阅读说明：本技术 稠环芳香类色素和高分子材料的混合物、其制备方法及其下游产品 (Mixture of condensed ring aromatic pigment and high molecular material, preparation method and downstream product thereof ) 是由 李辰 魏文山 段若蒙 赵雁飞 刘志宏 田禾 于 2019-10-30 设计创作，主要内容包括：本申请涉及稠环芳香类色素和高分子材料的混合物、其制备方法及其下游产品。该方法可选用不同的热塑性高分子材料与用于生成稠环芳香类色素的反应物混合,通过调节各原料之间的反应摩尔比以及在整个反应体系中的用量,使反应物和高分子材料的混合物能够通过挤出或捏合,一步得到稠环芳香类色素和高分子材料的混合物,相较于色素,色素的原料反应物在高分子材料中有更好的分散性,因此经挤出或捏合,色素能够直接生成并均匀分散在高分子材料中,并且挤出或捏合过程中无需加入任何溶剂,邻二胺化合物也几乎完全被消耗,得到的混合物无需提纯,避免了传统色素合成过程中三废的产生,极大地简化了工艺流程,降低了能耗。(The application relates to a mixture of condensed ring aromatic pigments and high molecular materials, a preparation method thereof and downstream products thereof. The method can select different thermoplastic high polymer materials to be mixed with reactants for generating the condensed ring aromatic pigment, and the mixture of the reactants and the high polymer materials can be extruded or kneaded by adjusting the reaction molar ratio among the raw materials and the dosage in the whole reaction system to obtain the mixture of the condensed ring aromatic pigment and the high polymer materials in one step.)

1. A preparation method of a mixture of a condensed ring aromatic pigment and a high polymer material is characterized by comprising the following steps:

mixing a thermoplastic high polymer material and a reactant for forming the condensed ring aromatic pigment, and kneading or extruding to obtain a mixture of the condensed ring aromatic pigment and the high polymer material; the reactants for forming the condensed ring aromatic pigment comprise an anhydride functionalized condensed ring aromatic compound derivative, an o-diamine compound and a catalyst, wherein the mass content of the condensed ring aromatic pigment in a mixture of the condensed ring aromatic pigment and a high polymer material is 0.1-50%, the molar ratio of the o-diamine compound to an anhydride functional group in the anhydride functionalized condensed ring aromatic compound derivative is 1 (1-1.1), and the molar ratio of the catalyst to the anhydride functionalized condensed ring aromatic compound derivative is (0.01-10) 1.

2. The method for producing a mixture of a fused ring aromatic dye and a polymer material according to claim 1, wherein the acid anhydride-functionalized fused ring aromatic compound derivative is at least one compound selected from the group consisting of:

wherein R is₁-R₁₂Each independently selected from one of H, halogen, amino, substituted amino, C1-C30 alkyl, C1-C20 alkoxy, phenolic hydroxyl, substituted phenolic hydroxyl, phenyl, substituted phenyl, naphthyl, substituted naphthyl, sulfydryl, substituted sulfydryl, cyano, silyl, carboxylate, sulfonic acid group, sulfonate group, phosphoric acid group and phosphate group;

r' is selected from one of H, C1-C30 alkyl, C1-C20 alkoxy, phenyl, substituted phenyl, naphthyl, substituted naphthyl and silyl;

X₁and X₂Are each independently selected from CH₂CHR ", CR" R' ", NR", O, S, S ═ O and SO₂Wherein R 'and R' are respectively and independently selected from H, C1-C30 alkyl, C1-C20 alkoxy and substituted aromatic group.

3. The method for producing a mixture of a condensed ring aromatic dye and a polymer material according to claim 1, wherein the o-diamine compound is at least one compound selected from the group consisting of:

wherein R is₁、R₂、R₃、R₄Each independently selected from at least one of H, halogen, cyano, nitro, aldehyde group, carboxyl, anhydride, amide, imide, ester group, alkyl, alkoxy or sulfydryl;

r' is respectively and independently selected from H, C1-C30 alkyl, C1-C20 alkoxy and substituted aromatic group;

x is S, N, O, CO, SO₂Or a five or six membered ring structure of the C group.

4. The method for producing a mixture of a condensed ring aromatic dye and a polymeric material according to claim 1, wherein the catalyst is at least one selected from the group consisting of a water scavenger, a lewis acid, a lewis base, and a metal oxide.

5. The method for producing a mixture of a condensed ring aromatic pigment and a polymer material according to any one of claims 1 to 4, wherein the extrusion temperature is 120 to 330 ℃ in the feed section, 150 to 360 ℃ in the extrusion section, and 180 to 380 ℃ in the discharge section, respectively, in the material advancing direction.

6. A mixture of the condensed ring aromatic pigment prepared by the preparation method of any one of claims 1 to 5 and a polymer material.

7. A crude masterbatch, which is characterized in that the crude masterbatch is prepared from the mixture of the condensed ring aromatic pigment of claim 6 and a high molecular material through cooling, drying and granulating.

8. A color masterbatch product, characterized in that, the color masterbatch product is obtained by mixing the raw material of the mixture of the condensed ring aromatic pigment and the high molecular material of claim 6 with additives, extruding, cooling, drying and cutting into particles; or mixing the crude masterbatch of claim 7 with additives, extruding, cooling, drying, and granulating.

9. The masterbatch product according to claim 8, wherein the particle size of the masterbatch product is 200 μm to 0.5 cm.

10. A polymeric pigment obtained by milling the crude masterbatch of claim 7 or the masterbatch of claim 8.

11. The polymeric pigment according to claim 10, wherein the polymeric pigment has a particle diameter of 0.01 to 100 μm.

Technical Field

The invention relates to the technical field of pigments, in particular to a mixture of condensed ring aromatic pigments and high molecular materials, a preparation method and downstream products thereof.

Background

The fused ring aromatic Vat dye (Vat Dyes) has bright color, excellent fastness and excellent performance in the aspects of light resistance, solvent resistance and the like. However, the fused ring aromatic compounds have poor dispersibility in the production process, and need a solvent with a high boiling point and difficult removal, so that a large amount of waste liquid is generated, and the purification of dye molecules is also very difficult, so that the dyes have low reaction yield and high price, and the processing process is relatively more complex, thereby greatly limiting the application and development of the dyes.

US20080139813 uses metal catalysts such as ammonium molybdate, molybdenum oxide, molybdenum carbonyl, titanium carbonyl, iron carbonyl and the like, and perylene-3, 4,9, 10-tetracarboxylic acid, 1,4,5, 8-naphthalene-tetracarboxylic acid and anhydrides and imides thereof are reacted with amine in the presence of solvent azomethylpyrrolidone (NMP) to obtain reaction products of perylene dianhydride and phenylenediamine, wherein the reaction yield is up to 96.7%, the whole reaction needs to be carried out at about 200 ℃, the reaction time exceeds 20 hours, and the products after the reaction need to be washed and purified by NMP and sulfuric acid to obtain final products, and the process inevitably generates a large amount of waste liquid containing NMP, sulfuric acid and alkali.

US20070151478 is a process for the synthesis of black pigments by reaction of perylene or naphthalene dianhydrides with aromatic diamines using high boiling solvents such as nitrobenzene, trichlorobenzene, N-Dimethylformamide (DMF) etc. at 150 ℃ to 250 ℃ and using zinc chloride, zinc acetate, acetic acid, hydrochloric acid, piperazine etc. as catalysts. Therefore, most of reaction solvents designed under the conditions are very toxic, and waste liquid after reaction can also damage the environment.

WO2009074504 uses tetracarboxylic acid and derivatives, amine compounds, additives and wetting agents to synthesize perylene dyes or pigments by using a mixing device, has the advantages of long synthesis time and high temperature, needs alcohol solvents in synthesis, needs various solvents, acids and bases for purification of crude products after reaction, and does not reduce the amount of waste liquid generated in the synthesis of the pigments.

CN108329466 uses in situ polymerization to link perylenetetracarboxylic dianhydride to the polymer chain of nylon 6 to obtain nylon 6 material containing perylene dye, but the reaction temperature is high, the reaction time is long, and the use of toxic organic solvent such as chloroform is not excluded.

EP0892018 reports a composite of a pigment and a polymer obtained by mixing common organic pigment molecules with a polymerizable substance and heating and cooling. The pigment molecules used in this process have great limitations and require functional substituents that can react. And most of the polymerizable substances are liquid at normal temperature, so that an extruder which has higher processing performance and can be used for liquid sampling is required for processing the materials. In contrast, EP654711, EP542669 and EP456610 likewise produce fluorescent pigments. Since these pigments are not prepared by a method of truly synthesizing pigment molecules, waste liquids, waste solids, waste gases, etc. generated when synthesizing the pigment molecules are not avoided. Also J.APPL.POLYM.SCI.2015, DOI:10.1002/APP.42172 report the synthesis of polymerizable naphthalimide fluorescent dyes to prepare polyethylene fluorescent polymers, but the polymerizable naphthalimide also needs to be synthesized by a traditional method and the generation of waste liquid cannot be avoided.

Disclosure of Invention

Based on the above, there is a need for a method for preparing a mixture of fused ring aromatic pigments and polymer materials without purification and generation of three wastes, which comprises the following steps:

a preparation method of a mixture of a condensed ring aromatic pigment and a high polymer material comprises the following steps:

mixing a thermoplastic high polymer material and a reactant for forming the condensed ring aromatic pigment, and kneading or extruding to obtain a mixture of the condensed ring aromatic pigment and the high polymer material; the reactants for forming the condensed ring aromatic pigment comprise an anhydride functionalized condensed ring aromatic compound derivative, an o-diamine compound and a catalyst, wherein the mass content of the condensed ring aromatic pigment in a mixture of the condensed ring aromatic pigment and a high polymer material is 0.1-50%, the molar ratio of the o-diamine compound to an anhydride functional group in the anhydride functionalized condensed ring aromatic compound derivative is 1 (1-1.1), and the molar ratio of the catalyst to the anhydride functionalized condensed ring aromatic compound derivative is (0.01-10) 1.

In one embodiment, the anhydride functionalized fused ring aromatic compound derivative is selected from at least one of the following compounds:

wherein R is₁-R₁₂Each independently selected from H, halogen, amino, substituted amino, C1-C30 alkyl, C1-C20 alkoxy, phenolic hydroxyl, substituted aminoOne of substituted phenolic hydroxyl, phenyl with substituent, naphthyl with substituent, mercapto with substituent, cyano, silyl, carboxylate, sulfonic acid group, sulfonate group, phosphoric acid group and phosphate group;

r' is selected from one of H, C1-C30 alkyl, C1-C20 alkoxy, phenyl, substituted phenyl, naphthyl, substituted naphthyl and silyl;

X₁and X₂Are each independently selected from CH₂CHR ", CR" R' ", NR", O, S, S ═ O and SO₂Wherein R 'and R' are respectively and independently selected from H, C1-C30 alkyl, C1-C20 alkoxy and substituted aromatic group.

In one embodiment, the ortho-diamine compound is selected from at least one of the following compounds:

wherein R is₁、R₂、R₃、R₄Each independently selected from at least one of H, halogen, cyano, nitro, aldehyde group, carboxyl, anhydride, amide, imide, ester group, alkyl, alkoxy or sulfydryl;

r' is respectively and independently selected from H, C1-C30 alkyl, C1-C20 alkoxy and substituted aromatic group;

x is S, N, O, CO, SO₂Or a five or six membered ring structure of the C group.

In one embodiment, the catalyst is selected from at least one of a water scavenger, a lewis acid, a lewis base, and a metal oxide.

In one embodiment, the extrusion temperature is 120-330 ℃ in the feeding section, 150-360 ℃ in the extrusion section and 180-380 ℃ in the sample outlet section along the material advancing direction.

The application also provides a mixture of the condensed ring aromatic pigment prepared by the preparation method and a high polymer material.

In addition, the application also provides downstream products of the mixture of the fused ring aromatic pigment and the high polymer material, such as a crude masterbatch product, a masterbatch product and a high polymer pigment, and the specific scheme is as follows:

the crude color master batch is prepared by cooling, drying and granulating the mixture of the condensed ring aromatic pigment and a high polymer material.

A color master batch product is prepared by mixing the raw materials of the mixture of the condensed ring aromatic pigment and the high polymer material with additives, extruding, cooling, drying and granulating; or mixing the crude color master batch with an additive, extruding, cooling, drying and granulating to obtain the color master batch.

In one embodiment, the particle size of the color master batch product is 200 micrometers to 0.5 cm.

The polymer pigment is prepared by grinding the crude color master batch or the product of the color master batch.

In one embodiment, the particle size of the polymer pigment is 0.01-100 μm.

The method for preparing the mixture of the fused ring aromatic pigment and the polymer material can select different thermoplastic polymer materials to be mixed with reactants (anhydride functionalized fused ring aromatic compound derivative, o-diamine compound and catalyst) for forming the fused ring aromatic pigment according to the compatibility, the processing temperature and the polarity, the mixture of the raw materials can be extruded or kneaded by adjusting the reaction molar ratio among the raw materials and the dosage in the whole reaction system, the mixture of the fused ring aromatic pigment and the polymer material can be obtained by one step, compared with the pigment, the raw material reactants of the pigment have better dispersibility in the polymer material, therefore, the pigment can be directly generated and uniformly dispersed in the polymer material by extrusion or kneading, and the o-diamine compound is almost completely consumed without adding any solvent in the extrusion or kneading process, the obtained mixture does not need to be separated and purified, the generation of three wastes in the traditional pigment synthesis process is avoided, the process flow is greatly simplified, the energy consumption is reduced, the required labor is reduced, and the production cost is also reduced.

In addition, according to the preparation method of the mixture of the fused ring aromatic pigment and the high polymer material, reactants for generating different pigments can be selected according to needs, the possible colors of the product are combined, more colors can be obtained, and compared with the traditional method for mixing different pigments, the color of the mixture obtained by the method is more uniform.

In addition, because the raw material reactant of the pigment has better dispersibility in the high polymer material, the pigment can be directly generated and uniformly dispersed in the thermoplastic high polymer material after being extruded or kneaded, and compared with the primary pigment, the mixture obtained by mixing the pigment and the thermoplastic high polymer material has better compatibility.

Drawings

FIG. 1 is a reflection spectrum of a crude masterbatch prepared in example 4 mixed with ABS;

FIG. 2 is a reflection spectrum of a crude masterbatch prepared in example 7 mixed with ABS;

FIG. 3 is a reflection spectrum of a crude masterbatch prepared in example 9 mixed with ABS;

FIG. 4 is a chart of the reflectance spectrum of the crude masterbatch prepared in example 10 mixed with ABS;

FIG. 5 is a chart of the reflectance of crude masterbatch prepared in example 13 mixed with ABS;

FIG. 6 is a reflection spectrum of a crude masterbatch prepared in example 14 mixed with ABS;

FIG. 7 is a chart of the reflectance of crude masterbatch prepared in example 15 mixed with ABS;

FIG. 8 is a chart of the reflectance of crude masterbatch prepared in example 16 mixed with ABS.

Detailed Description

In order that the invention may be more fully understood, a more particular description of the invention will now be rendered by reference to specific embodiments thereof that are illustrated in the appended drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.

A method for preparing a mixture of a condensed ring aromatic dye and a polymer material according to an embodiment includes the steps of:

and mixing the thermoplastic high polymer material and the reactant for forming the condensed ring aromatic pigment, and kneading or extruding to obtain a mixture of the condensed ring aromatic pigment and the high polymer material.

The reactants for forming the condensed ring aromatic pigment comprise an anhydride functionalized condensed ring aromatic compound derivative, an o-diamine compound and a catalyst.

In the kneading or extruding process, the acid anhydride functionalized fused ring aromatic compound derivative and the o-diamine compound can react under the action of a catalyst to obtain the fused ring aromatic pigment.

Further, the acid anhydride functionalized fused ring aromatic compound derivative is selected from at least one of the following compounds:

wherein R is₁-R₁₂Each independently selected from H, halogen, amino, substituted amino, C1-C30 alkyl, C1-C20 alkoxy, phenolic hydroxyl, substituted phenolic hydroxyl, phenyl, substituted phenyl, naphthyl, substituted naphthyl, mercapto, substituted mercapto, cyano, silyl, carboxylate, sulfonic acid group, sulfonate group, phosphoric acid group and phosphate group；

R' is selected from one of H, C1-C30 alkyl, C1-C20 alkoxy, phenyl, substituted phenyl, naphthyl, substituted naphthyl and silyl;

X₁and X₂Are each independently selected from CH₂CHR ", CR" R' ", NR", O, S, S ═ O and SO₂Wherein R 'and R' are respectively and independently selected from H, C1-C30 alkyl, C1-C20 alkoxy and substituted aromatic group.

Further, the ortho-diamine compound is selected from at least one of the following compounds:

wherein R is₁、R₂、R₃、R₄Each independently selected from at least one of H, halogen, cyano, nitro, aldehyde group, carboxyl, anhydride, amide, imide, ester group, alkyl, alkoxy or sulfydryl;

r' is respectively and independently selected from H, C1-C30 alkyl, C1-C20 alkoxy and substituted aromatic group;

x is S, N, O, CO, SO₂Or a five or six membered ring structure of the C group.

In the present embodiment, the fused ring aromatic dye in the mixture of the fused ring aromatic dye and the polymer material is selected from at least one of the following compounds:

it is to be understood that the fused ring aromatic pigments which can be produced by the present application are not limited to the above-described ones, and any fused ring aromatic pigments which can be obtained by reacting an acid anhydride-functionalized fused ring aromatic compound derivative with an ortho-diamine compound are within the scope of the present application and are not exemplified herein.

Furthermore, the mass content of the condensed ring aromatic pigment in the mixture of the condensed ring aromatic pigment and the high molecular material is 0.1-50%.

The method can be understood that the molar ratio of the o-diamine compound to the anhydride functional group in the anhydride functionalized fused ring aromatic compound derivative is controlled to be 1 (1-1.1), the molar ratio of the catalyst to the anhydride functionalized fused ring aromatic compound derivative is controlled to be 0.1-10: 1, so that the o-diamine compound and the anhydride functionalized fused ring aromatic compound derivative are basically and completely reacted under the action of the catalyst, the content of the o-diamine compound in the obtained mixture is lower than 10ppm, and the toxicity and the carcinogenicity of the product are reduced.

Further, the catalyst is selected from at least one of water removing agents (such as quicklime, activated alumina, calcium chloride, calcium sulfate, lithium chloride, sodium sulfate, etc.), lewis acids, lewis bases (such as zinc chloride, zinc acetate, titanium chloride, alkylamine, etc.), and metal oxides (such as titanium oxide, zinc oxide, alumina, etc.).

Further, the thermoplastic polymer material is at least one selected from the group consisting of polyolefin, polyaromatic substituted olefin, polyacrylate, polyhalogenated olefin, polyimide, polyester, polyoxymethylene, polylactic acid, acrylonitrile-butadiene-styrene copolymer (ABS resin), Polybenzimidazole (PBI), Polyetheretherketone (PEEK), Polyetherimide (PEI), Polyethersulfone (PES), polyphenylene oxide (PPO), polyphenylene sulfide (PPS), polyvinylidene fluoride (PVDF), Polycarbonate (PC), and Polyamide (PA).

Further, extrusion is carried out in an extruder. The extruder may be a single screw extruder or a twin screw extruder.

Further, the extrusion temperature along the material advancing direction is respectively: the feeding section is 120-330 ℃, the extrusion section is 150-360 ℃, and the sample outlet section is 180-380 ℃.

It will be appreciated that the temperature profile of the extrusion reaction is adapted to the total length of the extruder, for example for a twin-screw extruder having 10 sections, the temperature profile application zones of the extrusion reaction are shown in the following table:

for a single screw extruder with 10 sections, the temperature profile application region for the extrusion reaction is shown in the following table:

of course, the temperature profile described above may also be applied to a greater or lesser number of extruder stages, generally depending on the reactants and thermoplastic polymeric materials selected for forming the fused ring aromatic colorant.

The method for preparing the mixture of the fused ring aromatic pigment and the polymer material can select different thermoplastic polymer materials to be mixed with reactants (an acid anhydride derivative, an o-diamine compound and a catalyst) for forming the fused ring aromatic pigment according to compatibility, processing temperature and polarity, the mixture of the reactants can be extruded or kneaded by adjusting the reaction molar ratio among the raw materials and the amount of the reactants in the whole reaction system, the mixture of the fused ring aromatic pigment and the polymer material can be obtained in one step, compared with the pigment, the raw material reactants of the pigment have better dispersibility in the polymer material, therefore, the pigment can be directly generated and uniformly dispersed in the polymer material by extrusion or kneading, no solvent is added in the extrusion or kneading process, the o-diamine compound is almost completely consumed, and the obtained mixture does not need to be separated and purified, avoids the generation of three wastes in the traditional pigment synthesis process, greatly simplifies the process flow, and not only can reduce energy consumption and labor required, but also can reduce production cost.

It will be appreciated that by selecting the reactants for forming the different pigments, in combination with the possible colours of the product, it is possible to formulate colours other than the three primary colours, such as black, during extrusion or kneading, i.e. by processing using reactants which produce red, yellow and blue pigments; green, it can be processed by using reactants that produce yellow and blue pigments. Compared with the traditional method for mixing different pigments, the color of the mixture obtained by the method is more uniform.

In addition, because the raw material reactant of the pigment has better dispersibility in the high polymer material, the pigment can be directly generated and uniformly dispersed in the thermoplastic high polymer material through extrusion or kneading, and compared with a method of firstly generating the pigment and then mixing the pigment and the thermoplastic high polymer material, the mixture has better compatibility.

Further, the mixture of the condensed ring aromatic pigment and the high polymer material is cooled, dried and granulated to obtain a crude color master batch.

Furthermore, in order to obtain a high-quality color master batch product, additives (such as a flame retardant, a fluorescent whitening agent, an ultraviolet absorbent, an antioxidant, a lubricant, a plasticizer, an antibacterial agent and other fillers required by high polymers) required by the traditional color master batch can be selectively mixed with the crude color master batch, and the color master batch product can be obtained by extrusion, cooling, drying and granulating. Or selectively mixing the additive and the raw materials of the mixture of the condensed ring aromatic pigment and the high polymer material, and then extruding, cooling, drying and granulating to obtain the color master batch product.

Wherein the particle size of the color master batch product is 200 mu m-0.5 cm.

And further grinding the crude color master batch or the color master batch product to obtain the high-quality high-molecular pigment.

Further, the particle diameter of the polymer pigment is 0.01 to 100 μm.

The following are specific examples.

In order to better test the performance of the crude master batch, the crude master batch is mixed with ABS at the concentration of 1 percent and then is subjected to injection molding to obtain an opaque sheet, and the reflection spectrum of the opaque sheet is tested.