CN-122011032-A - Phosphorus flame retardant of acenaphthylene and preparation method thereof

CN122011032ACN 122011032 ACN122011032 ACN 122011032ACN-122011032-A

Abstract

The invention discloses a structure of an acenaphthylene phosphorus flame retardant and a preparation method thereof, and relates to the technical field of flame retardant preparation. According to the invention, the acenaphthylene-DOPO flame retardant with a regular structure is prepared through stereoselective synthesis. The molecule has both rigid acenaphthylene skeleton and high-efficiency phosphorus flame-retardant group, and has remarkable synergistic effect. When the high-frequency high-speed copper-clad laminate is applied to a PPO resin or hydrocarbon resin substrate, excellent thermal stability and halogen-free flame retardant efficiency are shown on the premise of keeping extremely low dielectric constant and loss, meanwhile, the high-frequency high-speed copper-clad laminate has good compatibility with a substrate, does not damage the mechanical property of the substrate, and meets the harsh requirements of 5G communication and the like on the comprehensive performance of materials.

Inventors

CHEN XUDONG
ZHEN ZHIYONG
MA ZETONG
YUAN ZHONGKE

Assignees

广东工业大学

Dates

Publication Date: 20260512
Application Date: 20260130

Claims (7)

1. An acenaphthylene-based phosphorus flame retardant has the following structure: 。
2. The process for producing acenaphthylene-based phosphorus flame retardant according to claim 1, comprising the steps of: S1, preparation of dihaloacenaphthylene Adding organic amine or organic ammonium salt into an organic solvent in a nitrogen atmosphere, slowly dripping high-concentration halogen acid, controlling the temperature to be less than 55 ℃, reacting for 0.5-6h, and then cooling to 0 ℃; Simultaneously dropwise adding elemental halogen and acenaphthylene, controlling the reaction temperature at 0-25 ℃, continuing to react for 3-9 hours until the color of the elemental halogen disappears, heating to 55-85 ℃ until the acenaphthylene is completely consumed, and purifying to obtain two dihaloacthylene with substituted carbon atoms of (R, S) configuration respectively; s2, preparation of DOPO derivative with acenaphthylene structure Adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, namely DOPO structural monomer, into a polar organic solvent, stirring at 50 ℃ until DOPO is completely dissolved, then adding dihaloacenaphthene, slowly adding organic amine, raising the reaction temperature to be more than 120 ℃ after the dripping is finished, continuing to react for 18-36h, and purifying to obtain the DOPO derivative with acenaphthylene structure, namely the acenaphthylene phosphorus flame retardant.
3. The preparation process of acenaphthylene based phosphorus flame retardant according to claim 2, characterized in that the organic solvent is saturated organic solvent with weak polarity, such as cyclohexane, n-hexane, n-heptane and carbon tetrachloride; the organic amine in S1 is at least one of fatty amine or heterocyclic organic amine, wherein the fatty amine is preferably ethylenediamine, triethylamine, N-butylamine, tri-N-butylamine, 1, 4-butanediamine, N-diisopropylethylamine and trimethylene tetramine, the heterocyclic organic amine is preferably pyridine, 4- (dimethylamino) pyridine and 3-methylimidazole, and the organic ammonium salt is preferably tetrabutylammonium bromide, tetramethylammonium bromide, octyltrimethylammonium bromide, dodecyltrimethylammonium bromide and octadecyl methylammonium bromide; the high-concentration hydrohalic acid is one of 36.5% concentrated hydrochloric acid, hydrobromic acid with mass fraction of more than 45% or hydroiodic acid aqueous solution; The molar ratio of the halogen acid to the organic amine or the organic ammonium salt is 1-1.3:1.
4. The preparation method of the acenaphthylene phosphorus flame retardant according to claim 2, wherein in S1, halogen of the same species as halogen acid with high concentration is selected, and the molar ratio of the halogen element to organic amine or ammonium salt is 1-1.2:1; The molar ratio of the halogen simple substance to the acenaphthylene is 1.05-1.5:1.
5. The preparation method of acenaphthylene based phosphorus flame retardant according to claim 2, wherein in S2, the polar organic solvent is a polar solvent with boiling point of >120 ℃, and comprises dimethylbenzene, cyclohexanone, dimethyl sulfoxide, formamide and N-methylpyrrolidone; the molar ratio of DOPO to dihaloacenaphthylene is 2-2.1:1; The organic amine in S2 is selected from any one of aliphatic amine, aromatic amine or heterocyclic organic amine, wherein the aliphatic amine is preferably selected from triethylamine, N-butylamine, tri-N-butylamine and N, N-diisopropylethylamine, the aromatic amine is preferably selected from diphenylamine, p-methylaniline, dimethylaniline, o-ethoxyaniline, 2, 6-diethylaniline and N-butylaniline with electron donating effect, and the heterocyclic organic amine is preferably selected from pyridine, 4- (dimethylamino) pyridine and 3-methylimidazole; The ratio of the amount of organic amine to the amount of DOPO material is 1.3-2:1.
6. A process for preparing a phosphorus-based flame retardant containing acenaphthylene as claimed in claim 2, wherein the two chiral carbon atoms of the acenaphthylene structural DOPO derivative synthesized in S2 are dominant (R, S) configuration, and the sum of the (R, R) configuration and the (S, S) configuration is less than 50%.
7. An application of the acenaphthylene phosphorus flame retardant prepared by the preparation method according to any one of claims 2-6, which is characterized in that the acenaphthylene phosphorus flame retardant can be used as a flame retardant for high-application scenes, and is especially suitable for high-frequency high-speed copper-clad plates of PPO resin and hydrocarbon resin base materials.

Description

Phosphorus flame retardant of acenaphthylene and preparation method thereof Technical Field The invention relates to the technical field of preparation of flame retardants, in particular to an acenaphthylene phosphorus flame retardant and a preparation method thereof. Background The 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) derivative is a novel flame retardant which is widely researched at present, has no toxicity and no harm and has good flame retardant effect. Among the DOPO derivatives, the P-C bond-containing derivatives have a great advantage in high temperature flame retardance because of better heat resistance and water absorbability than the P-O derivatives. Early methods of constructing P-C linkages were accomplished primarily by Arbuzov or Arbuzov-like reactions. The method uses the tri-coordination phosphorus compound to react with alkyl halide, the atom economy of the reaction is poor (one molecule of halogenated alkane needs to be eliminated), and the reaction substrate is relatively single, especially the condition is relatively harsh when constructing the organic phosphine compound with a special structure. Patent US9522927B2, CN102428092a and patent CN105153233B describe a 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) -derived compound structure and a process for its preparation, involving the preparation of DOPO-derived compounds by reacting DOPO with a diol compound in the presence of a catalyst. Patent CN201610601334.3 discloses a preparation method of a di-DOPO derivative, which adopts DOPO derivative and alcohol or reaction, and DOPO is connected through ether bond. DOPO in the structure of the flame retardant is connected through flexible structures such as aliphatic hydrocarbon or ether bond, so that the heat-resistant temperature of the flame retardant is insufficient, the carbon forming effect is poor during combustion, and a large amount of DOPO needs to be added to achieve the qualified flame retardant effect. The patent CN201410333261.5 is a phosphorus flame retardant with a double DOPO structure, which is prepared from aryl ketone and DOPO compounds under the action of an acid catalyst, wherein DOPO is formed by vinyl bridging chains with aromatic group substitution, DOPO is connected through flexible chains, and the aromatic group substitution breaks the symmetry of a molecular structure, so that the dielectric property of the flame retardant is insufficient. Disclosure of Invention The invention aims to solve the defects in the prior art, and provides a compound with a novel structure and a preparation method thereof. In order to achieve the above purpose, the present invention adopts the following technical scheme: the invention firstly provides an acenaphthylene phosphorus flame retardant compound, which has the following structure: 。 The invention also provides a preparation method of the acenaphthylene phosphorus flame retardant, which comprises the following steps: S1, preparation of dihaloacenaphthylene Adding organic amine or organic ammonium salt into an organic solvent in a nitrogen atmosphere, slowly dripping high-concentration halogen acid, controlling the temperature to be less than 55 ℃, reacting for 0.5-6h, and then cooling to 0 ℃; Simultaneously dropwise adding elemental halogen and acenaphthylene, controlling the reaction temperature at 0-25 ℃, continuing to react for 3-9 hours until the color of the elemental halogen disappears, heating to 55-85 ℃ until the acenaphthylene is completely consumed, and purifying to obtain two dihaloacthylene with substituted carbon atoms of (R, S) configuration respectively; The acenaphthylene (molecular formula C 12H8) and a halogen simple substance (such as Cl 2、Br2 or I 2) are subjected to electrophilic addition reaction in the presence of organic amine/organic ammonium salt and halogen acid to generate dihaloacacenaphthylene, and bromine is taken as an example: An organic amine (e.g., triethylamine) or an organic ammonium salt (e.g., tetrabutylammonium bromide) is reacted with a high concentration of a hydrohalic acid (e.g., hydrobromic acid) to form a quaternary ammonium salt or a protonated amine species (e.g., R 3NH+X-). These species act as phase transfer catalysts or activators to promote the polarization and dissociation of elemental halogens. Five-membered ring double bond in acenaphthylene molecule is located at 1, 2-position of acenaphthylene and is attacked by halogen positive ion to form halonium ion intermediate. Because of the rigid planar structure of acenaphthylene, attack occurs mainly from the opposite side of the double bond, resulting in trans-addition. Subsequently, the halogen anion (X -) attacks from the back side to produce dihaloacenaphthylene. The reaction is carried out at low temperature, which is favorable for kinetic control of trans-addition, and mainly generates diastereoisomers with (R, S) configuration. This is because the planarity of the acenaphthylene double b