CN114437129B - Phosphorus-nitrogen synergistic flame retardant, flame-retardant nylon 6 resin and preparation method thereof - Google Patents
Phosphorus-nitrogen synergistic flame retardant, flame-retardant nylon 6 resin and preparation method thereof Download PDFInfo
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- CN114437129B CN114437129B CN202111666196.4A CN202111666196A CN114437129B CN 114437129 B CN114437129 B CN 114437129B CN 202111666196 A CN202111666196 A CN 202111666196A CN 114437129 B CN114437129 B CN 114437129B
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- 229920002292 Nylon 6 Polymers 0.000 title claims abstract description 137
- 239000003063 flame retardant Substances 0.000 title claims abstract description 125
- 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 121
- 229920005989 resin Polymers 0.000 title claims abstract description 78
- 239000011347 resin Substances 0.000 title claims abstract description 78
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 230000002195 synergetic effect Effects 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000003960 organic solvent Substances 0.000 claims abstract description 14
- 239000002262 Schiff base Substances 0.000 claims abstract description 10
- 150000004753 Schiff bases Chemical class 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- JWYUFVNJZUSCSM-UHFFFAOYSA-N 2-aminobenzimidazole Chemical compound C1=CC=C2NC(N)=NC2=C1 JWYUFVNJZUSCSM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 238000007259 addition reaction Methods 0.000 claims abstract description 6
- 238000006482 condensation reaction Methods 0.000 claims abstract description 6
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 claims abstract description 4
- QVTPWONEVZJCCS-UHFFFAOYSA-N 2-formylbenzonitrile Chemical compound O=CC1=CC=CC=C1C#N QVTPWONEVZJCCS-UHFFFAOYSA-N 0.000 claims abstract description 3
- 150000001412 amines Chemical class 0.000 claims abstract description 3
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 claims abstract 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 90
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 57
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 42
- 238000010992 reflux Methods 0.000 claims description 34
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 18
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 16
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 14
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 9
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 8
- 229960000583 acetic acid Drugs 0.000 claims description 8
- 239000012362 glacial acetic acid Substances 0.000 claims description 8
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 125000003277 amino group Chemical group 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- -1 aldehyde amine Chemical class 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- 230000009477 glass transition Effects 0.000 abstract description 24
- 239000002994 raw material Substances 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 46
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 24
- 229910052760 oxygen Inorganic materials 0.000 description 24
- 239000001301 oxygen Substances 0.000 description 24
- 238000000354 decomposition reaction Methods 0.000 description 23
- 239000008367 deionised water Substances 0.000 description 23
- 229910021641 deionized water Inorganic materials 0.000 description 23
- 229910052757 nitrogen Inorganic materials 0.000 description 23
- 239000000843 powder Substances 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 239000012299 nitrogen atmosphere Substances 0.000 description 22
- WZWIQYMTQZCSKI-UHFFFAOYSA-N 4-cyanobenzaldehyde Chemical class O=CC1=CC=C(C#N)C=C1 WZWIQYMTQZCSKI-UHFFFAOYSA-N 0.000 description 7
- XMNVHPRNQXBJDI-UHFFFAOYSA-N 4-formyl-2-methylbenzonitrile Chemical compound CC1=CC(C=O)=CC=C1C#N XMNVHPRNQXBJDI-UHFFFAOYSA-N 0.000 description 5
- 229920006391 phthalonitrile polymer Polymers 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- YPFQISHSXCFZMU-UHFFFAOYSA-N 5,6-dimethyl-1h-benzimidazol-2-amine Chemical compound C1=C(C)C(C)=CC2=C1NC(N)=N2 YPFQISHSXCFZMU-UHFFFAOYSA-N 0.000 description 4
- MZZZAWDOYQWKMR-UHFFFAOYSA-N 6-methyl-1h-benzimidazol-2-amine Chemical compound CC1=CC=C2N=C(N)NC2=C1 MZZZAWDOYQWKMR-UHFFFAOYSA-N 0.000 description 4
- DLBCZNBWXJPPER-UHFFFAOYSA-N 6-phenyl-1h-benzimidazol-2-amine Chemical compound C=1C=C2NC(N)=NC2=CC=1C1=CC=CC=C1 DLBCZNBWXJPPER-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000006006 cyclotrimerization reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 125000002467 phosphate group Chemical class [H]OP(=O)(O[H])O[*] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 238000005829 trimerization reaction Methods 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657172—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Abstract
The invention relates to a phosphorus-nitrogen synergistic flame retardant, flame retardant nylon 6 resin and a preparation method thereof. The preparation method of the flame retardant comprises the following steps: dissolving cyano benzaldehyde or derivatives thereof and amino benzimidazole or derivatives thereof in an organic solvent, dripping a catalyst, performing aldehyde-amine condensation reaction, dispersing the obtained Schiff base intermediate in the organic solvent, adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide DOPO, and performing addition reaction. The method is simple, and the raw materials are easy to obtain; the flame retardant has good thermal stability and high purity; the flame-retardant nylon 6 resin has better flame retardance, glass transition temperature, mechanical property and processability.
Description
Technical Field
The invention belongs to the field of halogen-free flame retardants and preparation thereof, and particularly relates to a phosphorus-nitrogen synergistic flame retardant, flame retardant nylon 6 resin and a preparation method thereof.
Background
Since the invention of nylon 6, the nylon has the advantages of high strength, wear resistance, self lubrication, heat resistance, corrosion resistance, easy processing and forming and the like, and is widely applied to various fields. However, its use is severely limited by its flammable nature (limiting oxygen index value LOI up to 21.5%, UL94 rating NR). In the combustion process, nylon 6 has fast flame propagation speed, high heat generation and high smoke generation, is accompanied with serious flame dripping phenomenon, is extremely easy to ignite other materials, has serious fire hidden danger, seriously threatens the life and property safety of human beings, and simultaneously causes non-negligible harm to the ecological environment. With the enhancement of environmental awareness, halogen flame retardants are gradually disabled, so that the development of halogen-free efficient flame retardants is a current research hotspot.
9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) is used as a novel phosphorus-containing flame-retardant intermediate, the derivative is quite numerous, and the synthesized flame retardant is halogen-free, smokeless, nontoxic, non-migrating and durable in flame retardant performance; due to the active phosphorus-hydrogen bonds, various derivatives can be prepared. Chinese patent CN101880395a discloses a method for preparing flame retardant by reacting DOPO modified aromatic dihydric phenol or dihydric alcohol with dichlorinated substituted phosphate, which is used for flame retarding of epoxy resin; chinese patent CN110157041B discloses a reactive flame retardant containing a di-DOPO group and nitrogen, and the reactive group on the molecule of the reactive flame retardant reacts with epoxy resin, so that the flame retardant property of the epoxy resin is effectively improved.
The DOPO derivative flame retardant related to the patent has good flame retardant performance, but the heat stability is insufficient, so that the subsequent processing of nylon 6 is difficult to meet, and the anti-dripping performance also needs to be enhanced.
Disclosure of Invention
The invention aims to solve the technical problem of providing a phosphorus-nitrogen synergistic flame retardant, flame retardant nylon 6 resin and a preparation method thereof, so as to overcome the defect of poor thermal stability and melt drip resistance of DOPO derivative flame retardants in the prior art.
The invention provides a phosphorus-nitrogen synergistic flame retardant, which has the following structural formula:
wherein R is 1 、R 2 Comprising hydrogen atoms, methyl groups, or cyano groups, R 3 、R 4 Including a hydrogen atom, a methyl group, or a phenyl group.
The invention also provides a preparation method of the phosphorus-nitrogen synergistic flame retardant, which comprises the following steps:
(1) Dissolving cyano benzaldehyde or derivatives thereof and amino benzimidazole or derivatives thereof in an organic solvent, dripping a catalyst, performing aldehyde-amine condensation reaction, precipitating, filtering and drying to obtain a Schiff base intermediate;
(2) Dispersing the Schiff base intermediate in the step (1) in an organic solvent, adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide DOPO, carrying out addition reaction, filtering, washing and drying to obtain the phosphorus-nitrogen synergistic flame retardant.
Preferably, the cyano group-containing benzaldehyde or derivative thereof in the step (1) has a structural formula:wherein R is 1 、R 2 Including a hydrogen atom, a methyl group, or a cyano group.
Preferably, the benzimidazole or derivative thereof containing an amino group in the step (1) has a structural formula:wherein R is 3 、R 4 Including a hydrogen atom, a methyl group, or a phenyl group.
Preferably, the mass ratio of the cyano group-containing benzaldehyde or derivative thereof and the amino group-containing benzimidazole or derivative thereof in the step (1) is 1:0.8 to 1:1.2.
preferably, the weight of the organic solvent in the step (1) is 5 to 20 times of the total weight of the cyano group-containing benzaldehyde or derivative thereof and the amino group-containing benzimidazole or derivative thereof.
Preferably, the weight of the catalyst in the step (1) is 0.1 to 0.5 times of the total weight of the cyano group-containing benzaldehyde or derivative thereof and the amino group-containing benzimidazole or derivative thereof.
Preferably, the organic solvent in the step (1) comprises one or more of methanol, ethanol and N, N-dimethylformamide.
Preferably, the catalyst in the step (1) comprises one or more of hydrochloric acid, glacial acetic acid and hydrofluoric acid.
Preferably, the aldehyde-amine condensation reaction in the step (1) is: heating to 60-80 deg.c and maintaining for 6-8 hr.
Preferably, the precipitation in step (1) is a precipitation in deionized water after cooling.
Preferably, the organic solvent in the step (2) comprises one or more of methanol, ethanol and N, N-dimethylformamide.
Preferably, the weight of the organic solvent in the step (2) is 5-10 times of the total weight of the Schiff base intermediate and DOPO.
Preferably, the mass ratio of schiff base intermediate to DOPO in step (2) is 1:0.8 to 1:1.2.
preferably, the addition reaction in the step (2) is as follows: heating to 60-80 ℃ and refluxing for 2-10 h.
The invention also provides a flame-retardant nylon 6 resin, which comprises the phosphorus-nitrogen synergistic flame retardant.
The invention also provides a preparation method of the flame-retardant nylon 6 resin, which comprises the following steps:
and drying the nylon 6 slice, and blending the dried nylon 6 slice with a phosphorus-nitrogen synergistic flame retardant by using a double-screw extruder to obtain the flame-retardant nylon 6 resin.
Preferably, the drying is: vacuum drying at 100-120 deg.c for 24-36 hr.
Preferably, the blending temperature is 240 to 260 ℃.
Preferably, the mass ratio of the dried nylon 6 chips to the phosphorus-nitrogen synergistic flame retardant is 92:8-96:4.
The invention firstly uses aldehyde-amine condensation reaction of the p-cyanobenzaldehyde derivative and the 2-aminobenzimidazole derivative to prepare the Schiff base intermediate, and then prepares the flame retardant with excellent flame retardant property through addition reaction with DOPO. The C=N and-NH in the benzimidazole structure of the flame retardant can form a hydrogen bond physical crosslinking network which is still molten with an amide bond in a nylon 6 main chain; the cyano group can generate a cyclic trimerization reaction under the flame response to generate a triazine ring chemical cross-linking network, and the reduction of melt viscosity is reduced under the action of the double cross-linking network, so that the nylon 6 has an anti-dripping effect.
Advantageous effects
The invention has simple synthetic route and easily obtained raw materials; the product has good thermal stability and high purity.
The UL94 index of the flame retardant nylon 6 is V-0 grade, and the LOI is about 32.0%.
The flame-retardant nylon 6 also exhibits higher glass transition temperature, better mechanical properties and good processability.
Drawings
FIG. 1 is a schematic representation of the reaction scheme of a phosphorus-nitrogen synergistic flame retardant intermediate of the present invention.
FIG. 2 is a schematic representation of the reaction scheme of the phosphorus-nitrogen synergistic flame retardant of the present invention.
FIG. 3 is a high resolution mass spectrum of the phosphorus-nitrogen synergistic flame retardant of example 1 of the present invention.
FIG. 4 is a thermogram of DOPO and phosphorus-nitrogen synergistic flame retardant (designated FR) in example 1 of the present invention.
Detailed Description
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents are intended to fall within the scope of the claims appended hereto.
The reagents involved in the invention are all reagent grade, and are directly used without purification.
The test standards of the breaking strength and the breaking elongation are GB/T1040.2-2006, and the test standards of the UL94 index and the limiting oxygen index are ASTM D3801 and ASTM D2863 respectively.
Example 1
Preparation of phosphorus-nitrogen synergistic flame retardant:
(1) 13.1g of p-cyanobenzaldehyde and 12.2g of 2-aminobenzimidazole were dissolved in 150mL of methanol in a three-necked flask equipped with a nitrogen inlet, a reflux condenser and a magnetic stirrer, then 4mL of hydrochloric acid was added dropwise thereto, the solution was heated to 60℃and held for 8 hours, cooled, precipitated in deionized water, filtered, and vacuum-dried to obtain an intermediate.
(2) 12.4g of the intermediate was dispersed with 150mL of methanol and poured into a three-necked flask, then 9.7g of DOPO was added, heated to 80℃and refluxed for 2 hours, filtered, washed 3 times with methanol, and dried in vacuo to give a white powder. The relative molecular weight test result of the white powder is shown in fig. 3, and the molecular weight measured by the high-resolution mass spectrum is consistent with the theoretical molecular weight of the flame retardant, so that the phosphorus-nitrogen synergistic flame retardant is proved to be successfully prepared; as shown in the figure 4, the initial decomposition temperature of the phosphorus-nitrogen synergistic flame retardant in nitrogen atmosphere is 346 ℃, which is far higher than the initial decomposition temperature of DOPO 191 ℃ and the processing temperature of PA6 (about 260 ℃), and the thermal stability of the prepared flame retardant is obviously improved, and the phosphorus-nitrogen synergistic flame retardant can be used as an additive flame retardant for improving the flame retardance of PA 6.
Preparing phosphorus-nitrogen synergistic flame retardant nylon 6 resin:
(3) Nylon 6 chips were vacuum dried at 120 ℃ for 24 hours and 92g of nylon 6 chips were blended with 8g of flame retardant using a twin screw extruder at 240 ℃ to give nylon 6 resin. The glass transition temperature of the obtained nylon 6 resin is 58 ℃, the breaking strength is 55.3+/-0.8 MPa, the breaking elongation is 70.3+/-1.6%, the limiting oxygen index is 32.0%, and the UL94 index is increased to V-0 level.
Example 2
Preparation of phosphorus-nitrogen synergistic flame retardant:
(1) In a three-necked flask equipped with a nitrogen inlet, a reflux condenser and a magnetic stirrer, 15.9g of 4-carbaldehyde-2, 6-dimethylbenzonitrile and 9.7g of 2-aminobenzimidazole were dissolved in 200mL of ethanol, then 6mL of hydrofluoric acid was added dropwise thereto, the solution was heated to 70℃and held for 7 hours, cooled, precipitated in deionized water, filtered, and dried under vacuum to obtain an intermediate.
(2) 15.3g of intermediate was dispersed with 200mL of ethanol and poured into a three-necked flask, then 10.8g of DOPO was added, heated to 70℃under reflux for 5 hours, filtered, washed with ethanol 4 times, and dried in vacuo to give a white powder having an initial decomposition temperature of 354℃in a nitrogen atmosphere.
Preparing phosphorus-nitrogen synergistic flame retardant nylon 6 resin:
(3) Nylon 6 chips were dried under vacuum at 110 ℃ for 30 hours, and 94g of nylon 6 chips were blended with 6g of flame retardant at 250 ℃ using a twin screw extruder to obtain nylon 6 resin. The glass transition temperature of the obtained nylon 6 resin is 59 ℃, the breaking strength is 58.3+/-0.3 MPa, the breaking elongation is 73.2+/-1.3%, the limiting oxygen index is 31.5%, and the UL94 index is increased to V-0 level.
Example 3
Preparation of phosphorus-nitrogen synergistic flame retardant:
(1) In a three-necked flask equipped with a nitrogen inlet, a reflux condenser and a magnetic stirrer, 14.5g of 4-cyano-3-methylbenzaldehyde and 14.6g of 2-aminobenzimidazole were dissolved in 250mLN, N-dimethylformamide, then 6mL of glacial acetic acid was added dropwise thereto, the solution was heated to 80℃and held for 6 hours, cooled, precipitated in deionized water, filtered, and dried under vacuum to obtain an intermediate.
(2) 15.4g of the intermediate was dispersed with 250mLN, N-dimethylformamide and poured into a three-necked flask, then 11.9g of DOPO was added, heated to 80℃and refluxed for 10 hours, filtered, washed 5 times with N, N-dimethylformamide, and dried in vacuo to give a white powder having an initial decomposition temperature of 335℃in a nitrogen atmosphere.
Preparing phosphorus-nitrogen synergistic flame retardant nylon 6 resin:
(3) Nylon 6 chips were vacuum dried at 100 ℃ for 36 hours, and 94g of nylon 6 chips were blended with 6g of flame retardant at 260 ℃ using a twin screw extruder to obtain nylon 6 resin. The glass transition temperature of the obtained nylon 6 resin is 58 ℃, the breaking strength is 57.9+/-0.5 MPa, the breaking elongation is 65.5+/-1.1%, the limiting oxygen index is 31.8%, and the UL94 index is increased to V-0 level.
Example 4
Preparation of phosphorus-nitrogen synergistic flame retardant:
(1) In a three-necked flask equipped with a nitrogen inlet, a reflux condenser and a magnetic stirrer, 15.6g of 4-carbaldehyde-1, 2-phthalonitrile and 13.4g of 2-aminobenzimidazole were dissolved in 150mL of methanol, then 4mL of hydrofluoric acid was dropped thereinto, the solution was heated to 80℃and kept for 8 hours, cooled, precipitated in deionized water, filtered, and vacuum-dried to obtain an intermediate.
(2) 12.4g of intermediate was dispersed with 150mL of methanol and poured into a three-necked flask, then 9.7g of DOPO was added, heated to 80℃and refluxed for 7 hours, filtered, washed 3 times with methanol, and dried in vacuo to give a white powder having an initial decomposition temperature of 342℃in a nitrogen atmosphere.
Preparing phosphorus-nitrogen synergistic flame retardant nylon 6 resin:
(3) Nylon 6 chips were vacuum dried at 120 ℃ for 24 hours and 96g of nylon 6 chips were blended with 4g of flame retardant at 250 ℃ using a twin screw extruder to obtain nylon 6 resin. The glass transition temperature of the obtained nylon 6 resin is 56 ℃, the breaking strength is 57.2+/-0.4 MPa, the breaking elongation is 70.2+/-1.2%, the limiting oxygen index is 30.0%, and the UL94 index is increased to V-0 level.
Example 5
Preparation of phosphorus-nitrogen synergistic flame retardant:
(1) 13.1g of p-cyanobenzaldehyde and 16.1g of 2-amino-5, 6-dimethylbenzimidazole were dissolved in 200mL of ethanol in a three-necked flask equipped with a nitrogen inlet, a reflux condenser and a magnetic stirrer, then 10mL of glacial acetic acid was added dropwise thereto, the solution was heated to 60℃and held for 8 hours, cooled, precipitated in deionized water, filtered, and dried under vacuum to obtain an intermediate.
(2) 12.7g of intermediate was dispersed with 200mL of ethanol and poured into a three-necked flask, then 10.8g of DOPO was added, heated to 80℃and refluxed for 10 hours, filtered, washed 3 times with ethanol, and dried in vacuo to give a white powder having an initial decomposition temperature of 328℃in a nitrogen atmosphere.
Preparing phosphorus-nitrogen synergistic flame retardant nylon 6 resin:
(3) Nylon 6 chips were vacuum dried at 120 ℃ for 24 hours and 96g of nylon 6 chips were blended with 4g of flame retardant at 240 ℃ using a twin screw extruder to give nylon 6 resin. The glass transition temperature of the obtained nylon 6 resin is 59 ℃, the breaking strength is 56.3+/-0.5 MPa, the breaking elongation is 73.3+/-1.0%, the limiting oxygen index is 30.2%, and the UL94 index is increased to V-0 level.
Example 6
Preparation of phosphorus-nitrogen synergistic flame retardant:
(1) In a three-necked flask equipped with a nitrogen inlet, a reflux condenser and a magnetic stirrer, 15.9g of 4-carbaldehyde-2, 6-dimethylbenzonitrile and 12.8g of 2-amino-5, 6-dimethylbenzimidazole were dissolved in 250mLN, N-dimethylformamide, then 10mL of hydrochloric acid was added dropwise thereto, the solution was heated to 60℃and held for 8 hours, cooled, precipitated in deionized water, filtered, and vacuum-dried to obtain an intermediate.
(2) 15.4g of the intermediate was dispersed with 250mLN, N-dimethylformamide and poured into a three-necked flask, then 11.9g of DOPO was added, heated to 80℃and refluxed for 3 hours, filtered, washed 3 times with N, N-dimethylformamide, and dried in vacuo to give a white powder having an initial decomposition temperature of 332℃in a nitrogen atmosphere.
Preparing phosphorus-nitrogen synergistic flame retardant nylon 6 resin:
(3) Nylon 6 chips were vacuum dried at 120 ℃ for 24 hours and 96g of nylon 6 chips were blended with 4g of flame retardant at 240 ℃ using a twin screw extruder to give nylon 6 resin. The glass transition temperature of the obtained nylon 6 resin is 57 ℃, the breaking strength is 55.2+/-0.5 MPa, the breaking elongation is 84.3+/-1.2%, the limiting oxygen index is 30.5%, and the UL94 index is increased to V-0 level.
Example 7
Preparation of phosphorus-nitrogen synergistic flame retardant:
(1) In a three-necked flask equipped with a nitrogen inlet, a reflux condenser and a magnetic stirrer, 14.5g of 4-cyano-3-methylbenzaldehyde and 19.3g of 2-amino-5, 6-dimethylbenzimidazole were dissolved in 150mL of methanol, then 4mL of hydrochloric acid was dropped thereto, the solution was heated to 60℃and held for 8 hours, precipitated in deionized water after cooling, filtered, and dried in vacuo to obtain an intermediate.
(2) 16.7g of the intermediate was dispersed with 150mL of methanol and poured into a three-necked flask, then 9.7g of DOPO was added, heated to 80℃under reflux for 6 hours, filtered, washed 3 times with methanol, and dried in vacuo to give a white powder having an initial decomposition temperature of 342℃under a nitrogen atmosphere.
Preparing phosphorus-nitrogen synergistic flame retardant nylon 6 resin:
(3) Nylon 6 chips were vacuum dried at 120 ℃ for 24 hours and 92g of nylon 6 chips were blended with 8g of flame retardant using a twin screw extruder at 240 ℃ to give nylon 6 resin. The glass transition temperature of the obtained nylon 6 resin is 60 ℃, the breaking strength is 51.7+/-0.9 MPa, the breaking elongation is 68.8+/-1.9%, the limiting oxygen index is 30.0%, and the UL94 index is increased to V-0 level.
Example 8
Preparation of phosphorus-nitrogen synergistic flame retardant:
(1) In a three-necked flask equipped with a nitrogen inlet, a reflux condenser and a magnetic stirrer, 15.6g of 4-carbaldehyde-1, 2-phthalonitrile and 14.5g of 2-amino-5, 6-dimethylbenzimidazole were dissolved in 200mL of ethanol, then 6mL of hydrofluoric acid was dropped thereinto, the solution was heated to 70℃and kept for 7 hours, cooled, precipitated in deionized water, filtered, and vacuum-dried to obtain an intermediate.
(2) 15.3g of the intermediate was dispersed with 200mL of ethanol and poured into a three-necked flask, then 10.8g of DOPO was added, heated to 70℃under reflux for 9 hours, filtered, washed with ethanol 4 times, and dried in vacuo to give a white powder having an initial decomposition temperature of 346℃in a nitrogen atmosphere.
Preparing phosphorus-nitrogen synergistic flame retardant nylon 6 resin:
(3) Nylon 6 chips were dried under vacuum at 110 ℃ for 30 hours, and 94g of nylon 6 chips were blended with 6g of flame retardant at 250 ℃ using a twin screw extruder to obtain nylon 6 resin. The glass transition temperature of the obtained nylon 6 resin is 58 ℃, the breaking strength is 54.2+/-0.9 MPa, the breaking elongation is 72.3+/-1.5%, the limiting oxygen index is 29.5%, and the UL94 index is increased to V-0 level.
Example 9
Preparation of phosphorus-nitrogen synergistic flame retardant:
(1) 13.1g of p-cyanobenzaldehyde and 14.7g of 2-amino-5-methylbenzimidazole were dissolved in 250mLN, N-dimethylformamide in a three-necked flask equipped with a nitrogen inlet, a reflux condenser and a magnetic stirrer, 6mL of glacial acetic acid was then added dropwise thereto, the solution was heated to 80℃and held for 6 hours, cooled, precipitated in deionized water, filtered, and dried under vacuum to obtain an intermediate.
(2) 13.4g of the intermediate was dispersed with 250mLN, N-dimethylformamide and poured into a three-necked flask, followed by addition of 11.9g of DOPO, heating to 80℃and refluxing for 8 hours, filtration, washing with N, N-dimethylformamide 5 times, and vacuum drying to give a white powder having an initial decomposition temperature of 329℃in a nitrogen atmosphere.
Preparing phosphorus-nitrogen synergistic flame retardant nylon 6 resin:
(3) Nylon 6 chips were vacuum dried at 100 ℃ for 36 hours, and 94g of nylon 6 chips were blended with 6g of flame retardant at 260 ℃ using a twin screw extruder to obtain nylon 6 resin. The glass transition temperature of the obtained nylon 6 resin is 58 ℃, the breaking strength is 56.3+/-1.1 MPa, the breaking elongation is 65.3+/-1.7%, the limiting oxygen index is 30.8%, and the UL94 index is increased to V-0 level.
Example 10
Preparation of phosphorus-nitrogen synergistic flame retardant:
(1) In a three-necked flask equipped with a nitrogen inlet, a reflux condenser and a magnetic stirrer, 15.9g of 4-carbaldehyde-2, 6-dimethylbenzonitrile and 11.8g of 2-amino-5-methylbenzimidazole were dissolved in 150mL of methanol, then 4mL of hydrofluoric acid was dropped thereinto, the solution was heated to 80℃and held for 8 hours, cooled, precipitated in deionized water, filtered, and vacuum-dried to obtain an intermediate.
(2) 13.9g of the intermediate was dispersed with 150mL of methanol and poured into a three-necked flask, then 9.7g of DOPO was added, heated to 80℃and refluxed for 7 hours, filtered, washed 3 times with methanol, and dried in vacuo to give a white powder having an initial decomposition temperature of 336℃in a nitrogen atmosphere.
Preparing phosphorus-nitrogen synergistic flame retardant nylon 6 resin:
(3) Nylon 6 chips were vacuum dried at 120 ℃ for 24 hours and 96g of nylon 6 chips were blended with 4g of flame retardant at 250 ℃ using a twin screw extruder to obtain nylon 6 resin. The glass transition temperature of the obtained nylon 6 resin is 57 ℃, the breaking strength is 53.2+/-1.0 MPa, the breaking elongation is 62.7+/-1.6%, the limiting oxygen index is 30.4%, and the UL94 index is increased to V-0 level.
Example 11
Preparation of phosphorus-nitrogen synergistic flame retardant:
(1) In a three-necked flask equipped with a nitrogen inlet, a reflux condenser and a magnetic stirrer, 14.5g of 4-cyano-3-methylbenzaldehyde and 17.6g of 2-amino-5-methylbenzimidazole were dissolved in 200mL of ethanol, then 10mL of glacial acetic acid was added dropwise thereto, the solution was heated to 60℃and held for 8 hours, precipitated in deionized water after cooling, filtered, and dried under vacuum to obtain an intermediate.
(2) 15.5g of intermediate was dispersed with 200mL of ethanol and poured into a three-necked flask, then 10.8g of DOPO was added, heated to 80℃and refluxed for 10 hours, filtered, washed 3 times with ethanol, and dried in vacuo to give a white powder having an initial decomposition temperature of 320℃in a nitrogen atmosphere.
Preparing phosphorus-nitrogen synergistic flame retardant nylon 6 resin:
(3) Nylon 6 chips were vacuum dried at 120 ℃ for 24 hours and 96g of nylon 6 chips were blended with 4g of flame retardant at 240 ℃ using a twin screw extruder to give nylon 6 resin. The glass transition temperature of the obtained nylon 6 resin is 59 ℃, the breaking strength is 56.5+/-0.7 MPa, the breaking elongation is 74.3+/-1.5%, the limiting oxygen index is 30.2%, and the UL94 index is increased to V-0 level.
Example 12
Preparation of phosphorus-nitrogen synergistic flame retardant:
(1) 15.6g of 4-carbaldehyde-1, 2-phthalonitrile and 16.1g of 2-amino-5-methylbenzimidazole were dissolved in 250mLN, N-dimethylformamide in a three-necked flask equipped with a nitrogen inlet, a reflux condenser and a magnetic stirrer, 10mL of hydrochloric acid was then added dropwise thereto, the solution was heated to 60℃and held for 8 hours, cooled, precipitated in deionized water, filtered, and dried under vacuum to obtain an intermediate.
(2) 14.4g of the intermediate was dispersed with 250mLN, N-dimethylformamide and poured into a three-necked flask, then 11.9g of DOPO was added, heated to 80℃and refluxed for 8 hours, filtered, washed 3 times with N, N-dimethylformamide, and dried in vacuo to give a white powder having an initial decomposition temperature of 330℃in a nitrogen atmosphere.
Preparing phosphorus-nitrogen synergistic flame retardant nylon 6 resin:
(3) Nylon 6 chips were vacuum dried at 120 ℃ for 24 hours and 96g of nylon 6 chips were blended with 4g of flame retardant at 240 ℃ using a twin screw extruder to give nylon 6 resin. The glass transition temperature of the obtained nylon 6 resin is 56 ℃, the breaking strength is 54.5+/-0.9 MPa, the breaking elongation is 75.5+/-1.9%, the limiting oxygen index is 29.9%, and the UL94 index is increased to V-0 level.
Example 13
Preparation of phosphorus-nitrogen synergistic flame retardant:
(1) 13.1g of p-cyanobenzaldehyde and 20.9g of 6-phenyl-1H-benzimidazol-2-amine were dissolved in 150mL of methanol in a three-necked flask equipped with a nitrogen inlet, a reflux condenser and a magnetic stirrer, then 4mL of hydrochloric acid was added dropwise thereto, the solution was heated to 60℃and kept for 8 hours, and after cooling, precipitated in deionized water, filtered, and dried under vacuum to obtain an intermediate.
(2) 16.4g of the intermediate was dispersed with 150mL of methanol and poured into a three-necked flask, then 9.7g of DOPO was added, heated to 80℃under reflux for 8 hours, filtered, washed 3 times with methanol, and dried in vacuo to give a white powder having an initial decomposition temperature of 336℃in a nitrogen atmosphere.
Preparing phosphorus-nitrogen synergistic flame retardant nylon 6 resin:
(3) Nylon 6 chips were vacuum dried at 120 ℃ for 24 hours and 92g of nylon 6 chips were blended with 8g of flame retardant using a twin screw extruder at 240 ℃ to give nylon 6 resin. The glass transition temperature of the obtained nylon 6 resin is 56 ℃, the breaking strength is 51.5+/-0.5 MPa, the breaking elongation is 67.1+/-1.4%, the limiting oxygen index is 30.6%, and the UL94 index is increased to V-0 level.
Example 14
Preparation of phosphorus-nitrogen synergistic flame retardant:
(1) In a three-necked flask equipped with a nitrogen inlet, a reflux condenser and a magnetic stirrer, 15.9g of 4-carbaldehyde-2, 6-dimethylbenzonitrile and 16.7g of 6-phenyl-1H-benzimidazol-2-amine were dissolved in 200mL of ethanol, 6mL of hydrofluoric acid was then dropped thereinto, the solution was heated to 70℃and kept for 7 hours, cooled, precipitated in deionized water, filtered, and vacuum-dried to obtain an intermediate.
(2) 18.3g of the intermediate was dispersed with 200mL of ethanol and poured into a three-necked flask, then 10.8g of DOPO was added, heated to 70℃under reflux for 9 hours, filtered, washed with ethanol 4 times, and dried in vacuo to give a white powder having an initial decomposition temperature of 329℃in a nitrogen atmosphere.
Preparing phosphorus-nitrogen synergistic flame retardant nylon 6 resin:
(3) Nylon 6 chips were dried under vacuum at 110 ℃ for 30 hours, and 94g of nylon 6 chips were blended with 6g of flame retardant at 250 ℃ using a twin screw extruder to obtain nylon 6 resin. The glass transition temperature of the obtained nylon 6 resin is 60 ℃, the breaking strength is 55.0+/-0.7 MPa, the breaking elongation is 69.9+/-1.7%, the limiting oxygen index is 31.5%, and the UL94 index is increased to V-0 level.
Example 15
Preparation of phosphorus-nitrogen synergistic flame retardant:
(1) 14.5g of 4-cyano-3-methylbenzaldehyde and 25.1g of 6-phenyl-1H-benzimidazol-2-amine were dissolved in 250mLN, N-dimethylformamide in a three-necked flask equipped with a nitrogen inlet, a reflux condenser and a magnetic stirrer, 6mL of glacial acetic acid was then added dropwise thereto, the solution was heated to 80℃and kept for 6 hours, cooled, precipitated in deionized water, filtered, and dried under vacuum to obtain an intermediate.
(2) 16.3g of the intermediate was dispersed with 250mLN, N-dimethylformamide and poured into a three-necked flask, followed by addition of 11.9g of DOPO, heating to 80℃and refluxing for 5 hours, filtration, washing with N, N-dimethylformamide 5 times, and vacuum drying to give a white powder having an initial decomposition temperature of 326℃in a nitrogen atmosphere.
Preparing phosphorus-nitrogen synergistic flame retardant nylon 6 resin:
(3) Nylon 6 chips were vacuum dried at 100 ℃ for 36 hours, and 94g of nylon 6 chips were blended with 6g of flame retardant at 260 ℃ using a twin screw extruder to obtain nylon 6 resin. The glass transition temperature of the obtained nylon 6 resin is 58 ℃, the breaking strength is 55.2+/-0.7 MPa, the breaking elongation is 71.4+/-1.2%, the limiting oxygen index is 31.2%, and the UL94 index is increased to V-0 level.
Example 16
Preparation of phosphorus-nitrogen synergistic flame retardant:
(1) In a three-necked flask equipped with a nitrogen inlet, a reflux condenser and a magnetic stirrer, 15.6g of 4-carbaldehyde-1, 2-phthalonitrile and 18.8g of 6-phenyl-1H-benzimidazol-2-amine were dissolved in 150mL of methanol, then 4mL of hydrofluoric acid was dropped thereinto, the solution was heated to 80℃and kept for 8 hours, cooled, precipitated in deionized water, filtered, and dried under vacuum to obtain an intermediate.
(2) 16.5g of the intermediate was dispersed with 150mL of methanol and poured into a three-necked flask, then 9.7g of DOPO was added, heated to 80℃and refluxed for 7 hours, filtered, washed 3 times with methanol, and dried in vacuo to give a white powder having an initial decomposition temperature of 341℃in a nitrogen atmosphere.
Preparing phosphorus-nitrogen synergistic flame retardant nylon 6 resin:
(3) Nylon 6 chips were vacuum dried at 120 ℃ for 24 hours and 96g of nylon 6 chips were blended with 4g of flame retardant at 250 ℃ using a twin screw extruder to obtain nylon 6 resin. The glass transition temperature of the obtained nylon 6 resin is 58 ℃, the breaking strength is 58.2+/-1.0 MPa, the breaking elongation is 65.3+/-1.8%, the limiting oxygen index is 30.5%, and the UL94 index is increased to V-0 level.
Example 17
Preparation of phosphorus-nitrogen synergistic flame retardant:
(1) 13.1g of p-cyanobenzaldehyde and 28.5g of 5, 6-diphenyl-1H-benzimidazol-2-amine were dissolved in 200mL of ethanol in a three-necked flask equipped with a nitrogen inlet, a reflux condenser and a magnetic stirrer, 10mL of glacial acetic acid was then added dropwise thereto, the solution was heated to 60℃and kept for 8 hours, cooled, precipitated in deionized water, filtered, and dried under vacuum to obtain an intermediate.
(2) 17.0g of the intermediate was dispersed with 200mL of ethanol and poured into a three-necked flask, then 10.8g of DOPO was added, heated to 80℃and refluxed for 10 hours, filtered, washed 3 times with ethanol, and dried in vacuo to give a white powder having an initial decomposition temperature of 351℃in a nitrogen atmosphere.
Preparing phosphorus-nitrogen synergistic flame retardant nylon 6 resin:
(3) Nylon 6 chips were vacuum dried at 120 ℃ for 24 hours and 96g of nylon 6 chips were blended with 4g of flame retardant at 240 ℃ using a twin screw extruder to give nylon 6 resin. The glass transition temperature of the obtained nylon 6 resin is 56 ℃, the breaking strength is 56.5+/-0.9 MPa, the breaking elongation is 69.8+/-1.6%, the limiting oxygen index is 30.2%, and the UL94 index is increased to V-0 level.
Example 18
Preparation of phosphorus-nitrogen synergistic flame retardant:
(1) In a three-necked flask equipped with a nitrogen inlet, a reflux condenser and a magnetic stirrer, 15.9g of 4-carbaldehyde-2, 6-dimethylbenzonitrile and 22.8g of 5, 6-diphenyl-1H-benzimidazol-2-amine were dissolved in 250mLN, N-dimethylformamide, then 10mL of hydrochloric acid was added dropwise thereto, the solution was heated to 60℃and held for 8 hours, cooled, precipitated in deionized water, filtered, and dried under vacuum to obtain an intermediate.
(2) 16.4g of the intermediate was dispersed with 250mLN, N-dimethylformamide and poured into a three-necked flask, followed by addition of 11.9g of DOPO, heating to 80℃and refluxing for 8 hours, filtration, washing with N, N-dimethylformamide 3 times, and vacuum drying to give a white powder having an initial decomposition temperature of 330℃in a nitrogen atmosphere.
Preparing phosphorus-nitrogen synergistic flame retardant nylon 6 resin:
(3) Nylon 6 chips were vacuum dried at 120 ℃ for 24 hours and 96g of nylon 6 chips were blended with 4g of flame retardant at 240 ℃ using a twin screw extruder to give nylon 6 resin. The glass transition temperature of the obtained nylon 6 resin is 58 ℃, the breaking strength is 54.8+/-0.9 MPa, the breaking elongation is 71.3+/-1.4%, the limiting oxygen index is 30.8%, and the UL94 index is increased to V-0 level.
Example 19
Preparation of phosphorus-nitrogen synergistic flame retardant:
(1) In a three-necked flask equipped with a nitrogen inlet, a reflux condenser and a magnetic stirrer, 14.5g of 4-cyano-3-methylbenzaldehyde and 34.2g of 5, 6-diphenyl-1H-benzimidazol-2-amine were dissolved in 150mL of methanol, 4mL of hydrochloric acid was then dropped thereto, the solution was heated to 60℃and maintained for 8 hours, cooled, precipitated in deionized water, filtered, and dried under vacuum to obtain an intermediate.
(2) 15.1 intermediate was dispersed with 150mL of methanol and poured into a three-necked flask, then 9.7g of DOPO was added, heated to 80℃under reflux for 10 hours, filtered, washed 3 times with methanol, and dried in vacuo to give a white powder having an initial decomposition temperature of 328℃in a nitrogen atmosphere.
Preparing phosphorus-nitrogen synergistic flame retardant nylon 6 resin:
(3) Nylon 6 chips were vacuum dried at 120 ℃ for 24 hours and 92g of nylon 6 chips were blended with 8g of flame retardant using a twin screw extruder at 240 ℃ to give nylon 6 resin. The glass transition temperature of the obtained nylon 6 resin is 61 ℃, the breaking strength is 54.9+/-1.1 MPa, the breaking elongation is 75.5+/-1.9%, the limiting oxygen index is 32.0%, and the UL94 index is increased to V-0 level.
Example 20
Preparation of phosphorus-nitrogen synergistic flame retardant:
(1) In a three-necked flask equipped with a nitrogen inlet, a reflux condenser and a magnetic stirrer, 15.6g of 4-carbaldehyde-1, 2-phthalonitrile and 31.3g of 5, 6-diphenyl-1H-benzimidazol-2-amine were dissolved in 200mL of ethanol, 6mL of hydrofluoric acid was then dropped thereinto, the solution was heated to 70℃and held for 7 hours, cooled, precipitated in deionized water, filtered, and vacuum-dried to obtain an intermediate.
(2) 15.3g of intermediate was dispersed with 200mL of ethanol and poured into a three-necked flask, then 10.8g of DOPO was added, heated to 70℃under reflux for 9 hours, filtered, washed with ethanol 4 times, and dried in vacuo to give a white powder having an initial decomposition temperature of 331℃in a nitrogen atmosphere.
Preparing phosphorus-nitrogen synergistic flame retardant nylon 6 resin:
(3) Nylon 6 chips were dried under vacuum at 110 ℃ for 30 hours, and 94g of nylon 6 chips were blended with 6g of flame retardant at 250 ℃ using a twin screw extruder to obtain nylon 6 resin. The glass transition temperature of the obtained nylon 6 resin is 58 ℃, the breaking strength is 57.3+/-0.5 MPa, the breaking elongation is 68.3+/-1.4%, the limiting oxygen index is 31.0%, and the UL94 index is increased to V-0 level.
Comparative example 1
Preparation of phosphorus-nitrogen synergistic flame retardant:
(1) 13.1g of p-cyanobenzaldehyde and 9.4g of aniline were dissolved in 150mL of methanol in a three-necked flask equipped with a nitrogen inlet, a reflux condenser and a magnetic stirrer, then 4mL of hydrochloric acid was added dropwise thereto, the solution was heated to 60℃and held for 8 hours, cooled, precipitated in deionized water, filtered, and dried under vacuum to obtain an intermediate.
(2) 19.3g of the intermediate was dispersed with 150mL of methanol and poured into a three-necked flask, then 9.7g of DOPO was added, heated to 80℃and refluxed for 2 hours, filtered, washed 3 times with methanol, and dried in vacuo to give a white powder having an initial decomposition temperature of 328℃in a nitrogen atmosphere.
Preparing phosphorus-nitrogen synergistic flame retardant nylon 6 resin:
(3) Nylon 6 chips were vacuum dried at 120 ℃ for 24 hours and 92g of nylon 6 chips were blended with 8g of flame retardant using a twin screw extruder at 240 ℃ to give nylon 6 resin. The glass transition temperature of the obtained nylon 6 resin is 55 ℃, the breaking strength is 52.3+/-0.8 MPa, the breaking elongation is 71.3+/-2.0%, the limiting oxygen index is 29.0%, and the UL94 index V-1 grade generates a large number of molten drops in the test process. Therefore, when the benzimidazole structure is absent, a hydrogen bond physical crosslinking network which is still present in melting cannot be formed, and the anti-dripping effect is damaged to a certain extent.
Comparative example 2
Preparation of phosphorus-nitrogen synergistic flame retardant:
(1) In a three-necked flask equipped with a nitrogen inlet, a reflux condenser and a magnetic stirrer, 10.6g of benzaldehyde and 9.4g of aminobenzimidazole were dissolved in 150mL of methanol, then 4mL of hydrochloric acid was added dropwise thereto, the solution was heated to 60℃and held for 8 hours, cooled, precipitated in deionized water, filtered, and vacuum-dried to obtain an intermediate.
(2) 18.0g of the intermediate was dispersed with 150mL of ethanol and poured into a three-necked flask, then 9.7g of DOPO was added, heated to 80℃and refluxed for 2 hours, filtered, washed 3 times with methanol, and dried in vacuo to give a white powder having an initial decomposition temperature of 325℃in a nitrogen atmosphere.
Preparing phosphorus-nitrogen synergistic flame retardant nylon 6 resin:
(3) Nylon 6 chips were vacuum dried at 120 ℃ for 24 hours and 92g of nylon 6 chips were blended with 8g of flame retardant using a twin screw extruder at 240 ℃ to give nylon 6 resin. The glass transition temperature of the obtained nylon 6 resin is 56 ℃, the breaking strength is 52.8+/-0.4 MPa, the breaking elongation is 69.6+/-1.8%, the limiting oxygen index is 28.3%, and the UL94 index is V-2 grade, so that a large amount of molten drops are generated and absorbent cotton is ignited in the test process. It was thus demonstrated that when the cyano structure is absent, the cyclotrimerization reaction cannot take place in combustion and thus a triazine ring chemical cross-linked network is formed, with a certain degree of disruption of the anti-droplet effect.
Claims (9)
1. The phosphorus-nitrogen synergistic flame retardant is characterized by having the following structural formula:
wherein R is 1 、R 2 Selected from hydrogen, methyl or cyano, R 3 、R 4 Selected from a hydrogen atom, a methyl group or a phenyl group.
2. A method for preparing the phosphorus-nitrogen synergistic flame retardant of claim 1, comprising the steps of:
(1) Dissolving cyano benzaldehyde or derivatives thereof and amino benzimidazole or derivatives thereof in an organic solvent, dripping a catalyst, performing aldehyde-amine condensation reaction, precipitating, filtering and drying to obtain a Schiff base intermediate; wherein the structural formula of the benzaldehyde or the derivative thereof containing cyano is as follows:wherein R is 1 、R 2 Selected from a hydrogen atom, a methyl group or a cyano group; the structural formula of the benzimidazole containing amino or the derivative thereof is as follows: />Wherein R is 3 、R 4 Selected from a hydrogen atom, a methyl group or a phenyl group;
(2) Dispersing the Schiff base intermediate in the step (1) in an organic solvent, adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide DOPO, carrying out addition reaction, filtering, washing and drying to obtain the phosphorus-nitrogen synergistic flame retardant.
3. The method according to claim 2, wherein the mass ratio of the cyano group-containing benzaldehyde or derivative thereof to the amino group-containing benzimidazole or derivative thereof in the step (1) is 1:0.8 to 1:1.2; the weight of the organic solvent is 5-20 times of the total weight of the benzaldehyde or the derivative thereof containing cyano groups and the benzimidazole or the derivative thereof containing amino groups; the weight of the catalyst is 0.1 to 0.5 times of the total weight of the benzaldehyde or the derivative thereof containing cyano groups and the benzimidazole or the derivative thereof containing amino groups.
4. The preparation method according to claim 2, wherein the organic solvent in the step (1) is one or more selected from methanol, ethanol, and N, N-dimethylformamide; the catalyst is one or more of hydrochloric acid, glacial acetic acid and hydrofluoric acid; the aldehyde amine condensation reaction is as follows: heating to 60-80 deg.c and maintaining for 6-8 hr.
5. The preparation method according to claim 2, wherein the organic solvent in the step (2) is one or more selected from methanol, ethanol, and N, N-dimethylformamide; the weight of the organic solvent is 5-10 times of the total weight of the Schiff base intermediate and DOPO; the mass ratio of the schiff base intermediate to the DOPO is 1:0.8 to 1:1.2.
6. the method according to claim 2, wherein the addition reaction in the step (2) is: heating to 60-80 ℃ and refluxing for 2-10 h.
7. A flame retardant nylon 6 resin comprising a phosphorus-nitrogen synergistic flame retardant prepared by the method of claim 2.
8. A method for preparing the flame retardant nylon 6 resin of claim 7, comprising the steps of:
and drying the nylon 6 slice, and blending the dried nylon 6 slice with a phosphorus-nitrogen synergistic flame retardant by using a double-screw extruder to obtain the flame-retardant nylon 6 resin.
9. The method of claim 8, wherein the blending temperature is 240-260 ℃; the mass ratio of the dried nylon 6 slice to the phosphorus-nitrogen synergistic flame retardant is 92:8-96:4.
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| CN115651359A (en) * | 2022-10-14 | 2023-01-31 | 南京工业大学 | Preparation method of epoxy resin composite material with excellent transparency, mechanics, hydrophobicity and flame retardance |
Citations (1)
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| CN110734462A (en) * | 2019-09-14 | 2020-01-31 | 武汉工程大学 | Synthesis and application of nitrogen-phosphorus efficient flame retardants containing benzimidazole structure |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110734462A (en) * | 2019-09-14 | 2020-01-31 | 武汉工程大学 | Synthesis and application of nitrogen-phosphorus efficient flame retardants containing benzimidazole structure |
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| Huo Siqi,et al.Sythesis of a phosphaphenanthrene/benzimidazole-based curing agent and its application in flame-retardant.《Polymer Degradation and Stability》.2019,第163卷第100-109页. * |
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