Synthesis method of novel acrylate monomer with bifunctional structure

Abstract

The invention belongs to the field of organic synthesis, and provides a synthesis method of a novel acrylate monomer with a bifunctional structure, which comprises the following steps: S1, reacting an ester group-containing alcohol compound with a carbonylation reagent to obtain an intermediate product A; s2, acidifying an alcohol amine compound, and reacting with an acryloyl reagent to obtain an intermediate product B; s3, reacting the intermediate product A with the intermediate product B to obtain a target product C, namely the novel acrylate monomer with the bifunctional structure; wherein R1 is hydrogen or alkyl, R2 is an organic group containing an ester group, m is an integer greater than or equal to 1, R3 and R4 are independently selected from at least one of arene oxyl, halogenated hydrocarbon oxyl or heterocyclic ring containing nitrogen atoms, R5 is alkylene, and L is selected from at least one of halogen atoms, hydroxyl or hydrocarbon oxyl. The method is simple to operate, the reaction process is easy to control and realize, and industrial production is easy.

Description

Technical Field

[0001] This invention belongs to the field of organic synthesis, and particularly relates to a method for synthesizing a novel acrylate monomer with a bifunctional structure. Background Technology

[0002] Organic carbonate-based liquid electrolytes commonly used in lithium-ion batteries pose safety hazards such as leakage, fire, and explosion. The formation of lithium dendrites can also lead to poor battery cycle performance, gas buildup, and even short circuits. To improve battery safety, researchers have been dedicated to developing new structures.

[0003] Acrylates containing cyclic ester groups possess excellent flexibility and lithium-ion transport promoting properties, facilitating the full wetting and spreading of binders on the electrode particle surface, forming a more robust adhesive network, and reducing interfacial impedance. For example, KR20120106985A uses (meth)acrylate monomers with cyclic ester residues in the binder composition of conductive films, improving the adhesive strength of anisotropic conductive films and reducing on-resistance. Meanwhile, acrylates containing urethane exhibit strong mechanical strength and good electrochemical stability. The strong hydrogen bond network formed by their urethane bonds endows the material with extremely high cohesive energy and adhesive force, preventing electrode delamination and failure during long-term cycling and maintaining long-term structural integrity. For instance, CN107078342B solves the safety issues of liquid electrolytes by using a gel polymer electrolyte composed of urethane, acrylate, and fluorinated alkyl groups in lithium secondary batteries, improving the battery's mechanical strength and ionic conductivity, and extending battery life. Introducing both urethane and cyclic esters into acrylates offers synergistic advantages unmatched by single-structure materials. It achieves a balance between strength and toughness, constructs a stable and ion-conducting interface layer, reduces interfacial impedance, improves rate performance, provides a high safety factor for high-performance separator coatings, offers better adhesion to electrodes, and contributes to the long-term cycle stability of batteries. When used as a solid electrolyte matrix, it introduces lithium salts into a "rigid-flexible" polymer network, resulting in good mechanical properties and high ionic conductivity. For example, CN110218276A uses acrylate compounds containing cyclic carbonate structures as monomers to prepare polymer electrolytes through in-situ polymerization. This results in a wide electrochemical window, high lithium-ion conductivity, and good mechanical properties, effectively suppressing lithium dendrite formation and improving high-voltage cycle stability. Japanese patent JP2008127498A uses (meth)acrylate compounds containing cyclic carbonates as solid electrolyte polymers, achieving excellent ionic conductivity.

[0004] There are few existing technologies involving the preparation of such compounds, mainly relying on isocyanate precursor compounds for synthesis. For example, Japanese Patent JP2008127498A involves the reaction of 2-(meth)acryloyloxyethyl isocyanate with an alcohol containing a cyclic ester, but this requires the removal of water as much as possible from the reaction system and the use of alkyltin noble metal catalysts, which can easily leave metal ions in the product. The literature Chem. Mater. 2020, 32, 9167-9175 uses 4-hydroxymethyl-1,3-dioxane-2-one with 2-isocyanoethyl methacrylate, which requires strict control of reaction conditions and involves complex post-processing steps. Summary of the Invention

[0005] The purpose of this invention is to solve the problems of harsh conditions, cumbersome steps, and the easy retention of heavy metal ions in the products of existing methods for synthesizing novel acrylate monomers with bifunctional structures. This invention provides a method for synthesizing novel acrylate monomers with bifunctional structures. This method is characterized by mild conditions, simple operation, easy control and implementation of the reaction process, and ease of industrial production. The resulting product has high purity, is free of residual heavy metal ions, and can be directly used in lithium batteries, polymer modification, adhesives, solid electrolyte polymer monomers, and other fields.

[0006] To achieve the above technical objectives, the technical solution adopted by this invention is as follows: a method for synthesizing a novel acrylate monomer with a bifunctional structure, comprising the following steps: S1: An ester-containing alcohol compound (compound I) is reacted with a carbonylating agent (compound II) to give intermediate product A; S2: An acidified alkanolamine compound (compound III) reacts with an acryloyl reagent (compound IV) to give intermediate product B; S3: The intermediate product A obtained in step S1 reacts with the intermediate product B obtained in step S2 to obtain the target product C, which is a novel acrylate monomer with a bifunctional structure.

[0007] Wherein, R1 is a hydrogen or hydrocarbon group, R2 is an organic group containing an ester group, m is an integer ≥1, R3 and R4 are independently selected from at least one of aryloxy groups, halooxy groups or nitrogen-containing heterocycles, R5 is a hydrocarbon group, and L is selected from at least one of halogen atoms, hydroxyl groups or hydrocarbon groups.

[0008] Further, R1 is selected from hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, m is selected from an integer of 1 to 6, and R2 is selected from at least one of cyclic carbonate group, cyclic sulfite group, cyclic carboxylic acid ester group, linear carbonate group, linear sulfite group, or linear carboxylic acid ester group.

[0009] Furthermore, the structural formula of compound I is selected from... , , , , , , or At least one of them; wherein R6 is a hydrocarbon group.

[0010] Furthermore, R3 and R4 are independently selected from at least one of phenoxy, pentafluorophenoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2,2,3,3-tetrafluoropropoxy, 2,2,3,3,3-pentafluoropropoxy, hexafluoroisopropoxy, perfluorobutoxy, (2-perfluorobutyl)ethoxy, trichloromethoxy, 2,2,2-trichloroethoxy, imidazolyl, 1,2,4-triazolyl or succinimideoxy.

[0011] Furthermore, in step S1, the molar ratio of the ester-containing alcohol compound (compound I) to the carbonylating agent (compound II) is 0.5~5:1, and the reaction temperature is 10~35℃.

[0012] Furthermore, in step S2, the alkanolamine compound (compound III) is acidified with hydrochloric acid, sulfuric acid or phosphoric acid to form an alkanolamine salt.

[0013] Furthermore, the alcoholamine salt is selected from at least one of ethanolamine hydrochloride, ethanolamine sulfate, ethanolamine phosphate, 3-amino-1-propanol hydrochloride, 3-amino-1-propanol sulfate, and 3-amino-1-propanol phosphate.

[0014] Furthermore, in step S2, the molar ratio of the alkanolamine compound (compound III) to the acryloyl reagent (compound IV) is 1:1~5, and the reaction temperature is 0~140℃.

[0015] Furthermore, in step S3, the molar ratio of intermediate product B to intermediate product A is 1:1~5, and the reaction temperature is 0~120℃.

[0016] Furthermore, after the reaction in step S3 is completed, the target product is obtained by column chromatography or recrystallization.

[0017] The beneficial effects of this invention are: The present invention provides a method for synthesizing novel acrylate monomers containing a bifunctional structure. The method involves synthesizing intermediate A using an ester-containing alcohol compound and a carbonylating reagent, followed by acidification of an alkanolamine compound and reaction with an acryloyl reagent to obtain intermediate B. Intermediate A is then further reacted with intermediate B to obtain a product containing acrylate, carbamate, and ester groups in its structural formula. This synthesis process is mild, simple to operate, and easy to control and implement, facilitating industrial production. The resulting product has a purity of over 99%, is free of residual heavy metal ions, and can be directly used in lithium batteries, polymer modification, adhesives, solid electrolyte polymer monomers, and other fields, demonstrating good technical performance. Attached Figure Description

[0018] Figure 1 The image shows the 1H NMR spectrum of a novel acrylate monomer with a bifunctional structure prepared in Example 1.

[0019] Figure 2 The image shows a liquid chromatogram for purity determination of a novel acrylate monomer with a bifunctional structure prepared in Example 1. Detailed Implementation

[0020] The technical solution of the present invention will be further explained and described below with reference to specific embodiments. However, the following embodiments are only examples of explanation of this application and are not intended to limit the content of this application. Those skilled in the art can make improvements or modifications to the content of the present invention without creative contribution as needed under the guidance of this specification, and all such improvements or modifications fall within the protection scope of the present invention.

[0021] Unless otherwise specified, reaction temperature generally refers to the internal temperature of the reactants.

[0022] Unless otherwise specified, reaction pressure generally refers to gauge pressure; gauge pressure is defined as the difference between absolute pressure and atmospheric pressure.

[0023]

Example 1

[0024] S1: Under nitrogen protection, 5L of dichloromethane and 470g of carbonyl diimidazole were added to a 20L reactor equipped with a mechanical stirrer, a constant pressure dropping funnel and a thermometer. Then, 311g of glycerol carbonate was added to the constant pressure dropping funnel and added dropwise into the reactor over 1-2 hours. After the addition was completed, the temperature was controlled at 15-20℃ and stirred for 24 hours. The mixture was then washed with water to obtain a solution containing intermediate product A-1.

[0025] S2: Under nitrogen protection, 665g of methacrylamide chloride and 400g of ethanolamine hydrochloride were added to a 2L reactor equipped with a mechanical stirrer, a constant pressure dropping funnel and a thermometer. The mixture was stirred at 90℃ for 4 hours. After cooling to room temperature, tetrahydrofuran was added to the mixture for recrystallization. After filtration, 554g of off-white solid intermediate product B-1 was obtained. It was used directly in the next step without purification.

[0026] S3: 363g of intermediate product B-1 was added to the intermediate product A-1 solution prepared in step S1, stirred at room temperature for 4 hours, the organic phase was washed with water, and the organic phase was purified by column chromatography to obtain 524g of target product C-1, with a total yield of 71.4%. The product purity was determined to be 99.7%. : δ6.13 (t, 1H), δ5.61 (p, 1H), δ5.24 (s, 1H), δ4.90 (m, 1H), δ4.54 (t, 1H), δ4.30 (m, 5H), δ3.51 (td, 2H), δ1.95 (t, 3H).

[0027]

Example 2

[0028] S1: Under nitrogen protection, 5L of dichloromethane and 656g of bis(2,2,2-trifluoroethyl) carbonate were added to a 20L reactor equipped with a mechanical stirrer, a constant pressure dropping funnel and a thermometer. Then, 311g of glyceryl carbonate was added to the constant pressure dropping funnel and added dropwise into the reactor over 1-2 hours. After the addition was completed, the temperature was controlled at 15-20℃ and stirred for 24 hours. The mixture was then washed with water to obtain a solution containing intermediate product A-2.

[0029] S2: Under nitrogen protection, 576g of acryloyl chloride and 400g of ethanolamine hydrochloride were added to a 2L reactor equipped with a mechanical stirrer, a constant pressure dropping funnel and a thermometer. The mixture was stirred at 90℃ for 4 hours. After cooling to room temperature, tetrahydrofuran was added to the mixture for recrystallization. After filtration, 522g of off-white solid intermediate product B-2 was obtained. It was not purified and was used directly for the next step.

[0030] S3: Intermediate product B-2 (332 g) was added to the intermediate product A-2 solution prepared in step S1. The mixture was stirred at room temperature for 4 hours. The organic phase was washed with water and purified by column chromatography to obtain 439 g of the target product C-2, with a total yield of 64.9%. The purity of the product was determined to be 99.5%. : δ7.5 (t, 1H), δ6.44 (dd, 1H), δ6.15 (dd, 1H), δ5.88 (dd, 1H), δ5.0 (m, 1H), δ4.6-4.0 (m, 6H), δ3.3-3.1(m, 2H).

[0031]

Example 3

[0032] S1: Under nitrogen protection, 5L of dichloromethane and 470g of carbonyl diimidazole were added to a 20L reactor equipped with a mechanical stirrer, a constant pressure dropping funnel and a thermometer. Then, 305g of 5-(hydroxymethyl)dihydrofuran-2(3H)-one was added to the constant pressure dropping funnel and added dropwise into the reactor over 1-2 hours. After the addition was completed, the temperature was controlled at 15-20℃ and stirred for 24 hours. The mixture was then washed with water to obtain a solution containing intermediate product A-3.

[0033] S2: Under nitrogen protection, 665g of methacryloyl chloride and 400g of ethanolamine hydrochloride were added to a 2L reactor equipped with a mechanical stirrer, a constant pressure dropping funnel and a thermometer. The mixture was stirred at 90℃ for 4 hours. After cooling to room temperature, tetrahydrofuran was added to the mixture for recrystallization. After filtration, 599g of off-white solid intermediate product B-1 was obtained. It was not purified and was used directly for the next step.

[0034] S3: Intermediate product B-1 was added to the intermediate product A-3 solution prepared in step S1, stirred at room temperature for 4 hours, the organic phase was washed with water, and the organic phase was purified by column chromatography to obtain 456 g of target product C-3, with a total yield of 67.7%. The product purity was determined to be 99.7%. 1 H NMR (500 Mhz, CDCl3): δ5.96 (dq, 1H), δ5.65 (dq, 1H), δ5.45 (t, 1H), δ4.97 (m, 1H), δ4.31(dd, 2H), δ4.26-4.05 (m, 2H), δ3.50(dt, 2H), δ2.39(t, 2H), δ2.27-2.02(m, 2H), δ1.93 (dd, 3H).

[0035]

Example 4

[0036] S1: Under nitrogen protection, 5L of dichloromethane and 476g of carbonyl di(1,2,4-triazole) were added to a 20L reactor equipped with a mechanical stirrer, a constant pressure dropping funnel and a thermometer. Then, 305g of 3-hydroxymethyl-4-butyrolactone was added to the constant pressure dropping funnel and added dropwise into the reactor over 1-2 hours. After the addition was completed, the temperature was controlled at 15-20℃ and stirred for 24 hours. The mixture was then washed with water to obtain a solution containing intermediate product A-4.

[0037] S2: Under nitrogen protection, 665g of methacryloyl chloride and 457g of 3-amino-1-propanol hydrochloride were added to a 2L reactor equipped with a mechanical stirrer, a constant pressure dropping funnel, and a thermometer. The mixture was stirred at 90℃ for 4 hours. After cooling to room temperature, tetrahydrofuran was added for recrystallization. After filtration, 501g of off-white solid intermediate product B-3 was obtained. It was used directly in the next step without purification.

[0038] S3: Intermediate product B-3 was added to the intermediate product A-4 solution prepared in step S1, stirred at room temperature for 4 hours, the organic phase was washed with water, and the organic phase was purified by column chromatography to obtain 519 g of target product C-4, with a total yield of 70.9%. The product purity was determined to be 99.7%. 1 H NMR (500 Mhz, CDCl3): δ5.80 (dq, 1H), δ5.73 (dq, 1H), δ5.13 (t, 1H), δ4.29 (d, 2H), δ4.25-4.04(m, 4H), δ3.25 (qd, 2H), δ2.67(m, 1H), δ2.62-2.30(m, 2H), δ2.01(q, 2H), δ1.93 (dd, 3H).

[0039] As can be seen, the method for synthesizing novel acrylate monomers containing bifunctional structures provided by this invention is mild, simple to operate, easy to control and realize, easy to industrialize, and the resulting product has a purity of over 99% and no residual heavy metal ions. It can be directly used in the fields of lithium batteries, polymer modification, adhesives, and solid electrolyte polymer monomers.

Claims

1. A method for synthesizing a novel acrylate monomer with a bifunctional structure, characterized in that, Includes the following steps: S1: An ester-containing alcohol compound (compound I) is reacted with a carbonylating agent (compound II) to give intermediate product A; S2: An acidified alkanolamine compound (compound III) reacts with an acryloyl reagent (compound IV) to give intermediate product B; S3: The intermediate product A obtained in step S1 reacts with the intermediate product B obtained in step S2 to obtain the target product C, which is a novel acrylate monomer with a bifunctional structure. ； Wherein, R1 is a hydrogen or hydrocarbon group, R2 is an organic group containing an ester group, m is an integer ≥1, R3 and R4 are independently selected from at least one of aryloxy groups, halooxy groups or nitrogen-containing heterocycles, R5 is a hydrocarbon group, and L is selected from at least one of halogen atoms, hydroxyl groups or hydrocarbon groups.

2. The method for synthesizing the novel acrylate monomer with a bifunctional structure according to claim 1, characterized in that, R1 is selected from hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, m is selected from an integer of 1 to 6, and R2 is selected from at least one of cyclic carbonate group, cyclic sulfite group, cyclic carboxylic acid ester group, linear carbonate group, linear sulfite group, or linear carboxylic acid ester group.

3. The method for synthesizing the novel acrylate monomer with a bifunctional structure according to claim 2, characterized in that, The structural formula of compound I is selected from , , , , , , or At least one of them; wherein R6 is a hydrocarbon group.

4. The method for synthesizing the novel acrylate monomer with a bifunctional structure according to claim 1, characterized in that, R3 and R4 are independently selected from at least one of phenoxy, pentafluorophenoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2,2,3,3-tetrafluoropropoxy, 2,2,3,3,3-pentafluoropropoxy, hexafluoroisopropoxy, perfluorobutoxy, (2-perfluorobutyl)ethoxy, trichloromethoxy, 2,2,2-trichloroethoxy, imidazolyl, 1,2,4-triazolyl or succinimideoxy.

5. The method for synthesizing the novel acrylate monomer with a bifunctional structure according to claim 1, characterized in that, In step S1, the molar ratio of the ester-containing alcohol compound (compound I) to the carbonylating agent (compound II) is 0.5~5:1, and the reaction temperature is 10~35℃.

6. The method for synthesizing the novel acrylate monomer with a bifunctional structure according to claim 1, characterized in that, In step S2, the alkanolamine compound (compound III) is acidified with hydrochloric acid, sulfuric acid or phosphoric acid to form an alkanolamine salt.

7. The method for synthesizing the novel acrylate monomer with a bifunctional structure according to claim 6, characterized in that, The alcoholamine salt is selected from at least one of ethanolamine hydrochloride, ethanolamine sulfate, ethanolamine phosphate, 3-amino-1-propanol hydrochloride, 3-amino-1-propanol sulfate, and 3-amino-1-propanol phosphate.

8. The method for synthesizing the novel acrylate monomer with a bifunctional structure according to claim 1, characterized in that, In step S2, the molar ratio of the alkanolamine compound (compound III) to the acryloyl reagent (compound IV) is 1:1~5, and the reaction temperature is 0~140℃.

9. The method for synthesizing the novel acrylate monomer with a bifunctional structure according to claim 1, characterized in that, In step S3, the molar ratio of intermediate product B to intermediate product A is 1:1~5, and the reaction temperature is 0~120℃.

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