CN112457190B - Dimer acid modified polyether polyamine compound, preparation method and application thereof - Google Patents
Dimer acid modified polyether polyamine compound, preparation method and application thereof Download PDFInfo
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- CN112457190B CN112457190B CN202011166811.0A CN202011166811A CN112457190B CN 112457190 B CN112457190 B CN 112457190B CN 202011166811 A CN202011166811 A CN 202011166811A CN 112457190 B CN112457190 B CN 112457190B
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- C07C67/00—Preparation of carboxylic acid esters
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- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
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- C07C233/02—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
- C07C233/08—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with carbon atoms of carboxamide groups bound to acyclic carbon atoms of a saturated carbon skeleton containing rings
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- C07C69/608—Esters of carboxylic acids having a carboxyl group bound to an acyclic carbon atom and having a ring other than a six-membered aromatic ring in the acid moiety
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Abstract
The invention relates to a dimer acid modified polyether polyamine compound, a preparation method and application thereof, wherein the polyether polyamine compound has a novel structure, a multi-arm ether bond-containing alkyl chain exists, the flexibility is higher, meanwhile, six-membered aliphatic rings in molecules endow the polyether polyamine compound with higher temperature resistance, and the compound is used as a curing agent, has high curing activity and can realize room temperature curing; the invention also provides a preparation method of the dimer acid modified polyether polyamine compound, which comprises the steps of generating a hydrogenated dimethyl ester compound by the hydrogenated dimer acid under the action of a catalyst and methanol, and heating and aminolysis the hydrogenated dimethyl ester compound and terminal amino ether to prepare the polyether polyamine compound.
Description
Technical Field
The invention relates to polyether polyamine and a preparation method thereof, in particular to dimer acid modified polyether polyamine compound, a preparation method and application thereof, and belongs to the technical field of polymer synthesis.
Background
The polyether amine is a polyalkoxyolefin compound containing amino, and is often used as an epoxy resin curing agent and a toughening agent or used for reaction injection molding and polyurethane elastomer spray molding. In the current report, the structure of the polyether amine is mainly linear structures such as polyoxyethylene diamine, polyoxypropylene diamine, polyoxyethylene-oxypropylene-oxyethylene diamine, polyoxypropylene-oxyethylene-oxypropylene diamine, polysilane diamine, and the like, and the structure is single, so that the synergy of functionality and manufacturability is difficult to realize in practical engineering application. In addition, the synthesis method of the polyether amine mainly comprises an ammonolysis method, a leaving group method, a nitrile group hydrogenation method, an azide hydrogenation method, an epoxy compound ring opening method and the like, the reaction route is long, the used catalyst is expensive and high in danger, the reaction is usually carried out at high temperature and high pressure, the control is not easy, and the large-scale preparation is difficult to realize.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a dimer acid modified polyether polyamine compound and a preparation method thereof, wherein the structure of the polyether polyamine compound has a multi-arm ether bond-containing alkyl chain, so that the flexibility is higher, and meanwhile, six-membered aliphatic rings in molecules endow the polyether polyamine compound with higher temperature resistance; the raw materials used for synthesis are safe and easy to obtain, the reaction is simple, the route is short, and the reaction is mild.
The invention also aims to provide application of the dimer acid modified polyether polyamine compound.
The above purpose of the invention is mainly realized by the following technical scheme:
a dimer acid modified polyether polyamine compound, the structural formula of which is as follows:
wherein: m and o are integers of 0-12, n and p are integers of 0-14, R is CH 2 ，CH 2 CH 2 ，CH 2 CH 2 CH 2 Or CH 2 CH 2 CH 2 CH 2 X is CH 2 CH 2 ，CH 2 CH 2 CH 2 ，CH 2 CH 2 CH 2 CH 2 ，CH 2 CH 2 OCH 2 CH 2 ，CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 Or CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 。
A preparation method of dimer acid modified polyether polyamine compound comprises the following steps:
the method comprises the following steps of (1) generating a hydrogenated dimethyl ester compound (III) from hydrogenated dimer acid (II) under the action of a catalyst and methanol, and heating and aminolysis the hydrogenated dimethyl ester compound (III) and terminal aminoether (IV) to prepare polyether polyamine compound (I), wherein the specific reaction route is as follows:
wherein m and o in the structures of the compounds (I), (II) and (III) are integers of 0-12, n and p are integers of 0-14, and R is CH 2 ，CH 2 CH 2 ，CH 2 CH 2 CH 2 Or CH 2 CH 2 CH 2 CH 2 X is CH 2 CH 2 ，CH 2 CH 2 CH 2 ，CH 2 CH 2 CH 2 CH 2 ，CH 2 CH 2 OCH 2 CH 2 ，CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 Or CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 。
In the above method for producing a dimer acid-modified polyether polyamine compound, the hydrogenated dimer acid (ii): methanol: the molar ratio of the catalyst is 100: 200-40000: 2 to 10.
In the preparation method of the dimer acid modified polyether polyamine compound, the catalyst is concentrated sulfuric acid.
In the preparation method of the dimer acid modified polyether polyamine compound, the generated dimethyl hydride compound (III) is post-treated and then subjected to subsequent reaction, wherein the post-treatment method comprises the steps of distilling under reduced pressure, adding a saturated sodium bicarbonate solution at minus 4 ℃ to plus minus 4 ℃, stirring for 20-60 min, extracting with diethyl ether, washing with a saturated sodium chloride solution, and performing rotary evaporation to remove the solvent.
In the preparation method of the dimer acid modified polyether polyamine compound, the molar ratio of the hydrogenated dimethyl ester compound (III) to the terminal amino ether (IV) is 1: 1.6-2.4.
In the preparation method of the dimer acid modified polyether polyamine compound, the aminolysis reaction of the hydrogenated dimethyl ester compound (III) and the terminal amino ether (IV) is carried out in an argon environment at the temperature of 200-230 ℃.
In the preparation method of the dimer acid modified polyether polyamine compound, the method for post-treating the prepared polyether polyamine compound (I) is reduced pressure distillation, and the pressure is-0.08 to-0.10 MPa.
The dimer acid modified polyether polyamine compound is prepared by the preparation method.
In the application of the dimer acid modified polyether polyamine compound, the polyether polyamine compound is used as a curing agent.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention provides a novel dimer acid modified polyether polyamine compound, which is novel in structure, has a multi-arm ether bond-containing alkyl chain, is high in flexibility, and meanwhile, six-membered aliphatic rings in molecules endow the compound with high temperature resistance.
(2) The invention provides a novel preparation method of dimer acid modified polyether polyamine compound, which comprises the steps of generating hydrogenated dimethyl ester compound by hydrogenated dimer acid under the action of a catalyst and methanol, and preparing the polyether polyamine compound by heating and aminolysis of the hydrogenated dimethyl ester compound and terminal amino ether.
Drawings
FIG. 1 shows dimer acid-modified polyether polyamine curing agent provided in example 1 of the present invention 1 H NMR spectrum.
Detailed Description
The invention is described in further detail below with reference to the following figures and specific examples:
the invention provides a dimer acid modified polyether polyamine compound, which relates to the following molecular structure:
1. hydrogenated dimer acid (II) having the structure
Wherein m and o are integers of 0-12, and n and p are integers of 0-14.
2. A terminal amino ether (IV) having the structure
Wherein R is CH 2 ，CH 2 CH 2 ，CH 2 CH 2 CH 2 Or CH 2 CH 2 CH 2 CH 2 X is CH 2 CH 2 ，CH 2 CH 2 CH 2 ，CH 2 CH 2 CH 2 CH 2 ，CH 2 CH 2 OCH 2 CH 2 ，CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 Or CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 。
3. A dimethyl hydride compound (III) having the structure
Wherein m and o are integers of 0-12, and n and p are integers of 0-14.
4. Dimer acid modified polyether polyamine (I) with the structure of
Wherein m and o are integers of 0-12, n and p are integers of 0-14, and R is CH 2 ，CH 2 CH 2 ，CH 2 CH 2 CH 2 Or CH 2 CH 2 CH 2 CH 2 X is CH 2 CH 2 ，CH 2 CH 2 CH 2 ，CH 2 CH 2 CH 2 CH 2 ，CH 2 CH 2 OCH 2 CH 2 ，CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 Or CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 。
The invention provides a preparation method of dimer acid modified polyether polyamine, which comprises the following steps:
using hydrogenated dimer acid type raw material (II), generating corresponding hydrogenated dimethyl ester compound (III) under the action of a catalyst and methanol, and then heating and aminolysis the hydrogenated dimethyl ester compound (III) and terminal aminoether (IV) to prepare the polyamide compound (I).
Wherein m and o in the structures of the compounds (I), (II) and (III) are integers of 0-12, n and p are integers of 0-14, and R is CH 2 ，CH 2 CH 2 ，CH 2 CH 2 CH 2 Or CH 2 CH 2 CH 2 CH 2 X is CH 2 CH 2 ，CH 2 CH 2 CH 2 ，CH 2 CH 2 CH 2 CH 2 ，CH 2 CH 2 OCH 2 CH 2 ，CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 Or CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 。
Hydrogenation of dimer acid in the above reaction: methanol: the molar ratio of the catalyst is 100: (200-40000): (2-10).
The catalyst used in the above reaction is concentrated sulfuric acid.
The post-treatment method of the dimethyl hydride compound (III) in the reaction comprises the steps of carrying out reduced pressure distillation, adding a saturated sodium bicarbonate solution at 0 +/-4 ℃, stirring for 20-60 min, extracting with diethyl ether, washing with a saturated sodium chloride solution, and carrying out rotary evaporation on the solvent.
In the reaction, the molar ratio of the dimethyl hydride compound (III) to the terminal amino ether (IV) is 1 (1.6-2.4).
In the reaction, the reaction of the hydrogenated dimethyl ester compound (III) and the terminal amino ether (IV) is carried out in an argon atmosphere at the temperature of 200-230 ℃.
The post-treatment method of the dimer acid modified polyether polyamine prepared in the reaction is reduced pressure distillation, and the pressure is-0.08 to-0.10 MPa.
Example 1
After 1.2kg of hydrogenated dimer acid and 2L of methanol were stirred uniformly, 2.13mL of concentrated sulfuric acid was added at room temperature, the weight ratio of hydrogenated dimer acid: methanol: the molar ratio of concentrated sulfuric acid is 100: 2470: and 2, refluxing and stirring until the raw materials completely react. Distilling under reduced pressure to remove most of solvent, adding saturated sodium bicarbonate solution at 0 deg.C, stirring for 30min, extracting with diethyl ether, washing with saturated sodium chloride solution, and rotary evaporating solvent to obtain hydrogenated dimer acid dimethyl ester.
Mixing hydrogenated dimer acid dimethyl ester and diethylene glycol di (3-aminopropyl) ether at a molar ratio of 1:2, reacting at 220 ℃ under an argon atmosphere, and distilling off a byproduct at intervals of 2h under reduced pressure until the raw materials react completely to finally obtain the dimer acid modified polyether polyamine.
FIG. 1 shows dimer acid modified polyether polyamine curing agent provided in example 1 of the present invention 1 The H NMR spectrum showed that Δ 6.26ppm was assigned to the proton peak of the amino hydrogen in the (-CONH-) amide bond, Δ 3.69-3.49 ppm was assigned to the proton peak of the methylene hydrogen bonded to oxygen in the polyether chain, and Δ 3.35ppm was assigned to the (-CONHCH) 2 -) proton peak of methylene hydrogen attached to nitrogen, delta 2.79ppm was assigned to (-CH) 2 NH 2 ) The proton peak of the mid-methylene hydrogen, delta 2.14ppm, is attributed to (-CH) 2 Proton peak of methylene hydrogen at CONH-) carbonyl position, delta 1.7ppm is assigned toBelongs to a proton peak of methylene hydrogen connected with nitrogen, and delta 1.63-0.90 ppm belongs to a proton peak of hydrogen in an aliphatic chain. The dimer acid modified polyether polyamine with clear structure is proved to be obtained.
Example 2
After 1.2kg of hydrogenated dimer acid and 162mL of methanol were stirred uniformly, 2.13mL of concentrated sulfuric acid, hydrogenated dimer acid: methanol: the molar ratio of concentrated sulfuric acid is 100: 200: and 2, refluxing and stirring until the raw materials completely react. Distilling under reduced pressure to remove most of solvent, adding saturated sodium bicarbonate solution at 0 deg.C, stirring for 30min, extracting with diethyl ether, washing with saturated sodium chloride solution, and rotary evaporating solvent to obtain hydrogenated dimer acid dimethyl ester.
Mixing hydrogenated dimer acid dimethyl ester and ethylene glycol di (3-aminopropyl) ether in a molar ratio of 1:2, reacting at 220 ℃ in an argon environment, distilling off a by-product at intervals of 2h under reduced pressure until the raw materials react completely, and finally obtaining the dimer acid modified polyether polyamine.
Example 3
After 1.5kg of hydrogenated dimer acid and 1.42L of methanol were stirred uniformly, 8.0mL of concentrated sulfuric acid, hydrogenated dimer acid: methanol: the molar ratio of concentrated sulfuric acid is 100: 1400: and 6, refluxing and stirring until the raw materials completely react. Distilling under reduced pressure to remove most of solvent, adding saturated sodium bicarbonate solution at 0 deg.C, stirring for 60min, extracting with diethyl ether, washing with saturated sodium chloride solution, and rotary evaporating solvent to obtain hydrogenated dimer acid dimethyl ester.
The molar ratio of hydrogenated dimer acid dimethyl ester to ethylene glycol di (3-aminopropyl) ether is 1: and 2.4, mixing, reacting at 230 ℃ under an argon atmosphere, and distilling off a byproduct at intervals of 3h under reduced pressure until the raw materials react completely to finally obtain the dimer acid modified polyether polyamine.
Example 4
After 0.9kg of hydrogenated dimer acid and 1.52L of methanol were stirred uniformly, 8.0mL of concentrated sulfuric acid, hydrogenated dimer acid: methanol: the molar ratio of concentrated sulfuric acid is 100: 2500: and 10, refluxing and stirring until the raw materials completely react. Distilling under reduced pressure to remove most of solvent, adding saturated sodium bicarbonate solution at 0 deg.C, stirring for 20min, extracting with diethyl ether, washing with saturated sodium chloride solution, and rotary evaporating solvent to obtain dimethyl dimer acid.
The molar ratio of hydrogenated dimer acid dimethyl ester to ethylene glycol di (3-aminopropyl) ether is 1:1.6, mixing, reacting at 200 ℃ under an argon atmosphere, and distilling off by-products at intervals of 1h under reduced pressure until the raw materials react completely to finally obtain the dimer acid modified polyether polyamine.
The above description is only for the best mode of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Those skilled in the art will appreciate that the invention may be practiced without these specific details.
Claims (9)
1. A dimer acid modified polyether polyamine compound is characterized in that: the structural formula of the compound is as follows:
wherein: m and o are integers of 0-12, n and p are integers of 0-14, R is CH 2 ，CH 2 CH 2 ，CH 2 CH 2 CH 2 Or CH 2 CH 2 CH 2 CH 2 X is CH 2 CH 2 ，CH 2 CH 2 CH 2 ，CH 2 CH 2 CH 2 CH 2 ，CH 2 CH 2 OCH 2 CH 2 ，CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 Or CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 。
2. A preparation method of dimer acid modified polyether polyamine compound is characterized by comprising the following steps: the method comprises the following steps:
the method comprises the following steps of (1) generating a hydrogenated dimethyl ester compound (III) from hydrogenated dimer acid (II) under the action of a catalyst and methanol, and heating and aminolysis the hydrogenated dimethyl ester compound (III) and terminal aminoether (IV) to prepare polyether polyamine compound (I), wherein the specific reaction route is as follows:
wherein m and o in the structures of the compounds (I), (II) and (III) are integers of 0-12, n and p are integers of 0-14, and R is CH 2 ，CH 2 CH 2 ，CH 2 CH 2 CH 2 Or CH 2 CH 2 CH 2 CH 2 X is CH 2 CH 2 ，CH 2 CH 2 CH 2 ，CH 2 CH 2 CH 2 CH 2 ，CH 2 CH 2 OCH 2 CH 2 ，CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 Or CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 。
3. The method for preparing a dimer acid-modified polyether polyamine compound according to claim 2, characterized in that: the hydrogenated dimer acid (II): methanol: the molar ratio of the catalyst is 100: 200-40000: 2 to 10.
4. The method for preparing a dimer acid-modified polyether polyamine compound according to claim 2 or 3, wherein the dimer acid-modified polyether polyamine compound comprises: the catalyst is concentrated sulfuric acid.
5. The method for preparing a dimer acid-modified polyether polyamine compound according to claim 2, characterized in that: and (3) carrying out post-treatment on the generated dimethyl hydride compound (III) and then carrying out subsequent reaction, wherein the post-treatment method comprises the steps of distilling under reduced pressure, adding a saturated sodium bicarbonate solution at the temperature of minus 4 ℃ to plus 4 ℃, stirring for 20-60 min, extracting with diethyl ether, washing with a saturated sodium chloride solution, and carrying out rotary evaporation to remove the solvent.
6. The method for preparing a dimer acid-modified polyether polyamine compound according to claim 2, characterized in that: the molar ratio of the dimethyl hydride compound (III) to the terminal amino ether (IV) is 1: 1.6-2.4.
7. The method for preparing a dimer acid-modified polyether polyamine compound according to claim 2 or 6, wherein: and carrying out aminolysis reaction on the dimethyl hydride compound (III) and the terminal amino ether (IV) in an argon environment at the temperature of 200-230 ℃.
8. The method for preparing a dimer acid-modified polyether polyamine compound according to claim 2 or 6, wherein: the method for post-treating the polyether polyamine compound (I) is reduced pressure distillation, and the pressure is-0.08 to-0.10 MPa.
9. The use of the dimer acid-modified polyether polyamine compound of claim 1, wherein: the polyether polyamine compound is used as a curing agent.
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