阅读说明：本技术 一种用于双组份美缝剂的环氧树脂固化剂及其制备方法 (Epoxy resin curing agent for two-component seam beautifying agent and preparation method thereof ) 是由 王玉琪 蒲恒斐 刘扬 于 2020-09-29 设计创作，主要内容包括：本发明提供一种用于双组份美缝剂的环氧树脂固化剂及其制备方法。一种用于双组份美缝剂的环氧树脂固化剂及其制备方法,包括下述重量份的组分：环氧树脂100份,羟基胺40-60份,脂肪族多胺25-40份,酚类3-8份。(The invention provides an epoxy resin curing agent for a two-component seam beautifying agent and a preparation method thereof. An epoxy resin curing agent for a two-component seam beautifying agent and a preparation method thereof comprise the following components in parts by weight: 100 parts of epoxy resin, 40-60 parts of hydroxylamine, 25-40 parts of aliphatic polyamine and 3-8 parts of phenols.)

1. An epoxy resin curing agent for a two-component seam beautifying agent is characterized by comprising the following components in parts by weight: 100 parts of epoxy resin, 40-60 parts of hydroxylamine, 25-40 parts of aliphatic polyamine and 3-8 parts of phenols.

2. The epoxy resin curing agent for the two-component crack sealer according to claim 1, wherein the epoxy resin is glycidyl ether type epoxy resin, and the glycidyl ether type epoxy resin comprises bisphenol A type, bisphenol F type and phenolic aldehyde type epoxy resin.

3. The method of claim 2, wherein: the epoxy resin is bisphenol A type epoxy resin, and the epoxy value of the epoxy resin is 150-450.

4. The curing agent for epoxy resin of two-component seam beautifying agent according to claim 1, characterized in that the hydroxylamine is one or more selected from monoethanolamine, diethanolamine, triethanolamine, diisopropanolamine, m-hydroxy diphenylamine and 4-aminophenol.

5. The epoxy resin curing agent for the two-component crack sealer according to claim 1, wherein the aliphatic polyamine is any one or more of diethylenetriamine, triethylenetetramine and tetraethylenepentamine.

6. The curing agent for epoxy resin of two-component jointing agent according to claim 1, wherein the phenol is any one or more of nonylphenol, dodecylphenol, styrenated phenol.

7. The curing agent for the epoxy resin of the two-component crack sealer according to claim 1, wherein the type of the epoxy resin is E51, the hydroxylamine is preferably ethanolamine, the aliphatic polyamine is preferably diethylenetriamine, and the phenol is preferably dodecylphenol.

8. A preparation method of an epoxy resin curing agent for a two-component seam beautifying agent comprises the following steps:

step S1: adding monoethanolamine and diethylenetriamine into a reactor, starting cooling water and stirring, and stirring for 5min to ensure uniform mixing;

step S2: adding 1/3 epoxy resin at intervals of 20-30min under stirring according to the temperature of the reactor, and continuing stirring for 90min after the addition is finished;

step S3: stirring at 40Hz under vacuum condition of 60 deg.C and-0.09 MPa, and keeping the temperature for 60 min;

step S4: adding dodecylphenol, and stirring under vacuum at-0.09 MPa for 30 min;

step S5: and naturally cooling under stirring to obtain the epoxy resin curing agent product.

Technical Field

The invention relates to the technical field of decoration in the plastic industry and the building industry, in particular to a preparation method of a two-component epoxy type crack sealer curing agent.

Background

The two-component crack sealer on the market at present is an oily solvent-free epoxy resin system, namely comprising A, B components. The component A is generally filled into a transparent tube and comprises main film-forming substances, namely epoxy resin and auxiliary additives such as a filler, a diluent, a flow stopping agent and the like; the component B is a color tube and generally comprises a curing agent, a diluent, a filler, a thixotropic agent, a pigment and the like.

The curing agent is a key component for curing the epoxy resin, and is also called a hardener and a vulcanizing agent. The curing agent is widely used, and mainly includes amines (heterocyclic compounds containing an N atom such as imidazole) and acid anhydrides. The curing method mainly comprises room temperature curing and heating curing, wherein the room temperature curing temperature is generally 5-30 ℃, and the heating curing temperature is divided into medium temperature curing temperature (60-120 ℃) and high temperature curing temperature (120-. The epoxy resin curing agent of the two-component seam beautifying agent belongs to an amine room temperature curing agent.

The epoxy resin curing agent of the two-component seam beautifying agent in the current market mainly takes a compound type as a main component, and the difference of the raw and auxiliary materials and the difference of the formula cause that the seam beautifying agent product has poor quality stability, such as easy whitening. Meanwhile, in the prior art, the curing agent of the crack sealer is gelled during production or storage, loses fluidity and cannot be used.

Disclosure of Invention

The invention aims to provide a preparation method of an epoxy resin curing agent for a two-component seam beautifying agent, which avoids the phenomena of whitening of the seam beautifying agent and gelation during production or storage, and keeps the fluidity of the curing agent, so that the product stability is higher.

In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:

an epoxy resin curing agent for a two-component seam beautifying agent comprises the following components in parts by weight: 100 parts of epoxy resin, 40-60 parts of hydroxylamine, 25-40 parts of aliphatic polyamine and 3-8 parts of phenols.

As a preferred technical solution, the epoxy resin is glycidyl ether epoxy resin, and the glycidyl ether epoxy resin includes bisphenol a type, bisphenol F type and novolac type epoxy resin.

As a preferred technical scheme, the epoxy resin is bisphenol A type epoxy resin, and the epoxy value is 150-450.

The epoxy resin is bisphenol A type epoxy resin, and the epoxy value of the epoxy resin is 150-450.

In a preferable mode, the hydroxylamine is one or more of monoethanolamine, diethanolamine, triethanolamine, diisopropanolamine, m-hydroxy diphenylamine and 4-aminophenol.

In a preferable mode, the aliphatic polyamine is one or more of diethylenetriamine, triethylene tetramine and tetraethylene pentamine.

In a preferred mode, the phenols are any one or more of nonyl phenol, dodecyl phenol and styrenated phenol.

In a preferred embodiment, the epoxy resin is E51, the hydroxylamine is preferably ethanolamine, the aliphatic polyamine is preferably diethylenetriamine, and the phenol is preferably dodecylphenol.

A preparation method of an epoxy resin curing agent for a two-component seam beautifying agent comprises the following steps:

step S1: adding monoethanolamine and diethylenetriamine into a reactor, starting cooling water and stirring, and stirring for 5min to ensure uniform mixing;

step S2: adding 1/3 epoxy resin at intervals of 20-30min under stirring according to the temperature of the reactor, and continuing stirring for 90min after the addition is finished;

step S3: stirring at 40Hz under vacuum condition of 60 deg.C and-0.09 MPa, and keeping the temperature for 60 min;

step S4: adding dodecylphenol, and stirring under vacuum at-0.09 MPa for 30 min;

step S5: and naturally cooling under stirring to obtain the epoxy resin curing agent product.

The invention has the following action principle: according to the invention, monoethanolamine is firstly utilized to carry out ring-opening reaction on epoxy groups of the epoxy resin, so that the effect of chain extension on the epoxy resin is achieved, part of the epoxy groups are consumed, and a polyhydroxy epoxy compound is formed, thereby avoiding gelation of the epoxy resin during production or storage. And then, continuously carrying out ring-opening reaction on the residual epoxy group of the epoxy resin by using diethylenetriamine, reserving partial amino group, and then adding dodecylphenol for absorbing moisture and carbon dioxide in the air to ensure that the crack sealer is not whitened, and finally obtaining transparent pale yellow viscous odorless liquid, namely the epoxy resin curing agent of the two-component crack sealer.

The reason for whitening of the crack sealer is that water in the air reacts with carbon dioxide to generate carbonic acid, the carbonic acid or the carbon dioxide continuously reacts with the organic amine substance which is the effective component of the curing agent to generate ammonium carbonate, the effective component of the curing agent is consumed, the generated ammonium carbonate has poor compatibility with a system, is milky white, and can seriously cause the crack sealer not to be cured. The phenolic compound is added into the system to prevent or delay the occurrence of the active reaction.

The reason of curing agent gelation is that for amine curing agents, according to the chemical principle, active hydrogen on one curing agent amino consumes epoxy in one epoxy resin, and if the proportion of the epoxy and the active hydrogen is proper, macromolecules are formed by crosslinking to generate gel, so that the use value is lost; on the contrary, a suitable excess of amine compound is capable of both dissolving the epoxy amine adduct and playing the role of a curing agent.

As is well known, in the process of synthesizing the epoxy resin curing agent base resin of the two-component seam beautifying agent, the reaction temperature, the feeding sequence and the feeding mode have great influence on the state and the quality of a product. The invention adopts the method that the epoxy resin is added into the mixed solution of the ethanolamine and the diethylenetriamine in batches, and the reaction temperature is strictly controlled not to exceed 100 ℃ so as to ensure that the system has good fluidity and moderate viscosity.

In the present invention, ethanolamine is divided into three groups: monoethanolamine (primary amine), diethanol (secondary amine) amine and triethanolamine (tertiary amine). Aiming at an epoxy resin system, primary amine has the function of chain extension, secondary amine has the function of end capping, and tertiary amine has the function of a curing accelerator. The ideal primary amine chain extension equation is as follows:

likewise, the ideal chain extension equation for diethylenetriamine is as follows:

the purpose of chain extension is as follows: 1. the epoxy group of the bisphenol A epoxy resin is consumed in advance, and the system (crack sealer) can be cured at room temperature when the component A/the component B is 1/1 (volume ratio); 2. the viscosity of the system is increased, so that the viscosity of the group A is convenient to match, and the uniform mixing is ensured; 3. n-hydroxyethyl is introduced into the bisphenol A epoxy resin, so that the bisphenol A epoxy resin has the function of a curing accelerator and even directly participates in curing; 4. the volatility of ethanolamine and diethylenetriamine is reduced.

In addition, the addition of ethanolamine/diethanolamine to bisphenol A epoxy resins at elevated temperatures results in curing of the bisphenol A epoxy resins, but is relatively stable at room temperature.

Detailed Description

The invention discloses a shampoo containing traditional Chinese medicine components for preventing alopecia, which can be appropriately improved and realized by persons skilled in the art by taking the contents of the shampoo into consideration. It is expressly intended that all such similar substitutes and modifications which would be obvious to one skilled in the art are deemed to be included in the invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications in the methods and applications described herein, as well as other suitable variations and combinations, may be made to implement and use the techniques of this invention without departing from the spirit and scope of the invention.

In each of the following examples and comparative examples, the epoxy resin E51 was purchased from south china star synthetic materials ltd, ethanolamine was purchased from guangzhou excellence chemical engineering ltd, and diethylenetriamine was purchased from south china comet chemical product ltd; dodecylphenol was purchased from Shanghai Longfa chemical Co., Ltd.

Example 1

An epoxy resin curing agent for a two-component seam beautifying agent comprises the following components in parts by weight: 100 parts of epoxy resin, 40 parts of hydroxylamine, 25 parts of aliphatic polyamine and 3 parts of phenols.

The epoxy resin is E51, the hydroxylamine is monoethanolamine, the aliphatic polyamine is diethylenetriamine, and the phenol is dodecylphenol.

The preparation method of the curing agent in this embodiment includes the following steps: 1. adding ethanolamine and diethylenetriamine according to the weight parts in a reactor with heating and cooling, and stirring for 5 min; 2. adding one third of E51 epoxy resin every 20min while stirring; 3. after the feeding is finished, continuously stirring for 90 min; 4. heating to 60 deg.C, vacuum-maintaining at-0.09 MPa under stirring at 40Hz for 60 min; 5. adding the dodecyl phenol in parts by weight, and stirring for 30min under vacuum of-0.09 MPa; 6. naturally cooling under stirring, and discharging.

The product state of the curing agent obtained in this example was ungelled.

Example 2

An epoxy resin curing agent for a two-component seam beautifying agent comprises the following components in parts by weight: 100 parts of epoxy resin, 60 parts of hydroxylamine, 40 parts of aliphatic polyamine and 8 parts of phenols.

The epoxy resin is E51, the hydroxylamine is monoethanolamine, the aliphatic polyamine is diethylenetriamine, and the phenol is dodecylphenol.

The preparation method of the curing agent in this embodiment includes the following steps: 1. adding ethanolamine and diethylenetriamine according to the weight parts in a reactor with heating and cooling, and stirring for 5 min; 2. adding one third of E51 epoxy resin every 20min while stirring; 3. after the feeding is finished, continuously stirring for 90 min; 4. heating to 60 deg.C, vacuum-maintaining at-0.09 MPa under stirring at 40Hz for 60 min; 5. adding the dodecyl phenol in parts by weight, and stirring for 30min under vacuum of-0.09 MPa; 6. naturally cooling under stirring, and discharging.

The product state of the curing agent obtained in this example was ungelled.

Example 3

An epoxy resin curing agent for a two-component seam beautifying agent comprises the following components in parts by weight: 100 parts of epoxy resin, 57 parts of hydroxylamine, 28 parts of aliphatic polyamine and 6 parts of phenols.

The epoxy resin is E51, the hydroxylamine is monoethanolamine, the aliphatic polyamine is diethylenetriamine, and the phenol is dodecylphenol.

The preparation method of the curing agent in this embodiment includes the following steps: 1. adding ethanolamine and diethylenetriamine according to the weight parts in a reactor with heating and cooling, and stirring for 5 min; 2. adding one third of E51 epoxy resin every 20min while stirring; 3. after the feeding is finished, continuously stirring for 90 min; 4. heating to 60 deg.C, vacuum-maintaining at-0.09 MPa under stirring at 40Hz for 60 min; 5. adding the dodecyl phenol in parts by weight, and stirring for 30min under vacuum of-0.09 MPa; 6. naturally cooling under stirring, and discharging.

The product state of the curing agent obtained in this example was ungelled.

Example 4

An epoxy resin curing agent for a two-component seam beautifying agent comprises the following components in parts by weight: 100 parts of epoxy resin, 47 parts of hydroxylamine, 34 parts of aliphatic polyamine and 6 parts of phenols.

The epoxy resin is E51, the hydroxylamine is monoethanolamine, the aliphatic polyamine is diethylenetriamine, and the phenol is dodecylphenol.

The preparation method of the curing agent in this embodiment includes the following steps: 1. adding ethanolamine and diethylenetriamine according to the weight parts in a reactor with heating and cooling, and stirring for 5 min; 2. adding one third of E51 epoxy resin every 20min while stirring; 3. after the feeding is finished, continuously stirring for 90 min; 4. heating to 60 deg.C, vacuum-maintaining at-0.09 MPa under stirring at 40Hz for 60 min; 5. adding the dodecyl phenol in parts by weight, and stirring for 30min under vacuum of-0.09 MPa; 6. naturally cooling under stirring, and discharging.

The product state of the curing agent obtained in this example was ungelled.

Comparative example 1

An epoxy resin curing agent for a two-component seam beautifying agent comprises the following components in parts by weight: 100 parts of epoxy resin, 66 parts of aliphatic polyamine and 6 parts of phenols.

The epoxy resin is E51, the aliphatic polyamine is diethylenetriamine, and the phenol is dodecylphenol.

The preparation method of the curing agent in the comparative example comprises the following steps: 1. adding diethylenetriamine in the above weight parts into a reactor with heating and cooling, and stirring for 5 min; 2. adding one third of E51 epoxy resin every 20min while stirring; 3. after the feeding is finished, continuously stirring for 90 min; 4. heating to 60 deg.C, vacuum-maintaining at-0.09 MPa under stirring at 40Hz for 60 min; 5. adding the dodecyl phenol in parts by weight, and stirring for 30min under vacuum of-0.09 MPa; 6. naturally cooling under stirring, and discharging.

The product state of the curing agent obtained in this comparative example was gel.

Comparative example 2

An epoxy resin curing agent for a two-component seam beautifying agent comprises the following components in parts by weight: 100 parts of epoxy resin, 19 parts of hydroxylamine, 54 parts of aliphatic polyamine and 6 parts of phenols.

The epoxy resin is E51, the hydroxylamine is monoethanolamine, the aliphatic polyamine is diethylenetriamine, and the phenol is dodecylphenol.

The preparation method of the curing agent in the comparative example comprises the following steps: 1. adding ethanolamine and diethylenetriamine according to the weight parts in a reactor with heating and cooling, and stirring for 5 min; 2. adding one third of E51 epoxy resin every 20min while stirring; 3. after the feeding is finished, continuously stirring for 90 min; 4. heating to 60 deg.C, vacuum-maintaining at-0.09 MPa under stirring at 40Hz for 60 min; 5. adding the dodecyl phenol in parts by weight, and stirring for 30min under vacuum of-0.09 MPa; 6. naturally cooling under stirring, and discharging.

The product state of the curing agent obtained in this comparative example was gel.

Comparative example 3

An epoxy resin curing agent for a two-component seam beautifying agent comprises the following components in parts by weight: 100 parts of epoxy resin, 66 parts of aliphatic polyamine and 21 parts of phenols.

The epoxy resin is E51, the hydroxylamine is monoethanolamine, the aliphatic polyamine is diethylenetriamine, and the phenol is dodecylphenol.

The preparation method of the curing agent in the comparative example comprises the following steps: 1. adding diethylenetriamine in the above weight parts into a reactor with heating and cooling, and stirring for 5 min; 2. adding one third of E51 epoxy resin every 20min while stirring; 3. after the feeding is finished, continuously stirring for 90 min; 4. heating to 60 deg.C, vacuum-maintaining at-0.09 MPa under stirring at 40Hz for 60 min; 5. adding the dodecyl phenol in parts by weight, and stirring for 30min under vacuum of-0.09 MPa; 6. naturally cooling under stirring, and discharging.

The product state of the curing agent obtained in this comparative example was gel.

Comparative example 4

An epoxy resin curing agent for a two-component seam beautifying agent comprises the following components in parts by weight: 100 parts of epoxy resin, 38 parts of hydroxylamine, 40 parts of aliphatic polyamine and 6 parts of phenols.

The epoxy resin is E51, the hydroxylamine is monoethanolamine, the aliphatic polyamine is diethylenetriamine, and the phenol is dodecylphenol.

The preparation method of the curing agent in the comparative example comprises the following steps: 1. adding ethanolamine and diethylenetriamine according to the weight parts in a reactor with heating and cooling, and stirring for 5 min; 2. adding one third of E51 epoxy resin every 20min while stirring; 3. after the feeding is finished, continuously stirring for 90 min; 4. heating to 60 deg.C, vacuum-maintaining at-0.09 MPa under stirring at 40Hz for 60 min; 5. adding the dodecyl phenol in parts by weight, and stirring for 30min under vacuum of-0.09 MPa; 6. naturally cooling under stirring, and discharging.

The product state of the curing agent obtained in this comparative example was a slight gel.

The curing agent of the embodiment is applied to the component B of the seam beautifying agent to form the component B, and the performance indexes of finishing seam beautifying by matching with the component A are as follows:

the above-mentioned group A components are shown in Table 1, and the group B components are shown in Table 2.

Table 1:

table 2:

the invention is well implemented in accordance with the above-described embodiments. It should be noted that, based on the above structural design, in order to solve the same technical problems, even if some insubstantial modifications or colorings are made on the present invention, the adopted technical solution is still the same as the present invention, and therefore, the technical solution should be within the protection scope of the present invention.