CN-122011031-A - DPP phosphorus-containing color flame retardant, and preparation method and application thereof

CN122011031ACN 122011031 ACN122011031 ACN 122011031ACN-122011031-A

Abstract

The invention discloses a DPP phosphorus-containing color flame retardant, a preparation method and application thereof, and relates to the technical field of polymer material additives and functional organic molecules, wherein the general structure of the DPP phosphorus-containing color flame retardant compound is DPP- [ N- (CH 2) m -O-P (=O) (OR) (OR ') ]2, wherein DPP is a diketopyrrolopyrrole chromogenic skeleton; N is a lactam nitrogen atom of DPP skeleton, CH2 is a methylene group, m is an integer from 2 to 6, O-P (=O) (OR) (OR ') is a phosphate OR phosphonate structural unit, R and R ' are independently selected from C1-C12 alkyl, C6-C14 aryl, substituted phenoxy OR substituted alkoxy. According to the invention, through covalently introducing a phosphorus-containing flame-retardant side chain on a lactam nitrogen atom of a DPP (dipeptidyl peptidase) chromogenic skeleton, a single molecule has stable coloring capability and flame-retardant contribution.

Inventors

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Assignees

浙江材华科技有限公司

Dates

Publication Date: 20260512
Application Date: 20260204

Claims (10)

1. The DPP type phosphorus-containing color flame retardant is characterized in that the general structure of the DPP type phosphorus-containing color flame retardant compound is shown as a formula (I): DPP-[N-(CH 2 ) m -O-P(=O)(OR)(OR′)] 2 (I) Wherein DPP is a diketopyrrolopyrrole chromogenic framework, the DPP framework is provided with Ar1 and Ar2 substituent groups at the 3,6 positions, and Ar1 and Ar2 are the same or different; N is a lactam nitrogen atom of a DPP skeleton; CH 2 is a methylene group consisting of a carbon atom and a hydrogen atom; m is an integer of 2 to 6; -O-P (=o) (OR') is a phosphate OR phosphonate structural unit; R and R' are independently selected from a single group of C 1 -C 12 alkyl, C 6 -C 14 aryl, substituted phenoxy or substituted alkoxy.
2. The DPP-type phosphorus-containing colored flame retardant according to claim 1, wherein Ar1 and Ar2 are independently selected from a single group of phenyl, p-methylphenyl, pyridyl, thienyl, pyrrolyl, tetrahydropyrrolyl and pyrazolidinyl.
3. The DPP-based phosphorus-containing colored flame retardant according to claim 2, wherein when Ar1/Ar2 is selected as phenyl, the DPP-based phosphorus-containing colored flame retardant compound is: When Ar1/Ar2 is selected as p-methylphenyl, the DPP phosphorus-containing color flame retardant compound is as follows: when Ar1/Ar2 is selected as pyridyl, the DPP phosphorus-containing color flame retardant compound is as follows: when Ar1/Ar2 is selected as thienyl, the DPP phosphorus-containing color flame retardant compound is as follows: When Ar1/Ar2 is selected as a pyrrole group, the DPP phosphorus-containing color flame retardant compound is as follows: When Ar1/Ar2 is selected as the tetrahydropyrrole, the DPP phosphorus-containing color flame retardant compound is as follows: when Ar1/Ar2 is selected as the tetrahydropyrrole, the DPP phosphorus-containing color flame retardant compound can be: when Ar1/Ar2 is selected as pyrazolidinyl, the DPP phosphorus-containing color flame retardant compound is as follows: 。
4. The DPP type phosphorus-containing color flame retardant according to claim 1, wherein R is ethyl, propyl or butyl, and R' is phenoxy or p-alkyl substituted phenoxy.
5. The DPP-type phosphorus-containing colored flame retardant according to claim 1, wherein m is 2 or 3.
6. A process for the preparation of a DPP-based phosphorus-containing colored flame retardant according to any one of claims 1-5, comprising: Ar-CN and dialkyl succinate or dialkyl succinate are used as raw materials, strong alkali is added into an alcohol solvent for condensation cyclization to obtain 3, 6-disubstituted DPP with a lactam structure of which the two ends are N-H, and different Ar-CN is selected to obtain DPP mother cores with different colors and electronic structures, wherein the reaction formula is shown as follows: Taking substituted phosphorus oxychloride or phosphorus dichlorophosphate as a phosphorus source, carrying out alcoholysis with alcohol/phenol, and further reacting with halogenated alcohol to obtain a phosphate activated intermediate with halogenated alkyl at the tail end; Performing N-alkylation reaction on a DPP mother nucleus and a phosphate activated intermediate with a halogenated alkyl at the tail end in a polar solvent in the presence of alkali to enable lactam nitrogen at the two ends to be substituted, thereby obtaining the target DPP phosphorus-containing color flame retardant, wherein the reaction formula is as follows: After the reaction is finished, the target DPP phosphorus-containing color flame retardant is subjected to water washing, extraction, solvent recrystallization or column chromatography purification to obtain a pure product.
7. A polymeric flame retardant coloring composition, characterized in that the polymeric flame retardant coloring composition comprises a polymeric resin and the DPP-type phosphorus-containing colored flame retardant according to any one of claims 1 to 5; The mass fraction of the DPP phosphorus-containing color flame retardant in the high polymer material flame-retardant coloring composition is 0.05-2.0 wt%.
8. The flame-retardant and colored composition of claim 7, wherein the polymer resin is selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate, polyamide, thermoplastic polyurethane, polycarbonate, and polypropylene.
9. The polymeric flame retardant coloring composition of claim 8, further comprising one or more phosphorus/nitrogen containing flame retardants selected from one or more combinations of aluminum phosphinate, intumescent flame retardants, phosphate based flame retardants.
10. The method for coloring and flame-retarding modification of the stock solution of the high polymer material is characterized in that the DPP type phosphorus-containing color flame retardant according to any one of claims 1-5 is melt-blended with high polymer resin and molded to obtain a flame-retarding colored product, wherein the melt-blending temperature is 200-300 ℃.

Description

DPP phosphorus-containing color flame retardant, and preparation method and application thereof Technical Field The invention relates to the technical field of polymer material additives and functional organic molecules, in particular to a DPP phosphorus-containing color flame retardant, a preparation method and application thereof. Background In the field of engineering plastics and fiber materials, the color effect and flame-retardant safety often need to be met simultaneously. In the prior industrial practice, the colorant (pigment/dye) and the flame retardant are usually added in parallel as two independent auxiliary agents, and the parallel scheme of combining the colorant with the flame retardant is easy to cause the following problems: (1) The small molecular flame retardant can volatilize or migrate in high-temperature processing, so that the long-term flame retardant effect is attenuated; (2) Compatibility or thermal stability interference may occur between the flame retardant and the pigment, causing color phase drift, dispersion deterioration and even precipitation; (3) To achieve the target flame retardant rating, the addition of the flame retardant is increased, thereby diluting the effective content of the pigment, resulting in insufficient color strength or requiring additional pigment addition, further increasing the formulation complexity. The DPP color development system is an important high-performance organic pigment/dye matrix, and has the advantages of high molar absorptivity, good color purity, excellent light resistance and weather resistance, good thermal stability in a plastic processing temperature range and the like. By adjusting the aryl/heteroaryl substitution of the DPP skeleton at the 3,6 positions, the controllable adjustment of colors from yellow orange, red to purplish red and the like can be realized, and the compatibility of different polymer systems can be considered. However, the existing DPP pigment mainly bears the coloring function and cannot provide flame retardant contribution, while the traditional phosphorus-containing flame retardant is mostly non-chromophoric molecules, so that the flame retardant effect is difficult to achieve on the premise of not affecting the color. Accordingly, there is a need to provide a new class of colored flame retardants that are self-colored, while also having a phosphorus-containing flame retardant structure to reduce migration, improve processing stability, and simplify formulation systems. For the problems in the related art, no effective solution has been proposed at present. Disclosure of Invention Aiming at the problems in the related art, the invention provides a DPP phosphorus-containing color flame retardant, and a preparation method and application thereof, so as to overcome the technical problems in the prior art. For this purpose, the invention adopts the following specific technical scheme: according to a first aspect of the present invention, there is provided a DPP-type phosphorus-containing colored flame retardant, wherein the general structure of the DPP-type phosphorus-containing colored flame retardant compound is shown as formula (I): DPP-[N-(CH2)m-O-P(=O)(OR)(OR′)]2(I) Wherein DPP is a diketopyrrolopyrrole chromogenic skeleton, the DPP skeleton carries Ar1 substituent and Ar2 substituent at the 3,6 positions respectively, ar1 and Ar2 are the same OR different, N is a lactam nitrogen atom of the DPP skeleton, CH 2 is a methylene group formed by a carbon atom and a hydrogen atom, m is an integer of 2-6, O-P (=O) (OR) (OR ') is a phosphate OR phosphonate structural unit, and R' are independent of each other and are selected from single groups in C 1-C12 alkyl, C 6-C14 aryl, substituted phenoxy OR substituted alkoxy. Preferably, ar1 and Ar2 are independently selected from a single group of phenyl, p-methylphenyl, pyridinyl, thiophenyl, pyrrolyl, tetrahydropyrrolyl, and pyrazolidinyl. Preferably, when Ar1/Ar2 is selected as phenyl, the DPP-based phosphorus-containing colored flame retardant compound is: When Ar1/Ar2 is selected as p-methylphenyl, the DPP phosphorus-containing color flame retardant compound is as follows: when Ar1/Ar2 is selected as pyridyl, the DPP phosphorus-containing color flame retardant compound is as follows: when Ar1/Ar2 is selected as thienyl, the DPP phosphorus-containing color flame retardant compound is as follows: When Ar1/Ar2 is selected as a pyrrole group, the DPP phosphorus-containing color flame retardant compound is as follows: When Ar1/Ar2 is selected as the tetrahydropyrrole, the DPP phosphorus-containing color flame retardant compound is as follows: when Ar1/Ar2 is selected as the tetrahydropyrrole, the DPP phosphorus-containing color flame retardant compound can be: when Ar1/Ar2 is selected as pyrazolidinyl, the DPP phosphorus-containing color flame retardant compound is as follows: 。 preferably, R is ethyl, propyl or butyl, R' is phenoxy or p-alkyl substituted phenoxy. Preferab