Propargyl ether resin with main chain containing pyridine ring aromatic bisphenol-type terminal and preparation method thereof

Abstract

The invention discloses a propargyl ether resin with a main chain containing a pyridine ring aromatic bisphenol-type terminal and a preparation method thereof. The resin is characterized in that the structural formula is shown in the specification and the resin is prepared by utilizing a phase transfer catalysis reaction method. The prepared resin structurally comprises a propargyl ether structure, and pyridine ring is introduced in the resin, so that the cured products of the resin are excellent in heat resistance. The propargyl ether resin disclosed by the invention can be applied to the fields of resin matrixes, high-temperature-resistant adhesives, special coatings, ceramic precursors, functional materials and the like.

Description

Technical field

[0001] The present invention relates to a high temperature resistant resin, more particularly, to a main chain containing pyridine ring aromatic bisphenol type terminal propargyl ether resin and a preparation method thereof. Background technique

[0002] In recent years, applications in aviation and electronics require thermosetting resin materials with special properties. However, most industrially produced thermosetting resins, such as epoxy resins and bismaleimide resins, are hydrophilic, and their high water absorption makes them have poor thermal-physical and mechanical properties, which makes these materials difficult to long-term under humid and hot conditions. use. The propargyl-terminated compounds developed by Stoil Dirlikov and others at the Coatings Research Institute of Eastern Michigan University show a wide range of reactivity and are easily polymerized by light, heat, and electricity. In addition, this compound will not release small molecules in...

Examples

Embodiment 1

[0068] 2,6-bis(4-propargyl-oxy-styryl)pyridine is prepared by phase transfer catalytic reaction method, the specific preparation steps are as follows:

[0069] (A) Prepare an aqueous sodium hydroxide solution with a concentration of 20% by mass;

[0070] (B) Mix 2,6-bis(4-hydroxystyryl)pyridine, aqueous sodium hydroxide solution and tetrabutylammonium bromide to obtain a mixed solution;

[0071] Dosage: Add 1000 mL of sodium hydroxide aqueous solution and 0.1 mol of tetrabutylammonium bromide to 1mol of 2,6-bis(4-hydroxystyryl)pyridine;

[0072] The structural formula of the 2,6-bis(4-hydroxystyryl)pyridine is as shown in formula 3:

[0073] Formula 3

[0074] In formula 3, HO is a hydroxyl group, OH is a hydroxyl group, the hydroxyl group is at the para position of the vinyl HCHC, A is the vinyl HCHC; Y is hydrogen.

[0075] The structure of Formula 3 in Example 1 can be prepared according to the method disclosed in the "NEW STYRYLPWRIDINE-BASED POLYESTERS AND POLYURETHANES" document. ...

Embodiment 2

[0105] The phase transfer catalytic reaction method is used to prepare 2,6-bis(4-propargyl-oxy-benzoyl)pyridine. The specific steps are as follows:

[0106] (A) Prepare an aqueous potassium hydroxide solution with a concentration of 15% by mass;

[0107] (B) Mix 2,6-bis(4-hydroxybenzoyl)pyridine, potassium hydroxide aqueous solution and benzyltrimethylammonium bromide to obtain a mixed solution;

[0108] Dosage: Add 1500 mL of potassium hydroxide aqueous solution and 0.12 mol of benzyltrimethylammonium bromide to 1mol of 2,6-bis(4-hydroxybenzoyl)pyridine;

[0109] The structural formula of the 2,6-bis(4-hydroxybenzoyl)pyridine is as shown in formula 5:

[0110] Formula 5

[0111] In formula 5, HO is a hydroxyl group, OH is a hydroxyl group, and a hydroxyl group is at a carbonyl group. The para position, A is the carbonyl group Y is hydrogen.

[0112] The structure of Formula 5 in Example 2 can be prepared according to the method disclosed in the document "Synthesis and Performance Rese...

Embodiment 3

[0142] The phase transfer catalytic reaction method is used to prepare 4-chloro-2,6-bis(4-propargyl-oxy-styryl)pyridine. The specific steps are as follows:

[0143] (A) Prepare an aqueous solution of sodium hydroxide with a concentration of 30% by mass;

[0144] (B) Combine 4-chloro-2,6-bis(4-hydroxystyryl)pyridine, aqueous sodium hydroxide and tetraethylammonium bromide to obtain a mixed solution;

[0145] Dosage: 500mL of sodium hydroxide aqueous solution and 0.008mol of tetraethylammonium bromide are added to 1mol of 4-chloro-2,6-bis(4-hydroxystyryl)pyridine;

[0146] The structural formula of the 4-chloro-2,6-bis(4-hydroxystyryl)pyridine is as shown in formula 7:

[0147] Formula 7

[0148] In formula 7, HO is a hydroxyl group, OH is a hydroxyl group, and the hydroxyl group is at the para position of vinyl-HC=HC-, A is vinyl*HC=HC-, and Y is chlorine.

[0149] The structure of Formula 7 in Example 3 can be prepared according to the method disclosed in the "NEW STYRYLPWRIDINE-BASED PO...

Technical field

[0001] The present invention relates to a high temperature resistant resin, more particularly, to a main chain containing pyridine ring aromatic bisphenol type terminal propargyl ether resin and a preparation method thereof. Background technique

[0002] In recent years, applications in aviation and electronics require thermosetting resin materials with special properties. However, most industrially produced thermosetting resins, such as epoxy resins and bismaleimide resins, are hydrophilic, and their high water absorption makes them have poor thermal-physical and mechanical properties, which makes these materials difficult to long-term under humid and hot conditions. use. The propargyl-terminated compounds developed by Stoil Dirlikov and others at the Coatings Research Institute of Eastern Michigan University show a wide range of reactivity and are easily polymerized by light, heat, and electricity. In addition, this compound will not release small molecules in...

Examples

Embodiment 1

[0068] 2,6-bis(4-propargyl-oxy-styryl)pyridine is prepared by phase transfer catalytic reaction method, the specific preparation steps are as follows:

[0069] (A) Prepare an aqueous sodium hydroxide solution with a concentration of 20% by mass;

[0070] (B) Mix 2,6-bis(4-hydroxystyryl)pyridine, aqueous sodium hydroxide solution and tetrabutylammonium bromide to obtain a mixed solution;

[0071] Dosage: Add 1000 mL of sodium hydroxide aqueous solution and 0.1 mol of tetrabutylammonium bromide to 1mol of 2,6-bis(4-hydroxystyryl)pyridine;

[0072] The structural formula of the 2,6-bis(4-hydroxystyryl)pyridine is as shown in formula 3:

[0073] Formula 3

[0074] In formula 3, HO is a hydroxyl group, OH is a hydroxyl group, the hydroxyl group is at the para position of the vinyl HCHC, A is the vinyl HCHC; Y is hydrogen.

[0075] The structure of Formula 3 in Example 1 can be prepared according to the method disclosed in the "NEW STYRYLPWRIDINE-BASED POLYESTERS AND POLYURETHANES" document. ...

Embodiment 2

[0105] The phase transfer catalytic reaction method is used to prepare 2,6-bis(4-propargyl-oxy-benzoyl)pyridine. The specific steps are as follows:

[0106] (A) Prepare an aqueous potassium hydroxide solution with a concentration of 15% by mass;

[0107] (B) Mix 2,6-bis(4-hydroxybenzoyl)pyridine, potassium hydroxide aqueous solution and benzyltrimethylammonium bromide to obtain a mixed solution;

[0108] Dosage: Add 1500 mL of potassium hydroxide aqueous solution and 0.12 mol of benzyltrimethylammonium bromide to 1mol of 2,6-bis(4-hydroxybenzoyl)pyridine;

[0109] The structural formula of the 2,6-bis(4-hydroxybenzoyl)pyridine is as shown in formula 5:

[0110] Formula 5

[0111] In formula 5, HO is a hydroxyl group, OH is a hydroxyl group, and a hydroxyl group is at a carbonyl group. The para position, A is the carbonyl group Y is hydrogen.

[0112] The structure of Formula 5 in Example 2 can be prepared according to the method disclosed in the document "Synthesis and Performance Rese...

Embodiment 3

[0142] The phase transfer catalytic reaction method is used to prepare 4-chloro-2,6-bis(4-propargyl-oxy-styryl)pyridine. The specific steps are as follows:

[0143] (A) Prepare an aqueous solution of sodium hydroxide with a concentration of 30% by mass;

[0144] (B) Combine 4-chloro-2,6-bis(4-hydroxystyryl)pyridine, aqueous sodium hydroxide and tetraethylammonium bromide to obtain a mixed solution;

[0145] Dosage: 500mL of sodium hydroxide aqueous solution and 0.008mol of tetraethylammonium bromide are added to 1mol of 4-chloro-2,6-bis(4-hydroxystyryl)pyridine;

[0146] The structural formula of the 4-chloro-2,6-bis(4-hydroxystyryl)pyridine is as shown in formula 7:

[0147] Formula 7

[0148] In formula 7, HO is a hydroxyl group, OH is a hydroxyl group, and the hydroxyl group is at the para position of vinyl-HC=HC-, A is vinyl*HC=HC-, and Y is chlorine.

[0149] The structure of Formula 7 in Example 3 can be prepared according to the method disclosed in the "NEW STYRYLPWRIDINE-BASED PO...

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