Preparation and application of nucleating agent

Abstract

The invention discloses a preparation method of a nucleating agent and application of the nucleating agent in transparent modification of polypropylene, and belongs to the field of organic synthesis. The preparation method comprises the following steps: preparing substituted sugar alcohol by using monosaccharide and halide as reaction raw materials in the presence of metal, and then reacting the obtained substituted sugar alcohol with polysubstituted aldehyde in the presence of acid to prepare the nucleating agent. The method is mild in reaction condition and can be realized without harsh water-free and oxygen-free conditions, the obtained nucleating agent can be successfully applied to transparent modification of the polypropylene, the yellow index of the modified polypropylene after multiple times of extrusion is still at a lower level, and the transparency is better.

Description

Technical Field

[0001] This invention belongs to the field of organic synthesis, specifically relating to a method for preparing a nucleating agent and its application in the transparent modification of plastics. Background Technology

[0002] Transparent nucleating agents are mainly used to improve the transparency of polyolefins, promote the nucleation and crystallization of polypropylene, reduce spherulite size, and increase nucleus density; increase crystallization temperature, shorten crystallization time, reduce nucleation interface free energy, and accelerate crystallization speed; increase crystallinity and improve physical properties; reduce molding shrinkage, shorten molding time, and improve production efficiency. They are suitable for the preparation of polyolefin products used in food contact materials, medical devices, infant products, and household appliances.

[0003] Sorbitol acetals are currently the most widely used transparent nucleating agents in the market and are extensively applied in the plastics processing industry. After a long period of development, third- and fourth-generation sorbitol-based antireflective nucleating agents are now more commonly used. However, these types of sorbitol-based antireflective nucleating agents are heavily reliant on imports and are extremely expensive.

[0004] In the prior art, there are many reported methods for synthesizing 3,4-dimethylbenzylsorbitol. Among them, Chinese patent CN1903857 A reports a batch synthesis method for 3,4-dimethylbenzylsorbitol, in which the molar ratio of D-sorbitol to 3,4-dimethylbenzaldehyde is 1:2.2, the yield is 80-85%, the product purity is >98%, and the reaction time is 6 hours. However, this method suffers from low synthesis efficiency. The one-pot synthesis method for 3,4-dimethylbenzylsorbitol reported in patent 1775780A has a yield of 85%, but the product needs to be purified with acetone, with a purification yield of 93%. The total product yield (preparation and purification steps) is <80%. Chinese patent CN114315852A reports a batch reactor method for synthesizing 3,4-dimethylbenzylsorbitol, where the molar ratio of D-sorbitol to 3,4-dimethylbenzaldehyde is 1:2-2.5, with a yield of 95.14% and a purity ≥98%. However, the post-processing involves high energy consumption and complex operation due to the need for vacuum distillation to recover excess 3,4-dimethylbenzaldehyde. Meanwhile, the synthesis methods for sorbitol-based permeability-enhancing nucleating agents mainly improve the substituents on the benzene ring, which may alter the adaptability of the nucleating agent. The improvement in patent CN101772481A involves introducing an allyl group onto a sugar alcohol; however, this reaction requires strictly anaerobic operation, has harsh reaction conditions, and results in poor coupling effects. Therefore, it is essential to develop a safer, simpler, and more efficient synthetic method for sorbitol-based permeabilizing nucleating agents. Summary of the Invention

[0005] The purpose of this invention is to address the shortcomings of existing technologies by providing a method for preparing nucleating agents and their application in plastic modification. The method for preparing nucleating agents provided by this invention can solve problems such as strong odor and excessive fine powder in existing nucleating agent synthesis processes.

[0006] To achieve the above objectives, the present invention adopts the following technical solution: A method for preparing a nucleating agent includes the following steps: 1) Add monosaccharide, metal, halide, and solvent to a flask in sequence, mix and stir, and slowly heat to reflux. After keeping the reaction at this temperature for a period of time, stop the reaction. Add alkali solution to the reaction solution to adjust the pH to 7, and dry by rotary evaporation to obtain the substituted sugar alcohol. 2) Add substituted sugar alcohol, polysubstituted aldehyde, acid and solvent to the flask in sequence, mix and stir for a period of time and then stop the reaction; add alkali solution to the reaction solution to adjust the pH to 7, filter, wash and dry to obtain the target product.

[0007] Further, the monosaccharide mentioned in step 1) is one or more of glucose, fructose, allose, arbutin, mannose, gulose, idooose, galactose, and tarose.

[0008] Furthermore, the metal mentioned in step 1) is one or more of tin, zinc, and magnesium.

[0009] Furthermore, the general structural formula of the halogenated product described in step 1) is XR. 1 , or One of them, where R 1 It is one or more of H, ester group, cyano group, straight-chain alkyl, cyclic alkyl, substituted aryl, substituted furanyl, substituted thiophene, and substituted pyridinyl, X is one of Cl, Br, and I, and n = 0-10.

[0010] Further, in step 1), the amount of metal used is 10%-300% of the mass of the monosaccharide, preferably 50%-100%.

[0011] Furthermore, in step 1), the amount of halogenated product used is 10%-300% of the mass of the monosaccharide, preferably 50%-100%.

[0012] Furthermore, the heat preservation reaction time in step 1) is 1 s-96 h, preferably 12 h-36 h.

[0013] Further, the general structural formula of the substituted sugar alcohol obtained in step 1) is: , or , where R 1It is one or more of H, ester group, cyano group, straight-chain alkyl, cyclic alkyl, substituted aryl, substituted furanyl, substituted thiophene group, and substituted pyridinyl group, n=0-10.

[0014] Further, the polysubstituted aldehyde in step 2) is one or more of benzaldehyde, 4-methylbenzaldehyde, 4-ethylbenzaldehyde, 3,4-dimethylbenzaldehyde, 2,4,6-trimethylbenzaldehyde, 2,3,4,5,6-pentamethylbenzaldehyde, 4-methoxybenzaldehyde, 3,4-dimethoxybenzaldehyde, 4-ethylbenzaldehyde, 4-isopropylbenzaldehyde, 4-tert-butylbenzaldehyde, 4-fluorobenzaldehyde, 4-chlorobenzaldehyde, 3,4-dichlorobenzaldehyde, 4-bromobenzaldehyde, 3,4-dibromobenzaldehyde, 4-iodobenzaldehyde, 4-(trifluoromethyl)benzaldehyde, 3,4-difluoro-2-methylbenzaldehyde, 4-cyanobenzaldehyde, 4-carboxybenzaldehyde, 4-phenylbenzaldehyde, and 4-benzylbenzaldehyde.

[0015] Further, the acid mentioned in step 2) is one or more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, p-toluenesulfonic acid, and trifluoromethanesulfonic acid.

[0016] Furthermore, in step 2), the amount of the polysubstituted aldehyde is 10%-500% of the mass of the substituted sugar alcohol, preferably 50%-100%.

[0017] Further, in step 2), the amount of acid used is 10%-300% of the mass of the sugar alcohol being replaced, preferably 50%-100%.

[0018] Furthermore, the temperature of the stirring reaction in step 2) is 5-100℃, and the time is 1 s-96 h.

[0019] Furthermore, the solvent used in the operation is one or more of water, methanol, ethanol, ethylene glycol, isopropanol, and tert-butanol.

[0020] Furthermore, the alkali used in the operation is one or more of the following: sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, magnesium ethoxide, sodium isopropoxide, potassium isopropoxide, magnesium isopropoxide, sodium tert-butoxide, potassium tert-butoxide, magnesium tert-butoxide, etc.

[0021] Furthermore, the amount of alkali used is 10%-300% of the mass of the monosaccharide or substituted sugar alcohol, preferably 50%-100%.

[0022] Furthermore, the general structural formula of the obtained nucleating agent is as follows: , or , where R 1It is one or more of H, ester group, cyano group, straight-chain alkyl group, cyclic alkyl group, substituted aryl group, substituted furanyl group, substituted thiophene group, and substituted pyridinyl group, n=0-10; R m 2 Derived from polysubstituted aldehydes, namely H, OCH3, Me, Et, i Pr, t One or more of Bu, F, Cl, Br, I, CF3, CN, COOEt, Ph, and Bn, and each of them can occupy different sites on the aromatic ring structure, m=0-5.

[0023] The nucleating agent prepared in this invention can be applied to the blending modification or grafting modification of propylene or propylene copolymers to prepare transparent polypropylene.

[0024] The beneficial effects of this invention are: The nucleating agent synthesis method employed in this invention overcomes the harsh reaction conditions and strict anhydrous and oxygen-free operation required in traditional nucleating agent synthesis processes. It is a safer and simpler synthesis method, yielding a nucleating agent with a high yield of up to 99%, exhibiting minimal odor and low fine powder content. This nucleating agent can be successfully applied to the transparent modification of polypropylene, resulting in modified polypropylene with a low yellow index and good transparency. Attached Figure Description

[0025] Figure 1 This is a flowchart of the synthesis reaction of the nucleating agent of the present invention.

[0026] Figure 2 The image shows the 1H NMR spectrum of nucleating agent A obtained in Example 1.

[0027] Figure 3 The image shows the infrared spectrum of nucleating agent A obtained in Example 1.

[0028] Figure 4 The thermogravimetric spectrum of nucleating agent A obtained in Example 1 is shown.

[0029] Figure 5 The image shows the 1H NMR spectrum of nucleating agent B obtained in Example 2.

[0030] Figure 6 The image shows the proton NMR spectrum of nucleating agent C obtained in Example 3.

[0031] Figure 7 The image shows the proton NMR spectrum of nucleating agent D obtained in Example 4. Detailed Implementation

[0032] Unless otherwise specified, all raw materials, reagents, instruments and equipment used in this invention can be purchased from the market or prepared by existing methods.

[0033] Unless otherwise stated, the terms used in this invention generally have the meanings commonly understood by those skilled in the art.

[0034] The nucleating agent prepared in this invention ( The polysubstituted aldehydes and substituted sugar alcohols used include, but are not limited to, the structures listed in Table 1, and R' and R'' in the table are not in a one-to-one correspondence.

[0035] Table 1 , , , , , .

[0036] In the following embodiments, the various processes and methods not described in detail are conventional methods known in the art. Furthermore, due to the large variety of acids and bases, and the diverse structural proportions of aldehydes and substituted sugar alcohols, not all preparation methods are described in detail; instead, typical examples are used to illustrate the specific process steps of the present invention.

[0037] Example 1

[0038] 1) In a 500 mL flask, add 30 g of glucose, 20 g of allyl bromide, 20 g of tin powder, 150 mL of ethanol, and 25 mL of water. Stir the mixture at 80 °C for 48 h, then stop the reaction. After the reaction solution returns to room temperature, add 30 wt.% sodium hydroxide aqueous solution to adjust the pH to 7. Filter, wash with water, collect the filtrate, and dry by rotary evaporation to obtain 36.5 g of yellow liquid allyl glucol, with a yield of 99%. 1 H NMR (400MHz, D2O, ppm): 2.34-2.37 (m, 2H), 3.64-3.95 (m, 7H), 5.13-5.20 (m, 2H), 5.88-5.89 (m, 1H).

[0039]

[0040] 2) In a 500 mL flask, add 10 g of allyl glucose alcohol, 12 g of 3,4-dimethylbenzaldehyde, 9 mL of concentrated hydrochloric acid, 72 mL of methanol, and 9 mL of water. Stir the mixture at room temperature for 48 h, then stop the reaction. Adjust the pH to 7 with 30 wt.% sodium hydroxide aqueous solution, filter, wash, and dry to obtain 16.8 g of a white solid nucleating agent (A), with a yield of 82%. 1H NMR (400MHz, DMSO-d6, ppm): 2.21 (s, 12H), 2.39-2.50 (m, 2H), 3.33-3.42 (m, 2H), 3.79-3.80(m, 3H), 4.04-4.60 (m, 2H), 4.40 (s, 1H), 4.81-4.82 (m, 1H), 5.11-5.15 (m,2H), 5.55-5.59 (d, 2H), 5.92-5.95 (m, 1H), 7.13-7.21 (m, 6H).

[0041] Example 2 1) Prepare allyl glucose alcohol according to step 1) of Example 1.

[0042]

[0043] 2) In a 500 mL flask, add 10 g of allyl glucose alcohol, 12 g of 4-ethylbenzaldehyde, 9 mL of concentrated hydrochloric acid, 72 mL of methanol, and 9 mL of water. Stir the mixture at room temperature for 48 h, then stop the reaction. Adjust the pH to 7 with 30 wt.% sodium hydroxide aqueous solution, filter, wash, and dry to obtain 17.2 g of white solid nucleating agent (B), with a yield of 84%. 1 H NMR (400MHz, DMSO-d6, ppm): 1.15-1.16 (s, 6H), 2.41 (s, 2H), 2.59-2.60 (m, 4H), 3.34-3.76(m, 5H), 3.84-4.01 (m, 2H), 4.08 (s,1H), 4.81-4.83 (m, 1H), 5.01-5.18 (m,2H), 5.55-5.60 (d, 2H), 5.62-5.63 (m, 1H), 7.21-7.23 (m, 4H), 7.36 (m, 4H).

[0044] Example 3 1) Prepare allyl glucose alcohol according to step 1) of Example 1.

[0045]

[0046] 2) In a 500 mL flask, add 10 g of allyl glucose alcohol, 12 g of 4-chlorobenzaldehyde, 9 mL of concentrated hydrochloric acid, 72 mL of methanol, and 9 mL of water. Stir the mixture at room temperature for 48 h, then stop the reaction. Adjust the pH to 7 with 30 wt.% sodium hydroxide aqueous solution, filter, wash, and dry to obtain 11.8 g of a white solid nucleating agent (C), with a yield of 56%.

[0047] Example 4 1) Prepare allyl glucose alcohol according to step 1) of Example 1.

[0048]

[0049] 2) In a 500 mL flask, add 10 g of allyl glucose alcohol, 12 g of 4-bromobenzaldehyde, 9 mL of concentrated hydrochloric acid, 72 mL of methanol, and 9 mL of water. Stir the mixture at room temperature for 48 h, then stop the reaction. Adjust the pH to 7 with 30 wt.% sodium hydroxide aqueous solution, filter, wash, and dry to obtain 12.0 g of a white solid nucleating agent (D), with a yield of 48%.

[0050] Example 5 1) Prepare allyl glucose alcohol according to step 1) of Example 1.

[0051]

[0052] 2) In a 500 mL flask, add 10 g of allyl glucose alcohol, 12 g of 4-methoxybenzaldehyde, 9 mL of concentrated hydrochloric acid, 72 mL of methanol, and 9 mL of water. Stir the mixture at room temperature for 48 h, then stop the reaction. Adjust the pH to 7 with 30 wt.% sodium hydroxide aqueous solution, filter, wash, and dry to obtain 11.2 g of a white solid nucleating agent (E), with a yield of 55%.

[0053] Example 6 1) Prepare allyl glucose alcohol according to step 1) of Example 1.

[0054] 2) In a 500 mL flask, add 10 g of allyl glucose alcohol, 12 g of 3,4-dimethylbenzaldehyde, 9 mL of concentrated hydrochloric acid, 72 mL of ethanol, and 9 mL of water. Stir the mixture at room temperature for 48 h, then stop the reaction. Adjust the pH to 7 with 30 wt.% sodium hydroxide aqueous solution, filter, wash, and dry to obtain 16.0 g of white solid nucleating agent (A), with a yield of 78%.

[0055] Example 7 1) Prepare allyl glucose alcohol according to step 1) of Example 1.

[0056]

[0057] 2) In a 500 mL flask, add 10 g of allyl glucose alcohol, 12 g of 3,4-dimethylbenzaldehyde, 9 mL of concentrated sulfuric acid, 72 mL of methanol, and 9 mL of water. Stir the mixture at room temperature for 48 h, then stop the reaction. Adjust the pH to 7 with 30 wt.% sodium hydroxide aqueous solution, filter, wash, and dry to obtain 14.3 g of a white solid nucleating agent (A), with a yield of 70%.

[0058] Example 8 1) Prepare allyl glucose alcohol according to step 1) of Example 1.

[0059] 2) In a 500 mL flask, add 10 g of allyl glucose alcohol, 12 g of 3,4-dimethylbenzaldehyde, 9 mL of concentrated hydrochloric acid, 72 mL of methanol, and 9 mL of water. Stir the mixture at room temperature for 96 h, then stop the reaction. Adjust the pH to 7 with 30 wt.% sodium hydroxide aqueous solution, filter, wash, and dry to obtain 17.5 g of a white solid nucleating agent (A), with a yield of 86%.

[0060] Example 9 1) Prepare allyl glucose alcohol according to step 1) of Example 1.

[0061] 2) In a 500 mL flask, add 10 g of allyl glucose alcohol, 12 g of 3,4-dimethylbenzaldehyde, 9 mL of concentrated hydrochloric acid, 72 mL of methanol, and 18 mL of water. Stir the mixture at room temperature for 48 h, then stop the reaction. Adjust the pH to 7 with 30 wt.% sodium hydroxide aqueous solution, filter, wash, and dry to obtain 15.7 g of a white solid nucleating agent (A), with a yield of 77%.

[0062] Example 10 1) Prepare allyl glucose alcohol according to step 1) of Example 1.

[0063] 2) In a 500 mL flask, add 10 g of allyl sugar alcohol, 12 g of 3,4-dimethylbenzaldehyde, 9 mL of concentrated hydrochloric acid, 72 mL of methanol, and 9 mL of water. Stir the mixture at room temperature for 48 h, then stop the reaction. Adjust the pH to 7 with 50 wt.% potassium hydroxide aqueous solution, filter, wash, and dry to obtain 16.6 g of white solid nucleating agent (A), with a yield of 81%.

[0064] Example 11 1) Prepare allyl glucose alcohol according to step 1) of Example 1.

[0065]

[0066] 2) In a 500 mL flask, add 10 g of allyl glucose alcohol, 15.6 g of 3,4-dichlorobenzaldehyde, 9 mL of concentrated hydrochloric acid, 72 mL of methanol, and 9 mL of water. Stir the mixture at room temperature for 48 h, then stop the reaction. Adjust the pH to 7 with 30 wt.% sodium hydroxide aqueous solution, filter, wash, and dry to obtain 17.4 g of a white solid nucleating agent (F), with a yield of 75%.

[0067] Example 12 1) In a 500 mL flask, add 30 g of glucose, 20 g of allyl bromide, 20 g of tin powder, 150 mL of methanol, and 25 mL of water. Stir the mixture at 80 °C for 48 h, then stop the reaction. After the reaction solution returns to room temperature, add 30 wt.% sodium hydroxide aqueous solution to adjust the pH to 7. Filter, wash with water, collect the filtrate, and dry by rotary evaporation to obtain 36.0 g of yellow liquid allyl glucol, with a yield of 97%.

[0068] 2) In a 500 mL flask, add 10 g of allyl glucose alcohol, 12 g of 3,4-dimethylbenzaldehyde, 9 mL of concentrated hydrochloric acid, 72 mL of methanol, and 9 mL of water. Stir the mixture at room temperature for 48 h, then stop the reaction. Adjust the pH to 7 with 30 wt.% sodium hydroxide aqueous solution, filter, wash, and dry to obtain 16.8 g of a white solid nucleating agent (A), with a yield of 82%.

[0069] Example 13 1) In a 500 mL flask, add 30 g of glucose, 20 g of allyl bromide, 20 g of tin powder, 150 mL of ethanol, and 25 mL of water. Stir the mixture at 80 °C for 48 h, then stop the reaction. After the reaction solution returns to room temperature, add 50 wt.% potassium hydroxide aqueous solution to adjust the pH to 7. Filter, wash with water, collect the filtrate, and dry by rotary evaporation to obtain 36.4 g of yellow liquid allyl glucol, with a yield of 99%.

[0070] 2) In a 500 mL flask, add 10 g of allyl glucose alcohol, 12 g of 3,4-dimethylbenzaldehyde, 9 mL of concentrated hydrochloric acid, 72 mL of methanol, and 9 mL of water. Stir the mixture at room temperature for 48 h, then stop the reaction. Adjust the pH to 7 with 30 wt.% sodium hydroxide aqueous solution, filter, wash, and dry to obtain 16.8 g of a white solid nucleating agent (A), with a yield of 82%.

[0071] Example 14

[0072] 1) In a 500 mL flask, add 30 g of glucose, 32 g of (E)-(3-bromoprop-1-en-1-yl)benzene (CAS: 26146-77-0), 20 g of tin powder, 150 mL of ethanol, and 25 mL of water. Stir the mixture at 80 °C for 48 h, then stop the reaction. After the reaction solution returns to room temperature, add 30 wt.% sodium hydroxide aqueous solution to adjust the pH to 7, filter, wash with water, collect the filtrate, and evaporate by rotary evaporation to obtain 46.6 g of a yellow liquid, with a yield of 93%.

[0073]

[0074] 2) Add 10 g of the above yellow liquid, 12 g of 3,4-dimethylbenzaldehyde, 9 mL of concentrated hydrochloric acid, 72 mL of methanol, and 9 mL of water to a 500 mL flask. Stir the mixture at room temperature for 48 h and then stop the reaction. Adjust the pH to 7 by adding 30 wt.% sodium hydroxide aqueous solution, filter, wash, and dry to obtain 15.3 g of white solid nucleating agent (G).

[0075] Example 15 1) In a 500 mL flask, add 30 g of galactose, 20 g of allyl bromide, 20 g of tin powder, 150 mL of ethanol, and 50 mL of water. Stir the mixture at 80 °C for 48 h, then stop the reaction. After the reaction solution returns to room temperature, add 30 wt.% sodium hydroxide aqueous solution to adjust the pH to 7. Filter, wash with water, collect the filtrate, and dry by rotary evaporation to obtain 35.2 g of yellow liquid allyl glucol, with a yield of 95%.

[0076] 2) In a 500 mL flask, add 10 g of allyl glucose alcohol, 12 g of 3,4-dimethylbenzaldehyde, 9 mL of concentrated hydrochloric acid, 72 mL of methanol, and 9 mL of water. Stir the mixture at room temperature for 48 h, then stop the reaction. Adjust the pH to 7 with 30 wt.% sodium hydroxide aqueous solution, filter, wash, and dry to obtain 16.8 g of a white solid nucleating agent (H), with a yield of 82%.

[0077] Example 16 1) In a 500 mL flask, add 30 g of galactose, 20 g of allyl bromide, 20 g of tin powder, 150 mL of ethanol, and 25 mL of water. Stir the mixture at 80 °C for 96 h, then stop the reaction. After the reaction solution returns to room temperature, add 30 wt.% sodium hydroxide aqueous solution to adjust the pH to 7. Filter, wash with water, collect the filtrate, and dry by rotary evaporation to obtain 36.3 g of yellow liquid allyl glucol, with a yield of 98%.

[0078]

[0079] 2) In a 500 mL flask, add 10 g of allyl glucose alcohol, 12 g of 4-methylbenzaldehyde, 9 mL of concentrated hydrochloric acid, 72 mL of methanol, and 9 mL of water. Stir the mixture at room temperature for 48 h, then stop the reaction. Adjust the pH to 7 with 30 wt.% sodium hydroxide aqueous solution, filter, wash, and dry to obtain 16.8 g of a white solid nucleating agent (I), with a yield of 82%.

[0080] Example 17

[0081] 1) In a 500 mL flask, add 30 g of glucose, 20 g of n-butyl bromide, 20 g of tin powder, 150 mL of ethanol, and 25 mL of water. Stir the mixture at 80 °C for 48 h, then stop the reaction. After the reaction solution returns to room temperature, add 30 wt.% sodium hydroxide aqueous solution to adjust the pH to 7. Filter, wash with water, collect the filtrate, and dry by rotary evaporation to obtain 37.1 g of yellow liquid n-butylglucan, with a yield of 97%.

[0082]

[0083] 2) In a 500 mL flask, add 10 g of n-butyl sugar alcohol, 12 g of 3,4-dimethylbenzaldehyde, 9 mL of concentrated hydrochloric acid, 72 mL of methanol, and 9 mL of water. Stir the mixture at room temperature for 48 h, then stop the reaction. Adjust the pH to 7 with 30 wt.% sodium hydroxide aqueous solution, filter, wash, and dry to obtain 15.3 g of a white solid nucleating agent (J), with a yield of 75%.

[0084] Example 18

[0085] 1) In a 500 mL flask, add 30 g of glucose, 20 g of propargyl bromide, 20 g of tin powder, 150 mL of ethanol, and 25 mL of water. Stir the mixture at 80 °C for 48 h, then stop the reaction. After the reaction solution returns to room temperature, add 30 wt.% sodium hydroxide aqueous solution to adjust the pH to 7. Filter, wash with water, collect the filtrate, and dry by rotary evaporation to obtain 19.9 g of yellow liquid propargyl glucol, with a yield of 54%.

[0086]

[0087] 2) In a 500 mL flask, add 10 g of propargyl glucol, 12 g of 3,4-dimethylbenzaldehyde, 9 mL of concentrated hydrochloric acid, 72 mL of methanol, and 9 mL of water. Stir the mixture at room temperature for 48 h, then stop the reaction. Adjust the pH to 7 with 30 wt.% sodium hydroxide aqueous solution, filter, wash, and dry to obtain 4.9 g of white solid nucleating agent (K), with a yield of 24%.

[0088] Example 19 The nucleating agents prepared in the examples were subjected to thermal stability tests, specifically thermal decomposition tests on the compounds prepared in the examples. The test temperature range was set from room temperature to 800°C, the heating rate was 10°C / min, and the test atmosphere was nitrogen. The initial thermal decomposition temperature and the maximum weight loss temperature of different samples were recorded to determine the thermal stability of different samples (the temperature at which the sample mass loss was 5% was recorded as the initial decomposition temperature). The data for the nucleating agents are listed in Table 2.

[0089] Table 2

[0090] As shown in Table 2, the decomposition temperature of the synthesized nucleating agent is between 226 and 257 °C, which can meet the processing requirements of polypropylene.

[0091] Example 20 PP (R7250N, Sinochem Quanzhou Petrochemical), the nucleating agent, antioxidant 1010, auxiliary antioxidant 168, calcium stearate, and release agent from the examples were respectively prepared in 10... 9 The mixture was prepared by mixing materials in a mass ratio of 2000:500:750:300:200. After homogenization in a high-speed mixer, the mixture was fed into a twin-screw extruder through the main feed port. The extruder was set to operate at temperatures of 60℃, 90℃, 130℃, 180℃, 200℃, 220℃, 220℃, 210℃, 190℃, and 180℃ from the feed zone to the die head, with a screw speed of 200 r / min. Modified PP granules were obtained by extrusion granulation. The yellow index, haze, and mechanical properties of the obtained modified PP granules were tested. The data are listed in Table 3.

[0092] Table 3

[0093] As shown in Table 3, adding 2000 ppm of nucleating agent can reduce the product's haze, while the product's yellow index, mechanical properties, and other data remain basically unchanged. Among them, the product modified with nucleating agent K has the lowest haze and exhibits the best effect.

[0094] Example 21 PP (R7250N, Sinochem Quanzhou Petrochemical), the nucleating agent, antioxidant 1010, auxiliary antioxidant 168, calcium stearate, and release agent from the examples were respectively prepared in 10... 9The mixture was prepared by mixing materials in a mass ratio of 5000:500:750:300:200. After homogenization in a high-speed mixer, the mixture was fed into a twin-screw extruder through the main feed port. The extruder was set to operate at temperatures of 60℃, 90℃, 130℃, 180℃, 200℃, 220℃, 220℃, 210℃, 190℃, and 180℃ from the feed zone to the die head, with a screw speed of 200 r / min. Modified PP granules were obtained by extrusion granulation. The yellow index and haze of the obtained modified PP granules were tested. The data are listed in Table 4.

[0095] Table 4

[0096] As shown in Table 4, adding 5000 ppm of nucleating agent significantly reduces the product's haze, and the yellow index is also lower than that at 2000 ppm. Among them, the product modified with nucleating agent E has the lowest haze and exhibits the best effect.

[0097] Example 22 The PP (R7250N, Sinochem Quanzhou Petrochemical), nucleating agent, antioxidant 1010, auxiliary antioxidant 168, calcium stearate, zinc stearate, and release agent were prepared according to a 10:1 ratio. 9 The mixture was prepared by mixing materials in a mass ratio of 2000:500:750:200:200:200. After homogenization in a high-speed mixer, the mixture was fed into a twin-screw extruder through the main feed port. The extruder was set to operate at temperatures of 60℃, 90℃, 130℃, 180℃, 200℃, 220℃, 220℃, 210℃, 190℃, and 180℃ from the feed zone to the die head, with a screw speed of 200 r / min. Modified PP granules were obtained by extrusion granulation. The yellow index and haze of the obtained modified PP granules were tested. The data are listed in Table 5.

[0098] Table 5

[0099] As shown in Table 5, the addition of zinc stearate to the formulation system has little effect on the modification effect, proving that the nucleating agent prepared is suitable for different polypropylene modification systems.

[0100] Example 23 PP (R7250N, Sinochem Quanzhou Petrochemical), the nucleating agent, antioxidant 1010, auxiliary antioxidant 168, calcium stearate, release agent, and crosslinking agent dicumyl peroxide were prepared in a 10:1 ratio. 9The mixture was prepared by mixing materials in a mass ratio of 2000:500:750:300:200:100. After homogenization in a high-speed mixer, the mixture was fed into a twin-screw extruder through the main feed port. The extruder was set to operate at temperatures of 60℃, 90℃, 130℃, 180℃, 200℃, 220℃, 220℃, 210℃, 190℃, and 180℃ from the feed zone to the die head, with a screw speed of 200 r / min. Modified PP granules were obtained by extrusion granulation. The yellow index and haze of the obtained modified PP granules were tested. The data are listed in Table 6.

[0101] Table 6

[0102] As shown in Table 6, the addition of crosslinking agent to the formulation system has little effect on the modification effect, proving that the prepared nucleating agent is suitable for different polypropylene modification systems.

[0103] The above description is only a preferred embodiment of the present invention. All equivalent changes and modifications made within the scope of the claims of the present invention should be included in the scope of the present invention.

Claims

1. A method for preparing a nucleating agent, characterized in that, Includes the following steps: 1) Add monosaccharide, metal, halide, and solvent to a flask in sequence, mix and stir, and slowly heat to reflux. After keeping the reaction at this temperature for a period of time, stop the reaction. Adjust the pH of the reaction solution to 7 and dry by rotary evaporation to obtain the substituted sugar alcohol. 2) Add substituted sugar alcohol, polysubstituted aldehyde, acid and solvent to the flask in sequence, mix and stir for a period of time and then stop the reaction; adjust the pH of the reaction solution to 7, filter, wash and dry to obtain the target product.

2. The method for preparing the nucleating agent according to claim 1, characterized in that, The monosaccharide mentioned in step 1) is one or more of glucose, fructose, allose, arbutin, mannose, gulose, idooose, galactose, and tarose.

3. The method for preparing the nucleating agent according to claim 1, characterized in that, The metal mentioned in step 1) is one or more of tin, zinc, and magnesium.

4. The method for preparing the nucleating agent according to claim 1, characterized in that, The general structural formula of the halogenated product described in step 1) is XR. 1 , or One of them, where R 1 It is one or more of H, ester group, cyano group, straight-chain alkyl, cyclic alkyl, substituted aryl, substituted furanyl, substituted thiophene, and substituted pyridinyl, X is one of Cl, Br, and I, and n = 0-10.

5. The method for preparing the nucleating agent according to claim 1, characterized in that, In step 1), the amount of metal used is 10%-300% of the mass of the monosaccharide, and the amount of halogenated product used is 10%-300% of the mass of the monosaccharide; the time for the heat preservation reaction is 1 s-96 h.

6. The method for preparing the nucleating agent according to claim 1, characterized in that, The polysubstituted aldehyde mentioned in step 2) is one or more of benzaldehyde, 4-methylbenzaldehyde, 4-ethylbenzaldehyde, 3,4-dimethylbenzaldehyde, 2,4,6-trimethylbenzaldehyde, 2,3,4,5,6-pentamethylbenzaldehyde, 4-methoxybenzaldehyde, 3,4-dimethoxybenzaldehyde, 4-ethylbenzaldehyde, 4-isopropylbenzaldehyde, 4-tert-butylbenzaldehyde, 4-fluorobenzaldehyde, 4-chlorobenzaldehyde, 3,4-dichlorobenzaldehyde, 4-bromobenzaldehyde, 3,4-dibromobenzaldehyde, 4-iodobenzaldehyde, 4-(trifluoromethyl)benzaldehyde, 3,4-difluoro-2-methylbenzaldehyde, 4-cyanobenzaldehyde, 4-carboxybenzaldehyde, 4-phenylbenzaldehyde, and 4-benzylbenzaldehyde.

7. The method for preparing the nucleating agent according to claim 1, characterized in that, The acid mentioned in step 2) is one or more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, p-toluenesulfonic acid, and trifluoromethanesulfonic acid.

8. The method for preparing the nucleating agent according to claim 1, characterized in that, In step 2), the amount of polysubstituted aldehyde is 10%-500% of the mass of the substituted sugar alcohol; the amount of acid is 10%-300% of the mass of the substituted sugar alcohol; the temperature of the stirring reaction is 5-100℃, and the time is 1 s-96 h.

9. The method for preparing the nucleating agent according to claim 1, characterized in that, The solvent used in the operation is one or more of water, methanol, ethanol, ethylene glycol, isopropanol, and tert-butanol.

10. The application of a nucleating agent prepared by the method of claim 1 in the preparation of transparent polypropylene through blending modification or grafting modification.

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