阅读说明：本技术 一种高性能黑色色膏及其制备方法 (High-performance black color paste and preparation method thereof ) 是由 李辰 魏文山 段若蒙 赵雁飞 王佳星 田禾 于 2021-07-27 设计创作，主要内容包括：本发明涉及黑色颜料技术领域,具体涉及一种高性能黑色色膏及其制备方法,本发明的高性能黑色色膏,包括组分含酸酐基团的化合物、含胺基的化合物和低熔点两亲固体,所述含酸酐基团的化合物和所述含胺基的化合物等摩尔量,所述低熔点两亲固体的添加量为所述含酸酐基团的化合物和所述含胺基的化合物的质量之和的10％～1000％,其组分简单,无溶剂,绿色环保,制备过程无需分散,制备容易,且本发明的黑色色膏无需碾磨处理,可在低熔点两亲固体物中高度分散,可有效提高其可加工性,可重复性,并减小色差；本发明的制备方法,使各组分在捏合机中反应变色,最终得到黑色色膏,其制备步骤简单,操作简便,制备容易,具有良好的应用前景。(The invention relates to the technical field of black pigments, in particular to a high-performance black paste and a preparation method thereof, wherein the high-performance black paste comprises components including an acid anhydride group-containing compound, an amino group-containing compound and a low-melting-point amphiphilic solid, the acid anhydride group-containing compound and the amino group-containing compound are in equimolar amount, the addition amount of the low-melting-point amphiphilic solid is 10-1000% of the sum of the mass of the acid anhydride group-containing compound and the amino group-containing compound, the components are simple, the solvent is not needed, the environment is protected, the preparation process is not needed to disperse, the preparation is easy, the black paste is not needed to be milled and can be highly dispersed in the low-melting-point amphiphilic solid, the processability and the repeatability of the black paste can be effectively improved, and the color difference is reduced; the preparation method provided by the invention has the advantages that the components react in the kneading machine to change color, and finally the black paste is obtained.)

1. The high-performance black paste is characterized by comprising components of an anhydride group-containing compound, an amine group-containing compound and a low-melting-point amphiphilic solid, wherein the molar amount of the anhydride group-containing compound and the amine group-containing compound is equal to the molar amount of the low-melting-point amphiphilic solid, and the addition amount of the low-melting-point amphiphilic solid is 10% -1000% of the sum of the mass of the anhydride group-containing compound and the mass of the amine group-containing compound.

2. The high-performance black paste according to claim 1, further comprising a component auxiliary agent, wherein the addition amount of the component auxiliary agent is 0.01 to 1% by mole of the acid anhydride group-containing compound.

3. The high performance black paste of claim 1, wherein the anhydride group containing compound is at least one of a perylene containing one anhydride group, a naphthalene containing one anhydride group, a perylene containing two anhydride groups, a naphthalene containing two anhydride groups, a benzene derivative containing one anhydride group, and a benzene derivative containing two anhydride groups.

4. The high performance black paste according to claim 1, wherein the amine group containing compound is at least one of benzene substituted with amine group at adjacent position, naphthalene substituted with amine group at adjacent position, or phenylalkylamine.

5. The high performance black paste according to claim 1, wherein the low melting amphiphilic solid is at least one of alkyl alkoxide, ethylene oxide-ethylene oxide polymer, styrene-acrylic polymer, acrylate-acrylic polymer, amphiphilic polyurethane, amphiphilic polyester, oxidized polyethylene, oxidized polypropylene, polypyrrolidone, phenolic resin, and benzene sulfonic acid-formaldehyde copolymer.

6. The high-performance black paste according to claim 2, wherein the auxiliary agent is a condensation reaction catalyst and/or a wetting agent.

7. The high performance black paste according to claim 1, wherein said anhydride group containing compound is selected from at least one of the following compounds:

。

8. the high performance black paste according to claim 1, wherein said amine group containing compound is at least one of the following compounds:

。

9. a method of preparing a high performance black paste according to any one of claims 2 to 8, comprising the steps of:

s1, weighing a compound containing an anhydride group, a compound containing an amino group, a low-melting-point amphiphilic solid and an auxiliary agent according to the addition amount for later use;

s2, adding the weighed compound containing the acid anhydride group, the weighed compound containing the amino group and the weighed low-melting-point amphiphilic solid into a kneader for reaction;

and S3, monitoring the reaction condition by adopting an infrared spectrum, and obtaining black color paste after the characteristic peak of the anhydride disappears, or adding an auxiliary agent to continue the reaction to obtain the black color paste.

10. The method for preparing a high performance black paste according to claim 9, wherein:

in S2, the added raw materials are kept at 80-130 ℃ in a kneader, stirred for 10 min-2 h in a nitrogen environment, and then heated to 150-300 ℃ for reaction;

and in S3, stopping heating after the characteristic peak of the acid anhydride disappears to obtain black color paste, or stopping heating after the characteristic peak of the acid anhydride disappears, cooling to room temperature, adding an auxiliary agent, then heating to 130-300 ℃ and continuing to react for 10 nin-1 h to obtain the black color paste.

Technical Field

The invention relates to the technical field of black pigments, in particular to a high-performance black paste and a preparation method thereof.

Background

In the pigment market, black and white are the two most dominant colors, where black is dominated by carbon black, including pigment black 6 and pigment black 7, however, carbon black not only absorbs visible light, but also absorbs a large amount of infrared light, and since the Total Solar Reflectance (TSR) of carbon black is usually only about 5%, the absorbed sunlight of carbon black under sunlight is quickly converted into heat, and due to the strong absorption of infrared light by carbon black, infrared light cannot reflect or penetrate the surface of an object containing carbon black, which may cause the infrared sensor for distance measurement or plastic classification to malfunction or the accuracy to be greatly reduced, therefore, organic black pigments and dyes other than carbon black are receiving more and more attention, such black pigments mainly absorb in the visible region, forming black seen with the naked eye, and have little or no absorption in the infrared region not seen with the naked eye, their TSR values may even be above 40%, so such pigments are also referred to as infrared-reflective or infrared-transmissive pigments, and as such pigments, in the prior art, WO2005030878 reports infrared-reflective black pigments obtained from mixtures of phthalocyanine and perylene diimide pigments; WO2013037928 reports infrared-reflective black pigments based on perylene diimide pigment mixtures with a TSR up to 41%; WO2012075369 reports a non-white dark (e.g. grey, black, brown) ir-transmissive coating of moderate viscosity, in which the pigments are mainly inorganic pigments but also perylene and phthalocyanine pigments, and other ir-reflective organic pigments, with a TSR of up to 41.5%; WO2020131841 reports a paint system which can be used for solar thermal management, wherein the black pigment contained therein is a perylene pigment and the TSR of the paint can reach more than 40%. It follows that perylene black pigments, due to their high TSR values, can replace carbon black as the preferred infrared reflective high performance black pigment. At present, for the preparation of perylene black pigments, WO2005078023 reports a preparation method of perylene black pigments, wherein 3,4,9, 10-perylenetetracarboxylic dianhydride and o-phenylenediamine or 1, 8-naphthalene diamine are used as raw materials, piperazine is used as an auxiliary agent, phenol is used as a solvent, and after the reaction is finished, the perylene black pigment powder is obtained by precipitation, filtration, washing, ball milling, refining, filtration and drying and finally air drying; WO2009074504 reports a method for preparing perylene pigment by using a mixing device, wherein a mixture of 3,4,9, 10-perylenetetracarboxylic dianhydride, an amine compound, piperazine and triethylene glycol is used for synthesizing the perylene pigment in a kneading machine, and after the steps of cooling, precipitating, washing, filtering, washing with water, acid washing, rehydration and the like are carried out after reaction, perylene pigment powder is obtained by drying; WO2020230293 reports a process for precipitation dispersion of perylene black pigments to give ultrafine powder pigments, which comprises hindering agglomeration of the pigment particles with alkali metal salts; therefore, the synthetic steps of the perylene black compound are complicated, and the dispersion of the perylene pigment also needs many steps, which involve a large amount of solvent and waste water.

To this end, chem.commun.2017,53,1229-1232 reported a process for the synthesis of alkyl chain substituted perylene pigments in an autoclave with water as solvent, with a conversion rate close to 100%, and the product obtained by drying after the reaction by filtration; while org.Lett.2011,13,4882-4885 reported that perylene and pyrene pigments were synthesized under the catalysis of zinc acetate under the solvent-free high-temperature solid melting condition, and the products could be purified by thermal sublimation.

In summary, perylene black pigments are one of the most popular infrared reflective pigments, but the preparation and synthesis thereof are complicated, the number of steps is large, the pigment particles are easy to agglomerate, and the pigment product with high dispersion rate and small particles is obtained by dispersion or grinding treatment, so a new black pigment preparation method is needed to better solve the above technical problems.

Disclosure of Invention

In order to solve the problems, the invention provides the high-performance black paste and the preparation method thereof, and the black paste has simple components, is green and environment-friendly and is easy to prepare; the preparation method of the commercial one has simple process flow and easy operation and preparation.

The technical scheme adopted by the invention is as follows:

the high-performance black paste comprises components of an anhydride group-containing compound, an amine group-containing compound and a low-melting-point amphiphilic solid, wherein the molar amount of the anhydride group-containing compound and the amine group-containing compound is equal to the molar amount of the low-melting-point amphiphilic solid, and the addition amount of the low-melting-point amphiphilic solid is 10% -1000% of the sum of the mass of the anhydride group-containing compound and the mass of the amine group-containing compound.

The adhesive further comprises a component auxiliary agent, and the addition amount of the auxiliary agent is 0.01-1% of the molar weight of the compound containing the acid anhydride group.

Further, the compound containing the acid anhydride group is at least one of perylene containing one acid anhydride group, naphthalene containing one acid anhydride group, perylene containing two acid anhydride groups, naphthalene containing two acid anhydride groups, benzene derivative containing one acid anhydride group and benzene derivative containing two acid anhydride groups.

Further, the compound containing the amine group is at least one of benzene with an adjacent position substituted by the amine group, naphthalene with an adjacent position substituted by the amine group or phenylalkylamine.

Further, the low melting point amphiphilic solid is at least one of alkyl alkoxide, ethylene oxide-ethylene oxide polymer, styrene acrylic acid polymer, acrylate acrylic acid polymer, amphiphilic polyurethane, amphiphilic polyester, oxidized polyethylene, oxidized polypropylene, polypyrrolidone, phenolic resin and benzene sulfonic acid-formaldehyde copolymer.

Further, the auxiliary agent is a condensation reaction catalyst and/or a wetting agent.

Further, the anhydride group-containing compound is selected from at least one of the following compounds:

further, the compound containing the amine group is at least one of the following compounds:

the preparation method of the high-performance black paste comprises the following steps:

s1, weighing a compound containing an anhydride group, a compound containing an amino group, a low-melting-point amphiphilic solid and an auxiliary agent according to the addition amount for later use;

s2, adding the weighed compound containing the acid anhydride group, the weighed compound containing the amino group and the weighed low-melting-point amphiphilic solid into a kneader for reaction;

and S3, monitoring the reaction condition by adopting an infrared spectrum, and obtaining black color paste after the characteristic peak of the anhydride disappears, or adding an auxiliary agent to continue the reaction to obtain the black color paste.

Further, the air conditioner is provided with a fan,

in S2, the added raw materials are kept at 80-130 ℃ in a kneader, stirred for 10 min-2 h in a nitrogen environment, and then heated to 150-300 ℃ for reaction;

and in S3, stopping heating after the characteristic peak of the acid anhydride disappears to obtain black color paste, or stopping heating after the characteristic peak of the acid anhydride disappears, cooling to room temperature, adding an auxiliary agent, then heating to 130-300 ℃ and continuing to react for 10 nin-1 h to obtain the black color paste.

The invention has the following beneficial effects:

1. the high-performance black paste comprises components including an acid anhydride group-containing compound, an amine group-containing compound and a low-melting-point amphiphilic solid, wherein the acid anhydride group-containing compound and the amine group-containing compound are in equimolar amount, and the addition amount of the low-melting-point amphiphilic solid is 10-1000% of the sum of the mass of the acid anhydride group-containing compound and the amine group-containing compound, so that the high-performance black paste is simple in component, free of solvent, green and environment-friendly, free of dispersion in the preparation process and easy to prepare, does not need to be milled, can be highly dispersed in the low-melting-point amphiphilic solid, and can effectively improve the processability and repeatability and reduce color difference;

2. the preparation method provided by the invention has the advantages that the components react in the kneading machine to change color, and finally the black paste is obtained.

Detailed Description

The invention will be further described with reference to preferred embodiments.

Example 1

Taking 1 molar equivalent of compound 1, 2 molar equivalents of compound b, 0.5 molar equivalent of diethanolamine, and 50 wt% of alkyl polyethylene oxide of the total weight of the compound 1, the compound b and the diethanolamine, stirring in a kneader at 110 ℃ for 1 hour under nitrogen environment, raising the temperature to 240 ℃, continuing the reaction, and monitoring the reaction completion condition by infrared spectrum until 1770cm in the infrared spectrum^-1Stopping heating after the characteristic peak of the acid anhydride at the position disappears, cooling to room temperature, adding 0.5 molar equivalent of alkyl diacid, then heating to 150 ℃, and continuing to react for 1 hour to obtain a black pasty product, wherein the main components of the black pasty product are as follows:

example 2

Taking 1 mol equivalent of compound 1, 2 mol equivalents of compound c, and copolymer of styrene and acrylic acid with 95% of the weight of the mixture of compounds 1 and c, stirring in a kneader at 110 deg.C under nitrogen for 1 hr, slowly raising the temperature to 180 deg.C within 3 hr, continuing the reaction, and monitoring the completion of the reaction by infrared spectroscopy, such as 1770cm in infrared spectroscopy^-1And (3) continuing the reaction if the characteristic peak of the acid anhydride at the position does not disappear, and finally obtaining a black pasty product, which mainly comprises the following components:

example 3

1 molar equivalent of compound 1, 2 molar equivalents of compound d, and1 and d copolymer of acrylonitrile and acrylic acid in an amount of 80% by weight of the mixture, stirred in a kneader at 110 ℃ for 1 hour under nitrogen, the temperature is slowly raised to 180 ℃ over 3 hours, the reaction is continued, the completion of the reaction is monitored by means of infrared spectroscopy, for example 1770cm in infrared spectroscopy^-1And (3) continuing the reaction if the characteristic peak of the acid anhydride at the position does not disappear, and finally obtaining a black pasty product, which mainly comprises the following components:

example 4

Taking 1 mol equivalent of compound 1, 2 mol equivalent of compound a, 0.5 mol equivalent of diethanolamine and copolymer of ethylene oxide and propylene oxide accounting for 110 percent of the total weight of the compound 1, a and the diethanolamine, stirring the mixture in a kneader for 1 hour at 110 ℃ under the nitrogen environment, raising the temperature to 240 ℃, continuing the reaction, and monitoring the completion of the reaction by infrared spectroscopy until 1770cm in the infrared spectroscopy^-1After the characteristic peak of the acid anhydride at the position disappears, stopping heating and cooling to room temperature, adding 0.5 molar equivalent of isocyanate polymer, heating to 150 ℃, and continuing to react for 1 hour to obtain a black pasty product, wherein the main components of the black pasty product are as follows:

example 5

Taking 1 molar equivalent of compound 3,1 molar equivalent of compound 5, 3 molar equivalents of compound a, 0.3 molar equivalent of zinc acetate and 50 wt% of copolymer of vinyl pyrrolidine and acrylic ester based on the total weight of the compounds 3, 5 and a, stirring for 1 hour at 110 ℃ in a kneader under nitrogen environment, raising the temperature to 180 ℃, continuing the reaction, and monitoring the completion of the reaction by infrared spectroscopy until 1770cm in the infrared spectroscopy^-1After the characteristic peak of the acid anhydride at the position disappears, the heating is stopped to obtain a black pasty product, which comprises the following main components:

example 6

Taking 1 mol equivalent of compound 3,1 mol equivalent of compound 4, 3 mol equivalent of compound a and 100 percent of copolymer of ethylene and vinyl alcohol by weight of the total weight of the compounds 3,4 and a, stirring the mixture in a kneader at 110 ℃ under nitrogen for 1 hour, raising the temperature to 200 ℃, continuing the reaction, and monitoring the completion of the reaction by infrared spectroscopy until 1770cm in the infrared spectroscopy^-1After the characteristic peak of the acid anhydride at the position disappears, the heating is stopped to obtain a black pasty product, which comprises the following main components:

example 7

Taking 1 molar equivalent of the compound 3,1 molar equivalent of the compound a, 3 molar equivalents of the compound b and 70 weight percent of polyester of the total weight of the compound 3, a and b, stirring the mixture in a kneader for 1 hour at 110 ℃ under a nitrogen environment, raising the temperature to 220 ℃, continuing the reaction, and monitoring the completion of the reaction by infrared spectroscopy until 1770cm in the infrared spectroscopy^-1After the characteristic peak of the acid anhydride at the position disappears, the heating is stopped to obtain a black pasty product, which comprises the following main components:

example 8

Taking 1 molar equivalent of compound 1, 2 molar equivalents of compound e and 100 wt% of copolymer of acrylic acid and ethylene based on the total weight of the compounds 1 and e, stirring in a kneader at 110 ℃ for 1 hour under nitrogen atmosphere, raising the temperature to 160 ℃, continuing to react for 5 hours, raising the temperature to 155 ℃, monitoring the completion of the reaction by infrared spectroscopy after the reaction is carried out overnightE.g. 1770cm in the infrared spectrum^-1And (3) continuing the reaction if the characteristic peak of the acid anhydride at the position does not disappear, or stopping heating to obtain a black pasty product, wherein the main components are as follows:

the black pastes obtained in examples 1, 2, 4 and 5 were mixed with PMMA and injection molded to obtain black flakes having a pigment content of 0.2 to 1% by weight, the black paste obtained in example 3 was mixed with EBA and injection molded to obtain black flakes having a pigment content of 0.2 to 1% by weight, the black flakes produced using the black paste of examples 1 to 5 were compared in chromaticity value with carbon black and organic pigment black CAS79534-91-1(PTCBI), and L, a and b of CIELAB color difference coordinates were obtained using a color difference meter, and the results were as follows:

examples	1	2	3EBA	4	5	Carbon black	PTCBI
								L	28	27	38	25	29	28	27
a*	1.27	-1.99	-1.26	-0.49	0.06	0.17	1.02
								b*	2.95	2.91	22.39	0.27	-1.35	0.92	2.33

The solar reflectance of the black flake in example 1 and PTCBI was calculated by a reflectance spectrum, and the obtained PTCBI was 20.5% and the sample 1 was 20.4% in the wavelength range of 280-2000nm under the condition of a white substrate; in the infrared wavelength range of 750-2000nm, the sample is 36.6 percent, and the PTCBI is 35.9 percent; the TSR data for the no-floor condition were: in the wavelength range of 280-2000nm, PTCBI is 13.2%, and sample 1 is 15.1%; in the infrared wavelength range of 750-2000nm, the PTCBI was 20.4%, and that of sample 1 was 24.8%.

The black pigment color paste based on perylene and naphthalene prepared by the invention has the advantages of simple preparation process, simple and convenient operation, no grinding treatment and high dispersion of organic pigment in amphiphilic solid, so that the preparation process does not need dispersion, and the black pigment color paste can be directly mixed and dyed with plastics, coatings, paints, printing ink, ink and the like to obtain corresponding infrared reflection black products.

The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.