PU / CPE modified material and preparation method thereof

Abstract

The invention discloses a PU / CPE modified material and a preparation method thereof, and relates to the technical field of high polymer materials. The PU / CPE modified material comprises the following raw materials in parts by weight: 20-40 parts of PU, 80-100 parts of CPE, 10-20 parts of a plasticizer, 3-5 parts of a compatilizer, 4-8 parts of a modified anti-aging agent, 3-5 parts of a modified flexibilizer, 2-3 parts of a stabilizer and 1-2 parts of a lubricant. The preparation method comprises the following steps: reacting bis (o-aminophenyl) disulfide with cyanuric chloride to generate an intermediate 1, and reacting the intermediate 1 with dodecyl primary amine to generate a modified anti-aging agent; the PU / CPE modified material prepared by the invention has good anti-aging performance, mechanical property and self-repairing performance.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, and in particular to a PU / CPE modified material and a preparation method thereof. Background Art

[0002] Polyurethane (PU), known as the "fifth plastic," is an organic polymer material with exceptional performance, boasting excellent wear resistance, elasticity, and mechanical strength. It is widely used in elastomers, coatings, and other fields. However, PU itself suffers from poor weather resistance, flame retardancy, and processing stability, making it particularly susceptible to aging in high-temperature or outdoor environments. Chlorinated polyethylene (CPE) is a saturated polymer material produced by the chlorination of polyethylene. It is ozone-resistant, weather-resistant, and flame-retardant, and is widely used in a wide range of fields, including cables, adhesive tapes, rubber and plastic products, sealing materials, flame-retardant conveyor belts, and waterproof membranes. Therefore, the introduction of CPE into PU can significantly enhance its heat resistance, impact resistance, and flame retardancy, while reducing material costs. However, due to compatibility issues between PU and CPE, improving the performance of PU / CPE modified materials presents significant challenges, requiring further improvements in their aging resistance, impact resistance, self-healing properties, and compatibility.

[0003] Chinese invention patent publication number CN101712797A discloses a novel thermoplastic polyurethane (TPU) and chlorinated polyethylene (CPE) blend material prepared by dynamic vulcanization. This invention combines 40-90% TPU, 5-50% CPE, 0.1-5% vulcanization system, 0-50% reinforcing filler system, and 0-20% additives in a mixer at high temperature, while simultaneously dynamically vulcanizing the CPE phase. The resulting blend alloy exhibits excellent mechanical properties, wear resistance, low-temperature resistance, aging resistance, flame retardancy, and good processing properties, but its self-healing properties are poor. Summary of the Invention

[0004] In view of the shortcomings of the prior art, the object of the present invention is to provide a PU / CPE modified material and a preparation method thereof.

[0005] To achieve the above object, the present invention is implemented through the following technical solutions: A PU / CPE modified material comprises the following raw materials in parts by weight: PU: 20-40 parts; CPE: 80-100 copies; Plasticizer: 10-20 parts; Compatibilizer: 3-5 parts; Modified antioxidant: 4-8 parts; Modified toughening agent: 3-5 parts; Stabilizer: 2-3 parts; Lubricant: 1-2 parts; The modified antioxidant is prepared by the following method: S1: Under nitrogen protection, bis(o-aminophenyl) disulfide, cyanuric chloride and anhydrous acetonitrile were mixed, and N,N-diisopropylethylamine was added to react to obtain intermediate 1; S2: Under nitrogen protection, the intermediate 1 was mixed with anhydrous toluene, and dodecyl primary amine and N,N-diisopropylethylamine were added to react to obtain a modified antioxidant.

[0006] In step S1, the molar ratio of bis(o-aminophenyl) disulfide to cyanuric chloride is 1:(2-2.2).

[0007] In step S2, the molar ratio of the intermediate 1 to dodecyl primary amine is 1:(4-4.5).

[0008] The modified toughening agent is prepared by the following method: N1: Under nitrogen protection, 2-amino-4,6-dichloro-S-triazine, 4,4'-dithio-butyryl chloride and anhydrous tetrahydrofuran (THF) were mixed, and 4,4'-dithio-butyryl chloride and N,N-diisopropylethylamine were added to react to obtain 4,4'-dithiobis[N-(4,6-dichloro-1,3,5-triazin-2-yl)butyramide]; N2: Under nitrogen protection, 4,4'-dithiobis[N-(4,6-dichloro-1,3,5-triazin-2-yl)butanamide], 4-phenylbutylamine, and anhydrous THF were mixed, and N,N-diisopropylethylamine was added to react to obtain 4,4'-dithiobis[N-(4-chloro-6-((4-phenylbutyl)amino)-1,3,5-triazin-2-yl)butanamide]; N3: Under nitrogen protection, 4,4'-dithiobis[N-(4-chloro-6-((4-phenylbutyl)amino)-1,3,5-triazin-2-yl)butyramide], 4-aminobutyltriethoxysilane and anhydrous toluene were mixed, and N,N-diisopropylethylamine was added to react to obtain a modified toughening agent.

[0009] In step N1, the molar ratio of 2-amino-4,6-dichloro-S-triazine to 4,4'-dithio-butyryl chloride is (2-2.2):1.

[0010] In step N2, the molar ratio of the 4,4'-dithiobis[N-(4,6-dichloro-1,3,5-triazin-2-yl)butyramide] to 4-phenylbutylamine is 1:(2-2.2).

[0011] In step N3, the molar ratio of the feed materials of 4,4'-dithiobis[N-(4-chloro-6-((4-phenylbutyl)amino)-1,3,5-triazin-2-yl)butanamide] and 4-aminobutyltriethoxysilane is 1:(2-2.2).

[0012] The plasticizer is one of dibutyl phthalate, diisononyl phthalate, and diisodecyl phthalate; and the compatibilizer is one of PE-g-MAH and PP-g-MAH.

[0013] The stabilizer is one of calcium stearate, zinc stearate and aluminum distearate; and the lubricant is pentaerythritol stearate.

[0014] A method for preparing a PU / CPE modified material comprises the following steps: (1) Weigh by weight: PU: ​​20-40 parts, CPE: 80-100 parts, plasticizer: 10-20 parts, compatibilizer: 3-5 parts, modified antioxidant: 4-8 parts, modified toughening agent: 3-5 parts, stabilizer: 2-3 parts, lubricant: 1-2 parts; (2) Add PU, CPE, modified antioxidant, modified toughening agent, stabilizer, compatibilizer, plasticizer and lubricant into a high-speed blender, stir at 90-110°C for 20-30 minutes, and then extrude and granulate through a twin-screw extruder to obtain PU / CPE modified material.

[0015] Due to the adoption of the above technical solution, the beneficial effects of the present invention include: (1) The modified antioxidant prepared by the present invention is an amine antioxidant, which can efficiently capture the active free radicals generated by PU / CPE under the action of heat, oxygen and light, terminate the oxidation chain reaction, and inhibit the breakage or cross-linking of molecular chains; the introduction of long-chain alkyl groups can increase the solubility of molecules in CPE, avoid the migration and precipitation of antioxidants, and prolong the antioxidant effect; the disulfide bonds can undergo reversible breakage and recombination when subjected to stress, helping the material resist fatigue aging, and is particularly suitable for dynamic stress scenarios.

[0016] (2) The modified toughening agent prepared by the present invention contains a triazine ring rigid core, a disulfide bond dynamic unit, a flexible long chain and a siloxane group. The rigid core and the flexible long chain work synergistically to significantly improve the impact resistance of the PU / CPE modified material. The disulfide bond has dynamic reversibility and breaks and reorganizes under the action of external force, giving the PU / CPE modified material a certain self-repairing property. In addition, the presence of the flexible long chain further improves the compatibility of the PU / CPE modified material. DETAILED DESCRIPTION

[0017] The present invention will be further described below with reference to the embodiments, but the present invention is not limited to these embodiments.

[0018] Example 1 Preparation of modified antioxidant: S1: Under nitrogen protection, 0.1 mol of bis(o-aminophenyl) disulfide and 0.2 mol of cyanuric chloride were added to 300 ml of anhydrous acetonitrile and stirred to mix. 0.25 mol of N,N-diisopropylethylamine was added and the mixture was reacted at 0°C for 12 h. After the reaction, 100 ml of 0.1 M hydrochloric acid was added, the mixture was stirred thoroughly, and filtered. The filter cake was washed with deionized water until neutral and dried in a vacuum at 60°C for 8 h to obtain intermediate 1. The reaction equation is shown below: .

[0019] Its H-NMR spectrum data are as follows: 1 H NMR (500 MHz, Chloroform- d ) δ 7.49-7.36 (m, 10H), 7.35-7.27 (m,4H), 7.17 (td, J = 7.3, 2.4 Hz, 2H), 7.09 (tt, J = 7.6, 2.1 Hz, 2H).

[0020] S2: Under nitrogen protection, 0.1 mol of intermediate 1 was added to 300 ml of anhydrous toluene, stirred for 30 min, 0.4 mol of dodecyl primary amine and 0.5 mol of N,N-diisopropylethylamine were added, and the mixture was reacted at 30°C for 6 h, then heated to 80°C for 10 h. After the reaction, 100 ml of 0.1 M hydrochloric acid was added, the mixture was thoroughly stirred and filtered, the filter cake was washed with deionized water until neutral, and vacuum dried at 60°C for 12 h to obtain a modified antioxidant. The reaction equation is shown below: .

[0021] Its H-NMR spectrum data are as follows: 1 H NMR (500 MHz, Chloroform- d ) δ 7.51-7.03 (m, 18H), 5.48 (s, 4H), 3.46 (s, 8H), 1.67-1.20 (m, 80H), 0.89 (s, 12H).

[0022] Example 2 Preparation of modified antioxidant: S1: Under nitrogen protection, 0.1 mol of bis(o-aminophenyl) disulfide and 0.21 mol of cyanuric chloride were added to 300 ml of anhydrous acetonitrile, stirred and mixed, and 0.28 mol of N,N-diisopropylethylamine was added. The mixture was reacted at 5°C for 8 h. After the reaction, 100 ml of 0.1 M hydrochloric acid was added, the mixture was stirred thoroughly, and filtered. The filter cake was washed with deionized water until neutral, and dried in a vacuum at 60°C for 8 h to obtain intermediate 1. S2: Under nitrogen protection, 0.1 mol of intermediate 1 was added to 300 ml of anhydrous toluene, stirred for 30 min, 0.43 mol of dodecyl primary amine and 0.55 mol of N,N-diisopropylethylamine were added, and the mixture was reacted at 35°C for 5 h, and then the temperature was raised to 80°C for 10 h. After the reaction, 100 ml of 0.1 M hydrochloric acid was added, the mixture was thoroughly stirred and filtered, and the filter cake was washed with deionized water until neutral, and vacuum dried at 60°C for 12 h to obtain a modified antioxidant. Example 3 Preparation of modified antioxidant: S1: Under nitrogen protection, 0.1 mol of bis(o-aminophenyl) disulfide and 0.22 mol of cyanuric chloride were added to 300 ml of anhydrous acetonitrile, stirred and mixed, and 0.3 mol of N,N-diisopropylethylamine was added. The mixture was reacted at 5°C for 8 h. After the reaction, 100 ml of 0.1 M hydrochloric acid was added, the mixture was stirred thoroughly, and filtered. The filter cake was washed with deionized water until neutral, and dried in a vacuum at 60°C for 10 h to obtain intermediate 1. S2: Under nitrogen protection, 0.1 mol of intermediate 1 was added to 300 ml of anhydrous toluene, stirred for 30 min, 0.45 mol of dodecyl primary amine and 0.6 mol of N,N-diisopropylethylamine were added, and the mixture was reacted at 40°C for 4 h, then heated to 85°C for 8 h. After the reaction, 100 ml of 0.1 M hydrochloric acid was added, the mixture was thoroughly stirred and filtered, and the filter cake was washed with deionized water until neutral, and vacuum dried at 60°C for 12 h to obtain a modified antioxidant. Example 4 Preparation of modified toughening agent: N1: Under nitrogen protection, 0.2 mol of 2-amino-4,6-dichloro-S-triazine was added to 200 ml of anhydrous THF. Under ice bath, a mixed solution of 0.1 mol of 4,4'-dithiobutyryl chloride and 0.2 mol of N,N-diisopropylethylamine was slowly added dropwise over 20 min. After completion of the addition, the temperature was raised to 30°C and the reaction was continued for 6 h. After the reaction, 60 ml of 0.1 M hydrochloric acid was added, the mixture was stirred thoroughly, and filtered. The filter cake was washed with deionized water until neutral, and dried in vacuo at 60°C for 8 h to obtain 4,4'-dithiobis[N-(4,6-dichloro-1,3,5-triazin-2-yl)butyramide]. The reaction equation is shown below: .

[0023] Its H-NMR spectrum data are as follows: 1 H NMR (500 MHz, Chloroform- d ) δ 11.07 (s, 2H), 2.75 (s, 4H), 2.50 (s, 4H), 2.08 (s, 4H).

[0024] N2: Under nitrogen protection, 0.1 mol of 4,4'-dithiobis[N-(4,6-dichloro-1,3,5-triazin-2-yl)butanamide] and 0.2 mol of 4-phenylbutylamine were added to 300 ml of anhydrous THF, stirred for 20 min, and 0.2 mol of N,N-diisopropylethylamine was added. The mixture was reacted at 30°C for 10 h. After the reaction, 100 ml of 0.1 M hydrochloric acid was added, the mixture was thoroughly stirred, and filtered. The filter cake was washed with deionized water until neutral, and dried in vacuo at 60°C for 8 h to obtain 4,4'-dithiobis[N-(4-chloro-6-((4-phenylbutyl)amino)-1,3,5-triazin-2-yl)butanamide]. The reaction equation is shown below: .

[0025] Its H-NMR spectrum data are as follows: 1 H NMR (500 MHz, Chloroform- d ) δ 11.20 (s, 2H), 7.29-7.16 (m, 10H), 5.64 (s, 2H), 3.47 (s, 4H), 2.75 (s, 4H), 2.64 (d, J = 2.0 Hz, 4H), 2.50 (s,4H), 2.15-1.57 (m, 12H).

[0026] N3: Under nitrogen protection, 0.1 mol 4,4'-dithiobis[N-(4-chloro-6-((4-phenylbutyl)amino)-1,3,5-triazin-2-yl)butyramide] and 0.2 mol 4-aminobutyltriethoxysilane were added to 400 ml of anhydrous toluene and stirred for 20 min. 0.2 mol N,N-diisopropylethylamine was added and the mixture was reacted at 80°C for 16 h. After the reaction was completed, the mixture was cooled to room temperature and 100 ml of 0.1 M hydrochloric acid was added. After sufficient stirring, the mixture was filtered and the filter cake was washed with deionized water until neutral. The filter cake was vacuum dried at 60°C for 12 h to obtain a modified toughening agent. The reaction equation is shown below: .

[0027] Its H-NMR spectrum data are as follows: 1 H NMR (500 MHz, Chloroform-d ) δ 11.05 (s, 2H), 7.28-7.17 (m, 10H), 5.60 (s, 2H), 5.51 (s, 2H), 3.65 (s, 12H), 3.47 (s, 4H), 3.42 (s, 4H), 2.75(s, 4H), 2.64 (d, J = 1.8 Hz, 4H), 2.54 (s, 4H), 2.08 (s, 4H), 1.90-1.52 (m,16H), 1.30 (s, 4H), 1.24 (s, 18H).

[0028] Example 5 Preparation of modified toughening agent: N1: Under nitrogen protection, 0.21 mol of 2-amino-4,6-dichloro-S-triazine was added to 200 ml of anhydrous THF. Under an ice bath, a mixed solution of 0.1 mol of 4,4'-dithiobutyryl chloride and 0.2 mol of N,N-diisopropylethylamine was slowly added dropwise over 20 min. After completion of the addition, the temperature was raised to 45°C and the reaction was continued for 5 h. After the reaction, 60 ml of 0.1 M hydrochloric acid was added, the mixture was thoroughly stirred, and then filtered. The filter cake was washed with deionized water until neutral and dried in a vacuum at 60°C for 8 h to obtain 4,4'-dithiobis[N-(4,6-dichloro-1,3,5-triazin-2-yl)butyramide]. N2: Under nitrogen protection, 0.1 mol of 4,4'-dithiobis[N-(4,6-dichloro-1,3,5-triazin-2-yl)butanamide] and 0.21 mol of 4-phenylbutylamine were added to 300 ml of anhydrous THF, stirred for 20 min, and 0.2 mol of N,N-diisopropylethylamine was added. The mixture was reacted at 35°C for 9 h. After the reaction, 100 ml of 0.1 M hydrochloric acid was added, the mixture was stirred thoroughly, and filtered. The filter cake was washed with deionized water until neutral, and dried in a vacuum at 60°C for 8 h to obtain 4,4'-dithiobis[N-(4-chloro-6-((4-phenylbutyl)amino)-1,3,5-triazin-2-yl)butanamide]. N3: Under nitrogen protection, 0.1 mol 4,4'-dithiobis[N-(4-chloro-6-((4-phenylbutyl)amino)-1,3,5-triazin-2-yl)butyramide] and 0.21 mol 4-aminobutyltriethoxysilane were added to 400 ml of anhydrous toluene, stirred for 20 min, 0.2 mol N,N-diisopropylethylamine was added, and the mixture was reacted at 85 ° C for 14 h; after the reaction was completed, it was cooled to room temperature, 100 ml of 0.1M hydrochloric acid was added, and the mixture was fully stirred and filtered. The filter cake was washed with deionized water until neutral and dried in vacuum at 60 ° C for 12 h to obtain a modified toughening agent.

[0029] Example 6 Preparation of modified toughening agent: N1: Under nitrogen protection, 0.22 mol of 2-amino-4,6-dichloro-S-triazine was added to 200 ml of anhydrous THF. Under an ice bath, a mixed solution of 0.1 mol of 4,4'-dithiobutyryl chloride and 0.2 mol of N,N-diisopropylethylamine was slowly added dropwise over 20 min. After completion of the addition, the temperature was raised to 60°C and the reaction was continued for 4 h. After the reaction, 60 ml of 0.1 M hydrochloric acid was added, the mixture was thoroughly stirred, and then filtered. The filter cake was washed with deionized water until neutral, and vacuum dried at 60°C for 8 h to obtain 4,4'-dithiobis[N-(4,6-dichloro-1,3,5-triazin-2-yl)butyramide]. N2: Under nitrogen protection, 0.1 mol of 4,4'-dithiobis[N-(4,6-dichloro-1,3,5-triazin-2-yl)butanamide] and 0.22 mol of 4-phenylbutylamine were added to 300 ml of anhydrous THF, stirred for 20 min, and 0.2 mol of N,N-diisopropylethylamine was added. The mixture was reacted at 40°C for 8 h. After the reaction, 100 ml of 0.1 M hydrochloric acid was added, the mixture was stirred thoroughly, and filtered. The filter cake was washed with deionized water until neutral, and dried in vacuo at 60°C for 9 h to obtain 4,4'-dithiobis[N-(4-chloro-6-((4-phenylbutyl)amino)-1,3,5-triazin-2-yl)butanamide]. N3: Under nitrogen protection, 0.1 mol 4,4'-dithiobis[N-(4-chloro-6-((4-phenylbutyl)amino)-1,3,5-triazin-2-yl)butyramide] and 0.22 mol 4-aminobutyltriethoxysilane were added to 400 ml of anhydrous toluene, stirred for 20 min, 0.2 mol N,N-diisopropylethylamine was added, and the mixture was reacted at 90 ° C for 12 h; after the reaction was completed, it was cooled to room temperature, 100 ml of 0.1M hydrochloric acid was added, and the mixture was fully stirred and filtered. The filter cake was washed with deionized water until neutral and dried in vacuo at 60 ° C for 12 h to obtain a modified toughening agent.

[0030] Example 7 Preparation of PU / CPE modified material: (1) Weigh by weight: PU 200g, CPE 800g, plasticizer (dibutyl phthalate) 100g, compatibilizer (PE-g-MAH) 30g, modified antioxidant (prepared in Example 1) 40g, modified toughening agent (prepared in Example 4) 30g, stabilizer (calcium stearate) 20g, lubricant (pentaerythritol stearate) 10g; (2) PU, CPE, modified antioxidant, modified toughening agent, stabilizer, compatibilizer, plasticizer and lubricant were added to a high-speed blender, stirred at 90°C for 30 minutes, and then extruded and granulated through a twin-screw extruder to obtain a PU / CPE modified material; the zone temperatures of the twin-screw extruder were: 125°C for the feeding section, 155°C for the compression section, 155°C for the melting section, 165°C for the metering section, 175°C for the extrusion die section, and 180°C for the die section.

[0031] Example 8 Preparation of PU / CPE modified material: (1) Weigh by weight: PU 300g, CPE 900g, plasticizer (diisononyl phthalate) 150g, compatibilizer (PP-g-MAH) 40g, modified antioxidant (prepared in Example 2) 60g, modified toughening agent (prepared in Example 5) 40g, stabilizer (zinc stearate) 25g, lubricant (pentaerythritol stearate) 15g; (2) PU, CPE, modified antioxidant, modified toughening agent, stabilizer, compatibilizer, plasticizer and lubricant were added to a high-speed blender, stirred at 100°C for 25 minutes, and then extruded and granulated through a twin-screw extruder to obtain a PU / CPE modified material; the zone temperatures of the twin-screw extruder were: 125°C for the feeding section, 155°C for the compression section, 155°C for the melting section, 165°C for the metering section, 175°C for the extrusion die section, and 180°C for the die section.

[0032] Example 9 Preparation of PU / CPE modified material: (1) Weigh by weight: PU 400g, CPE 1000g, plasticizer (diisodecyl phthalate) 200g, compatibilizer (PE-g-MAH) 50g, modified antioxidant (prepared in Example 3) 80g, modified toughening agent (prepared in Example 6) 50g, stabilizer (aluminum distearate) 30g, lubricant (pentaerythritol stearate) 20g; (2) PU, CPE, modified antioxidant, modified toughening agent, stabilizer, compatibilizer, plasticizer and lubricant were added to a high-speed blender, stirred at 110°C for 20 minutes, and then extruded and granulated through a twin-screw extruder to obtain a PU / CPE modified material; the zone temperatures of the twin-screw extruder were: 125°C for the feeding section, 155°C for the compression section, 155°C for the melting section, 165°C for the metering section, 175°C for the extrusion die section, and 180°C for the die section.

[0033] Comparative Example 1 The raw material composition and process of the PU / CPE modified material are basically the same as those of Example 8, except that no modified antioxidant is added to the components.

[0034] Comparative Example 2 The raw material composition and process of the PU / CPE modified material are basically the same as those of Example 8, except that no modifying toughening agent is added to the components.

[0035] Comparative Example 3 The raw material composition and process of the PU / CPE modified material are basically the same as those of Example 8, except that the modified antioxidant is replaced by an equal weight of a modified antioxidant prepared by the following method: The preparation method of the modified antioxidant is basically the same as that of Example 2, except that the bis(o-aminophenyl) disulfide in step S1 is replaced by 0.2 mol of phenothiazine.

[0036] Comparative Example 4 The raw material composition and process of the PU / CPE modified material are basically the same as those of Example 8, except that the modified toughening agent is replaced by an equal weight of a modified toughening agent prepared by the following method: The preparation method of the modified toughening agent is basically the same as that of Example 5, except that the 4,4'-dithio-butyryl chloride in step N1 is replaced by an equimolar amount of 2,5-thiophenyl dicarbonyl dichloride (CAS: 18614-21-6).

[0037] Comparative Example 5 The raw material composition and process of the PU / CPE modified material are basically the same as those of Example 8, except that the modified toughening agent is replaced by an equal weight of a modified toughening agent prepared by the following method: The preparation method of the modified toughening agent is basically the same as that of Example 5, except that the 4-aminobutyltriethoxysilane in step N3 is replaced by an equal molar amount of 11-aminoundecyltriethoxysilane.

[0038] Comparative Example 6 The raw material composition and process of the PU / CPE modified material are basically the same as those of Example 8, except that the modified toughening agent is replaced by an equal weight of a modified toughening agent prepared by the following method: A1: Under nitrogen, add 0.21 mol of 2-amino-4,6-dichloro-S-triazine to 200 ml of anhydrous THF. In an ice bath, slowly add a mixed solution of 0.1 mol of 4,4'-dithiobutyryl chloride and 0.2 mol of N,N-diisopropylethylamine dropwise over 20 min. After completion of the addition, raise the temperature to 45°C and react for 5 h. After the reaction, add 60 ml of 0.1 M hydrochloric acid, stir thoroughly, and filter. The filter cake is washed with deionized water until neutral and dried in a vacuum at 60°C for 4 h to obtain 4,4'-dithiobis[N-(4,6-dichloro-1,3,5-triazin-2-yl)butyramide]. A2: Under nitrogen protection, 0.1 mol of 4,4'-dithiobis[N-(4,6-dichloro-1,3,5-triazin-2-yl)butyramide] and 0.21 mol of 4-aminobutyltriethoxysilane were added to 400 ml of anhydrous toluene, stirred for 20 min, and 0.2 mol of N,N-diisopropylethylamine was added. The mixture was reacted at 85°C for 14 h. After the reaction, the mixture was cooled to room temperature, 100 ml of 0.1 M hydrochloric acid was added, and the mixture was thoroughly stirred and filtered. The filter cake was washed with deionized water until neutral and dried under vacuum at 100°C for 6 h to obtain a modified toughening agent.

[0039] Comparative Example 7 The raw material composition and process of the PU / CPE modified material are basically the same as those of Example 8, except that the modified toughening agent is replaced by an equal weight of a modified toughening agent prepared by the following method: The preparation method of the modified toughening agent is basically the same as that of Example 5, except that 2-amino-4,6-dichloro-S-triazine and 4,4'-dithio-butyryl chloride in step N1 are replaced by equimolar amounts of cyanuric chloride and cystamine, respectively.

[0040] The PU used in the examples and comparative examples of the present application is PU850, produced by Lamberti Specialty Chemicals (Shanghai) Co., Ltd.; the CPE is 135A, produced by Zibo Huaxing Additive Co., Ltd.; the PE-g-MAH is CMG5804, produced by Jiayirong Polymer (Shanghai) Co., Ltd.; the PP-g-MAH is CMG9801, produced by Jiayirong Polymer (Shanghai) Co., Ltd.; the CAS number of bis(o-aminophenyl) disulfide is 54287-76-2; the CAS number of 4,4'-dithio-butyryl chloride is 1002-22-8.

[0041] The PU / CPE modified materials prepared in Examples 7-9 and Comparative Examples 1-7 were subjected to tensile strength and elongation at break tests according to GB / T1040.2-2006. Type 1A dumbbell specimens were used, tested at a temperature of 23°C and a tensile speed of 50 mm / min. The self-healing performance of the PU / CPE modified materials was characterized by the retention of tensile strength between the initial and repaired specimens. The self-healing efficiency (H) = tensile strength after repair / initial tensile strength × 100%. The test results are shown in Table 1.

[0042] Preparation of samples of Examples 7-9 and Comparative Examples 1-7: Place the mold for the sample to be made on a flat hot press, add PU / CPE modified material, set the mold temperature to 180°C, set the heating time to 300s, exhaust twice, maintain the pressure at 5 MPa for 20s, and naturally cool to room temperature to obtain the sample.

[0043] Specimen destruction test: Use a blade to preform a standard damage (0.5 mm deep, 10 mm long) at the center of the specimen gauge section. Place the damaged specimen in an 80 °C oven and heat it for 2 h to prepare a self-healed specimen.

[0044] The samples prepared in Examples 7-9 and Comparative Examples 1-7 were placed in a hot air aging oven and aged at 100° C. for 4 days, and then subjected to tensile strength and elongation at break tests. The test results are shown in Table 1.

[0045] Table 1 Performance indicators of PU / CPE modified materials

[0046] It can be seen from the data in Table 1 that the PU / CPE modified material prepared in this application has excellent anti-aging properties, mechanical properties and self-repair properties.

[0047] Comparative Example 1 is a comparative example in which no modified antioxidant is added. Its tensile strength after aging is 19.7 MPa and its elongation at break is 346%, which are significantly lower than those in the embodiment. This shows that the modified antioxidant prepared in this application can significantly improve the anti-aging properties of PU / CPE modified materials.

[0048] Comparative Example 2 is a comparative example in which no modified toughening agent is added. Its tensile strength before aging is 28.6 MPa, and its elongation at break is 387%, which is lower than that of the embodiment, indicating that the modified toughening agent prepared in this application can significantly improve the mechanical properties of the PU / CPE modified material.

[0049] The self-healing properties of the PU / CPE modified materials prepared in Comparative Examples 3 and 4 were inferior to those of the Examples. This was primarily due to the lack of dynamic disulfide bonds in the phenothiazine and 2,5-thiophenylenedicarbonyl dichloride used to prepare the modified toughening agent. This made it difficult to restructure these bonds under external forces, resulting in a decrease in the self-healing properties of the PU / CPE modified materials. Furthermore, the aging resistance of the PU / CPE modified material prepared in Comparative Example 3 was also somewhat inferior to that of the Examples. This was primarily due to the reduced imine content in the modified antioxidant prepared using phenothiazine, which resulted in a decrease in the aging resistance of the PU / CPE modified material.

[0050] Comparative Example 5 is a comparative example of using 11-aminoundecyltriethoxysilane to prepare a modified toughening agent. The prepared PU / CPE modified material has a tensile strength of 30.6 MPa when not aged, and an elongation at break of 391%, which is lower than that of the embodiment. This is mainly because the alkyl chain of 11-aminoundecyltriethoxysilane is longer, and excessive deformation occurs when subjected to force, thereby reducing the mechanical properties of the PU / CPE modified material.

[0051] The tensile strength and elongation at break of the PU / CPE modified material prepared in Comparative Example 6 are worse than those in Example 1. This is mainly because the long-chain alkylamine group is missing from the prepared modified toughening agent molecule, the flexibility of the chain segment is reduced, and the brittleness of the rigid triazine ring and the siloxane cannot be balanced, resulting in a decrease in the mechanical properties of the PU / CPE modified material.

[0052] The tensile strength of the PU / CPE modified material prepared in Comparative Example 7 is worse than that of the embodiment, mainly because the modified toughening agent molecules prepared using cyanuric chloride and cystamine as initial raw materials lack amide bonds. The C=O and NH between amide bond molecules can form intramolecular / intermolecular hydrogen bonds to construct a physical cross-linked network. The hydrogen bonds serve as "temporary cross-linking points", maintaining the material morphology under low stress and dissociating and absorbing energy under high stress, thereby improving the tensile strength of the PU / CPE modified material.

[0053] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. However, any equivalent changes, modifications and evolutions made by ordinary technicians in this field without departing from the scope of the technical solution of the present invention by using the technical content disclosed above are all equivalent embodiments of the present invention. At the same time, any equivalent changes, modifications and evolutions made to the above embodiments based on the essential technology of the present invention are still within the scope of protection of the technical solution of the present invention.

Claims

1. A PU / CPE modified material, characterized in that: The composition comprises the following raw materials in parts by weight: PU: 20-40 parts; CPE: 80-100 copies; Plasticizer: 10-20 parts; Compatibilizer: 3-5 parts; Modified antioxidant: 4-8 parts; Modified toughening agent: 3-5 parts; Stabilizer: 2-3 parts; Lubricant: 1-2 parts; The modified antioxidant is prepared by the following method: S1: Under nitrogen protection, bis(o-aminophenyl) disulfide, cyanuric chloride and anhydrous acetonitrile were mixed, and N,N-diisopropylethylamine was added to react to obtain intermediate 1; S2: Under nitrogen protection, the intermediate 1 was mixed with anhydrous toluene, and dodecyl primary amine and N,N-diisopropylethylamine were added to react to obtain a modified antioxidant.

2. A PU / CPE modified material according to claim 1, characterized in that, In step S1, the molar ratio of bis(o-aminophenyl) disulfide to cyanuric chloride is 1:(2-2.2).

3. A PU / CPE modified material according to claim 1, characterized in that, In step S2, the molar ratio of the intermediate 1 to dodecyl primary amine is 1:(4-4.5).

4. A PU / CPE modified material according to claim 1, characterized in that: The modified toughening agent is prepared by the following method: N1: Under nitrogen protection, 2-amino-4,6-dichloro-S-triazine and anhydrous THF were mixed, and 4,4'-dithio-butyryl chloride and N,N-diisopropylethylamine were added to react to obtain 4,4'-dithiobis[N-(4,6-dichloro-1,3,5-triazin-2-yl)butyramide]; N2: Under nitrogen protection, 4,4'-dithiobis[N-(4,6-dichloro-1,3,5-triazin-2-yl)butanamide], 4-phenylbutylamine, and anhydrous THF were mixed, and N,N-diisopropylethylamine was added to react to obtain 4,4'-dithiobis[N-(4-chloro-6-((4-phenylbutyl)amino)-1,3,5-triazin-2-yl)butanamide]; N3: Under nitrogen protection, 4,4'-dithiobis[N-(4-chloro-6-((4-phenylbutyl)amino)-1,3,5-triazin-2-yl)butyramide], 4-aminobutyltriethoxysilane and anhydrous toluene were mixed, and N,N-diisopropylethylamine was added to react to obtain a modified toughening agent.

5. A PU / CPE modified material according to claim 4, characterized in that: In step N1, the molar ratio of 2-amino-4,6-dichloro-S-triazine to 4,4'-dithio-butyryl chloride is (2-2.2):

1.

6. A PU / CPE modified material according to claim 4, characterized in that: In step N2, the molar ratio of the 4,4'-dithiobis[N-(4,6-dichloro-1,3,5-triazin-2-yl)butyramide] to 4-phenylbutylamine is 1:(2-2.2).

7. The PU / CPE modified material according to claim 4, characterized in that: In step N3, the molar ratio of the feed materials of 4,4'-dithiobis[N-(4-chloro-6-((4-phenylbutyl)amino)-1,3,5-triazin-2-yl)butanamide] and 4-aminobutyltriethoxysilane is 1:(2-2.2).

8. The PU / CPE modified material according to claim 1, characterized in that: The plasticizer is one of dibutyl phthalate, diisononyl phthalate, and diisodecyl phthalate; and the compatibilizer is one of PE-g-MAH and PP-g-MAH.

9. The PU / CPE modified material according to claim 1, characterized in that: The stabilizer is one of calcium stearate, zinc stearate and aluminum distearate; and the lubricant is pentaerythritol stearate.

10. A method for preparing the PU / CPE modified material according to any one of claims 1 to 9, characterized in that: The following steps are involved: S1: Weigh by weight: PU: ​​20-40 parts, CPE: 80-100 parts, plasticizer: 10-20 parts, compatibilizer: 3-5 parts, modified antioxidant: 4-8 parts, modified toughening agent: 3-5 parts, stabilizer: 2-3 parts, lubricant: 1-2 parts; S2: Add PU, CPE, modified antioxidant, modified toughening agent, stabilizer, compatibilizer, plasticizer, and lubricant into a high-speed blender, stir at 90-110°C for 20-30 minutes, and then extrude and granulate through a twin-screw extruder to obtain a PU / CPE modified material.

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