Method capable of realizing preparation and in-situ separation of oligomeric ricinoleate

Patent metadata

Field	Value
Publication number	US-2021363095-A1
Application number	US-202117339940-A
Country	US
Kind code	A1
Filing date	Jun 5, 2021
Priority date	Feb 27, 2020
Publication date	Nov 25, 2021
Grant date	—

Abstract

The disclosure is about a method capable of realizing the preparation and in-situ separation of the oligomeric ricinoleate, which uses the ricinoleic acid as raw material, and uses a protonic acid-type ionic liquid as a catalyst to cause the dehydration and esterification reactions between ricinoleic acid molecules. By continuously distilling out the generated water under a reduced pressure, the oligomeric ricinoleate with a polymerization degree of 2 to 10 is obtained. After the reaction, a method of washing with water or static stratification is selected to recover the catalyst according to the miscibility of the catalyst and reaction system. In his disclosure, renewable raw materials are used, the process is clean and pollution-free, and the operation is simple.

First claim

What is claimed is:

1 . A method capable of realizing preparation and in-situ separation of the oligomeric ricinoleate, which uses the ricinoleic acid as raw material, and uses a Bronsted acidic ionic liquid as catalyst to cause dehydration and esterification reactions between ricinoleic acid molecules, and takes out generated water by using a vacuum pump, thus being capable of obtaining an oligomeric ricinoleate with a polymerization degree lower than 10, comprising the following steps of:
step 1: putting the ricinoleic acid and the catalyst into a reaction flask; step 2: starting the vacuum pump to adjust the vacuum degree of the reaction system, heating to a reaction temperature under a stirring condition, and starting the dehydration and esterification reactions; step 3: after the reaction, removing the catalyst, and finally obtaining a product, which is the oligomeric ricinoleate.

2 . The method capable of realizing the preparation and in-situ separation of the oligomeric ricinoleate according to claim 1 , wherein after the reaction, the catalyst is removed by a method of washing with water or static stratification according to miscibility of the ionic liquid catalyst with the reaction system; for the ionic liquid that is soluble in the reaction system at room temperature, water washing was used to separate the catalyst with the product while for the ionic liquid which is immiscible with the reaction system at room temperature, static stratification and dumpling was applied.

3 . The method capable of realizing the preparation and the in-situ separation of the oligomeric ricinoleate according to claim 1 , wherein the used raw material ricinoleic acid has an acid value of 150 mg KOH/g to 190 mg KOH/g.

4 . The method capable of realizing the preparation and the in-situ separation of the oligomeric ricinoleate according to claim 1 , wherein the cation of the ionic liquid catalyst is one or more of N-methylpyrrolidone ion ([NMP] + ), N-butylsulfonate pyridinium ion ([HSO 3 -BPy] + ), N-(4-butanesulfonic acid)triethylamine ion ([HSO 3 -BNEt 3 ] + ), 1-butanesulfonic acid-3-methylimidazole ion ([HSO 3 -BMim] + ), or 1-butanesulfonic acid-1,8-diazabicyclo[5.4.0]undec-7-ene ion ([HSO 3 -BDBU]) + ); and the anion of the ionic liquid catalyst is one or more of hydrogen sulfate (HSO 4 − ), dihydrogen phosphate (H 2 PO 4 − ), trifluoromethanesulfonic acid ion (CF 3 SO 3 − ), or p-toluenesulfonic acid ion PTSA − ).

5 . The method capable of realizing the preparation and the in-situ separation of the oligomeric ricinoleate according to claim I wherein a dosage of the catalyst ranges from 1 wt. % to 30 wt. %.

6 . The method capable of realizing the preparation and the in-sitz separation of the oligomeric ricinoleate according to claim 1 , wherein the dehydration and esterification reactions are performed at the temperature of 160° C. to 230° C. and a vacuum degree of 70 kPa to 0 kPa, and last for 2 hours to 16 hours.

7 . The method capable of realizing the preparation and the in-situ separation of the oligomeric ricinoleate according to claim 1 , wherein the obtained oligomeric ricinoleate has an acid value of 10 mg KOH/g to 90 mg KOH/g, which corresponds to a polymerization degree less than or equal to 10; at 40° C., the kinematic viscosity of the product is less than or equal to 1,000 mm 2 /s; and at 100° C. the kinematic viscosity is less than or equal to 100 mm 2 /s.

8 . An oligomeric ricinoleate prepared by the method of claim 1 , wherein the final product oligomeric ricinoleate has a structural formula as follows:

wherein, n is an integer from 2 to 10.

9 . The oligomeric ricinoleate according to claim 8 , wherein after the reaction, the catalyst is removed by a method of washing with water or static stratification according to miscibility of the ionic liquid catalyst with the reaction system; for the ionic liquid that is soluble in the reaction system at room temperature, water washing was used to separate the catalyst with the product while for the ionic liquid which is immiscible with the reaction system at room temperature, static stratification and dumpling was applied.

10 . The oligomeric ricinoleate according to claim 8 , wherein the used raw material ricinoleic acid has an acid value of 150 mg KOH/g to 190 mg KOH/g.

11 . The oligomeric ricinoleate according to claim 8 , wherein the cation of the ionic liquid catalyst is one or more of N-methylpyrrolidone ion ([NMP ] + ), N-butylsulfonate pyridinium ion ([HSS 3 -BPyr] + ), N-(4-butanesulfonic acid)triethylamine ion ([HSO 3 -BNEt 3 ] + ), 1-butanesulfonic acid-3-methylimidazole ion ([HSO 3 -BMim] + ), or 1-butanesulfonic acid-1,8-diazabicyclo[5.4.0]undec-7-ene ion ([HSO 3 -BDBU]) + ); and the anion of the ionic liquid catalyst is one or more of hydrogen sulfate (HSO 4 − ), dihydrogen phosphate (H 2 PO 4 − ), trifluoromethanesulfonic acid ion (CF 3 SO 3 − ), or p-toluenesulfonic acid ion PTSA − ).

12 . The oligomeric ricinoleate according to claim 8 , wherein a dosage of the catalyst ranges from 1 wt. % to 30 wt. %.

13 . The oligomeric ricinoleate according to claim 8 , wherein the dehydration and esterification reactions are performed at the temperature of 160° C. to 230° C. and a vacuum degree of 70 kPa to 0 kPa, and last for 2 hours to 16 hours.

14 . The oligomeric ricinoleate according to claim 8 , wherein the obtained oligomeric ricinoleate has an acid value of 10 mg KOH/g to 90 mg KOH/g, which corresponds to a polymerization degree less than or equal to 10; at 40° C., the kinematic viscosity of the product is less than or equal to 1,000 mm 2 /s; and at 100° C., the kinematic viscosity is less than or equal to 100 mm 2 /s.

Assignees

• Univ Nankai
• Tianjin Nankai Univ Castor Engineering S&T Co Ltd

Inventors

• Ye Feng
• He Liangnian
• Li Hongru
• Li Gang
• You Fei
• Wang Qingrui
• Gao Song
• He Xing
• Cui Xiaoying

Classifications

• B01J31/0298

  the ionic liquids being characterised by the counter-anions · CPC title

• B01J31/0285

  also containing elements or functional groups covered by B01J31/0201 - B01J31/0274 · CPC title

• B01J31/0284

  of an aromatic ring, e.g. pyridinium · CPC title

• B01J31/0282

  of an aliphatic ring, e.g. morpholinium · CPC title

• B01J31/0279

  the cationic portion being acyclic or nitrogen being a substituent on a ring · CPC title