阅读说明：本技术 一种高防腐性能腰果酚改性多元胺固化剂的制备方法 (Preparation method of cardanol modified polyamine curing agent with high corrosion resistance ) 是由 王秋伟 顾奇 李旭峰 陈建 吕云兴 于 2020-06-29 设计创作，主要内容包括：本发明公开了一种高防腐性能腰果酚改性多元胺固化剂的制备方法,它将腰果酚、多聚甲醛和胺类化合物进行曼尼希反应,反应结束后加入水溶性引发剂进行聚合反应,反应结束后减压蒸除水分及过量的胺类化合物,得到腰果酚改性多元胺固化剂,固化剂与环氧树脂固化得到的涂料耐化学、耐腐蚀性能有很大的提高,表明本发明采用水溶性引发剂能够使很好烯烃聚合,聚合后分子明显的加强,从而使耐化学、耐腐蚀性能大大的提高。(The invention discloses a preparation method of a cardanol modified polyamine curing agent with high corrosion resistance, which comprises the steps of carrying out Mannich reaction on cardanol, paraformaldehyde and an amine compound, adding a water-soluble initiator for polymerization reaction after the reaction is finished, and carrying out reduced pressure evaporation to remove water and excessive amine compound after the reaction is finished to obtain the cardanol modified polyamine curing agent.)

1. A preparation method of a cardanol modified polyamine curing agent with high corrosion resistance is characterized in that cardanol, paraformaldehyde and an amine compound are subjected to Mannich reaction, a water-soluble initiator is added after the reaction speed to carry out polymerization reaction, water and excessive amine compound are removed through reduced pressure evaporation after the reaction is finished, the cardanol modified polyamine with high corrosion resistance is obtained,

2. the preparation method of the cardanol modified polyamine curing agent with high anticorrosion performance as claimed in claim 1, wherein the molar ratio of cardanol, paraformaldehyde and amine compound is 1:1-2: 1.05-2.

3. The preparation method of the cardanol modified polyamine curing agent with high corrosion resistance as claimed in claim 1, wherein the amine compound is aliphatic amine, alicyclic amine or aromatic amine.

4. The preparation method of the cardanol modified polyamine curing agent with high corrosion resistance as claimed in claim 1, wherein the amine compound is one or a mixture of two of ethylenediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine.

5. The preparation method of the cardanol modified polyamine curing agent with high corrosion resistance as claimed in claim 1, wherein the mannich reaction temperature is 30-85 ℃.

6. The preparation method of the cardanol modified polyamine curing agent with high corrosion resistance as claimed in claim 1, wherein the polymerization temperature is 70-100 ℃ and the polymerization time is 3-5 hours.

7. The preparation method of the cardanol modified polyamine curing agent with high anticorrosion performance as claimed in claim 1, wherein the water-soluble initiator is azobisisobutyramidine hydrochloride, azobisisobutyrimidazoline hydrochloric acid or azobisisobutyronitrile formamide, and the dosage of the water-soluble initiator is 1-5% of the mass of cardanol.

8. The preparation method of the cardanol modified polyamine curing agent with high corrosion resistance as claimed in claim 1, wherein the temperature for removing water by reduced pressure distillation after reaction is 50-90 ℃ and the vacuum degree is 10-50 KPa.

9. The preparation method of the cardanol modified polyamine curing agent with high anticorrosive performance according to any one of claims 1 to 8, characterized by adding cardanol and paraformaldehyde into a reactor according to a feeding ratio, slowly dropwise adding ethylenediamine at room temperature, controlling the temperature of dropwise adding to be 50-80 ℃, the dropwise adding time to be 2-2.5 hours, keeping the temperature at 75-80 ℃ for 3.5-4.5 hours after dropwise adding, adding a water-soluble initiator after keeping the temperature, controlling the temperature to be 95-100 ℃ for reflux reaction for 4-5 hours, cooling to 80-85 ℃ after reaction, and distilling and dehydrating under the vacuum degree of 10-15 KPa to obtain a reddish brown solution, namely the cardanol modified polyamine curing agent with high anticorrosive performance.

Technical Field

The invention relates to the technical field of organic synthesis, in particular to a preparation method of a cardanol modified polyamine curing agent with high corrosion resistance.

Background

Cardanol (Cardanol) is extracted from cashew nut shells, has a phenolic hydroxyl structure, can replace part of phenolic compounds to participate in chemical reaction, is a renewable biological resource, and can solve part of petroleum energy crisis.

Because cardanol has reproducibility, cardanol is utilized to develop and apply a lot of products, cardanol curing agent is mainly prepared in the application of cardanol, the prepared curing agent is cured with epoxy resin to obtain a paint film with high stability, high temperature resistance and good operation at low temperature, and the paint film is mainly applied to paint film coatings on ships and containers.

As in the Chinese patent: CN101333286, cardanol, formaldehyde and polyamine are adopted to react, and after the reaction, the cardanol modified amine curing agent is obtained through reduced pressure dehydration, wherein molecules of the curing agent are mainly monomolecular compounds, molecular double bonds on chains are unstable, the corrosion resistance is poor, and the coating is easy to turn yellow under the condition of long-time illumination, so that the appearance of a paint film is affected.

Chinese patent CN107973899, by adding cardanol glyceryl ether and cardanol to react with formaldehyde and polyamine, the performance of the product is changed, such as the color, hardness and the like of the product are improved, and the problems of the color, chemical resistance and corrosion resistance of the product are not fundamentally solved.

Disclosure of Invention

In view of the above problems in the prior art, the present invention aims to provide a preparation method of a cardanol modified polyamine curing agent with high corrosion resistance.

The preparation method of the cardanol modified polyamine curing agent with high corrosion resistance is characterized in that cardanol, paraformaldehyde and amine compounds are subjected to Mannich reaction, a water-soluble initiator is added after the reaction speed to carry out polymerization reaction, water and excessive amine compounds are removed by reduced pressure after the reaction is finished, so that cardanol modified polyamine with high corrosion resistance is obtained,

the preparation method of the cardanol modified polyamine curing agent with high corrosion resistance is characterized in that the molar ratio of cardanol, paraformaldehyde and amine compounds is 1:1-2: 1.05-2.

The preparation method of the cardanol modified polyamine curing agent with high corrosion resistance is characterized in that the amine compound is aliphatic amine, alicyclic amine or aromatic amine.

The preparation method of the cardanol modified polyamine curing agent with high corrosion resistance is characterized in that the amine compound is one or a mixture of two of ethylenediamine, diethylenetriamine, triethylene tetramine and tetraethylenepentamine.

The preparation method of the cardanol modified polyamine curing agent with high corrosion resistance is characterized in that the Mannich reaction temperature is 30-85 ℃.

The preparation method of the cardanol modified polyamine curing agent with high corrosion resistance is characterized in that the polymerization reaction temperature is 70-100 ℃, and the polymerization time is 3-5 hours.

The preparation method of the cardanol modified polyamine curing agent with high corrosion resistance is characterized in that the water-soluble initiator is azobisisobutyramidine hydrochloride, azobisisobutyrimidazoline hydrochloric acid or azobisisobutyronitrile formamide, and the feeding amount of the water-soluble initiator is 1-5% of the mass of cardanol.

The preparation method of the cardanol modified polyamine curing agent with high corrosion resistance is characterized in that the temperature for removing water through reduced pressure distillation after reaction is 50-90 ℃, and the vacuum degree is 10-50 KPa.

The preparation method of the cardanol modified polyamine curing agent with high anti-corrosion performance is characterized by adding cardanol and paraformaldehyde into a reactor according to a feeding ratio, slowly dropwise adding ethylenediamine at room temperature, controlling the temperature of dropwise adding to be 50-80 ℃, dropwise adding time to be 2-2.5 hours, keeping the temperature for 3.5-4.5 hours at 75-80 ℃ after dropwise adding, adding a water-soluble initiator after finishing heat preservation, controlling the temperature to be 95-100 ℃ for reflux reaction for 4-5 hours, reducing the temperature to 80-85 ℃ after reaction, and distilling and dehydrating under the vacuum degree of 10-15 KPa to obtain a reddish brown solution cardanol modified polyamine curing agent with high anti-corrosion performance.

By adopting the technology, compared with the prior art, the invention has the following beneficial effects:

1) the method changes the characteristics of the cardanol modified polyamine by adopting a chemical polymerization method, greatly improves the stability of the cardanol modified polyamine, and the high molecular weight compound is more stable than a single molecular chain compound, and the stability is particularly represented by high chemical corrosion resistance, so that the performance of the product is fundamentally changed, and the amount of chemical combination of small molecules is reduced;

2) according to the preparation method of the cardanol modified polyamine, after the Mannich reaction, a water-soluble initiator is used for initiating a direct polymerization reaction, no special treatment is needed, the problems that a plurality of initiators are easy to decompose in water and the polymerization reaction conditions are harsh are solved, the repeatability is good, the operation is simple, and raw materials of a curing agent can be stably and industrially produced;

3) according to the invention, the obtained polymerized high molecular weight compound is compounded with epoxy resin to obtain a novel curing agent, and small molecules are changed into compounds with larger polymerized molecular weight through polymerization reaction of branched chain olefin bonds in cardanol, so that the stability of the compound is improved, and the obtained curing agent has the phenomena of high chemical resistance and corrosion resistance and yellowing after long-time light irradiation.

Detailed Description

The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.