirring is continued at 80°C for 30 minutes. After the reaction is completed, the mixture is filtered and dried to obtain a beige solid powder, which is tung oil-based amic acid zirconium.

[0051] (3) Add tung oil anhydride and N,N-dimethylformamide into the reactor at a mass ratio of 1:2, and heat to 50°C under nitrogen atmosphere. Add 3-amino-1,2,4-triazole at a molar ratio of 1:1 to tung oil anhydride, and react at 60°C for 5 hours. After filtration and rotary evaporation, a light yellow liquid is obtained, which is tung oil-based triazole acid.

[0052] (4) Tung oil-based nitroaniline and anhydrous ethanol were added to a reaction vessel in a mass ratio of 1:2, and sodium hydroxide was added in multiple batches at a molar ratio of 0.48:1 to tung oil-based nitroaniline at 60-70°C, and stirring was continued at 70°C for 1 hour; then zinc sulfate heptahydrate was completely dissolved in anhydrous ethanol at a molar ratio of 0.48:1 to tung oil-based nitroaniline and added to the reactor in batches; after the reaction was completed, the mixture was filtered, washed with deionized water, and vacuum dried to obtain tung oil-derived imidazole carboxylic acid zinc. As shown in Figure 2, the tung oil-based imidazole adduct was successfully converted into the corresponding zinc salt, tung oil-derived imidazole carboxylic acid zinc.

[0053] (5) 1 part of tung oil-derived zirconium amide acid, 1 part of tung oil-derived imidazole carboxylate zinc, 0.25 parts of antioxidant 1010, 0.25 parts of antioxidant 168, and 0.5 parts of stearic acid were compounded to obtain a PVC modifier containing a tung oil-derived nitrogen-containing zirconium carboxylate composite heat stabilizer.

[0054] Example 5

[0055] (1) Add 95 g of tung oil anhydride and 50 mL of acetone to a reactor, then add 20 g of p-aminobenzoic acid under a nitrogen atmosphere, and react at 60° C. for 4 h. After the reaction, evaporate and dry to obtain a light yellow solid, which is tung oil-based amic acid.

[0056] (2) Tung oil-based amic acid and isopropyl alcohol are added to a reactor in a mass ratio of 1:2. When the temperature is raised to 65°C, a zirconium acetate solution with a zirconium content of 15wt.%-16wt.% is added in a mass ratio of 3.2:1 to oleyl amic acid, and then stirring is continued at 80°C for 30 minutes. After the reaction is completed, the mixture is filtered and dried to obtain a beige solid powder, which is tung oil-based amic acid zirconium.

[0057] (3) Add tung oil anhydride and N,N-dimethylformamide into the reactor at a mass ratio of 1:2, and heat to 60°C under nitrogen atmosphere. Add 3-amino-1,2,4-triazole at a molar ratio of 1.1:1 to tung oil anhydride, and react at 60°C for 3 hours. After filtration and rotary evaporation, a light yellow liquid is obtained, which is tung oil-based triazole acid.

[0058] (4) Tung oil-based imidazole acid and anhydrous ethanol are added to a reaction vessel in a mass ratio of 1:2, and sodium hydroxide with a molar ratio of 0.48:1 to tung oil-based imidazole acid is added in multiple batches at 70°C, and stirring is continued at 70°C for 1 hour; then zinc sulfate heptahydrate with a molar ratio of 0.48:1 to tung oil-based imidazole acid is completely dissolved in anhydrous ethanol and added to the reactor in batches; after the reaction is completed, the mixture is filtered, washed with deionized water, and vacuum dried to obtain tung oil-based imidazole carboxylic acid zinc.

[0059] (5) 0.67 parts of tung oil-derived zirconium amide acid, 1.33 parts of tung oil-derived imidazole carboxylate zinc, 0.25 parts of antioxidant 1010, 0.25 parts of antioxidant 168, and 0.5 parts of stearic acid were compounded to obtain a PVC modifier containing a tung oil-derived nitrogen-containing zirconium carboxylate composite heat stabilizer.

[0060] Example 6

[0061] (1) Add 95 g of tung oil anhydride and 50 mL of acetone to a reactor, then add 20 g of p-aminobenzoic acid under a nitrogen atmosphere, and react at 60° C. for 4 h. After the reaction, evaporate and dry to obtain a light yellow solid, which is tung oil-based amic acid.

[0062] (2) Tung oil-based amic acid and isopropyl alcohol are added to a reactor in a mass ratio of 1:2. When the temperature is raised to 65°C, a zirconium acetate solution having a zirconium content of 15wt.%-16wt.% is added in a mass ratio of 4.8:1 to oleyl amic acid, and then stirring is continued at 80°C for 30 minutes. After the reaction is completed, the mixture is filtered and dried to obtain a beige solid powder, which is tung oil-based amic acid zirconium.

[0063] (3) Add tung oil anhydride and N,N-dimethylformamide into the reactor at a mass ratio of 1:2, and heat to 60°C under nitrogen atmosphere. Add 4-amino-4H-1,2,4-triazole at a molar ratio of 1.1:1 to tung oil anhydride, and react at 50°C for 5 hours. After filtration and rotary evaporation, a light yellow liquid is obtained, which is tung oil-based triazole acid.

[0064] (4) Tung oil-based imidazole acid and anhydrous ethanol are added to a reaction vessel in a mass ratio of 1:2, and sodium hydroxide with a molar ratio of 0.48:1 to tung oil-based imidazole acid is added in multiple batches at 60°C, and stirring is continued at 70°C for 1 hour; then zinc sulfate heptahydrate with a molar ratio of 0.48:1 to tung oil-based imidazole acid is completely dissolved in anhydrous ethanol and added to the reactor in batches; after the reaction is completed, the mixture is filtered, washed with deionized water, and vacuum dried to obtain tung oil-based imidazole carboxylic acid zinc.

[0065] (5) 1.33 parts of tung oil-derived zirconium amide acid, 0.67 parts of tung oil-derived imidazole carboxylate zinc, 0.25 parts of antioxidant 1010, 0.25 parts of antioxidant 168, and 0.5 parts of stearic acid were compounded to obtain a PVC modifier containing a tung oil-derived nitrogen-containing zirconium carboxylate composite heat stabilizer.

[0066] Example 7

[0067] (1) Add 95 g of tung oil anhydride and 50 mL of acetone to a reactor, then add 20 g of p-aminobenzoic acid under a nitrogen atmosphere, and react at 60° C. for 4 h. After the reaction, evaporate and dry to obtain a light yellow solid, which is tung oil-based amic acid.

[0068] (2) Tung oil-based amic acid and isopropyl alcohol are added to a reactor in a mass ratio of 1:2. When the temperature is raised to 65°C, a zirconium acetate solution having a zirconium content of 15wt.%-16wt.% is added in a mass ratio of 4.2:1 to oleyl amic acid, and then stirring is continued at 75°C for 30 minutes. After the reaction is completed, the mixture is filtered and dried to obtain a beige solid powder, which is tung oil-based amic acid zirconium.

[0069] (3) Add tung oil anhydride and N,N-dimethylformamide into the reactor at a mass ratio of 1:2, and heat to 60°C under nitrogen atmosphere. Add 5-amino-1H-tetrazole at a molar ratio of 1.05:1 to tung oil anhydride, and react at 50°C for 5 hours. After filtration and rotary evaporation, a light yellow liquid is obtained, which is tung oil-based azole acid.

[0070] (4) Tung oil-based imidazole acid and anhydrous ethanol are added to a reaction vessel in a mass ratio of 1:2, and sodium hydroxide with a molar ratio of 0.48:1 to tung oil-based imidazole acid is added in multiple batches at 60-70°C, and stirring is continued at 70°C for 1 hour; then calcium chloride with a molar ratio of 0.48:1 to tung oil-based imidazole acid is completely dissolved in anhydrous ethanol and added to the reactor in batches; after the reaction is completed, the mixture is filtered, washed with deionized water, and vacuum dried to obtain tung oil-based imidazole carboxylate calcium.

[0071] (5) 0.67 parts of tung oil-derived zirconium amide acid, 1.33 parts of tung oil-derived imidazole carboxylate calcium, 0.25 parts of antioxidant 1010, 0.25 parts of antioxidant 168, and 0.5 parts of stearic acid were compounded to obtain a PVC modifier containing a tung oil-derived nitrogen-containing zirconium carboxylate composite heat stabilizer.

[0072] Example 8

[0073] (1) Add 95 g of tung oil anhydride and 50 mL of acetone to a reactor, then add 20 g of p-aminobenzoic acid under a nitrogen atmosphere, and react at 60° C. for 4 h. After the reaction, evaporate and dry to obtain a light yellow solid, which is tung oil-based amic acid.

[0074] (2) Tung oil-based amic acid and isopropyl alcohol are added to a reactor in a mass ratio of 1:2. When the temperature is raised to 65°C, a zirconium acetate solution with a zirconium content of 15wt.%-16wt.% is added in a mass ratio of 3.2:1 to oleyl amic acid, and then stirring is continued at 80°C for 30 minutes. After the reaction is completed, the mixture is filtered and dried to obtain a beige solid powder, which is tung oil-based amic acid zirconium.

[0075] (3) Add tung oil anhydride and N,N-dimethylformamide into the reactor at a mass ratio of 1:2, and heat to 60°C under nitrogen atmosphere. Add 3-amino-1,2,4-triazole at a molar ratio of 1:1 to tung oil anhydride, and react at 60°C for 3 hours. After filtration and rotary evaporation, a light yellow liquid is obtained, which is tung oil-based triazole acid.

[0076] (4) Tung oil-based imidazole acid and anhydrous ethanol are added to a reaction vessel in a mass ratio of 1:2, and sodium hydroxide with a molar ratio of 0.48:1 to tung oil-based imidazole acid is added in multiple batches at 70°C, and stirring is continued at 70°C for 1 hour; then calcium chloride with a molar ratio of 0.48:1 to tung oil-based imidazole acid is completely dissolved in anhydrous ethanol and added to the reactor in batches; after the reaction is completed, the mixture is filtered, washed with deionized water, and vacuum dried to obtain tung oil-based imidazole carboxylate calcium.

[0077] (5) 1.33 parts of tung oil-derived zirconium amide acid, 0.67 parts of tung oil-derived imidazole carboxylate calcium, 0.25 parts of antioxidant 1010, 0.25 parts of antioxidant 168, and 0.5 parts of stearic acid were compounded to obtain a PVC modifier containing a tung oil-derived nitrogen-containing zirconium carboxylate composite heat stabilizer.

[0078] Example 9

[0079] (1) Add 95 g of tung oil anhydride and 50 mL of acetone to a reactor, then add 20 g of p-aminobenzoic acid under a nitrogen atmosphere, and react at 60° C. for 4 h. After the reaction, evaporate and dry to obtain a light yellow solid, which is tung oil-based amic acid.

[0080] (2) Tung oil-based amic acid and isopropyl alcohol are added to a reactor in a mass ratio of 1:2. When the temperature is raised to 65°C, a zirconium acetate solution having a zirconium content of 15wt.%-16wt.% is added in a mass ratio of 3.2:1 to oleyl amic acid, and then stirring is continued at 80°C for 30 minutes. After the reaction is completed, the mixture is filtered and dried to obtain a beige solid powder, which is tung oil-based amic acid zirconium.

[0081] (3) 2 parts of tung oil-derived zirconium amide acid, 0.25 parts of antioxidant 1010, 0.25 parts of antioxidant 168, and 0.5 parts of stearic acid were compounded to obtain a PVC modifier containing a tung oil-derived nitrogen-containing zirconium carboxylate composite heat stabilizer.

[0082] Comparative Example:

[0083] The thermal stability of PVC products was compared between the commonly used calcium-zinc heat stabilizer on the market and the homemade calcium / zinc heat stabilizer under the same formula and the same solid calcium and zinc dosage.

[0084] Experimental Group 1:

[0085] Table 1 Composition of experimental group 1

[0086] Experimental Group 2:

[0087] Table 2 Composition of experimental group 2

[0088] Experimental Group 3:

[0089] Table 3 Composition of experimental group 3

[0090] Comparison Group 1:

[0091] Table 4 Composition of comparison group 1

[0092] Static Thermal Stability Test: The materials from Experimental Groups 1, 2, and 3, as well as Comparative Group 1, were uniformly mixed. 60.0g of the mixture was plasticized on a torque rheometer at 160-165°C and 40 rpm for 3 minutes, and then pressed into 1mm thick test pieces. The thermal stability of the products was evaluated according to ISO 182-1-1990 Congo Red Test Method and ISO 305-1990(E).

[0093] Without compromising plasticizing properties, the effects of a self-made modifier containing a tung oil-derived nitrogen-containing zirconium carboxylate composite heat stabilizer on the thermal stability of PVC were investigated. The thermal stability test results for Experimental Groups 1, 2, and 3, as well as Comparative Group 1, are shown in Table 5. These results demonstrate that the self-made modifier containing a tung oil-derived nitrogen-containing zirconium carboxylate composite heat stabilizer exhibits superior long-term thermal stability compared to the commonly used calcium stearate / zinc stearate composite heat stabilizer.

[0094] Table 5 Comparison of static thermal stability of thermal stabilizers in the experimental group and the control group

[0095] The embodiments described are preferred implementations of the present invention, but the present invention is not limited to the above implementations. Any obvious improvements, substitutions or modifications that can be made by those skilled in the art without departing from the essence of the present invention are within the scope of protection of the present invention.

Claims

1. A tung oil-derived nitrogen-containing zirconium carboxylate heat stabilizer for PVC, characterized in that: The structural formula of the tung oil-derived zirconium amidate is:

2. The method for preparing the tung oil-derived nitrogen-containing zirconium carboxylate heat stabilizer for PVC according to claim 1, characterized in that: Prepared by the following steps: Step 1: Add 90-100g of tung oil anhydride into the reactor 50mL acetone, add 20g p-aminobenzoic acid under nitrogen atmosphere, react at 50-60℃ for 3-4h; after the reaction, evaporate and dry to obtain a light yellow solid, which is tung oil-based amic acid; Step 2: Add tung oil-based amic acid and isopropanol into the reactor at a mass ratio of 1:(1-2), and when the temperature is raised to 65°C, add zirconium acetate solution with a zirconium content of 15wt.%-16wt.% at a mass ratio of (3.0-5.0) to tung oil-based amic acid:1, and then continue stirring at 75-80°C for 30 minutes; after the reaction is completed, filter and dry to obtain a beige solid powder, which is tung oil-based amic acid zirconium.

3. The method for preparing the tung oil-derived nitrogen-containing zirconium carboxylate heat stabilizer for PVC as claimed in claim 2, characterized in that: The mass ratio of the zirconium acetate solution to tung oil-based amic acid is (3.20-4.80):

1.

4. A tung oil-derived imidazole carboxylic acid calcium / zinc heat stabilizer for PVC, characterized in that: The molecular structure formula of tung oil-derived imidazole carboxylate calcium and tung oil-derived imidazole carboxylate zinc is: Wherein, R1 is Ca or Zn, and R2 is any one selected from the following 5. The method for preparing the tung oil-derived imidazole carboxylic acid calcium / zinc heat stabilizer for PVC according to claim 4, characterized in that: Prepared by the following steps: Step 1: Add tauridic anhydride and N,N-dimethylformamide into the reactor at a mass ratio of 1:(1-2) under nitrogen atmosphere. Raise the temperature to 45-60°C, add compound A at a molar ratio of (1-1.1):1 to tung oil anhydride, and react at 45-60°C for 3-5h; filter and rotary evaporate to obtain a light yellow liquid, which is tung oil-based oxadiazole acid; Step 2: Tung oil-based nitropropionic acid and anhydrous ethanol are added into a reaction vessel at a mass ratio of 1:2, sodium hydroxide is added in multiple batches at a molar ratio of (0.45-0.50) to tung oil-based nitropropionic acid at 60-70°C, and stirring is continued at 70°C for 1 hour; calcium chloride or zinc sulfate heptahydrate is completely dissolved in anhydrous ethanol at a molar ratio of (0.45-0.50) to tung oil-based nitropropionic acid at 1 is added into the reactor in batches; after the reaction is completed, tung oil-based imidazole carboxylate calcium or tung oil-based imidazole carboxylate zinc is obtained by filtering, washing with deionized water, and vacuum drying.

6. The method for preparing the tung oil-derived imidazole carboxylate calcium / zinc heat stabilizer for PVC as claimed in claim 5, characterized in that , the compound A is at least one of 5-amino-1H-tetrazole, 3-amino-1,2,4-triazole, and 4-amino-4H-1,2,4-triazole.

7. A composite heat stabilizer containing the tung oil-derived nitrogen-containing zirconium carboxylate for PVC according to claim 1, characterized in that: The tung oil-derived nitrogen-containing carboxylic acid zirconium / calcium / zinc heat stabilizer comprises the following components in parts by weight: 0.67-2 parts of tung oil-derived zirconium amide acid, 0-1.33 parts of tung oil-derived imidazole carboxylate calcium or 0-1.33 parts of tung oil-derived imidazole carboxylate zinc.

8. The composite heat stabilizer of tung oil-derived nitrogen-containing zirconium carboxylate for PVC as claimed in claim 7, characterized in that: The mass ratio of the tung oil-derived zirconium amic acid to the tung oil-derived imidazole carboxylate calcium is 1:

1.

9. A PVC modifier containing the composite heat stabilizer of tung oil-derived nitrogen-containing zirconium carboxylate according to claim 7 or 8, characterized in that: The invention is composed of the following components in parts by weight: 2 parts of tung oil-derived nitrogen-containing carboxylic acid zirconium / calcium / zinc heat stabilizer, 0.25 parts of antioxidant 1010, 0.25 parts of antioxidant 168, and 0.5 parts of stearic acid.

10. The use of the PVC modifier according to claim 9, characterized in that: Used to prepare PVC products and improve the thermal stability of PVC products.

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