Search

CN-121974797-A - Preparation method of nucleating agent and composition thereof

CN121974797ACN 121974797 ACN121974797 ACN 121974797ACN-121974797-A

Abstract

The invention relates to a preparation method and application of a nucleating agent, wherein the preparation method comprises the following steps of mixing solvent pure water, calcium hydroxide and fatty acid methyl ester sulfonate, and heating; and then dripping hexahydrophthalic anhydride into the mixed solution, and carrying out heat preservation reaction after dripping is finished to obtain calcium hexahydrophthalate. The product is used for thermoplastic resins such as polyolefin and the like and has excellent performance.

Inventors

  • YANG LEI
  • WANG ZI
  • SUN XUE
  • ZHANG JI
  • LI RUI
  • LIU BINBIN

Assignees

  • 利安隆（中卫）新材料有限公司
  • 天津利安隆新材料股份有限公司
  • 利安隆（珠海）新材料有限公司

Dates

Publication Date
20260505
Application Date
20260114
Priority Date
20250901

Claims (10)

  1. 1. A method of preparing a nucleating agent comprising the steps of: (1) Mixing solvent pure water, calcium hydroxide and fatty acid methyl ester sulfonate, and heating; (2) And (3) dropwise adding hexahydrophthalic anhydride into the mixed solution, and carrying out heat preservation reaction after the dropwise adding is finished to obtain calcium hexahydrophthalate.
  2. 2. The process according to claim 1, wherein the molar ratio of hexahydrophthalic anhydride to calcium hydroxide in the starting material is 1 (0.9-1.1), preferably 1 (0.95-1.05).
  3. 3. The preparation method according to claim 1, wherein the fatty acid methyl ester sulfonate comprises sodium C 16 -C 18 fatty acid methyl ester sulfonate, and the structure of the fatty acid methyl ester sulfonate is shown in the following formula I, wherein R in the formula I is an alkyl group of C 16 -C 18 ; I。
  4. 4. The method of preparation according to claim 1, characterized in that the fatty acid methyl ester sulfonate is used in an amount of 1% -5%, preferably 2% -4%, more preferably 2.5% -3.5% by weight of hexahydrophthalic anhydride.
  5. 5. The process according to claim 1, wherein the pure water is used in an amount of 5 to 10 times, preferably 6 to 8 times, the mass of hexahydrophthalic anhydride in terms of volume to weight ratio (ml/g), and/or, The reaction temperature is 20-90 ℃, preferably 30-80 ℃.
  6. 6. A nucleating agent calcium hexahydrophthalate characterized in that the particle size of the calcium hexahydrophthalate, D97, is less than 20 μm.
  7. 7. A nucleating agent composition is characterized by comprising calcium hexahydrophthalate, stearate and magnesium oxide, wherein preferably the calcium hexahydrophthalate is calcium hexahydrophthalate obtained by the preparation method of any one of claims 1-5 or calcium hexahydrophthalate of claim 6, and preferably comprises 65-85% of calcium hexahydrophthalate, 15-35% of stearate and 3-7% of magnesium oxide by total weight.
  8. 8. A thermoplastic resin composition comprising a thermoplastic resin and the nucleating agent composition of claim 7, wherein the nucleating agent composition is present in the thermoplastic resin in an amount of 50ppm to 20000ppm by weight.
  9. 9. The thermoplastic resin composition of claim 8, wherein the thermoplastic composition is selected from the group consisting of polyolefin and polyurethane.
  10. 10. The thermoplastic resin composition of claim 9, wherein said polyolefin is polyethylene, polypropylene, polybutylene, poly (4-methyl) pentene, and mixtures or copolymers of any of them.

Description

Preparation method of nucleating agent and composition thereof Technical Field The invention relates to the field of nucleating agent additives, in particular to a preparation method and a composition of a nucleating agent. Background Polypropylene is one of five general plastics in the world, and its main uses are in food packaging and automotive parts, etc. The polypropylene has the characteristics of good mechanical property, no toxicity, low relative density, heat resistance, chemical resistance, low price, easy processing and forming and the like, and is widely applied. However, polypropylene is a partially crystalline resin, and the volume of spherulites obtained under normal processing conditions is large, the crystallization is imperfect, so that the strength of the polypropylene is low, and the secant modulus and chordwise modulus of the material are low. The stiffening nucleating agent is actively replaced to form crystal nuclei of crystalline substances in the crystallization process, the formation process of autonomous crystallization of the crystalline substances under the condition that no nucleating agent exists is quickened, polymer molecules are continuously adsorbed to form more fine crystal nuclei, the crystallization speed of the polymer is quickened under the condition that the growth speed of spherulites is kept unchanged, a series of crystallization parameters such as the spherulites size and the crystallinity of the polymer are reduced, the hardness and the rigidity of the polypropylene material are finally improved, and the stiffening or stiffening effect is achieved. The dicarboxylic acid salt with a double-ring structure is a novel aliphatic nucleating agent, and researches show that the dicarboxylic acid salt can greatly improve the crystallization temperature of polypropylene and the isotropy of modified polypropylene, and has remarkable effect on improving the rigidity of polypropylene. Patent US6599971B reports a synthesis method of calcium hexahydrophthalate, which takes cis-hexahydrophthalic anhydride and calcium hydroxide as raw materials, takes water as a solvent for neutralization reaction, filters after the reaction is finished, and is washed and dried by pure water to obtain a final product, wherein the reaction yield is 93%, and the melting point of the final product is more than 400 ℃. Patent CN 119569563a reports a preparation method of calcium hexahydrophthalate, which uses hexahydrophthalic acid and calcium hydroxide as raw materials, uses methanol as a solvent, dissolves hexahydrophthalic acid in methanol to form hexahydrophthalic acid-methanol solution, then puts calcium hydroxide into a reaction solution to perform neutralization reaction, and dries at 120 ℃ for 0.5h after the reaction is finished to obtain a final product. Disclosure of Invention The research shows that the product obtained by the preparation method of the nucleating agent calcium hexahydrophthalate in the background technology has larger particle size, the particle size D97 of the detection product is between 25 and 35 mu m even after physical crushing, and the particle size distribution of the product is dispersed relatively due to the physical crushing, so that the dispersion of the product in the application process is limited, and the application effect is poor. The invention provides a novel synthesis method of calcium hexahydrophthalate nucleating agent, which is used for preparing a product with small particle size and good application performance. The first aspect of the present invention provides a method for preparing a nucleating agent, comprising the steps of: (1) Mixing solvent pure water, calcium hydroxide and fatty acid methyl ester sulfonate, and heating; (2) And (3) dropwise adding hexahydrophthalic anhydride into the mixed solution, and carrying out heat preservation reaction after the dropwise adding is finished to obtain calcium hexahydrophthalate. Since the nucleator compound is typically provided to downstream polyolefin manufacturers in a powdered or granular form, and since small, uniform particles of the nucleator are essential to provide the necessary uniform dispersion and performance, such compounds must remain small during storage. In the invention, the anionic surfactant fatty acid Methyl Ester Sulfonate (MES) can improve the dispersion of calcium hexahydrophthalate molecules in water, improve the fluidity of the reaction solution and has remarkable effect on reducing the particle size of the finished product. Meanwhile, the fatty acid methyl ester sulfonate is used as a third-generation surfactant, is safe and nontoxic, can be completely biodegraded, is green and environment-friendly, and does not cause environmental pollution, and the process of firstly mixing calcium hydroxide, a surfactant and pure water and then dropwise adding molten hexahydrophthalic anhydride can also reduce the average particle size of a finished product and improve the application effect