CN113620994A - Reactive phosphorus-containing flame retardant and preparation method and application thereof - Google Patents
Reactive phosphorus-containing flame retardant and preparation method and application thereof Download PDFInfo
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- CN113620994A CN113620994A CN202110920766.1A CN202110920766A CN113620994A CN 113620994 A CN113620994 A CN 113620994A CN 202110920766 A CN202110920766 A CN 202110920766A CN 113620994 A CN113620994 A CN 113620994A
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- 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)
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- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
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Abstract
The invention relates to a reactive phosphorus-containing flame retardant, a preparation method and application thereof, wherein the structural formula of the reactive phosphorus-containing flame retardant is
The invention takes the DOPO-based flame retardant DOPO-HQ as an initiator to obtain the reactive phosphorus-containing flame retardant through chemical modification, and the molecular structure does not contain polar groups, so the reactive phosphorus-containing flame retardant is not easy to absorb moisture, is easy to react and is not easy to migrate; can react with polymer resin containing unsaturated double bonds, and is grafted into the molecular chain of the polymer to achieve the effect of flame retardance and durability; can be dissolved in ketone solvent, aromatic solvent, polar solvent such as DMF, DMSO, methanol, ethanol, ethyl acetate, butyl acetate, etc., and has convenient processing and application. The invention prepares the reactive phosphorus-containing flame retardantThe method of the agent has short reaction time, easy realization of reaction conditions, convenient post-treatment and high yield; the flame retardant is particularly suitable for the flame retardant of insulating plates and high-frequency and high-speed copper-clad plates, and has the characteristics of high heat resistance, good dielectric property, no delamination, high flame retardant grade and the like.
Description
Technical Field
The invention belongs to the field of high-molecular flame retardant additives, and particularly relates to a phosphorus-containing reactive flame retardant used in high-molecular resins and polymer-based copper-clad laminates, and a preparation method and application thereof.
Background
The polymer material has the advantages of excellent mechanical, electrical and chemical corrosion resistance and the like, and is widely applied to the fields of aviation, aerospace, electronics, machinery and chemical industry. However, most of the high molecular materials are flammable or combustible in air, and release a large amount of toxic gases and smoke during combustion, thereby causing environmental pollution and seriously threatening the life and property safety of people. The flammability and flammability of the polymer greatly limit the application field of the polymer material, so that the improvement of the flame retardant property of the polymer material receives more and more attention.
Flame retardancy of polymeric materials is generally achieved by adding flame retardants. At present, the flame retardant comprises two main types of additive flame retardant and reactive flame retardant. The additive flame retardant is added into the high polymer material by methods such as blending and the like so as to prepare the high polymer material with flame retardant property, for example, Chinese patent CN101712875B discloses a method for preparing flame retardant polyolefin cable material by taking magnesium hydroxide as the flame retardant, the method for adding the flame retardant leads the compatibility of the flame retardant and matrix high polymer resin to be poor, the interfacial bonding force is poor, a large amount of the additive flame retardant is required to be added, and finally the additive flame retardant is slowly separated out on the surface of the high polymer material, so that the flame retardant effect is reduced, and the material property is poor; the reactive flame retardant is added into a reaction system as a monomer in the synthesis of a high polymer material, and finally becomes a part of a high polymer chain through a chemical bond, so that the persistent flame retardant effect is achieved. For example, chinese patent CN112442071A discloses a phosphorus-containing reactive flame retardant, which contains hydroxyl and alkenyl groups, and is added to the material as active sites or becomes a part of the high molecular polymer as a reactive monomer, thereby achieving the purpose of flame retardation.
The phosphorus-containing flame retardant 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) has wide application range, and can be used in materials such as epoxy, polyurethane, polyester resin, liquid crystal polymer and the like to prepare halogen-free flame retardant polymer materials. However, DOPO has a small molecular weight, is easy to migrate, has hydrolyzability, and is easy to absorb moisture. Therefore, the majority of the phosphorus-containing reactive flame retardant is prepared by taking DOPO as a flame retardant intermediate and modifying the DOPO by using active hydrogen atoms in P-H bonds in molecules of the DOPO as a flame retardant intermediate. For example, chinese patent CN108997714A discloses a DOPO derivative flame retardant for epoxy resin, in which amino groups in the molecular structure of the flame retardant can react with epoxy resin to solve the migration problem of the flame retardant. For another example, chinese patent CN112745500A discloses a reactive DOPO derivative flame retardant containing hydroxyl group, which is used for flame retardant modification of polyether amide. The reactive DOPO derivative flame retardant has higher temperature resistance in use, is grafted into a molecular chain through reaction without migration, but the modified flame retardant has amino, alcoholic hydroxyl, phenolic hydroxyl, epoxy and other reactive groups introduced into the DOPO derivative molecule, and the amino, alcoholic hydroxyl, phenolic hydroxyl, epoxy and other groups have polarity, so that the DOPO derivative flame retardant still has hygroscopicity and higher dielectric loss and dielectric constant, and the derivative flame retardant can not be used for flame retardance of organic materials in the high-frequency and high-speed electronic communication field, and the application range is limited.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a reactive phosphorus-containing flame retardant and a preparation method and application thereof, the reactive phosphorus-containing flame retardant is obtained by taking DOPO-based flame retardant 10- (2, 5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-HQ for short, CAS: 99208-50-1) as an initiator through chemical modification, and the molecular structure of the obtained flame retardant does not contain polar groups such as amino, alcoholic hydroxyl, phenolic hydroxyl, epoxy and the like, so that the flame retardant is difficult to absorb moisture, is easy to react and is difficult to migrate. The obtained flame retardant can react with polymer resin, especially with polymer resin containing unsaturated double bonds, and is grafted into the molecular chain of the polymer to achieve the effect of flame retardance and durability; the flame retardant obtained by the invention can be dissolved in ketone solvents such as acetone and butanone, aromatic solvents such as benzene, toluene and xylene, polar solvents such as DMF, DMSO, methanol, ethanol, ethyl acetate and butyl acetate, and is convenient to process and apply.
The technical problem is solved by adopting the following technical scheme, and the molecular structural formula of the reactive phosphorus-containing flame retardant provided by the invention is shown as the formula (1):
the group R in the formula (1)1And R2Each independently selected from the following structural formula (2), structural formula (3), and structural formula (4):
wherein, the substituent R in the structural formula (2) and the structural formula (3)3And R4At ortho-, meta-or para-position of the phenyl ring and each is independently selected from-H, -CH ═ CH2A group, and R3And R4In which at least one-CH ═ CH2A group; substituent R in structural formula (4)5、R6、R7Each independently selected from-H, -CH3、-CH2-CH3A group.
The invention also provides a preparation method of the reactive phosphorus-containing flame retardant, the method can obtain the flame retardant through one-step reaction, the reaction condition is easy to realize, the reaction time is short, the post-treatment is convenient, and the yield is high, and the method specifically comprises the following steps:
stirring and dissolving DOPO-HQ in a solvent, introducing nitrogen, adding a catalyst, a modifier and a polymerization inhibitor into the system, continuously stirring, controlling the reaction temperature to be 0-100 ℃, and controlling the reaction time to be 1-10 hours; after the reaction is finished, filtering and removing impurities from the reaction liquid to obtain a filtrate, then adding the filtrate into a poor solvent to separate out a crude product, and washing the crude product for 3-5 times by using the poor solvent to finally obtain the reactive phosphorus-containing flame retardant, wherein the molecular structural formula of the obtained reactive phosphorus-containing flame retardant is as follows:
wherein the radical R1And R2Each independently selected from the following structural formula (2), structural formula (3), and structural formula (4):
substituent R in structural formula (2) and structural formula (3)3And R4At ortho-, meta-or para-position of the phenyl ring and each is independently selected from-H, -CH ═ CH2A group, and R3And R4In which at least one-CH ═ CH2A group; substituent R in structural formula (4)5、R6、R7Each independently selected from-H, -CH3，-CH2-CH3A group.
Preferably, the solvent for dissolving DOPO-HQ is one or more selected from acetone, butanone, benzene, toluene, xylene, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, methanol, ethanol, ethyl acetate and butyl acetate, and the solvent is used in an amount of 1-10 parts by weight based on 1 part by weight of DOPO-HQ.
Preferably, the catalyst consists of one or more of the following reagents: potassium bicarbonate, sodium bicarbonate, potassium carbonate, sodium carbonate, cesium carbonate, potassium iodide, sodium hydroxide, potassium hydroxide, sulfuric acid, phosphoric acid, benzyltriethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, pyridine, picoline, triethylamine, diisopropylethylamine, dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide, measured in 1 part by weight of DOPO-HQ, the catalyst being used in 0.01 to 6.0 parts by weight.
Preferably, the modifier consists of one or more of the following agents: p-chloromethyl styrene, acrylic acid, methacrylic anhydride, acryloyl chloride, methacryloyl chloride, methyl acrylate, methyl methacrylate, 4-vinylbenzoic acid, 4-vinylbenzoyl chloride, the weight portion of DOPO-HQ being 1 part, the modifier being used in an amount of 0.01 to 4.0 parts.
Preferably, the polymerization inhibitor consists of one or more of the following agents: hydroquinone, p-hydroxyanisole, 2-tertiary butyl hydroquinone, 2, 5-di-tertiary butyl hydroquinone, p-benzoquinone, methyl hydroquinone, tetrachlorobenzoquinone, ferric chloride, cuprous chloride and copper sulfate, wherein the weight part of DOPO-HQ is 1 part, and the weight part of the polymerization inhibitor is 0.001-0.1 part.
Preferably, the poor solvent is one or more selected from pentane, hexane, cyclohexane, petroleum ether and water. The weight portion of DOPO-HQ is 1 portion, and the weight portion of the poor solvent is 1-80 portions.
The invention also provides the flame retardant application of the reactive phosphorus-containing flame retardant in high polymer resin, especially in high polymer resin containing unsaturated double bonds, and the application of the reactive phosphorus-containing flame retardant in halogen-free flame retardant of polymer-based copper-clad laminates and insulating plates.
Compared with the prior art, the invention has the following advantages:
(1) the two ends of each molecule of the reactive phosphorus-containing flame retardant prepared by the invention respectively contain an unsaturated carbon-carbon double bond, and polar groups such as amino, alcoholic hydroxyl, phenolic hydroxyl, epoxy and the like are not contained, so that moisture absorption is not easy to occur in the storage process.
(2) When the flame retardant is used, the flame retardant can easily generate free radical addition reaction with polymer resin containing unsaturated double bonds under the action of heat and an initiator, so that the flame retardant is grafted into a main chain or a side chain of a polymer, the flame retardant lasting effect is achieved, and the characteristics of no precipitation and no migration of the flame retardant are shown.
(3) Compared with DOPO-HQ or other DOPO-based flame retardants, the flame retardant obtained by the invention has good solubility after chemical modification, can be dissolved in ketone solvents such as acetone and butanone, aromatic solvents such as benzene, toluene and xylene, polar solvents such as DMF, DMSO, methanol, ethanol, ethyl acetate and butyl acetate, and has the solubility of 50% in DMF and ethyl acetate at 25 ℃, so the processing and application are convenient.
(4) The preparation method of the reactive phosphorus-containing flame retardant can obtain the flame retardant through one-step reaction, and has the advantages of easily realized reaction conditions, short reaction time, convenient post-treatment, high yield and high product purity.
(5) Particularly, the reactive phosphorus-containing flame retardant prepared by the invention does not contain polar groups such as amino, alcoholic hydroxyl, phenolic hydroxyl, epoxy group and the like, has good electrical properties, is suitable for flame retardance of high molecular materials on insulated electrical equipment, is particularly suitable for flame retardance of insulating plates and high-frequency and high-speed copper-clad plates, and shows the characteristics of high heat resistance, no delamination, high flame retardance grade and the like of the plates.
Drawings
FIG. 1 is a graph comparing infrared of a reactive phosphorus-containing flame retardant made in accordance with the present invention with DOPO-HQ, wherein, 1-the reactive phosphorus-containing flame retardant made in accordance with the present invention; 2-reactant DOPO-HQ.
FIG. 2 is a diagram of a reactive phosphorus-containing flame retardant prepared by the present invention1H-NMR spectrum.
Detailed Description
For a better understanding of the contents of the invention, reference will now be made to the following examples and accompanying drawings which illustrate the invention. The present embodiment is implemented based on the technology of the present invention, and a detailed implementation manner and operation steps are given, but the scope of the present invention is not limited to the following embodiments.
The reactive phosphorus-containing flame retardant is prepared by the following steps:
firstly stirring and dissolving DOPO-HQ in a solvent, introducing nitrogen to replace air to prevent oxygen in the air from participating in a reaction, then adding a catalyst, a modifier and a polymerization inhibitor into the system, continuously stirring, keeping the reaction temperature at 0-100 ℃, reacting for 1-10 hours, filtering and removing impurities from reaction liquid after the reaction is finished to obtain filtrate, then adding the filtrate into a poor solvent to separate out a crude product, and washing the crude product for 3-5 times by using the poor solvent to finally obtain the reactive phosphorus-containing flame retardant product shown in the structural formula (1).
The group R in the formula (1)1、R2Each independently selected from the following structural formula (2), structural formula (3), and structural formula (4):
wherein R is1、R2May or may not be the same. And, substituent R in the structural formulae (2) and (3)3、R4In ortho-, meta-or para-position of the phenyl ring and are each independently selected from-H, -CH ═ CH2Radical, substituent R3、R4May be the same or different, but contains at least one-CH ═ CH2A group.
Substituent R in structural formula (4)5、R6、R7Each independently selected from-H, -CH3，-CH2-CH3A group; substituent R5、R6、R7May or may not be the same.
Preferably, in the above preparation method, the solvent for dissolving DOPO-HQ is one or more selected from acetone, butanone, benzene, toluene, xylene, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, methanol, ethanol, ethyl acetate, and butyl acetate, and is used in an amount of 1 to 10 parts by weight based on 1 part by weight of DOPO-HQ.
Preferably, in the above preparation method, the catalyst is composed of one or more of the following reagents: potassium bicarbonate, sodium bicarbonate, potassium carbonate, sodium carbonate, cesium carbonate, potassium iodide, sodium hydroxide, potassium hydroxide, sulfuric acid, phosphoric acid, benzyltriethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, pyridine, picoline, triethylamine, diisopropylethylamine, dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide, measured in 1 part by weight of DOPO-HQ, the catalyst being used in 0.01 to 6.0 parts by weight.
Preferably, in the above preparation method, the modifier is composed of one or more of the following reagents: p-chloromethyl styrene, acrylic acid, methacrylic anhydride, acryloyl chloride, methacryloyl chloride, methyl acrylate, methyl methacrylate, 4-vinylbenzoic acid, 4-vinylbenzoyl chloride, the weight portion of DOPO-HQ being 1 part, the modifier being used in an amount of 0.01 to 4.0 parts.
Preferably, in the above preparation method, the polymerization inhibitor is composed of one or more of the following reagents: hydroquinone, p-hydroxyanisole, 2-tertiary butyl hydroquinone, 2, 5-di-tertiary butyl hydroquinone, p-benzoquinone, methyl hydroquinone, tetrachlorobenzoquinone, ferric chloride, cuprous chloride and copper sulfate, wherein the weight part of DOPO-HQ is 1 part, and the weight part of the polymerization inhibitor is 0.001-0.1 part.
Preferably, in the above preparation method, the poor solvent is selected from one or more of pentane, hexane, cyclohexane, petroleum ether and water. The weight portion of DOPO-HQ is 1 portion, and the weight portion of the poor solvent is 1-80 portions.
The reactive phosphorus-containing flame retardant prepared by the preparation method is applied to flame retardance of high polymer resin, particularly high polymer resin containing unsaturated double bonds, and can achieve the effect of halogen-free flame retardance in polymer-based copper-clad laminates and insulating plates.
FIG. 1 is a graph of the infrared comparison of the reactive phosphorus-containing flame retardant prepared in example 3 with DOPO-HQ, from which it can be seen that: the wave number in the product is 1734cm relative to the raw material DOPO-HQ-1The peak of (2) is the carbonyl absorption peak of the product structure obtained in example 3, and the wave number in the product is 16371 cm-1The peak of (a) is a C ═ C absorption peak of the structure of the product obtained in example 3, indicating that the modifier reacted with DOPO-HQ, and incorporated into the molecule of DOPO-HQ to obtain the product obtained in example 3.
FIG. 2 is a depiction of a reactive phosphorus-containing flame retardant prepared in example 31The H-NMR spectrum showed that the product obtained in example 3 had a vibrational absorption peak of the hydrogen atom at the double bond between chemical shifts 5.3 and 6.4. While DOPO-HQ has no absorption peak of double bond hydrogen, which indicates that the modifier reacts with the DOPO-HQ and is grafted into the molecule of the DOPO-HQ to obtain the product obtained in example 3.
Example 1:
32.427 g of DOPO-HQ is stirred, dispersed and dissolved in 162.135 g of N, N-dimethylformamide, nitrogen is introduced to replace air, oxygen in the air is prevented from participating in a reaction, 97.281 g of potassium carbonate and 3.24 g of potassium iodide mixture are added into the system as catalysts, 64.854 g of p-chloromethyl styrene and 0.0324 g of hydroquinone are continuously stirred, the reaction temperature is kept at 50 ℃, the reaction time is 10 hours, after the reaction is finished, reaction liquid is filtered to remove impurities, filtrate is obtained, the filtrate is added into 1945.6 g of water, a crude product is separated out, the crude product is washed for 5 times by water, and finally the reactive phosphorus-containing flame retardant is obtained, wherein the yield is 96.5%, and the structural formula is as follows:
example 2:
32.427 g of DOPO-HQ is stirred, dispersed and dissolved in 162.135 g of dimethyl sulfoxide, nitrogen is introduced to replace air, oxygen in the air is prevented from participating in a reaction, 97.281 g of cesium carbonate, 64.854 g of p-chloromethyl styrene and 0.0324 g of polymerization inhibitor 2, 5-di-tert-butyl hydroquinone are added to the system, the stirring is continuously kept, the reaction temperature is kept at 60 ℃, the reaction time is 8 hours, after the reaction is finished, the reaction liquid is filtered and impurity-removed to obtain a filtrate, then the filtrate is added into 1945.6 g of water to separate out a crude product, the crude product is washed for 5 times by using a poor solvent, and finally a reaction type phosphorus-containing flame retardant product is obtained, wherein the yield is 97.2%, and the structural formula is as follows:
example 3:
firstly stirring 32.427 g of DOPO-HQ, dispersing and dissolving in 162.135 g of N, N-dimethylformamide, introducing nitrogen to replace air, preventing oxygen in the air from participating in a reaction, then adding 3.243 g of 96% concentrated sulfuric acid, 51.60 g of methacrylic acid and 0.0324 g of polymerization inhibitor hydroquinone into the system, continuously stirring, keeping the reaction temperature at 30 ℃, reacting for 5 hours, filtering and removing impurities from the reaction liquid after the reaction is finished, obtaining a filtrate, then adding the filtrate into 2594.2 g of water, separating out a crude product, washing the crude product for 5 times by using water, and finally obtaining a reactive phosphorus-containing flame retardant product, wherein the yield is 99.2%, and the structural formula is as follows:
example 4:
32.427 g of DOPO-HQ is stirred, dispersed and dissolved in 324.27 g of N, N-dimethylformamide, nitrogen is introduced to replace air, oxygen in the air is prevented from participating in a reaction, 9.8 g of phosphoric acid with the mass fraction of 75-85% and 24.76 g of dicyclohexylcarbodiimide are added into the system as catalysts, 18.252 g of acrylic acid as a modifier and 0.0324 g of p-hydroxyanisole as a polymerization inhibitor, stirring is continuously kept, the reaction temperature is kept at 80 ℃, the reaction time is 6 hours, after the reaction is finished, reaction liquid is filtered and impurities are removed to obtain filtrate, the filtrate is added into 2594.2 g of water, a crude product is separated out, the crude product is washed with water for 5 times, and finally the reaction type phosphorus-containing flame retardant product is obtained, wherein the yield is 98.4%, and the structural formula is as follows:
example 5:
32.427 g of DOPO-HQ is stirred, dispersed and dissolved in 324.27 g of N, N-dimethylformamide, nitrogen is introduced to replace air, oxygen in the air is prevented from participating in a reaction, 47.4 g of pyridine, 23.53 g of acryloyl chloride and 0.0324 g of polymerization inhibitor 2, 5-di-tert-butylhydroquinone are added into a system, stirring is continuously kept, the reaction temperature is kept at 80 ℃, the reaction time is 6 hours, after the reaction is finished, the reaction liquid is filtered and impurity is removed, filtrate is obtained, then the filtrate is added into 2594.2 g of water, a crude product is separated out, the crude product is washed for 5 times, and finally the reaction type phosphorus-containing flame retardant product is obtained, wherein the yield is 98.1%, and the structural formula is as follows:
example 6:
32.427 g of DOPO-HQ is stirred, dispersed and dissolved in 324.27 g of N, N-dimethylformamide, nitrogen is introduced to replace air, oxygen in the air is prevented from participating in a reaction, 50.0 g of pyridine, 27.18 g of methacryloyl chloride and 0.0324 g of polymerization inhibitor hydroquinone are added into a system, stirring is continuously kept, the reaction temperature is kept at 80 ℃, the reaction time is 6 hours, after the reaction is finished, the reaction liquid is filtered and impurities are removed to obtain a filtrate, the filtrate is added into 2594.2 g of water, a crude product is separated out, the crude product is washed for 5 times by water, and finally a reaction type phosphorus-containing flame retardant product is obtained, wherein the yield is 97.8%, and the structural formula is as follows:
example 7:
32.427 g of DOPO-HQ is stirred, dispersed and dissolved in 324.27 g of N, N-dimethylacetamide, nitrogen is introduced to replace air, oxygen in the air is prevented from participating in a reaction, 100.0 g of methylpyridine, 97.28 g of 4-vinylbenzoyl chloride and 0.0324 g of polymerization inhibitor hydroquinone are added into a system, stirring is continuously kept, the reaction temperature is kept at 10 ℃, the reaction time is 8 hours, after the reaction is finished, the reaction liquid is filtered and impurity-removed to obtain a filtrate, then the filtrate is added into 2594.2 g of water to separate out a crude product, the crude product is washed for 5 times, and finally the reaction type phosphorus-containing flame retardant product is obtained, wherein the yield is 98.6 percent, and the structural formula is as follows:
example 8:
32.427 g of DOPO-HQ is stirred, dispersed and dissolved in 324.27 g of N, N-dimethylacetamide, nitrogen is introduced to replace air, oxygen in the air is prevented from participating in a reaction, 100.0 g of methylpyridine, 118.56 g of 4-vinylbenzoic acid and 0.0324 g of polymerization inhibitor 2-tert-butylhydroquinone are added to the system, the stirring is continuously kept, the reaction temperature is kept at 90 ℃, the reaction time is 7 hours, after the reaction is finished, the reaction liquid is filtered to remove impurities, a filtrate is obtained, then the filtrate is added into 2594.2 g of water, a crude product is separated out, the crude product is washed for 5 times, and finally the reaction type phosphorus-containing flame retardant product is obtained, wherein the yield is 98.8%, and the structural formula is as follows:
example 9:
32.427 g of DOPO-HQ is stirred, dispersed and dissolved in 324.270 g of N, N-dimethylacetamide, nitrogen is introduced to replace air, oxygen in the air is prevented from participating in a reaction, a mixture of 97.281 g of potassium carbonate and 3.24 g of potassium iodide is added to the system as a catalyst, 19.840 g of p-chloromethyl styrene and 0.0324 g of polymerization inhibitor hydroquinone are added, the stirring is continuously kept, the reaction temperature is kept at 30 ℃, after 4 hours of reaction, 13.59 g of methacryloyl chloride is added, the stirring is continuously kept, the reaction temperature is kept at 30 ℃, the reaction time is 3 hours, after the reaction is finished, the reaction liquid is filtered to remove impurities, a filtrate is obtained, the filtrate is added into 2594.2 g of water, a crude product is separated out, the crude product is washed for 5 times by water, and a reaction type phosphorus-containing flame retardant product is finally obtained, the yield is 96.5%, and the structural formula of the main product is as follows:
example 10:
32.427 g of DOPO-HQ is stirred, dispersed and dissolved in 324.270 g of N, N-dimethylacetamide, nitrogen is introduced to replace air, oxygen in the air is prevented from participating in a reaction, 97.281 g of potassium carbonate is added into the system, 13.59 g of methacryloyl chloride and 0.0324 g of polymerization inhibitor hydroquinone are added, the stirring is continuously kept, the reaction temperature is kept at 30 ℃, after 4 hours of reaction, 3.24 g of potassium iodide and 19.840 g of p-chloromethyl styrene are added, the stirring is continuously carried out, the reaction temperature is kept at 30 ℃, the reaction time is 3 hours, after the reaction is finished, reaction liquid is filtered and impurities are removed, filtrate is obtained, the filtrate is added into 2594.2 g of water, a crude product is separated out, the crude product is washed for 5 times by using water, and a reaction type phosphorus-containing flame retardant product is finally obtained, the yield is 96.1%, and the structural formula of the main product is as follows:
example 11:
firstly stirring 32.427 g of DOPO-HQ, dispersing and dissolving in 324.270 g of N, N-dimethylacetamide, introducing nitrogen to replace air, preventing oxygen in the air from participating in a reaction, adding 100.0 g of pyridine, 16.878 g of 4-vinylbenzoyl chloride and 0.0324 g of polymerization inhibitor hydroquinone into the system, continuously stirring, keeping the reaction temperature at 10 ℃, reacting for 3 hours, then adding 13.59 g of methacryloyl chloride, continuously stirring, keeping the reaction temperature at 10 ℃, and reacting for 4 hours; after the reaction is finished, filtering the reaction solution to remove impurities to obtain a filtrate, adding the filtrate into 2594.2 g of water to separate out a crude product, washing the crude product with water for 5 times to finally obtain a reactive phosphorus-containing flame retardant product, wherein the yield is 96.6%, and the structural formula of a main product is as follows:
example 12:
firstly stirring 32.427 g of DOPO-HQ, dispersing and dissolving in 324.270 g of N, N-dimethylacetamide, introducing nitrogen to replace air, preventing oxygen in the air from participating in a reaction, adding 100.0 g of pyridine into the system, adding 13.59 g of methacryloyl chloride and 0.0324 g of polymerization inhibitor hydroquinone, continuously stirring, keeping the reaction temperature at 10 ℃, reacting for 3 hours, then adding 16.878 g of 4-vinylbenzoyl chloride, continuously stirring, keeping the reaction temperature at 10 ℃, and reacting for 4 hours; after the reaction is finished, filtering the reaction solution to remove impurities to obtain a filtrate, adding the filtrate into 2594.2 g of water to separate out a crude product, washing the crude product with water for 5 times to finally obtain a reactive phosphorus-containing flame retardant product, wherein the yield is 96.2%, and the structural formula of a main product is as follows:
the above description is only an embodiment of the present invention, and is not intended to limit the present invention in any way, and the present invention may also have other embodiments according to the above structures and functions, and is not listed again. Therefore, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention by those skilled in the art can be made within the technical scope of the present invention.
Claims (9)
1. A reactive phosphorus-containing flame retardant is characterized in that the molecular structural formula is shown as formula (1):
the group R in the formula (1)1、R2Each independently selected from the following structural formula (2), structural formula (3), and structural formula (4):
wherein, the substituent R in the structural formula (2) and the structural formula (3)3And R4At ortho-, meta-or para-position of the phenyl ring and each is independently selected from-H, -CH ═ CH2A group, and R3And R4In which at least one-CH ═ CH2A group; substituent R in structural formula (4)5、R6、R7Each independently selected from-H, -CH3，-CH2-CH3A group.
2. A preparation method of a reactive phosphorus-containing flame retardant is characterized by comprising the following steps:
stirring and dissolving DOPO-HQ in a solvent, introducing nitrogen, adding a catalyst, a modifier and a polymerization inhibitor into the system, continuously stirring, controlling the reaction temperature to be 0-100 ℃, and controlling the reaction time to be 1-10 hours; after the reaction is finished, filtering and removing impurities from the reaction liquid to obtain a filtrate, then adding the filtrate into a poor solvent to separate out a crude product, and washing the crude product for 3-5 times by using the poor solvent to finally obtain the reactive phosphorus-containing flame retardant, wherein the molecular structural formula of the reactive phosphorus-containing flame retardant is as follows:
wherein the radical R1And R2Each independently selected from the following structural formula (2) and structural formula (3)And structural formula (4):
substituent R in structural formula (2) and structural formula (3)3And R4At ortho-, meta-or para-position of the phenyl ring and each is independently selected from-H, -CH ═ CH2A group, and R3And R4In which at least one-CH ═ CH2A group; substituent R in structural formula (4)5、R6、R7Each independently selected from-H, -CH3，-CH2-CH3A group.
3. The method for preparing a reactive phosphorus-containing flame retardant according to claim 2, wherein the solvent for dissolving DOPO-HQ is one or more selected from the group consisting of acetone, methyl ethyl ketone, benzene, toluene, xylene, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, methanol, ethanol, ethyl acetate and butyl acetate, and is used in an amount of 1 to 10 parts by weight based on 1 part by weight of DOPO-HQ.
4. The process of claim 2, wherein the catalyst comprises one or more of the following: potassium bicarbonate, sodium bicarbonate, potassium carbonate, sodium carbonate, cesium carbonate, potassium iodide, sodium hydroxide, potassium hydroxide, sulfuric acid, phosphoric acid, benzyltriethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, pyridine, picoline, triethylamine, diisopropylethylamine, dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide, measured in 1 part by weight of DOPO-HQ, the catalyst being used in 0.01 to 6.0 parts by weight.
5. The method of claim 2, wherein the modifier is comprised of one or more of the following: p-chloromethyl styrene, acrylic acid, methacrylic anhydride, acryloyl chloride, methacryloyl chloride, methyl acrylate, methyl methacrylate, 4-vinylbenzoic acid, 4-vinylbenzoyl chloride, the weight portion of DOPO-HQ being 1 part, the modifier being used in an amount of 0.01 to 4.0 parts.
6. The process for preparing a reactive phosphorus-containing flame retardant according to claim 2, wherein the polymerization inhibitor is composed of one or more of the following agents: hydroquinone, p-hydroxyanisole, 2-tertiary butyl hydroquinone, 2, 5-di-tertiary butyl hydroquinone, p-benzoquinone, methyl hydroquinone, tetrachlorobenzoquinone, ferric chloride, cuprous chloride and copper sulfate, wherein the weight part of DOPO-HQ is 1 part, and the weight part of the polymerization inhibitor is 0.001-0.1 part.
7. The method for preparing a reactive phosphorus-containing flame retardant according to claim 2, wherein the poor solvent is one or more selected from the group consisting of pentane, hexane, cyclohexane, petroleum ether, and water, and is used in an amount of 1 part by weight based on 1 part by weight of DOPO-HQ, and 1 to 80 parts by weight based on 1 part by weight of the poor solvent.
8. The reactive phosphorus-containing flame retardant is applied to flame retardance of high polymer resin, particularly high polymer resin containing unsaturated double bonds.
9. The application of the reactive phosphorus-containing flame retardant in halogen-free flame retardance of polymer-based copper-clad laminates and insulating plates.
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