An amide type β-crystal nucleating agent and its preparation method and application

Abstract

The present invention discloses an amide type β crystal nucleating agent and a preparation method and application thereof. The amide type β crystal nucleating agent of the present invention is prepared by an amidation reaction between tetrahydrophthalic anhydride / phthalic anhydride and an aliphatic diamine, or is prepared by an amidation reaction between tetrahydrophthalic anhydride / phthalic anhydride and an aliphatic diamine and then a salt-forming reaction with a metal salt. The amide type β crystal nucleating agent of the present invention has the advantages of low dosage, low production cost, high nucleation efficiency, good thermal stability, etc., and can be synthesized at room temperature, the synthesis conditions are mild, the raw material cost is low, and it is suitable for large-scale industrial application.

Description

Technical Field

[0001] The invention relates to the technical field of functional additives, and in particular to an amide beta crystal nucleating agent and a preparation method and application thereof. Background Art

[0002] Polypropylene (PP) is a low-cost, widely used semi-crystalline thermoplastic synthetic resin, and its usage is second only to polyethylene. Polypropylene has five crystal forms: α, β, γ, δ and pseudo-hexagonal. The ones with application value are α-crystalline polypropylene and β-crystalline polypropylene. α-crystalline polypropylene is in a thermodynamically stable state and can be obtained under general processing conditions. It has a large bending modulus and tensile strength, but low impact strength and poor toughness. β-crystalline polypropylene is in a thermodynamically unstable state and is difficult to obtain under general processing conditions. The crystal structure is relatively loose, and the crystals are loosely stacked. When subjected to external forces, the crystals can move and absorb energy, so it has good impact resistance and toughness.

[0003] The main methods for producing β-crystals include shear-induced crystallization, melt quenching-induced crystallization, temperature gradient-induced crystallization, vibration-induced crystallization, and nucleating agent-induced crystallization. Nucleating agent-induced crystallization has the advantages of simple process and low cost, and is recognized as the best method for producing β-crystals. Studies have found that by melt-blending nucleating agents with polypropylene, the nucleating agents will induce polypropylene to produce β-spherulites during the cooling crystallization process, and β-crystal polypropylene can be finally obtained.

[0004] At present, the β-crystal nucleating agents used for polypropylene are mainly the following:

[0005] 1) Inorganic nucleating agents: ZnO, La2O3, CaCO3, etc. This type of nucleating agent has poor compatibility with polypropylene melt, uneven dispersion, easy agglomeration, large dosage and poor nucleating effect;

[0006] 2) Organic nucleating agents: a) Condensed ring nucleating agents: This type of nucleating agent has a large conjugated structure, so most of them are colored, and the dosage is large, and the nucleating effect is poor; b) Organic carboxylate nucleating agents: organic dicarboxylates such as succinates, adipates, and terephthalates. This type of nucleating agent has a good nucleating effect, but poor thermal stability and high production costs; c) Amide nucleating agents: This type of nucleating agent has good compatibility with polypropylene, good nucleating effect, and high thermal stability, but it requires the use of toxic and harmful chemical reagents in the production process;

[0007] 3) Rare earth nucleating agents: metal oxides corresponding to rare earth elements and some stearates. The structure and nucleation mechanism of this type of nucleating agent are unknown and the cost is relatively high;

[0008] 4) Polymer nucleating agents: This type of nucleating agent has good dispersibility in polypropylene, but the existing polymer nucleating agents have poor nucleating effects and large dosages, which will affect the mechanical properties, gloss, rheological properties and other properties of polypropylene.

[0009] Therefore, it is of great significance to develop a β-crystal nucleating agent with low dosage, low cost, high nucleation efficiency and good thermal stability. Summary of the invention

[0010] The purpose of the present invention is to provide an amide-based β-crystal nucleating agent and a preparation method and application thereof.

[0011] The technical solution adopted by the present invention is:

[0012] An amide-based β-crystal nucleating agent, the general structural formula of which is any one of formulas (I) to (IV):

[0013] Formula (I):

[0014] Formula (II):

[0015] Formula (III):

[0016] Formula (IV):

[0017] In formulae (I) to (IV), n is an integer of 0 to 4, x is 2 or 3, and M is selected from one of lanthanum, zinc, calcium, barium and magnesium.

[0018] Preferably, the value of n is 0 or 1.

[0019] A method for preparing the amide β-crystal nucleating agent as described above comprises the following steps:

[0020] Dispersing tetrahydrophthalic anhydride and aliphatic diamine in an organic solvent for amidation reaction to obtain an amide type β-crystal nucleating agent represented by formula (I), neutralizing with alkali, and then adding a metal salt for salt formation reaction to obtain an amide type β-crystal nucleating agent represented by formula (II);

[0021] Phthalic anhydride and aliphatic diamine are dispersed in an organic solvent for amidation reaction to obtain an amide type β-crystal nucleating agent shown in formula (III), and then a base is added for neutralization and a metal salt is added for salt formation reaction to obtain an amide type β-crystal nucleating agent shown in formula (IV).

[0022] Preferably, the molar ratio of tetrahydrophthalic anhydride to aliphatic diamine is 2-3:1.

[0023] More preferably, the molar ratio of tetrahydrophthalic anhydride to aliphatic diamine is 2.2-2.5:1.

[0024] Preferably, the molar ratio of the phthalic anhydride to the aliphatic diamine is 2 to 3:1.

[0025] More preferably, the molar ratio of the phthalic anhydride to the aliphatic diamine is 2.2-2.5:1.

[0026] Preferably, the aliphatic diamine is one of 1,2-ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, 1,5-pentanediamine and 1,6-hexanediamine.

[0027] More preferably, the aliphatic diamine is one of 1,2-ethylenediamine and 1,3-propylenediamine.

[0028] Preferably, the organic solvent is at least one of tetrahydrofuran, ether, chloroform, dichloromethane, benzene, toluene and N,N-dimethylformamide.

[0029] Preferably, the amidation reaction is carried out at room temperature (25°C±5°C) and the reaction time is 12h to 24h.

[0030] Preferably, the base is at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate.

[0031] Further preferably, the base is sodium bicarbonate.

[0032] Preferably, the metal salt is one of lanthanum nitrate, lanthanum chloride, lanthanum sulfate, zinc nitrate, zinc chloride, zinc sulfate, calcium nitrate, calcium chloride, barium nitrate, barium chloride, magnesium nitrate, magnesium chloride, and magnesium sulfate.

[0033] Preferably, the salt-forming reaction is carried out at room temperature (25°C±5°C) and the reaction time is 20h to 30h.

[0034] Preferably, the salt-forming reaction is carried out at 60° C. to 80° C., and the reaction time is 10 h to 24 h.

[0035] An application of the above-mentioned amide β-crystal nucleating agent in isotactic homopolymer polypropylene or random copolymer polypropylene.

[0036] The beneficial effects of the present invention are as follows: the amide β-crystal nucleating agent of the present invention has the advantages of low dosage, low production cost, high nucleation efficiency, good thermal stability, etc., and it can be synthesized at room temperature, the synthesis conditions are mild, the raw material cost is low, and it is suitable for large-scale industrial application. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 It is the infrared spectra of the amide β-crystal nucleating agent in Examples 1 to 6.

[0038] Figure 2 It is the infrared spectra of the amide β-crystal nucleating agent in Examples 7 to 12.

[0039] Figure 3 This is the hydrogen nuclear magnetic resonance spectrum of the amide β-crystal nucleating agent in Example 1.

[0040] Figure 4 This is the carbon NMR spectrum of the amide β-crystal nucleating agent in Example 1.

[0041] Figure 5 This is a partially enlarged view of the carbon nuclear magnetic resonance spectrum of the amide β-crystal nucleating agent in Example 1.

[0042] Figure 6 This is the hydrogen nuclear magnetic resonance spectrum of the amide β-crystal nucleating agent in Example 7.

[0043] Figure 7 This is the carbon NMR spectrum of the amide β-crystal nucleating agent in Example 7.

[0044] Figure 8 It is the DSC curve of the test formula 1 in the present invention.

[0045] Fig. 9 It is the DSC curve of test formula 2 in the present invention.

[0046] Fig.10 It is the DSC curve of test formula 3 in the present invention.

[0047] Fig.11 It is the DSC curve of test formula 4 in the present invention.

[0048] Fig.12 This is the TG curve of NA-1Ca in Example 2.

[0049] Fig.13 This is the TG curve of NA-2 in Example 7.

[0050] Fig.14 The hydrogen nuclear magnetic resonance spectrum of the amide β-crystal nucleating agent in Example 13.

[0051] Fig.15 The carbon NMR spectrum of the amide β-crystal nucleating agent in Example 13.

[0052] Fig.16 The hydrogen nuclear magnetic resonance spectrum of the amide β-crystal nucleating agent in Example 14.

[0053] Fig.17 The carbon NMR spectrum of the amide β-crystal nucleating agent in Example 14.

[0054] Fig.18The hydrogen nuclear magnetic resonance spectrum of the amide β-crystal nucleating agent in Example 15.

[0055] Fig.19 The carbon NMR spectrum of the amide β-crystal nucleating agent in Example 15.

[0056] Fig. 20 A partially enlarged view of the carbon NMR spectrum of the amide β-crystal nucleating agent in Example 15.

[0057] Fig.21 The hydrogen nuclear magnetic resonance spectrum of the amide β-crystal nucleating agent in Example 16.

[0058] Fig. 22 The carbon NMR spectrum of the amide β-crystal nucleating agent in Example 16.

[0059] Fig.23 The hydrogen nuclear magnetic resonance spectrum of the amide β-crystal nucleating agent in Example 17.

[0060] Fig.24 The carbon NMR spectrum of the amide β-crystal nucleating agent in Example 17.

[0061] Fig.25 The hydrogen nuclear magnetic resonance spectrum of the amide β-crystal nucleating agent in Example 18.

[0062] Fig.26 The carbon NMR spectrum of the amide β-crystal nucleating agent in Example 18. DETAILED DESCRIPTION

[0063] The present invention will be further explained and illustrated below in conjunction with specific embodiments.

[0064] Embodiment 1:

[0065] An amide type β-crystal nucleating agent, the preparation method of which comprises the following steps:

[0066] Disperse 0.022 mol of phthalic anhydride in 60 mL of tetrahydrofuran, and then add 0.01 mol of 1,2-ethylenediamine in batches, react at room temperature for 24 hours, centrifuge, wash the solid obtained by centrifugation with 30 mL of tetrahydrofuran, and then place it in a vacuum drying oven at 60°C for 12 hours to obtain an amide β-crystal nucleating agent (denoted as NA-1).

[0067] After testing, NA-1 can also be prepared by replacing the reaction solvent from tetrahydrofuran with ether, chloroform, dichloromethane, benzene, toluene or N,N-dimethylformamide.

[0068] Embodiment 2:

[0069] An amide type β-crystal nucleating agent, the preparation method of which comprises the following steps:

[0070] 15 mmol of NA-1 was dispersed in 50 mL of water to prepare a dispersion, and then a saturated sodium bicarbonate solution was added dropwise until the pH of the dispersion reached 7, and then 20 mL of a 0.375 mol / L calcium chloride solution was added dropwise. After the addition, the mixture was stirred at 80°C for 12 h, and then at 60°C for 12 h. The filtered solid was washed three times with water, and then placed in a vacuum drying oven at 100°C for 12 h to obtain an amide β-crystal nucleating agent (denoted as NA-1Ca).

[0071] Embodiment 3:

[0072] An amide type β-crystal nucleating agent, the preparation method of which comprises the following steps:

[0073] 15 mmol of NA-1 was dispersed in 50 mL of water to prepare a dispersion, and then a saturated sodium bicarbonate solution was added dropwise until the pH of the dispersion reached 7, and then 20 mL of a 0.375 mol / L magnesium chloride solution was added dropwise. After the addition, the mixture was stirred at 80°C for 12 h, and then at 60°C for 12 h. The mixture was filtered, and the filtered solid was washed three times with water, and then placed in a vacuum drying oven at 100°C for 12 h to obtain an amide β-crystal nucleating agent (denoted as NA-1Mg).

[0074] Embodiment 4:

[0075] An amide type β-crystal nucleating agent, the preparation method of which comprises the following steps:

[0076] Disperse 15 mmol of NA-1 in 50 mL of water to prepare a dispersion, then add saturated sodium bicarbonate solution until the pH of the dispersion reaches 7, then add 20 mL of 0.375 mol / L lanthanum chloride solution, stir at 80°C for 12 h, then stir at 60°C for 12 h, filter, wash the filtered solid three times with water, and then place it in a vacuum drying oven at 100°C for 12 h to obtain an amide β-crystal nucleating agent (denoted as NA-1La).

[0077] Embodiment 5:

[0078] An amide type β-crystal nucleating agent, the preparation method of which comprises the following steps:

[0079] 15 mmol of NA-1 was dispersed in 50 mL of water to prepare a dispersion, and then a saturated sodium bicarbonate solution was added dropwise until the pH of the dispersion reached 7, and then 20 mL of a 0.375 mol / L zinc chloride solution was added dropwise. After the addition, the mixture was stirred at 80°C for 12 h, and then at 60°C for 12 h. The filtered solid was washed three times with water, and then placed in a vacuum drying oven at 100°C for 12 h to obtain an amide β-crystal nucleating agent (denoted as NA-1Zn).

[0080] Embodiment 6:

[0081] An amide type β-crystal nucleating agent, the preparation method of which comprises the following steps:

[0082] Disperse 15 mmol of NA-1 in 50 mL of water to prepare a dispersion, then add saturated sodium bicarbonate solution until the pH of the dispersion reaches 7, then add 20 mL of 0.375 mol / L barium chloride solution, stir at 80°C for 12 h, then stir at 60°C for 12 h, filter, wash the filtered solid three times with water, and then place it in a vacuum drying oven at 100°C for 12 h to obtain an amide β-crystal nucleating agent (denoted as NA-1Ba).

[0083] Embodiment 7:

[0084] An amide type β-crystal nucleating agent, the preparation method of which comprises the following steps:

[0085] Disperse 0.025 mol of tetrahydrophthalic anhydride in 60 mL of tetrahydrofuran, then add 0.01 mol of 1,2-ethylenediamine in batches, react at room temperature for 24 hours, centrifuge, wash the solid obtained by centrifugation with 30 mL of tetrahydrofuran, and then place it in a vacuum drying oven at 60°C for 12 hours to obtain an amide β-crystal nucleating agent (denoted as NA-2).

[0086] After testing, NA-2 can also be prepared by replacing the reaction solvent from tetrahydrofuran with ether, chloroform, dichloromethane, benzene, toluene or N,N-dimethylformamide.

[0087] Embodiment 8:

[0088] An amide type β-crystal nucleating agent, the preparation method of which comprises the following steps:

[0089] Disperse 15 mmol of NA-2 in 50 mL of water to prepare a dispersion, then add saturated sodium bicarbonate solution until the pH of the dispersion reaches 7, then add 20 mL of 0.375 mol / L calcium chloride solution, stir at room temperature for 12 hours after the addition, filter, wash the filtered solid three times with water, and then place it in a vacuum drying oven at 100°C for 12 hours to obtain an amide β-crystal nucleating agent (denoted as NA-2Ca).

[0090] Embodiment 9:

[0091] An amide type β-crystal nucleating agent, the preparation method of which comprises the following steps:

[0092] Disperse 15 mmol of NA-2 in 50 mL of water to prepare a dispersion, then add saturated sodium bicarbonate solution until the pH of the dispersion reaches 7, then add 20 mL of 0.375 mol / L magnesium chloride solution, stir at room temperature for 12 hours after the addition, filter, wash the filtered solid three times with water, and then place it in a vacuum drying oven at 100°C for 12 hours to obtain an amide β-crystal nucleating agent (denoted as NA-2Mg).

[0093] Embodiment 10:

[0094] An amide type β-crystal nucleating agent, the preparation method of which comprises the following steps:

[0095] Disperse 15 mmol of NA-2 in 50 mL of water to prepare a dispersion, then add saturated sodium bicarbonate solution until the pH of the dispersion reaches 7, then add 20 mL of 0.375 mol / L lanthanum chloride solution, stir at room temperature for 12 hours after the addition, filter, wash the filtered solid three times with water, and then place it in a vacuum drying oven at 100°C for 12 hours to obtain an amide β-crystal nucleating agent (denoted as NA-2La).

[0096] Embodiment 11:

[0097] An amide type β-crystal nucleating agent, the preparation method of which comprises the following steps:

[0098] Disperse 15 mmol of NA-2 in 50 mL of water to prepare a dispersion, then add saturated sodium bicarbonate solution until the pH of the dispersion reaches 7, then add 20 mL of 0.375 mol / L zinc nitrate solution, stir at room temperature for 12 hours after the addition, filter, wash the filtered solid three times with water, and then place it in a vacuum drying oven at 100°C for 12 hours to obtain an amide β-crystal nucleating agent (denoted as NA-2Zn).

[0099] Embodiment 12:

[0100] An amide type β-crystal nucleating agent, the preparation method of which comprises the following steps:

[0101] Disperse 15 mmol of NA-2 in 50 mL of water to prepare a dispersion, then add saturated sodium bicarbonate solution until the pH of the dispersion reaches 7, then add 20 mL of 0.375 mol / L barium chloride solution, stir at room temperature for 12 hours after addition, filter, wash the filtered solid three times with water, and then place it in a vacuum drying oven at 100°C for 12 hours to obtain an amide β-crystal nucleating agent (denoted as NA-2Ba).

[0102] Performance Test:

[0103] 1) The infrared spectra of the amide β-crystal nucleating agents (NA-1, NA-1Ca, NA-1Mg, NA-1La, NA-1Zn and NA-1Ba) in Examples 1 to 6 are as follows: Figure 1 shown.

[0104] Depend on Figure 1 It can be seen that NA-1 has NH (3259cm -1 )、CN(1252cm -1 ) and C=O(1650cm -1 ), indicating that phthalic anhydride and 1,2-ethylenediamine reacted to form a product containing an amide bond, while the antisymmetric stretching vibration of the free carboxyl group -COOH (1530 cm -1 ) and symmetrical stretching vibration (1443cm -1 ), the stretching vibration absorption peak of hydroxyl OH (3383cm -1 ) indicates that the product is carboxylic acid with a -COOH structure; 3200 cm -1 There are weak absorption peaks around 800cm -1 Strong absorption peaks appear on the left and right, indicating a benzene ring structure derived from phthalic anhydride; by comparing the infrared spectra of carboxylic acid (NA-1) and carboxylate salts (NA-1Ca, NA-1Mg, NA-1La, NA-1Zn and NA-1Ba), it can be found that after salt formation, the absorption peak of the free carboxyl group disappears, and the absorption peak of the symmetric stretching vibration of the carbonyl group of the carboxylic acid disappears.

[0105] 2) The infrared spectra of the amide β-crystal nucleating agents (NA-2, NA-2Ca, NA-2Mg, NA-2La, NA-2Zn and NA-2Ba) in Examples 7 to 12 are as follows: Figure 2 shown.

[0106] Depend on Figure 2 It can be seen that NA-2 has NH (3259cm -1 )、CN(1252cm -1 ) and C=O(1650cm -1 ), indicating that tetrahydrophthalic anhydride and 1,2-ethylenediamine react to generate a product containing an amide bond, while the antisymmetric stretching vibration of the free carboxyl group -COOH (1530 cm -1 ) and symmetrical stretching vibration (1443cm -1 ), the stretching vibration absorption peak of hydroxyl OH (3383cm -1 ) indicates that the product is carboxylic acid with a -COOH structure; 3000 cm -1Strong absorption peaks appear on the left and right, indicating a C=C double bond structure, which comes from tetrahydrophthalic anhydride; by comparing the infrared spectra of carboxylic acid (NA-2) and carboxylate salts (NA-2Ca, NA-2Mg, NA-2La, NA-2Zn and NA-2Ba), it can be found that after salt formation, the absorption peak of the free carboxyl group disappears, and the absorption peak of the carbonyl symmetric stretching vibration of the carboxylic acid disappears.

[0107] 3) The nuclear magnetic resonance hydrogen spectrum of the amide β-crystal nucleating agent NA-1 in Example 1 is as follows Figure 3 As shown, the magnetic resonance carbon spectrum is as follows Figure 4 and Figure 5 ( Figure 4 The partial enlarged view) is shown; the nuclear magnetic resonance hydrogen spectrum of the beta crystal nucleating agent NA-2 in Example 7 is as shown Figure 6 As shown, the magnetic resonance carbon spectrum is as follows Figure 7 shown.

[0108] Depend on Figures 3 to 5 It can be seen that Example 1 indeed prepared the amide β-crystal nucleating agent NA-1 with the expected structure.

[0109] Depend on Figure 6 and Figure 7 It can be seen that Example 7 indeed prepared the amide β-crystal nucleating agent NA-2 with the expected structure.

[0110] 4) The test formulas 1 to 4 were kneaded using a torque rheometer. The temperature of the four zones of the torque rheometer was 200°C, the speed was 50r / min, and the kneading was performed for 500s to obtain the final test sample. The DSC curve test was then performed using a differential scanning calorimeter. The DSC curve test conditions were as follows: the heating rate was 10°C / min, the temperature was increased from 50°C to 210°C, the temperature was maintained for 4min, the temperature was then lowered to 50°C, the temperature was maintained for 4min, and the temperature was then increased from room temperature to 210°C. The first heating was to eliminate the thermal history, and the second heating melting curve was taken as the test result. The temperature range was 50°C to 210°C. The DSC curves of the test formulas 1 to 4 obtained by the test were as follows: Figures 8 to 11 As shown, the β-crystal content of the test formula calculated according to the DSC curve test results is shown in Tables 1 to 4:

[0111] a) The composition of test formula 1 is as follows:

[0112] Common components:

[0113] Base material iPP-T30S (Guangdong Weilinna New Materials Technology Co., Ltd.): 40g;

[0114] Antioxidant 1010: 0.04g;

[0115] Antioxidant 168: 0.08g;

[0116] Unique components:

[0117] Nucleating agent;

[0118] Nucleating agents have the following parallel groupings:

[0119] 1. None (blank control);

[0120] 2. NAB-82 (Chenghe Technology Co., Ltd.): 0.08 g (the amount of nucleating agent is 0.2% of the base material mass);

[0121] 3. NA-1Ca: 0.04 g (the amount of nucleating agent is 0.1% of the base material mass);

[0122] 4. NA-1Ca: 0.08 g (the amount of nucleating agent is 0.2% of the base material mass);

[0123] 5. NA-1Ca: 0.16 g (the amount of nucleating agent is 0.4% of the base material mass);

[0124] 6. NA-1Ca: 0.24 g (the amount of nucleating agent is 0.6% of the base material mass);

[0125] 7. NA-1Ca: 0.32 g (the amount of nucleating agent is 0.8% of the base material mass);

[0126] 8. NA-1Ca: 0.40 g (the amount of nucleating agent is 1.0% of the base material mass);

[0127] 9. NA-2: 0.04 g (the amount of nucleating agent is 0.1% of the base material mass);

[0128] 10. NA-2: 0.08 g (the amount of nucleating agent is 0.2% of the base material mass);

[0129] 11. NA-2: 0.16 g (the amount of nucleating agent is 0.4% of the base material mass);

[0130] 12. NA-2: 0.24 g (the amount of nucleating agent is 0.6% of the base material mass);

[0131] 13. NA-2: 0.32 g (the amount of nucleating agent is 0.8% of the base material mass);

[0132] 14. NA-2: 0.40 g (the amount of nucleating agent is 1.0% of the base material mass);

[0133] Table 1 β crystal content of test formula 1

[0134]

[0135] Depend on Figure 8As shown in Table 1, when the two nucleating agents NA-1Ca and NA-2 are used alone and the addition amount is consistent with the commercial nucleating agent NAB-82, they have a good nucleating effect, indicating that NA-1Ca and NA-2 have a good β-nucleating effect in homopolymer polypropylene.

[0136] b) The composition of test formula 2 is as follows:

[0137] Common components:

[0138] Base material iPP-T30S (Guangdong Weilinna New Materials Technology Co., Ltd.): 40g;

[0139] Antioxidant 1010: 0.04g;

[0140] Antioxidant 168: 0.08g;

[0141] Unique components:

[0142] Nucleating agent;

[0143] Nucleating agents have the following parallel groupings:

[0144] 1. None (blank control);

[0145] 2. NAB-82 (Chenghe Technology Co., Ltd.): 0.08 g (the amount of nucleating agent is 0.2% of the base material mass);

[0146] 3. NA-1: 0.02g NA-1Ca: 0.02g (the amount of nucleating agent is 0.1% of the base material mass);

[0147] 4. NA-1: 0.04g NA-1Ca: 0.04g (the amount of nucleating agent is 0.2% of the base material mass);

[0148] 5. NA-1: 0.08g NA-1Ca: 0.08g (the amount of nucleating agent is 0.4% of the base material mass);

[0149] 6. NA-1: 0.12g NA-1Ca: 0.12g (the amount of nucleating agent is 0.6% of the base material mass);

[0150] 7. NA-1: 0.16g NA-1Ca: 0.16g (the amount of nucleating agent is 0.8% of the base material mass);

[0151] 8. NA-1: 0.20g NA-1Ca: 0.20g (the amount of nucleating agent is 1.0% of the base material mass);

[0152] Table 2 β-crystal content of test formula 2

[0153]

[0154] Depend on Fig. 9 As shown in Table 2, after NA-1 and NA-1Ca are compounded in a mass ratio of 1:1, at an addition amount of 0.1wt%, the β-crystal content is almost the same as when NA-1Ca is used alone, but when the addition amount is increased to 0.2wt%, the β-crystal content is significantly increased to 73.51%, and when the addition amount is increased to 0.4wt%, the β-crystal content can reach 88.14%, which is very close to the commercial nucleating agent NAB-82; when 0.4wt% of NA-1Ca nucleating agent is added alone, the β-crystal content is only 48.23%, indicating that the compound use of NA-1 and NA-1Ca can improve the nucleation effect, and can achieve better nucleation effect at a lower addition amount.

[0155] c) The composition of test formula 3 is as follows:

[0156] Common components:

[0157] Base material iPP-T30S (Guangdong Weilinna New Materials Technology Co., Ltd.): 40g;

[0158] Antioxidant 1010: 0.04g;

[0159] Antioxidant 168: 0.08g;

[0160] Unique components:

[0161] Nucleating agent;

[0162] Nucleating agents have the following parallel groupings:

[0163] 1. None (blank control);

[0164] 2. NAB-82 (Chenghe Technology Co., Ltd.): 0.08 g (the amount of nucleating agent is 0.2% of the base material mass);

[0165] 3. NA-2: 0.02g NA-2Ca: 0.02g (the amount of nucleating agent is 0.1% of the base material mass);

[0166] 4. NA-2: 0.04g NA-2Ca: 0.04g (the amount of nucleating agent is 0.2% of the base material mass);

[0167] 5. NA-2: 0.08g NA-2Ca: 0.08g (the amount of nucleating agent is 0.4% of the base material mass);

[0168] 6. NA-2: 0.12g NA-2Ca: 0.12g (the amount of nucleating agent is 0.6% of the base material mass);

[0169] 7. NA-2: 0.16g NA-2Ca: 0.16g (the amount of nucleating agent is 0.8% of the base material mass);

[0170] 8. NA-2: 0.20g NA-2Ca: 0.20g (the amount of nucleating agent is 1.0% of the base material mass);

[0171] Table 3 β-crystal content of test formula 3

[0172]

[0173] Depend on Fig.10 It can be seen from Table 3 that after compounding NA-2 and NA-2Ca in a mass ratio of 1:1, when the addition amount is 0.4wt%, the β-crystal content can reach 88%, which is slightly higher than the effect of the commercial nucleating agent NAB-82 when the addition amount is 0.2wt%. With the increase of the addition amount of the compounded nucleating agent, the nucleation efficiency shows a trend of first increasing and then maintaining stability (slightly decreasing). At the addition amount of 0.4wt%, the β-crystal content reaches a maximum value of 88.57%, and the nucleation efficiency is the highest.

[0174] d) The composition of test formula 4 is as follows:

[0175] Common components:

[0176] Base material iPP-T30S (Guangdong Weilinna New Materials Technology Co., Ltd.): 40g;

[0177] Antioxidant 1010: 0.04g;

[0178] Antioxidant 168: 0.08g;

[0179] Unique components:

[0180] Nucleating agent;

[0181] Nucleating agents have the following parallel groupings:

[0182] 1. None (blank control);

[0183] 2. NAB-82 (Chenghe Technology Co., Ltd.): 0.08 g (the amount of nucleating agent is 0.2% of the base material mass);

[0184] 3. NA-2: 0.02g NA-2Zn: 0.02g (the amount of nucleating agent is 0.1% of the base material mass);

[0185] 4. NA-2: 0.04g NA-2Zn: 0.04g (the amount of nucleating agent is 0.2% of the base material mass);

[0186] 5. NA-2: 0.08g NA-2Zn: 0.08g (the amount of nucleating agent is 0.4% of the base material mass);

[0187] 6. NA-2: 0.12g NA-2Zn: 0.12g (the amount of nucleating agent is 0.6% of the base material mass);

[0188] 7. NA-2: 0.16g NA-2Zn: 0.16g (the amount of nucleating agent is 0.8% of the base material mass);

[0189] 8. NA-2: 0.20g NA-2Zn: 0.20g (the amount of nucleating agent is 1.0% of the base material mass);

[0190] Table 4 β-crystal content of test formula 4

[0191]

[0192] Depend on Fig.11 As shown in Table 4, after NA-2 and NA-2Zn were compounded in a mass ratio of 1:1, the β-crystal content was close to 50% when the addition amount was 0.2wt%, which was lower than that when NA-2 was used alone, indicating that the nucleation effect of the compounding scheme was related to the type of amide carboxylate metal element.

[0193] 5) The TG curve of NA-1Ca in Example 2 is as follows Fig.12 As shown, the TG curve of NA-2 in Example 7 is as follows Fig.13 shown.

[0194] Depend on Fig.12 and Fig.13 It is found that NA-1Ca and NA-2 have excellent thermal stability.

[0195] Embodiment 13:

[0196] An amide type β-crystal nucleating agent, the preparation method of which comprises the following steps:

[0197] Disperse 0.022 mol of phthalic anhydride in 60 mL of tetrahydrofuran, and then add 0.01 mol of 1,3-propylenediamine in batches, react at room temperature for 24 hours, centrifuge, wash the solid obtained by centrifugation with 30 mL of tetrahydrofuran, and then place it in a vacuum drying oven at 60°C for 12 hours to obtain an amide β-crystal nucleating agent (denoted as NA-3).

[0198] Performance Test:

[0199] 1) The nuclear magnetic resonance hydrogen spectrum of the amide β-crystal nucleating agent NA-3 in this example is as follows Fig.14 As shown, the magnetic resonance carbon spectrum is as follows Fig.15 shown.

[0200] Depend on Fig.14 and Fig.15 It can be seen that: this example indeed prepared the amide β-crystal nucleating agent NA-3 with the expected structure.

[0201] 2) After testing (the testing method is the same as that of the amide β-crystal nucleating agent NA-1 in Example 1), the nucleating effect of the amide β-crystal nucleating agent NA-3 in this example is close to that of the amide β-crystal nucleating agent NA-1 in Example 1.

[0202] Embodiment 14:

[0203] An amide type β-crystal nucleating agent, the preparation method of which comprises the following steps:

[0204] Disperse 0.022 mol of phthalic anhydride in 60 mL of tetrahydrofuran, then add 0.01 mol of 1,4-butanediamine in batches, react at room temperature for 24 hours, centrifuge, wash the solid obtained by centrifugation with 30 mL of tetrahydrofuran, and then place it in a vacuum drying oven at 60°C for 12 hours to obtain an amide β-crystal nucleating agent (denoted as NA-4).

[0205] Performance Test:

[0206] 1) The nuclear magnetic resonance hydrogen spectrum of the amide β-crystal nucleating agent NA-4 in this example is as follows Fig.16 As shown, the magnetic resonance carbon spectrum is as follows Fig.17 shown.

[0207] Depend on Fig.16 and Fig.17 It can be seen that: this example indeed prepared the amide β-crystal nucleating agent NA-4 with the expected structure.

[0208] 2) After testing (the testing method is the same as that of the amide β-crystal nucleating agent NA-1 in Example 1), the nucleating effect of the amide β-crystal nucleating agent NA-4 in this example is close to that of the amide β-crystal nucleating agent NA-1 in Example 1.

[0209] Embodiment 15:

[0210] An amide type β-crystal nucleating agent, the preparation method of which comprises the following steps:

[0211] Disperse 0.022 mol of phthalic anhydride in 60 mL of tetrahydrofuran, and then add 0.01 mol of 1,5-pentanediamine in batches, react at room temperature for 24 hours, centrifuge, wash the solid obtained by centrifugation with 30 mL of tetrahydrofuran, and then place it in a vacuum drying oven at 60°C for 12 hours to obtain an amide β-crystal nucleating agent (denoted as NA-5).

[0212] Performance Test:

[0213] 1) The nuclear magnetic resonance hydrogen spectrum of the amide β-crystal nucleating agent NA-5 in this embodiment is as follows Fig.18 As shown, the magnetic resonance carbon spectrum is as follows Fig.19 and Fig. 20 ( Fig.19 (partially enlarged view) shown in FIG.

[0214] Depend on Figures 18 to 20 It can be seen that: this example indeed prepared the amide β-crystal nucleating agent NA-5 with the expected structure.

[0215] 2) After testing (the testing method is the same as that of the amide β-crystal nucleating agent NA-1 in Example 1), the nucleating effect of the amide β-crystal nucleating agent NA-5 in this example is close to that of the amide β-crystal nucleating agent NA-1 in Example 1.

[0216] Embodiment 16:

[0217] An amide type β-crystal nucleating agent, the preparation method of which comprises the following steps:

[0218] Disperse 0.022 mol of phthalic anhydride in 60 mL of tetrahydrofuran, then add 0.01 mol of 1,6-hexanediamine in batches, react at room temperature for 24 hours, centrifuge, wash the solid obtained by centrifugation with 30 mL of tetrahydrofuran, and then place it in a vacuum drying oven at 60°C for 12 hours to obtain an amide β-crystal nucleating agent (denoted as NA-6).

[0219] Performance Test:

[0220] 1) The nuclear magnetic resonance hydrogen spectrum of the amide β-crystal nucleating agent NA-6 in this example is as follows Fig.21 As shown, the magnetic resonance carbon spectrum is as follows Fig. 22 shown.

[0221] Depend on Fig.21 and Fig. 22 It can be seen that: this example indeed prepared the amide β-crystal nucleating agent NA-6 with the expected structure.

[0222] 2) After testing (the testing method is the same as that of the amide β-crystal nucleating agent NA-1 in Example 1), the nucleating effect of the amide β-crystal nucleating agent NA-6 in this example is close to that of the amide β-crystal nucleating agent NA-1 in Example 1.

[0223] Embodiment 17:

[0224] An amide type β-crystal nucleating agent, the preparation method of which comprises the following steps:

[0225] Disperse 0.022 mol of tetrahydrophthalic anhydride in 60 mL of tetrahydrofuran, and then add 0.01 mol of 1,4-butanediamine in batches, react at room temperature for 24 hours, centrifuge, wash the solid obtained by centrifugation with 30 mL of tetrahydrofuran, and then place it in a vacuum drying oven at 60°C for 12 hours to obtain an amide β-crystal nucleating agent (denoted as NA-7).

[0226] Performance Test:

[0227] 1) The nuclear magnetic resonance hydrogen spectrum of the amide β-crystal nucleating agent NA-7 in this example is as follows Fig.23 As shown, the magnetic resonance carbon spectrum is as follows Fig.24 shown.

[0228] Depend on Fig.23 and Fig.24 It can be seen that: this example indeed prepared the amide β-crystal nucleating agent NA-7 with the expected structure.

[0229] 2) After testing (the testing method is the same as that of the amide β-crystal nucleating agent NA-2 in Example 7), the nucleating effect of the amide β-crystal nucleating agent NA-7 in this example is close to that of the amide β-crystal nucleating agent NA-2 in Example 7.

[0230] Embodiment 18:

[0231] An amide type β-crystal nucleating agent, the preparation method of which comprises the following steps:

[0232] Disperse 0.022 mol of tetrahydrophthalic anhydride in 60 mL of tetrahydrofuran, then add 0.01 mol of 1,6-hexanediamine in batches, react at room temperature for 24 hours, centrifuge, wash the solid obtained by centrifugation with 30 mL of tetrahydrofuran, and then place it in a vacuum drying oven at 60°C for 12 hours to obtain an amide β-crystal nucleating agent (denoted as NA-8).

[0233] Performance Test:

[0234] 1) The nuclear magnetic resonance hydrogen spectrum of the amide β-crystal nucleating agent NA-8 in this example is as follows Fig.25 As shown, the magnetic resonance carbon spectrum is as follows Fig.26 shown.

[0235] Depend on Fig.25 and Fig.26 It can be seen that: this example indeed prepared the amide β-crystal nucleating agent NA-8 with the expected structure.

[0236] 2) After testing (the testing method is the same as that of the amide β-crystal nucleating agent NA-2 in Example 7), the nucleating effect of the amide β-crystal nucleating agent NA-8 in this example is close to that of the amide β-crystal nucleating agent NA-2 in Example 7.

[0237] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.

Claims

1. Use of an amide-based β-crystal nucleating agent in isotactic homopolymer polypropylene or random copolymer polypropylene; the general structural formula of the amide-based β-crystal nucleating agent is any one of formulas (I) to (IV): Formula (I): ; Formula (II): ; Formula (III): ; Formula (IV): ; In formulae (I) to (IV), n is an integer of 0 to 4, x is 2 or 3, and M is selected from one of lanthanum, zinc, calcium, barium and magnesium.

2. The use according to claim 1, characterized in that: The preparation method of the amide β-crystal nucleating agent comprises the following steps: Tetrahydrophthalic anhydride and aliphatic diamine are dispersed in an organic solvent for amidation reaction to obtain an amide type β-crystal nucleating agent represented by formula (I), and then a base is added for neutralization and a metal salt is added for salt formation reaction to obtain an amide type β-crystal nucleating agent represented by formula (II); Phthalic anhydride and aliphatic diamine are dispersed in an organic solvent for amidation reaction to obtain an amide type β-crystal nucleating agent represented by formula (III), and then a base is added for neutralization and a metal salt is added for salt formation reaction to obtain an amide type β-crystal nucleating agent represented by formula (IV).

3. The use according to claim 2, characterized in that: The molar ratio of the tetrahydrophthalic anhydride to the aliphatic diamine is 2 to 3:1; the molar ratio of the phthalic anhydride to the aliphatic diamine is 2 to 3:

1.

4. The use according to claim 2 or 3, characterized in that: The aliphatic diamine is one of 1,2-ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, 1,5-pentanediamine and 1,6-hexanediamine.

5. The use according to claim 2 or 3, characterized in that: The amidation reaction is carried out at room temperature, and the reaction time is 12h to 24h.

6. The use according to claim 2 or 3, characterized in that: The alkali is at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate.

7. The use according to claim 2 or 3, characterized in that: The metal salt is one of lanthanum nitrate, lanthanum chloride, lanthanum sulfate, zinc nitrate, zinc chloride, zinc sulfate, calcium nitrate, calcium chloride, barium nitrate, barium chloride, magnesium nitrate, magnesium chloride, and magnesium sulfate.

8. The use according to claim 2 or 3, characterized in that: The salt-forming reaction is carried out at room temperature, and the reaction time is 20 h to 30 h.

9. The use according to claim 2 or 3, characterized in that: The salt-forming reaction is carried out at 60° C. to 80° C., and the reaction time is 10 h to 24 h.

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