Nucleating agent composition containing multiple sorbierite-aromatic aldehyde acetal and preparation method and application thereof
By combining various sorbitol-aromatic acetal compounds, the problem of high melting point of sorbitol nucleating agents was solved, achieving high transparency and good dispersibility of polymer products, and reducing processing temperature and energy consumption.
Patent Information
- Application Number
- CN202511258611.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-09-03
- Publication Date
- 2025-11-07
AI Technical Summary
Existing sorbitol-based nucleating agents have high melting points, leading to processing difficulties, uneven dispersion, and affecting the transparency and gloss of polypropylene products, especially in thick products where the effect deteriorates significantly.
Nucleating agent compositions with a wider processing temperature window are formed by using a variety of sorbitol-aromatic aldehyde acetal compounds and controlling the ratio of aromatic aldehydes to sorbitol and reaction conditions, including diacetal and triacetal compounds.
Lowering the processing temperature improves the transparency and gloss of polymer products, reduces crystal points, and improves the crystallization rate and dispersibility of products such as polypropylene.
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Abstract
Description
TECHNICAL FIELD
[0001] The present application belongs to the technical field of polymer nucleating agent, and particularly relates to a nucleating agent composition containing multiple sorbitol-aromatic aldehyde acetal and a preparation method and application thereof. BACKGROUND
[0002] Polymer, such as polypropylene, is widely used in packaging, daily necessities, household appliances and automobile parts due to its excellent performance and low cost. However, ordinary polypropylene has problems such as slow crystallization speed and uneven crystallization, which leads to low transparency, poor surface gloss, insufficient rigidity and easy shrinkage and deformation of the product. In order to improve the performance of polypropylene, especially to improve the transparency, a transparent nucleating agent is usually added in industry.
[0003] Among them, the sorbitol derivative nucleating agent is one of the most widely used types. However, the sorbitol nucleating agent commonly used in industry has the following main shortcomings in actual application, which limits the full play of its effect and the expansion of its application range:
[0004] High melting point: the melting point of the existing mainstream sorbitol nucleating agent is usually significantly higher than the conventional processing temperature of polypropylene. This makes it difficult for the nucleating agent to fully melt and uniformly disperse in the polypropylene melt under normal processing conditions, not only increasing the processing energy consumption, but also bringing the risk of degradation and yellowing of the polypropylene raw material due to high temperature, and affecting the performance of the nucleating agent.
[0005] Poor dispersibility: due to high melting point, compatibility and other factors, traditional sorbitol nucleating agent is prone to agglomeration in polypropylene melt, and it is difficult to achieve ideal uniform dispersion. This uneven dispersion problem can form small agglomeration points (hereinafter referred to as "crystal points") in the final product, which becomes an obstacle to light transmission, directly damaging the transparency and appearance smoothness of the product, and may cause inconsistent performance in different areas of the product. Especially for polypropylene products such as containers and plates with a thickness of more than 2mm, the existing sorbitol nucleating agent has a significantly poor transparency effect. When light passes through thicker products, the chances of encountering unevenly dispersed nucleating agent agglomeration points or crystalline structure defects increase, resulting in a significant increase in haze and a significant decrease in transparency and clarity of the product. SUMMARY
[0006] To solve the above technical problems, the present application provides a nucleating agent composition containing multiple sorbitol-aromatic aldehyde acetal, which contains diacetal and triacetal compounds formed by multiple aromatic aldehydes and sorbitol, has a wider processing temperature window, can meet the processing temperature below 200℃, and can improve the transparency of the product, achieving the technical effect that the polymer (especially polypropylene) material has fast crystallization rate, good processing dispersibility, high transparency and fewer product crystal points under a processing temperature below 200℃.
[0007] In a first aspect, the present application provides a nucleating agent composition comprising a plurality of sorbitol-aromatic aldehyde acetales, comprising one or two of the following compounds of formula (A), (B), (C) and (D), one or more of the following compounds of formula (E) to (L):
[0008]
[0009] R1are each independently selected from halogen, R2are each independently selected from C1-C8 alkyl, n, m are each independently 1 or 2;
[0010] The sum of the weight fractions of the compounds of formula (A) to (D) in the composition is 95.0-98.5%, and the sum of the weight fractions of the compounds of formula (E) to (L) is 1.5-5.0%.
[0011] In one set of embodiments, R1are each independently selected from F, Cl, Br and I, and R2are each independently selected from C1-C6 alkyl (such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, pentyl, hexyl, etc.). Preferably, R1is selected from Cl, and R2is selected from methyl.
[0012] In one set of embodiments, n = 1, preferably R1is located at the para position; n = 2, preferably R2is located at the 3,4-position. More preferably, R1is selected from Cl, and R2is selected from methyl; the names of the compounds of formula (A) to (L) are as follows:
[0013] (A) 1,3:2,4-bis(p-chlorobenzylidene)-sorbitol
[0014] (B) 1,3:2,4-bis(3,4-dimethylbenzylidene)-sorbitol
[0015] (C) 1,3-p-chlorobenzylidene-2,4-(3,4-dimethylbenzylidene)-sorbitol
[0016] (D) 1,3-(3,4-dimethylbenzylidene)-2,4-p-chlorobenzylidene-sorbitol
[0017] (E) 1,3:2,4:5,6-tris(3,4-dimethylbenzylidene)-sorbitol
[0018] (F) 1,3:5,6-bis(3,4-dimethylbenzylidene)-2,4-p-chlorobenzylidene-sorbitol
[0019] (G) 1,3:2,4-bis(3,4-dimethylbenzylidene)-5,6-p-chlorobenzylidene-sorbitol
[0020] (H) 2,4:5,6-bis(3,4-dimethylbenzylidene)-l,3-p-chlorobenzylidene-sorbitol
[0021] (I) 1,3-(3,4-dimethylbenzylidene)-2,4:5,6-bis(p-chlorobenzylidene)-sorbitol
[0022] (J) 5,6-(3,4-dimethylbenzylidene)-l,3:2,4-bis(p-chlorobenzylidene)-sorbitol
[0023] (K) 2,4-(3,4-dimethylbenzylidene)-l,3:5,6-bis(p-chlorobenzylidene)-sorbitol
[0024] (L) 1,3:2,4:5,6-tris(p-chlorobenzylidene)-sorbitol
[0025] In one set of embodiments, the nucleating agent composition consists of one or two of the compounds of formula (A), (B), (C), and (D), one or more of the compounds of formula (E) through (L).
[0026] In one set of embodiments, the nucleating agent composition comprises one or two of the compounds of formula (A), (B), (C), and (D), the compound of formula (L).
[0027] In one set of embodiments, the nucleating agent composition consists of one or two of the compounds of formula (A), (B), (C), and (D), the compound of formula (L).
[0028] In one set of embodiments, the nucleating agent composition comprises one or two of the compounds of formula (A), (B), (C), and (D), the compound of formula (E), the compound of formula (L).
[0029] In one set of embodiments, the nucleating agent composition consists of one or two of the compounds of formula (A), (B), (C), and (D), the compound of formula (E), the compound of formula (L).
[0030] In one set of embodiments, the nucleating agent composition comprises one or two of the compounds of formula (A), (B), (C), and (D), one or more of the compounds of formula (I) through (K), the compound of formula (L).
[0031] In one set of embodiments, the nucleating agent composition consists of one or two of the compounds of formula (A), (B), (C), and (D), one or more of the compounds of formula (I)-(K), the compound of formula (L).
[0032] In one set of embodiments, the nucleating agent composition comprises one or two of the compounds of formula (A), (B), (C), and (D), the compound of formula (E), one or more of the compounds of formula (F)-(H), one or more of the compounds of formula (I)-(K), the compound of formula (L).
[0033] In one set of embodiments, the nucleating agent composition consists of one or two of the compounds of formula (A), (B), (C), and (D), the compound of formula (E), one or more of the compounds of formula (F)-(H), one or more of the compounds of formula (I)-(K), the compound of formula (L).
[0034] In one set of embodiments, the nucleating agent composition comprises one or two of the compounds of formula (A), (B), (C), and (D), the compound of formula (E), one or more of the compounds of formula (F)-(H), one or more of the compounds of formula (I)-(K), the compound of formula (L).
[0035] In one set of embodiments, the nucleating agent composition consists of one or two of the compounds of formula (A), (B), (C), and (D), the compound of formula (E), one or more of the compounds of formula (F)-(H), one or more of the compounds of formula (I)-(K), the compound of formula (L).
[0036] In one set of embodiments, the sum of the weight fractions of the compounds of formula (A)-(D) in the nucleating agent composition can be 95.0%, 95.5%, 96.0%, 96.5%, 97.0%, 97.5%, 98.0%, 98.5%; the sum of the weight fractions of the compounds of formula (E)-(L) can be 1.5%, 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5%, 5.0%.
[0037] In one set of embodiments, the weight fraction of the compound of formula (A) in the nucleating agent composition is 3.0% to 85.0%, the weight fraction of the compound of formula (B) is 3.0% to 85.0%, the sum of the weight fractions of the compounds of formula (C) and formula (D) is 5.0% to 60.0%, and the sum of the weight fractions of formula (E) to formula (I) is 1.5 to 5.0%. Specifically, the weight fraction of the compound of formula (A) can be 3.0%, 5.0%, 10.0%, 15.0%, 20.0%, 25.0%, 30.0%, 35.0%, 40.0%, 45.0%, 50.0%, 55.0%, 60.0%, 65.0%, 70.0%, 75.0%, 80.0%, 85.0%, preferably 3.0-60.0%; the weight fraction of the compound of formula (B) can be 3.0%, 5.0%, 10.0%, 15.0%, 20.0%, 25.0%, 30.0%, 35.0%, 40.0%, 45.0%, 50.0%, 55.0%, 60.0%, 65.0%, 70.0%, 75.0%, 80.0%, 85.0%, preferably 3.0-60.0%; the sum of the weight fractions of the compounds of formula (C) and formula (D) can be 5.0%, 10.0%, 15.0%, 20.0%, 25.0%, 30.0%, 35.0%, 40.0%, 45.0%, 50.0%, 55.0%, 60.0%, preferably 20.0-55.0%.
[0038] In one set of embodiments, the weight fraction of the compound of formula (A) in the nucleating agent composition is 30.0% to 60.0%, the weight fraction of the compound of formula (B) is 3.0% to 30.0%, and the sum of the weight fractions of the compounds of formula (C) and formula (D) is 20.0% to 50.0%.
[0039] In a second aspect, the present application provides a method for preparing the nucleating agent composition of the first aspect, comprising the following steps:
[0040] 1) adding aromatic aldehyde (I) and sorbitol into a container, stirring to form a mixture;
[0041] 2) adding cyclohexane into the mixture of step 1);
[0042] 3) adding a catalyst into the mixture of step 2);
[0043] 4) heating the mixture of step 3) to cyclohexane reflux, maintaining reflux reaction;
[0044] 5) adding aromatic aldehyde (II) into the product of step 4);
[0045] 6) adding cyclohexane into the product of step 5);
[0046] 7) heating the product of step 6) to the reflux of cyclohexane, maintaining the reflux reaction until the ratio of the moles of water collected in the oil-water separator to the moles of sorbitol is 1.5-2.1:1.0;
[0047] 8) cooling, reducing pressure distillation of cyclohexane and water to obtain a crude product;
[0048] 9) dispersing the obtained crude product in water, and then adding sodium hydroxide and hydrogen peroxide and stirring;
[0049] 10) pressure filtration, water washing, drying, and crushing to obtain a nucleating agent composition;
[0050] wherein the aromatic aldehyde (I) is a compound of formula (a) and the aromatic aldehyde (II) is a compound of formula (b), or the aromatic aldehyde (I) is a compound of formula (b) and the aromatic aldehyde (II) is a compound of formula (a),
[0051]
[0052] wherein, R 1 , R 2 , n, m are as described in the first aspect.
[0053] In one group of embodiments, the aromatic aldehyde (I) is a compound of formula (a) and the aromatic aldehyde (II) is a compound of formula (b).
[0054] In one group of embodiments, formula (a) is p-chlorobenzaldehyde and formula (b) is 3,4-dimethylbenzaldehyde. Preferably, the aromatic aldehyde (I) is p-chlorobenzaldehyde and the aromatic aldehyde (II) is 3,4-dimethylbenzaldehyde.
[0055] In one group of embodiments, the ratio of the total amount of aromatic aldehyde (I) and aromatic aldehyde (II) to the moles of sorbitol is 1.8-2.2:1.0, preferably 1.9-2.1:1.0, more preferably 2.0:1.0.
[0056] In one set of embodiments, the ratio of the moles of aromatic aldehyde (I) to the moles of sorbitol is 0.1-1.9:1.0, such as 0.1:1.0, 0.2:1.0, 0.3:1.0, 0.4:1.0, 0.5:1.0, 0.6:1.0, 0.7:1.0, 0.8:1.0, 0.9:1.0, 1.0:1.0, 1.1:1.0, 1.2:1.0, 1.3:1.0, 1.4:1.0, 1.5:1.0, 1.6:1.0, 1.7:1.0, 1.8:1.0, 1.9:1.0, preferably 1.0-1.6:1.0. The ratio of the moles of aromatic aldehyde (II) to the moles of sorbitol is 0.1-1.9:1.0, such as 0.1:1.0, 0.2:1.0, 0.3:1.0, 0.4:1.0, 0.5:1.0, 0.6:1.0, 0.7:1.0, 0.8:1.0, 0.9:1.0, 1.0:1.0, 1.1:1.0, 1.2:1.0, 1.3:1.0, 1.4:1.0, 1.5:1.0, 1.6:1.0, 1.7:1.0, 1.8:1.0, 1.9:1.0, preferably 0.4-1.0:1.0. The ratio of the moles of aromatic aldehyde (I) to the moles of aromatic aldehyde (II) is 0.1-1.9:1.9-0.1, preferably 1.0-1.6:0.4-1.0.
[0057] In one set of embodiments, the catalyst is benzenesulfonic acid, methylbenzenesulfonic acid, preferably p-toluenesulfonic acid. The catalyst is used in a molar amount of 0.01-0.03:1.0, preferably 0.02-0.025:1.0, relative to the moles of sorbitol.
[0058] In one set of embodiments, in step 4), the reaction is refluxed for 20 min-1 hour, such as 20 min, 25 min, 30 min, 35 min, 40 min, 45 min, 50 min, 55 min, 1 h, preferably 30 min. In step 7), the reaction is refluxed for 1-4 hours, such as 1, 1.5, 2, 2.5, 3, 3.5, 4 h, preferably 2-3 h. In step 7), the ratio of the moles of water collected in the water-oil separator to the moles of sorbitol is 1.5-2.1:1.0, such as 1.5:1.0, 1.6:1.0, 1.7:1.0, 1.8:1.0, 1.85:1.0, 1.9:1.0, 1.95:1.0, 2.0:1.0, 2.01:1.0, 2.02:1.0, 2.03:1.0, 2.04:1.0, 2.05:1.0, 2.06:1.0, 2.07:1.0, 2.08:1.0, 2.09:1.0, 2.1:1.0, preferably 1.8-2.02:1.
[0059] In one set of embodiments, the cyclohexane added in step 2), step 6) is used to remove the water generated in the reaction by azeotropic distillation, which promotes the two-step acetalization reaction, wherein the amount of cyclohexane used should be greater than or equal to the content of aromatic aldehyde added step by step.
[0060] In one set of embodiments, the sodium hydroxide, hydrogen peroxide added in step 9) is used for impurity removal and product purity improvement.
[0061] In a third aspect, the present application provides the use of the nucleating agent composition of the first aspect, or the nucleating agent composition prepared by the method of the second aspect, wherein the nucleating agent composition is added to a polymer to prepare a polymer article.
[0062] The present application can achieve one or more effects of reducing the extrusion temperature, improving the dispersibility, improving the transparency, glossiness of the polymer article, and reducing the number of crystal points of the article by adding the nucleating agent composition to the polymer; the resulting polymer at least has (a) a lower extrusion temperature, (b) a higher transparency of the article, and (c) a lower number of crystal points of the article.
[0063] In one set of embodiments, the weight percentage of the nucleating agent composition to the polymer is 0.20-0.30%, such as 0.20%, 0.21%, 0.22%, 0.23%, 0.24%, 0.25%, 0.26%, 0.27%, 0.28%, 0.29%, 0.30%, preferably 0.20-0.25%.
[0064] In one set of embodiments, the polymer is one or more of polyolefins, such as polypropylene, polyethylene, and the like, and the polypropylene is selected from isotactic polypropylene, atactic polypropylene, syndiotactic polypropylene, chlorinated polypropylene, grafted polypropylene, and the like.
[0065] In one set of embodiments, the polymer article is a polymer film, a polymer sheet, a polymer plate, a polymer molded article, and the like.
[0066] In a fourth aspect, the present application provides a polymer composition comprising a polymer and a nucleating agent composition, wherein the nucleating agent composition is the nucleating agent composition of the first aspect, or the nucleating agent composition prepared by the method of the second aspect. The polymer composition can be used to prepare a polymer article.
[0067] In one set of embodiments, the weight percentage of the nucleating agent composition to the polymer in the polymer composition is 0.20-0.30%, such as 0.20%, 0.21%, 0.22%, 0.23%, 0.24%, 0.25%, 0.26%, 0.27%, 0.28%, 0.29%, 0.30%, preferably 0.20-0.25%.
[0068] In one embodiment, the polymer composition, the polymer is one or more of polyolefins such as polypropylene, polyethylene and the like, the polypropylene is selected from isotactic polypropylene, atactic polypropylene, syndiotactic polypropylene, chlorinated polypropylene and grafted polypropylene and the like.
[0069] In a fifth aspect, the present application provides a polymer article made from the polymer composition of the fourth aspect. Preferably, the polymer article is a polymer film, a polymer sheet, a polymer plate, a polymer molded article and the like.
[0070] The present application has the following excellent technical effects over the prior art:
[0071] The nucleating agent composition provided by the present application contains a plurality of sorbitol diacetal and sorbitol triacetal, and compared with the existing mainstream sorbitol nucleating agent, the extrusion temperature is reduced by more than 20℃, greatly reducing the processing temperature and the energy consumption in the processing.
[0072] The nucleating agent composition provided by the present application has unexpected effects in improving the performance of polymers (especially polypropylene), can improve the crystallization temperature and crystallization rate, improve the dispersibility, improve the transparency, gloss, flexural modulus and tensile strength of polymer articles such as films, sheets and molded articles, and reduce the crystal point of the articles.
[0073] In particular, the nucleating agent composition provided by the present application has a significant effect on improving the transparency of polypropylene (PP) thick articles, while reducing the crystal point of the articles.
[0074] The present application uses a plurality of, for example, two aromatic aldehydes and sorbitol to perform condensation reaction under the action of an acid catalyst, and a nucleating agent composition containing a plurality of diacetal and triacetal is obtained by controlling the order of adding different aromatic aldehydes or the content of different aromatic aldehydes. The content of the triacetal is in the range of 1.5-5.0%, the obtained nucleating agent composition greatly reduces the processing temperature and the energy consumption in the processing, and has the above unexpected effects in improving the performance of polymers (especially polypropylene). DETAILED DESCRIPTION
[0075] The present application will be further described in conjunction with specific embodiments, but the present application is not limited to these specific embodiments. Those skilled in the art should recognize that the present application encompasses all alternatives, improvements and equivalents within the scope of the claims.
[0076] The terms "containing", "including" and "comprising" used in the present application are synonymous terms, which are inclusive or open, and do not exclude additional, unmentioned members, elements or method steps.
[0077] In the present application, "preferably", "more preferably", "most preferably", "advantageously" are only used to describe the embodiments or examples with better effects, and should be understood as not constituting a limitation to the scope of protection of the present application. In the present application, "optionally", "optionally" means optional, that is, selected from "yes" or "no" two parallel schemes. If there are multiple "optionally", "optionally" in a technical solution, unless otherwise specified, there is no contradiction or mutual restriction relationship, and each "optionally", "optionally" is independent.
[0078] In the present application, "multiple" refers to two or more, such as 3, 4, 5, 6, 7, 8.
[0079] In the present application, the numerical range expressed by endpoints includes all numerical values and fractions contained in the range and the cited endpoints.
[0080] In the present application, the concentration value involves a certain range of fluctuations. For example, it can fluctuate within a certain range of accuracy. For example, 2% can be allowed to fluctuate within ±0.1%. For larger values or values that do not need to be controlled too finely, the meaning also includes larger fluctuations.
[0081] In the present application, the technical features described in an open manner include both the closed technical solution consisting of the listed features and the open technical solution containing the listed features.
[0082] The method for analyzing and measuring the products of Examples 1-3 and Comparative Examples 1-3 using gas chromatography-mass spectrometry is as follows:
[0083] About 0.0200 g of the product of the example or comparative example was weighed into a 10.0 mL volumetric flask,
[0084] Dissolve to volume with dimethyl sulfoxide under ultrasonic;
[0085] The full component determination was carried out by GCMS, and the determination results were automatically calculated by the GCMSsolution 4.11SU1 software by area normalization method.
[0086] The conditions of gas chromatography are as follows:
[0087] The column oven temperature is 200℃,
[0088] The injection temperature is 260℃,
[0089] The injection time is 1.0 minute,
[0090] The pressure is 99.6 kPa,
[0091] The total flow rate is 18.0 mL / min,
[0092] The column flow rate is 2.50 mL / min,
[0093] Linear velocity 62.4 cm / sec,
[0094] Purge flow 3 mL / min, Temperature program: 200 °C (0.00 min) - 30 °C / min - 300 °C (10.00 min).
[0095] Split ratio: 5.0
[0096] The conditions for mass spectrometry were:
[0097] Ion source temperature 260 °C,
[0098] Interface temperature 290 °C,
[0099] Scan speed 3333,
[0100] Scan range m / z 80 - m / z 1000,
[0101] Solvent delay time 0.50 min,
[0102] Acquisition start time 1.0 min,
[0103] Acquisition end time 13.00 min.
[0104] Example 1 : Nucleating agent composition 1
[0105] In a 1000 mL reaction kettle, first add 21.72 g of solid sorbitol and 9.9 g of p-chlorobenzaldehyde to initiate stirring for initial dispersion. Subsequently, add 19.8 g of cyclohexane and add 0.5 g of p-toluene sulfonic acid catalyst in one shot. Heat to 80-85 °C to reflux the cyclohexane and maintain the stirring reaction at this temperature for 30 minutes to start the dehydration process. Thereafter, add 23.1 g of 3,4-dimethylbenzaldehyde and add 23.1 g of cyclohexane to continue the reflux reaction for 2-3 hours. During the reaction, continuously monitor the dehydration amount through the oil-water separator, and when the cumulative amount of water generated from the condensation reaction reaches about 4.0-4.3 g, stop heating. Subsequently, perform solvent recovery by reducing the temperature and distilling the remaining cyclohexane and water under reduced pressure. Cool the product in the kettle to 60-70 °C, add 500-550 mL of deionized water for dispersion, and then sequentially add 0.8 g of sodium hydroxide and 0.5 g of 30% wt hydrogen peroxide and stir for 60 minutes. Subsequently, filter and wash the filter cake with deionized water, and dry the filter cake under vacuum at 80-90 °C for 4-6 hours to finally obtain the target product, white powder product 1.
[0106] The composition and content of product 1 were analyzed by gas chromatography-mass spectrometry (GC-MS), and the results showed that product 1 contained 6.01% 1,3:2,4-di(p-chlorobenzylidene)-sorbitol, 52.12% 1,3:2,4-di(3,4-dimethylbenzylidene)-sorbitol, 38.20% 1,3-p-chlorobenzylidene-2,4-(3,4-dimethylbenzylidene)-sorbitol and 1,3-(3,4-dimethylbenzylidene)-2,4-p-chlorobenzylidene-sorbitol, 3.43% 1,3:2,4:5,6-tri(p-chlorobenzylidene)-sorbitol and 0.24% 1,3:2,4:5,6-tri(3,4-dimethylbenzylidene)-sorbitol.
[0107] Example 2: Nucleating agent composition 2
[0108] In a 1000 mL reaction kettle, 21.76 g of solid sorbitol and 26.4 g of p-chlorobenzaldehyde were first added and stirring was started for initial dispersion. Subsequently, 52.8 g of cyclohexane was added, and 0.5 g of p-toluenesulfonic acid catalyst was added at once. Heating was performed to 80-85°C until the cyclohexane refluxed, and the stirring reaction was maintained at this temperature for 30 minutes to start the dehydration process. Then, 6.6 g of 3,4-dimethylbenzaldehyde was added, and 6.6 g of cyclohexane was added to continue the reflux reaction for 2-3 hours. During the reaction, the dehydration amount was continuously monitored through an oil-water separator, and when the cumulative amount of condensed reaction generated water reached about 4.3 g, the heating was stopped. Subsequently, solvent recovery was performed, and the remaining cyclohexane and water were recovered by cooling and reduced pressure distillation. The kettle product was cooled to 60-70°C, 500-550 mL of deionized water was added for dispersion, and then 0.8 g of sodium hydroxide and 0.5 g of 30%wt hydrogen peroxide were sequentially added and stirred for 60 minutes. Subsequently, filtration was performed and the filter cake was washed with deionized water, and the filter cake was vacuum dried at 80-90°C for 4-6 hours to obtain the target product, white powder product 2.
[0109] The composition and content of product 2 were analyzed by gas chromatography-mass spectrometry (GC-MS), and the results showed that product 2 contained 58.37% 1,3:2,4-di(p-chlorobenzylidene)-sorbitol, 3.56% 1,3:2,4-di(3,4-dimethylbenzylidene)-sorbitol, 33.19% 1,3-p-chlorobenzylidene-2,4-(3,4-dimethylbenzylidene)-sorbitol and 1,3-(3,4-dimethylbenzylidene)-2,4-p-chlorobenzylidene-sorbitol, 1.70% 1,3-(3,4-dimethylbenzylidene)-2,4:5,6-di(p-chlorobenzylidene)-sorbitol and or 5,6-(3,4-dimethylbenzylidene)-1,3:2,4-di(p-chlorobenzylidene)-sorbitol and or 2,4-(3,4-dimethylbenzylidene)-1,3:5,6-di(p-chlorobenzylidene)-sorbitol, 3.18% 1,3:2,4:5,6-tri(p-chlorobenzylidene)-sorbitol.
[0110] Example 3: Nucleating agent composition 3
[0111] In a 1000 mL reaction kettle, 21.8 g of solid sorbitol and 16.5 g of p-chlorobenzaldehyde were added and stirring was initiated for initial dispersion. Subsequently, 33 g of cyclohexane was added and 0.5 g of p-toluenesulfonic acid catalyst was added in one portion. Heating was initiated to 80-85 °C to cyclohexane reflux and the reaction was maintained at this temperature with stirring for 30 minutes to initiate the dehydration process. Thereafter, 16.5 g of 3,4-dimethylbenzaldehyde was added and 16.5 g of cyclohexane was added to continue the reflux reaction for 2-3 hours. During the reaction, the amount of dehydration was continuously monitored by an oil-water separator and when the cumulative amount of condensation reaction water collected reached about 4.0-4.3 g, heating was stopped. Subsequently, solvent recovery was performed and the remaining cyclohexane and water were recovered by distillation under reduced pressure with cooling. The kettle product was cooled to 60-70 °C, dispersed in 500-550 mL of deionized water, and 0.8 g of sodium hydroxide and 0.5 g of 30% wt hydrogen peroxide were sequentially added with stirring for 60 minutes. Subsequently, filtration was performed and the filter cake was washed with deionized water and the filter cake was vacuum dried at 80-90 °C for 4-6 hours to ultimately obtain the target product, white powder product 3.
[0112] The composition and content of product 3 was analyzed by gas chromatography-mass spectrometry (GC-MS) and product 3 contained 22.72% 1,3:2,4-di(p-chlorobenzylidene)-sorbitol, 23.60% 1,3:2,4-di(3,4-dimethylbenzylidene)-sorbitol, 51.89% 1,3-p-chlorobenzylidene-2,4-(3,4-dimethylbenzylidene)-sorbitol and 1,3-(3,4-dimethylbenzylidene)-2,4-p-chlorobenzylidene-sorbitol, and 1.79% 1,3:2,4:5,6-tri(p-chlorobenzylidene)-sorbitol.
[0113] Comparative Example 1: Nucleating agent composition 4
[0114] In a 1000 mL reaction kettle, 21.8 g of solid sorbitol and 16.5 g of p-chlorobenzaldehyde, 16.5 g of 3,4-dimethylbenzaldehyde were added and stirring was initiated for initial dispersion. Subsequently, 99 g of cyclohexane was added and 0.5 g of p-toluenesulfonic acid catalyst was added in one portion. Heating was initiated to 80-85 °C to cyclohexane reflux and the reaction was maintained at this temperature for 3-4 hours and during the reaction, the amount of dehydration was continuously monitored by an oil-water separator and when the cumulative amount of condensation reaction water collected reached about 4.3 g, heating was stopped. Subsequently, solvent recovery was performed and the remaining cyclohexane and water were recovered by distillation under reduced pressure with cooling. The kettle product was cooled to 60-70 °C, dispersed in 500-550 mL of deionized water, and 0.8 g of sodium hydroxide, 1.0 g of 30% wt hydrogen peroxide were sequentially added with stirring for 2 hours, filtration was performed, the filter cake was washed with deionized water and the filter cake was vacuum dried at 80-90 °C for 4-6 hours to ultimately obtain the target product, white powder product 4.
[0115] The composition and content of product 4 were analyzed by gas chromatography-mass spectrometry (GC-MS), and the results showed that it only contained diacetal sorbitol compounds, including 24.8% 1,3:2,4-di(p-chlorobenzylidene)-sorbitol, 24.04% 1,3:2,4-di(3,4-dimethylbenzylidene)-sorbitol, 51.16% 1,3-p-chlorobenzylidene-2,4-dimethylbenzylidene-sorbitol, and 1,3-dimethylbenzylidene-2,4-p-chlorobenzylidene-sorbitol.
[0116] Comparative Example 2: Synthesis of nucleating agent 1,3-2,4-(3,4-dimethylbenzaldehyde) sorbitol
[0117] In a 1000 mL reaction kettle, 21.8 g of solid sorbitol and 33 g of 3,4-dimethylbenzaldehyde were first added and stirred for 30 minutes for initial dispersion. Then, 66 g of cyclohexane and 0.5 g of p-toluenesulfonic acid catalyst were added at once. Heating to 80-85°C to cyclohexane reflux, refluxing at this temperature for 3-4 hours, during which the amount of dehydration was continuously monitored by an oil-water separator, and when the cumulative amount of condensation reaction water collected reached about 4.3 g, the heating was stopped. Then solvent recovery was carried out, and the remaining cyclohexane and water were recovered by cooling and reduced pressure distillation. The product in the kettle was cooled to 60-70°C, 500-550 mL of deionized water was added for dispersion, and then 0.8 g of sodium hydroxide and 0.5 g of 30%wt hydrogen peroxide were added in sequence and stirred for 60 minutes. Finally, filtration was carried out, and the filter cake was washed with deionized water, and the filter cake was vacuum dried at 80-90°C for 4-6 hours, and finally the target product, white powder product 5, was obtained.
[0118] The composition and content of product 5 were analyzed by gas chromatography-mass spectrometry (GC-MS), and the results showed that it contained 99.86% 1,3:2,4-di(3,4-dimethylbenzylidene)-D-sorbitol and 0.14% 1,3:2,4:5,6-tri(3,4-dimethylbenzylidene)-sorbitol.
[0119] Comparative Example 3: Synthesis of nucleating agent 1,3-2,4-(p-chlorobenzaldehyde) sorbitol
[0120] In a 1000 mL reactor, 21.8 g of solid sorbitol and 34.5 g of p-chlorobenzaldehyde were first added and initial dispersion was performed with stirring. Subsequently, 66 g of cyclohexane and 0.5 g of p-toluenesulfonic acid catalyst were added at once. Heating was performed to 80-85 °C to reflux the cyclohexane, and the reaction was refluxed at this temperature for 3-4 hours. During the reaction, the amount of dehydration was continuously monitored by an oil-water separator, and when the cumulative amount of water generated by the condensation reaction reached about 4.3 g, heating was stopped. Subsequently, solvent recovery was performed, and the remaining cyclohexane and water were recovered by distillation at reduced pressure. The product in the reactor was cooled to 60-70 °C, 500-550 mL of deionized water was added for dispersion, and then 0.8 g of sodium hydroxide and 0.5 g of 30% wt hydrogen peroxide were sequentially added and stirred for 60 minutes. Finally, filtration was performed, the filter cake was washed with deionized water, and the filter cake was vacuum dried at 80-90 °C for 4-6 hours to obtain the target product, white powder product 6.
[0121] The product was analyzed by gas chromatography-mass spectrometry (GC-MS) to contain 99.28% of 1,3:2,4-di(p-chlorobenzylidene)sorbitol and 0.72% of 1,3:2,4:5,6-tri(p-chlorobenzylidene)-sorbitol.
[0122] Melting point test of nucleating agent composition of test example one
[0123] The melting points of the nucleating agent compositions of test examples 1-3 and comparative examples 1-3 were tested according to GB / T 617.
[0124]
[0125] Effect of nucleating agent composition of test example two on the properties of PP (polypropylene)
[0126] The nucleating agent composition white powder products 1-3 obtained from examples 1-3 and comparative products 4-6 of comparative examples 1-3 were added to polypropylene to test the effect on the polymer.
[0127] In order to test the effect of the nucleating agent composition on the PP product, different addition amounts and different injection molding temperatures were investigated to verify the performance in low temperature processing, haze of thick products, etc.
[0128] Application 1:
[0129] 2.0 g and 2.5 g of the nucleating agent composition products 1-3 of examples 1-3 and products 4-6 of comparative examples were respectively added to 1000 g of polypropylene resin according to the addition amount, mixed in a high-speed mixer for 5 minutes to become a resin mixture, and then extruded and pelletized by a twin-screw mixer. The extrusion temperature was 210 °C, and a polypropylene composition was obtained.
[0130] The polypropylene composition was injection molded at 230°C to prepare haze test samples, wherein the thickness of the polypropylene haze test samples was 1.0 and 2.0 mm, respectively.
[0131]
[0132] Application 2:
[0133] 2.0 g and 2.5 g of the nucleating agent composition products 1-3 of Examples 1-3 and products 4-6 of Comparative Examples were added to 1000 g of polypropylene resin, respectively, and after mixing in a high-speed mixer for 5 minutes, resin mixtures were obtained, and then double-screw extrusion granulation was performed. The extrusion temperature was 200°C, and polypropylene compositions were obtained.
[0134] The polypropylene composition was injection molded at 190°C to prepare haze test samples, wherein the thickness of the polypropylene haze test samples was 1.0 and 2.0 mm, respectively.
[0135]
[0136] Application 3:
[0137] 2.0 g of the nucleating agent composition products 1-3 of Examples 1-3 and products 4-6 of Comparative Examples 1-3 were added to 1000 g of polypropylene PPH-M17 resin, respectively, and a film drawing test was performed at a film drawing temperature of 200°C, and after the film drawing was completed, a certain area of the film was taken and observed for crystal point conditions.
[0138]
[0139] As can be seen from the above experimental results, the products of Examples 1-3 of the present application have good dispersibility in polypropylene, and after being used to prepare polypropylene products, the transparency of the polymer is improved. Moreover, the transparent nucleating agent containing a plurality of sorbitol-aromatic aldehyde acetal compositions of the present application produces more excellent transparency than the transparent nucleating agent containing only sorbitol diacetal or the sorbitol diacetal triacetal nucleating agent containing only one aldehyde.
[0140] In the description of the specification, the description referring to the terms "one embodiment", "one configuration", "some embodiments", "some configurations", "exemplary", "one specific embodiment", etc. means that the particular feature, structure, material, or characteristic following the term is included in at least one embodiment or configuration of the present application. The illustrative examples of the present application should not be construed as being limiting in all respects to the particular examples described herein but should be construed to provide those skilled in the art with a full and enabling disclosure, including the best mode contemplated at this time of the application. The description of the present application is intended to cover any and all modifications and variations of the various embodiments thereof that are apparent to those skilled in the art upon employment of the teachings of the present application. The intended scope of the application is, therefore, indicated and limited only by the following claims.
[0141] The scope of the application is not limited to the embodiments described above, and it is obvious to those skilled in the art that various modifications and changes can be made to the present application without departing from the scope and spirit of the application. If these modifications and changes fall within the scope of the claims of the present application and their equivalents, the intention of the present application also includes these modifications and changes.
Claims
1. A nucleator composition comprising a plurality of sorbitol-aromatic aldehyde aceta ls, characterized in that, one or two of the compounds of formula (A), (B), (C) and (D), one or more of the compounds of formula (E) to (I): R1is independently selected from Cl, R2is independently selected from methyl; preferably, n = 1, R1is at the para position, n = 2, R2is at the 3,4-position. The sum of the weight fractions of the compounds of formula (A) to (D) in the composition is 95.0-98.5%, and the sum of the weight fractions of the compounds of formula (E) to (L) is 1.5-5.0%.
2. The nucleating agent composition of claim 1, wherein R1is independently selected from Cl, R2is independently selected from methyl; preferably, n = 1, R1is at the para position, n = 2, R2is at the 3,4-position.
3. The nucleating agent composition according to claim 1 or 2, characterized in that, one or two of the compounds of formula (A), (B), (C) and (D), the compound of formula (L); preferably, one or two of the compounds of formula (A), (B), (C) and (D), the compound of formula (E), the compound of formula (L); or one or more of the compounds of formula (I) to (K), the compound of formula (L).
4. The nucleating agent composition according to any one of claims 1 to 3, characterized in that, The weight fraction of the compound of formula (A) is 3.0-85.0%, the weight fraction of the compound of formula (B) is 3.0-85.0%, and the sum of the weight fractions of the compounds of formula (C) and (D) is 5.0-60.0%. preferably, the weight fraction of the compound of formula (A) is 30.0-60.0%, the weight fraction of the compound of formula (B) is 3.0-30.0%, and the sum of the weight fractions of the compounds of formula (C) and (D) is 20.0-50.0%.
5. The method of producing a nucleating agent composition according to any one of claims 1 to 4, characterized by, comprising the following steps: 1) adding an aromatic aldehyde (I) and sorbitol into a container, stirring to form a mixture; 2) adding cyclohexane into the mixture of step 1); 3) adding a catalyst into the mixture of step 2); 4) heating the mixture of step 3) to cyclohexane reflux, maintaining the reflux reaction; 5) adding an aromatic aldehyde (II) into the product of step 4); 6) adding cyclohexane into the product of step 5); 7) heating the product of step 6) to cyclohexane reflux, maintaining the reflux reaction, until the ratio of the number of moles of water collected by the oil-water separator to the number of moles of sorbitol is 1.5-2.1:1.0; 8) cooling, reducing pressure distillation of cyclohexane and water to obtain a crude product; 9) dispersing the obtained crude product into water, adding sodium hydroxide and hydrogen peroxide, and stirring; 10) pressure filtration, water washing, drying, and crushing to obtain a nucleating agent composition; wherein the aromatic aldehyde (I) is a compound of formula (a), and the aromatic aldehyde (II) is a compound of formula (b), or the aromatic aldehyde (I) is a compound of formula (b), and the aromatic aldehyde (II) is a compound of formula (a), wherein R1, R2, n, and m are as defined in any one of claims 1-4.
6. The production method according to claim 5, wherein The ratio of the total amount of aromatic aldehyde (I) and aromatic aldehyde (II) to the molar amount of sorbitol is 1.8-2.2:1.0, preferably 1.9-2.1:1.
0.
7. The production method according to claim 5 or 6, characterized by, The ratio of the molar amount of aromatic aldehyde (I) to the molar amount of sorbitol is 0.1-1.9:1.0, and the ratio of the molar amount of aromatic aldehyde (II) to the molar amount of sorbitol is 0.1-1.9:1.0; preferably, the ratio of the molar amount of aromatic aldehyde (I) to the molar amount of sorbitol is 1.0-1.6:1.0, and the ratio of the molar amount of aromatic aldehyde (II) to the molar amount of sorbitol is 0.4-1.0:1.
0.
8. The method of any one of claims 5-7, wherein, The catalyst is benzene sulfonic acid, methyl benzene sulfonic acid; preferably, the molar amount of the catalyst is 0.01-0.03:1 of the molar amount of sorbitol.
9. The method of any one of claims 5-8, wherein, In step 4), the reaction is refluxed for 20 min-1h, and in step 7), the reaction is refluxed for 1-4h, until the ratio of the molar amount of water collected in the oil-water separator to the molar amount of sorbitol is 1.8-2.02:
1.
10. Use of a nucleating agent composition according to any one of claims 1 to 4, or a nucleating agent composition prepared according to any one of claims 5 to 9, characterized in that, The nucleating agent composition is added to a polymer to produce a polymer article.
11. A polymer composition comprising a polymer and a nucleating agent composition, characterized in that, The nucleating agent composition is prepared according to the method of any one of claims 5-9.
12. The use according to claim 10 or the polymer composition according to claim 11, characterized in that The weight percentage of the nucleating agent composition to the polymer is 0.20-0.30%, preferably 0.20-0.25%.
13. Use or polymer composition according to any of claims 10 to 12, characterized in that The polymer is polyolefin, preferably one or more of polypropylene, polyethylene.
14. A polymeric article characterized by, The polymer article is made of the polymer composition of any one of claims 11-13.