CN114835953A - Hydrophobic piperazine pyrophosphate and efficient preparation method thereof - Google Patents
Hydrophobic piperazine pyrophosphate and efficient preparation method thereof Download PDFInfo
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- CN114835953A CN114835953A CN202210647887.8A CN202210647887A CN114835953A CN 114835953 A CN114835953 A CN 114835953A CN 202210647887 A CN202210647887 A CN 202210647887A CN 114835953 A CN114835953 A CN 114835953A
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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
- C08F212/36—Divinylbenzene
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- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3462—Six-membered rings
Abstract
The invention relates to a preparation method of modified piperazine pyrophosphate, and provides an efficient preparation method of hydrophobic piperazine pyrophosphate for improving the preparation efficiency of the hydrophobic piperazine pyrophosphate, which comprises the following preparation steps: (1) mixing and stirring pyrophosphoric acid, divinylbenzene, styrene, a solvent and an emulsifier to form a water-in-oil emulsion; (2) sequentially adding anhydrous piperazine, melamine and an initiator into the emulsion prepared in the step (1); (3) and (3) condensing and recovering the product obtained in the step (2) to obtain the hydrophobic piperazine pyrophosphate. The hydrophobic piperazine pyrophosphate and the efficient preparation method thereof can efficiently prepare the hydrophobic piperazine pyrophosphate at low cost.
Description
Technical Field
The invention relates to a preparation method of modified piperazine pyrophosphate, and particularly relates to hydrophobic piperazine pyrophosphate and an efficient preparation method thereof.
Background
Piperazine pyrophosphate is a phosphorus flame retardant which attracts attention in recent years, has good thermal stability and high flame retardant efficiency, particularly has high flame retardant efficiency in the aspect of flame retardant polyolefin, and has been widely applied to flame retardant polyolefin materials.
The traditional piperazine pyrophosphate production is mainly prepared by dehydrating and condensing piperazine diphosphate at high temperature, the production has higher requirement on temperature control, and improper control easily causes poor whiteness of products. Meanwhile, although the pyrophosphate piperazine system flame retardant PP has better water resistance, namely migration resistance, compared with the APP system, the market still has higher requirements.
Therefore, the invention of a method for efficiently preparing hydrophobic piperazine pyrophosphate, which can solve the above problems, is a problem to be solved at present.
Disclosure of Invention
The purpose of the present invention is to provide a hydrophobic piperazine pyrophosphate which can be produced efficiently at low cost, and a method for efficiently producing the hydrophobic piperazine pyrophosphate.
The embodiment of the invention is realized by the following technical scheme: the efficient preparation method of the hydrophobic piperazine pyrophosphate comprises the following preparation steps:
(1) mixing and stirring pyrophosphoric acid, divinylbenzene, styrene, a solvent and an emulsifier to form a water-in-oil emulsion;
(2) sequentially adding anhydrous piperazine, melamine and an initiator into the emulsion prepared in the step (1);
(3) and (3) condensing and recovering the product obtained in the step (2) to obtain the hydrophobic piperazine pyrophosphate.
Further, the mass fraction ratio in the step (2) is as follows: 200 parts of pyrophosphoric acid 180-.
More specifically, the mass fraction ratio in the step (1) is as follows: 200 portions of pyrophosphoric acid 180-.
Further, in the step (1), the solvent is xylene, and the emulsifier is span 20.
Further, in the step (3), the emulsion prepared in the step (2) is transferred into a kneader, stirring is started, anhydrous piperazine is added into the kneader, melamine is added after 20-40min for reaction for 5-10min, then initiator is added, and the temperature is raised to 140-160 ℃ after 20-40 min.
More specifically, in the step (3), the emulsion comprises 200-250 parts of anhydrous piperazine, 60-80 parts of melamine and 0.5-1 part of initiator.
Further, in the step (2), the initiator is azobisisobutyronitrile.
The invention also provides hydrophobic piperazine pyrophosphate prepared by the efficient preparation method of the hydrophobic piperazine pyrophosphate.
The technical scheme of the embodiment of the invention at least has the following advantages and beneficial effects: the efficient preparation method of the hydrophobic piperazine pyrophosphate has the advantages of high production efficiency, compact and stable coating layer and high thermal stability: the solubility is low; the coating material has low cost, and the solvent can be recycled, so the cost is lower; the production operation is simple, the requirement on the temperature control accuracy of the equipment is low, and the subsequent drying and crushing are not needed.
Detailed Description
Example 1
The embodiment provides an efficient preparation method of hydrophobic piperazine pyrophosphate, which comprises the following preparation steps:
(1) adding 100 parts by mass of 85% phosphoric acid into a ceramic reaction kettle, diluting with 90 parts of water, slowly adding 120 parts of phosphorus pentoxide into the ceramic reaction kettle, quickly stirring, starting an oil bath for heating, and setting the oil temperature to 230 ℃ for reaction for 1 h;
(2) transferring 180 parts of the prepared pyrophosphoric acid into an emulsifying kettle, cooling the pyrophosphoric acid to below 70 ℃ by introducing condensed water, slowly stirring, slowly adding 200 parts of dimethylbenzene, 5 parts of divinylbenzene and 5 parts of styrene, adding 1 part of span 20, and quickly stirring to form a stable water-in-oil emulsion;
(3) transferring 200 parts of the emulsion prepared in the step (2) into a kneader, starting stirring, adding 80 parts of anhydrous piperazine into the kneader, introducing nitrogen to remove air and heat, adding 3 parts of melamine after 30min to react for 10min, adding 0.5 part of azobisisobutyronitrile, heating to 150 ℃ after 30min, and regulating the nitrogen flow;
(4) condensing and recovering dimethylbenzene, and discharging after 1.5h of evaporation is finished to obtain the hydrophobic piperazine pyrophosphate.
Example 2
The embodiment provides an efficient preparation method of hydrophobic piperazine pyrophosphate, which comprises the following preparation steps:
(1) adding 100 parts by mass of 85% phosphoric acid into a ceramic reaction kettle, diluting with 90 parts of water, slowly adding 120 parts of phosphorus pentoxide into the ceramic reaction kettle, quickly stirring, starting an oil bath for heating, and setting the oil temperature to 230 ℃ for reaction for 1 h;
(2) 200 parts of the prepared pyrophosphoric acid is transferred to an emulsifying kettle and cooled to below 70 ℃ by introducing condensed water, and then the pyrophosphoric acid is slowly stirred, 180 parts of dimethylbenzene, 6 parts of divinylbenzene and 6 parts of styrene are slowly added, 0.5 part of span 20 is added, and then the mixture is quickly stirred to form a stable water-in-oil emulsion;
(3) transferring 250 parts of the emulsion prepared in the step (2) into a kneader, starting stirring, adding 73 parts of anhydrous piperazine into the kneader, introducing nitrogen to remove air and heat, adding 5 parts of melamine after 30min to react for 10min, adding 0.5 part of azobisisobutyronitrile, heating to 150 ℃ after 30min, and regulating the nitrogen flow;
(4) condensing and recovering dimethylbenzene, and discharging after 1.5h of evaporation is finished to obtain the hydrophobic piperazine pyrophosphate.
Example 3
The embodiment provides an efficient preparation method of hydrophobic piperazine pyrophosphate, which comprises the following preparation steps:
(1) adding 100 parts by mass of 85% phosphoric acid into a ceramic reaction kettle, diluting with 90 parts of water, slowly adding 120 parts of phosphorus pentoxide into the ceramic reaction kettle, quickly stirring, starting an oil bath for heating, and setting the oil temperature to 230 ℃ for reaction for 1 h;
(2) transferring 190 parts of the prepared pyrophosphoric acid into an emulsifying kettle, cooling the pyrophosphoric acid to below 70 ℃ by introducing condensed water, slowly stirring, slowly adding 190 parts of xylene, 6 parts of divinylbenzene and 6 parts of styrene, adding 0.5 part of span 20, and quickly stirring to form a stable water-in-oil emulsion;
(3) transferring 220 parts of the emulsion prepared in the step (2) into a kneader, starting stirring, adding 60 parts of anhydrous piperazine into the kneader, introducing nitrogen to remove air and heat, adding 5 parts of melamine after 30min to react for 10min, adding 0.5 part of azobisisobutyronitrile, heating to 150 ℃ after 30min, and regulating the nitrogen flow;
(4) condensing and recovering dimethylbenzene, and discharging after 1.5h of evaporation is finished to obtain the hydrophobic piperazine pyrophosphate.
Example 4
The embodiment provides an efficient preparation method of hydrophobic piperazine pyrophosphate, which comprises the following preparation steps:
(1) adding 100 parts by mass of 85% phosphoric acid into a ceramic reaction kettle, diluting with 90 parts of water, slowly adding 120 parts of phosphorus pentoxide into the ceramic reaction kettle, quickly stirring, starting an oil bath for heating, and setting the oil temperature to 230 ℃ for reaction for 1 h;
(2) 200 parts of the prepared pyrophosphoric acid is transferred to an emulsifying kettle and cooled to below 70 ℃ by cooling water, and then 200 parts of dimethylbenzene, 10 parts of divinylbenzene and 10 parts of styrene are slowly added, 0.5 part of span 20 is added, and then the mixture is quickly stirred to form a stable water-in-oil emulsion;
(3) transferring 200 parts of the emulsion prepared in the step (2) into a kneader, starting stirring, adding 68 parts of anhydrous piperazine into the kneader, introducing nitrogen to remove air and heat, adding 8 parts of melamine after 30min to react for 10min, adding 1 part of azobisisobutyronitrile, heating to 150 ℃ after 30min, and regulating the nitrogen flow;
(4) condensing and recovering dimethylbenzene, and discharging after 1.5h of evaporation is finished to obtain the hydrophobic piperazine pyrophosphate.
Comparative example 1
The embodiment provides a preparation method of piperazine pyrophosphate, which comprises the following preparation steps:
(1) adding 100 parts by mass of 85% phosphoric acid into a ceramic reaction kettle, diluting with 90 parts of water, slowly adding 120 parts of phosphorus pentoxide into the ceramic reaction kettle, quickly stirring, starting an oil bath for heating, and setting the oil temperature to 230 ℃ for reaction for 1 h;
(2) 200 parts of the prepared pyrophosphoric acid is transferred to an emulsifying kettle and cooled to below 70 ℃ by cooling water, and then 200 parts of dimethylbenzene, 0.5 part of divinylbenzene, 5 parts of styrene are slowly added, 0.5 part of span 20 is added, and then the mixture is quickly stirred to form stable water-in-oil emulsion;
(3) transferring 200 parts of the emulsion prepared in the step (2) into a kneader, starting stirring, adding 80 parts of anhydrous piperazine into the kneader, introducing nitrogen to remove air and heat, adding 3 parts of melamine after 30min to react for 10min, adding 0.5 part of azobisisobutyronitrile, heating to 150 ℃ after 30min, and regulating the nitrogen flow;
(4) condensing and recovering dimethylbenzene, and discharging after 1.5h of evaporation is finished to obtain the hydrophobic piperazine pyrophosphate.
Comparative example 2
The embodiment provides an efficient preparation method of hydrophobic piperazine pyrophosphate, which comprises the following preparation steps:
(1) adding 100 parts by mass of 85% phosphoric acid into a ceramic reaction kettle, diluting with 90 parts of water, slowly adding 120 parts of phosphorus pentoxide into the ceramic reaction kettle, quickly stirring, starting an oil bath for heating, and setting the oil temperature to 230 ℃ for reaction for 1 h;
(2) 200 parts of the prepared pyrophosphoric acid is transferred to an emulsifying kettle and cooled to below 70 ℃ by cooling water, and then the pyrophosphoric acid is slowly stirred, 180 parts of dimethylbenzene, 6 parts of divinylbenzene and 0.5 part of styrene are slowly added, 0.5 part of span-20 is added, and then the mixture is quickly stirred to form stable water-in-oil emulsion;
(3) transferring 250 parts of the emulsion prepared in the step (2) into a kneader, starting stirring, adding 73 parts of anhydrous piperazine into the kneader, introducing nitrogen to remove air and heat, adding 5 parts of melamine after 30min to react for 10min, adding 0.5 part of azobisisobutyronitrile, heating to 150 ℃ after 30min, and regulating the nitrogen flow;
(4) condensing and recovering dimethylbenzene, and discharging after 1.5h of evaporation is finished to obtain the hydrophobic piperazine pyrophosphate.
Comparative example 3
The embodiment provides an efficient preparation method of hydrophobic piperazine pyrophosphate, which comprises the following preparation steps:
(1) adding 100 parts by mass of 85% phosphoric acid into a ceramic reaction kettle, diluting with 90 parts of water, slowly adding 120 parts of phosphorus pentoxide into the ceramic reaction kettle, quickly stirring, starting an oil bath for heating, and setting the oil temperature to 230 ℃ for reaction for 1 h;
(2) transferring 190 parts of the prepared pyrophosphoric acid into an emulsifying kettle, cooling the pyrophosphoric acid to below 70 ℃ by introducing condensed water, slowly stirring, slowly adding 190 parts of xylene, 6 parts of divinylbenzene and 6 parts of styrene, adding 0.5 part of span 20, and quickly stirring to form a stable water-in-oil emulsion;
(3) transferring 100 parts of the emulsion prepared in the step (2) into a kneader, starting stirring, adding 60 parts of anhydrous piperazine into the kneader, introducing nitrogen to remove air and heat, adding 5 parts of melamine after 30min to react for 10min, adding 0.5 part of azobisisobutyronitrile, heating to 150 ℃ after 30min, and regulating the nitrogen flow;
(4) condensing and recovering dimethylbenzene, and discharging after 1.5h of evaporation is finished to obtain the hydrophobic piperazine pyrophosphate.
Comparative example 4
The embodiment provides an efficient preparation method of hydrophobic piperazine pyrophosphate, which comprises the following preparation steps:
(1) adding 100 parts by mass of 85% phosphoric acid into a ceramic reaction kettle, diluting with 90 parts of water, slowly adding 120 parts of phosphorus pentoxide into the ceramic reaction kettle, quickly stirring, starting an oil bath for heating, and setting the oil temperature to 230 ℃ for reaction for 1 h;
(2) 200 parts of the prepared pyrophosphoric acid is transferred to an emulsifying kettle and cooled to below 70 ℃ by cooling water, and then 200 parts of dimethylbenzene, 10 parts of divinylbenzene and 10 parts of styrene are slowly added, 0.5 part of span 20 is added, and then the mixture is quickly stirred to form a stable water-in-oil emulsion;
(3) transferring 200 parts of the emulsion prepared in the step (2) into a kneader, starting stirring, adding 68 parts of anhydrous piperazine into the kneader, introducing nitrogen to remove air and heat, adding 1 part of azobisisobutyronitrile after 30min, heating to 150 ℃ after 30min, and increasing the nitrogen flow;
(4) condensing and recovering dimethylbenzene, and discharging after 1.5h of evaporation is finished to obtain the hydrophobic piperazine pyrophosphate.
Examples of the experiments
Piperazine pyrophosphate was prepared using the methods of examples 1 to 4, comparative examples 1 to 4, respectively, and commercially available piperazine pyrophosphate was subjected to an initial decomposition temperature test and a solubility test; wherein the initial decomposition temperature is taken as the temperature of the residual 99 percent of the mass in the thermogravimetric test, and the solubility test method is the standard method given in GB/T21845-2008. The results are shown in table 1 below.
Table 1 initial decomposition temperature and solubility for each group
| Sample numbering | Initial decomposition temperature (T99, deg.C.) | Solubility (g/100g) |
| Example 1 | 341 | 0.68 |
| Example 2 | 337 | 0.62 |
| Example 3 | 335 | 0.54 |
| Example 4 | 342 | 0.70 |
| Comparative example 1 | 293 | 6.6 |
| Comparative example 2 | 311 | 3.5 |
| Comparative example 3 | 328 | 2.5 |
| Comparative example 4 | 278 | 4.3 |
| Piperazine pyrophosphate on the market | 288 | 6.5 |
From the test results, the hydrophobic piperazine pyrophosphate prepared by the method of the invention has higher initial decomposition temperature compared with the comparative example and the commercial piperazine pyrophosphate, and shows that the coating layer is compact and stable, the thermal stability is high, and the solubility is lower (the solubility is less than 0.8).
In addition, the coating material has low cost, and the solvent can be recycled, so the cost is lower; the production operation is simple, the requirement on the temperature control accuracy of the equipment is low, and the subsequent drying and crushing are not needed.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. The efficient preparation method of the hydrophobic piperazine pyrophosphate is characterized by comprising the following preparation steps:
(1) mixing and stirring pyrophosphoric acid, divinylbenzene, styrene, a solvent and an emulsifier to form a water-in-oil emulsion;
(2) sequentially adding anhydrous piperazine, melamine and an initiator into the emulsion prepared in the step (1);
(3) and (3) condensing and recovering the product obtained in the step (2) to obtain the hydrophobic piperazine pyrophosphate.
2. The efficient preparation method of hydrophobic piperazine pyrophosphate according to claim 1, wherein the mass fraction ratio in the step (1) is as follows: 200 portions of pyrophosphoric acid 180-.
3. The efficient preparation method of hydrophobic piperazine pyrophosphate according to claim 1, wherein the solvent in step (1) is xylene, and the emulsifier is span 20.
4. The efficient preparation method of hydrophobic piperazine pyrophosphate according to claim 1, wherein in the step (2), the emulsion prepared in the step (1) is transferred to a kneader, stirring is started, anhydrous piperazine is added into the kneader, melamine is added for reaction for 5-10min after 20-40min, then initiator is added, and the temperature is raised to 140-160 ℃ after 20-40 min.
5. The efficient preparation method of hydrophobic piperazine pyrophosphate according to claim 1, wherein in step (3), the emulsion comprises 200-250 parts of anhydrous piperazine, 60-80 parts of anhydrous piperazine, 3-8 parts of melamine, and 0.5-1 part of initiator.
6. The method for efficiently preparing the hydrophobic piperazine pyrophosphate according to claim 1, wherein the initiator in the step (2) is azobisisobutyronitrile.
7. The hydrophobic piperazine pyrophosphate prepared by the efficient preparation method of the hydrophobic piperazine pyrophosphate according to any one of claims 1 to 6.
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2022
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