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Synthesis of epoxy plasticizers
2017-12-26 17:42:55
Synthesis of epoxy plasticizers
The synthesis method of epoxy plasticizer is introduced in this paper. The synthetic method of epoxide plasticizer is based on the chemical method for the synthesis of epoxide oil. The principle is that organic acids (usually formic acid or acetic acid) react with hydrogen peroxide to form peroxic acid under the action of catalyst and react with neutral oils to form epoxide oil. The chemical method mainly includes two kinds of solvent method and solvent free method.
Solvent method, because all solvents are benzene, the environment is easy to be polluted, and the production process is long, the equipment is large, the amount of waste disposal is large, and the quality of products is poor, so it is basically eliminated. The solvent-free process has the advantages of short production process, low reaction temperature, short reaction time, less by-products, high product quality and high thermal stability. The thermal stability of epoxy group (the retention rate of epoxy value) is increased from 60% to 80% of solvent process to 95%.
In the study method, peroxy acetic acid and peroxy formic acid are mainly used for the epoxidation reagents. The synthesis of epoxy soybean oil by peracetic acid mainly includes the Situ method and the Swern method. The Situ method uses acetaldehyde as the raw material, and oxidize it to peroxy acetic acid with oxygen and peroxy acetic acid to complete the epoxidation of oil. The operation characteristic of this method is that the cost is low, but the requirement of the technical operation is high.
The Swern method uses acetic acid and hydrogen peroxide as the reaction material to prepare peroxy acetic acid with strong acid catalyst and peroxy acetic acid for the epoxidation of oil. This method has the advantages of simple process and low cost.
The difference between the two is mainly due to the different methods for the formation of peroxy acetic acid. At present, the synthetic technology of epoxy oil is mostly used by Swern method. There are two methods for the preparation of oxidants used in the process of epoxidation: one is in situ preparation of organic peric acid. This method is soybean oil and organic acid is added to the first reactor, and then slowly adding hydrogen peroxide, epoxidation; the other is the prior preparation of organic acids, which let the effect of hydrogen peroxide and organic acid, organic acid and generation, organic acid in soybean oil were added to the drop. Epoxidation reaction.
Inorganic acids (sulfuric acid, phosphoric acid, hydrochloric acid) are used as catalysts in chemical process. In addition, with the development of science and technology in recent years, cation exchange resin and other catalysts can also be used to synthesize epoxy plasticizers.
Inorganic acid catalysis. The focus of the chemical method is the selection of the catalyst. Catalysts often use strong acids such as sulfuric acid and phosphoric acid. Many scholars have studied this. Sulfuric acid can promote the generation of organic superacid, but strong acids also promote the ring opening of epoxy groups in epoxidized soybean oil.
Two octyl terephthalate (plasticizer DOTP) information:
Shipping port: Shanghai port
Price quotation validity: 15 days
Entry time: 15 days (inspection declaration)
Export authority: the company's right to import and export
Use of two octyl terephthalate (plasticizer DOTP)
1.DOTP has good electrical and thermal properties. It can be used to replace DOP in the sheath of PVC plastic wire and can also be used in the production of artificial leather membrane. In addition, with excellent compatibility, terephthalic acid ester is two PVC acrylonitrile derivatives plastic plasticizer, plasticizer, plasticizer, polyvinyl butyral nitrile rubber plasticizer, plasticizer for cellulose nitrate. The improvement of the product and plays the role of hardness and deformation, can be used as softener in NBR, chloroprene rubber, EPDM rubber and other products three. Especially for cable material, it has good plasticizing effect and low volatility. It is widely used in various products that require heat resistance and high insulation. It is an ideal plasticizer for producing 70 PVC cable material and other volatile resistant products.
2.DOTP is used for the PVC products in the car, which can solve the fog problem of the glass window. DOTP is also used for high quality lubricants or lubricant additives furniture and interior decoration paint, and precision instruments, nitro varnish additives, paper softener, biaxially oriented polyester amide membrane film, plastic bags and other crafts, plasma storage.
3. because the linear molecular structure of DOTP is similar to DOS and DOA, its cold resistance is also better.
The volume resistivity of 4.DOTP is 10-20 times higher than that of DOP, and its mobility is excellent.
5., because DOTP does not contain o-phthalate two formate, it is not an environmental friendly plasticizer in the range of 16 16 kinds of plasticizers containing o-phthalic acid in the European Union and other countries.
Using strong acid as catalyst, the coarse product has deep color, complex post-processing and strong acidity, which results in the occurrence of side reactions. The epoxy value of products decreases, and the equipment is seriously corroded. Finally, it needs neutralization and removal from products.
In addition to chemical methods, epoxy plasticizer synthesis can also be catalyzed by cation exchange resin, aluminum sulfate, heteropoly acid and metal compounds to synthesize epoxy plasticizers. The use of these catalysts has overcome the shortcomings of strong acid and strong corrosion in chemical methods, and has not attracted much attention because of the high price of lipase.
The products with strong acid cation exchange resin as a catalyst for epoxidation are much lighter in color. Rubeen Mungroo et al. Studied the epoxidation of castor oil with cation exchange resin. The optimum reaction conditions were temperature 65 C, the ratio of acetic acid to unsaturated double bond 1.5, cation exchange resin 22% and conversion rate 90%. Petrovic Z S and others studied the kinetics of epoxidation of soybean oil under the condition of cation exchange resin as catalyst.
At the temperature of 40, 60 and 80 DEG C, compared the two kinds of peroxyformic acid and peracetic acid epoxidation agent, the results show that the rate constants for the epoxidation reaction with peroxide acetic acid were 0.118, 0.451 and 1.278h 1, the activation energy of 54.7 kJ / mol; epoxidation reaction rate constants were used oxidation of formic acid were 0.264, 0.734 and 1.250h1, reaction activation of 35.9kJ / mol.
Using aluminum sulfate as catalyst can also catalyze the synthesis of epoxidized soybean oil, which has high reactivity, and is easier to deal with after strong acid than that of cation exchange resin. Cao Weidong used aluminum sulfate as catalyst to synthesize epoxidized soybean oil. This method has high reaction activity, easy post-treatment and high yield, and it reduces the cost of catalyst compared with cation exchange resin catalysis.
Heteropoly acid catalyzed epoxidation has the advantages of light color and selectivity, so many scholars have begun to pay attention to the catalytic epoxidation of heteropoly acid in recent years. He Muguang and others catalyze the epoxidation of soybean oil with heteropolyacid salts as a catalyst and peroxic formic acid formed by formic acid and hydrogen peroxide as a epoxidation reagent. Under the condition of no solvent, the reaction can be done at 45 C under the condition of 3.5H. The process is simple, the reaction time is short, the product color is shallow, and the epoxy value of the product is high.
Copyright: Zhang Jia Gang YaRui Chemical co.,Ltd
http://www.yaruichem.com
The synthesis method of epoxy plasticizer is introduced in this paper. The synthetic method of epoxide plasticizer is based on the chemical method for the synthesis of epoxide oil. The principle is that organic acids (usually formic acid or acetic acid) react with hydrogen peroxide to form peroxic acid under the action of catalyst and react with neutral oils to form epoxide oil. The chemical method mainly includes two kinds of solvent method and solvent free method.
Solvent method, because all solvents are benzene, the environment is easy to be polluted, and the production process is long, the equipment is large, the amount of waste disposal is large, and the quality of products is poor, so it is basically eliminated. The solvent-free process has the advantages of short production process, low reaction temperature, short reaction time, less by-products, high product quality and high thermal stability. The thermal stability of epoxy group (the retention rate of epoxy value) is increased from 60% to 80% of solvent process to 95%.
In the study method, peroxy acetic acid and peroxy formic acid are mainly used for the epoxidation reagents. The synthesis of epoxy soybean oil by peracetic acid mainly includes the Situ method and the Swern method. The Situ method uses acetaldehyde as the raw material, and oxidize it to peroxy acetic acid with oxygen and peroxy acetic acid to complete the epoxidation of oil. The operation characteristic of this method is that the cost is low, but the requirement of the technical operation is high.
The Swern method uses acetic acid and hydrogen peroxide as the reaction material to prepare peroxy acetic acid with strong acid catalyst and peroxy acetic acid for the epoxidation of oil. This method has the advantages of simple process and low cost.
The difference between the two is mainly due to the different methods for the formation of peroxy acetic acid. At present, the synthetic technology of epoxy oil is mostly used by Swern method. There are two methods for the preparation of oxidants used in the process of epoxidation: one is in situ preparation of organic peric acid. This method is soybean oil and organic acid is added to the first reactor, and then slowly adding hydrogen peroxide, epoxidation; the other is the prior preparation of organic acids, which let the effect of hydrogen peroxide and organic acid, organic acid and generation, organic acid in soybean oil were added to the drop. Epoxidation reaction.
Inorganic acids (sulfuric acid, phosphoric acid, hydrochloric acid) are used as catalysts in chemical process. In addition, with the development of science and technology in recent years, cation exchange resin and other catalysts can also be used to synthesize epoxy plasticizers.
Inorganic acid catalysis. The focus of the chemical method is the selection of the catalyst. Catalysts often use strong acids such as sulfuric acid and phosphoric acid. Many scholars have studied this. Sulfuric acid can promote the generation of organic superacid, but strong acids also promote the ring opening of epoxy groups in epoxidized soybean oil.
Two octyl terephthalate (plasticizer DOTP) information:
Shipping port: Shanghai port
Price quotation validity: 15 days
Entry time: 15 days (inspection declaration)
Export authority: the company's right to import and export
Use of two octyl terephthalate (plasticizer DOTP)
1.DOTP has good electrical and thermal properties. It can be used to replace DOP in the sheath of PVC plastic wire and can also be used in the production of artificial leather membrane. In addition, with excellent compatibility, terephthalic acid ester is two PVC acrylonitrile derivatives plastic plasticizer, plasticizer, plasticizer, polyvinyl butyral nitrile rubber plasticizer, plasticizer for cellulose nitrate. The improvement of the product and plays the role of hardness and deformation, can be used as softener in NBR, chloroprene rubber, EPDM rubber and other products three. Especially for cable material, it has good plasticizing effect and low volatility. It is widely used in various products that require heat resistance and high insulation. It is an ideal plasticizer for producing 70 PVC cable material and other volatile resistant products.
2.DOTP is used for the PVC products in the car, which can solve the fog problem of the glass window. DOTP is also used for high quality lubricants or lubricant additives furniture and interior decoration paint, and precision instruments, nitro varnish additives, paper softener, biaxially oriented polyester amide membrane film, plastic bags and other crafts, plasma storage.
3. because the linear molecular structure of DOTP is similar to DOS and DOA, its cold resistance is also better.
The volume resistivity of 4.DOTP is 10-20 times higher than that of DOP, and its mobility is excellent.
5., because DOTP does not contain o-phthalate two formate, it is not an environmental friendly plasticizer in the range of 16 16 kinds of plasticizers containing o-phthalic acid in the European Union and other countries.
Using strong acid as catalyst, the coarse product has deep color, complex post-processing and strong acidity, which results in the occurrence of side reactions. The epoxy value of products decreases, and the equipment is seriously corroded. Finally, it needs neutralization and removal from products.
In addition to chemical methods, epoxy plasticizer synthesis can also be catalyzed by cation exchange resin, aluminum sulfate, heteropoly acid and metal compounds to synthesize epoxy plasticizers. The use of these catalysts has overcome the shortcomings of strong acid and strong corrosion in chemical methods, and has not attracted much attention because of the high price of lipase.
The products with strong acid cation exchange resin as a catalyst for epoxidation are much lighter in color. Rubeen Mungroo et al. Studied the epoxidation of castor oil with cation exchange resin. The optimum reaction conditions were temperature 65 C, the ratio of acetic acid to unsaturated double bond 1.5, cation exchange resin 22% and conversion rate 90%. Petrovic Z S and others studied the kinetics of epoxidation of soybean oil under the condition of cation exchange resin as catalyst.
At the temperature of 40, 60 and 80 DEG C, compared the two kinds of peroxyformic acid and peracetic acid epoxidation agent, the results show that the rate constants for the epoxidation reaction with peroxide acetic acid were 0.118, 0.451 and 1.278h 1, the activation energy of 54.7 kJ / mol; epoxidation reaction rate constants were used oxidation of formic acid were 0.264, 0.734 and 1.250h1, reaction activation of 35.9kJ / mol.
Using aluminum sulfate as catalyst can also catalyze the synthesis of epoxidized soybean oil, which has high reactivity, and is easier to deal with after strong acid than that of cation exchange resin. Cao Weidong used aluminum sulfate as catalyst to synthesize epoxidized soybean oil. This method has high reaction activity, easy post-treatment and high yield, and it reduces the cost of catalyst compared with cation exchange resin catalysis.
Heteropoly acid catalyzed epoxidation has the advantages of light color and selectivity, so many scholars have begun to pay attention to the catalytic epoxidation of heteropoly acid in recent years. He Muguang and others catalyze the epoxidation of soybean oil with heteropolyacid salts as a catalyst and peroxic formic acid formed by formic acid and hydrogen peroxide as a epoxidation reagent. Under the condition of no solvent, the reaction can be done at 45 C under the condition of 3.5H. The process is simple, the reaction time is short, the product color is shallow, and the epoxy value of the product is high.
Copyright: Zhang Jia Gang YaRui Chemical co.,Ltd
http://www.yaruichem.com
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