CN106366310B - Carboxyl-containing high-refractive-index hyperbranched polyesteramide, preparation method thereof and application thereof in plastic modification - Google Patents
Carboxyl-containing high-refractive-index hyperbranched polyesteramide, preparation method thereof and application thereof in plastic modification Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G69/44—Polyester-amides
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Abstract
The invention provides carboxyl-containing high-refractive-index hyperbranched polyesteramide, a preparation method thereof and application thereof in plastic modification, belongs to the field of hyperbranched polymers, can shorten the reaction period, simplify the production process, reduce the cost and meet the requirement of industrial large-scale production. The preparation method comprises the following steps: adding an aromatic polycarboxylic acid/polyanhydride monomer and a monoamino monohydroxy monomer into a reactor, adding a catalyst into the reactor, and carrying out prepolymerization reaction for 0.5 to 48 hours at a temperature of between 80 and 180 ℃ under the protection of inert gas to form a polymerized monomer; then the temperature is raised to 120 ℃ to 250 ℃ and the reaction is carried out for 0.5 to 120 hours, thus obtaining the carboxyl-containing hyperbranched polyesteramide with high refractive index. The preparation method provided by the invention can be used in the industrial production process of the carboxyl-containing high-refractive-index hyperbranched polyesteramide, the prepared carboxyl-containing hyperbranched polyesteramide has the heat resistance of more than 350 ℃ and higher refractive index, and the carboxyl-containing hyperbranched polyesteramide is used as a modifier to be applied to a plastic system, so that the mechanical property can be improved without affecting the transparency of the carboxyl-containing hyperbranched polyesteramide.
Description
Technical Field
The invention relates to the field of hyperbranched polymers, in particular to carboxyl-containing hyperbranched polyesteramide with high refractive index, a preparation method thereof and application thereof in plastic modification.
Background
The hyperbranched polymer has a highly branched three-dimensional spherical structure and a large number of terminal functional groups, has the advantages of good solubility, small solution and melt viscosity, high fluidity and the like, and is widely applied to the field of plastic rubber at present.
Hyperbranched polymers are generally composed of ABn(n.gtoreq.2) type monomer or A2+Bn(n.gtoreq.2) type monomers in solution to form (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 polymerization method involves solvent extraction and product purificationThe method has the problems of long reaction period, complex treatment process, environmental pollution, high cost and the like, so that the method has certain limitation on industrial production, and the polymerization degree and the heat resistance of the product obtained by the solution polymerization method are required to be improved. In addition, when people use hyperbranched polymers for plastic modification, the matching of the refractive index of the hyperbranched polymers is rarely considered, so that the influence of inconsistent refractive index on the transparency is further caused, and the conventional aliphatic hyperbranched polymerization has lower refractive index and is not suitable for a high-refractive-index plastic system, so that the application of the high-refractive-index hyperbranched polymers in the plastic is a substance with great innovative significance. In conclusion, how to provide a reasonable synthesis method of hyperbranched polyesteramide containing carboxyl and having high refractive index, which can shorten the reaction period, simplify the production process, reduce the cost, and meet the requirement of industrial mass production becomes an important research topic in the field.
Disclosure of Invention
The invention aims to provide a carboxyl-containing hyperbranched polyesteramide with high refractive index, a preparation method thereof and application thereof in plastic modification, which can shorten the reaction period, simplify the production process, reduce the cost and meet the requirement of industrial large-scale production.
The invention provides a preparation method of carboxyl-containing high-refractive-index hyperbranched polyesteramide, which comprises the following steps:
adding an aromatic polycarboxylic acid/polyanhydride monomer and a monoamino monohydroxy monomer into a reactor, adding a catalyst into the reactor, and carrying out prepolymerization reaction for 0.5 to 48 hours at a temperature of between 80 and 180 ℃ under the protection of inert gas to form a polymerized monomer;
then the temperature is raised to 120 ℃ to 250 ℃ and the reaction is carried out for 0.5 to 120 hours, thus obtaining the carboxyl-containing hyperbranched polyesteramide with high refractive index.
Preferably, the prepolymerization is carried out for 1-10 hours at 80-180 ℃ under the protection of inert gas to form polymerized monomer, and then the temperature is raised to 120-250 ℃ for 1-10 hours.
Preferably, the molar ratio of the aromatic polycarboxylic acid/polyanhydride monomer to the monoamino monohydroxy monomer is 1:1 to 1: 3.
Preferably, the addition amount of the catalyst is 0.1-5% of the total mass of the aromatic polycarboxylic acid/polyanhydride monomer and the monoamino monohydroxy monomer.
Optionally, the aromatic polycarboxylic acid/polyacid anhydride monomer is selected from any one of trimellitic anhydride, pyromellitic anhydride, anisole tetracarboxylic anhydride, benzophenone tetracarboxylic anhydride, biphenyl tetracarboxylic dianhydride or 3,3',4,4' -diphenyl sulfone tetracarboxylic dianhydride.
Optionally, the monoamino monohydroxy monomer is selected from ethanolamine, propanolamine, isopropanolamine, butanolamine, isobutanolamine, pentanolamine, hexanolamine, N- (2-hydroxyethyl) piperazine, any one of 2-hydroxy-3-amino-5-methylpyridine, 1- (2-aminoethyl) -3-hydroxypyrrolidine, 3 '-amino-2' -hydroxyacetophenone, 1- (4-aminophenyl) -4- (4-hydroxyphenyl) piperazine, 4 '-amino-2' -hydroxyacetophenone, 4-hydroxy-2-aminobenzothiazole, 2-amino-3-hydroxyphenyloxazine, 2-amino-5-hydroxypyridine, and isomers of 2-amino-5-hydroxypyridine.
Optionally, the catalyst is selected from any one of concentrated sulfuric acid, phosphoric acid, zinc acetate, dibutyl tin dilaurate, p-toluenesulfonic acid, tetraisopropyl titanate, tetraisobutyl titanate or thionyl chloride.
The invention also provides the carboxyl-containing high-refractive-index hyperbranched polyester amide prepared by the preparation method of the carboxyl-containing high-refractive-index hyperbranched polyester amide in any technical scheme.
The invention further provides an application of the carboxyl-containing high-refractive-index hyperbranched polyester amide as a modifier in modification of a plastic system.
Preferably, in the modification process of the carboxyl-containing high-refractive-index hyperbranched polyester amide on a plastic system, particularly on the plastic system with the refractive index similar to that of the carboxyl-containing high-refractive-index hyperbranched polyester amide, the addition amount of the carboxyl-containing hyperbranched polyester amide is 0.01-20%.
Compared with the existing preparation method, the preparation method utilizes the difference of the reaction activities of different functional groups, adopts the direct melt reaction of a commercialized aromatic polycarboxyl/polyanhydride monomer and a monoamino monohydroxy monomer, and adopts a one-pot polymerization method to obtain the hyperbranched polymer. The method is mature, the reaction device and the operation are extremely simple, the solvent is not needed in the reaction process, the steps of solvent extraction, product purification and the like are omitted, the production process is simplified, the reaction period is shortened, and the method can be used in the process of preparing the carboxyl-containing hyperbranched polyesteramide in an industrial production manner.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. 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 embodiment of one aspect of the invention provides a preparation method of carboxyl-containing hyperbranched polyesteramide, which comprises the following steps:
s1: adding an aromatic polycarboxylic acid/polyanhydride monomer and a monoamino monohydroxy monomer into a reactor, adding a catalyst into the reactor, and carrying out prepolymerization reaction for 0.5 to 48 hours at a temperature of between 80 and 180 ℃ under the protection of inert gas to form a polymerized monomer;
s2: then the temperature is raised to 120 ℃ to 250 ℃ and the reaction is carried out for 0.5 to 120 hours, thus obtaining the carboxyl-containing hyperbranched polyesteramide.
In the embodiment, the hyperbranched polymer is mainly obtained by directly melting and reacting a commercial polycarboxyl/polyanhydride monomer and a monoamino monohydroxy monomer and polymerizing the monomers in a one-pot method. Specifically, the raw materials are prepolymerized under the reaction condition to form the polymerized monomer (AB)2) Then further reacting to generate the hyperbranched polyester amide. Specifically, in the process, a temperature programming mode is adopted, pre-polymerization is firstly carried out to form a polymerized monomer, and then the reaction is continued to generate the required hyperbranched polyesteramide. Compared with the existing preparation method, the method is mature, and no solvent or solvent is needed in the reaction processPost-treatment of the agent, no pollution, and effective application in the industrial production and preparation process of carboxyl-containing hyperbranched polyesteramide.
It is understood that, in the step S1, the above reaction temperature and reaction time may be favorable for the pre-polymerization of the raw materials to form the polymerized monomers, wherein the temperature may also be 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, etc. and any other point in the range, and the reaction time may also be 1, 5, 10, 15, 20, 25, 30, 35, 40, 45 hours, etc. In a preferred embodiment, the reaction time can be further specifically 2, 3, 4, 6, 7, 8, 9 hours, etc., and can be adjusted by one skilled in the art according to the actual reaction condition. In the above step S2, the temperature may be 140 ℃, 160 ℃, 180 ℃, 200 ℃, 220 ℃, 240 ℃ or the like, or any other value within the range, and the reaction time may be 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115 hours or the like. In a preferred embodiment, the reaction time can be 2, 3, 4, 6, 7, 8, 9 hours, etc., and can be adjusted by one skilled in the art according to the actual reaction situation.
In a preferred embodiment, the molar ratio of the aromatic polycarboxylic acid/polyanhydride monomer to the monoamino monohydroxy monomer is from 1:1 to 1: 3. In this embodiment, the molar ratio of the aromatic polycarboxylic acid/polyanhydride monomer to the monoamino monohydroxy monomer is limited to the above range, which can effectively promote the reaction of the aromatic polycarboxylic acid/polyanhydride monomer and the monoamino monohydroxy monomer under the action of the catalyst to generate the polymerized monomer, thereby facilitating the further preparation of the carboxyl-containing hyperbranched polyesteramide protected by the present application. It is understood that the molar ratio of the aromatic polycarboxylic acid/polyanhydride monomer to the monoamino monohydroxy monomer may preferably be 1:1.5, 1:2, 1:2.5, etc., and those skilled in the art can select the molar ratio within the above range according to actual needs.
In a preferred embodiment, the amount of the catalyst added is 0.1-5% of the total mass of the aromatic polycarboxylic acid/polyanhydride monomer and the monoamino monohydroxy monomer. In this example, the amount of the catalyst is specifically limited, and it is understood that the catalyst mainly catalyzes the reaction between the aromatic polycarboxylic acid/polyanhydride monomer and the monoamino monohydroxy monomer, and therefore, the amount of the catalyst is not so large as to be added, and only the catalytic effect is required. Within the above range, the amount of the catalyst added may be 0.5%, 1%, 2%, 3%, 4%, etc. of the total mass of the aromatic polycarboxylic acid/polyanhydride monomer and the monoamino monohydroxy monomer, and those skilled in the art can add the catalyst according to actual reaction requirements.
In an alternative embodiment, the aromatic polycarboxylic acid/polyacid anhydride monomer is selected from any one of trimellitic anhydride, pyromellitic anhydride, anisole tetracarboxylic anhydride, benzophenone tetracarboxylic anhydride, biphenyl tetracarboxylic dianhydride, or 3,3',4,4' -diphenyl sulfone tetracarboxylic dianhydride. In an alternative embodiment, the monoamino monohydroxy monomer is selected from the group consisting of ethanolamine, propanolamine, isopropanolamine, butanolamine, isobutanolamine, pentanolamine, hexanolamine, N- (2-hydroxyethyl) piperazine, any one of 2-hydroxy-3-amino-5-methylpyridine, 1- (2-aminoethyl) -3-hydroxypyrrolidine, 3 '-amino-2' -hydroxyacetophenone, 1- (4-aminophenyl) -4- (4-hydroxyphenyl) piperazine, 4 '-amino-2' -hydroxyacetophenone, 4-hydroxy-2-aminobenzothiazole, 2-amino-3-hydroxyphenyloxazine, 2-amino-5-hydroxypyridine, and isomers of 2-amino-5-hydroxypyridine. In an alternative embodiment, the catalyst is selected from any one of concentrated sulfuric acid, phosphoric acid, zinc acetate, dibutyl tin dilaurate, p-toluenesulfonic acid, tetraisopropyl titanate, tetraisobutyl titanate, or thionyl chloride.
It is to be understood that in the above examples, the aromatic polycarboxylic acid/polyanhydride monomer, the monoaminomonohydroxy monomer, and the catalyst are preferred compounds for facilitating the above reaction, and it is to be understood that the compounds listed in the examples are not limited to those listed above, and may be other compounds known in the art, and those skilled in the art may alternatively use the compounds as long as they can satisfy the above reaction mechanism.
Embodiments of another aspect of the present invention provide a carboxyl-containing high refractive index hyperbranched polyester amide prepared by the method for preparing a carboxyl-containing high refractive index hyperbranched polyester amide described in any one of the above embodiments. The hyperbranched polyester amide containing carboxyl prepared by the preparation method provided by the embodiment can be dissolved in an organic solvent, has a branched molecular structure and a large number of carboxyl functional groups on the structure, has a refractive index of 1.54-1.58, has a higher refractive index than that of a conventional hyperbranched polymer, can reduce the influence on the transparency of plastics in the modification of plastics, and can overcome the limitation that the applicable processing temperature of the common hyperbranched polyester amide can only be within 300 ℃ because the 5% thermal weight loss temperature can be as high as 390 ℃, so that the hyperbranched polyester amide can be widely applied to paint curing, fiber dyeing auxiliaries, plastic processing auxiliaries, plastic modifiers and pigment dispersing auxiliaries.
An embodiment of another aspect of the present invention provides a use of the carboxyl-containing high refractive index hyperbranched polyester amide described in the above embodiment as a modifier in modification of a plastic system. The carboxyl-containing high-refractive-index hyperbranched polyester provided by the embodiment of the invention has the characteristics of branched molecular structure, high refractive index, high heat resistance and the like, can play a role in improving processing fluidity, dispersion and compatibility, improving the surface of a product, improving mechanical properties and the like, and does not influence the transparency of the product, so that the application of the hyperbranched polymer in the field of plastics is greatly expanded. Plastic systems may include, among others, polycarbonate plastic systems (e.g., unfilled, filled polycarbonate plastic systems, and polycarbonate alloy systems), nylon systems, polyethylene terephthalate systems, polybutylene terephthalate systems, and the like. It will be appreciated that the present embodiment is not limited to the plastic systems listed above, but may also be other types of reasonable plastic systems, and may even be the corresponding alloy systems of the above systems.
In a preferred embodiment, the carboxyl-containing hyperbranched polyester amide is added in an amount of 0.01 to 20% during the modification of a plastic system, in particular a plastic system having a refractive index similar to that of the carboxyl-containing hyperbranched polyester amide. In this example, the amount added may also be 0.1%, 0.2%, 0.5%, 1%, 5%, 10%, 15%, etc. when modifying a plastic system with a hyperbranched polyester amide containing carboxyl groups. The plastic system is modified by the modifier, and the processing rheological property of the plastic system can be improved while the mechanical property is improved or not influenced.
In order to more clearly and specifically describe the carboxyl-containing hyperbranched polyester amide provided in the embodiments of the present invention, the preparation method thereof, and the application thereof in the modification of plastics, the following detailed description will be made with reference to specific embodiments.
Example 1
Under the protection of nitrogen, 0.2mol of trimellitic anhydride and 0.2mol of ethanolamine are added into a three-neck flask, and p-toluenesulfonic acid with the mass fraction of 0.2% is added as a catalyst; raising the temperature to 80 ℃ for reaction for 8 hours, then raising the temperature to 120 ℃, and stirring for reaction for 10 hours; stopping the reaction, directly discharging and condensing to obtain a light yellow transparent solid, and obtaining the carboxyl-containing hyperbranched polyesteramide 1 with the yield of 90 percent. The product has a 5% thermal decomposition temperature of 390 ℃ and a refractive index of 1.572.
Example 2
Under the protection of nitrogen, 0.2mol of trimellitic anhydride and 0.2mol of butanol amine are added into a three-neck flask, and tetraisopropyl titanate with the mass fraction of 0.5 percent is added as a catalyst; raising the temperature to 180 ℃ for reaction for 4 hours, then raising the temperature to 250 ℃ and stirring for reaction for 1 hour; stopping the reaction, directly discharging and condensing to obtain a light yellow transparent solid, and obtaining the carboxyl-containing hyperbranched polyesteramide 2 with the yield of 91%. The product has 5% thermal decomposition temperature of 387 ℃ and refractive index of 1.575.
Example 3
Under the protection of nitrogen, 0.1mol of trimellitic anhydride and 0.2mol of propanolamine are added into a three-neck flask, and tetraisopropyl titanate with the mass fraction of 2% is added as a catalyst; raising the temperature to 120 ℃ for reaction for 6 hours, then raising the temperature to 190 ℃ and stirring for reaction for 5 hours; stopping the reaction, directly discharging and condensing to obtain a light yellow transparent solid, and obtaining the carboxyl-containing hyperbranched polyesteramide 3 with the yield of 91%. The product has a 5% thermal decomposition temperature of 391 ℃ and a refractive index of 1.577.
Example 4
Under the protection of nitrogen, 0.1mol of anisole tetra-anhydride and 0.3mol of ethanolamine are added into a three-neck flask, and tetraisopropyl titanate with the mass fraction of 5 percent is added as a catalyst; raising the temperature to 140 ℃ for reaction for 3 hours, then raising the temperature to 190 ℃ and stirring for reaction for 6 hours; stopping the reaction, directly discharging and condensing to obtain a light yellow transparent solid, and obtaining the carboxyl-containing hyperbranched polyesteramide 4 with the yield of 91%. The product has a 5% thermal decomposition temperature of 395 deg.C and a refractive index of 1.572.
Comparative example 1
Dissolving 0.2mol of ethanolamine in 150ml of ethanol solution, placing the solution in a low-temperature reaction bath, uniformly adding 0.2mol of trimellitic anhydride in 3 batches, stirring the solution for 20 minutes, placing the solution in an oil bath at 55 ℃ to completely dissolve the trimellitic anhydride, and then placing the solution in an oil bath at 25 ℃ to stir and react for 5 hours; the oil bath temperature was raised to 140 ℃ and the ethanol was pumped off with a water pump over 20 hours until the product was a white solid, i.e. polymerized monomer. And then, further polymerizing on the basis of the polymerized monomers, adding p-toluenesulfonic acid with the mass fraction of 0.5 percent as a catalyst, introducing nitrogen for protection, heating the reaction system to 220 ℃, stirring and reacting for 4 hours after the white solid is melted, stopping the reaction when the viscosity of the system is increased, and cooling to obtain a yellow transparent solid product, thus obtaining the carboxyl-containing hyperbranched polyesteramide 5 with the yield of 80 percent. The 5% thermal decomposition temperature of the product is 370 ℃, and the refractive index of the product is 1.57.
The following will use polycarbonate plastic systems as examples to illustrate the application effects of the carboxyl-containing hyperbranched polyesteramides 1-5 obtained in examples 1-4 and comparative example 1 in polycarbonate plastic systems, and see tables 1 and 2 for comparison of specific effects.
Example 5
0.01 part of carboxyl-containing hyperbranched polyesteramide 1 and 100 parts of Bayer 2405 polycarbonate granules are placed in a high-speed mixer to be mixed for 4 minutes and then are introduced into a sealed drying discharge hopper for standby; ten temperature zones in a double-screw extruder are heated to 300 ℃, preheated for 1.2 hours, and then fed, extruded and granulated to obtain the modified polycarbonate 1 based on the carboxyl-containing hyperbranched polyesteramide.
Example 6
2 parts of carboxyl-containing hyperbranched polyesteramide 1 and 100 parts of Bayer 2405 polycarbonate granules are placed in a high-speed mixer to be mixed for 4 minutes, and then the mixture is introduced into a sealed drying discharge hopper for standby; ten temperature zones in a double-screw extruder are heated to 300 ℃, preheated for 1.2 hours, and then fed, extruded and granulated to obtain the modified polycarbonate 2 based on the carboxyl-containing hyperbranched polyesteramide.
Example 7
10 parts of hyperbranched polyesteramide containing carboxyl 1 and 100 parts of Bayer 2405 polycarbonate granules are placed in a high-speed mixer to be mixed for 4 minutes, and then the mixture is introduced into a sealed drying discharge hopper for standby; ten temperature zones in a double-screw extruder are heated to 300 ℃, preheated for 1.2 hours, and then fed, extruded and granulated to obtain the modified polycarbonate 3 based on the carboxyl-containing hyperbranched polyesteramide.
Comparative example 2
100 parts of Bayer 2405 polycarbonate granules are introduced into a sealed dry discharge hopper for standby; ten temperature zones in the double-screw extruder are heated to 300 ℃, preheated for 1.2 hours, and then fed, extruded and granulated to obtain the polycarbonate which passes through the double screws once.
Example 8
0.5 part of carboxyl-containing hyperbranched polyesteramide 2, 80 parts of Bayer 2405 polycarbonate granules and 20 parts of calcium carbonate are placed in a high-speed mixer to be mixed for 4 minutes, and then the mixture is introduced into a sealed drying discharging hopper for standby; ten temperature zones in a double-screw extruder are heated to 300 ℃, preheated for 1.2 hours, and then fed, extruded and granulated to obtain the modified polycarbonate 4 based on the carboxyl-containing hyperbranched polyesteramide.
Example 9
Placing 5 parts of carboxyl-containing hyperbranched polyesteramide 4, 80 parts of Bayer 2405 polycarbonate granules, 20 parts of calcium carbonate and other certain amounts of heat stabilizer, antioxidant and the like into a high-speed mixer for mixing for 4 minutes, and then introducing into a sealed drying discharge hopper for later use; ten temperature zones in a double-screw extruder are heated to 300 ℃, preheated for 1.2 hours, and then fed, extruded and granulated to obtain the modified polycarbonate 5 based on the carboxyl-containing hyperbranched polyesteramide.
Example 10
Placing 8 parts of carboxyl-containing hyperbranched polyesteramide 3, 80 parts of Bayer 2405 polycarbonate granules, 20 parts of calcium carbonate and other certain amounts of heat stabilizer, antioxidant and the like into a high-speed mixer for mixing for 4 minutes, and then introducing into a sealed drying discharge hopper for later use; ten temperature zones in a double-screw extruder are heated to 300 ℃, preheated for 1.2 hours, and then fed, extruded and granulated to obtain the modified polycarbonate 6 based on the carboxyl-containing hyperbranched polyesteramide.
Comparative example 3
Placing 80 parts of Bayer 2405 polycarbonate granules, 20 parts of calcium carbonate and other certain amounts of heat stabilizer, antioxidant and the like into a high-speed mixer for mixing for 4 minutes, and then introducing into a sealed drying discharge hopper for later use; ten temperature zones in the double-screw extruder are heated to 300 ℃, preheated for 1.2 hours, and then fed, extruded and granulated to obtain the polycarbonate which passes through the double screws once.
TABLE 1 comparison of the Property parameters of the polycarbonate of comparative example 2 and of the modified polycarbonates of examples 5 to 7
TABLE 2 comparison of the Property parameters of the polycarbonate of comparative example 3 and of the modified polycarbonates of examples 8 to 9
As can be seen from the data in tables 1 and 2, compared with the unmodified polycarbonate, the carboxyl-containing hyperbranched polyester amide prepared by the preparation method of the carboxyl-containing hyperbranched polyester amide provided in the embodiment of the present application can improve the processing rheological property of the polycarbonate while improving or not affecting the mechanical property, and particularly, when more than 5 parts (corresponding to about 5% of the added amount of the carboxyl-containing hyperbranched polyester amide) of the carboxyl-containing hyperbranched polyester amide is added, the melt index of the polycarbonate or the polycarbonate/calcium carbonate composite material can be significantly increased, and the calcium carbonate can be better dispersed, so that the reinforcing effect of the polycarbonate can be improved.
Claims (6)
1. The carboxyl-containing high-refractive-index hyperbranched polyester amide is characterized by being prepared by the following method:
adding an aromatic polycarboxylic acid/polyanhydride monomer and a monoamino monohydroxy monomer into a reactor, adding a catalyst into the reactor, and carrying out prepolymerization reaction for 1-10 hours at 80-180 ℃ under the protection of inert gas to form a polymerized monomer;
then the temperature is raised to 120-250 ℃ and the reaction is carried out for 1-10 hours to obtain the carboxyl-containing hyperbranched polyesteramide with high refractive index;
the refractive index of the carboxyl-containing high-refractive-index hyperbranched polyesteramide is between 1.54 and 1.58, and the 5 percent thermal weight loss temperature can be higher than 390 ℃;
the aromatic polycarboxylic acid/polyacid anhydride monomer is selected from any one of trimellitic anhydride, pyromellitic anhydride, diphenylmethyl ether tetracarboxylic anhydride, benzophenone tetracarboxylic anhydride, biphenyl tetracarboxylic dianhydride or 3,3',4,4' -diphenyl sulfone tetracarboxylic dianhydride;
the monoamino monohydroxy monomer is selected from ethanolamine, propanolamine, isopropanolamine, butanolamine, isobutanolamine, pentanolamine, hexanolamine, N- (2-hydroxyethyl) piperazine, any one of 2-hydroxy-3-amino-5-methylpyridine, 1- (2-aminoethyl) -3-hydroxypyrrolidine, 3 '-amino-2' -hydroxyacetophenone, 1- (4-aminophenyl) -4- (4-hydroxyphenyl) piperazine, 4 '-amino-2' -hydroxyacetophenone, 4-hydroxy-2-aminobenzothiazole, 2-amino-3-hydroxyphenyloxazine, 2-amino-5-hydroxypyridine, and isomers of 2-amino-5-hydroxypyridine.
2. The carboxyl-containing high-refractive-index hyperbranched polyester amide as claimed in claim 1, wherein the molar ratio of the aromatic polycarboxylic acid/polyanhydride monomer to the monoamino monohydroxy monomer is 1:1 to 1: 3.
3. The carboxyl-containing high-refractive-index hyperbranched polyester amide as claimed in claim 1, wherein the amount of the catalyst added is 0.1-5% of the total mass of the aromatic polycarboxylic acid/polyanhydride monomer and the monoamino monohydroxy monomer.
4. The carboxyl group-containing high refractive index hyperbranched polyesteramide as claimed in claim 1 or 3, wherein the catalyst is selected from any one of concentrated sulfuric acid, phosphoric acid, zinc acetate, dibutyltin dilaurate, p-toluenesulfonic acid, tetraisopropyl titanate, tetraisobutyl titanate or thionyl chloride.
5. Use of the carboxyl-containing, high refractive index hyperbranched polyester amide according to any one of claims 1 to 4 as a modifier in the modification of plastic systems.
6. The use according to claim 5, wherein the carboxyl-containing hyperbranched polyester amide is added in an amount of 0.01 to 20% during the modification of a plastic system with a similar refractive index to the carboxyl-containing hyperbranched polyester amide.
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| CN112920436B (en) * | 2021-01-26 | 2022-05-20 | 安徽农业大学 | Application of polyesteramide as high-temperature-resistant heat-shrinkable film |
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