CN115011113A - Flame-retardant material and preparation method thereof - Google Patents
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Abstract
The invention discloses a flame-retardant material and a preparation method thereof. The method comprises the following steps: uniformly mixing 50-70 parts of nylon 66, 5-15 parts of reinforcing fiber, 6-12 parts of wear-resistant additive, 0.5-5 parts of reaction additive, 0.5-4 parts of antioxidant and 2-20 parts of flame retardant by weight to obtain a premix; adding the premix into a hopper of a double-screw extruder feeder, adding the fibers from a side feeding port, and performing melt mixing, extrusion and granulation. The flame-retardant material prepared by the invention has higher thermal stability and higher minimum temperature in the thermal weight loss process.
Description
Technical Field
The invention belongs to the field of phosphorus-nitrogen flame retardants, and particularly relates to a pyrophosphoric acid imidazole flame retardant and a preparation method thereof.
Background
Polymeric materials are commonly used in various fields, but they are extremely flammable. The flame retardant can effectively inhibit the inflammability of the high polymer material and reduce the fire risk. Early halogen-containing flame retardants were widely used, but with the increasing environmental requirements, the halogen-free flame retardants were used in increasing amounts year by year and becoming a trend in the development of flame retardants. The phosphorus-nitrogen flame retardant has excellent performance in the halogen-free flame retardant due to the phosphorus-nitrogen synergistic effect. However, the phosphorus-nitrogen flame retardants in the current market are few in types, and mainly comprise ammonium polyphosphate and melamine polyphosphate.
Disclosure of Invention
The first object of the present invention is: the invention provides a novel phosphorus-nitrogen flame retardant, wherein imidazole heterocycle has the functions of nitrogen source and carbon formation induction. The material can be used as a novel halogen-free environment-friendly phosphorus-nitrogen flame retardant, wherein imidazole heterocycle is used as a nitrogen source. The material has high cost performance, and the preparation method is simple, convenient and practical and is suitable for industrial production.
The second object of the present invention is: the flame-retardant nylon material is provided, and has higher flame-retardant grade; and the mechanical property of the nylon material is improved by processing the reinforced fiber in the nylon material.
The technical scheme is as follows:
in a first aspect of the present invention, there is provided:
the preparation method of the pyropolyimidazole phosphate flame retardant comprises the following steps:
the structure of the imidazolyl compound is shown as a formula (II):
wherein R is 1 is-H or-SH; r 2 And R 3 Each independently may be selected from-H or C1-C4 hydrocarbyl, and R 2 And R 3 And cannot be the same.
In one embodiment, in step 1, the molar ratio of phosphoric acid to imidazolyl compound is 1: 0.8 to 1.2, water is used as solvent, the reaction temperature is 90 to 110 ℃, and the reaction time is 1 to 3 hours.
In one embodiment, in the step 2, dehydration reaction is carried out under the protection of inert gas, the reaction temperature is 250-300 ℃, and the reaction time is 0.5-3 hours; the inert gas is nitrogen, carbon dioxide or argon.
In one embodiment, the reaction apparatus in step 2 may be an internal mixer, a vacuum kneader, a vacuum oven, or the like.
In one embodiment, in step 2, the high boiling point solvent has a boiling point of more than 300 ℃ at normal pressure, and may be high temperature silicone oil, liquid paraffin, or the like, preferably triphenyl phosphate.
In a second aspect of the present invention, there is provided:
the application of the pyropolyphosphate imidazole flame retardant in preparing flame-retardant nylon materials.
In one embodiment, the preparation method of the flame retardant nylon material comprises the following steps:
uniformly mixing 50-70 parts of nylon 66, 5-15 parts of reinforcing fiber, 6-12 parts of wear-resistant additive, 0.5-5 parts of reaction additive, 0.5-4 parts of antioxidant and 2-20 parts of flame retardant by weight to obtain a premix; adding the premix into a hopper of a double-screw extruder feeder, adding the fibers from a side feeding port, and performing melt mixing, extrusion and granulation.
In one embodiment, the temperatures of the extrusion process sections of the twin-screw extruder are respectively as follows: the conveying section is 250-260 ℃, the melting section is 270-290 ℃, the shearing section is 270-290 ℃, the exhaust section is 260-280 ℃ and the extrusion section is 260-280 ℃.
In one embodiment, the method for preparing the reinforcing fiber comprises the following steps:
according to the parts by weight, taking 10-18 parts of octamethylcyclotetrasiloxane, 0.5-5 parts of silane coupling agent and 0.1-0.5 part of catalyst, and carrying out a first reaction in a nitrogen atmosphere to obtain polysiloxane; adding 0.2-1 part of anhydride to continue the second reaction to obtain carboxyl modified polysiloxane; and then, immersing the glass fiber in a solution containing carboxyl modified polysiloxane, and drying to obtain the modified glass fiber.
In one embodiment, the anti-wear additive is plasma treated ultra high molecular weight polyethylene; plasma treatment process using O 2 、CO 2 And NH 3 And (4) mixing the gases.
Advantageous effects
1. The pyrophosphoric acid imidazole is a novel phosphorus-nitrogen synergistic environment-friendly flame retardant. The imidazole ring is not only a nitrogen source provider, but also a condensed ring structure of the imidazole ring can effectively induce carbon formation, so that the flame retardant efficiency is improved. The pyrophosphoric acid imidazole has high cost performance, and the preparation method is simple, convenient and practical and is suitable for industrial production.
2. The flame retardant material is applied to nylon materials, and can enable the nylon materials to reach a flame retardant grade of more than V1.
3. The flame-retardant material prepared by the invention has higher thermal stability and higher minimum temperature in the thermal weight loss process.
4. In the nylon flame-retardant material provided by the invention, the glass fiber subjected to surface carboxylation treatment is adopted, so that condensation effect can be generated between the glass fiber and carboxyl of the nylon material, and the mechanical property of the nylon material is effectively improved.
Drawings
FIG. 1 is a thermogravimetric plot of a flame retardant prepared according to the present invention;
FIG. 2 is a burned specimen of the nylon material prepared in accordance with the present invention; specimens No. 1 to 3 were prepared in examples 7 to 9, respectively.
FIG. 3 is a flame retardant prepared in example 1 of the present invention.
Detailed Description
The percentages stated in the present invention are percentages by mass unless otherwise specified.
Example 1
10 kg of 85% phosphoric acid solution are added to the reactor, the speed is increased to 60rmp and the temperature is increased to 100 ℃. Saturated aqueous imidazole solution was added by spraying, the imidazole content being 12.25 kg. After 1 hour of reaction, the reaction mixture was distilled under reduced pressure to remove water, whereby 20.5 kg of an imidazole phosphate white solid was obtained. And adding the imidazole phosphate into a vacuum kneader, increasing the rotating speed to 50rpm, replacing the imidazole phosphate with nitrogen for more than three times, heating to 280 ℃, and reacting for 3 hours to obtain the pyrophosphate imidazole.
Example 2
10 kg of 85% phosphoric acid solution is added into the reaction kettle, the rotation speed is increased to 60rmp, and the temperature is increased to 100 ℃. Adding saturated imidazole solution in a spraying mode, wherein the content of imidazole is 12.25 kg, and stopping adding the saturated imidazole solution when the pH of the solution is regulated to 5-6. After 1 hour of reaction, the reaction mixture was distilled under reduced pressure to remove water, whereby 22.7 kg of a phosphoric acid imidazolium salt white solid was obtained. And adding the imidazole phosphate into a vacuum kneader, increasing the rotating speed to 50rpm, replacing the imidazole phosphate with nitrogen for more than three times, heating to 280 ℃, and reacting for 3 hours to obtain the pyrophosphate imidazole.
Example 3
10 kg of 85% phosphoric acid solution are added to the reactor, the speed is increased to 60rmp and the temperature is increased to 100 ℃. And (3) adding an imidazole saturated aqueous solution in a spraying manner, wherein the content of imidazole is 12.25 kg, and stopping adding the imidazole saturated aqueous solution when the pH of the solution is regulated to 5-6. After the reaction for 1 hour, the reaction mixture was distilled under reduced pressure to remove water, whereby 23.1 kg of a white phosphoric acid imidazolium salt solid was obtained. And adding the imidazole phosphate into a vacuum kneader, increasing the rotating speed to 50rpm, replacing the imidazole phosphate with nitrogen for more than three times, increasing the temperature to 300 ℃, and reacting for 1.5 hours to obtain the pyrophosphate imidazole phosphate.
Example 4
10 kg of 85% phosphoric acid solution are added to the reactor, the speed is increased to 60rmp and the temperature is increased to 100 ℃. Adding a 2-mercaptoimidazole saturated aqueous solution in a spraying mode, wherein the content of 2-mercaptoimidazole is 17.98 kg, regulating the pH of the solution to 5-6, and stopping adding the 2-mercaptoimidazole saturated aqueous solution. After 1 hour of the reaction, the reaction mixture was distilled under reduced pressure to remove water, whereby 26.6 kg of an imidazole phosphate white solid was obtained. And adding the imidazole phosphate into a vacuum kneader, increasing the rotation speed to 50rpm, replacing the imidazole phosphate with nitrogen for more than three times, heating to 280 ℃, and reacting for 3 hours to obtain the pyrophosphate sulfhydryl imidazole.
Example 5
10 kg of 85% phosphoric acid solution are added to the reactor, the speed is increased to 60rmp and the temperature is increased to 100 ℃. Adding a 2-mercaptoimidazole saturated aqueous solution in a spraying mode, wherein the content of 2-mercaptoimidazole is 19.98 kg, regulating the pH of the solution to 5-6, and stopping adding the 2-mercaptoimidazole saturated aqueous solution. After 1 hour of the reaction, the reaction mixture was distilled under reduced pressure to remove water, whereby 28.7 kg of an imidazole phosphate white solid was obtained. And adding the imidazole phosphate into a vacuum kneader, increasing the rotation speed to 50rpm, replacing the imidazole phosphate with nitrogen for more than three times, heating to 280 ℃, and reacting for 3 hours to obtain the pyrophosphate sulfhydryl imidazole.
Example 6
10 kg of 85% phosphoric acid solution are added to the reactor, the speed is increased to 60rmp and the temperature is increased to 100 ℃. Adding a 2-mercaptoimidazole saturated aqueous solution in a spraying mode, wherein the content of 2-mercaptoimidazole is 16.5 kg, regulating the pH of the solution to 5-6, and stopping adding the 2-mercaptoimidazole saturated aqueous solution. After 1 hour of reaction, distillation under reduced pressure was carried out to remove water, whereby 25.3 kg of an imidazole phosphate white solid was obtained. And adding the imidazole phosphate into a vacuum kneader, increasing the rotation speed to 50rpm, replacing the imidazole phosphate with nitrogen for more than three times, heating to 300 ℃, and reacting for 1.5 hours to obtain the pyrophosphate sulfhydryl imidazole.
In the above examples, the thermogravimetric curves of the pyrophosphoimidazole and pyrophosphatomercaptoimidazole prepared in examples 1 and 4 are shown in FIGS. 1 and 2. As can be seen from the figure, the initial weight loss temperature of the flame retardant prepared by the invention can be kept high, wherein the temperature of the flame retardant prepared in example 1 when the weight loss is 1% is 301 ℃, and the temperature of the flame retardant prepared in example 4 when the weight loss is 1% is 319 ℃, which shows that sulfur element in mercapto group in the flame retardant can mainly improve the stability of the flame retardant material in the initial stage of combustion, so that the initial weight loss temperature is improved, mainly because sulfur is also a flame retardant element, the flame retardant effect can be achieved in a condensed phase, and the main surface is in the decomposition and ignition stages of the material.
Example 7
The pyropolyimidazole phosphate flame retardant prepared in example 1 was used to prepare a flame retardant nylon 66 material.
The preparation of the nylon flame-retardant composite material takes the matrix resin as nylon 66 as an example: weighing 64 parts by weight of nylon 66, 10 parts by weight of chopped alkali-free glass fiber, 10 parts by weight of modified ultrahigh molecular weight polyethylene, 2 parts by weight of multifunctional reaction additive (2, 2-bis- (2-oxazoline)), 2 parts by weight of antioxidant and 12 parts by weight of flame retardant, adding into a mixer, and uniformly stirring to obtain a premix; wherein the modified ultra-high molecular weight polyethylene is UHMWPE with Mw of about 3500000 at O 2 、CO 2 、NH 3 The nano-titanium dioxide particles are obtained after the plasma treatment of 400W and 40MHz for 360s under the atmosphere (volume ratio is 2: 1: 1).
Adding the premix into a hopper of a double-screw extruder feeder, adding the fibers from a side feeding port, and performing melt mixing, extrusion and granulation. The temperature of each section of the extrusion process is respectively as follows: the nylon flame retardant material is prepared at 255 ℃ in the conveying section, 280 ℃ in the melting section, 280 ℃ in the shearing section, 270 ℃ in the exhaust section and 265 ℃ in the extrusion section.
Example 8
The pyropolyphosphate imidazole flame retardant prepared in example 4 was used to prepare a flame retardant nylon 66 material.
The preparation of the nylon flame-retardant composite material takes the matrix resin nylon 66 as an example: weighing 64 parts by weight of nylon 66, 10 parts by weight of chopped alkali-free glass fiber, 10 parts by weight of modified ultrahigh molecular weight polyethylene, 2 parts by weight of multifunctional reaction additive (2, 2-bis- (2-oxazoline)), 2 parts by weight of antioxidant and 12 parts by weight of flame retardant, adding into a mixer, and uniformly stirring to obtain a premix; wherein the modified ultra-high molecular weight polyethylene is UHMWPE with Mw of about 3500000 at O 2 、CO 2 、NH 3 (volume ratio is 2: 1: 1) and is treated by plasma of 400W and 40MHz for 360s to obtain the product。
Adding the premix into a hopper of a double-screw extruder feeder, adding the fibers from a side feeding port, and performing melt mixing, extrusion and granulation. The temperature of each section of the extrusion process is respectively as follows: the nylon flame retardant material is prepared at the temperature of 250-260 ℃ in the conveying section, 270-290 ℃ in the melting section, 270-290 ℃ in the shearing section, 260-280 ℃ in the exhaust section and 260-280 ℃ in the extrusion section.
Example 9
The differences from example 7 are: the glass fiber subjected to surface treatment is adopted in the preparation of the flame retardant material.
The preparation of the modified glass fiber comprises the steps of firstly, mixing 12 parts by weight of decamethylcyclopentasiloxane, 1 part by weight of an end-capping reagent (1, 3-bis (3-hydroxypropyl) -1, 3-dimethyl-1, 3-diethyldisiloxane), 2 parts by weight of a silane coupling agent (KH551) and 0.3 part by weight of a catalyst (tetramethylammonium hydroxide), reacting in a nitrogen atmosphere at the reaction temperature of 90-100 ℃ for 6 hours, and after the reaction is finished, evaporating low-boiling-point substances to obtain polysiloxane; then adding 0.4 part of anhydride modifier (succinic anhydride), heating to 80 ℃ and reacting for 1.5h to obtain carboxyl modified polysiloxane; preparing a naphtha solution with the concentration of about 3 wt% by using carboxyl modified polysiloxane, soaking the chopped alkali-free glass fiber in the naphtha solution for about 20s, taking out the chopped alkali-free glass fiber, and naturally drying to obtain the surface-treated chopped alkali-free glass fiber.
The preparation of the nylon flame-retardant composite material takes the matrix resin as nylon 66 as an example: weighing 64 parts by weight of nylon 66, 10 parts by weight of surface-treated chopped alkali-free glass fiber, 10 parts by weight of modified ultrahigh molecular weight polyethylene, 2 parts by weight of multifunctional reaction additive (2, 2-bis- (2-oxazoline)), 2 parts by weight of antioxidant and 12 parts by weight of flame retardant, adding into a mixer, and uniformly stirring to obtain a premix; wherein the modified ultra-high molecular weight polyethylene is UHMWPE with Mw of about 3500000 at O 2 、CO 2 、NH 3 The nano-titanium dioxide particles are obtained after the plasma treatment of 400W and 40MHz for 360s under the atmosphere (volume ratio is 2: 1: 1).
Adding the premix into a hopper of a double-screw extruder feeder, adding the fibers from a side feeding port, and performing melt mixing, extrusion and granulation. The temperature of each section of the extrusion process is respectively as follows: the nylon flame retardant material is prepared at 255 ℃ in the conveying section, 280 ℃ in the melting section, 280 ℃ in the shearing section, 270 ℃ in the exhaust section and 265 ℃ in the extrusion section.
Example 10
The differences from example 8 are: the glass fiber subjected to surface treatment is adopted in the preparation of the flame retardant material.
The preparation of the modified glass fiber comprises the steps of firstly, mixing 18 parts by weight of decamethylcyclopentasiloxane, 0.4 part by weight of an end-capping agent (1, 3-bis (3-hydroxypropyl) -1, 3-dimethyl-1, 3-diethyldisiloxane), 4 parts by weight of a silane coupling agent (KH551) and 0.10 part by weight of a catalyst (tetramethylammonium hydroxide), reacting in a nitrogen atmosphere at the reaction temperature of 100 ℃ and the reaction time of 4 hours, and after the reaction is finished, evaporating low-boiling-point substances to obtain polysiloxane; adding 1 part of anhydride modifier (succinic anhydride), heating to 70 ℃ and reacting for 3 hours to obtain carboxyl modified polysiloxane; preparing a naphtha solution with the concentration of about 1.5 wt% by using carboxyl modified polysiloxane, soaking the chopped alkali-free glass fiber in the naphtha solution for about 40s, taking out the chopped alkali-free glass fiber, and naturally drying to obtain the surface-treated chopped alkali-free glass fiber.
The preparation of the nylon flame-retardant composite material takes the matrix resin as nylon 66 as an example: weighing 64 parts by weight of nylon 66, 10 parts by weight of surface-treated chopped alkali-free glass fiber, 10 parts by weight of modified ultrahigh molecular weight polyethylene, 2 parts by weight of multifunctional reaction additive (2, 2-bis- (2-oxazoline)), 2 parts by weight of antioxidant and 12 parts by weight of flame retardant, adding into a mixer, and uniformly stirring to obtain a premix; wherein the modified ultra-high molecular weight polyethylene is UHMWPE with Mw of about 3500000 at O 2 、CO 2 、NH 3 The nano-particles are obtained after the plasma treatment of 400W and 40MHz for 360s under the atmosphere (volume ratio of 2: 1: 1).
Adding the premix into a hopper of a double-screw extruder feeder, adding the fibers from a side feeding port, and performing melt mixing, extrusion and granulation. The temperature of each section of the extrusion process is respectively as follows: the nylon flame retardant material is prepared at the temperature of 250-260 ℃ in the conveying section, 270-290 ℃ in the melting section, 270-290 ℃ in the shearing section, 260-280 ℃ in the exhaust section and 260-280 ℃ in the extrusion section.
As can be seen from the table above, the flame retardant prepared by the invention can be successfully applied to nylon materials to obtain flame retardant nylon materials with V1 grade or above, and further proves the application prospect of the materials. In addition, the flame retardant nylon adopting the flame retardant material of the embodiment 4 has a flame retardant effect reaching V0 level; it can be seen from the comparison between example 10 and example 8 that, in the nylon material, because a large number of terminal amino groups exist on the nylon molecules, and because a large number of amino groups are also introduced into the material when the surface plasma treatment is performed on the ultra-high molecular weight polyethylene, the carboxyl modified polysiloxane treatment is adopted to perform the surface treatment on the glass fibers, so that on one hand, the compatibility between the inorganic fibers and the nylon is improved by introducing the polysiloxane, and on the other hand, a large number of carboxyl groups are introduced into the glass fibers through the polysiloxane, so that the carboxyl groups perform condensation reaction with the terminal amino groups of the nylon and the amino groups on the UHMWPE, and the tensile and flexural strength performance of the composite material is improved.
Claims (10)
1. The preparation method of the flame retardant material is characterized by comprising the following steps of:
uniformly mixing 50-70 parts by weight of nylon 66, 5-15 parts by weight of reinforcing fiber, 6-12 parts by weight of wear-resistant additive, 0.5-5 parts by weight of reaction additive, 0.5-4 parts by weight of antioxidant and 2-20 parts by weight of flame retardant to obtain a premix; adding the premix into a hopper of a double-screw extruder feeder, adding the fibers from a side feeding port, and performing melt mixing extrusion granulation;
the preparation method of the reinforced fiber comprises the following steps: according to the parts by weight, taking 10-18 parts of octamethylcyclotetrasiloxane, 0.5-5 parts of silane coupling agent and 0.1-0.5 part of catalyst, and carrying out a first reaction in a nitrogen atmosphere to obtain polysiloxane; adding 0.2-1 part of anhydride to continue the second reaction to obtain carboxyl modified polysiloxane; and then, immersing the glass fiber in a solution containing carboxyl modified polysiloxane, and drying to obtain the modified glass fiber.
2. The method for preparing the flame retardant material according to claim 1, wherein the abrasion resistant additive is ultra-high molecular weight polyethylene after plasma treatment; plasma treatment process using O 2 、CO 2 And NH 3 Mixing the gas.
3. The method for preparing the flame retardant material according to claim 1, wherein the temperatures of all sections of the extrusion process of the twin-screw extruder are respectively as follows: the conveying section is 250-260 ℃, the melting section is 270-290 ℃, the shearing section is 270-290 ℃, the exhaust section is 260-280 ℃ and the extrusion section is 260-280 ℃.
4. The method for preparing a flame retardant material according to claim 1, wherein the method for preparing the flame retardant comprises the following steps:
step 1, reacting phosphoric acid with an imidazole compound to generate an imidazole phosphate;
step 2, carrying out dehydration reaction on imidazole phosphate to obtain pyrophosphoric imidazole;
the structure of the imidazolyl compound is shown as a formula (II):
wherein R is 1 is-H or-SH; r 2 And R 3 Each independently may be selected from-H or C1-C4 hydrocarbyl, and R 2 And R 3 And cannot be the same.
5. The method of claim 4, wherein in step 1, the molar ratio of phosphoric acid to the imidazole-based compound is 1: 0.8 to 1.2, water is used as a solvent, the reaction temperature is 90 to 110 ℃, and the reaction time is 1 to 3 hours.
6. The method of claim 4, wherein the dehydration reaction is performed under the protection of inert gas in step 2, the reaction temperature is 250 ℃ to 300 ℃, and the reaction time is 0.5 to 3 hours.
7. The method for preparing a flame retardant material according to claim 6, wherein the inert gas is nitrogen, carbon dioxide or argon.
8. The method of claim 4, wherein the reaction device in step 2 is an internal mixer, a vacuum kneader, a vacuum oven, or the like.
9. The method of claim 4, wherein the high boiling point solvent in step 2 has a boiling point of greater than 300 ℃ at normal pressure, and may be high temperature silicone oil, liquid paraffin, or the like, preferably triphenyl phosphate.
10. A flame retardant material directly obtainable by the process of any one of claims 1 to 9.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210448306.8A CN115011113B (en) | 2019-12-18 | 2019-12-18 | Flame-retardant material and preparation method thereof |
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| CN201911309386.3A CN111040245B (en) | 2019-12-18 | 2019-12-18 | Pyropolyphosphoric acid imidazole flame retardant and preparation method thereof |
| CN202210448306.8A CN115011113B (en) | 2019-12-18 | 2019-12-18 | Flame-retardant material and preparation method thereof |
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| CN201911309386.3A Division CN111040245B (en) | 2019-12-18 | 2019-12-18 | Pyropolyphosphoric acid imidazole flame retardant and preparation method thereof |
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| CN115011113A true CN115011113A (en) | 2022-09-06 |
| CN115011113B CN115011113B (en) | 2023-07-21 |
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| CN105732717A (en) * | 2016-04-08 | 2016-07-06 | 四川大学 | Imidazolium liquid flame-retardant agent containing caged phosphate structure and preparation method thereof |
| CN106751585A (en) * | 2016-12-28 | 2017-05-31 | 宁波优科泰科技发展有限公司 | A kind of flame retardant plastics using ionic liquid as fire retardant and preparation method thereof |
| CN107418201A (en) * | 2017-08-30 | 2017-12-01 | 惠州市华聚塑化科技有限公司 | A kind of efficient halogen-free anti-inflaming enhancing nylon composite materials and preparation method thereof |
| CN108424535A (en) * | 2018-03-30 | 2018-08-21 | 南京菲锐迪新材料科技有限公司 | A kind of polar polymeric powder by Low Temperature Plasma Treating |
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| DE102005024255A1 (en) * | 2005-05-27 | 2006-11-30 | Henkel Kgaa | Imidazole salts, process for their preparation, their use and epoxy resins containing them |
| SI2940030T1 (en) * | 2012-12-28 | 2017-09-29 | Yamasa Corporation | Method for producing p1,p4-di(uridine 5'-)tetraphosphate |
| US10035896B2 (en) * | 2014-07-29 | 2018-07-31 | Lanxess Solutions Us Inc. | Salts of pyrophosphonic acid as flame retardants |
| CN106928269B (en) * | 2017-03-30 | 2020-03-24 | 长春普华制药股份有限公司 | Preparation method of phosphate |
| CN107556255A (en) * | 2017-07-26 | 2018-01-09 | 东华大学 | A kind of organic amine modified melamine polyphosphate and preparation method thereof |
| CN107459492A (en) * | 2017-07-26 | 2017-12-12 | 东华大学 | A kind of organically-modified melamine polyphosphate and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105732717A (en) * | 2016-04-08 | 2016-07-06 | 四川大学 | Imidazolium liquid flame-retardant agent containing caged phosphate structure and preparation method thereof |
| CN106751585A (en) * | 2016-12-28 | 2017-05-31 | 宁波优科泰科技发展有限公司 | A kind of flame retardant plastics using ionic liquid as fire retardant and preparation method thereof |
| CN107418201A (en) * | 2017-08-30 | 2017-12-01 | 惠州市华聚塑化科技有限公司 | A kind of efficient halogen-free anti-inflaming enhancing nylon composite materials and preparation method thereof |
| CN108424535A (en) * | 2018-03-30 | 2018-08-21 | 南京菲锐迪新材料科技有限公司 | A kind of polar polymeric powder by Low Temperature Plasma Treating |
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| CN111040245B (en) | 2022-05-31 |
| CN115011113B (en) | 2023-07-21 |
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