CN112574707A - Vacuum environment crack repairing agent and preparation method thereof - Google Patents
Vacuum environment crack repairing agent and preparation method thereof Download PDFInfo
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- CN112574707A CN112574707A CN202011474983.4A CN202011474983A CN112574707A CN 112574707 A CN112574707 A CN 112574707A CN 202011474983 A CN202011474983 A CN 202011474983A CN 112574707 A CN112574707 A CN 112574707A
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- aminoethyl piperazine
- vacuum environment
- epoxy resin
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- preparation
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5046—Amines heterocyclic
- C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
- C08G59/5073—Amines heterocyclic containing only nitrogen as a heteroatom having two nitrogen atoms in the ring
Abstract
The invention discloses a vacuum environment crack repairing agent and a preparation method thereof, wherein the preparation method comprises the following steps: (1) adding N-aminoethyl piperazine into a three-neck flask, and adding weak acid to perform amino protection on the N-aminoethyl piperazine. Wherein the weak acid is carbonic acid or oxalic acid, and the molar ratio of the N-aminoethyl piperazine to the weak acid is 2 (1-1.3). (2) Dissolving epoxy resin E44 in an organic solvent, dispersing N-aminoethyl piperazine protected by amino group in the organic solvent by using an emulsifier, and stirring to obtain the vacuum environment crack healant. Wherein the organic solvent is toluene, the addition amount is 30 wt%, the mass ratio of the epoxy resin E44 to the amino-protected N-aminoethyl piperazine is 100 (20-30), the emulsifier is Span-80, and the addition amount is 0.1-0.2 wt%. The vacuum environment crack repairing agent has stable property at normal temperature, and the N-aminoethyl piperazine protected amino group is deprotected along with the reduction of pressure, so that the epoxy resin is cured, and the effect of repairing cracks is achieved.
Description
Technical Field
The invention relates to preparation and application of a repairing agent, in particular to a vacuum environment crack repairing agent and a preparation method thereof.
Background
Factory equipment is very easy to damage due to reasons such as narrow space, misoperation and the like in the using process, and the replacement of instruments can cause resource waste and economic loss, so that the repair materials are produced at the right moment. However, the existing repair materials in the market have more use limiting factors, cannot play a role in some low-pressure or vacuum environments, and cannot meet the operation requirements of some special environments. For example, the use of a freeze dryer requires a vacuum environment, but the existing repair materials cannot be repaired under such a condition.
Disclosure of Invention
In order to solve the problems of repair materials in the prior art, the invention provides a vacuum environment crack repair agent and a preparation method thereof. Can be used for repairing cracks by expanding the range of the traditional repairing agent at present. The repairing agent is stable in property and can not be cured at normal temperature without using a solid repairing material or a soft material, and is coated on a crack, and when the pressure is reduced or the vacuum condition is adopted, the repairing agent can be automatically cured to repair the crack.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a vacuum environment crack repairing agent comprises viscous liquid prepared from amino-protected N-aminoethyl piperazine, an emulsifier, epoxy resin and an organic solvent;
the amino-protected N-aminoethyl piperazine is formed by adding a weak acid into N-aminoethyl piperazine, wherein the molar ratio of the N-aminoethyl piperazine to the weak acid is 2 (1-1.3);
the addition amount of the organic solvent is 30 wt%; the mass ratio of the epoxy resin to the amino-protected N-aminoethyl piperazine is 100 (20-30), and the addition amount of the emulsifier is 0.1-0.2 wt%.
A preparation method of a crack repairing agent in a vacuum environment comprises the following steps:
adding a weak acid to the N-aminoethylpiperazine;
dissolving epoxy resin E44 in an organic solvent, dispersing N-aminoethyl piperazine in the organic solvent by using an emulsifier, and stirring to obtain the crack repairing agent in the vacuum environment.
As a further improvement of the invention, the weak acid is carbonic acid or oxalic acid.
According to a further improvement of the invention, the molar ratio of the N-aminoethyl piperazine to the weak acid is 2 (1-1.3).
As a further improvement of the invention, the organic solvent is toluene and the amount added is 30 wt%.
According to a further improvement of the invention, the mass ratio of the epoxy resin E44 to the amino-protected N-aminoethylpiperazine is 100 (20-30).
As a further improvement of the invention, the emulsifier is Span-80, and the addition amount is 0.1-0.2 wt%.
As a further improvement of the present invention, the epoxy resin is epoxy resin E44.
Compared with the prior art, the invention has the following advantages:
compared with the traditional repairing system added with a solid material for bonding, the preparation method provided by the invention utilizes the viscous liquid prepared by dispersing the N-aminoethyl piperazine containing the curing inhibitor in the organic solvent dissolved with the epoxy resin E44 through the emulsifier, the liquid has stable property at normal temperature, the liquid is smeared at the crack, and the liquid can be cured automatically when the pressure is reduced or in a vacuum environment, so that the crack repairing effect is realized. The repairing agent has the characteristics of convenient smearing and low-pressure automatic curing, so that the repairing agent is suitable for repairing cracks in various vacuum environments. Meanwhile, the problems of inconvenient operation, material waste and the like are solved. Because the system is viscous liquid, the adhesive can be effectively adhered at the crack and cannot easily fall off, and the problems existing in the traditional repairing system at the present stage are solved.
According to the vacuum environment crack healant system prepared by the invention, the amino group of the N-aminoethyl piperazine is protected by the curing agent, so that the curing effect of the curing agent on the epoxy resin E44 is delayed, the protected amino group is deprotected in a low-pressure or vacuum environment, the epoxy resin E44 is cured, the crack repairing effect is realized, and the range of the traditional equal-solid repairing material at the present stage can be enlarged.
Description of the drawings:
FIG. 1 is a schematic of the synthesis and cure route for a vacuum environment fracture repair agent obtained in example 4;
FIG. 2 is a graph showing the shear strength and compressive strength of a vacuum environment fracture healant obtained in example 4;
Detailed Description
The technical solution in the embodiments of the present invention will be clearly and completely described below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention relates to a preparation method of a vacuum environment crack healant, wherein a vacuum environment crack healant system contains a viscous liquid prepared by dispersing N-aminoethyl piperazine of a curing inhibitor in an organic solvent dissolved with epoxy resin E44 through an emulsifier, wherein the N-aminoethyl piperazine is subjected to amino protection through a weak acid, the weak acid is carbonic acid or oxalic acid, the molar ratio of the N-aminoethyl piperazine to the weak acid is 2 (1-1.3), the emulsifier is Span-80, and the addition amount is 0.1-0.2 wt%.
The principle is as follows: the amino protection is carried out on curing agent N-aminoethyl piperazine by weak acid, so that the curing process of epoxy resin is delayed, the amino protected N-aminoethyl piperazine is dispersed in a solvent dissolved with epoxy resin E44 through an emulsifier to form a viscous liquid to prepare the vacuum environment crack repairing agent, the vacuum environment crack repairing agent has stable property at normal temperature, the N-aminoethyl piperazine protected amino is deprotected along with the reduction of pressure, the epoxy resin is cured, and the effect of repairing cracks is achieved.
N-aminoethyl piperazine carries out amino protection through weak acid, and can automatically carry out deprotection under low pressure or vacuum conditions, wherein the deprotection mechanism is as follows:
the protection-deprotection and curing mechanism is as follows:
specifically, the preparation of the vacuum environment crack healant comprises the following steps:
(1) adding N-aminoethyl piperazine into a three-neck flask, and adding weak acid to perform amino protection on the N-aminoethyl piperazine. Wherein the weak acid is carbonic acid or oxalic acid, and the molar ratio of the N-aminoethyl piperazine to the weak acid is 2 (1-1.3).
(2) Dissolving epoxy resin E44 in an organic solvent, dispersing N-aminoethyl piperazine protected by amino group in the organic solvent by using an emulsifier, and stirring to obtain the vacuum environment crack healant. Wherein the organic solvent is toluene, the addition amount is 30 wt%, the mass ratio of the epoxy resin E44 to the amino-protected N-aminoethyl piperazine is 100 (20-30), the emulsifier is Span-80, and the addition amount is 0.1-0.2 wt%.
The vacuum environment crack healer has stable property at normal temperature, and can be gradually polymerized and cured to generate cured resin when the pressure is reduced or under a vacuum condition, so that the effect of repairing cracks is achieved.
The vacuum environment crack healant can enlarge the range of solid repairing materials in the traditional repairing system at present, and can be applied to crack repair in a low-pressure environment or a vacuum operation environment.
The invention is further illustrated by the following specific examples and figures:
example 1
Adding 25.8g (0.2mol) of N-aminoethyl piperazine into a three-neck flask, then adding 6.2g (0.1mol) of oxalic acid into the three-neck flask, stirring for 15min to obtain amino-protected N-aminoethyl piperazine, then adding 70g of epoxy resin E44 into 30g of toluene solvent, then adding 14g of amino-protected N-aminoethyl piperazine, dropwise adding 0.1g of Span-80 emulsifier, and stirring for 1h to obtain a stable viscous liquid, namely the vacuum environment crack repairing agent.
Example 2
Adding 25.8g (0.2mol) of N-aminoethyl piperazine into a three-neck flask, then adding 6.2g (0.1mol) of oxalic acid into the three-neck flask, stirring for 15min to obtain amino-protected N-aminoethyl piperazine, then adding 70g of epoxy resin E44 into 30g of toluene solvent, then adding 17.5g of amino-protected N-aminoethyl piperazine, dropwise adding 0.1g of Span-80 emulsifier, and stirring for 1h to obtain a stable viscous liquid, namely the vacuum environment crack repairing agent.
Example 3
Adding 25.8g (0.2mol) of N-aminoethyl piperazine into a three-neck flask, then adding 6.2g (0.1mol) of oxalic acid into the three-neck flask, stirring for 15min to obtain amino-protected N-aminoethyl piperazine, then adding 70g of epoxy resin E44 into 30g of toluene solvent, then adding 21g of amino-protected N-aminoethyl piperazine, dropwise adding 0.2g of Span-80 emulsifier, and stirring for 1h to obtain a stable viscous liquid, namely the vacuum environment crack repairing agent.
Example 4
Adding 25.8g (0.2mol) of N-aminoethyl piperazine into a three-neck flask, then adding 6.82g (0.1mol) of oxalic acid into the three-neck flask, stirring for 15min to obtain amino-protected N-aminoethyl piperazine, then adding 70g of epoxy resin E44 into 30g of toluene solvent, then adding 14g of amino-protected N-aminoethyl piperazine, dropwise adding 0.1g of Span-80 emulsifier, and stirring for 1h to obtain a stable viscous liquid, namely the vacuum environment crack repairing agent.
Example 5
Adding 25.8g (0.2mol) of N-aminoethyl piperazine into a three-neck flask, then adding 6.82g (0.1mol) of oxalic acid into the three-neck flask, stirring for 15min to obtain amino-protected N-aminoethyl piperazine, then adding 70g of epoxy resin E44 into 30g of toluene solvent, then adding 17.5g of amino-protected N-aminoethyl piperazine, dropwise adding 0.2g of Span-80 emulsifier, and stirring for 1h to obtain a stable viscous liquid, namely the vacuum environment crack repairing agent.
Example 6
Adding 25.8g (0.2mol) of N-aminoethyl piperazine into a three-neck flask, then adding 7.44g (0.1mol) of oxalic acid into the three-neck flask, stirring for 15min to obtain amino-protected N-aminoethyl piperazine, then adding 70g of epoxy resin E44 into 30g of toluene solvent, then adding 14g of amino-protected N-aminoethyl piperazine, dropwise adding 0.1g of Span-80 emulsifier, and stirring for 1h to obtain a stable viscous liquid, namely the vacuum environment crack repairing agent.
Example 7
Adding 25.8g (0.2mol) of N-aminoethyl piperazine into a three-neck flask, then adding 7.44g (0.1mol) of oxalic acid into the three-neck flask, stirring for 15min to obtain amino-protected N-aminoethyl piperazine, then adding 70g of epoxy resin E44 into 30g of toluene solvent, then adding 21g of amino-protected N-aminoethyl piperazine, dropwise adding 0.2g of Span-80 emulsifier, and stirring for 1h to obtain a stable viscous liquid, namely the vacuum environment crack repairing agent.
Example 8
Adding 25.8g (0.2mol) of N-aminoethyl piperazine into a three-neck flask, then adding 8.06g (0.1mol) of oxalic acid into the three-neck flask, stirring for 15min to obtain amino-protected N-aminoethyl piperazine, then adding 70g of epoxy resin E44 into 30g of toluene solvent, then adding 14g of amino-protected N-aminoethyl piperazine, dropwise adding 0.1g of Span-80 emulsifier, and stirring for 1h to obtain a stable viscous liquid, namely the vacuum environment crack repairing agent.
Example 9
Adding 25.8g (0.2mol) of N-aminoethyl piperazine into a three-neck flask, then adding 8.06g (0.1mol) of oxalic acid into the three-neck flask, stirring for 15min to obtain amino-protected N-aminoethyl piperazine, then adding 70g of epoxy resin E44 into 30g of toluene solvent, then adding 21g of amino-protected N-aminoethyl piperazine, dropwise adding 0.2g of Span-80 emulsifier, and stirring for 1h to obtain a stable viscous liquid, namely the vacuum environment crack repairing agent.
In order to characterize the sensitivity of a vacuum environment crack healant to pressure, the crack healant system liquid prepared in example 4 was placed in a beaker, placed in a freeze-dryer, the pressure was reduced, and the phase change in the bottle was observed, with the following observations as shown in the table:
| pressure intensity (kPa) | 100 | 80 | 60 | 40 | 20 | 10 |
| Phase state | Liquid state | Liquid state | Liquid state | Solid state | Solid state | Solid state |
As can be seen from the table, the crack healer system appeared solid resin from 40KPa with decreasing pressure, and the curing of the solid resin became more apparent with decreasing pressure. This demonstrates that the fracture healer system has good pressure sensitive properties.
In order to characterize the shear and compressive properties of a vacuum environment fracture healant, the fracture healant system liquid prepared in example 4 was divided equally into four portions, and the resulting solid resins were tested for shear strength and compressive strength, respectively, under conditions of 10, 20, 30 and 40kPa, respectively, and the results are shown in fig. 2. As can be seen from the graph, the shear strength and the compressive strength become larger as the pressure is lowered, and when the pressure is 10kPa, the shear strength and the compressive strength become maximum, and are 21.3MPa and 23.7MPa, respectively.
The foregoing is a more detailed description of the invention and it is not intended that the invention be limited to the specific embodiments described herein, but that various modifications, alterations, and substitutions may be made by those skilled in the art without departing from the spirit of the invention, which should be construed to fall within the scope of the invention as defined by the appended claims.
Claims (8)
1. The vacuum environment crack repairing agent is characterized by comprising viscous liquid prepared from amino-protected N-aminoethyl piperazine, an emulsifier, epoxy resin and an organic solvent;
the amino-protected N-aminoethyl piperazine is formed by adding a weak acid into N-aminoethyl piperazine, wherein the molar ratio of the N-aminoethyl piperazine to the weak acid is 2 (1-1.3);
the addition amount of the organic solvent is 30 wt%; the mass ratio of the epoxy resin E44 to the amino-protected N-aminoethylpiperazine is 100 (20-30), and the addition amount of the emulsifier is 0.1-0.2 wt%.
2. A preparation method of a crack healant in a vacuum environment is characterized by comprising the following steps:
adding a weak acid to the N-aminoethylpiperazine;
dissolving epoxy resin in an organic solvent, dispersing N-aminoethyl piperazine in the organic solvent by using an emulsifier, and stirring to obtain the vacuum environment crack repairing agent.
3. The preparation and application of the novel vacuum environment healant as claimed in claim 2, wherein the weak acid is carbonic acid or oxalic acid.
4. The preparation and application of the vacuum environment crack healant are characterized in that the molar ratio of the N-aminoethyl piperazine to the weak acid is 2 (1-1.3).
5. The preparation and application of the vacuum environment crack healer according to claim 2, wherein the organic solvent is toluene, and the addition amount is 30 wt%.
6. The preparation and application of the vacuum environment crack healant are characterized in that the mass ratio of the epoxy resin E44 to the amino-protected N-aminoethyl piperazine is 100 (20-30).
7. The preparation and application of the vacuum environment crack healant as claimed in claim 2, wherein the emulsifier is Span-80, and the addition amount is 0.1-0.2 wt%.
8. The preparation and application of the vacuum environment crack healer according to claim 2, wherein the epoxy resin is epoxy resin E44.
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| CN112574707B CN112574707B (en) | 2022-09-27 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112442354A (en) * | 2020-12-15 | 2021-03-05 | 陕西科技大学 | Self-supporting fracturing system and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020164485A1 (en) * | 2001-02-26 | 2002-11-07 | Martin Laura Lee | Structural modified epoxy adhesive compositions |
| CN102627931A (en) * | 2012-03-23 | 2012-08-08 | 烟台德邦科技有限公司 | Pre-catalytic bonding glue and preparation method thereof |
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2020
- 2020-12-15 CN CN202011474983.4A patent/CN112574707B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020164485A1 (en) * | 2001-02-26 | 2002-11-07 | Martin Laura Lee | Structural modified epoxy adhesive compositions |
| CN102627931A (en) * | 2012-03-23 | 2012-08-08 | 烟台德邦科技有限公司 | Pre-catalytic bonding glue and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112442354A (en) * | 2020-12-15 | 2021-03-05 | 陕西科技大学 | Self-supporting fracturing system and preparation method and application thereof |
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