An organic phosphaphenanthrene derivative with hydroxyl structure and preparation method thereof

Abstract

The present invention provides an organophosphaphenanthrene derivative with a hydroxyl structure and a preparation method thereof. The organophosphaphenanthrene derivative with a hydroxyl structure is obtained by reacting an organophosphaphenanthrene compound and a polyester derivative. The phosphorus content of the organophosphaphenanthrene derivative with a hydroxyl structure is not less than 7.8%. The polyester derivative is obtained by reacting a diol or a polyol with a carboxylic acid, an acyl chloride compound and a derivative thereof. The diol or the polyol has at least one hydroxyl group that does not participate in the reaction. Through the above scheme, while ensuring the phosphorus content and improving the flame retardant performance, the flame retardant performance of the organophosphaphenanthrene derivative with a hydroxyl structure is further improved by retaining multiple hydroxyl groups.

Description

Technical Field

[0001] The invention belongs to the field of organophosphorus halogen-free flame retardant synergistic additives, and particularly relates to an organophosphorus phenanthrene derivative with a hydroxyl structure and a preparation method thereof. Background Art

[0002] 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) is a novel phosphorus-containing flame retardant. DOPO possesses a reactive PH group, which can undergo free radical addition reactions with quinones, aldehydes, ketones, carbon-carbon double bonds, carbon-nitrogen triple or double bonds, epoxides, and other unsaturated groups, as well as dehydration reactions with alcohols and transesterification reactions with esters. Therefore, DOPO derivatives are structurally designable, and the phosphaphenanthrene group can be easily introduced into other molecules to produce DOPO derivatives. Chinese invention patent application number CN2016101272568 discloses an organophosphaphenanthrene derivative and its preparation method. In this scheme, DOPO is bridged with glycerol to produce a flame retardant. Due to its high thermal stability and excellent flame retardant properties, it is particularly suitable for use in polar engineering plastics with high processing temperatures, including thermoplastic polyesters (PBT and PET), polycarbonate (PC), and polyamides (PA6 and PA66).

[0003] Studies have shown that DOPO derivatives generate phosphoric acid structures during combustion, which catalyzes carbonization. Therefore, carbon source polyhydroxy compounds can be introduced into the structural design of DOPO derivatives to form an intumescent flame retardant system with DOPO, thereby achieving a more excellent flame retardant effect.

[0004] In view of this, the present invention is proposed. Summary of the Invention

[0005] The purpose of the present invention is to provide an organophosphaphenanthrene derivative having a hydroxyl structure to address the above-mentioned problems in the prior art. By introducing a hydroxyl structure into the organophosphaphenanthrene derivative, the flame retardant properties of the organophosphaphenanthrene derivative are improved.

[0006] The present invention also provides a method for preparing an organophosphaphenanthrene derivative having a hydroxyl structure, which uses at least one of the following methods: controlling the ratio of carboxylic acids, acyl chloride compounds and their derivatives to diols or polyols during the reaction, thereby achieving the goal of retaining the hydroxyl groups that do not participate in the reaction while preparing the organophosphaphenanthrene derivative.

[0007] The present invention further provides an application of an organic phosphaphenanthrene derivative having a hydroxyl structure as a synergist. By adding the organic phosphaphenanthrene derivative having a hydroxyl structure, the flame retardant properties of the material are further improved.

[0008] In order to achieve the above object, the first aspect of the present invention provides an organophosphaphenanthrene derivative having a hydroxyl structure, wherein the organophosphaphenanthrene derivative having a hydroxyl structure comprises an organophosphaphenanthrene compound having a structural formula as shown in Formula-I;

[0009]

[0010] A on the organophosphaphenanthrene compound reacts with a polyester derivative to obtain an organophosphaphenanthrene derivative having a hydroxy structure. The polyester derivative has at least one hydroxy group that does not participate in the reaction. The phosphorus element in the organophosphaphenanthrene derivative having a hydroxy structure accounts for no less than 7.8%.

[0011] In the above scheme, the elemental ratio of phosphorus is the minimum value of phosphorus ratio obtained by technicians based on a large number of experiments that does not affect the flame retardant properties of the organophosphorus phenanthrene derivative with a hydroxyl structure. A phosphorus ratio lower than 7.8% will significantly reduce the flame retardant properties of the organophosphorus phenanthrene derivative with a hydroxyl structure.

[0012] The polyester derivative has at least one hydroxyl group which does not participate in the reaction, and can improve the flame retardant performance of the organic phosphaphenanthrene derivative having a hydroxyl structure.

[0013] Furthermore, the polyester derivatives are obtained by reacting diols or polyols with carboxylic acids, acyl chloride compounds and their derivatives.

[0014] Furthermore, the carboxylic acid, acyl chloride compound and its derivatives have at least one -COOH or -COCl group, and the -COOH or -COCl group reacts with the -OH group on the diol or polyol to obtain the polyester derivative.

[0015] The above scheme introduces a hydroxyl group that does not participate in the reaction into the polyester derivative by reacting a -COOH or -COCl group with a -OH group on a diol or polyol.

[0016] Furthermore, the polyester derivative has at least one active group in addition to the -COOH group or the -COCl group, and the active group on the polyester derivative reacts with the organophosphaphenanthrene compound to obtain an organophosphaphenanthrene derivative having a hydroxyl structure.

[0017] Furthermore, the active group includes at least an isocyanate group, an acetylene group, a vinyl group, a carboxyl group, an epoxy group, an amino group or a halogen atom.

[0018] Furthermore, -A in the organophosphorus phenanthrene compound is selected from any one of the following structures:

[0019]

[0020] The -A in the organophosphaphenanthrene compound reacts with the active group in the polyester derivative to obtain the organophosphaphenanthrene derivative having a hydroxyl structure, thereby introducing a hydroxyl structure into the organophosphaphenanthrene derivative.

[0021] Furthermore, the general structural formula of the diol or polyol is:

[0022] Wherein, R1, R2, and R3 are -H, -OH, and -(CH2) n One of OH, and only one of R1, R2, and R3 is -OH;

[0023] R4 is -H, -OH, -(CH2) n OH, and at least two of R1, R2, R3 and R4 have an -OH structure;

[0024] -(CH2) n In OH, n is not less than 1.

[0025] Furthermore, the diol or polyol is pentaerythritol, and the ratio of -OH groups on the pentaerythritol that react with the carboxylic acids, acyl chloride compounds and their derivatives to -OH groups that do not participate in the reaction is 1:3-3:1.

[0026] Pentaerythritol is a relatively preferred polyol obtained by technicians based on a large number of experiments. Since the distance between each -OH group on pentaerythritol and the central carbon atom is consistent, it can maintain a high phosphorus content while retaining the -OH group, further improving the flame retardant properties of organic phosphorus phenanthrene derivatives with a hydroxyl structure.

[0027] The second aspect of the present invention provides a method for preparing an organophosphaphenanthrene derivative having a hydroxyl structure, characterized in that it comprises the following steps:

[0028] S1. preparing polyester derivatives;

[0029] S2. Prepare organic phosphaphenanthrene derivatives with hydroxyl structure.

[0030] Furthermore, in step S1, a diol or polyol having N -OH groups is dissolved in an organic solvent to form a solution, and then a carboxylic acid or acyl chloride compound and its derivative are added, and the solution is stirred, filtered, extracted, and dried to obtain a polyester derivative, wherein the molar ratio of the diol or polyol, the organic solvent, and the carboxylic acid or acyl chloride derivative is 1:10-25:1-(N-1);

[0031] Where N≥2.

[0032] In the above scheme, by controlling the ratio of carboxylic acid or acyl chloride compounds and their derivatives to diol or polyol, the diol or polyol has at least one unsubstituted -OH group.

[0033] The above scheme is specifically as follows:

[0034] Dispersing and dissolving 1 mole portion of a diol or polyol in 10 to 25 mole portions of an organic solvent to form a diol or polyol solution;

[0035] Adding carboxylic acid or acyl chloride compounds and their derivatives to a diol or polyol solution in an ice-water bath, then heating and stirring to react, and then filtering to obtain a crude polyester derivative product;

[0036] The crude polyester derivative product was evaporated to dryness, 15 molar parts of an organic solvent was added, and then a saturated sodium bicarbonate aqueous solution was added for multiple extractions. The organic phase was added with anhydrous magnesium sulfate for drying, and the solvent was evaporated under reduced pressure to obtain a pure polyester derivative product.

[0037] In the above process, when a basic catalyst is used, the diol or polyol solution reacts with carboxylic acids, acyl chloride compounds and their derivatives at room temperature, and the basic catalyst is 4-dimethylaminopyridine;

[0038] When an acidic catalyst is used, the temperature range for the reaction between the diol or polyol solution and the carboxylic acid, acyl chloride compounds and their derivatives is 75-120°C. The acidic catalyst is one or more of concentrated sulfuric acid, p-toluenesulfonic acid, phosphoric acid, boric acid, etc.

[0039] Furthermore, the diol or polyol solution reacts with carboxylic acids, acyl chloride compounds and derivatives thereof in the presence of a dehydrating agent, wherein the dehydrating agent is N,N-dicyclohexylcarbodiimide or N,N-carbonyldiimidazole.

[0040] Furthermore, in step S1, when the acyl chloride compound and its derivatives are reacted with the diol or polyol, an acid binding agent is added to the diol or polyol solution before adding the acyl chloride compound and its derivatives to the diol or polyol solution, and the molar ratio of the diol or polyol to the acid binding agent is 1:1.1-1.3;

[0041] Preferably, the acid binding agent is triethylamine.

[0042] In the above scheme, HCl is released when -COCl in the acyl chloride compound and its derivative reacts with -OH in the diol or polyol. The generated HCl is consumed by triethylamine to maintain a stable pH of the system. Due to the rapid reaction, in order to allow triethylamine to eliminate the generated HCl in a timely manner, triethylamine is first added to the diol or polyol solution, followed by the acyl chloride compound and its derivative.

[0043] Furthermore, in step S2, the polyester derivative is dissolved in an organic solvent, and the polyester derivative solution is added dropwise to the organophosphaphenanthrene compound solution mixed with a catalyst to prepare the organophosphaphenanthrene derivative having a hydroxyl structure.

[0044] The specific method for preparing the organophosphorus phenanthrene derivative having a hydroxyl structure is as follows:

[0045] Dissolving 1.2-1.5 mole parts of an organophosphorus phenanthrene compound in 10-25 mole parts of an organic solution to prepare an organophosphorus phenanthrene solution;

[0046] dissolving a polyester derivative in 10 to 25 mole parts of an organic solution to obtain a polyester derivative solution;

[0047] 0.1-0.025 mol fraction of catalyst is added to the organic phosphaphenanthrene solution, and then polyester derivative solution is added dropwise to the organic phosphaphenanthrene solution, and the mixture is heated and stirred for reaction, washed, and dried to obtain the organic phosphaphenanthrene derivative with hydroxy structure.

[0048] Furthermore, the dropping speed of the polyester derivative solution is controlled so that the dropping is completed within 3-8 hours.

[0049] Furthermore, nitrogen is always introduced into the system during the process of preparing the organophosphaphenanthrene solution and the organophosphaphenanthrene derivative having a hydroxyl structure.

[0050] In the above scheme, by introducing nitrogen into the reaction system, the occurrence of double bond polymerization is effectively avoided, and the consistency of the chain structure of the organic phosphaphenanthrene derivative having a hydroxyl structure is improved.

[0051] The organic solvent described in the above scheme is selected from one or more of benzene, toluene, xylene, chloroform, dichloromethane, dimethylformamide, dimethylacetamide, dioxane, acetone, tetrahydrofuran, and acetonitrile;

[0052] The solvent used in the extraction process is one or more of benzene, toluene, xylene, chloroform, dichloromethane, dioxane, tetrahydrofuran, and aniline;

[0053] The catalyst for the reaction between the organic phosphorus phenanthrene solution and the polyester derivative solution is one or more of pyridine, sodium hydroxide, potassium hydroxide, tertiary potassium butoxide, sodium amide, quaternary ammonium base, triethylamine, trimethylamine, quinoline, picoline, xylidine, sodium methoxide, and sodium ethoxide.

[0054] The beneficial effects of the present invention are:

[0055] By introducing -OH groups into organophosphaphenanthrene derivatives, the flame retardant properties of the organophosphaphenanthrene derivatives are improved; by limiting the phosphorus content in the organophosphaphenanthrene derivatives with a hydroxyl structure to no less than 7.8%, the organophosphaphenanthrene derivatives with a hydroxyl structure maintain high flame retardant properties; pentaerythritol is selected to introduce hydroxyl groups into the phosphaphenanthrene compounds. Since the distance between each -OH group on pentaerythritol and the central carbon atom is consistent, a high phosphorus content can be maintained while retaining the -OH groups, while avoiding the reduction in flame retardant properties caused by longer carbon chains; and by introducing nitrogen into the reaction system, the occurrence of double bond polymerization is effectively avoided, thereby improving the consistency of the chain structure of the organophosphaphenanthrene derivatives with a hydroxyl structure. BRIEF DESCRIPTION OF THE DRAWINGS

[0056] Figure 1 The figure is a hydrogen nuclear magnetic resonance spectrum of the organophosphorus phenanthrene compound described in the present invention.

[0057] Figure 2 This is a hydrogen nuclear magnetic resonance spectrum of an organophosphaphenanthrene derivative with a hydroxyl structure described in the present invention.

[0058] Figure 3 This is a graph showing the test results of the steady-state fluorescence spectrum test on the organophosphorus phenanthrene derivative in Experimental Example 3. DETAILED DESCRIPTION

[0059] Exemplary embodiments of the present invention will be described in more detail below with reference to the accompanying drawings. Those skilled in the art will appreciate that the following embodiments are only used to explain the technical principles of the present invention and are not intended to limit the scope of protection of the present invention.

[0060] The present invention provides an organic phosphaphenanthrene derivative having a hydroxyl structure, which is obtained by reacting an organic phosphaphenanthrene compound with a polyester derivative.

[0061] The general structural formula of the organophosphorus phenanthrene compound is shown in Formula-I:

[0062] The H NMR spectrum of the organophosphorus phenanthrene compound is as follows: Figure 1 shown.

[0063] -A in the general structural formula is selected from any one of the following structures:

[0064]

[0065] The polyester derivative has an active group that reacts with -A, and the active group at least includes an isocyanate group, an acetylene group, a vinyl group, a carboxyl group, an epoxy group, an amino group or a halogen atom.

[0066] The -A in the organophosphaphenanthrene compound reacts with the active group in the fatty alcohol ester to obtain the organophosphaphenanthrene derivative with a fatty chain structure.

[0067] The polyester derivative has at least one -OH group which does not participate in the reaction, and the phosphorus content of the organic phosphaphenanthrene derivative having a hydroxyl structure is not less than 7.8%.

[0068] Example 1

[0069] As an embodiment of the present invention, this embodiment provides an organophosphaphenanthrene derivative having a hydroxyl structure, which is obtained by reacting an organophosphaphenanthrene compound and a polyester derivative. The structural formula of the organophosphaphenanthrene compound is:

[0070] In this embodiment, the polyester derivative is pentaerythritol triacrylate obtained by reacting pentaerythritol and acrylic acid, wherein the molar ratio of pentaerythritol to acrylic acid is 1:3, and the H NMR spectrum of the organic phosphaphenanthrene derivative having a hydroxyl structure is as follows: Figure 2 shown.

[0071] Furthermore, the specific preparation method of the pentaerythritol triacrylate is as follows:

[0072] 1 mol portion of pentaerythritol is dispersed and dissolved in 25 mol portions of toluene to form a pentaerythritol solution.

[0073] 3 molar portions of acrylic acid were added to the pentaerythritol solution in an ice-water bath, along with concentrated sulfuric acid as a catalyst and N,N-dicyclohexylcarbodiimide as a dehydrating agent. The temperature was then raised to 120° C. for reaction. Stirring was continued during the reaction. After the reaction was completed, the filtrate was filtered to obtain a crude pentaerythritol triacrylate product.

[0074] The crude pentaerythritol triacrylate was subjected to rotary evaporation, 15 mol parts of toluene was added, and then a saturated sodium bicarbonate aqueous solution was added for multiple extractions. The organic phase was added with anhydrous magnesium sulfate for drying, and the solvent was evaporated under reduced pressure to obtain pure pentaerythritol triacrylate.

[0075] Furthermore, pentaerythritol triacrylate is added dropwise into the solution of the organophosphaphenanthrene compound mixed with the catalyst to react to obtain an organophosphaphenanthrene derivative having a hydroxyl structure.

[0076] In the above process, the three unsaturated double bonds on pentaerythritol triacrylate react with the H on the PH bond of three organophosphaphenanthrene compounds to obtain an organophosphaphenanthrene derivative having a hydroxyl structure.

[0077] The specific method for preparing the organophosphorus phenanthrene derivative having a hydroxyl structure is as follows:

[0078] Dissolving 1.5 moles of an organophosphorus phenanthrene compound in 25 moles of toluene to prepare an organophosphorus phenanthrene solution;

[0079] dissolving pentaerythritol triacrylate in 25 mole parts of toluene to form a pentaerythritol triacrylate solution;

[0080] 0.025 mol of catalyst triethylamine is added to an organic phosphaphenanthrene solution, and then a pentaerythritol triacrylate solution is gradually added dropwise to the organic phosphaphenanthrene solution. The mixture is reacted under heating and stirring conditions, and the organic phosphaphenanthrene derivative having a hydroxyl structure is obtained after washing and drying.

[0081] Furthermore, the pentaerythritol triacrylate solution was added dropwise within 8 hours.

[0082] Furthermore, nitrogen is always introduced into the system during the process of preparing the organophosphaphenanthrene solution and the organophosphaphenanthrene derivative having a hydroxyl structure.

[0083] In the above scheme, by introducing nitrogen into the reaction system, the occurrence of double bond polymerization is effectively avoided, and the consistency of the chain structure of the organic phosphaphenanthrene derivative having a hydroxyl structure is improved.

[0084] Example 2

[0085] As another embodiment of the present invention, this embodiment provides an organophosphaphenanthrene derivative having a hydroxyl structure, which has the same preparation method and raw materials as the organophosphaphenanthrene derivative having a hydroxyl structure described in Example 1, except that the molar ratio of pentaerythritol to acrylic acid is 1:2.

[0086] Furthermore, pentaerythritol and acrylic acid react to obtain pentaerythritol diacrylate, and the specific preparation method of the pentaerythritol diacrylate is as follows:

[0087] 1 mol portion of pentaerythritol is dispersed and dissolved in 25 mol portions of toluene to form a pentaerythritol solution.

[0088] 2 molar portions of acrylic acid were added to the pentaerythritol solution in an ice-water bath, along with concentrated sulfuric acid as a catalyst and N,N-dicyclohexylcarbodiimide as a dehydrating agent. The temperature was then raised to 95° C. for reaction. Stirring was continued during the reaction. After the reaction was completed, the filtrate was filtered to obtain a crude pentaerythritol diacrylate product.

[0089] The crude pentaerythritol diacrylate was subjected to rotary evaporation, 15 mol parts of toluene was added, and then a saturated sodium bicarbonate aqueous solution was added for multiple extractions. The organic phase was added with anhydrous magnesium sulfate for drying, and the solvent was evaporated under reduced pressure to obtain pure pentaerythritol diacrylate.

[0090] Furthermore, pentaerythritol diacrylate is added dropwise to the solution of the organophosphaphenanthrene compound mixed with the catalyst, and the two unsaturated double bonds on the pentaerythritol diacrylate react with the H on the PH bonds of the two organophosphaphenanthrene compounds to obtain an organophosphaphenanthrene derivative having a hydroxyl structure.

[0091] In the above scheme, by reducing the molar fraction of acrylic acid, the pentaerythritol has two hydroxyl groups that do not participate in the reaction. Although the phosphorus content is reduced, by increasing the number of hydroxyl groups that do not participate in the reaction, an organophosphorus phenanthrene derivative with a hydroxyl structure and good flame retardancy can still be obtained.

[0092] Example 3

[0093] As another embodiment of the present invention, this embodiment provides an organophosphaphenanthrene derivative having a hydroxyl structure, which has the same preparation method and raw materials as the organophosphaphenanthrene derivative having a hydroxyl structure described in Example 1, except that the molar ratio of pentaerythritol to acrylic acid is 1:1.

[0094] Furthermore, pentaerythritol and acrylic acid react to obtain pentaerythritol acrylate, and the specific preparation method of the pentaerythritol acrylate is as follows:

[0095] 1 mol portion of pentaerythritol is dispersed and dissolved in 21 mol portions of toluene to form a pentaerythritol solution.

[0096] 1 mol of acrylic acid was added to the pentaerythritol solution in an ice-water bath, along with concentrated sulfuric acid as a catalyst and N,N-dicyclohexylcarbodiimide as a dehydrating agent. The temperature was then raised to 75° C. for reaction. Stirring was continued during the reaction. After the reaction was completed, the filtrate was filtered to obtain a crude pentaerythritol acrylate product.

[0097] The crude pentaerythritol acrylate was subjected to rotary evaporation, 15 mol parts of toluene was added, and then a saturated sodium bicarbonate aqueous solution was added for multiple extractions. The organic phase was added with anhydrous magnesium sulfate for drying, and the solvent was evaporated under reduced pressure to obtain pure pentaerythritol acrylate.

[0098] Furthermore, pentaerythritol acrylate is added dropwise to the organophosphaphenanthrene compound solution mixed with a catalyst, and an unsaturated double bond on pentaerythritol acrylate reacts with H on the PH bond on the organophosphaphenanthrene compound to obtain an organophosphaphenanthrene derivative having a hydroxyl structure.

[0099] In the above scheme, by further reducing the phosphorus content, the number of hydroxyl groups on pentaerythritol that do not participate in the reaction is further increased, and the increase in the number of hydroxyl groups compensates for the reduction in flame retardancy caused by the low phosphorus content.

[0100] Example 4

[0101] As another embodiment of the present invention, this embodiment provides an organophosphaphenanthrene derivative having a hydroxyl structure, which is obtained by reacting an organophosphaphenanthrene compound with a polyester derivative. The structural formula of the organophosphaphenanthrene compound is:

[0102] In this embodiment, the polyester derivative is 2,2-bis(hydroxymethyl)propane-1,3-diaminoformate prepared by the reaction of pentaerythritol and dimethylaminoformyl chloride. The -COCl on the dimethylaminoformyl chloride and the -OH on the pentaerythritol react to obtain the polyester derivative. The molar ratio of pentaerythritol to dimethylaminoformyl chloride is 1:3.

[0103] Furthermore, the specific preparation method of the 2,2-bis(hydroxymethyl)propane-1,3-diaminocarbamic acid diester is as follows:

[0104] 1 mol portion of pentaerythritol is dispersed and dissolved in 10 mol portions of toluene to form a pentaerythritol solution.

[0105] 3 molar portions of dimethylaminoformyl chloride were added to the pentaerythritol solution under ice-water bath conditions, along with catalyst 4-dimethylaminopyridine and dehydrating agent N,N-dicyclohexylcarbodiimide. The temperature was then raised to room temperature for reaction. Stirring was continued during the reaction. After the reaction was completed, the filtrate was filtered to obtain a crude product of 2,2-bis(hydroxymethyl)propane-1,3-diaminoformic acid diester.

[0106] In the above reaction process, before adding methylaminoformyl chloride to the pentaerythritol solution, 1.1 molar portions of an acid-binding agent, triethylamine, need to be added to the pentaerythritol solution.

[0107] The reaction rate of dimethylaminecarbamoyl chloride and pentaerythritol is very fast. -COCl and -OH react to produce HCl gas. The pre-added triethylamine can consume the HCl in time to maintain the pH of the reaction system.

[0108] Furthermore, the crude product of 2,2-bis(hydroxymethyl)propane-1,3-diaminocarbamate was subjected to rotary evaporation, 15 molar portions of toluene were added, and then a saturated aqueous sodium bicarbonate solution was added for multiple extractions. The organic phase was dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure to obtain pure 2,2-bis(hydroxymethyl)propane-1,3-diaminocarbamate.

[0109] Furthermore, 2,2-bis(hydroxymethyl)propane-1,3-dicarbamic acid diester is added dropwise to the solution of the organophosphaphenanthrene compound mixed with the catalyst to react to obtain an organophosphaphenanthrene derivative having a hydroxyl structure.

[0110] The specific method for preparing the organophosphorus phenanthrene derivative having a hydroxyl structure is as follows:

[0111] Dissolving 1.2 moles of an organophosphorus phenanthrene compound in 10 moles of toluene to prepare an organophosphorus phenanthrene solution;

[0112] Dissolving 2,2-bis(hydroxymethyl)propane-1,3-dicarbamic acid diester in 10 molar portions of toluene to form a 2,2-bis(hydroxymethyl)propane-1,3-dicarbamic acid diester solution;

[0113] 0.1 mol of catalyst triethylamine is added to an organophosphaphenanthrene solution, and then a 2,2-bis(hydroxymethyl)propane-1,3-dicarbamic acid diester solution is gradually added dropwise to the organophosphaphenanthrene solution, and the mixture is reacted under heating and stirring conditions. The organophosphaphenanthrene derivative having a hydroxyl structure is obtained after washing and drying.

[0114] Furthermore, the 2,2-bis(hydroxymethyl)propane-1,3-dicarbamic acid diester solution was added dropwise over 3 hours.

[0115] Furthermore, nitrogen is always introduced into the system during the process of preparing the organophosphaphenanthrene solution and the organophosphaphenanthrene derivative having a hydroxyl structure.

[0116] Example 5

[0117] As another embodiment of the present invention, this embodiment provides an organophosphaphenanthrene derivative having a hydroxyl structure, which is obtained by reacting an organophosphaphenanthrene compound with a polyester derivative. The structural formula of the organophosphaphenanthrene compound is:

[0118] In this embodiment, the polyester derivative is 2,2-bis(hydroxymethyl)propane-1,3-diaminoformate prepared by the reaction of pentaerythritol and dimethylaminoformyl chloride. The -COCl on the dimethylaminoformyl chloride and the -OH on the pentaerythritol react to obtain the polyester derivative. The molar ratio of pentaerythritol to dimethylaminoformyl chloride is 1:1.

[0119] Furthermore, the specific preparation method of the 2,2-bis(hydroxymethyl)propane-1,3-diaminocarbamic acid diester is as follows:

[0120] 1 mol portion of pentaerythritol is dispersed and dissolved in 25 mol portions of toluene to form a pentaerythritol solution.

[0121] 1.2 molar portions of dimethylaminoformyl chloride were added to the pentaerythritol solution in an ice-water bath, along with a catalyst, 4-dimethylaminopyridine, and a dehydrating agent, N,N-dicyclohexylcarbodiimide. The temperature was then raised to room temperature for reaction. Stirring was continued during the reaction. After the reaction was completed, the filtrate was filtered to obtain a crude product of 2,2-bis(hydroxymethyl)propane-1,3-diaminoformic acid diester.

[0122] In the above reaction process, before adding methylaminoformyl chloride to the pentaerythritol solution, 1.3 molar portions of an acid-binding agent, triethylamine, need to be added to the pentaerythritol solution.

[0123] The reaction rate of dimethylaminecarbamoyl chloride and pentaerythritol is very fast. -COCl and -OH react to produce HCl gas. The pre-added triethylamine can consume the HCl in time to maintain the pH of the reaction system.

[0124] Furthermore, the crude product of 2,2-bis(hydroxymethyl)propane-1,3-diaminocarbamate was subjected to rotary evaporation, 15 molar portions of toluene were added, and then a saturated aqueous sodium bicarbonate solution was added for multiple extractions. The organic phase was dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure to obtain pure 2,2-bis(hydroxymethyl)propane-1,3-diaminocarbamate.

[0125] Furthermore, 2,2-bis(hydroxymethyl)propane-1,3-dicarbamic acid diester is added dropwise to the solution of the organophosphaphenanthrene compound mixed with the catalyst to react to obtain an organophosphaphenanthrene derivative having a hydroxyl structure.

[0126] The specific method for preparing the organophosphorus phenanthrene derivative having a hydroxyl structure is as follows:

[0127] Dissolving 1.5 moles of an organophosphorus phenanthrene compound in 25 moles of toluene to prepare an organophosphorus phenanthrene solution;

[0128] Dissolving 2,2-bis(hydroxymethyl)propane-1,3-dicarbamic acid diester in 25 mole parts of toluene to form a 2,2-bis(hydroxymethyl)propane-1,3-dicarbamic acid diester solution;

[0129] 0.025 mol of catalyst triethylamine is added to an organophosphaphenanthrene solution, and then a 2,2-bis(hydroxymethyl)propane-1,3-dicarbamic acid diester solution is gradually added dropwise to the organophosphaphenanthrene solution. The mixture is reacted under heating and stirring conditions, and the organophosphaphenanthrene derivative having a hydroxyl structure is obtained after washing and drying.

[0130] Furthermore, the 2,2-bis(hydroxymethyl)propane-1,3-dicarbamic acid diester solution was added dropwise over 8 hours.

[0131] Furthermore, nitrogen is always introduced into the system during the process of preparing the organophosphaphenanthrene solution and the organophosphaphenanthrene derivative having a hydroxyl structure.

[0132] Test Example 1

[0133] This test example provides an EVA / MH composite material using an organophosphaphenanthrene derivative as a flame retardant synergist. The organophosphaphenanthrene derivative having a hydroxyl structure as described in Example 1 is used as the flame retardant synergist.

[0134] In this test example, 50 parts of pure EVA, 48 parts of MH, and 2 parts of an organophosphorus phenanthrene derivative having a hydroxyl structure were uniformly mixed and blended in an internal mixer at a temperature of 140° C. for 6 minutes to obtain an EVA / MH / organophosphorus phenanthrene derivative having a hydroxyl structure composite material.

[0135] Test Example 2

[0136] This test example provides an EVA / MH composite material using an organophosphaphenanthrene derivative as a flame retardant synergist. The organophosphaphenanthrene derivative having a hydroxyl structure as described in Example 2 is used as the flame retardant synergist.

[0137] In this test example, 50 parts of pure EVA, 48 parts of MH, and 2 parts of an organophosphorus phenanthrene derivative having a hydroxyl structure were uniformly mixed and blended in an internal mixer at a temperature of 140° C. for 6 minutes to obtain an EVA / MH / organophosphorus phenanthrene derivative having a hydroxyl structure composite material.

[0138] Test Example 3

[0139] This test example provides an EVA / MH composite material using an organophosphaphenanthrene derivative as a flame retardant synergist. The organophosphaphenanthrene derivative having a hydroxyl structure as described in Example 3 is used as the flame retardant synergist.

[0140] In this test example, 50 parts of pure EVA, 48 parts of MH, and 2 parts of an organophosphorus phenanthrene derivative having a hydroxyl structure were uniformly mixed and blended in an internal mixer at a temperature of 140° C. for 6 minutes to obtain an EVA / MH / organophosphorus phenanthrene derivative having a hydroxyl structure composite material.

[0141] Comparative Example 1

[0142] This comparative example provides an EVA / MH composite material, and the specific preparation method is: 50 parts of pure EV-A and 50 parts of MH are blended in an internal mixer at a temperature of 140° C. for 6 minutes to obtain a processed EVA / MH composite material.

[0143] Comparative Example 2

[0144] This comparative example provides an EVA / MH / DOPO composite material, and the specific preparation method is as follows:

[0145] 50 parts of pure EVA, 48 parts of MH and 2 parts of organophosphorus phenanthrene DOPO were uniformly mixed and blended in an internal mixer at a temperature of 140° C. for 6 minutes to obtain an EVA / MH / DOPO composite material.

[0146] Experimental Example 1

[0147] The limiting oxygen index of comparative example 1 and test examples 1, 2 and 3 was measured using the FTT limiting oxygen index tester from the British FTT company. The test was carried out in accordance with the standard ISO4589. The test specimen size was 80×10×4mm. 3 .

[0148] The cone calorimeter FTT0007 from Fire Testing Technology, UK, was used to conduct cone calorimetry tests on Comparative Example 1 and Test Examples 1, 2 and 3 according to ISO 5660. The heat source power was set to 50 kW / m 2 The sample is a square sheet sample with a specification of 100×100×3mm 3 .

[0149] The test results are as follows:

[0150]

[0151] In the above test results, fire safety index = ignition time / peak heat release rate.

[0152] In the above test results, the molar ratios of pentaerythritol to organophosphorus phenanthrene compounds in Test Examples 1, 2, and 3 are 1:3, 1:2, and 1:1, respectively. From the test results, it can be seen that the limiting oxygen index, fire safety index, and ignition time in Test Examples 1, 2, and 3 are higher than those in Comparative Example 1, and the peak heat release is lower than that in Comparative Example 1, indicating that the addition of organophosphorus phenanthrene derivatives having a hydroxyl structure to the EVA / MH system has a better flame retardant effect.

[0153] It can also be seen from the test results that the limiting oxygen index, fire safety index and ignition time of Test Examples 1, 2 and 3 are higher than those of Comparative Example 2, and the peak heat release is lower than that of Comparative Example 2, which indicates that the organic phosphaphenanthrene derivative with a hydroxyl structure has a better flame retardant effect than DOPO.

[0154] It can also be seen from Test Examples 1, 2 and 3 that the flame retardant properties and the phosphorus content are not completely linearly correlated. The number of hydroxyl groups and the phosphorus content both affect the flame retardant properties. This is because the organic phosphorus phenanthrene derivatives with a hydroxyl structure form an intumescent flame retardant system, which requires a moderate ratio of acid and carbon source in the system. Test Example 2 has a better flame retardant effect, which shows that as the number of hydroxyl groups increases, the flame retardant properties of the organic phosphorus phenanthrene derivatives with a hydroxyl structure gradually improve and then gradually decrease.

[0155] Experimental Example 2

[0156] The color index of Comparative Example 1 and Test Example 1 was determined using a fully automatic colorimeter SC-80C from Beijing Kangguang Co., Ltd., China. Φ25 mm and 1 mm disc samples were placed on the sample stage, aligned with the light and pressed into the air, and the color index of the tested samples was measured.

[0157] Five whiteness indices (CIE86 whiteness: Wg; R457 whiteness: Wr; Hunter whiteness: Wh; Stensby whiteness: Ws; Stephansen whiteness: Wp) and two yellowness indices (ASTM (D1925) yellowness: YID; ASTM (E313) yellowness: YIE) were used to characterize the color of the material. The test was repeated three times, and the average and standard deviation of the results were recorded. The results are as follows:

[0158]

[0159]

[0160] From the test results, we can see that the W g 、W r 、W h 、W s 、W phigher than that of comparative example 1; at the same time, YID and YIE are lower than those of comparative example 1, indicating that the addition of organic phosphorus phenanthrene derivatives having a hydroxyl structure to the EVA / MH system will improve the whiteness of the material and reduce the yellowness of the material.

[0161] Experimental Example 3

[0162] The steady-state fluorescence spectrum test of Comparative Example 1 and Test Example 1 was conducted using the FluoroMax+ fluorescence spectrometer from HORIBA, France. The samples of EVA composite material were Φ25mm and 1mm discs. The instrument parameters were set as follows: the excitation wavelength of the emission spectrum was set to 350nm, and the detection wavelength range was 370~600nm. The test results are shown in Figure 2. Figure 3 shown.

[0163] From the test results, it can be seen that the fluorescence emission spectra of Comparative Example 1 and Test Example 1 show that the fluorescence emission intensity of Test Example 1 is higher than that of Comparative Example 1, indicating that the addition of an organic phosphaphenanthrene derivative with a hydroxyl structure to the EVA / MH system will enhance the brightness of the material.

[0164] The above description is merely a preferred embodiment of the present invention and does not constitute any form of limitation to the present invention. Although the present invention has been disclosed as above in terms of a preferred embodiment, it is not intended to limit the present invention. Any technician familiar with this patent can make slight changes or modifications to equivalent embodiments of equivalent changes using the above-mentioned technical contents without departing from the scope of the technical solution of the present invention. The implementation schemes in the above-mentioned embodiments can also be further combined or replaced. However, any simple modifications, equivalent changes and modifications made to the above-mentioned embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention are still within the scope of the solution of the present invention.

Claims

1. An organic phosphaphenanthrene derivative having a hydroxyl structure, characterized in that: The organophosphorus phenanthrene derivative having a hydroxyl structure includes an organophosphorus phenanthrene compound shown in the following structural formula: The -H connected to P on the organophosphaphenanthrene compound reacts with a polyester derivative to obtain an organophosphaphenanthrene derivative having a hydroxyl structure, wherein the polyester derivative is selected from pentaerythritol triacrylate, pentaerythritol diacrylate or pentaerythritol acrylate; The phosphorus content in the organic phosphaphenanthrene derivative having a hydroxyl structure is not less than 7.8%.

2. The organophosphaphenanthrene derivative having a hydroxyl structure according to claim 1, characterized in that The polyester derivative is obtained by reacting pentaerythritol with acrylic acid.

3. A method for preparing an organophosphaphenanthrene derivative having a hydroxyl structure as claimed in claim 1 or 2, characterized in that: The steps include: S1. preparing polyester derivatives; S2. Prepare organic phosphaphenanthrene derivatives with hydroxyl structure.

4. The method for preparing an organophosphaphenanthrene derivative having a hydroxy structure according to claim 3, characterized in that: In step S1, pentaerythritol is dissolved in an organic solvent to form a solution, and then acrylic acid is added, and the solution is stirred, filtered, extracted, and dried to obtain a polyester derivative, wherein the molar ratio of pentaerythritol, organic solvent, and acrylic acid is 1:10-25:n; Wherein n=3 or 2 or 1.

5. The method for preparing an organophosphaphenanthrene derivative having a hydroxy structure according to claim 4, characterized in that: The organic solvent is toluene.

Images