Polypropylene nucleating agent as well as preparation method and application thereof

Abstract

The invention discloses a polypropylene nucleating agent, which has a structure as shown in formula I: # imgabs0, the polypropylene nucleating agent has a polyhydroxy and amido bond symmetrical coplanar structure, and the amido bond is beneficial to the formation of beta crystal, so that the impact resistance of a polypropylene material is improved. Because the amide bond and the hydroxyl can form an intermolecular hydrogen bond, the hydrogen bond is dissociated during heating, free nucleating agent molecules are generated in the polypropylene melt, and the single molecules rotate towards the coplanar direction under the action of a benzene ring; during cooling, hydrogen bonds are combined to initiate self-assembly of free nucleating agent molecules to form a spatial reticular supramolecular aggregate, and four hydroxyl structures at the end group position support a hexagonal structure formed between two adjacent nucleating agent molecules, so that the spatial reticular structure of the supramolecular aggregate is favorably stabilized, a nucleation site is provided for a polypropylene chain, and the molecular weight of the supramolecular aggregate is reduced; the neat arrangement and accumulation of molecular chains are promoted, and the nucleation is promoted, so that the haze of the polypropylene material is reduced.

Description

Technical Field

[0001] The invention belongs to the technical field of nucleating agents, and in particular relates to a polypropylene nucleating agent and a preparation method and application thereof. Background Art

[0002] Polypropylene (PP) is a semi-crystalline polymer, with molecules in the amorphous part in a disordered distribution state and molecules in the crystalline part in a spiral regular arrangement state. The crystallization process of PP includes two stages: nucleation and grain growth. Nucleation is divided into homogeneous nucleation and heterogeneous nucleation. Homogeneous nucleation is formed by the thermal motion of polymer chain segments in the melt to form orderly arranged chain bundles, which further form crystal nuclei. This method makes the processing and application performance of PP products poor; when there are "solid phase impurities" or undestroyed PP crystal nuclei in the PP melt, the PP molecular chains are adsorbed on the surface of the "impurities" and arranged in an orderly manner to form crystal nuclei. This is called heterogeneous nucleation. The presence of impurities has a great influence on the crystallization process of PP. The substance that plays a nucleation role and promotes crystallization in the crystallization process is called a nucleating agent.

[0003] When the PP melt is homogeneously nucleated and crystallized at a temperature slightly lower than the melting point, when the cooling rate is slow, the grain growth rate is greater than the nucleus formation rate, and it is easy to obtain a small amount of spherulites with large particles and high crystallinity; when the cooling rate is fast, the nucleus formation rate is large, and it is easy to generate fine spherulites with low crystallinity, and the mechanical properties of PP products are poor. The introduction of nucleating agents accelerates the formation of nuclei and has no effect on the grain growth rate. This allows PP to obtain finer grains at higher temperatures and higher grain density, which is completely opposite to the phenomenon observed in homogeneous nucleation. Therefore, nucleating agents can accelerate PP crystallization, increase the PP crystallization temperature by about 20°C, and increase the crystallization rate and overall crystallinity. By improving the crystallization behavior and crystal form, promoting PP to form regular crystals, improving the crystallinity and crystallization temperature of products, reducing the processing production cycle, and improving the performance of materials (such as transparency, surface gloss, load deformation temperature, and impact resistance, etc.), it is the basis of PP crystallization modification. At present, nucleating agents have been widely used in the production and processing of PP.

[0004] According to the different chemical structures, PP nucleating agents can be divided into inorganic nucleating agents and organic nucleating agents. Among them, inorganic nucleating agents have poor compatibility with PP and uneven dispersion. Compared with inorganic nucleating agents, organic nucleating agents have good compatibility with the polypropylene matrix, high nucleation efficiency, and obvious advantages in nucleation effect. They are the main polypropylene nucleating agents currently used. α crystal and β crystal are common crystal forms of PP. Commercial PP is mainly α crystal. The stability of β crystal is not as good as α crystal. It requires specific conditions (such as rapidly cooling the melt to a certain temperature for crystallization, vibration-induced crystallization, shearing and stretching during crystallization, or adding β crystal nucleating agents) to form. Based on this, PP nucleating agents can be divided into α crystal nucleating agents and β crystal nucleating agents. α crystal nucleating agents can improve the rigidity and transparency of PP, and β crystal nucleating agents can improve the toughness and load deformation temperature of PP. The research on β nucleating agents began in the 1980s, and a series of products with high practical value have been developed so far. For example, Chinese patent document CN 114835949 A discloses a polypropylene composite nucleating agent based on glucose acetal derivatives, which is composed of two components, glucose acetal derivatives and organic phosphates. The glucose acetal derivatives have multiple hydrogen bonding sites, and form fibrous crystals under the action of intermolecular hydrogen bonds, providing active nucleation sites for the crystallization of macromolecular chains. The prepared glucose acetal derivative nucleating agent can improve the transparency and processing performance of the material. Chinese patent document CN113621175A discloses a high-efficiency isotactic polypropylene β-crystal nucleating agent, which has two symmetrical or asymmetrical amide structures. The impact performance of the polypropylene modified by the nucleating agent is improved by 3-4 times compared with the unmodified polypropylene sample. Chinese patent document CN102898724A discloses a micronized amide-type β-polypropylene nucleating agent, which has a narrow number average particle size distribution and can be evenly dispersed. When used to prepare polypropylene materials, it can significantly improve the impact strength of polypropylene materials and improve the physical properties of polypropylene materials such as bending modulus and crystallization temperature.

[0005] However, polypropylene produced by using existing β-nucleating agents generally has the problems of high haze and low impact strength, and cannot meet the application requirements in the field of low-temperature transparent food packaging. Summary of the invention

[0006] In view of the problems existing in the prior art and the directions for improvement, the present invention provides a polypropylene nucleating agent to solve the problems that the polypropylene prepared by the existing polypropylene nucleating agent has high haze and the impact strength needs to be improved.

[0007] To achieve the above object, the present invention provides the following technical solutions:

[0008] A polypropylene nucleating agent having a structure shown in Formula I:

[0009]

[0010] Wherein, R1 is selected from unsubstituted or substituted C6-C20 arylene, or Among them, * is the connection with oxygen atom, It is the connection point with nitrogen atom;

[0011] R2 is selected from a C1-C20 linear or branched alkylene group, a C6-C20 cycloalkylene group, or a C6-C20 arylene group.

[0012] In the above definition of R1, the substituted C6-C20 arylene group means that at least one H in the C6-C20 arylene group is substituted by a C1-C6 straight-chain or branched alkyl group, such as methyl, ethyl, propyl, isopropyl, tert-butyl, isopentyl, and the like.

[0013] Optionally, in the polypropylene nucleating agent provided by the present invention, R1 is selected from

[0014] Among them, * is the connection with oxygen atom, is the connection point with nitrogen atom).

[0015] Optionally, in the polypropylene nucleating agent provided by the present invention, R2 is selected from methylene, ethylene, propylene (-CH2CH2CH2-), Any of: It is the connection point with the carbonyl group (C=O).

[0016] The present invention also provides a method for preparing a polypropylene nucleating agent, comprising the following steps:

[0017]

[0018] Step 1: The alcohol amine compound represented by formula II and the dicarboxylic acid represented by formula III are subjected to an amidation reaction under the action of a condensing agent to obtain a compound represented by formula IV;

[0019] Step 2: The compound represented by formula IV is reacted with ethyl bromoacetate to obtain the compound represented by formula V;

[0020] Step 3: The compound represented by formula V and diethanolamine are subjected to an amine ester exchange reaction to obtain a polypropylene nucleating agent represented by formula I;

[0021] Wherein, R1 and R2 are as defined above.

[0022] Optionally, in the preparation method of the polypropylene nucleating agent provided by the present invention, the condensing agents used in the amidation reaction are 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide (EDC) and 1-hydroxybenzotriazole (HOBt); preferably, the molar ratio of the alcoholamine compound shown in formula II, the dicarboxylic acid shown in formula III, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide and 1-hydroxybenzotriazole is (2.2-3):1:(2.5-3.5):(1.1-1.3).

[0023] Optionally, in the method for preparing a polypropylene nucleating agent provided by the present invention, the substitution reaction is carried out under the action of an alkaline catalyst. Preferably, the alkaline catalyst is selected from potassium carbonate or sodium carbonate; more preferably, the molar ratio of the compound represented by formula IV, the ethyl bromoacetate and the alkaline catalyst is 1:(2-4):(3-4).

[0024] Optionally, in the preparation method of the polypropylene nucleating agent provided by the present invention, the compound represented by formula V and diethanolamine undergo an amine ester exchange reaction in the presence of a base; preferably, the base is selected from potassium carbonate or sodium carbonate; more preferably, the molar ratio of the compound represented by formula V, the diethanolamine and the alkaline substance is 1:(2-4):(3-4).

[0025] The present invention also provides a polypropylene composition, comprising polypropylene and a nucleating agent, wherein the nucleating agent is selected from the above-mentioned polypropylene nucleating agent or the polypropylene nucleating agent prepared by the above-mentioned method for preparing the polypropylene nucleating agent; preferably, the mass ratio of the polypropylene nucleating agent to the polypropylene is (2-5):100.

[0026] Optionally, in the polypropylene composition provided by the present invention, the polypropylene composition also includes an antioxidant and an acid scavenger; wherein, the dosage of the antioxidant and the acid scavenger is not limited, and can be adjusted according to the conventional industry practice based on actual conditions. The mass ratio of the antioxidant to the polypropylene recommended by the present invention is (0.05-0.2):100; the mass ratio of the acid scavenger to the polypropylene is (0.2-0.7):100.

[0027] Optionally, in the polypropylene composition provided by the present invention, the deoxidizer and the acid scavenger can be conventional ones in the industry, such as the antioxidant can be selected from at least one of hindered phenols, phosphites and sulfates; the antioxidant recommended by the present invention is selected from 1010 and / or 168;

[0028] The acid scavenger is selected from at least one of hydrotalcite, calcium stearate and zinc chloride.

[0029] Optionally, in the polypropylene composition provided by the present invention, the polypropylene is selected from homopolypropylene and / or copolymer polypropylene; preferably, the copolymer polypropylene is a random copolymer or block copolymer of terminal olefin / cyclic olefin and propylene, and the terminal olefin / cyclic olefin is selected from at least one of ethylene, C4-C8 α-olefin, vinyl cyclohexane, vinyl cyclohexene and norbornene; more preferably, the polypropylene is selected from at least one of homopolypropylene, a random copolymer of propylene and ethylene, and a block copolymer of propylene and ethylene.

[0030] Optionally, the preparation method of the polypropylene composition provided by the present invention is not specifically limited, and can be prepared by conventional methods in the industry, such as melt blending, granulation and processing of polypropylene, nucleating agent, antioxidant and acid scavenger to obtain a polypropylene composition product. Preferably, the processing method is selected from at least one of injection molding, extrusion, blow molding, thermoforming and foaming.

[0031] Compared with the prior art, the present invention has the following beneficial effects:

[0032] The polypropylene nucleating agent provided by the present invention has a symmetrical coplanar structure of multiple hydroxyl groups and amide bonds, wherein the amide bonds are conducive to the formation of β crystals and improve the impact resistance of polypropylene materials. In addition, since the amide bonds and hydroxyl groups can form intermolecular hydrogen bonds, when heated, the hydrogen bonds dissociate, and free nucleating agent molecules are generated in the polypropylene melt. Under the action of the benzene ring, the single molecule rotates in the coplanar direction; when cooled, the hydrogen bonds combine to trigger the self-assembly of the free nucleating agent molecules to form a spatial network supramolecular aggregate. The four hydroxyl structures at the end positions support the formation of a hexagonal structure between two adjacent nucleating agent molecules, which is conducive to stabilizing the spatial network structure of the supramolecular aggregate, providing nucleation sites for polypropylene chains, promoting the neat arrangement and stacking of molecular chains, and promoting nucleation, thereby reducing the haze of polypropylene materials. The polypropylene nucleating agent provided by the present invention can simultaneously improve the transparency and impact resistance of polypropylene materials, is a highly efficient nucleating agent, and has good industrial prospects. DETAILED DESCRIPTION

[0033] The present invention is described in detail below by way of examples. It is necessary to point out that the following examples are only used to further illustrate the present invention and cannot be understood as limiting the scope of protection of the present invention. Those skilled in the art in this field can make some non-essential improvements and adjustments to the present invention based on the above content of the present invention.

[0034] If no specific experimental steps or conditions are specified in the examples and comparative examples, the conventional experimental steps or conditions described in the literature in the art can be used. If no manufacturer is specified for the reagents or instruments used, they are all conventional reagent products that can be purchased commercially.

[0035] Example 1

[0036] The structure of nucleating agent N1 is shown below, and the specific preparation steps are as follows:

[0037]

[0038] (1) 2,6-naphthalenedicarboxylic acid (2.2 g, 10 mmol, 216.19 g / mol, Aladdin reagent, ≥98.0%), 4-amino-3-methylphenol (2.7 g, 22 mmol, 123.15 g / mol, Aladdin reagent, 98%), EDC (4.8 g, 25 mmol, 191.7 g / mol, Aladdin reagent, 98%), HOBt (1.5 g, 11 mmol, 135.13g / mol, MacLean reagent, ≥97.0%), 60mL anhydrous dichloromethane (Aladdin reagent, ≥99.8%), react at room temperature for 24 hours. After the reaction, wash with 10% NaOH solution and deionized water respectively and separate the liquids. Dry the organic phase with anhydrous sodium sulfate and distill under reduced pressure to obtain 4.1g of the intermediate (compound shown in formula IV, R2 is naphthylene, R1 is methyl-substituted phenylene) (9.5mmol, 426g / mol);

[0039] (2) 4.1 g of the intermediate (compound represented by Formula IV), anhydrous sodium carbonate (3.0 g, 28.5 mmol, 105.99 g / mol, Aladdin reagent, ≥99.5%), and 60 mL of acetone were added to a reaction vessel, and the mixture was stirred at room temperature until all the solid was dissolved. Then, ethyl bromoacetate (3.5 g, 21 mmol, 167 g / mol, Aladdin reagent, 98%) was added, and the mixture was refluxed for 20 hours under nitrogen protection, with petroleum ether / ethyl acetate as the mobile phase. 5.0 g of the intermediate product (compound represented by Formula V, R2 and R1 are the same as in step 1) (8.4 mmol, 598 g / mol) was obtained by column chromatography separation;

[0040] (3) 4.8 g of the intermediate (compound represented by Formula V), anhydrous sodium carbonate (2.7 g, 25.2 mmol, 105.99 g / mol, Aladdin reagent, ≥99.5%), diethanolamine (2.2 g, 21 mmol, 105.14 g / mol, Aladdin reagent, 99%), and 60 mL of ethanol were added to the reaction vessel. The mixture was refluxed under nitrogen protection for 8 hours with dichloromethane / methanol as the mobile phase. The nucleating agent N1 was separated by column chromatography. The structure was confirmed to be correct by NMR.

[0041] 1H NMR(400MHZ,DMSO)δ7.52(s,2H),7.37(t,2H),6.93(t,2H),6.85(t,2H),7.43-7.37(m,2H),6.6 1-6.69(m,4H),4.84(s,4H),4.59(dd,2H),4.47(dd,2H),3.39(t,8H),3.32(m,8H),2.42(d,6H).

[0042] Example 2

[0043] The structure of nucleating agent N2 is shown below, and the specific preparation steps are as follows:

[0044]

[0045] (1) Terephthalic acid (1.7 g, 10 mmol, 166.13 g / mol, Aladdin reagent, 99.0%), 4-amino-3,5-dimethylphenol (3.6 g, 26 mmol, 137.18 g / mol, Aladdin reagent, >98%), EDC (6.5 g, 34 mmol, 191.7 g / mol, Aladdin reagent, 98%), HOBt (1.8 g, 13 mmol, 135.13g / mol, MacLean reagent, ≥97.0%), 60mL anhydrous dichloromethane (Aladdin reagent, ≥99.8%), react at room temperature for 24 hours. After the reaction, wash with 10% NaOH solution and deionized water respectively and separate the liquids. Dry the organic phase with anhydrous sodium sulfate and distill under reduced pressure to obtain 3.6g of the intermediate (compound shown in formula IV, R2 is phenylene, R1 is dimethyl substituted phenylene) (8.8mmol, 404g / mol);

[0046] (2) 3.6 g of the intermediate (compound represented by Formula IV), anhydrous potassium carbonate (4.6 g, 33.4 mmol, 138.21 g / mol, Aladdin reagent, ≥99.5%), and 60 mL of acetone were added to a reaction vessel, and the mixture was stirred at room temperature until all the solid was dissolved. Then, ethyl bromoacetate (3.2 g, 19.4 mmol, 167 g / mol, Aladdin reagent, 98%) was added, and the mixture was refluxed for 20 hours under nitrogen protection, with petroleum ether / ethyl acetate as the mobile phase. 4.8 g of the intermediate product (compound represented by Formula V, R2 and R1 are the same as in step 1) (8.4 mmol, 576 g / mol) was obtained by column chromatography separation;

[0047] (3) 4.8 g of the intermediate (compound represented by Formula V), anhydrous sodium carbonate (3.2 g, 30.8 mmol, 105.14 g / mol, Aladdin reagent, 99%), diethanolamine (1.9 g, 17.6 mmol, 105.14 g / mol, Aladdin reagent, 99%), and 60 mL of ethanol were added to the reaction vessel, and refluxed under nitrogen protection for 8 hours with dichloromethane / methanol as the mobile phase. The nucleating agent N2 was separated by column chromatography, and the structure was confirmed to be correct by NMR verification.

[0048] Example 3

[0049] The structure of nucleating agent N3 is shown below, and the specific preparation steps are as follows:

[0050]

[0051] (1) p-Malonate (1.0 g, 10 mmol, 104.06 g / mol, Aladdin reagent, 99.0%), 4-(2-amino-2-methylpropyl)phenol (3.6 g, 22 mmol, 165.23 g / mol, Aladdin reagent, 98%), EDC (5.4 g, 28 mmol, 191.7 g / mol, Aladdin reagent, 98%), HOBt (1.6 g, 12 mmol, 135.13 g / mol, Macklin reagent, ≥97.0%), and 60 mL of anhydrous dichloromethane (Aladdin reagent, ≥99.8%) were added to a reaction vessel and reacted at room temperature for 24 hours. After the reaction was completed, the mixture was washed with 10% NaOH solution and deionized water, respectively, and the liquid was separated. The organic phase was dried over anhydrous sodium sulfate and distilled under reduced pressure to obtain 3.6 g of the intermediate (the compound represented by Formula IV, R2 is methylene, R1 is )(9.6mmol, 370.17g / mol);

[0052] (2) 3.6 g of the intermediate (compound represented by Formula IV), anhydrous potassium carbonate (4.6 g, 33.6 mmol, 138.21 g / mol, Aladdin reagent, ≥99.5%), and 60 mL of acetone were added to a reaction vessel, and the mixture was stirred at room temperature until all the solid was dissolved. Then, ethyl bromoacetate (5.9 g, 35.5 mmol, 167 g / mol, Aladdin reagent, 98%) was added, and the mixture was refluxed for 20 hours under nitrogen protection, with petroleum ether / ethyl acetate as the mobile phase. 4.9 g of the intermediate product (compound represented by Formula V, R2 and R1 are the same as in step 1) (9.0 mmol, 542 g / mol) was obtained by column chromatography separation;

[0053] (3) 4.9 g of the intermediate (compound represented by Formula V), anhydrous sodium carbonate (3.8 g, 36.0 mmol, 105.14 g / mol, Aladdin reagent, 99%), diethanolamine (3.6 g, 34.2 mmol, 105.14 g / mol, Aladdin reagent, 99%), and 60 mL of ethanol were added to the reaction vessel, and refluxed under nitrogen protection for 8 hours with dichloromethane / methanol as the mobile phase. The nucleating agent N3 was separated by column chromatography, and the structure was confirmed to be correct by NMR verification.

[0054] Example 4

[0055] The structure of nucleating agent N4 is shown below, and the specific preparation steps are as follows:

[0056]

[0057] (1) p-1,4-cyclohexanedicarboxylic acid (1.7 g, 10 mmol, 172.18 g / mol, Aladdin reagent, 99.0%), 2-amino-5-methylphenol (3.7 g, 30 mmol, 123.15 g / mol, Aladdin reagent, 98%), EDC (6.3 g, 33 mmol, 191.7 g / mol, Aladdin reagent, 98%), HOBt (1.8 g, 13 mmol, 1 35.13g / mol, MacLean reagent, ≥97.0%), 60mL anhydrous dichloromethane (Aladdin reagent, ≥99.8%), react at room temperature for 24 hours. After the reaction, wash with 10% NaOH solution and deionized water respectively and separate the liquids. Dry the organic phase with anhydrous sodium sulfate and distill under reduced pressure to obtain 3.1g of the intermediate (compound shown in formula IV, R2 is cyclohexylene, R1 is methyl-substituted phenylene) (8.1mmol, 382.17g / mol);

[0058] (2) 3.1 g of the intermediate (compound represented by Formula IV), anhydrous sodium carbonate (3.3 g, 31.6 mmol, 105.14 g / mol, Aladdin reagent, 99%), and 60 mL of acetone were added to a reaction vessel, and the mixture was stirred at room temperature until all the solid was dissolved. Then, ethyl bromoacetate (4.5 g, 26.7 mmol, 167 g / mol, Aladdin reagent, 98%) was added, and the mixture was refluxed for 20 hours under nitrogen protection, with petroleum ether / ethyl acetate as the mobile phase. Column chromatography was used to separate and obtain 3.9 g of the intermediate product (compound represented by Formula V, R2 and R1 are the same as in step 1) (7.1 mmol, 544.19 g / mol);

[0059] (3) 3.9 g of the intermediate (compound represented by Formula V), anhydrous potassium carbonate (3.0 g, 22 mmol, 138.21 g / mol, Aladdin reagent, ≥99.5%), diethanolamine (1.9 g, 17.8 mmol, 105.14 g / mol, Aladdin reagent, 99%), and 60 mL of ethanol were added to the reaction vessel. The mixture was refluxed under nitrogen protection for 8 hours with dichloromethane / methanol as the mobile phase. The nucleating agent N4 was separated by column chromatography. The structure was confirmed to be correct by NMR.

[0060] Example 5

[0061] The structure of nucleating agent N5 is shown below, and the specific preparation steps are as follows:

[0062]

[0063] (1) Add p-glutaric acid (1.3 g, 10 mmol, 132.11 g / mol, Aladdin reagent, 99.0%), p-aminophenol (2.4 g, 22 mmol, 109.13 g / mol, MacLean reagent, ≥98%), EDC (4.8 g, 25 mmol, 191.7 g / mol, Aladdin reagent, 98%), HOBt (1.5 g, 11 mmol, 135.13 g / mol, MacLean reagent, ≥97.0%), and 60 mL of anhydrous dichloromethane (Aladdin reagent, ≥99.8%) to a reaction container, and react at room temperature for 24 hours. After the reaction is completed, wash with 10% NaOH solution and deionized water respectively, separate the liquids, dry the organic phase with anhydrous sodium sulfate, and distill under reduced pressure to obtain 3.1 g of the intermediate (compound represented by formula IV, R2 is propylene and R1 is phenylene) (9.8 mmol, 314.11 g / mol);

[0064] (2) 3.1 g of the intermediate (compound represented by Formula IV), anhydrous sodium carbonate (3.1 g, 29.4 mmol, 105.14 g / mol, Aladdin reagent, 99%), and 60 mL of acetone were added to a reaction vessel, and the mixture was stirred at room temperature until all the solid was dissolved. Then, ethyl bromoacetate (3.6 g, 21.6 mmol, 167 g / mol, Aladdin reagent, 98%) was added, and the mixture was refluxed for 20 hours under nitrogen protection, with petroleum ether / ethyl acetate as the mobile phase. 4.4 g of the intermediate product (compound represented by Formula V, R2 and R1 are the same as in step 1) (9.1 mmol, 486.4 g / mol) was obtained by column chromatography separation;

[0065] (3) 4.4 g of the intermediate (compound represented by Formula V), anhydrous potassium carbonate (3.8 g, 27.3 mmol, 138.21 g / mol, Aladdin reagent, ≥99.5%), diethanolamine (2.5 g, 23.7 mmol, 105.14 g / mol, Aladdin reagent, 99%), and 60 mL of ethanol were added to the reaction vessel. The mixture was refluxed under nitrogen protection for 8 hours with dichloromethane / methanol as the mobile phase. The nucleating agent N5 was separated by column chromatography. The structure was confirmed to be correct by NMR.

[0066] Example 6

[0067] The structure of nucleating agent N6 is shown below, and the specific preparation steps are as follows:

[0068]

[0069] (1) Add terephthalic acid (1.7 g, 10 mmol, 166.13 g / mol, Aladdin reagent, 99.0%), p-aminophenol (2.7 g, 25 mmol, 109.13 g / mol, MacLean reagent, ≥98%), EDC (5.6 g, 29 mmol, 191.7 g / mol, Aladdin reagent, 98%), HOBt (1.6 g, 12 mmol, 135.13 g / mol, MacLean reagent, ≥97.0%), and 60 mL of anhydrous dichloromethane (Aladdin reagent, ≥99.8%) into a reaction container, and react at room temperature for 24 hours. After the reaction is completed, wash with 10% NaOH solution and deionized water respectively, separate the liquids, dry the organic phase with anhydrous sodium sulfate, and distill under reduced pressure to obtain 3.3 g of the intermediate (compound represented by formula IV, R2 is phenylene, R1 is phenylene) (9.5 mmol, 348.1 g / mol);

[0070] (2) 3.3 g of the intermediate (compound represented by Formula IV), anhydrous potassium carbonate (5.0 g, 36.1 mmol, 138.21 g / mol, Aladdin reagent, ≥99.5%), and 60 mL of acetone were added to a reaction vessel, and the mixture was stirred at room temperature until all the solid was dissolved. Then, ethyl bromoacetate (5.7 g, 34.2 mmol, 167 g / mol, Aladdin reagent, 98%) was added, and the mixture was refluxed for 20 hours under nitrogen protection, with petroleum ether / ethyl acetate as the mobile phase. 4.5 g of the intermediate product (compound represented by Formula V, R2 and R1 are the same as in step 1) (8.6 mmol, 520.12 g / mol) was obtained by column chromatography.

[0071] (3) 4.5 g of the intermediate (compound represented by Formula V), anhydrous potassium carbonate (3.9 g, 28.4 mmol, 138.21 g / mol, Aladdin reagent, ≥99.5%), diethanolamine (2.0 g, 18.9 mmol, 105.14 g / mol, Aladdin reagent, 99%), and 60 mL of ethanol were added to the reaction vessel. The mixture was refluxed under nitrogen protection for 8 hours with dichloromethane / methanol as the mobile phase. The nucleating agent N6 was separated by column chromatography. The structure was confirmed to be correct by NMR.

[0072] Example 7

[0073] The structure of nucleating agent N7 is shown below, and the specific preparation steps are as follows:

[0074]

[0075] (1) 1,4-cyclohexanedicarboxylic acid (1.7 g, 10 mmol, 172.18 g / mol, Aladdin reagent, 99.0%), 4-amino-3-methylphenol (2.8 g, 26 mmol, 123.15 g / mol, Aladdin reagent, 98%), EDC (6.3 g, 33 mmol, 191.7 g / mol, Aladdin reagent, 98%), HOBt (1.8 g, 13 mmol, 1 35.13g / mol, MacLean reagent, ≥97.0%), 60mL anhydrous dichloromethane (Aladdin reagent, ≥99.8%), react at room temperature for 24 hours. After the reaction, wash with 10% NaOH solution and deionized water respectively and separate the liquids. Dry the organic phase with anhydrous sodium sulfate and distill under reduced pressure to obtain 3.4g of the intermediate (compound shown in formula IV, R2 is cyclohexylene, R1 is methyl-substituted phenylene) (8.8mmol, 382.17g / mol);

[0076] (2) 3.4 g of the intermediate (compound represented by Formula IV), anhydrous potassium carbonate (4.3 g, 30.8 mmol, 138.21 g / mol, Aladdin reagent, ≥99.5%), and 60 mL of acetone were added to a reaction vessel, and the mixture was stirred at room temperature until all the solid was dissolved. Then, ethyl bromoacetate (4.4 g, 26.4 mmol, 167 g / mol, Aladdin reagent, 98%) was added, and the mixture was refluxed for 20 hours under nitrogen protection, with petroleum ether / ethyl acetate as the mobile phase. 4.2 g of the intermediate product (compound represented by Formula V, R2 and R1 are the same as in step 1) (7.5 mmol, 554.19 g / mol) was obtained by column chromatography.

[0077] (3) 4.2 g of the intermediate (compound represented by Formula V), anhydrous potassium carbonate (3.6 g, 26.3 mmol, 138.21 g / mol, Aladdin reagent, ≥99.5%), diethanolamine (2.0 g, 18.8 mmol, 105.14 g / mol, Aladdin reagent, 99%), and 60 mL of ethanol were added to the reaction vessel. The mixture was refluxed under nitrogen protection for 8 hours with dichloromethane / methanol as the mobile phase. The nucleating agent N7 was separated by column chromatography. The structure was confirmed to be correct by NMR.

[0078] Example 8

[0079] The structure of nucleating agent N8 is shown below, and the specific preparation steps are as follows:

[0080]

[0081] (1) Add terephthalic acid (1.7 g, 10 mmol, 166.13 g / mol, Aladdin reagent, 99.0%), 7-amino-2-naphthol (3.5 g, 22 mmol, 159.19 g / mol, Aladdin reagent), EDC (5.4 g, 28 mmol, 191.7 g / mol, Aladdin reagent, 98%), HOBt (1.8 g, 13 mmol, 135.13 g / mol, Macklin reagent, ≥97.0%), and 60 mL of anhydrous dichloromethane (Aladdin reagent, ≥99.8%) into a reaction container, and react at room temperature for 24 hours. After the reaction is completed, wash with 10% NaOH solution and deionized water respectively, separate the liquids, dry the organic phase with anhydrous sodium sulfate, and distill under reduced pressure to obtain 4.1 g of the intermediate (compound represented by formula IV, R2 is phenylene and R1 is naphthylene) (9.2 mmol, 448.13 g / mol);

[0082] (2) 4.1 g of the intermediate (compound represented by Formula IV), anhydrous potassium carbonate (3.8 g, 27.6 mmol, 138.21 g / mol, Aladdin reagent, ≥99.5%), and 60 mL of acetone were added to a reaction vessel, and the mixture was stirred at room temperature until all the solid was dissolved. Then, ethyl bromoacetate (5.1 g, 30.4 mmol, 167 g / mol, Aladdin reagent, 98%) was added, and the mixture was refluxed for 20 hours under nitrogen protection, with petroleum ether / ethyl acetate as the mobile phase. 5.4 g of the intermediate product (compound represented by Formula V, R2 and R1 are the same as in step 1) (8.7 mmol, 620.15 g / mol) was obtained by column chromatography separation;

[0083] (3) 5.4 g of the intermediate (compound represented by Formula V), anhydrous potassium carbonate (4.2 g, 30.5 mmol, 138.21 g / mol, Aladdin reagent, ≥99.5%), diethanolamine (2.0 g, 19.1 mmol, 105.14 g / mol, Aladdin reagent, 99%), and 60 mL of ethanol were added to the reaction vessel. The mixture was refluxed under nitrogen protection for 8 hours with dichloromethane / methanol as the mobile phase. The nucleating agent N8 was separated by column chromatography. The structure was confirmed to be correct by NMR.

[0084] Example 9

[0085] The specific preparation steps of nucleating agent N9 are as follows:

[0086]

[0087] (1) Add malonic acid (1.0 g, 10 mmol, 104.06 g / mol, Aladdin reagent, 99.0%), 2-amino-4-tert-amylphenol (5.0 g, 28 mmol, 179.25 g / mol, Aladdin reagent), EDC (5.4 g, 28 mmol, 191.7 g / mol, Aladdin reagent, 98%), HOBt (1.8 g, 13 mmol, 135.13 g / mol, Macklin reagent, ≥97.0%), and 60 mL of anhydrous dichloromethane (Aladdin reagent, ≥99.8%) to a reaction vessel, and react at room temperature for 24 hours. After the reaction is completed, wash with 10% NaOH solution and deionized water, respectively, and separate the liquids. Dry the organic phase with anhydrous sodium sulfate, and distill under reduced pressure to obtain 3.8 g of the intermediate (the compound represented by Formula IV, R2 is methylene, R1 is )(9.0mmol, 426.24g / mol);

[0088] (2) 3.8 g of the intermediate (compound represented by Formula IV), anhydrous potassium carbonate (4.7 g, 34.2 mmol, 138.21 g / mol, Aladdin reagent, ≥99.5%), and 60 mL of acetone were added to a reaction vessel, and the mixture was stirred at room temperature until all the solid was dissolved. Then, ethyl bromoacetate (5.4 g, 32.4 mmol, 167 g / mol, Aladdin reagent, 98%) was added, and the mixture was refluxed for 20 hours under nitrogen protection, with petroleum ether / ethyl acetate as the mobile phase. 5.1 g of the intermediate product (compound represented by Formula V, R2 and R1 are the same as in step 1) (8.5 mmol, 598.62 g / mol) was obtained by column chromatography separation;

[0089] (3) 5.1 g of the intermediate (compound represented by Formula V), anhydrous potassium carbonate (3.9 g, 28.1 mmol, 138.21 g / mol, Aladdin reagent, ≥99.5%), diethanolamine (2.6 g, 25.5 mmol, 105.14 g / mol, Aladdin reagent, 99%), and 60 mL of ethanol were added to the reaction vessel. The mixture was refluxed under nitrogen protection for 8 hours with dichloromethane / methanol as the mobile phase. The nucleating agent N9 was separated by column chromatography. The structure was confirmed to be correct by NMR.

[0090] Example 10

[0091] This embodiment provides a polypropylene composition, and the specific preparation steps are as follows:

[0092] Based on the weight of polypropylene as 100%, 12wt% of nucleating agent N, 0.15wt% of 1010 antioxidant, and 0.7wt% of calcium stearate were added into a high-speed mixer at a speed of 800r / min and mixed for 10 minutes. After being mixed in the high-speed mixer, the mixture was extruded and granulated using a twin-screw extruder granulator HAAKE 40 of German HAAKE Company at an extrusion temperature of 210°C. Then, the mixture was processed by UN-100 of Liuzhou Injection Molding Machinery Factory at an injection molding temperature of 230°C to make a standard specimen, which was recorded as specimen 1#.

[0093] Examples 11-23

[0094] The polypropylene compositions and preparation methods provided in Examples 11-23 are similar to those in Example 10, except that different raw materials and amounts are used, as shown in the table below.

[0095] Table 1

[0096]

[0097]

[0098] Note: The amount of each substance in each example in this table is based on the mass of the corresponding polypropylene as 100%.

[0099] Comparative Example 1

[0100] Homopolymer polypropylene with a melt index of 12 g / 10 min, 3 wt% of nucleating agent N,N'-diphenylterephthalamide (DPHT) accounting for the weight percentage of the homopolymer polypropylene, 0.15 wt% of antioxidant 1010, and 0.5 wt% of calcium stearate were added to a high-speed mixer at a speed of 800 r / min and mixed for 10 minutes. After being mixed in the high-speed mixer, they were extruded and granulated using a twin-screw extruder granulator HAAKE 40 of German HAAKE Company at an extrusion temperature of 210° C. Then, they were injected into the UN-100 of Liuzhou Injection Molding Machinery Factory at an injection temperature of 230° C. to prepare the sample of comparative example 1.

[0101] Comparative Example 2

[0102] Homopolymer polypropylene with a melt index of 12 g / 10 min, 3 wt% of nucleating agent (shown in the following formula VI) accounting for the weight percentage of the homopolymer polypropylene, 0.15 wt% of antioxidant 1010, and 0.5 wt% of calcium stearate were added to a high-speed mixer at a speed of 800 r / min and mixed for 10 minutes. After being mixed in the high-speed mixer, they were extruded and granulated using a twin-screw extruder granulator HAAKE 40 of German HAAKE Company at an extrusion temperature of 210° C. Then, they were injected into the UN-100 of Liuzhou Injection Molding Machinery Factory at an injection molding temperature of 230° C. to prepare the sample of comparative example 2.

[0103]

[0104] Comparative Example 3

[0105] Ethylene propylene random copolymer polypropylene with a melt index of 10g / 10min, 3wt% of nucleating agent N,N'-diphenyl terephthalamide (DPHT) accounting for the weight percentage of the ethylene propylene random copolymer polypropylene, 0.15wt% of antioxidant 1010, and 0.5wt% of calcium stearate were added into a high-speed mixer at a speed of 800r / min and mixed for 10 minutes. After being mixed in the high-speed mixer, they were extruded and granulated using a twin-screw extruder granulator HAAKE 40 of German HAAKE Company at an extrusion temperature of 210°C. Then, they were injected into the UN-100 of Liuzhou Injection Molding Machinery Factory at an injection temperature of 230°C to prepare the sample comparative example 3.

[0106] Comparative Example 4

[0107] Ethylene propylene random copolymer polypropylene with a melt index of 10g / 10min, 3wt% of nucleating agent (shown in Formula VI) accounting for the weight percentage of the ethylene propylene random copolymer polypropylene, 0.15wt% of antioxidant 1010, and 0.5wt% of calcium stearate were added to a high-speed mixer at a speed of 800r / min and mixed for 10 minutes. After being mixed in the high-speed mixer, they were extruded and granulated using a twin-screw extruder granulator HAAKE 40 of German HAAKE Company at an extrusion temperature of 210°C. Then, they were injected into the UN-100 of Liuzhou Injection Molding Machinery Factory at an injection molding temperature of 230°C to prepare sample comparative example 4.

[0108]

[0109] Comparative Example 5 Preparation of Blank Sample 1

[0110] Homopolymer polypropylene with a melt index of 12 g / 10 min, 0.15 wt% antioxidant 1010 and 0.5 wt% calcium stearate were added to a high-speed mixer at a speed of 800 r / min and mixed for 10 minutes. After being mixed in the high-speed mixer, they were extruded and granulated using a twin-screw extruder granulator HAAKE 40 of German HAAKE Company at an extrusion temperature of 210° C. Then, they were injected into a Liuzhou Injection Molding Machinery Factory UN-100 at an injection molding temperature of 230° C. to prepare a blank sample strip 1 as a blank control.

[0111] Comparative Example 6 Preparation of Blank Sample 2

[0112] Ethylene propylene random copolymer polypropylene with a melt index of 10g / 10min, 0.15wt% of antioxidant 1010 and 0.5wt% of calcium stearate were added into a high-speed mixer at a speed of 800r / min and mixed for 10 minutes. After being mixed in the high-speed mixer, they were extruded and granulated using a twin-screw extruder granulator HAAKE 40 of German HAAKE Company at an extrusion temperature of 210°C. Then, they were injected into the UN-100 of Liuzhou Injection Molding Machinery Factory at an injection molding temperature of 230°C to prepare a blank sample strip 2 as a blank control.

[0113] The samples prepared in each embodiment and comparative example were subjected to mechanical property tests according to the following methods: Mechanical property test: simply supported beam impact strength was tested according to GB / T 1043-2008, with a notch depth of 2.0 mm; Optical property test: haze was tested according to GB / T 2410-2008. The test results are shown in the table below.

[0114] Table 2 Sample performance test

[0115]

[0116]

[0117] From the data in the above table, it can be seen that the nucleating agent provided by the present invention can significantly reduce the haze of polypropylene compared with the β-nucleating agent without hydroxyl substitution; compared with the glucose derivative nucleating agent, it has lower haze and can also significantly improve the impact resistance of polypropylene. This shows that the polypropylene nucleating agent provided by the present invention has the function of improving the transparency and impact resistance of polypropylene, and is a highly efficient polypropylene additive.

[0118] Of course, the present invention may have many other embodiments. Without departing from the spirit and essence of the present invention, technicians familiar with the field may make various corresponding changes and deformations based on the present invention, but these corresponding changes and deformations should all fall within the scope of protection of the claims of the present invention.

Claims

1. A polypropylene nucleating agent, characterized in that: It has the structure shown in Formula I: Wherein, R1 is selected from unsubstituted or substituted C6-C20 arylene, Where * is the connection with oxygen atom, It is the connection point with nitrogen atom; R2 is selected from a C1-C20 linear or branched alkylene group, a C6-C20 cycloalkylene group, or a C6-C20 arylene group.

2. The polypropylene nucleating agent according to claim 1, characterized in that R1 is selected from 3. The polypropylene nucleating agent according to claim 1, characterized in that R2 is selected from methylene, ethylene, propylene, Any of .

4. A method for preparing a polypropylene nucleating agent, characterized in that: The steps include: Step 1: The alcohol amine compound represented by formula II and the dicarboxylic acid represented by formula III are subjected to an amidation reaction under the action of a condensing agent to obtain a compound represented by formula IV; Step 2: The compound represented by formula IV is reacted with ethyl bromoacetate to obtain the compound represented by formula V; Step 3: The compound represented by formula V and diethanolamine are subjected to an amine ester exchange reaction to obtain a polypropylene nucleating agent represented by formula I; Wherein, the definitions of R1 and R2 are as described in any one of claims 1-3.

5. The method for preparing a polypropylene nucleating agent according to claim 4, characterized in that: The condensing agent is 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide and 1-hydroxybenzotriazole; preferably, the molar ratio of the alcohol amine compound shown in formula II, the dicarboxylic acid shown in formula III, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide and 1-hydroxybenzotriazole is (2.2-3):1:(2.5-3.5):(1.1-1.3).

6. The method for preparing a polypropylene nucleating agent according to claim 4, characterized in that: The substitution reaction is carried out under the action of a basic catalyst. Preferably, the basic catalyst is selected from potassium carbonate or sodium carbonate. More preferably, the molar ratio of the compound represented by formula IV, the ethyl bromoacetate and the basic catalyst is 1:(2-4):(3-4).

7. The method for preparing a polypropylene nucleating agent according to claim 4, characterized in that: In the presence of a base, the compound represented by formula V undergoes an amine ester exchange reaction with diethanolamine; preferably, the base is selected from potassium carbonate or sodium carbonate; more preferably, the molar ratio of the compound represented by formula V, the diethanolamine and the base is 1:(2-4):(3-4).

8. A polypropylene composition, characterized in that The invention comprises polypropylene and a nucleating agent, wherein the nucleating agent is selected from the polypropylene nucleating agent described in any one of claims 1 to 3 or the polypropylene nucleating agent prepared by the preparation method of the polypropylene nucleating agent described in any one of claims 4 to 7; preferably, the mass ratio of the polypropylene nucleating agent to the polypropylene is (2-5):

100.

9. The polypropylene composition according to claim 8, characterized in that The polypropylene composition further comprises an antioxidant and an acid scavenger; preferably, the mass ratio of the antioxidant to the polypropylene is (0.05-0.2):100; the mass ratio of the acid scavenger to the polypropylene is (0.2-0.7):

100.

10. The polypropylene composition according to claim 9, characterized in that The antioxidant is selected from at least one of hindered phenols, phosphites and sulfates; preferably, the antioxidant is selected from 1010 and / or 168; The acid scavenger is selected from at least one of hydrotalcite, calcium stearate and zinc chloride.

11. The polypropylene composition according to claim 8, characterized in that The polypropylene is selected from homopolypropylene and / or copolymer polypropylene; preferably, the copolymer polypropylene is a random copolymer or block copolymer of terminal olefin / cyclic olefin and propylene, and the terminal olefin / cyclic olefin is selected from at least one of ethylene, C4-C8 α-olefin, vinyl cyclohexane, vinyl cyclohexene and norbornene; more preferably, the polypropylene is selected from at least one of homopolypropylene, a random copolymer of propylene and ethylene, and a block copolymer of propylene and ethylene.

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