CN115418026A - Synthesis and application of phosphorus flame retardant composition - Google Patents
Synthesis and application of phosphorus flame retardant composition Download PDFInfo
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
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- C08K3/32—Phosphorus-containing compounds
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Abstract
The invention provides synthesis and application of a phosphorus flame retardant composition, and belongs to the technical field of flame retardants. The phosphorus flame retardant composition comprises the following components: the component A is as follows: 10wt% -100wt%; and (B) component: 0wt% -60wt%; and (C) component: 0wt% -60wt%. Wherein, the component A is a compound shown in a structural formula I, the component B is a compound shown in a structural formula II, and the component C is phosphite shown in a structural formula III and hydrate or telomer thereof. Compared with the use of diethyl aluminum phosphinate, the composition can achieve the flame retardant rating of UL94-V0@1.6mm only by adding 8wt% in polyamide and achieve the flame retardant rating of UL94-V0@1.6mm only by adding 15wt% in 30wt% fiber reinforced polyamide.
Description
Technical Field
The invention belongs to the technical field of flame retardants, and particularly relates to synthesis and application of a phosphorus flame retardant composition.
Background
At present, organic phosphorus has wide application in the flame retardant industry, and particularly, an organic phosphorus system taking diethyl aluminum hypophosphite as a core substance is the key point of research of various large enterprises. In chinese patents CN98811627.8, CN 98811626.X, CN98811622.7, methods are described in which hypophosphorous acid or hypophosphites can form organophosphorus compounds under free radical conditions. The synthesis has the advantages of simple method, short synthetic route and water solubility of the product. The organic phosphorus compound obtained is reacted with another metal compound to obtain an organic phosphoric acid metal flame retardant. In the chinese patent No. cn201711175795.X, the inventor hydrolyzes alkyl phosphate ester by acid to obtain alkyl phosphoric acid, then reacts with aluminum salt solution to obtain alkyl aluminum phosphate, and adds the alkyl aluminum phosphate and diethyl aluminum hypophosphite into glass fiber reinforced nylon after mixing to obtain reinforced flame retardant nylon, wherein the addition amount is 20%. However, the method needs at least 22 percent of diethyl aluminum hypophosphite to be added into glass fiber reinforced nylon to achieve the flame retardant grade UL94-V0@1.6mm by singly using diethyl aluminum hypophosphite, and the cost is high.
Disclosure of Invention
The invention aims to provide a novel phosphorus flame retardant composition, so that the addition amount of a flame retardant is reduced from 22-23% to 15%, the cost of a modified material is reduced, and the physical properties of modified nylon are improved.
The invention provides a phosphorus flame retardant composition, which consists of the following components: the component A is as follows: 10wt% -100wt%; and (B) component: 0wt% -60wt%; and (C) component: 0wt% -60wt%;
the component A is a compound shown in a structural formula I:
the component B is a compound shown in a structural formula II:
the component C is phosphite and hydrate or telomer thereof shown as a structural formula III:
K s k+ (HPO 3 ) 2- y (H 2 O) Z (Ⅲ)。
wherein R is 1 ,R 2 ,R 3 ,R 4 All are ethyl, all of M, N and K are aluminum a +2b=3, a, b are positive numbers not less than 0.01 and not more than 10, including and not limited to positive integers; m = n = k =3, x = y =3/2, z is a positive real number from 0 to 7.
Preferably, the composition consists of: the component A is as follows: 40-90 wt%; and (B) component: 5-30 wt%; and (C) component: 5 to 30 weight percent.
Preferably, component A is diethyl phosphinic ethyl aluminum phosphite; the component B is ethyl aluminum phosphite; the component C is aluminum phosphite;
most preferably, component A is diethyl phosphinic ethyl aluminum phosphite in an amount of 80Wt%, component B is ethyl aluminum phosphite in an amount of 10Wt%, and component C is aluminum phosphite in an amount of 10Wt%;
preferably, the preparation method of the flame retardant composition comprises the following steps:
(1) Preparation of component A: diluting 1L of 1mol/L sodium ethyl phosphinate solution to the concentration of 0.5mol/L, adding 2L of 0.5mol/L sodium diethylphosphinate solution, uniformly mixing, dropwise adding 1.34L of 0.5mol/L aluminum sulfate solution, finishing dropwise adding within 2 hours, stirring for 3 hours after dropwise adding is finished, keeping the temperature of 50 ℃ in the whole process to obtain a turbid liquid of a component A, and filtering, washing, drying and crushing to obtain the component A;
(2) Preparation of component B: slowly dropwise adding 0.5mol/L aluminum salt aqueous solution (aluminum sulfate aqueous solution, aluminum nitrate aqueous solution and aluminum chloride aqueous solution) containing 0.66mol of aluminum ions into 1L 1mol/L sodium ethyl phosphinate solution for 2 hours, stirring for 1 hour after the dropwise adding is finished, keeping the temperature of 50 ℃ in the whole process to obtain suspension of the component B, and filtering, washing, drying and crushing to obtain the component B;
(3) Preparation of component C: putting 1L of 1mol/L phosphorous acid solution and aluminum oxide or aluminum hydroxide or aluminum monohydrate or aluminum dihydrate with the aluminum content of 0.5mol into a four-neck flask, refluxing for 2-20h under the reflux state, filtering, washing, drying and crushing to obtain the component C.
(4) Preparation of the resulting composition: and adding the component B and the component C into the turbid liquid of the component A according to the proportion, uniformly stirring, discharging, washing, drying and crushing to obtain the phosphorus flame retardant composition.
Preferably, the phosphorus-based flame retardant composition can be used alone in polyamide or in combination with other phosphorus-based flame retardants, phosphorus-nitrogen-based flame retardants, boron-based flame retardants, silicon-based flame retardants, or phosphorus-silicon-based flame retardants to improve flame retardant efficiency.
The invention further provides an application of the phosphorus flame retardant composition, and the phosphorus flame retardant composition can be used alone in polyamide or used together with other phosphorus flame retardants, phosphorus-nitrogen flame retardants, boron flame retardants, silicon flame retardants or phosphorus-silicon flame retardants to improve the flame retardant efficiency.
The invention has the beneficial effects that:
the phosphorus flame retardant composition can greatly reduce the addition amount of the flame retardant to achieve the same flame retardant effect, and has the advantages of no migration and no hydrolysis. The material cost of the material is reduced while the product performance is improved.
Drawings
FIG. 1 shows the residual carbon after combustion of the test specimen 11;
FIG. 2 is a scanning electron microscope micrograph of the carbon residue after specimen combustion of test experiment 11;
FIG. 3 shows the carbon residue after combustion of the test specimens of test experiment 13;
FIG. 4 is a scanning electron microscope micrograph of carbon residue after spline combustion of test experiment 13;
Detailed Description
The examples are given for the purpose of better illustration of the invention, but the invention is not limited to the examples. Therefore, those skilled in the art should make insubstantial modifications and adaptations to the embodiments of the present invention in light of the above teachings and remain within the scope of the invention.
The preparation method of the component A comprises the following steps:
taking 1L of 1mol/L sodium ethyl phosphinate solution, diluting to the concentration of 0.5mol/L, adding 2L of 0.5mol/L sodium diethylphosphinate solution, uniformly mixing, dropwise adding 1.34L of 0.5mol/L aluminum sulfate solution, finishing dropwise adding within 2 hours, stirring for 3 hours after dropwise adding is finished, keeping the temperature of 50 ℃ in the whole process to obtain a turbid liquid A of the component A, and filtering, washing, drying and crushing the turbid liquid A to the particle size of 0.1-1000 mu m to obtain the component A;
the preparation method of the component B comprises the following steps:
slowly dropwise adding 0.5mol/L aluminum salt aqueous solution (aluminum sulfate aqueous solution, aluminum nitrate aqueous solution and aluminum chloride aqueous solution) containing 0.66mol of aluminum ions into 1L 1mol/L sodium ethyl phosphinate solution for 2 hours, stirring for 1 hour after the dropwise adding is finished, keeping the temperature of 50 ℃ in the whole process to obtain suspension of the component B, and filtering, washing, drying and crushing the suspension until the particle size is 0.1-1000 mu m to obtain the component B;
preparation of component C
The method comprises the following steps: slowly dropwise adding 0.5mol/L aluminum salt aqueous solution (aluminum sulfate aqueous solution, aluminum nitrate aqueous solution and aluminum chloride aqueous solution) containing 0.66mol of aluminum ions into 1L 1mol/L sodium phosphinate solution for 2 hours, stirring for 1 hour after the dropwise adding is finished, keeping the temperature of 50 ℃ in the whole process to be constant, obtaining suspension of the component C, filtering, washing, drying and crushing to obtain the component C with the particle size of 0.1-1000 mu m;
the second method comprises the following steps: putting a phosphorous acid solution (the concentration is more than 0.5 mol/L) into a three-neck flask, adding 60 percent of aluminum hydroxide of phosphorous acid mole number, refluxing for 10 hours under the condition that the solution is boiling to obtain a suspension C, and filtering, washing, drying and crushing the suspension C until the particle size is 0.1-1000 mu m to obtain a component C;
the third method comprises the following steps: 6mol of phosphorous acid and 2mol of aluminum hydroxide are placed in a kneader and heated to 150 ℃ for kneading for 20 hours, and after the kneading is finished, the mixture is washed, dried and crushed to a particle size of 0.1 to 1000 μm to obtain a component C.
Example 1
Synthesizing a suspension A, a suspension B and a suspension C according to the synthesis method, mixing and stirring the suspension A, the suspension B and the suspension C according to the mixture ratio shown in the table I for 4 hours, filtering, washing, drying and crushing to obtain a flame retardant composition with the particle size D50 of 20-25 mu m; or the component A, the component B and the component C with the grain diameter of 0.1-1000 mu m are put into a high-speed mixing pot according to the mixture ratio shown in the table I and stirred at high speed, and the mixture is discharged after being stirred uniformly to obtain the flame retardant composition.
Example 2: the procedure was carried out in accordance with example 1, except that the ratio of component B to component A was adjusted, the specific formulation being as shown in Table 1.
Example 3: the procedure was carried out in accordance with example 1, except that the ratio of component B to component A was adjusted, the specific formulation being as shown in Table 1.
Example 4: the procedure was carried out in accordance with example 1, except that the ratio of component B to component A was adjusted, the specific formulation being as shown in Table 1.
Example 5: the procedure was carried out in accordance with example 1, except that the ratio of component B to component A was adjusted, the specific formulation being as shown in Table 1.
Example 6: the procedure was carried out in accordance with example 1, except that the ratio of component B to component A was adjusted, the specific formulation being as shown in Table 1.
Example 7: the procedure was carried out in accordance with example 1, except that the ratio of component B to component A was adjusted, the specific formulation being as shown in Table 1.
Example 8: the procedure was carried out in accordance with example 1, except that the ratio of component B to component A was adjusted, the specific formulation being as shown in Table 1.
Example 9: the procedure was carried out in accordance with example 1, except that the ratio of component B to component A was adjusted, the specific formulation being as shown in Table 1.
Example 10: the procedure was carried out in accordance with example 1, except that the ratio of component C to component A was adjusted, the specific formulation being as shown in Table 1.
Example 11: the procedure was carried out in accordance with example 1, except that the ratio of component C to component A was adjusted, the specific formulation being as shown in Table 1.
Example 12: the procedure was carried out in accordance with example 1, except that the ratio of component C to component A was adjusted, the specific formulation being as shown in Table 1.
Example 13: the procedure was carried out in accordance with example 1, except that the ratio of component C to component A was adjusted, the specific formulation being as shown in Table 1.
Example 14: the procedure was carried out in accordance with example 1, except that the ratio of component C to component A was adjusted, the specific formulation being as shown in Table 1.
Example 15: the procedure was carried out in accordance with example 1, except that the ratio of component B to component C was adjusted, the specific formulation being as shown in Table 1.
Example 16: the procedure was carried out in accordance with example 1, except that the ratio of component B to component C was adjusted, the specific formulation being as shown in Table 1.
Example 17: the procedure was carried out in accordance with example 1, except that the ratio of component B to component C was adjusted, the specific formulation being as shown in Table 1.
Example 18: the procedure was carried out in accordance with example 1, except that the ratio of component B to component C was adjusted, the specific formulation being as shown in Table 1.
Example 19: the procedure was carried out in accordance with example 1, except that the ratio of component B to component C was adjusted, the specific formulation being as shown in Table 1.
Example 20: the procedure was as in example 1 except that the ratio of component A to components B and C was adjusted, and the specific formulation is as shown in Table 1.
Example 21: the procedure was as in example 1 except that the ratio of component A to components B and C was adjusted, and the specific formulation is as shown in Table 1.
Example 22: the procedure was as in example 1 except that the ratio of component A to components B and C was adjusted, and the specific formulation is as shown in Table 1.
Example 23: the procedure was as in example 1, except that the ratio of component A to components B and C was adjusted, and the specific formulation is shown in Table 1.
Example 24: the procedure was as in example 1 except that the ratio of component A to components B and C was adjusted, and the specific formulation is as shown in Table 1.
Comparative example 1: the procedure was carried out in accordance with example 2, except that component A was replaced by aluminum diethylphosphinate.
Comparative example 2: the procedure was carried out in accordance with example 3, except that component A was replaced by aluminum diethylphosphinate.
Comparative example 3: the procedure was carried out in accordance with example 7, except that component A was replaced by aluminum diethylphosphinate.
Table 1-1 table of composition data of examples
Tables 1-2 comparative examples composition data Table
To demonstrate the flame retardant effectiveness of the flame retardant compositions to which this patent relates, we have conducted the following test experiments in the PA-66 system:
i) Non-reinforced polyamide strength systems
The method comprises the following steps: drying PA-66 and a flame retardant in a vacuum oven at 80 ℃ for 4 hours, then uniformly mixing, extruding and granulating by using a double-screw extruder, and drying the prepared PA-6 flame-retardant particles in the vacuum oven at 80 ℃ for 4 hours for later use;
step two: the completely dried PA-6/PA-66 flame-retardant particles were injection-molded into flame-retardant strips (1.6 mm), dumbbell strips, glow wire test specimens and tracking specimens using an injection molding machine, and were left to stand at 25 ℃ and 50% humidity for 24 hours to test flame-retardant properties, mechanical properties, electrical properties and glow wire properties.
ii) 30 wt.% glass fiber reinforced polyamide system
The test procedure was consistent with i) the non-reinforced polyamide system except that 30wt% fiberglass was added.
Test experiment 1 samples were prepared and tested according to i) the non-reinforced polyamide system, the flame retardant composition prepared in example 2 was selected from the flame retardant compositions, the specific compounding ratio data is shown in table 2, and the performance test is shown in table 3.
Test experiment 2 the flame retardant composition prepared in example 1 was selected as the flame retardant composition, the implementation process was identical to that of test experiment 1, the specific compounding ratio data is shown in table 2, and the performance test is shown in table 3.
Test experiment 3 except that the flame retardant composition prepared in example 7 was used as the flame retardant composition, the implementation process was consistent with that of test experiment 1, the specific compounding ratio data is shown in table 2, and the performance test is shown in table 3.
Test experiment 4 the flame retardant composition prepared in example 10 was selected as the flame retardant composition, the procedure was identical to that of test experiment 1, the specific compounding ratio data are shown in table 2, and the performance test is shown in table 3.
Test experiment 5 the flame retardant composition prepared in example 15 was selected, and the implementation procedure was consistent with that of test experiment 1, the specific compounding ratio data is shown in table 2, and the performance test is shown in table 3.
Test experiment 6 the procedure was identical to test experiment 1 except that the flame retardant composition prepared in example 19 was used as the flame retardant composition, the specific compounding ratio data is shown in table 2, and the performance test is shown in table 3.
Test experiment 7 the procedure of the test experiment 1 was identical, the specific compounding ratio data is shown in table 2, and the performance test is shown in table 3, except that the flame retardant composition prepared in example 25 was used.
Test experiment 8 the implementation process was consistent with test experiment 7 except that the addition amount of the flame retardant composition was adjusted, the specific compounding ratio data is shown in table 2, and the performance test is shown in table 3.
Test experiment 9 the implementation process was consistent with test experiment 7 except that the addition amount of the flame retardant composition was adjusted, the specific compounding ratio data is shown in table 2, and the performance test is shown in table 3.
Test experiment 10 the implementation process was consistent with test experiment 7 except that the addition amount of the flame retardant composition was adjusted, the specific compounding ratio data is shown in table 2, and the performance test is shown in table 3.
Test experiment 11 samples were prepared and tested according to ii) 30wt% glass fiber reinforced polyamide system, the flame retardant composition prepared in example 2 was selected from the flame retardant compositions, the specific proportioning data is shown in table 2, and the performance test is shown in table 3.
Test experiment 12 the procedure was identical to test experiment 11 except that the flame retardant composition prepared in example 1 was used as the flame retardant composition, the specific compounding ratio data is shown in table 2, and the performance test is shown in table 3.
Test experiment 13 the procedure of the test experiment 11 was identical, the specific compounding ratio data is shown in table 2, and the performance test is shown in table 3, except that the flame retardant composition prepared in example 7 was used.
Test experiment 14 the procedure was identical to test experiment 11 except that the flame retardant composition prepared in example 10 was used as the flame retardant composition, the specific compounding ratio data is shown in table 2, and the performance test is shown in table 3.
Test experiment 15 the procedure was identical to test experiment 11 except that the flame retardant composition prepared in example 15 was used, the specific compounding ratio data is shown in table 2, and the performance test is shown in table 3.
Test experiment 16 the procedure was identical to test experiment 11 except that the flame retardant composition prepared in example 19 was used, the specific compounding ratio data is shown in table 2, and the performance test is shown in table 3.
Test experiment 17 the procedure was identical to test experiment 11 except that the flame retardant composition prepared in example 25 was used, the specific compounding ratio data is shown in table 2, and the performance test is shown in table 3.
Test experiment 18 the implementation process was consistent with test experiment 17 except that the amount of the flame retardant composition added was adjusted, the specific compounding ratio data is shown in table 2, and the performance test is shown in table 3.
Test experiment 19 the implementation process was consistent with test experiment 17 except that the amount of the flame retardant composition added was adjusted, the specific compounding ratio data is shown in table 2, and the performance test is shown in table 3.
Test experiment 20 the implementation process was consistent with test experiment 17 except that the amount of the flame retardant composition added was adjusted, the specific compounding ratio data is shown in table 2, and the performance test is shown in table 3.
And (3) comparison test: the flame retardant adopts the conventional phosphorus-resistant flame retardant diethyl aluminum hypophosphite as a comparative experiment, and comprises the following specific steps:
comparative experiment 1 the implementation process was consistent with test experiment 1 except that the flame retardant composition was adjusted to Aluminum Diethylphosphinate (ADP), the specific compounding ratio data are shown in table 4, and the performance tests are shown in table 5.
Comparative experiment 2 except for adjusting the content of the flame retardant, the implementation process was consistent with comparative experiment 1, the specific proportioning data is shown in table 4, and the performance test is shown in table 5.
Comparative experiment 3 the implementation process was consistent with comparative experiment 1 except that the flame retardant content was adjusted, the specific compounding ratio data is shown in table 4, and the performance test is shown in table 5.
Comparative experiment 4 the implementation process was consistent with test experiment 7 except that the flame retardant composition was adjusted to Aluminum Diethylphosphinate (ADP), the specific compounding ratio data are shown in table 4, and the performance tests are shown in table 5.
Comparative experiment 5 the implementation process was consistent with test experiment 7 except that the flame retardant content was adjusted, the specific compounding ratio data is shown in table 4, and the performance test is shown in table 5.
Comparative experiment 6 the implementation process was consistent with test experiment 7 except that the flame retardant content was adjusted, the specific compounding ratio data is shown in table 4, and the performance test is shown in table 5.
Comparative experiment 7 the procedure was in accordance with test experiment 13 except that the flame retardant composition was adjusted to comparative example 1, the specific compounding ratio data is shown in table 4, and the performance test is shown in table 5.
Comparative experiment 8 the flame retardant composition was adjusted to comparative example 2, the procedure was identical to comparative experiment 4, the specific compounding ratio data is shown in table 4, and the performance test is shown in table 5.
Comparative experiment 9 the procedure was as in comparative experiment 4 except that the flame retardant composition was adjusted to comparative example 3, the specific compounding ratio data is shown in table 4, and the performance test is shown in table 5.
Comparative experiment 10 the implementation process was consistent with comparative experiment 4 except that the flame retardant content was adjusted, the specific compounding ratio data is shown in table 4, and the performance test is shown in table 5.
Comparative experiment 11 the implementation process was consistent with comparative experiment 4 except that the flame retardant content was adjusted, the specific compounding ratio data is shown in table 4, and the performance test is shown in table 5.
Comparative experiment 12 the implementation process was consistent with comparative experiment 4 except that the flame retardant content was adjusted, the specific compounding ratio data is shown in table 4, and the performance test is shown in table 5.
TABLE 2 Experimental proportioning data
Table 3 experimental test physical property data
TABLE 4 comparative experiment ratios
TABLE 5 comparative experimental physical Properties
It can be seen from tables 3 and 5 that when the flame retardant composition disclosed by the invention is applied to a PA system, no matter a reinforced system or a non-reinforced system, the flame retardant PA composite material can reach the flame retardant grade of UL94-V0@1.6mm under the condition of lower flame retardant usage amount, compared with the traditional ADP, the flame retardant requirement of UL94-V0@1.6mm cannot be met by adding the same proportion, particularly, the 30wt% glass fiber reinforced PA-66 system needs to be added by 23wt%, and the addition amount of the flame retardant can be greatly reduced to improve the physical property of the flame retardant polyamide. Meanwhile, when aluminum ethylphosphonite and aluminum phosphite are introduced, the addition amount of a flame retardant can be further reduced, and the two components have relatively poor synergy on ADP.
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.
Claims (6)
1. A phosphorus-based flame retardant composition, characterized in that the composition consists of the following components: the component A is as follows: 10wt% -100wt%; and (B) component: 0wt% -60wt%; and (C) component: 0wt% -60wt%;
the component A is a compound shown in a structural formula I:
the component B is a compound shown in a structural formula II:
the component C is phosphite and hydrate or telomer thereof shown as a structural formula III:
K s k+ (HPO 3 ) 2- y (H 2 O) Z (Ⅲ)。
2. the phosphorus-based flame retardant composition of claim 1, wherein R in the structural formula I 1 ,R 2 ,R 3 Is ethyl;
a and b are positive numbers not less than 0.01 and not more than 10, and a +2b = m number; m is aluminum and M is 3. In the structural formula II, R 4 Is ethyl, N is aluminum, and N is 3,x =3/2.
In the structural formula III, K is aluminum, K is 3, s is 2, y is 3, and z is a positive real number of 0-7.
3. The phosphorus-based flame retardant composition according to claim 1, wherein the preparation method of the phosphorus-based flame retardant composition comprises the steps of:
(1) Preparation of component A: diluting 1L of 1mol/L sodium alkyl phosphinate solution to the concentration of 0.5mol/L, adding 2L of 0.5mol/L sodium dialkyl phosphinate solution, uniformly mixing, dropwise adding 1.34L of 0.5mol/L aluminum sulfate solution, ending dropwise adding within 2 hours, stirring for 3 hours after the dropwise adding is ended, and keeping the temperature of 50 ℃ in the whole process to obtain a turbid liquid of the component A;
(2) Preparation of component B: carrying out double decomposition reaction on the sodium ethylphosphonite solution and an aluminum salt aqueous solution to obtain a component B;
or reacting ethylphosphonous acid with aluminum hydroxide or aluminum oxide at high temperature, washing, filtering, drying and crushing to obtain a component B;
(3) Preparation of component III: refluxing a phosphorous acid solution and an oxide or hydroxide containing the component aluminum-containing element for 2-20h under a reflux state, filtering, washing, drying and crushing to obtain a component C;
or mixing the sodium phosphite solution and the salt solution containing the aluminum element for reaction to obtain suspension of the component C, and filtering, washing, drying and crushing to obtain the component C.
(4) Preparation of the resulting composition: and adding the component B and the component C into the turbid liquid of the component A according to the proportion, uniformly stirring, discharging, washing, drying and crushing to obtain the phosphorus flame retardant composition.
4. The phosphorus-based flame retardant composition of claim 1, wherein the phosphorus-based flame retardant composition can be used alone or in combination with other phosphorus-based flame retardants, phosphorus-nitrogen-based flame retardants, boron-based flame retardants, silicon-based flame retardants, or phosphorus-silicon-based flame retardants in polyamide for improving flame retardant efficiency.
5. The method of preparing the phosphorus-based flame retardant composition of claim 1, comprising the steps of:
(1) Preparation of component A: diluting 1L of 1mol/L sodium ethyl phosphinate solution to the concentration of 0.5mol/L, adding 2L of 0.5mol/L sodium diethylphosphinate solution, uniformly mixing, dropwise adding 1.34L of 0.5mol/L aluminum sulfate solution, finishing dropwise adding within 2 hours, stirring for 3 hours after dropwise adding is finished, keeping the temperature of 50 ℃ in the whole process to obtain a turbid liquid of a component A, and filtering, washing, drying and crushing to obtain the component A;
(2) Preparation of component B: putting the sodium ethyl phosphonite aqueous solution into a four-neck flask, and dripping a metered aluminum salt aqueous solution into the flask for double decomposition to obtain a component B;
(3) Preparation of component C: refluxing 1mol of phosphorous acid solution and 0.5mol of aluminum oxide or aluminum hydroxide or aluminum hydrate containing aluminum element for 2-20h under reflux state, filtering, washing, drying and crushing to obtain the component C.
(4) Preparation of the resulting composition: adding the component B and the component C into the turbid liquid of the component A according to the proportion, uniformly stirring, discharging, washing, filtering, washing, drying and crushing to obtain the phosphorus flame retardant composition;
or putting the component A, the component B and the component C into a high-speed mixing pot according to the proportion, and stirring and mixing uniformly to obtain the phosphorus flame retardant composition.
6. The use of the phosphorus-based flame retardant composition according to claim 1, wherein the phosphorus-based flame retardant composition can be used alone in polyamide or in combination with other phosphorus-based flame retardants, phosphorus-nitrogen-based flame retardants, boron-based flame retardants, silicon-based flame retardants, or phosphorus-silicon-based flame retardants to improve flame retardant efficiency.
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| DE102013004046A1 (en) * | 2013-03-08 | 2014-09-11 | Clariant International Ltd. | Flame retardant polyamide composition |
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| CN111662323A (en) * | 2019-03-07 | 2020-09-15 | 黎杰 | Dialkyl phosphinic acid-alkyl phosphorous acid metal composite salt, preparation method and application thereof |
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| DE102013004046A1 (en) * | 2013-03-08 | 2014-09-11 | Clariant International Ltd. | Flame retardant polyamide composition |
| CN104371142A (en) * | 2014-10-29 | 2015-02-25 | 广州金凯新材料有限公司 | Additive composition for polymer, preparation method of additive composition and flame-retardant thermoplastic polymer molding material by using additive composition |
| CN111662323A (en) * | 2019-03-07 | 2020-09-15 | 黎杰 | Dialkyl phosphinic acid-alkyl phosphorous acid metal composite salt, preparation method and application thereof |
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