Phosphate ammonium salt and preparation method and application thereof
阅读说明：本技术 磷酸酯铵盐及其制备方法和应用 (Phosphate ammonium salt and preparation method and application thereof ) 是由 师文博 宋斌 刘超栋 李华亮 陈建良 薛丽 陆云 于 2020-12-03 设计创作，主要内容包括：本发明涉及一种磷酸酯铵盐及其制备方法和应用。该磷酸酯铵盐具有式I所示结构,由四苯基间苯二酚二磷酸酯和乙醇胺在催化剂的作用下反应得到。该磷酸酯铵盐可以作为阻燃剂,用于制备阻燃聚氨酯、阻燃聚酯、阻燃聚酰胺等阻燃高分子材料,其具有反应性官能团,其作为阻燃剂,用于制备阻燃高分子材料时,可以在聚合物合成的过程中添加并且参与聚合物的反应,从而能够极大的提高其与聚合物的相容性,从而可以提高其阻燃效果,以及所得材料的力学性能。本发明提供的磷酸酯铵盐的制备方法,其反应工艺简单,产率极高,适合工业化大规模生产。(The invention relates to phosphate ammonium salt and a preparation method and application thereof. The phosphate ammonium salt has a structure shown in formula I and is obtained by reacting tetraphenyl resorcinol diphosphate with ethanolamine under the action of a catalyst. The phosphate ammonium salt can be used as a flame retardant for preparing flame-retardant high polymer materials such as flame-retardant polyurethane, flame-retardant polyester, flame-retardant polyamide and the like, has a reactive functional group, and can be added in the polymer synthesis process and participate in the reaction of the polymer when being used as the flame retardant for preparing the flame-retardant high polymer materials, so that the compatibility of the phosphate ammonium salt and the polymer can be greatly improved, and the phosphate ammonium salt can be used for preparing the flame-retardant high polymer materialsThe flame retardant effect and the mechanical property of the obtained material are improved. The preparation method of the phosphate ammonium salt provided by the invention has the advantages of simple reaction process and extremely high yield, and is suitable for industrial large-scale production.)
1. An ammonium phosphate salt having the structure shown in formula I:
wherein m is 1-7.
2. The phosphate ammonium salt is characterized by being obtained by reacting tetraphenyl resorcinol diphosphate with ethanolamine under the action of a catalyst, wherein the tetraphenyl resorcinol diphosphate has the following structural formula:
wherein m is 1-7.
3. The ammonium phosphate according to claim 2, wherein the catalyst is at least one of trimethyl borate and dibutyl tin dilaurate; and/or the presence of a gas in the gas,
the molar ratio of the tetraphenylresorcinol diphosphate to the ethanolamine is 1: 1.8-2.3; and/or the presence of a gas in the gas,
the catalyst is 0.1-2 wt% of the total mass of tetraphenyl resorcinol diphosphate and ethanolamine.
4. The ammonium phosphate salt according to claim 3, wherein the molar ratio of tetraphenylresorcinol diphosphate to ethanolamine is 1: 2-2.2; and/or the presence of a gas in the gas,
the catalyst is 0.3-1.5 wt% of the total mass of tetraphenyl resorcinol diphosphate and ethanolamine.
5. The ammonium phosphate salt according to any one of claims 1 to 4, wherein the ammonium phosphate salt has a melting point of 55 to 65 ℃ and a density of 1.2 to 1.4g/cm3。
6. A process for the preparation of the ammonium phosphate salt according to any one of claims 1 to 5, comprising the steps of:
adding the tetraphenyl resorcinol diphosphate and ethanolamine into a reactor, stirring, adding the catalyst, sealing the reactor, enabling reactants in the reactor to be protected by inert gas, then enabling the reactants to react in the reactor at the temperature of 50-80 ℃, then reacting in the reactor at the temperature of 100-140 ℃, and cooling to obtain the phosphate ammonium salt.
7. The method for preparing an ammonium phosphate salt according to claim 6, comprising the steps of:
adding the tetraphenyl resorcinol diphosphate and ethanolamine into a reactor, stirring, adding the catalyst, sealing the reactor, enabling reactants in the reactor to be protected by inert gas in a vacuum pumping and inert gas introducing mode, then enabling the reactants to firstly react for 1-4h in the reactor with the temperature of 50-80 ℃, then reacting for 1-4h in the reactor with the temperature of 100-140 ℃, and cooling to obtain the phosphate ammonium salt; preferably, the reactants are reacted for 2-3h in a reactor at a temperature of 65-75 ℃ and then for 2-3h in a reactor at a temperature of 110-130 ℃.
8. The method for preparing an ammonium phosphate salt according to claim 6, comprising the steps of:
(1) adding the tetraphenyl resorcinol diphosphate and the ethanolamine which are dried in vacuum into a kettle type reactor with a stirring paddle, and adjusting the stirring speed of the kettle type reactor to be 30-100r/min and the stirring time to be 3-10 min;
(2) adding the catalyst into the kettle-type reactor under the stirring state, then sealing the reactor, vacuumizing for 3-10min, introducing inert gas for 3-10min, circulating for 4-6 times, and finally introducing the inert gas until the pressure in the kettle-type reactor is 0.3-0.9MPa, so that reactants in the kettle-type reactor are completely protected by the inert gas;
(3) setting the stirring speed of the kettle type reactor to be 30-100r/min, slowly heating the kettle type reactor to 50-80 ℃ within 0.8-1.2h, and reacting the reactants under the protection of inert gas at constant temperature and constant pressure for 1-4 h;
(4) setting the stirring speed of the kettle-type reactor to be 50-120r/min, slowly heating the kettle-type reactor to 100-140 ℃ within 0.8-1.2h, and reacting the reactants under the protection of inert gas at constant temperature and constant pressure for 1-4 h;
(5) setting the stirring speed of the kettle type reactor to be 60-130r/min, reducing the temperature of the kettle type reactor to 30-50 ℃ while the reactants are protected by inert gas, then discharging gas to normal pressure, and obtaining the phosphate ammonium salt after the reaction is finished;
preferably, the preparation method of the phosphate ammonium salt comprises the following steps:
(1) adding the tetraphenyl resorcinol diphosphate and the ethanolamine which are dried in vacuum into a kettle type reactor with a stirring paddle, and adjusting the stirring speed of the kettle type reactor to be 80-100r/min and the stirring time to be 3-4 min;
(2) adding the catalyst into the kettle-type reactor under the stirring state, then sealing the reactor, vacuumizing for 7-10min, introducing inert gas for 7-10min, circulating for 4-6 times, and finally introducing the inert gas until the pressure in the kettle-type reactor is 0.7-0.9MPa, so that reactants in the kettle-type reactor are completely protected by the inert gas;
(3) setting the stirring speed of the kettle type reactor to be 80-100r/min, slowly heating the kettle type reactor to 65-75 ℃ within 0.9-1.1h, and reacting the reactants under the protection of inert gas at constant temperature and constant pressure for 2-3 h;
(4) setting the stirring speed of the kettle-type reactor to be 50-70r/min, slowly heating the kettle-type reactor to 110-;
(5) setting the stirring speed of the kettle-type reactor at 110-130r/min, reducing the temperature of the kettle-type reactor to 35-50 ℃ while the reactants are protected by inert gas, then discharging the gas to normal pressure, and finishing the reaction to obtain the phosphate ammonium salt.
9. Use of the ammonium phosphate salt according to any one of claims 1 to 5 as a flame retardant in the preparation of flame retardant polymeric materials.
10. Use according to claim 9, wherein the polymeric material is polyurethane, polycarbonate, polyamide, polyvinyl alcohol, polyacrylonitrile, polyethylene glycol, polyethylene terephthalate, polyimide, polybutylene terephthalate.
Technical Field
The invention relates to the field of flame retardants, and in particular relates to a phosphate ammonium salt and a preparation method and application thereof.
Background
At present, with the continuous development and progress of polymer material industry, polymer materials are also increasingly used in the fields of electronics, electricity, automobiles, communication, architectural decoration and the like. However, due to the characteristic that the high polymer material is easy to burn, the wide application of the high polymer material in some fields is prevented, and the important significance and the wide market prospect are provided for the research and development of the flame retardant.
The conventional flame retardant system is a halogen flame retardant, which generates a large amount of smoke, toxic gas and corrosive gas during combustion. With the development of society, the requirements of people on environmental protection are continuously improved, and the halogen flame retardant is gradually quitting the historical stage. The novel nitrogen-phosphorus flame retardant has the advantages of low smoke, environmental protection, stable flame retardant effect and the like, and is paid more and more attention in recent years.
Chinese patent CN201510681620 discloses an organic phosphorus-nitrogen flame retardant and a preparation method thereof, wherein the flame retardant is prepared by reacting organic phosphonic acid and an amino compound in an aqueous solution, and has the characteristics of high molecular weight, good flame retardant effect, good weather resistance, high thermal decomposition temperature and the like. However, the procedure for synthesizing the flame retardant in this patent is relatively complicated.
Chinese patent CN201510317865 discloses a flame retardant and a preparation method thereof, and provides a use method of the flame retardant in copolyester. The flame retardant is prepared by reacting a phosphorus compound and dihydric alcohol, the acid value is 100-260mgKOH/g, and the DEG content in the flame retardant is below 1.0 wt%.
Disclosure of Invention
Accordingly, an object of the present invention is to provide an ammonium phosphate ester which is useful as a flame retardant for polymer materials such as polyesters and polyamides, and which has a reactive functional group so as to greatly improve the compatibility with the polymer materials, thereby improving the flame retardant effect thereof and the mechanical properties of the resulting materials.
In order to achieve the purpose, the invention adopts the following scheme:
an ammonium phosphate salt having the structure shown in formula I:
wherein m is 1-7.
An ammonium phosphate, which is obtained by reacting tetraphenyl resorcinol diphosphate with ethanolamine under the action of a catalyst, wherein the structural formula of the tetraphenyl resorcinol diphosphate is as follows:
wherein m is 1-7.
In some of these embodiments, the catalyst is at least one of trimethyl borate, dibutyl tin dilaurate.
In some of these embodiments, the molar ratio of tetraphenylresorcinol diphosphate to ethanolamine is 1: 1.8-2.3.
In some of these embodiments, the molar ratio of tetraphenylresorcinol diphosphate to ethanolamine is 1: 2-2.2.
In some of these embodiments, the catalyst is 0.1 to 2 wt% of the total mass of tetraphenylresorcinol diphosphate and ethanolamine.
In some of these embodiments, the catalyst is 0.3 to 1.5 wt% of the total mass of tetraphenylresorcinol diphosphate and ethanolamine.
In some of these embodiments, the ammonium phosphate salt has a melting point of 55-65 ℃ and a density of 1.2-1.4g/cm3。
The invention also provides a preparation method of the phosphate ammonium salt.
The specific technical scheme is as follows:
the preparation method of the phosphate ammonium salt comprises the following steps:
adding the tetraphenyl resorcinol diphosphate and ethanolamine into a reactor, stirring, adding the catalyst, sealing the reactor, enabling reactants in the reactor to be protected by inert gas, then enabling the reactants to react in the reactor at the temperature of 50-80 ℃, then reacting in the reactor at the temperature of 100-140 ℃, and cooling to obtain the phosphate ammonium salt.
In some of these embodiments, the method of preparing the ammonium phosphate salt comprises the steps of:
adding the tetraphenyl resorcinol diphosphate and ethanolamine into a reactor, stirring, adding the catalyst, sealing the reactor, enabling reactants in the reactor to be protected by inert gas in a vacuum pumping and inert gas introducing mode, then enabling the reactants to firstly react for 1-4h in the reactor with the temperature of 50-80 ℃, then reacting for 1-4h in the reactor with the temperature of 100-140 ℃, and cooling to obtain the phosphate ammonium salt.
In some of these examples, the reactants are first reacted in a reactor at 65-75 ℃ for 2-3h, and then in a reactor at 110-130 ℃ for 2-3 h.
In some of these embodiments, the method of preparing the ammonium phosphate salt comprises the steps of:
(1) adding the tetraphenyl resorcinol diphosphate and the ethanolamine which are dried in vacuum into a kettle type reactor with a stirring paddle, and adjusting the stirring speed of the kettle type reactor to be 30-100r/min and the stirring time to be 3-10 min;
(2) adding the catalyst into the kettle-type reactor under the stirring state, then sealing the reactor, vacuumizing for 3-10min, introducing inert gas for 3-10min, circulating for 4-6 times, and finally introducing the inert gas until the pressure in the kettle-type reactor is 0.3-0.9MPa, so that reactants in the kettle-type reactor are completely protected by the inert gas;
(3) setting the stirring speed of the kettle type reactor to be 30-100r/min, slowly heating the kettle type reactor to 50-80 ℃ within 0.8-1.2h, and reacting the reactants under the protection of inert gas at constant temperature and constant pressure for 1-4 h;
(4) setting the stirring speed of the kettle-type reactor to be 50-120r/min, slowly heating the kettle-type reactor to 100-140 ℃ within 0.8-1.2h, and reacting the reactants under the protection of inert gas at constant temperature and constant pressure for 1-4 h;
(5) setting the stirring speed of the kettle type reactor to be 60-130r/min, reducing the temperature of the kettle type reactor to 30-50 ℃ while the reactants are protected by inert gas, then discharging gas to normal pressure, and obtaining the phosphate ammonium salt after the reaction is finished.
In some of these embodiments, the method of preparing the ammonium phosphate salt comprises the steps of:
(1) adding the tetraphenyl resorcinol diphosphate and the ethanolamine which are dried in vacuum into a kettle type reactor with a stirring paddle, and adjusting the stirring speed of the kettle type reactor to be 80-100r/min and the stirring time to be 3-4 min;
(2) adding the catalyst into the kettle-type reactor under the stirring state, then sealing the reactor, vacuumizing for 7-10min, introducing inert gas for 7-10min, circulating for 4-6 times, and finally introducing the inert gas until the pressure in the kettle-type reactor is 0.7-0.9MPa, so that reactants in the kettle-type reactor are completely protected by the inert gas;
(3) setting the stirring speed of the kettle type reactor to be 80-100r/min, slowly heating the kettle type reactor to 65-75 ℃ within 0.9-1.1h, and reacting the reactants under the protection of inert gas at constant temperature and constant pressure for 2-3 h;
(4) setting the stirring speed of the kettle-type reactor to be 50-70r/min, slowly heating the kettle-type reactor to 110-;
(5) setting the stirring speed of the kettle-type reactor at 110-130r/min, reducing the temperature of the kettle-type reactor to 35-50 ℃ while the reactants are protected by inert gas, then discharging the gas to normal pressure, and finishing the reaction to obtain the phosphate ammonium salt.
In some of these embodiments, the molar ratio of tetraphenylresorcinol diphosphate to ethanolamine is 1: 1.8-2.3.
In some of these embodiments, the molar ratio of tetraphenylresorcinol diphosphate to ethanolamine is 1: 2-2.2.
In some of these embodiments, the catalyst is at least one of trimethyl borate, dibutyl tin dilaurate.
In some of these embodiments, the catalyst is 0.1 to 2 wt% of the total mass of tetraphenylresorcinol diphosphate and ethanolamine.
In some of these embodiments, the catalyst is 0.3 to 1.5 wt% of the total mass of tetraphenylresorcinol diphosphate and ethanolamine.
In some of these embodiments, the ammonium phosphate salt has a melting point of 55-65 ℃ and a density of 1.2-1.4g/cm3。
In some of these embodiments, the inert gas is nitrogen or argon.
The invention also provides application of the phosphate ammonium salt.
The specific technical scheme is as follows:
the phosphate ammonium salt is used as a flame retardant in the preparation of high polymer materials.
In some embodiments, the polymer material is polyurethane, polycarbonate, polyamide, polyvinyl alcohol, polyacrylonitrile, polyethylene glycol, polyethylene terephthalate, polyimide, polybutylene terephthalate.
The phosphate ammonium salt and the preparation method and application thereof provided by the invention have the following advantages:
(1) the invention takes tetraphenyl resorcinol diphosphate and ethanolamine as raw materials to react under the action of a catalyst to obtain a novel phosphate ammonium salt which has good flame retardant effect and can be used as a flame retardant for preparing flame-retardant high polymer materials such as flame-retardant polyurethane, flame-retardant polyester, flame-retardant polyamide and the like.
(2) The phosphate ammonium salt provided by the invention has reactive functional groups, and can be added in the polymer synthesis process and participate in the reaction of the polymer when being used as a flame retardant for preparing a flame-retardant high polymer material, so that the compatibility of the phosphate ammonium salt and the polymer can be greatly improved, the flame-retardant effect of the phosphate ammonium salt can be improved, and the mechanical property of the obtained material can be improved.
(3) The preparation method of the phosphate ammonium salt provided by the invention has the advantages of simple reaction process, simple operation and extremely high yield, is prepared by adopting the kettle type reactor, and is suitable for industrial large-scale production.
(4) The preparation method of the phosphate ammonium salt provided by the invention does not use toxic and harmful substances such as organic solvents and the like in the reaction process, does not generate byproducts harmful to the environment, and has the characteristics of environmental protection and low cost.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The terms "comprising" and "having," and any variations thereof, are intended to cover non-exclusive inclusions. For example, a process, method, apparatus, article, or device that comprises a list of steps is not limited to only those steps or modules listed, but may alternatively include other steps not listed or inherent to such process, method, article, or device.
The "plurality" referred to in the present invention means two or more. "and/or" describes the association relationship of the associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a exists alone, A and B exist simultaneously, and B exists alone. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
The starting materials and equipment in the following examples are all available from conventional commercial sources. The relevant tests for flame retardants are standard test methods known in the art unless otherwise specified.
The reaction mechanism for preparing the phosphate ammonium salt flame retardant is as follows:
wherein m is 1-7
As can be seen from the above reaction, the reactive ammonium phosphate flame retardant of the present invention can be prepared by reacting tetraphenyl resorcinol diphosphate and ethanolamine as raw materials in the presence of a catalyst.
The raw materials used in the examples of the present invention were as follows:
tetraphenylresorcinol diphosphate, available from Wansheng, Zhejiang, Inc.; the structural formula is as follows:
wherein m is 1-7.
Ethanolamine, purchased from the famous petrochemical Shihua corporation.
Trimethyl borate, available from Jiangsu Kogyang Chemicals, Inc.
The present invention will be described in detail with reference to specific examples.
Example 1
This example provides the preparation of ammonium phosphate salts according to the following reaction scheme:
wherein m is 1-7.
The preparation method comprises the following steps:
(1) adding the tetraphenyl resorcinol diphosphate and the ethanolamine which are dried in vacuum into a kettle type reactor with a stirring paddle according to the molar ratio of 1:1.8, and adjusting the stirring speed of the kettle type reactor to be 60r/min and the stirring time to be 3 min;
(2) under the stirring state, adding trimethyl borate accounting for 2 wt% of the total mass of the monomers into the kettle-type reactor as a catalyst, then sealing the reactor, vacuumizing for 5min, introducing inert gas for 5min, circulating for 5 times, and finally introducing inert gas nitrogen until the pressure in the reactor is 0.5MPa, so that the monomers in the kettle-type reactor are completely protected by the inert gas; the monomers refer to tetraphenyl resorcinol diphosphate and ethanolamine;
(3) setting the stirring speed of the kettle type reactor to be 60r/min, slowly heating the kettle type reactor to 60 ℃ within 1h, and reacting the reactants for 2h under constant temperature and pressure under the protection of inert gas;
(4) setting the stirring speed of the kettle type reactor to be 90r/min, slowly heating the kettle type reactor to 130 ℃ within 1h, and reacting the reactants for 3h under the constant temperature and pressure under the protection of inert gas;
(5) setting the stirring speed of the kettle type reactor to be 80r/min, reducing the temperature of the kettle type reactor to 35 ℃ while the reactants are protected by inert gas, then discharging the gas to normal pressure, and finishing the reaction. The phosphate ammonium salt was obtained as a white powder.
Example 2
This example provides the preparation of ammonium phosphate salts according to the following reaction scheme:
wherein m is 1-7.
The preparation method comprises the following steps:
(1) adding the tetraphenyl resorcinol diphosphate and the ethanolamine which are dried in vacuum into a kettle type reactor with a stirring paddle according to the molar ratio of 1:1.9, and adjusting the stirring speed of the kettle type reactor to be 30r/min and the stirring time to be 4 min;
(2) under the stirring state, adding trimethyl borate accounting for 1 wt% of the total mass of the monomers into the kettle-type reactor as a catalyst, then sealing the reactor, vacuumizing for 7min, introducing inert gas for 7min, circulating for 5 times, and finally introducing inert gas nitrogen until the pressure in the reactor is 0.4MPa, so that the monomers in the kettle-type reactor are completely protected by the inert gas; the monomers refer to tetraphenyl resorcinol diphosphate and ethanolamine;
(3) setting the stirring speed of the kettle type reactor to be 80r/min, slowly heating the kettle type reactor to 80 ℃ within 1h, and reacting the reactants for 4h under constant temperature and pressure under the protection of inert gas;
(4) setting the stirring speed of the kettle type reactor to be 120r/min, slowly heating the kettle type reactor to 130 ℃ within 1h, and reacting the reactants for 2h under constant temperature and pressure under the protection of inert gas;
(5) setting the stirring speed of the kettle type reactor to be 110r/min, reducing the temperature of the kettle type reactor to 30 ℃ while the reactants are protected by inert gas, then discharging the gas to normal pressure, and finishing the reaction. The phosphate ammonium salt was obtained as a white powder.
Example 3
This example provides the preparation of ammonium phosphate salts according to the following reaction scheme:
wherein m is 1-7.
The preparation method comprises the following steps:
(1) adding the tetraphenyl resorcinol diphosphate and the ethanolamine which are dried in vacuum into a kettle type reactor with a stirring paddle according to the molar ratio of 1:2, and adjusting the stirring speed of the kettle type reactor to be 90r/min and the stirring time to be 3 min;
(2) under the stirring state, adding trimethyl borate with the total mass of 0.8 wt% of the monomers into the kettle-type reactor as a catalyst, then sealing the reactor, vacuumizing for 8min, introducing inert gas for 8min, circulating for 5 times, and finally introducing inert gas nitrogen until the pressure in the reactor is 0.8MPa, so that the monomers in the kettle-type reactor are completely protected by the inert gas; the monomers refer to tetraphenyl resorcinol diphosphate and ethanolamine;
(3) setting the stirring speed of the kettle type reactor to be 90r/min, slowly heating the kettle type reactor to 70 ℃ within 1h, and reacting the reactants for 2h under the constant temperature and pressure under the protection of inert gas;
(4) setting the stirring speed of the kettle type reactor to be 60r/min, slowly heating the kettle type reactor to 120 ℃ within 1h, and reacting the reactants for 3h under the constant temperature and pressure under the protection of inert gas;
(5) setting the stirring speed of the kettle type reactor to be 120r/min, reducing the temperature of the kettle type reactor to 45 ℃ while the reactants are protected by inert gas, then discharging the gas to normal pressure, and finishing the reaction. The phosphate ammonium salt was obtained as a white powder.
Example 4
This example provides the preparation of ammonium phosphate salts according to the following reaction scheme:
wherein m is 1-7.
The preparation method comprises the following steps:
(1) adding the tetraphenyl resorcinol diphosphate and the ethanolamine which are dried in vacuum into a kettle type reactor with a stirring paddle according to the molar ratio of 1:2.1, and adjusting the stirring speed of the kettle type reactor to be 90r/min and the stirring time to be 10 min;
(2) under the stirring state, adding trimethyl borate with the total mass of 0.5 wt% of the monomers into the kettle-type reactor as a catalyst, then sealing the reactor, vacuumizing for 3min, introducing inert gas for 3min, circulating for 5 times, and finally introducing the inert gas argon until the pressure in the reactor is 0.3MPa, so that the monomers in the kettle-type reactor are completely protected by the inert gas; the monomers refer to tetraphenyl resorcinol diphosphate and ethanolamine;
(3) setting the stirring speed of the kettle type reactor to be 30r/min, slowly heating the kettle type reactor to 50 ℃ within 1h, and reacting the reactants for 1h under constant temperature and pressure under the protection of inert gas;
(4) setting the stirring speed of the kettle type reactor to be 60r/min, slowly heating the kettle type reactor to 100 ℃ within 1h, and reacting the reactants for 4h under the constant temperature and pressure under the protection of inert gas;
(5) setting the stirring speed of the kettle type reactor to be 60r/min, reducing the temperature of the kettle type reactor to 30 ℃ while the reactants are protected by inert gas, then discharging the gas to normal pressure, and finishing the reaction. The phosphate ammonium salt was obtained as a white powder.
Example 5
The preparation of ammonium phosphate provided in this example is represented by the following reaction scheme:
wherein m is 1-7.
The preparation method comprises the following steps:
(1) adding the tetraphenyl resorcinol diphosphate and the ethanolamine which are dried in vacuum into a kettle type reactor with a stirring paddle according to the molar ratio of 1:2.2, and adjusting the stirring speed of the kettle type reactor to be 30r/min and the stirring time to be 10 min;
(2) under the stirring state, adding trimethyl borate with the total mass of 0.3 wt% of the monomers into the kettle-type reactor as a catalyst, then sealing the reactor, vacuumizing for 3min, introducing inert gas for 3min, circulating for 5 times, and finally introducing the inert gas argon until the pressure in the reactor is 0.3MPa, so that the monomers in the kettle-type reactor are completely protected by the inert gas; the monomers refer to tetraphenyl resorcinol diphosphate and ethanolamine;
(3) setting the stirring speed of the kettle type reactor to be 30r/min, slowly heating the kettle type reactor to 80 ℃ within 1h, and reacting the reactants for 2h under constant temperature and pressure under the protection of inert gas;
(4) setting the stirring speed of the kettle type reactor to be 60r/min, slowly heating the kettle type reactor to 140 ℃ within 1h, and reacting the reactants for 3h under constant temperature and pressure under the protection of inert gas;
(5) setting the stirring speed of the kettle type reactor to be 120r/min, reducing the temperature of the kettle type reactor to 35 ℃ while the reactants are protected by inert gas, then discharging the gas to normal pressure, and finishing the reaction. The phosphate ammonium salt was obtained as a white powder.
Example 6
This example provides the preparation of ammonium phosphate salts according to the following reaction scheme:
wherein m is 1-7.
The preparation method comprises the following steps:
(1) adding the tetraphenyl resorcinol diphosphate and the ethanolamine which are dried in vacuum into a kettle type reactor with a stirring paddle according to the molar ratio of 1:2.3, adjusting the stirring speed of the kettle type reactor to be 30r/min, and stirring for 8 min;
(2) under the stirring state, adding trimethyl borate accounting for 0.1 wt% of the total mass of the monomers into the kettle-type reactor as a catalyst, then sealing the reactor, vacuumizing for 9min, introducing inert gas for 9min, circulating for 5 times, and finally introducing inert gas nitrogen until the pressure in the reactor is 0.6MPa, so that the monomers in the kettle-type reactor are completely protected by the inert gas; the monomers refer to tetraphenyl resorcinol diphosphate and ethanolamine;
(3) setting the stirring speed of the kettle type reactor to be 90r/min, slowly heating the kettle type reactor to 70 ℃ within 1h, and reacting the reactants for 3h under the constant temperature and pressure under the protection of inert gas;
(4) setting the stirring speed of the kettle type reactor to be 80r/min, slowly heating the kettle type reactor to 120 ℃ within 1h, and reacting the reactants for 2h under constant temperature and pressure under the protection of inert gas;
(5) setting the stirring speed of the kettle type reactor to be 70r/min, reducing the temperature of the kettle type reactor to 40 ℃ while the reactants are protected by inert gas, then discharging the gas to normal pressure, and finishing the reaction. The phosphate ammonium salt was obtained as a white powder.
The formulations of the reaction raw materials of the examples are shown in Table 1:
table 1 formulation of the reaction materials of the examples
The ammonium phosphate salts prepared in the above examples were tested for density and melting point according to the following criteria:
density: testing according to ISO 1183 standard;
melting point: testing according to ISO 3146 standard;
the results of the density and melting point tests on the ammonium phosphate salts prepared in the above examples are shown in Table 2:
TABLE 2 Density and melting Point of ammonium salts of phosphoric acid esters prepared in examples
As can be seen from the data in Table 2, the reactive ammonium phosphate flame retardants produced increased slightly in specific weight and decreased in melting point with increasing molar ratio of tetraphenylresorcinol diphosphate to ethanolamine.
The phosphate ammonium salt prepared in example 3 is used as a flame retardant, different flame retardant schemes are designed according to different proportions, and the phosphate ammonium salt and polyurethane (TPU) elastomer are blended and extruded in a double-screw extruder to prepare the flame retardant TPU material, wherein the extrusion temperature is 190 ℃, and the extrusion rotating speed is 300 r/min. And then testing the flame retardant property and the mechanical property of the prepared flame retardant TPU material.
The polyurethane elastomer used in the following scheme is WHT-8285 in Wanhua chemistry, and the flame retardant test method is used for testing according to UL-94 flame retardant test standard; tensile properties were tested according to ASTM D412; the right angle tear strength was tested according to ASTM D624.
The mass fractions of flame retardant and TPU in each flame retardant protocol are shown in table 3:
TABLE 3 Mass fractions of flame retardant and TPU in the flame retardant protocol
The flame retardant properties and mechanical properties of the flame retardant TPU material prepared according to the scheme of table 3 are shown in table 4:
TABLE 4 flame retardant effect and mechanical Properties of the flame retardant TPU materials
As can be seen from the data in table 4: the phosphate ammonium salt flame retardant prepared in the embodiment 3 can obviously improve the flame retardant property of TPU, has small influence on the mechanical property of TPU materials, and can reach the flame retardant grade of 3mm V-0 when the addition amount of the flame retardant is 20 wt% of the total formula. However, the same amount of tetraphenylresorcinol diphosphate as the ammonium phosphate flame retardant prepared in example 3 resulted in a severe decrease in the mechanical properties of the TPU material.
The phosphate ammonium salts prepared in examples 1 to 6 are respectively used as flame retardants, different flame retardant schemes are designed according to the same proportion, and the phosphate ammonium salts and polyurethane (TPU) elastomers are blended and extruded in a double screw extruder to prepare the flame retardant TPU material, wherein the extrusion temperature is 190 ℃, and the extrusion rotating speed is 300 r/min. And then testing the flame retardant property and the mechanical property of the prepared flame retardant TPU material.
The polyurethane elastomer used in the following scheme is WHT-8285 in Wanhua chemistry, and the flame retardant test method is used for testing according to UL-94 flame retardant test standard; tensile properties were tested according to ASTM D412; the right angle tear strength was tested according to ASTM D624.
The mass fractions of flame retardant and TPU in each flame retardant protocol are shown in table 5:
TABLE 5 flame retardant TPU flame retardant protocol and formula proportions
The flame retardant properties and mechanical properties of the flame retardant TPU material prepared according to the scheme of table 5 are shown in table 6:
TABLE 6 flame retardant effect and mechanical strength of flame retardant TPU materials
As can be seen from the data in Table 6, the phosphate ammonium salt flame retardant prepared in different examples has little influence on the flame retardant effect of the TPU material, but has certain difference on the influence on the mechanical property of the TPU material. By comparison, the ammonium phosphate salt prepared according to the process conditions and formulation of example 3 was found to be the most effective in combination.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
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