CN117886854A - Phosphorus-nitrogen-containing flame retardant and preparation method thereof - Google Patents
Phosphorus-nitrogen-containing flame retardant and preparation method thereof Download PDFInfo
- Publication number
- CN117886854A CN117886854A CN202311740708.6A CN202311740708A CN117886854A CN 117886854 A CN117886854 A CN 117886854A CN 202311740708 A CN202311740708 A CN 202311740708A CN 117886854 A CN117886854 A CN 117886854A
- Authority
- CN
- China
- Prior art keywords
- flame retardant
- nitrogen
- phosphorus
- containing flame
- diphenyl sulfone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 132
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 130
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title abstract description 20
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 102
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 63
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000012265 solid product Substances 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 239000002244 precipitate Substances 0.000 claims abstract description 35
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000005406 washing Methods 0.000 claims abstract description 34
- 238000001035 drying Methods 0.000 claims abstract description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001914 filtration Methods 0.000 claims abstract description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 18
- IBDMRHDXAQZJAP-UHFFFAOYSA-N dichlorophosphorylbenzene Chemical compound ClP(Cl)(=O)C1=CC=CC=C1 IBDMRHDXAQZJAP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 238000010992 reflux Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 31
- 239000000243 solution Substances 0.000 claims description 24
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 10
- 229920002292 Nylon 6 Polymers 0.000 claims description 6
- 239000004417 polycarbonate Substances 0.000 claims description 4
- 229920000515 polycarbonate Polymers 0.000 claims description 4
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- IMDXZWRLUZPMDH-UHFFFAOYSA-N dichlorophenylphosphine Chemical compound ClP(Cl)C1=CC=CC=C1 IMDXZWRLUZPMDH-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 15
- 239000003513 alkali Substances 0.000 abstract description 15
- 239000000047 product Substances 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 12
- 230000002195 synergetic effect Effects 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 239000000654 additive Substances 0.000 description 7
- 230000000996 additive effect Effects 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 238000002485 combustion reaction Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000001746 injection moulding Methods 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000004677 Nylon Substances 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229920001778 nylon Polymers 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229920000137 polyphosphoric acid Polymers 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910004856 P—O—P Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000005954 phosphonylation reaction Methods 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention discloses a phosphorus-nitrogen-containing flame retardant and a preparation method thereof. Firstly, drying and dehydrating 4, 4-diamino diphenyl sulfone, and then placing the dehydrated 4, 4-diamino diphenyl sulfone in a reaction container, and replacing the dehydrated 4, 4-diamino diphenyl sulfone with nitrogen; adding triethylamine and anhydrous acetonitrile after replacement, and stirring uniformly; then adding the phenylphosphonic dichloride solution dissolved in anhydrous acetonitrile into a reaction vessel for heating reflux reaction; cooling the obtained reaction solution to room temperature, filtering the precipitate, and washing with acetonitrile to obtain a pale yellow solid product; dissolving the pale yellow solid product in dimethyl sulfoxide, adding the solution obtained after dissolving into ethanol to separate out precipitate, filtering the precipitate, and washing with water to obtain a moist white solid product; and drying the obtained white solid product to obtain the white solid phosphorus-nitrogen-containing flame retardant. The phosphorus-nitrogen synergistic flame retardant prepared by the method has good flame retardant effect, and the flame retardant performance of the product prepared by the flame retardant is not obviously reduced after acid/alkali washing; the flame retardant prepared by the invention has the characteristics of high efficiency, environmental protection and acid and alkali washing resistance.
Description
1. Technical field:
the invention relates to the field of organic compound synthesis, in particular to a phosphorus-nitrogen-containing flame retardant and a preparation method thereof.
2. The background technology is as follows:
with the increasing awareness of global safety and environmental protection, halogen-free flame retardance has become the most basic requirement of high-performance resin materials. The flame retardant can be divided into an additive type and a reactive type according to the interaction between the flame retardant and the high polymer, the additive type flame retardant does not contain active groups capable of reacting with the polymer, the flame retardant effect can be achieved by simply blending the additive type flame retardant with the polymer, the operation process is simple, but the additive type flame retardant is easy to separate out due to poor compatibility with the material, so that the material performance is influenced; the reactive flame retardant has active groups, can directly participate in the polymerization reaction of the polymer, is a structural unit of the polymer, can not be separated out in the flame retardant process, has uniform flame retardant effect and lasting flame retardance, and can ensure that the material has good flame retardant effect by adding lower content. However, the process for preparing the flame retardant material by the reactive flame retardant is complex, and the additive flame retardant is relatively more economical and convenient, thus being suitable for mass production. At present, the additive flame retardant has the fatal defects of large addition amount, poor compatibility with materials, reduced mechanical properties of the materials and the like. Therefore, the development of the additive flame retardant which has low addition amount, high flame retardant effect and does not influence the mechanical property of the material has very important practical significance.
In recent years, the research of composite flame retardants has been greatly advanced, especially phosphorus-nitrogen flame retardants, do not contain halogen, do not generate toxic gas and smoke in the combustion process, have good compatibility with substances, are not easy to migrate, and have synergistic flame retardant effect. Therefore, the effective flame retardance can be achieved under the condition of low addition amount. The synergistic flame retardance of the phosphorus-nitrogen flame retardant is particularly shown by the existence of nitrogen atoms in the flame retardant, so that the phosphorus-series flame retardant is more beneficial to being decomposed into a polyphosphoric acid liquid film capable of isolating air, and meanwhile, the flame retardant is heated to release incombustible gases such as ammonia, nitrogen oxides and the like, so that a gas protective layer is formed, the supply of oxygen can be isolated, the concentration of the combustible gases is reduced, and the combustion is choked; and the nitrogen compound and the oxygen acid of the phosphorus form chemical bonds of P-N-P, P-O-P, P-C and the like to form a coke layer which is left in the residual carbon and covers the surface of the polymer to prevent the combustion of the polymer; in addition, P-N bonds formed by combining nitrogen and phosphorus can also inhibit the formation of inflammable substances. When the phosphorus-nitrogen synergistic flame retardant is combusted, phosphorus element can promote formation of a compact carbon layer, carbon residue contains components of orthophosphoric acid and polyphosphoric acid, and phosphorus-containing free radicals in gas phase can capture chain reaction free radicals to terminate combustion reaction; in the combustion process, the nitrogen element can generate ammonia gas to dilute the combustible gas, which is beneficial to forming the intumescent flame retardant material. At present, the synthesis process of the phosphorus-nitrogen flame retardant is relatively complex, so the cost is high, and the prepared product is acid-alkali washing resistant. Therefore, the development of novel halogen-free high-efficiency acid and alkali resistant flame retardant is a hot subject direction at present.
3. The invention comprises the following steps:
the invention aims to solve the technical problems that: according to the current situation and the existing problems of the prior phosphorus-nitrogen-containing flame retardant preparation technology, the invention provides a novel phosphorus-nitrogen-containing flame retardant and a preparation method thereof. The phosphorus-nitrogen synergistic flame retardant prepared by the technical scheme of the invention has good flame retardant effect, and the flame retardant property of the product prepared by the phosphorus-nitrogen synergistic flame retardant is not obviously reduced after acid/alkali washing; the flame retardant prepared by the invention has the characteristics of high efficiency, environmental protection and acid and alkali washing resistance.
In order to solve the problems, the invention adopts the following technical scheme:
the invention provides a phosphorus-nitrogen-containing flame retardant, which has the structural formula:
in addition, a preparation method of the phosphorus-nitrogen-containing flame retardant is provided, and the preparation method comprises the following steps:
a. drying and dehydrating 4, 4-diamino diphenyl sulfone DDS, and then placing the dried and dehydrated 4, 4-diamino diphenyl sulfone DDS in a reaction container, and replacing the dried and dehydrated 4, 4-diamino diphenyl sulfone DDS by adopting nitrogen; adding triethylamine TEA and anhydrous acetonitrile by injection after replacement, and uniformly stirring; then adding the phenylphosphonic dichloride PD solution dissolved in anhydrous acetonitrile (through a constant pressure dropping funnel) into a reaction container, wherein the dropping time is 1-2 h; heating after dripping to perform heating reflux reaction;
b. cooling the reaction solution obtained in the step a to room temperature, filtering the precipitate, and washing the obtained precipitate by adopting acetonitrile to obtain a pale yellow solid product;
c. b, dissolving the pale yellow solid product obtained in the step b in dimethyl sulfoxide (DMSO), adding the solution into ethanol to separate out precipitate, filtering the precipitate, and washing with water to obtain a wet white solid product;
d. and c, placing the wet white solid product obtained in the step c into a vacuum oven for drying to obtain the white solid phosphorus-nitrogen-containing flame retardant.
According to the preparation method of the phosphorus-nitrogen-containing flame retardant, the molar ratio of the 4, 4-diamino diphenyl sulfone DDS to the triethylamine TEA in the step a is 1:18 to 30, wherein the molar ratio of the phenylphosphonic dichloride PD to the 4, 4-diamino diphenyl sulfone DDS is 1:2.05 to 2.2.
According to the preparation method of the phosphorus-nitrogen-containing flame retardant, when triethylamine TEA and anhydrous acetonitrile are added after the replacement in the step a, the volume mass ratio of the added anhydrous acetonitrile to 4, 4-diamino diphenyl sulfone DDS is 3-5 mL:1g.
According to the preparation method of the phosphorus-nitrogen-containing flame retardant, in the step a, the volume mass ratio of the anhydrous acetonitrile to the phenylphosphonic dichloride PD which is dissolved in the anhydrous acetonitrile is 4-8 mL:1g.
According to the preparation method of the phosphorus-nitrogen-containing flame retardant, when the reflux reaction is carried out in the step a, the reaction temperature is controlled to be 30-90 ℃ and the reaction time is controlled to be 3-12 h.
According to the preparation method of the phosphorus-nitrogen-containing flame retardant, when the flame retardant is placed in a vacuum oven for drying in the step d, the drying temperature is 120 ℃, and the drying time is 4 hours.
The phosphorus-nitrogen-containing flame retardant is applied to flame retardant nylon 66, nylon 6 or polycarbonate.
The invention has the positive beneficial effects that:
1. the phosphorus-nitrogen-containing flame retardant prepared by the technical scheme of the invention has the characteristics of high efficiency, environmental protection and acid and alkali washing resistance. The phosphorus-nitrogen synergistic flame retardant system in the flame retardant has high efficiency, the phenylphosphonic dichloride structure contains flame retardant element phosphorus, the benzene ring structure can promote the formation of carbon, and the 4, 4-Diamino Diphenyl Sulfone (DDS) contains flame retardant element nitrogen, so that a large amount of gas is generated in the combustion process, and the oxygen in the space is diluted, thereby playing a good flame retardant effect. The flame retardant has the advantages of no halogen, environmental protection, simple synthesis method and easy industrialized production, and the product prepared by adding the flame retardant can still keep better flame retardant property after acid/alkali washing.
2. The phosphorus-nitrogen-containing flame retardant prepared by the invention has the advantages of readily available raw materials, low cost, simple synthesis method, mild production conditions and higher product yield.
3. The phosphorus-nitrogen-containing flame retardant prepared by the invention has good flame retardant effect through phosphorus-nitrogen synergy, and the flame retardant performance of the product prepared by the phosphorus-nitrogen-containing flame retardant is not obviously reduced after acid/alkali washing.
4. The phosphorus-nitrogen-containing flame retardant prepared by the invention can be applied to nylon 66, nylon 6, polycarbonate and the like, and has a good flame retardant effect.
4. Description of the drawings:
FIG. 1 is an infrared spectrum of a phosphorus-nitrogen flame retardant of the product prepared in example 1 of the present invention.
FIG. 2 is a TGA graph of the phosphorus-nitrogen flame retardant added to nylon 66 of the product prepared in example 1 of the present invention.
FIG. 3 is a graph showing the comparison of the inventive product of application example 2 with pure nylon 66 after vertical burning.
FIG. 4 is a graph showing the comparison of the untreated product of the present invention, after acid washing treatment, after alkali washing treatment, and after vertical burning of pure nylon 66.
5. The specific embodiment is as follows:
the invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
Example 1:
the preparation method of the phosphorus-nitrogen-containing flame retardant comprises the following detailed steps:
a. drying and dehydrating 2.60g of 4, 4-diamino diphenyl sulfone DDS, and then placing the dried and dehydrated 4, 4-diamino diphenyl sulfone DDS in a three-neck flask, and replacing the dried and dehydrated 4, 4-diamino diphenyl sulfone DDS with nitrogen for three times; 2.02g of triethylamine TEA and 10mL of anhydrous acetonitrile are added after replacement, and stirring reaction is carried out for 1h at 60 ℃; 0.975g of phenylphosphonic dichloride PD is dissolved in 5mL of anhydrous acetonitrile, and the obtained solution is added into a three-neck flask through a constant pressure dropping funnel, wherein the dropping time is 1h; heating to 80 ℃ after dropwise adding, and carrying out reflux reaction for 8 hours under the protection of nitrogen;
b. cooling the reaction solution obtained in the step a to room temperature, filtering the precipitate, and washing the obtained precipitate by adopting acetonitrile to obtain a pale yellow solid product;
c. dissolving the pale yellow solid product obtained in the step b in dimethyl sulfoxide (DMSO), adding the solution into excessive ethanol to separate out precipitate, filtering the precipitate, and washing with water to obtain a wet white solid product;
d. and c, drying the wet white solid product obtained in the step c in a vacuum oven at 80 ℃ to constant weight to obtain the white solid phosphorus-nitrogen-containing flame retardant PDDDS with the yield of 94%.
The specific characterization of the product obtained in this example is shown in figure 1. The infrared spectrum of PDDDS does not contain P-Cl peak of PD, and shows signals of N-H (3230 cm-1), P=O (1198 cm-1), P-NH-Ph (1390 cm-1) and other parts, the absorption peak of N-H (3230 cm-1) is weak but convincing, and the generation of N-H bond indicates that the phosphonylation is completed, namely the phosphorus-nitrogen-containing flame retardant is successfully prepared.
Example 2:
the preparation method of the phosphorus-nitrogen-containing flame retardant comprises the following detailed steps:
a. drying and dehydrating 2.35g of 4, 4-diamino diphenyl sulfone DDS, and then placing the dried and dehydrated 4, 4-diamino diphenyl sulfone DDS in a three-neck flask, and replacing the dried and dehydrated 4, 4-diamino diphenyl sulfone DDS with nitrogen for three times; 2.02g of triethylamine TEA and 10mL of anhydrous acetonitrile are added after replacement, and stirring reaction is carried out for 1h at 60 ℃; 0.975g of phenylphosphonic dichloride PD is dissolved in 5mL of anhydrous acetonitrile, and the obtained solution is added into a three-neck flask through a constant pressure dropping funnel, wherein the dropping time is 1h; heating to 80 ℃ after dropwise adding, and carrying out reflux reaction for 8 hours under the protection of nitrogen;
b. cooling the reaction solution obtained in the step a to room temperature, filtering the precipitate, and washing the obtained precipitate by adopting acetonitrile to obtain a pale yellow solid product;
c. dissolving the pale yellow solid product obtained in the step b in dimethyl sulfoxide (DMSO), adding the solution into excessive ethanol to separate out precipitate, filtering the precipitate, and washing with water to obtain a wet white solid product;
d. and c, drying the wet white solid product obtained in the step c in a vacuum oven at 80 ℃ to constant weight to obtain the white solid phosphorus-nitrogen-containing flame retardant PDDDS with the yield of 73%.
Example 3:
the preparation method of the phosphorus-nitrogen-containing flame retardant comprises the following detailed steps:
a. drying and dehydrating 2.60g of 4, 4-diamino diphenyl sulfone DDS, and then placing the dried and dehydrated 4, 4-diamino diphenyl sulfone DDS in a three-neck flask, and replacing the dried and dehydrated 4, 4-diamino diphenyl sulfone DDS with nitrogen for three times; 2.02g of triethylamine TEA and 10mL of anhydrous acetonitrile are added after replacement, and stirring reaction is carried out for 1h at 60 ℃; 0.975g of phenylphosphonic dichloride PD is dissolved in 5mL of anhydrous acetonitrile, and the obtained solution is added into a three-neck flask through a constant pressure dropping funnel, wherein the dropping time is 1h; heating to 80 ℃ after dropwise adding, and carrying out reflux reaction for 4 hours under the protection of nitrogen;
b. cooling the reaction solution obtained in the step a to room temperature, filtering the precipitate, and washing the obtained precipitate by adopting acetonitrile to obtain a pale yellow solid product;
c. dissolving the pale yellow solid product obtained in the step b in dimethyl sulfoxide (DMSO), adding the solution into excessive ethanol to separate out precipitate, filtering the precipitate, and washing with water to obtain a wet white solid product;
d. and c, drying the wet white solid product obtained in the step c in a vacuum oven at 80 ℃ to constant weight to obtain the white solid phosphorus-nitrogen-containing flame retardant PDDDS with the yield of 46%.
Example 4:
the preparation method of the phosphorus-nitrogen-containing flame retardant comprises the following detailed steps:
a. drying and dehydrating 2.60g of 4, 4-diamino diphenyl sulfone DDS, and then placing the dried and dehydrated 4, 4-diamino diphenyl sulfone DDS in a three-neck flask, and replacing the dried and dehydrated 4, 4-diamino diphenyl sulfone DDS with nitrogen for three times; 2.02g of triethylamine TEA and 10mL of anhydrous acetonitrile are added after replacement, and stirring reaction is carried out for 1h at 60 ℃; 0.975g of phenylphosphonic dichloride PD is dissolved in 5mL of anhydrous acetonitrile, and the obtained solution is added into a three-neck flask through a constant pressure dropping funnel, wherein the dropping time is 1h; heating to 70 ℃ after dropwise adding, and carrying out reflux reaction for 8 hours under the protection of nitrogen;
b. cooling the reaction solution obtained in the step a to room temperature, filtering the precipitate, and washing the obtained precipitate by adopting acetonitrile to obtain a pale yellow solid product;
c. b, dissolving the pale yellow solid product obtained in the step b into dimethyl sulfoxide (DMSO), adding the solution into excessive ethanol to separate out precipitate, filtering the precipitate, and washing with water to obtain a wet white solid product;
d. and c, drying the wet white solid product obtained in the step c in a vacuum oven at 80 ℃ to constant weight to obtain the white solid phosphorus-nitrogen-containing flame retardant PDDDS with the yield of 81%.
Example 5:
the preparation method of the phosphorus-nitrogen-containing flame retardant comprises the following detailed steps:
a. drying and dehydrating 2.60g of 4, 4-diamino diphenyl sulfone DDS, and then placing the dried and dehydrated 4, 4-diamino diphenyl sulfone DDS in a three-neck flask, and replacing the dried and dehydrated 4, 4-diamino diphenyl sulfone DDS with nitrogen for three times; 2.02g of triethylamine TEA and 10mL of anhydrous acetonitrile are added after replacement, and stirring reaction is carried out for 1h at 60 ℃; 0.975g of phenylphosphonic dichloride PD is dissolved in 5mL of anhydrous acetonitrile, and the obtained solution is added into a three-neck flask through a constant pressure dropping funnel, wherein the dropping time is 1h; heating to 90 ℃ after dropwise adding, and carrying out reflux reaction for 8 hours under the protection of nitrogen;
b. cooling the reaction solution obtained in the step a to room temperature, filtering the precipitate, and washing the obtained precipitate by adopting acetonitrile to obtain a pale yellow solid product;
c. dissolving the pale yellow solid product obtained in the step b in dimethyl sulfoxide (DMSO), adding the solution into excessive ethanol to separate out precipitate, filtering the precipitate, and washing with water to obtain a wet white solid product;
d. and c, drying the wet white solid product obtained in the step c in a vacuum oven at 80 ℃ to constant weight to obtain the white solid phosphorus-nitrogen-containing flame retardant PDDDS with the yield of 88%.
Example 6:
the preparation method of the phosphorus-nitrogen-containing flame retardant comprises the following detailed steps:
a. drying and dehydrating 2.61g of 4, 4-diamino diphenyl sulfone DDS, and then placing the dried and dehydrated 4, 4-diamino diphenyl sulfone DDS in a three-neck flask, and replacing the dried and dehydrated 4, 4-diamino diphenyl sulfone DDS with nitrogen for three times; 2.02g of triethylamine TEA and 10mL of anhydrous acetonitrile are added after replacement, and stirring reaction is carried out for 1h at 60 ℃; 0.975g of phenylphosphonic dichloride PD is dissolved in 5mL of anhydrous acetonitrile, and the obtained solution is added into a three-neck flask through a constant pressure dropping funnel, wherein the dropping time is 1h; heating to 80 ℃ after dropwise adding, and carrying out reflux reaction for 8 hours under the protection of nitrogen;
b. cooling the reaction solution obtained in the step a to room temperature, filtering the precipitate, and washing the obtained precipitate by adopting acetonitrile to obtain a pale yellow solid product;
c. dissolving the pale yellow solid product obtained in the step b in dimethyl sulfoxide (DMSO), adding the solution into excessive ethanol to separate out precipitate, filtering the precipitate, and washing with water to obtain a wet white solid product;
d. and c, drying the wet white solid product obtained in the step c in a vacuum oven at 80 ℃ to constant weight to obtain the white solid phosphorus-nitrogen-containing flame retardant PDDDS with the yield of 96%.
Application example 1:
nylon 66, nylon 6 and polycarbonate were dried in a vacuum oven at 105 ℃ for 8 to 10 hours, then 100 parts of nylon 66 and the flame retardant prepared in example 1 of the present invention (1 part, 2 parts and 3 parts respectively) were granulated by twin-screw mixing, and 3mm thick bars were prepared by an injection molding machine after drying. The vertical burning test result shows that when the adding amount of the flame retardant is 1 part, the UL 94V-0 grade can be achieved; when the addition amount of the flame retardant is 2 parts, the UL 94V-0 grade can be achieved; when the flame retardant is added in an amount of 3 parts, the UL 94V-0 grade can be achieved. When the addition amount of the flame retardant is 1 part in the preparation of the 2mm thick spline, the UL 94V-1 grade can be achieved; when the addition amount of the flame retardant is 2 parts, the UL 94V-0 grade can be achieved; when the flame retardant is added in an amount of 3 parts, the UL 94V-0 grade can be achieved.
The TG diagram of the flame retardant/nylon 66 composite is shown in detail in fig. 2, and as can be seen from fig. 2, its high initial decomposition temperature and high char yield indicate that it has good thermal stability and potentially high flame retardancy.
Application example 2:
1 part, 1.25 parts and 1.5 parts of the flame retardant prepared in example 1 of the present invention and 100 parts of nylon 66 were respectively granulated by twin-screw mixing, dried and then prepared into 2mm bars by an injection molding machine. The vertical burning test result shows that when the adding amount of the flame retardant is 1 part, the UL 94V-1 grade can be achieved; when the addition amount of the flame retardant is 1.25 parts, the UL 94V-0 grade can be achieved; when the flame retardant is added in an amount of 1.5 parts, UL 94V-0 grade (see FIG. 3 for details) can be achieved. FIG. 3 is a graph showing the comparison of the product of application example 2 with pure nylon 66 after vertical burning. As can be seen from fig. 3, the phosphorus-nitrogen flame retardant has a better flame retardant effect when being added into nylon 66.
Application example 3:
1 part, 1.25 parts and 1.5 parts of the flame retardant prepared in example 6 of the present invention and 100 parts of nylon 66 were respectively granulated by twin-screw mixing, dried and then prepared into 2mm bars by an injection molding machine. The vertical burning test result shows that when the adding amount of the flame retardant is 1 part, the UL 94V-1 grade can be achieved; when the addition amount of the flame retardant is 1.25 parts, the UL 94V-0 grade can be achieved; when the flame retardant is added in an amount of 1.5 parts, UL 94V-0 grade can be achieved.
Application example 4:
1 part, 1.25 parts and 1.5 parts of the flame retardant prepared in example 1 of the present invention and 100 parts of nylon 6 were respectively granulated by twin-screw mixing, dried and then prepared into 2mm bars by an injection molding machine. The vertical burning test result shows that when the adding amount of the flame retardant is 1 part, the UL 94V-1 grade can be achieved; when the addition amount of the flame retardant is 1.25 parts, the UL 94V-0 grade can be achieved; when the flame retardant is added in an amount of 1.5 parts, UL 94V-0 grade can be achieved.
Application example 5:
1 part, 1.25 parts and 1.5 parts of the flame retardant prepared in example 6 of the present invention and 100 parts of nylon 6 were respectively granulated by twin-screw mixing, dried and then prepared into 2mm bars by an injection molding machine. The vertical burning test result shows that when the adding amount of the flame retardant is 1 part, the UL 94V-1 grade can be achieved; when the addition amount of the flame retardant is 1.25 parts, the UL 94V-0 grade can be achieved; when the flame retardant is added in an amount of 1.5 parts, UL 94V-0 grade can be achieved.
Application example 6:
1.25 parts of the flame retardant prepared in example 1 of the present invention and 100 parts of nylon 66 were granulated by twin-screw mixing, dried, and then prepared into 2mm bars by an injection molding machine, and the prepared bars were subjected to acid/alkali washing at 60 ℃ respectively, the results of which are shown in fig. 4 in detail. Fig. 4 is a graph showing the effects of untreated product, acid washing treatment, alkali washing treatment and vertical burning of pure nylon 66, and as can be seen from fig. 4, the flame retardant performance is not changed significantly.
Application example 7:
1.25 parts of the flame retardant prepared in the embodiment 1 of the invention and 100 parts of nylon 66 are mixed and granulated through a double screw, are dried and are spun into nylon flame-retardant fibers through a screw spinning machine, the prepared nylon flame-retardant fibers are woven into cloth samples through a loom, and the prepared cloth samples are respectively subjected to acid/alkali washing at 60 ℃. The acid/alkali washing test results show that the flame retardant property is not changed obviously.
Application example 8:
1.25 parts of the flame retardant prepared in the embodiment 6 of the invention and 100 parts of nylon 66 are mixed and granulated through a double screw, and are dried and spun into nylon flame-retardant fibers through a screw spinning machine, the prepared nylon flame-retardant fibers are woven into cloth samples through a loom, and the prepared cloth samples are respectively subjected to acid/alkali washing at 60 ℃ without obvious change of flame retardant property.
Claims (8)
1. The phosphorus-nitrogen-containing flame retardant is characterized by having a structural formula as follows:
2. a method for preparing a phosphorus-nitrogen-containing flame retardant, which is characterized by comprising the following steps:
a. drying and dehydrating 4, 4-diamino diphenyl sulfone DDS, and then placing the dried and dehydrated 4, 4-diamino diphenyl sulfone DDS in a reaction container, and replacing the dried and dehydrated 4, 4-diamino diphenyl sulfone DDS by adopting nitrogen; adding triethylamine TEA and anhydrous acetonitrile by injection after replacement, and uniformly stirring; then adding the phenylphosphonic dichloride PD solution dissolved in anhydrous acetonitrile into a reaction vessel, wherein the dropwise adding time is 1-2 h; heating after dripping to perform heating reflux reaction;
b. cooling the reaction solution obtained in the step a to room temperature, filtering the precipitate, and washing the obtained precipitate by adopting acetonitrile to obtain a pale yellow solid product;
c. b, dissolving the pale yellow solid product obtained in the step b in dimethyl sulfoxide (DMSO), adding the solution into ethanol to separate out precipitate, filtering the precipitate, and washing with water to obtain a wet white solid product;
d. and c, placing the wet white solid product obtained in the step c into a vacuum oven for drying to obtain the white solid phosphorus-nitrogen-containing flame retardant.
3. The method for preparing the phosphorus-nitrogen-containing flame retardant according to claim 2, wherein: the molar ratio of the 4, 4-diamino diphenyl sulfone DDS and triethylamine TEA added in the step a is 1:18 to 30, wherein the molar ratio of the phenylphosphonic dichloride PD to the 4, 4-diamino diphenyl sulfone DDS is 1:2.05 to 2.2.
4. The method for preparing the phosphorus-nitrogen-containing flame retardant according to claim 2, wherein: when triethylamine TEA and anhydrous acetonitrile are added after the replacement in the step a, the volume mass ratio of the added anhydrous acetonitrile to 4, 4-diamino diphenyl sulfone DDS is 3-5 mL:1g.
5. The method for preparing the phosphorus-nitrogen-containing flame retardant according to claim 2, wherein: in the step a, the volume mass ratio of the anhydrous acetonitrile to the phenylphosphonous dichloride PD is 4-8 mL:1g.
6. The method for preparing the phosphorus-nitrogen-containing flame retardant according to claim 2, wherein: and c, controlling the reaction temperature to be 30-90 ℃ and the reaction time to be 3-12 h during the reflux reaction in the step a.
7. The method for preparing the phosphorus-nitrogen-containing flame retardant according to claim 1, wherein: and d, when the materials are placed in a vacuum oven for drying, the drying temperature is 120 ℃ and the drying time is 4 hours.
8. Use of the phosphorus-nitrogen containing flame retardant of claim 1 to flame retardant nylon 66, nylon 6 or polycarbonate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311740708.6A CN117886854A (en) | 2023-12-18 | 2023-12-18 | Phosphorus-nitrogen-containing flame retardant and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311740708.6A CN117886854A (en) | 2023-12-18 | 2023-12-18 | Phosphorus-nitrogen-containing flame retardant and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117886854A true CN117886854A (en) | 2024-04-16 |
Family
ID=90641820
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311740708.6A Pending CN117886854A (en) | 2023-12-18 | 2023-12-18 | Phosphorus-nitrogen-containing flame retardant and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117886854A (en) |
-
2023
- 2023-12-18 CN CN202311740708.6A patent/CN117886854A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2557085B1 (en) | Novel phosphonamidates - synthesis and flame retardant applications | |
| CN107417912B (en) | Phosphorus-nitrogen-silicon intumescent flame retardant containing triazine ring and cage structure and synthesis method thereof | |
| CN107118347B (en) | " Trinity " expansion type flame retardant and its synthetic method | |
| Liu et al. | Synthesis and flame‐retardant properties of phosphorus‐containing polymers based on poly (4‐hydroxystyrene) | |
| US8852468B2 (en) | Phosphonate-substituted lignin as a flame retardant | |
| CN108299633B (en) | ferrocene-DOPO double-base polyester type flame-retardant smoke suppressant and preparation method thereof and application of ferrocene-DOPO double-base polyester type flame-retardant smoke suppressant in flame-retardant polymer | |
| CN100463952C (en) | Triazine ring combustion inhibitor containing phosphorus and its preparing process | |
| CN109135189B (en) | P/N/Si-containing multi-element polyphosphazene silazane flame retardant for epoxy resin and preparation method thereof | |
| CN105348326A (en) | N-P flameresistant material and preparation method thereof and application in textiles | |
| WO2020019596A1 (en) | Phosphazene compound, composition comprising phosphazene compound, flame retardant comprising same, and use thereof | |
| KR20150052138A (en) | Method for producing phosphorus-containing flame retardants | |
| CN110643066B (en) | Phosphorus-nitrogen flame retardant and preparation method thereof | |
| CN110670351B (en) | Synthesis and application of triazine derivative flame retardant | |
| Liu et al. | Synthesis and performance of three flame retardant additives containing diethyl phosphite/phenyl phosphonic moieties | |
| CN113861241A (en) | Bridged DOPO phosphorus-nitrogen flame retardant and preparation method and application thereof | |
| Wu et al. | Recent progress of DOPO-containing compounds as flame retardants for versatile polymeric materials | |
| CN109111570B (en) | Linear phosphorus-containing Schiff base charring agent and synthesis method thereof | |
| EP4215575A1 (en) | Halogen-free flame-retardant compounded system having resistance to high heat and high shear and high flame resistance, and application thereof | |
| CN107652324B (en) | Three-source-in-one expansion type fire retardant and its synthetic method and application | |
| CN117886854A (en) | Phosphorus-nitrogen-containing flame retardant and preparation method thereof | |
| CN106045928A (en) | Method for preparing triazine ring carbon-forming agent containing polyhydroxyl | |
| CN110903512B (en) | Efficient halogen-free phosphorus gas-phase flame retardant and high polymer material containing same | |
| CN114539620A (en) | Nitrogen-phosphorus synergistic flame retardant and preparation method and application thereof | |
| KR101143387B1 (en) | Organic Phosphorous-nitrogen compound having oxazolinone derivatives, preparation method thereof and flame retardant composition containing the same | |
| Long et al. | Synthesis and properties of a new halogen-free flame retardant for polyethylene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |