Carboxyl-containing high refractive index hyperbranched polyester amide, its preparation method and its application in plastic modification

Abstract

The invention provides carboxyl-containing high-refractive-index hyperbranched polyesteramide and a preparation method thereof, as well as application of the carboxyl-containing high-refractive-index hyperbranched polyesteramide to plastic modification, and belongs to the field of hyperbranched polymers. The reaction period can be shortened, the production process can be simplified, the cost can be reduced, and industrial large-scale production can be met. The preparation method comprises the following steps: adding an aromatic polycarboxylic / multi-anhydride monomer and a single amino and single hydroxyl monomer into a reactor, adding a catalyst into the reactor, and performing prepolymerization reaction under the protection of inert gas at the temperature of 80 to 180 DEG C for 0.5 to 48 hours to form a polymeric monomer; and then heating to 120 to 250 DEG C, performing reaction for 0.5 to 120 hours to obtain the carboxyl-containing high-refractive-index hyperbranched polyesteramide. The preparation method provided by the invention can be applied to the industrial production process of the carboxyl-containing high-refractive-index hyperbranched polyesteramide; the prepared carboxyl-containing high-refractive-index hyperbranched polyesteramide can resist the temperature higher than 350 DEG C and is relatively high in refractive index; as an improving agent, the carboxyl-containing high-refractive-index hyperbranched polyesteramide is applied to a plastic system; the mechanical property can be improved without affecting the transparency of the plastic system.

Description

technical field

[0001] The invention relates to the field of hyperbranched polymers, in particular to a carboxyl group-containing high refractive index hyperbranched polyester amide, its preparation method and its application in plastic modification. Background technique

[0002] Hyperbranched polymers have a highly branched three-dimensional spherical structure and a large number of terminal functional groups. They have the advantages of good solubility, low solution and melt viscosity, and high fluidity. They are currently widely used in the field of plastics and rubber.

[0003] Hyperbranched polymers are generally composed of AB n (n≥2) type monomer or A 2 +B n (n≥2) type monomers are formed by polycondensation in solution (C. Gao, D. Yan. Prog. Polym. Sci. 29 (2004) 183-275). Patent 03156220.5 discloses a method for synthesizing hyperbranched polyester-amine, specifically, hyperbranched polyester-amide is synthesized by solution polymerization. However, the solution...

Examples

preparation example Construction

[0019] The embodiment of one aspect of the present invention provides a kind of preparation method containing carboxyl hyperbranched polyester amide, comprises the steps:

[0020] S1: Add aromatic polycarboxylic acid / polyanhydride monomer and monoamino monohydroxyl monomer into the reactor, and add catalyst to it, under the protection of inert gas, prepolymerize at 80°C-180°C for 0.5- 48 hours to form polymerized monomers;

[0021] S2: Then raise the temperature to 120°C-250°C and react for 0.5-120 hours to obtain carboxyl group-containing hyperbranched polyester amide.

[0022] In this example, the hyperbranched polymer was obtained by direct melt reaction of commercially available polycarboxylate / polyanhydride monomers and monoaminomonohydroxyl monomers through one-pot polymerization. Concretely, the above-mentioned raw materials are pre-polymerized under reaction conditions to form polymerized monomers (AB 2 ), and then further react to generate hyperbranched polyester am...

Embodiment 1

[0033] Under the protection of nitrogen, add 0.2 mol of metaphthalic anhydride and 0.2 mol of ethanolamine into a three-necked flask, and add p-toluenesulfonic acid with a mass fraction of 0.2% as a catalyst; raise the temperature to 80°C for 8 hours, and then heat up to Stir and react at 120° C. for 10 hours; stop the reaction, discharge and condense directly to obtain a light yellow transparent solid, and obtain carboxyl-containing hyperbranched polyester amide 1 with a yield of 90%. The 5% thermal decomposition temperature of the product is 390°C, and the refractive index is 1.572.

Embodiment 2

[0035] Under the protection of nitrogen, add 0.2 mol of metaphthalic anhydride and 0.2 mol of butanolamine into a three-necked flask, and add tetraisopropyl titanate with a mass fraction of 0.5% as a catalyst; raise the temperature to 180°C for 4 hours, Then the temperature was raised to 250° C. and the reaction was stirred for 1 hour; the reaction was stopped, and the material was directly discharged and condensed to obtain a light yellow transparent solid, and a carboxyl group-containing hyperbranched polyester amide 2 was obtained, and the yield was 91%. The 5% thermal decomposition temperature of the product is 387°C, and the refractive index is 1.575.

technical field

[0001] The invention relates to the field of hyperbranched polymers, in particular to a carboxyl group-containing high refractive index hyperbranched polyester amide, its preparation method and its application in plastic modification. Background technique

[0002] Hyperbranched polymers have a highly branched three-dimensional spherical structure and a large number of terminal functional groups. They have the advantages of good solubility, low solution and melt viscosity, and high fluidity. They are currently widely used in the field of plastics and rubber.

[0003] Hyperbranched polymers are generally composed of AB n (n≥2) type monomer or A 2 +B n (n≥2) type monomers are formed by polycondensation in solution (C. Gao, D. Yan. Prog. Polym. Sci. 29 (2004) 183-275). Patent 03156220.5 discloses a method for synthesizing hyperbranched polyester-amine, specifically, hyperbranched polyester-amide is synthesized by solution polymerization. However, the solution...

Examples

preparation example Construction

[0019] The embodiment of one aspect of the present invention provides a kind of preparation method containing carboxyl hyperbranched polyester amide, comprises the steps:

[0020] S1: Add aromatic polycarboxylic acid / polyanhydride monomer and monoamino monohydroxyl monomer into the reactor, and add catalyst to it, under the protection of inert gas, prepolymerize at 80°C-180°C for 0.5- 48 hours to form polymerized monomers;

[0021] S2: Then raise the temperature to 120°C-250°C and react for 0.5-120 hours to obtain carboxyl group-containing hyperbranched polyester amide.

[0022] In this example, the hyperbranched polymer was obtained by direct melt reaction of commercially available polycarboxylate / polyanhydride monomers and monoaminomonohydroxyl monomers through one-pot polymerization. Concretely, the above-mentioned raw materials are pre-polymerized under reaction conditions to form polymerized monomers (AB 2 ), and then further react to generate hyperbranched polyester am...

Embodiment 1

[0033] Under the protection of nitrogen, add 0.2 mol of metaphthalic anhydride and 0.2 mol of ethanolamine into a three-necked flask, and add p-toluenesulfonic acid with a mass fraction of 0.2% as a catalyst; raise the temperature to 80°C for 8 hours, and then heat up to Stir and react at 120° C. for 10 hours; stop the reaction, discharge and condense directly to obtain a light yellow transparent solid, and obtain carboxyl-containing hyperbranched polyester amide 1 with a yield of 90%. The 5% thermal decomposition temperature of the product is 390°C, and the refractive index is 1.572.

Embodiment 2

[0035] Under the protection of nitrogen, add 0.2 mol of metaphthalic anhydride and 0.2 mol of butanolamine into a three-necked flask, and add tetraisopropyl titanate with a mass fraction of 0.5% as a catalyst; raise the temperature to 180°C for 4 hours, Then the temperature was raised to 250° C. and the reaction was stirred for 1 hour; the reaction was stopped, and the material was directly discharged and condensed to obtain a light yellow transparent solid, and a carboxyl group-containing hyperbranched polyester amide 2 was obtained, and the yield was 91%. The 5% thermal decomposition temperature of the product is 387°C, and the refractive index is 1.575.

Images