WO2020150969A1 - Diallyl phtalate monomer synthesis method - Google Patents

Abstract

The present invention provides a diallyl phtalate monomer synthesis method, and belongs to the novel technical field of preparation of high molecular weight monomer by polymerization. An acrylate monomer having a phthalonitrile structure is prepared by introducing a cross-linkable and coordinated phhtalonitrile structure into a free-radically polymerizable acrylic monomer. Advantageously, the structure is characterized in that: 1. The phthalonitrile structure can form covalent and reversible coordination bonds through thermal crosslinking or coordination with transition metal salt. In the molecular structure into which a polymer has been introduced, a stimuli response material such as self-healing or intelligent material can be formed under thermochemical stimuli, spontaneous crosslinking or decrosslinking through mechanical or physical properties, such as color change. 2. Since the phthalocyanine structure formed by nitrile and crosslinking shows good biocompatibility, the monomer also has a wide application prospect in the field of biopolymers.

Description

Method for synthesizing phthalonitrile type acrylic ester monomer Technical field

The invention belongs to the technical field of preparation of novel polymer polymer monomers, and relates to a method for synthesizing phthalonitrile type acrylic ester monomers.

Background technique

Polyacrylate resin is a general-purpose linear polymer material with excellent processing, mechanical and optical properties and good chemical stability. It is widely used in medical, machinery, automobile, electronics, intelligence, shipbuilding, and other material fields .

Polyacrylate resin is a kind of linear polymer obtained by homo (co)polymerization of monomers containing acrylates. Since acrylic acid monomers are easy to chemically modify, they have been widely used in the field of smart materials in recent years. Yang et al. synthesized acrylate monomers containing terpyridine structure. Due to the presence of terpyridine, polymer monomers can coordinate with transition metal salts to obtain reversible crosslinked polymers. The material has good shape memory properties (AngewandteChemie-International Edition 2017,59(41),12599-12602.); Bode et al. used similar polymers with cobalt chloride as the coordination core, and the cross-linked polymer developed by Used as a self-healing material (Journal of Materials Chemistry A 2015, 3(44), 22145-22153.). Kumpfer et al. used the dibenzimidazole bipyridine structure as a ligand to prepare a reversible cross-linked polyacrylate resin. The material has good self-healing properties (Journal of the American Chemical Society 2011, 133(32), 12866-12874. ). However, the preparation process of the above-mentioned pyridyl-containing acrylate monomer is complicated, and the purification process is complicated, and it is difficult for commercial application. Phthalocyanine is a kind of strong polar group, which can form complexes containing phthalocyanine structure with more than 70 transition metal salts, thereby forming reversible coordination bonds (the latest research progress of high-performance resin matrix. Aerospace material technology 2012, (04), 1-6); It can also form permanent covalent bonds with organic diamines under heating conditions to form a cross-linked structure (Journal of Macromolecular Science: Part A-Chemistry: Pure and Applied Chemistry1982, A18(6) ), 931-937.). Phthalocyanine can also be used to prepare phthalocyanine dyes, which are used in electrode materials or storage materials, with high conversion rate and reusability (Journal of Materials Research 2011, 26(18), 2369-2372; Advanced Materials 2008 , 20(9), 1766-1771.). Sastri et al. used phthalonitrile resin and diamine to cross-link to prepare ultra-high temperature resistant polymers, which are used in aerospace, shipbuilding and other structural materials (Polymer 1996, 17, 816-822.).

In order to introduce reversible coordination covalent bonds in polyacrylate resins, based on the idea of exploring polyacrylate smart materials, the present invention introduces easy-to-crosslink coordinated phthalonitrile groups into the acrylic monomer skeleton in. Such monomers can be prepared by (controllable activity) free radical polymerization to prepare reversible cross-linked polyacrylates, and have good application prospects in the fields of smart materials and biopolymers.

Summary of the invention

The present invention provides a novel method for synthesizing and post-processing acrylate monomer containing phthalonitrile structure. The method is a one-step synthesis process, the reaction conditions are mild, the post-treatment process is simple and easy, and the commercial scale-up production is easy; the coordination reaction of phthalonitrile is easy to proceed, the selection range of transition metals is wide, and the stability is high. The monomer has broad application prospects in the fields of self-healing materials, smart materials and biopolymers.

The technical scheme of the present invention:

A method for synthesizing phthalonitrile type acrylic ester monomers, the steps are as follows:

Into the reactor where the air is purged with nitrogen, an acrylic monomer containing a hydroxyl structure, 4-nitrophthalonitrile, an inorganic base and an organic solvent, an acrylic monomer with a hydroxyl structure, and 4-nitro are sequentially added. The molar ratio of phthalonitrile and inorganic base is 1:1～2:0.5～3; among them, the preferred ratio is acrylic monomer with hydroxyl structure, 4-nitrophthalonitrile and inorganic base The molar ratio of the three is 1:1.2:0.7; the amount of organic solvent is 5-20 times (mL) of the mass (g) of the hydroxyl-containing acrylate monomer. The reaction is under the protection of nitrogen at room temperature (10-25°C) for 4 to 48 hours, then the heating is stopped, the product is poured into a 5wt.% NaOH aqueous solution, after filtration, the filter cake is collected and washed to neutral; After vacuum drying at 50°C for 24 hours, chloroform was used as the eluent, column chromatography was used to collect the main components; the product was collected by rotary evaporator and recrystallized with a recrystallization solvent at a ratio of 1:2-10g/mL. The product is obtained after filtration and vacuum drying.

The acrylate monomer containing a hydroxyl structure has the following general structural formula:

The inorganic base includes potassium carbonate, sodium carbonate or a mixture thereof.

The organic solvent includes: N-methylpyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, or a mixture of two or more of them.

The recrystallization solvent may include one or a mixture of methanol, ethanol, tetrahydrofuran, ethyl acetate and the like.

The beneficial effects of the present invention:

(1) The reaction raw materials are readily available, the conditions are mild, the synthesis and post-treatment processes are simple and easy to operate, and it is easy to realize industrial production.

(2) The phthalonitrile structure is also contained in the polymer prepared by using the monomer as a raw material, the coordination reaction is easy to proceed, the selection range of transition metals is wide, and the stability is high.

(3) The potential application fields of the present invention include self-healing materials, smart materials and biopolymers.

Description of the drawings

Figure 1 is the infrared spectrum of a typical monomer.

Figure 2 is the H-NMR spectrum of a typical monomer.

Figure 3 is a C-NMR spectrum of a typical monomer.

Figure 4 is a DSC spectrum of a typical monomer.

detailed description

The specific embodiments of the present invention will be further described below in conjunction with the drawings and technical solutions.

Example 1

Into a three-necked flask purged with nitrogen gas was sequentially added 21.2mL of acrylic monomer HEMA containing a hydroxyl structure as shown in Figure 1, 4-nitrophthalonitrile NPh 10g, potassium carbonate 20g, N,N- Dimethylacetamide 200mL. Under the protection of nitrogen, the reaction was conducted at room temperature (25°C) for 48 hours, the heating was stopped, and the product was poured into a 5% by mass NaOH aqueous solution. After filtration, the filter cake was collected and washed to neutrality. After drying in a vacuum at 50°C for 24 hours, column chromatography was performed with chloroform as the eluent to collect the main components. Use a rotary evaporator to spin dry to collect the product, and recrystallize with tetrahydrofuran, the ratio is 1:10g/mL. After filtration and vacuum drying, the product was obtained with a yield of 71%.

The reaction formula of Example 1

Example 2

Into a three-necked flask purged with nitrogen, add 22.6mL of acrylate monomer HPBA containing hydroxyl structure as shown in Figure 1, 4-nitrophthalonitrile NPh 10.3g, potassium carbonate 20g, dimethyl Sulfoxide 200mL. The reaction is under the protection of nitrogen, and after 24 hours of reaction at 15°C, the product is poured into a 5% mass fraction of NaOH aqueous solution, after filtration, the filter cake is collected and washed to neutrality. After drying in a vacuum at 50°C for 24 hours, column chromatography was performed with chloroform as the eluent to collect the main components. The product was collected by spin-drying using a rotary evaporator and recrystallized with chloroform at a ratio of 1:3g/mL. After filtration and vacuum drying, the product was obtained with a yield of 64%.

The reaction formula of Example 2

Example 3

Into a three-necked flask purged with nitrogen, 4.0 g of hydroxyl-containing acrylic ester monomer HPBA, 4-nitrophthalonitrile NPh 1.1 g, potassium carbonate 2.2 g, and N-methylpyrrolidone 20 mL were sequentially added. The reaction was under the protection of nitrogen, and after 36 hours of reaction at 20°C, the product was poured into a 5% mass fraction of NaOH aqueous solution, after filtration, the filter cake was collected and washed to neutrality. After drying in a vacuum at 50°C for 24 hours, column chromatography was performed with chloroform as the eluent to collect the main components. Use a rotary evaporator to spin dry to collect the product, and recrystallize with ethanol, the ratio is 1:6g/mL. After filtration and vacuum drying, the product was obtained with a yield of 52%.

The reaction formula of Example 3.

Example 4

To a three-necked flask purged with nitrogen, add 4.2g of HPMA monomer containing hydroxyl structure, 4-nitrophthalonitrile NPh 1.1g, sodium carbonate 2.2g, and N,N-dimethyl. Acetamide 20mL. The reaction was under the protection of nitrogen, and after 48 hours of reaction at 10°C, the product was poured into a 5% mass fraction of NaOH aqueous solution, after filtration, the filter cake was collected and washed to neutrality. After drying in a vacuum at 50°C for 24 hours, column chromatography was performed with chloroform as the eluent to collect the main components. The product was collected by rotary evaporator and recrystallized with methanol at a ratio of 1:1 g/mL. After filtration and vacuum drying, the product was obtained with a yield of 78%.

The reaction formula of Example 3.

Claims (8)

1. A method for synthesizing phthalonitrile-type acrylate monomers, which is characterized in that the steps are as follows:

   Into the reactor where the air is purged with nitrogen, an acrylic monomer containing a hydroxyl structure, 4-nitrophthalonitrile, an inorganic base and an organic solvent, an acrylic monomer with a hydroxyl structure, and 4-nitro are sequentially added. The molar ratio of phthalonitrile and inorganic base is 1:1～2:0.5～3; the amount of organic solvent mL is 5～20 times of the mass g of acrylic monomer containing hydroxyl structure; the reaction is in nitrogen Under protection, after reacting at 10-25℃ for 4～48 hours, stop heating, pour the product into 5wt.% NaOH aqueous solution, after filtration, collect filter cake and wash to neutral; vacuum 50℃ After drying for 24 hours, use chloroform as the eluent, column chromatography to collect the main components; use a rotary evaporator to spin dry to collect the product, and recrystallize with a recrystallization solvent, the ratio is 1: 2 ~ 10g/mL; The product is obtained after vacuum drying;

   The acrylate monomer containing a hydroxyl structure has the following general structural formula:

   
2. The synthesis method according to claim 1, characterized in that the inorganic alkali potassium carbonate and/or sodium carbonate.
3. The synthetic method according to claim 1 or 2, wherein the organic solvent is N-methylpyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylformamide, One or two or more of the base sulfoxides are mixed.
4. The synthesis method according to claim 1 or 2, wherein the recrystallization solvent is one or a mixture of two or more of methanol, ethanol, tetrahydrofuran, and ethyl acetate.
5. The synthesis method according to claim 3, wherein the recrystallization solvent is one or a mixture of two or more of methanol, ethanol, tetrahydrofuran, and ethyl acetate.
6. The synthesis method according to claim 1, 2 or 5, characterized in that the molar ratio of the acrylic monomer with hydroxyl structure, 4-nitrophthalonitrile and inorganic base is 1: 1.2: 0.7.
7. The synthesis method according to claim 3, characterized in that the molar ratio of the acrylic monomer of the hydroxyl structure, 4-nitrophthalonitrile and the inorganic base is 1:1.2:0.7.
8. The synthesis method according to claim 4, characterized in that the molar ratio of the acrylic monomer of the hydroxyl structure, 4-nitrophthalonitrile and the inorganic base is 1:1.2:0.7.

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