CN115433235B - An organic phosphaphenanthrene derivative with hydroxyl structure and preparation method thereof - Google Patents
An organic phosphaphenanthrene derivative with hydroxyl structure and preparation method thereofInfo
- Publication number
- CN115433235B CN115433235B CN202110613099.2A CN202110613099A CN115433235B CN 115433235 B CN115433235 B CN 115433235B CN 202110613099 A CN202110613099 A CN 202110613099A CN 115433235 B CN115433235 B CN 115433235B
- Authority
- CN
- China
- Prior art keywords
- derivative
- organic
- phosphaphenanthrene
- hydroxyl structure
- pentaerythritol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657172—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Abstract
本发明提供一种具有羟基结构的有机磷杂菲衍生物及其制备方法，所述具有羟基结构的有机磷杂菲衍生物由有机磷杂菲类化合物和聚酯类衍生物反应得到，具有羟基结构的有机磷杂菲衍生物中磷元素的元素含量不低于7.8％，所述聚酯类衍生物由二元醇或多元醇与羧酸类、酰氯类化合物及其衍生物反应得到，所述二元醇或多元醇上至少具有一个不参与反应的羟基，通过上述方案，在保证磷元素含量，提高阻燃性能的同时，通过保留多个羟基进一步提高了具有羟基结构的有机磷杂菲衍生物的阻燃性能。
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
The invention belongs to the field of organic phosphorus halogen-free flame-retardant synergistic auxiliary agents, and particularly relates to an organic phosphorus phenanthrene derivative with a hydroxyl structure and a preparation method thereof.
Background
9, 10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) is a novel phosphorus-containing flame retardant. DOPO has active P-H group, and through P-H bond, it can produce free radical addition reaction with quinone, aldehyde ketone, carbon-carbon double bond, carbon-nitrogen triple bond or other unsaturated groups such as double bond, epoxy, etc., or produce dehydration reaction with alcohol or ester exchange reaction with ester, so that DOPO derivative has structural designability, and phosphaphenanthrene group can be easily introduced into other molecules to obtain DOPO derivative. The Chinese patent application No. CN2016101272568 discloses an organic phosphaphenanthrene derivative and a preparation method thereof, wherein in the scheme, DOPO is bridged by glycerol to obtain a flame retardant, and the flame retardant is particularly suitable for polar engineering plastics with higher processing temperature, including thermoplastic polyesters (PBT and PET), polycarbonates (PC) and polyamides (PA 6 and PA 66) due to high thermal stability and excellent flame retardant property.
Research shows that DOPO derivative can generate phosphoric acid structure in combustion process to catalyze and form charcoal, so that charcoal source polyhydroxy compound can be introduced into structural design of DOPO derivative to form intumescent flame-retardant system with DOPO to obtain excellent flame-retardant effect.
The present invention has been made in view of this.
Disclosure of Invention
The invention aims to provide an organic phosphaphenanthrene derivative with a hydroxyl structure, which aims to solve the problems in the prior art, and the flame retardant property of the organic phosphaphenanthrene derivative is improved by introducing the hydroxyl structure into the organic phosphaphenanthrene derivative.
The invention also provides a preparation method of the organic phosphaphenanthrene derivative with a hydroxyl structure, and the preparation method of the organic phosphaphenanthrene derivative is realized by controlling the proportion of carboxylic acids, acyl chloride compounds and derivatives thereof to dihydric alcohol or polyhydric alcohol during the reaction, so that the hydroxyl which does not participate in the reaction is reserved at the same time of preparing the organic phosphaphenanthrene derivative.
The invention further provides application of the organic phosphaphenanthrene derivative with the hydroxyl structure as a synergist, and the flame retardant property of the material is further improved by adding the organic phosphaphenanthrene derivative with the hydroxyl structure.
In order to achieve the above object, a first aspect of the present invention provides an organic phosphaphenanthrene derivative having a hydroxyl structure, which comprises an organic phosphaphenanthrene compound having a structural formula as shown in formula-I;
The A on the organic phosphaphenanthrene compound reacts with a polyester derivative to obtain the organic phosphaphenanthrene derivative with a hydroxyl structure, wherein the polyester derivative is provided with at least one hydroxyl which does not participate in the reaction, and the element content of phosphorus element in the organic phosphaphenanthrene derivative with the hydroxyl structure is not less than 7.8 percent.
In the scheme, the element ratio of the phosphorus element is the lowest value of the phosphorus element ratio which is obtained by technicians on the basis of a large number of experiments and does not influence the flame retardant property of the organic phosphaphenanthrene derivative with the hydroxyl structure, and the flame retardant property of the organic phosphaphenanthrene derivative with the hydroxyl structure is obviously reduced when the element ratio of the phosphorus element is lower than 7.8%.
The polyester derivative has at least one hydroxyl group which does not participate in the reaction, so that the flame retardant property of the organic phosphaphenanthrene derivative with a hydroxyl structure can be improved.
Further, the polyester derivative is obtained by reacting dihydric alcohol or polyhydric alcohol with carboxylic acid, acyl chloride compound and derivative thereof.
Further, the carboxylic acid, the acyl chloride compound and the derivative thereof have at least one-COOH or-COCl group, and the-COOH or-COCl group reacts with the-OH group on the dihydric alcohol or the polyhydric alcohol to obtain the polyester derivative.
The above scheme introduces hydroxyl groups in the polyester derivatives which do not participate in the reaction by reacting a-COOH or-COCl group with one of the-OH groups on the diol or polyol.
Furthermore, the polyester derivative is provided with at least one active group besides a-COOH group or a-COCl group, and the active group on the polyester derivative reacts with the organic phosphaphenanthrene compound to obtain the organic phosphaphenanthrene derivative with a hydroxyl structure.
Further, the reactive 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.
Further, the-A in the organic phosphaphenanthrene compound is selected from any one of the following structures:
And (3) reacting-A in the organic phosphaphenanthrene compound with active groups in the polyester derivative to obtain the organic phosphaphenanthrene derivative with the hydroxyl structure, and further introducing the hydroxyl structure into the organic phosphaphenanthrene derivative.
Further, the structural general formula of the dihydric alcohol or the polyhydric alcohol is as follows:
Wherein R 1、R2、R3 is one of-H, -OH, - (CH 2)n OH) and only one of R 1、R2、R3 is-OH at the same time;
R 4 is one of-H, -OH, - (CH 2)n OH), and at least two of R 1、R2、R3 and R 4 have-OH structures;
N in- (CH 2)n OH) is not less than 1.
Further, the dihydric alcohol or the polyhydric alcohol is pentaerythritol, and the ratio of-OH reacted with the carboxylic acid compounds, the acyl chloride compounds and the derivatives thereof to-OH not reacted on the pentaerythritol is 1:3-3:1.
Pentaerythritol is a preferable polyol obtained by technicians on the basis of a large number of experiments, and because the distance from each-OH to the central carbon atom on the pentaerythritol is consistent, the pentaerythritol can keep higher phosphorus element content while keeping-OH, and the flame retardant property of the organic phosphaphenanthrene derivative with a hydroxyl structure is further improved.
The second aspect of the present invention provides a method for producing an organophosphorous phenanthrene derivative having a hydroxyl group structure, which is characterized by comprising the steps of:
s1, preparing polyester derivatives;
S2, preparing the organic phosphaphenanthrene derivative with a hydroxyl structure.
Further, in the step S1, dihydric alcohol or polyhydric alcohol with N-OH is dissolved in an organic solvent to form a solution, then carboxylic acid or acyl chloride compound and derivatives thereof are added, and polyester derivatives are obtained through stirring, filtering, extracting and drying, wherein the molar ratio of the dihydric alcohol or polyhydric alcohol to the organic solvent to the carboxylic acid or acyl chloride derivatives is 1:10-25:1- (N-1);
Wherein N is more than or equal to 2.
In the above scheme, the ratio of the carboxylic acid or the acyl chloride compound and the derivative thereof to the dihydric alcohol or the polyhydric alcohol is controlled to enable the dihydric alcohol or the polyhydric alcohol to have at least one unsubstituted-OH.
The scheme is specifically as follows:
Dispersing and dissolving 1 mol part of dihydric alcohol or polyhydric alcohol into 10-25 mol parts of organic solvent to form dihydric alcohol or polyhydric alcohol solution;
Adding carboxylic acid or acyl chloride compounds and derivatives thereof into dihydric alcohol or polyhydric alcohol solution under the condition of ice water bath, heating and stirring to react, filtering, and obtaining a crude product of polyester derivatives from the filtrate;
evaporating the crude product of the polyester derivative to dryness, adding 15 mole parts of organic solvent, adding saturated sodium bicarbonate aqueous solution for multiple extraction, taking the organic phase, drying over anhydrous magnesium sulfate, and evaporating the solvent under reduced pressure to obtain the pure polyester derivative product.
In the process, when an alkaline catalyst is used, dihydric alcohol or polyalcohol solution reacts with carboxylic acids, acyl chloride compounds and derivatives thereof at normal temperature, wherein the alkaline catalyst is 4-dimethylaminopyridine;
when an acid catalyst is used, the temperature range of the reaction of dihydric alcohol or polyhydric alcohol solution and carboxylic acid, acyl chloride compound and derivatives thereof is 75-120 ℃, and the acid catalyst is one or more of concentrated sulfuric acid, p-toluenesulfonic acid, phosphoric acid, boric acid and the like.
Further, the dihydric alcohol or the polyalcohol solution reacts with carboxylic acids, acyl chloride compounds and derivatives thereof under the condition of dehydrating agents, wherein the dehydrating agents are N, N-dicyclohexylcarbodiimide or N, N-carbonyl diimidazole.
Further, in the step S1, when the acyl chloride compound and the derivative thereof are used for reacting with the dihydric alcohol or the polyhydric alcohol, before the acyl chloride compound and the derivative thereof are added into the dihydric alcohol or the polyhydric alcohol solution, an acid-binding agent is also added into the dihydric alcohol or the polyhydric alcohol solution, and the mol part ratio of the dihydric alcohol or the polyhydric alcohol to the acid-binding agent is 1:1.1-1.3;
preferably, the acid binding agent is triethylamine.
In the scheme, HCl is released when-COCl in acyl chloride compounds and derivatives thereof reacts with-OH in dihydric alcohol or polyhydric alcohol, the generated HCl is consumed through triethylamine, the PH of the system is kept stable, and the triethylamine is firstly added into dihydric alcohol or polyhydric alcohol solution and then the acyl chloride compounds and derivatives thereof are added in order to enable the triethylamine to timely eliminate the HCl generated by the reaction.
Further, in step S2, the polyester derivative is dissolved in an organic solvent, and the polyester derivative solution is added dropwise to the organic phosphaphenanthrene compound solution mixed with the catalyst to prepare the organic phosphaphenanthrene derivative having a hydroxyl structure.
The specific method for preparing the organic phosphaphenanthrene derivative with the hydroxyl structure comprises the following steps:
Dissolving 1.2-1.5 mol parts of organic phosphaphenanthrene compound in 10-25 mol parts of organic solution to prepare organic phosphaphenanthrene solution;
dissolving a polyester derivative in 10-25 mol parts of organic solution to obtain a polyester derivative solution;
And adding 0.1-0.025 mol part of catalyst into the organic phosphaphenanthrene solution, then dripping the polyester derivative solution into the organic phosphaphenanthrene solution, heating, stirring, reacting, washing and drying to obtain the organic phosphaphenanthrene derivative with a hydroxyl structure.
Further, the dropping speed of the polyester derivative solution is controlled so that the dropping is completed within 3 to 8 hours.
Further, nitrogen is always introduced into the system during the preparation of the organic phosphaphenanthrene solution and the preparation of the organic phosphaphenanthrene derivative with the hydroxyl structure.
In the scheme, nitrogen is introduced into the reaction system, so that double-bond polymerization is effectively avoided, and the consistency of the chain structure of the organophosphorus phenanthrene derivative with the hydroxyl structure is improved.
The organic solvent in the above scheme is selected from one or more of benzene, toluene, xylene, chloroform, dichloromethane, dimethylformamide, dimethylacetamide, dioxane, acetone, tetrahydrofuran and acetonitrile;
The solvent used in the extraction process is one or more of benzene, toluene, xylene, chloroform, methylene dichloride, dioxane, tetrahydrofuran and aniline;
The catalyst for the reaction of the organic phosphaphenanthrene 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, dimethylaniline, sodium methoxide and sodium ethoxide.
The beneficial effects of the invention are as follows:
the flame retardant property of the organic phosphaphenanthrene derivative is improved by introducing-OH groups into the organic phosphaphenanthrene derivative, the organic phosphaphenanthrene derivative with a hydroxyl structure is kept high in flame retardant property by limiting the element content of phosphorus elements in the organic phosphaphenanthrene derivative with a hydroxyl structure to be not lower than 7.8%, pentaerythritol is selected to introduce hydroxyl groups into the phosphaphenanthrene compound, the distance from each-OH group on the pentaerythritol to a central carbon atom is consistent, the high phosphorus element content can be kept while the-OH group is kept, meanwhile, the flame retardant property is prevented from being reduced due to a longer carbon chain, and the occurrence of double-bond polymerization is effectively avoided by introducing nitrogen into a reaction system, so that the consistency of the chain structure of the organic phosphaphenanthrene derivative with the hydroxyl structure is improved.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of an organic phosphaphenanthrene compound according to the invention.
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of an organic phosphaphenanthrene derivative with a hydroxyl structure.
FIG. 3 is a graph showing the results of steady-state fluorescence spectrum test on an organic phosphaphenanthrene derivative in experiment III.
Detailed Description
Exemplary embodiments of the present invention will be described in more detail below with reference to the accompanying drawings, and it will be understood by those skilled in the art that the following embodiments are only for explaining the technical principles of the present invention and are not intended to limit the scope of the present invention.
The invention provides an organic phosphaphenanthrene derivative with a hydroxyl structure, which is obtained by reacting an organic phosphaphenanthrene compound with a polyester derivative,
The structural general formula of the organic phosphaphenanthrene compound is shown as the formula-I:
the nuclear magnetic resonance hydrogen spectrum of the organic phosphaphenanthrene compound is shown in figure 1.
-A in the general structural formula is selected from any one of the following structures:
The polyester derivative is provided with an active group which reacts with-A, and the active group at least comprises isocyanate groups, ethynyl groups, vinyl groups, carboxyl groups, epoxy groups, amino groups or halogen atoms.
And (3) reacting the-A in the organic phosphaphenanthrene compound with the active group in the fatty alcohol ester to obtain the organic phosphaphenanthrene derivative with the fatty chain structure.
The polyester derivative has at least one-OH which does not participate in the reaction, and the content of the element of phosphorus in the organic phosphaphenanthrene derivative with a hydroxyl structure is not less than 7.8 percent.
Example 1
As an embodiment of the present invention, the present embodiment provides an organic phosphaphenanthrene derivative having a hydroxyl structure, which is obtained by reacting an organic phosphaphenanthrene compound with a polyester derivative, wherein the structural formula of the organic phosphaphenanthrene compound is as follows:
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 nuclear magnetic resonance hydrogen spectrum of the organic phosphaphenanthrene derivative with a hydroxyl structure is shown in fig. 2.
Further, the specific preparation method of the pentaerythritol triacrylate comprises the following steps:
1 part by mole of pentaerythritol was dispersed and dissolved in 25 parts by mole of toluene to form a pentaerythritol solution.
Adding 3 mole parts of acrylic acid into a pentaerythritol solution under the condition of ice-water bath, simultaneously adding catalyst concentrated sulfuric acid and dehydrating agent N, N-dicyclohexylcarbodiimide, heating to 120 ℃ for reaction, continuously stirring in the reaction process, and filtering after the reaction is completed, wherein the obtained filtrate is a crude product of pentaerythritol triacrylate.
And (3) carrying out rotary evaporation on the crude product of pentaerythritol triacrylate, adding 15 mol parts of toluene, then adding saturated sodium bicarbonate aqueous solution for multiple extraction, taking an organic phase, drying over anhydrous magnesium sulfate, and evaporating the solvent under reduced pressure to obtain pure pentaerythritol triacrylate.
Further, pentaerythritol triacrylate is added into the organic phosphaphenanthrene compound solution mixed with the catalyst in a dropwise manner, and the organic phosphaphenanthrene derivative with a hydroxyl structure is obtained through reaction.
In the process, three unsaturated double bonds on pentaerythritol triacrylate react with H on P-H bonds on three organic phosphaphenanthrene compounds respectively to obtain the organic phosphaphenanthrene derivative with a hydroxyl structure.
The specific method for preparing the organic phosphaphenanthrene derivative with the hydroxyl structure comprises the following steps:
dissolving 1.5 mole parts of an organic phosphaphenanthrene compound in 25 mole parts of toluene to prepare an organic phosphaphenanthrene solution;
Dissolving pentaerythritol triacrylate in 25 parts by mole of toluene to form a pentaerythritol triacrylate solution;
Adding 0.025 mol portion of catalyst triethylamine into the organic phosphaphenanthrene solution, gradually adding pentaerythritol triacrylate solution into the organic phosphaphenanthrene solution in a dropwise manner, reacting under the condition of heating and stirring, washing and drying to obtain the organic phosphaphenanthrene derivative with a hydroxyl structure.
Further, the pentaerythritol triacrylate solution was added dropwise over 8 hours.
Further, nitrogen is always introduced into the system during the preparation of the organic phosphaphenanthrene solution and the preparation of the organic phosphaphenanthrene derivative with the hydroxyl structure.
In the scheme, nitrogen is introduced into the reaction system, so that double-bond polymerization is effectively avoided, and the consistency of the chain structure of the organophosphorus phenanthrene derivative with the hydroxyl structure is improved.
Example two
As another embodiment of the present invention, this embodiment provides an organophosphorous phenanthrene derivative having a hydroxyl structure, which has the same preparation method and preparation raw material as those of the organophosphorous phenanthrene derivative having a hydroxyl structure described in embodiment one, except that the molar part ratio of pentaerythritol and acrylic acid is 1:2.
Further, pentaerythritol reacts with acrylic acid to obtain pentaerythritol diacrylate, and the specific preparation method of the pentaerythritol diacrylate comprises the following steps:
1 part by mole of pentaerythritol was dispersed and dissolved in 25 parts by mole of toluene to form a pentaerythritol solution.
Adding 2 mole parts of acrylic acid into a pentaerythritol solution under the condition of ice-water bath, simultaneously adding catalyst concentrated sulfuric acid and dehydrating agent N, N-dicyclohexylcarbodiimide, heating to 95 ℃ for reaction, continuously stirring in the reaction process, and filtering after the reaction is completed, wherein the obtained filtrate is a crude product of pentaerythritol diacrylate.
And (3) carrying out rotary evaporation on the crude product of pentaerythritol diacrylate, adding 15 mole parts of toluene, then adding saturated sodium bicarbonate aqueous solution for multiple extraction, taking an organic phase, drying over anhydrous magnesium sulfate, and evaporating the solvent under reduced pressure to obtain pure pentaerythritol diacrylate.
Further, pentaerythritol diacrylate is added into the organic phosphaphenanthrene compound solution mixed with the catalyst in a dropwise adding mode, and two unsaturated double bonds on the pentaerythritol diacrylate react with H on P-H bonds on the two organic phosphaphenanthrene compounds respectively to obtain the organic phosphaphenanthrene derivative with a hydroxyl structure.
In the scheme, the molar fraction of the acrylic acid is reduced, so that the pentaerythritol is provided with two hydroxyl groups which do not participate in the reaction, and the content of elements of phosphorus is reduced, but the organic phosphaphenanthrene derivative with a hydroxyl structure and better flame retardant performance can be still obtained by increasing the number of the hydroxyl groups which do not participate in the reaction.
Example III
As another embodiment of the present invention, this embodiment provides an organophosphorous phenanthrene derivative having a hydroxyl structure, which has the same preparation method and preparation raw material as those of the organophosphorous phenanthrene derivative having a hydroxyl structure described in embodiment one, except that the molar part ratio of pentaerythritol and acrylic acid is 1:1.
Further, pentaerythritol reacts with acrylic acid to obtain pentaerythritol acrylic ester, and the specific preparation method of the pentaerythritol acrylic ester comprises the following steps:
1 part by mole of pentaerythritol was dispersed and dissolved in 21 parts by mole of toluene to form a pentaerythritol solution.
Adding 1 mol part of acrylic acid into pentaerythritol solution under the condition of ice-water bath, simultaneously adding catalyst concentrated sulfuric acid and dehydrating agent N, N-dicyclohexylcarbodiimide, heating to 75 ℃ for reaction, continuously stirring in the reaction process, and filtering after the reaction is completed, wherein the obtained filtrate is pentaerythritol acrylic ester crude product.
And (3) carrying out rotary evaporation on the crude product of pentaerythritol acrylic ester, adding 15 mol parts of toluene, then adding saturated sodium bicarbonate aqueous solution for multiple extraction, taking an organic phase, drying over anhydrous magnesium sulfate, and evaporating the solvent under reduced pressure to obtain pure pentaerythritol acrylic ester.
Further, pentaerythritol acrylic ester is added into an organic phosphaphenanthrene compound solution mixed with a catalyst in a dropwise manner, and one unsaturated double bond on the pentaerythritol acrylic ester reacts with H on a P-H bond on the organic phosphaphenanthrene compound to obtain the organic phosphaphenanthrene derivative with a hydroxyl structure.
In the scheme, the quantity of hydroxyl groups which do not participate in the reaction on pentaerythritol is further increased by further reducing the content of phosphorus, and the reduction of flame retardant property caused by lower content of phosphorus is compensated by increasing the quantity of hydroxyl groups.
Example IV
As another embodiment of the present invention, this embodiment provides an organophosphorous phenanthrene derivative having a hydroxyl structure, which is obtained by reacting an organophosphorous phenanthrene compound with a polyester derivative, wherein the organophosphorous phenanthrene compound has a structural formula as follows:
in this example, the polyester derivative is 2, 2-bis (hydroxymethyl) propane-1, 3-dicarbamate obtained by reacting pentaerythritol with dimethylcarbamoyl chloride, wherein-COCl on the dimethylcarbamoyl chloride and-OH on the pentaerythritol react to obtain the polyester derivative, and the mole ratio of the pentaerythritol to the dimethylcarbamoyl chloride is 1:3.
Further, the specific preparation method of the 2, 2-bis (hydroxymethyl) propane-1, 3-dicarbamate comprises the following steps:
1 part by mole of pentaerythritol was dispersed and dissolved in 10 parts by mole of toluene to form a pentaerythritol solution.
Adding 3 mole parts of dimethylcarbamoyl chloride into a pentaerythritol solution under the condition of ice-water bath, simultaneously adding a catalyst 4-dimethylaminopyridine and a dehydrating agent N, N-dicyclohexylcarbodiimide, heating to room temperature for reaction, continuously stirring in the reaction process, and filtering after the reaction is finished to obtain a filtrate which is a crude product of 2, 2-bis (hydroxymethyl) propane-1, 3-dicarbamate.
In the above reaction, 1.1 mole part of the acid-binding agent triethylamine is also added to the pentaerythritol solution before the methylcarbamoyl chloride is added to the pentaerythritol solution.
The reaction speed of the dimethylamine carbamoyl chloride and the pentaerythritol is high, HCl gas is generated by the reaction of-COCl and-OH, and the HCl can be timely consumed through the triethylamine which is added in advance, so that the pH value of a reaction system is maintained.
Further, the crude product of the 2, 2-bis (hydroxymethyl) propane-1, 3-dicarbamate is subjected to rotary evaporation, 15 mole parts of toluene is added, then saturated sodium bicarbonate aqueous solution is added for multiple extraction, an organic phase is taken, anhydrous magnesium sulfate is added for drying, and the solvent is evaporated under reduced pressure to obtain the pure 2, 2-bis (hydroxymethyl) propane-1, 3-dicarbamate.
Further, 2-bis (hydroxymethyl) propane-1, 3-dicarbamate is added into the organic phosphaphenanthrene compound solution mixed with the catalyst in a dropwise manner, and the organic phosphaphenanthrene derivative with a hydroxyl structure is obtained through reaction.
The specific method for preparing the organic phosphaphenanthrene derivative with the hydroxyl structure comprises the following steps:
dissolving 1.2 mole parts of an organic phosphaphenanthrene compound in 10 mole parts of toluene to prepare an organic phosphaphenanthrene solution;
Dissolving 2, 2-bis (hydroxymethyl) propane-1, 3-dicarbamate in 10 mole parts of toluene to form a2, 2-bis (hydroxymethyl) propane-1, 3-dicarbamate solution;
Adding 0.1 mol part of catalyst triethylamine into an organic phosphaphenanthrene solution, gradually adding 2, 2-bis (hydroxymethyl) propane-1, 3-dicarbamate solution into the organic phosphaphenanthrene solution in a dropwise manner, reacting under the condition of heating and stirring, washing, and drying to obtain the organic phosphaphenanthrene derivative with a hydroxyl structure.
Further, the 2, 2-bis (hydroxymethyl) propane-1, 3-dicarbamate solution was added dropwise within 3 hours.
Further, nitrogen is always introduced into the system during the preparation of the organic phosphaphenanthrene solution and the preparation of the organic phosphaphenanthrene derivative with the hydroxyl structure.
Example five
As another embodiment of the present invention, this embodiment provides an organophosphorous phenanthrene derivative having a hydroxyl structure, which is obtained by reacting an organophosphorous phenanthrene compound with a polyester derivative, wherein the organophosphorous phenanthrene compound has a structural formula as follows:
In this example, the polyester derivative is 2, 2-bis (hydroxymethyl) propane-1, 3-dicarbamate obtained by reacting pentaerythritol with dimethylcarbamoyl chloride, wherein-COCl on the dimethylcarbamoyl chloride and-OH on the pentaerythritol react to obtain the polyester derivative, and the molar ratio of the pentaerythritol to the dimethylcarbamoyl chloride is 1:1.
Further, the specific preparation method of the 2, 2-bis (hydroxymethyl) propane-1, 3-dicarbamate comprises the following steps:
1 part by mole of pentaerythritol was dispersed and dissolved in 25 parts by mole of toluene to form a pentaerythritol solution.
Adding 1.2 mol parts of dimethylcarbamoyl chloride into a pentaerythritol solution under the condition of ice-water bath, simultaneously adding a catalyst of 4-dimethylaminopyridine and a dehydrating agent of N, N-dicyclohexylcarbodiimide, heating to room temperature for reaction, continuously stirring in the reaction process, and filtering after the reaction is finished to obtain a filtrate which is a crude product of 2, 2-bis (hydroxymethyl) propane-1, 3-dicarbamate.
During the above reaction, 1.3 mole parts of the acid-binding agent triethylamine was also added to the pentaerythritol solution prior to the addition of the methylcarbamoyl chloride to the pentaerythritol solution.
The reaction speed of the dimethylamine carbamoyl chloride and the pentaerythritol is high, HCl gas is generated by the reaction of-COCl and-OH, and the HCl can be timely consumed through the triethylamine which is added in advance, so that the pH value of a reaction system is maintained.
Further, the crude product of the 2, 2-bis (hydroxymethyl) propane-1, 3-dicarbamate is subjected to rotary evaporation, 15 mole parts of toluene is added, then saturated sodium bicarbonate aqueous solution is added for multiple extraction, an organic phase is taken, anhydrous magnesium sulfate is added for drying, and the solvent is evaporated under reduced pressure to obtain the pure 2, 2-bis (hydroxymethyl) propane-1, 3-dicarbamate.
Further, 2-bis (hydroxymethyl) propane-1, 3-dicarbamate is added into the organic phosphaphenanthrene compound solution mixed with the catalyst in a dropwise manner, and the organic phosphaphenanthrene derivative with a hydroxyl structure is obtained through reaction.
The specific method for preparing the organic phosphaphenanthrene derivative with the hydroxyl structure comprises the following steps:
dissolving 1.5 mole parts of an organic phosphaphenanthrene compound in 25 mole parts of toluene to prepare an organic phosphaphenanthrene solution;
Dissolving 2, 2-bis (hydroxymethyl) propane-1, 3-dicarbamate in 25 mole parts of toluene to form a2, 2-bis (hydroxymethyl) propane-1, 3-dicarbamate solution;
Adding 0.025 mol portion of catalyst triethylamine into the organic phosphaphenanthrene solution, gradually adding 2, 2-bis (hydroxymethyl) propane-1, 3-dicarbamate solution into the organic phosphaphenanthrene solution in a dropwise manner, reacting under the condition of heating and stirring, washing, and drying to obtain the organic phosphaphenanthrene derivative with a hydroxyl structure.
Further, the 2, 2-bis (hydroxymethyl) propane-1, 3-dicarbamate solution was added dropwise within 8 hours.
Further, nitrogen is always introduced into the system during the preparation of the organic phosphaphenanthrene solution and the preparation of the organic phosphaphenanthrene derivative with the hydroxyl structure.
Detection example 1
The detection example provides an EVA/MH composite material taking an organic phosphaphenanthrene derivative as a flame-retardant synergistic auxiliary, and the organic phosphaphenanthrene derivative with a hydroxyl structure as described in the first example is used as the flame-retardant synergistic auxiliary.
In this test example, 50 parts by mass of pure EVA, 48 parts by mass of MH and 2 parts by mass of an organic phosphaphenanthrene derivative having a hydroxyl structure were uniformly mixed, and the mixture was blended in an internal mixer at a temperature of 140 ℃ for 6 minutes to obtain an EVA/MH/organic phosphaphenanthrene derivative composite material having a hydroxyl structure.
Detection example two
The detection example provides an EVA/MH composite material taking an organic phosphaphenanthrene derivative as a flame-retardant synergistic auxiliary, and the organic phosphaphenanthrene derivative with a hydroxyl structure as described in the second example is used as the flame-retardant synergistic auxiliary.
In this test example, 50 parts by mass of pure EVA, 48 parts by mass of MH and 2 parts by mass of an organic phosphaphenanthrene derivative having a hydroxyl structure were uniformly mixed, and the mixture was blended in an internal mixer at a temperature of 140 ℃ for 6 minutes to obtain an EVA/MH/organic phosphaphenanthrene derivative composite material having a hydroxyl structure.
Detection example III
The detection example provides an EVA/MH composite material with an organic phosphaphenanthrene derivative as a flame-retardant synergistic auxiliary, and the organic phosphaphenanthrene derivative with a hydroxyl structure as described in the third example is used as the flame-retardant synergistic auxiliary.
In this test example, 50 parts by mass of pure EVA, 48 parts by mass of MH and 2 parts by mass of an organic phosphaphenanthrene derivative having a hydroxyl structure were uniformly mixed, and the mixture was blended in an internal mixer at a temperature of 140 ℃ for 6 minutes to obtain an EVA/MH/organic phosphaphenanthrene derivative composite material having a hydroxyl structure.
Comparative example one
The comparative example provides an EVA/MH composite material, which is prepared by blending 50 parts of pure EV-A and 50 parts of MH in an internal mixer at 140 ℃ for 6 minutes to obtain the processed EVA/MH composite material.
Comparative example two
The comparative example provides an EVA/MH/DOPO composite material, which is prepared by the following steps:
50 parts of pure EVA, 48 parts of MH and 2 parts of organic phosphaphenanthrene DOPO are uniformly mixed, and the mixture is blended for 6 minutes in an internal mixer at the temperature of 140 ℃ to obtain the EVA/MH/DOPO composite material.
Experimental example 1
The limiting oxygen index of comparative example one and test example two and three were measured using an FTT limiting oxygen index meter from FTT corporation in the united kingdom, and tested according to standard ISO4589, test spline specification 80 x 10 x 4mm 3.
For comparative example one and test example two and three, cone calorimetric test was performed according to standard ISO5660 using FTT0007 cone calorimeter from FIRE TESTING Technology, uk, the heat source power was set at 50kW/m 2, the sample was a square plate-like template, 100 x 3mm 3.
The test results were as follows:
in the above detection results, fire safety index=ignition time/peak heat release rate.
In the test results, the mole parts ratio of isovaleryltetraol to organic phosphaphenanthrene compounds in the first, second and third test examples is 1:3, 1:2 and 1:1 respectively, and it can be seen from the test results that the limiting oxygen index, fire safety index and ignition time in the first, second and third test examples are higher than those in the first comparative example, and the peak heat release is lower than that in the first comparative example, which indicates that the addition of the organic phosphaphenanthrene derivative with hydroxyl structure in the EVA/MH system has better flame retardant effect.
From the test results, it can be seen that the limiting oxygen index, the fire safety index and the ignition time of the first, second and third test examples are higher than those of the second comparative example and the peak heat release is lower than that of the second comparative example, which indicates that the organic phosphaphenanthrene derivative with the hydroxyl structure has better flame retardant effect than DOPO.
It can be seen from the first, second and third detection examples that the flame retardant property and the phosphorus content are not completely linearly related, and the number of hydroxyl groups and the phosphorus content all affect the flame retardant property, because the organic phosphaphenanthrene derivative with a hydroxyl structure forms an intumescent flame retardant system, the acid and carbon source ratio in the system is required to be moderate, and the second detection example has a better flame retardant effect, which indicates that the flame retardant property of the organic phosphaphenanthrene derivative with a hydroxyl structure is gradually improved and then gradually reduced as the number of hydroxyl groups is increased.
Experimental example two
The color indexes of the first comparative example and the first detection example are measured by adopting a full-automatic color difference meter SC-80C of Beijing Kang Guang Limited company in China, a disc-shaped sample with phi of 25mm and 1mm is placed on a sample table, and the color indexes of the measured samples are measured by aiming at light air compression.
The color of the material was characterized by 5 whiteness indexes (CIE 86 whiteness: wg; R457 whiteness: wr; hunter whiteness: wh; stensby whiteness: ws; STEPHANSEN whiteness: wp) and two yellowness indexes (ASTM (D1925) yellowness: YID; ASTM (E313) yellowness: YIE), and the results were recorded as average and standard deviation as follows:
the test results show that the W g、Wr、Wh、Ws、Wp of the first detection example is higher than that of the first comparison example, and the YID and YIE are lower than those of the first comparison example, so that the addition of the organophosphorus phenanthrene derivative with a hydroxyl structure into the EVA/MH system can improve the whiteness of the material and reduce the yellowness of the material.
Experimental example III
Steady state fluorescence spectroscopy was performed on comparative example one and test example one using FluoroMax + fluorescence spectrometer from HORIBA, france. Samples of EVA composite materials are phi 25mm and 1mm wafers. The instrument parameters are set as follows, the excitation wavelength of the emission spectrum is respectively set to 350nm, and the detection wavelength range is 370-600 nm. The test results are shown in FIG. 3.
From the detection results, the fluorescence emission spectra of the first comparative example and the first detection example show that the fluorescence emission intensity of the first detection example is higher than that of the first comparative example, and the fact that the organic phosphaphenanthrene derivative with a hydroxyl structure is added into an EVA/MH system can improve the brightness of the material.
The foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited to the above-mentioned embodiment, but is not limited to the above-mentioned embodiment, and any simple modification, equivalent change and modification made by the technical matter of the present invention can be further combined or replaced by the equivalent embodiment without departing from the scope of the technical solution of the present invention.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110613099.2A CN115433235B (en) | 2021-06-02 | 2021-06-02 | An organic phosphaphenanthrene derivative with hydroxyl structure and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110613099.2A CN115433235B (en) | 2021-06-02 | 2021-06-02 | An organic phosphaphenanthrene derivative with hydroxyl structure and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115433235A CN115433235A (en) | 2022-12-06 |
| CN115433235B true CN115433235B (en) | 2025-08-22 |
Family
ID=84240463
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110613099.2A Active CN115433235B (en) | 2021-06-02 | 2021-06-02 | An organic phosphaphenanthrene derivative with hydroxyl structure and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115433235B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN119081063A (en) * | 2024-08-15 | 2024-12-06 | 黑龙江赞誉智能科技有限公司 | A flame retardant resin composition and printed circuit board prepared therefrom |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101663374A (en) * | 2007-04-03 | 2010-03-03 | 巴斯夫欧洲公司 | DOPO flame retardant compositions |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0429237A (en) * | 1990-05-25 | 1992-01-31 | Konica Corp | Method for preventing color fading of organic coloring material and color photographic material |
| DE102008012806A1 (en) * | 2008-03-06 | 2009-09-10 | Schill + Seilacher Ag | Halogen-free flame retardants |
| WO2015180165A1 (en) * | 2014-05-30 | 2015-12-03 | Dupont (China) Research & Development And Management Co., Ltd. | Flame retardants, preparation methods, and thermoplastic compositions thereof |
| CN105669760B (en) * | 2016-03-07 | 2017-06-06 | 中国科学院化学研究所 | A kind of organic phospha phenanthrene derivative and preparation method and application |
| CN112442071B (en) * | 2019-08-28 | 2023-11-07 | 广东广山新材料股份有限公司 | Phosphorus-containing reactive flame retardant, high-molecular flame retardant, preparation method and application |
-
2021
- 2021-06-02 CN CN202110613099.2A patent/CN115433235B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101663374A (en) * | 2007-04-03 | 2010-03-03 | 巴斯夫欧洲公司 | DOPO flame retardant compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115433235A (en) | 2022-12-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Fang et al. | An effective flame retardant for poly (ethylene terephthalate) synthesized by phosphaphenanthrene and cyclotriphosphazene | |
| CN112175242B (en) | A kind of microcapsule intumescent flame retardant and its preparation method and application | |
| CN104725665B (en) | A kind of spiro-phosphate fire retardant containing s-triazine structure, preparation method and applications | |
| CN105669760B (en) | A kind of organic phospha phenanthrene derivative and preparation method and application | |
| CN107739453A (en) | DOPO derivative flame retardants and its preparation method and application | |
| CN115433235B (en) | An organic phosphaphenanthrene derivative with hydroxyl structure and preparation method thereof | |
| CN108467514A (en) | A kind of Halogen phosphonitrile expansion type fire retardant and preparation method thereof | |
| CN106565959B (en) | Macromolecular phosphor nitrogen combustion inhibitor and preparation method with cage ring phosphate ester structure | |
| CN104558683A (en) | DOPO-containing cyclic phosphate flame retardant as well as preparation method and application thereof | |
| CN117306014B (en) | Flame-retardant polyester fiber and preparation method thereof | |
| CN105541917B (en) | A kind of phosphorus nitrogen collaboration polyester flame-retardant agent and preparation method thereof | |
| CN116102593A (en) | Bio-based phosphorus-containing Schiff base flame retardant and preparation method thereof | |
| CN109369957A (en) | A kind of phosphorus-based flame retardant with dual functions of ultraviolet absorption and flame retardant and its preparation and application | |
| CN111533894A (en) | Phosphorus-nitrogen-containing flame-retardant polyester and preparation method thereof | |
| CN113185873B (en) | A kind of preparation method of bio-based flame retardant and anti-photoaging PVA composite material | |
| CN117946583A (en) | Key materials for intelligent self-healing, flame-retardant, light-resistant waterborne polyurethane coatings | |
| CN101560227A (en) | Flame-retarding compound, flame-retardant prepared thereby and preparation method thereof | |
| CN105860594A (en) | Synthesis method of organosilicone modified superfine aluminum hypophosphite | |
| CN118754912A (en) | A small molecule phosphorus-nitrogen-containing polyol derivative and its preparation method and application | |
| CN114085246A (en) | A kind of bio-based phosphorus flame retardant and its preparation method and application | |
| CN118307766A (en) | Organic phase change material di-polyethylene glycol methyl phosphonate and preparation method and application thereof | |
| CN116751144A (en) | A new type of magnesium sulfonate flame retardant and its preparation method and application | |
| Shao et al. | A highly efficient gas-dominated and water-resistant flame retardant for non-charring polypropylene | |
| CN114671911B (en) | Amide type organic phosphine nitrogen flame retardant compound and preparation method thereof | |
| CN117510767A (en) | Phosphorus-nitrogen synergistic macromolecular flame retardant and application thereof in preparation of flame-retardant PET material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |