CN107417912B - Phosphorus-nitrogen-silicon intumescent flame retardant containing triazine ring and cage structure and synthesis method thereof - Google Patents
Phosphorus-nitrogen-silicon intumescent flame retardant containing triazine ring and cage structure and synthesis method thereof Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 49
- 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 46
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 title claims abstract description 32
- JQYOCVPEXWBLGO-UHFFFAOYSA-N [N].[Si].[P] Chemical compound [N].[Si].[P] JQYOCVPEXWBLGO-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000001308 synthesis method Methods 0.000 title description 5
- 239000002253 acid Substances 0.000 claims abstract description 28
- GTACSIONMHMRPD-UHFFFAOYSA-N 2-[4-[2-(benzenesulfonamido)ethylsulfanyl]-2,6-difluorophenoxy]acetamide Chemical compound C1=C(F)C(OCC(=O)N)=C(F)C=C1SCCNS(=O)(=O)C1=CC=CC=C1 GTACSIONMHMRPD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 101710130081 Aspergillopepsin-1 Proteins 0.000 claims abstract description 22
- 102100031007 Cytosolic non-specific dipeptidase Human genes 0.000 claims abstract description 22
- 239000011230 binding agent Substances 0.000 claims abstract description 22
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims abstract description 20
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 19
- 150000004985 diamines Chemical class 0.000 claims abstract description 17
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 16
- 239000011574 phosphorus Substances 0.000 claims abstract description 16
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 16
- 239000010703 silicon Substances 0.000 claims abstract description 16
- 238000001816 cooling Methods 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 239000007822 coupling agent Substances 0.000 claims abstract description 7
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000010992 reflux Methods 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims abstract description 3
- 238000010189 synthetic method Methods 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 48
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 48
- 125000001424 substituent group Chemical group 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- UOHMMEJUHBCKEE-UHFFFAOYSA-N prehnitene Chemical compound CC1=CC=C(C)C(C)=C1C UOHMMEJUHBCKEE-UHFFFAOYSA-N 0.000 claims description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 claims description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 claims description 2
- ZPZDIFSPRVHGIF-UHFFFAOYSA-N 3-aminopropylsilicon Chemical compound NCCC[Si] ZPZDIFSPRVHGIF-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 108010009736 Protein Hydrolysates Proteins 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- CTLDFURRFMJGON-UHFFFAOYSA-N dimethoxy-methyl-(3-piperazin-1-ylpropyl)silane Chemical compound CO[Si](C)(OC)CCCN1CCNCC1 CTLDFURRFMJGON-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 claims description 2
- KOVKEDGZABFDPF-UHFFFAOYSA-N n-(triethoxysilylmethyl)aniline Chemical compound CCO[Si](OCC)(OCC)CNC1=CC=CC=C1 KOVKEDGZABFDPF-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 description 15
- 230000001276 controlling effect Effects 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 238000002485 combustion reaction Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 150000003918 triazines Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 2
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- PVDVPOZEJCXUAM-UHFFFAOYSA-N acetonitrile;n,n-diethylethanamine Chemical compound CC#N.CCN(CC)CC PVDVPOZEJCXUAM-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 229920001276 ammonium polyphosphate Polymers 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
- C08G73/065—Preparatory processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention relates to a phosphorus-nitrogen-silicon intumescent flame retardant containing triazine ring and cage structure and a synthetic method thereof, comprising the following steps: adding a solvent into a container, adding phosphorus oxychloride, stirring and dispersing, and gradually dropwise adding 1-oxyphosphate-4-hydroxymethyl-2, 6, 7-trioxabicyclo [2.2.2] octane and an acid-binding agent to obtain a monobasic substitute containing PEPA; adding diamine or dihydric alcohol substances into another container, mixing with a solvent and an acid-binding agent, slowly dropwise adding a PEPA-containing monobasic substituent, and separating to obtain a phosphorus-containing diamine intermediate; adding a solvent into a container provided with a reflux condenser and the like, adding cyanuric chloride, stirring and dispersing, and gradually dropwise adding an aminosilane coupling agent and an acid-binding agent to obtain a silicon-containing monobasic substituent; slowly dripping a mixture of the phosphorus-containing diamine intermediate and an acid-binding agent into the monobasic substituent, cooling, washing and drying to obtain powdery solid, namely the phosphorus-nitrogen-silicon intumescent flame retardant containing the triazine ring and the cage structure. The carbon source has the advantages of certain polymerization degree, large molecular weight, proper proportion of an acid source, a carbon source and a gas source in a molecular structure, high carbon forming amount, good thermal stability and the like.
Description
Technical Field
The invention belongs to the technical field of environment-friendly halogen-free flame retardant products, and particularly relates to a phosphorus-nitrogen-silicon intumescent flame retardant containing triazine rings and cage structures and a synthesis method thereof.
Background
The polymer material has wide application, and brings convenience to production and life. However, their flammability limits their use in applications where flame retardancy is required, and therefore, flame retardancy modification of polymeric materials is one of the important aspects of their modification.
The halogen-containing flame retardant, especially the bromine-containing flame retardant has excellent flame retardant performance, but the flame retardant generates a large amount of dense smoke and corrosive gas during combustion, and has great environmental pollution. Based on the consideration of environmental protection, it is important to develop halogen-free flame retardant and reduce the toxic and harmful gases released during the combustion of the flame retardant. The Intumescent Flame Retardant (IFR) can form a compact carbon layer during combustion, plays a role in heat insulation and oxygen isolation, reduces the release of toxic and harmful gases and smoke, can effectively prevent the generation of molten drops in the combustion process of high polymer materials, and is considered as a green environment-friendly flame retardant with a very good application prospect. In the traditional intumescent flame retardant, the char-forming agent has high water solubility, easy migration and low thermal stability, and needs further improvement.
The triazine derivatives are compounds rich in tertiary nitrogen structures, and have excellent char-forming performance. The synthesis of the triazine derivatives usually uses cyanuric chloride as a starting material, and obtains the triazine derivatives with different purposes and properties by regulating and controlling reaction conditions; the synthesis process is simple and mature, is cheap and easy to obtain, and has cost advantage.
Most patents use triazine derivatives as char-forming agents, for example: JP patent No.0,583,065, Al (1994), patent ZL200510010243.4, a macromolecular triazine charring-foaming agent and a synthesis method thereof, and a triazine charring agent containing an aromatic chain structure and a preparation method thereof (publication No. CN 101586033A) are designed from different angles and modes to prepare the triazine charring agent, and have good effects. They can be applied to flame retardance of high molecular materials only by being compounded with ammonium polyphosphate and the like, and have no obvious flame retardance effect when being used alone.
Patent 201210002709.6 discloses the application of silicon-containing triazine char-forming agent in polypropylene, which has better flame retardant effect. Patent CN103980315B discloses a triazine ring-containing phosphorus-nitrogen-silicon compound and a preparation method thereof, the product concentrates phosphorus-nitrogen-silicon in one molecule, the flame-retardant synergistic effect is embodied, and chlorine exists in the compound, and the chlorine can be grafted to the surface of a fabric through reaction, so that the compound is suitable for flame-retardant treatment of the fabric. However, it is not suitable for use as an additive flame retardant in plastics, paints, and the like.
Therefore, the flame retardant is introduced with silicon, the strength of the formed carbon can be improved, and elements such as phosphorus, silicon and the like are introduced into the triazine ring, so that a better flame retardant effect is obtained.
In these patents and synthetic methods, there are problems that the ratio of acid source-carbon source and gas source is not suitable enough, and the char-forming property and flame retardant property need to be improved continuously, and therefore, there is a need to develop a flame retardant with better properties.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a phosphorus-silicon-nitrogen intumescent flame retardant containing triazine rings and cage structures, which has a certain degree of polymerization and a large molecular weight, and has the advantages of proper proportion of an acid source, a carbon source and a gas source in a molecular structure, high char formation amount and good thermal stability; it is also an object of the present invention to provide a process for the synthesis of phosphorus-silicon-nitrogen intumescent flame retardants containing triazine rings and cage structures.
In order to achieve the purpose of the invention, the phosphorus-nitrogen-silicon intumescent flame retardant containing triazine ring and cage structure is characterized in that the structural formula is as follows:
in the formula: y is NH or O;
r1 is one of linear or branched alkylene groups containing 1 to 18 carbons, or R1 is one of p-phenyl, m-phenyl or o-phenyl;
r2 is aminosilane coupling agent which is one of gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropylmethyldiethoxysilane, aminopropylsilane hydrolysate, gamma-aminopropylmethyldimethoxysilane, N-phenyl-gamma-aminopropyltrimethoxysilane, N- β - (aminoethyl) -gamma-aminopropylmethyldimethoxysilane, N-diethylaminopropyltrimethoxysilane, N-dimethylaminopropyltrimethoxysilane, N- β - (aminoethyl) -aminopropyltrimethoxysilane, N- β - (aminoethyl) -aminopropyltriethoxysilane, gamma-divinyltriaminopropylmethyldimethoxysilane, gamma-divinyltriaminopropyltrimethoxysilane, bis- (gamma-trimethoxysilylpropyl) amine, bis- (gamma-triethoxysilylpropyl) amine, gamma-piperazinylpropylmethyldimethoxysilane, N-phenylaminomethyltriethoxysilane, gamma-diethylaminomethyltriethoxysilane or their mixture.
In order to achieve the purpose of the invention, the synthesis method of the phosphorus-nitrogen-silicon intumescent flame retardant containing triazine ring and cage structure is characterized by comprising the following steps:
step one
Adding a solvent into a container, cooling to-10 ℃, adding phosphorus oxychloride (POCl 3), stirring and dispersing, gradually dropwise adding 1-oxyphosphate-4-hydroxymethyl-2, 6, 7-trioxabicyclo [2.2.2] octane (PEPA) and an acid-binding agent, and reacting for 1-4 hours to obtain a monobasic substituent (POCl 2-PEPA) containing PEPA; wherein the molar ratio of phosphorus oxychloride (POCl 3), 1-oxyphosphide-4-hydroxymethyl-2, 6, 7-trioxabicyclo [2.2.2] octane (PEPA) and the acid-binding agent is 1:1:1, 1mol of phosphorus oxychloride is dissolved in 50-500mL of solvent;
step two
Adding diamine or dihydric alcohol substances, a solvent and an acid-binding agent into another container, mixing, cooling to-10-10 ℃, slowly dropwise adding the monoprotic substituent (POCl 2-PEPA) containing PEPA obtained in the step one, reacting for 3-6 hours, and separating to obtain a phosphorus-containing diamine intermediate; wherein the mole ratio of the PEPA-containing monobasic substituent (POCl 2-PEPA), diamine or dihydric alcohol and the acid-binding agent is 1:2: 2-4; 1mol of PEPA-containing monobasic substituent (POCl 2-PEPA) with 50-500mL of solvent;
step three
Adding a solvent into a container provided with a reflux condenser, a stirrer and a constant-pressure dropping funnel, cooling to-10 ℃, adding cyanuric chloride (CNC), stirring and dispersing, gradually dropwise adding an aminosilane coupling agent and an acid-binding agent, controlling the pH to be 5-7, controlling the reaction temperature to be-5 ℃, and reacting for 1-4 hours to obtain a silicon-containing monobasic substituent (CNC-Si); wherein the molar ratio of cyanuric chloride (CNC), aminosilane coupling agent and acid-binding agent is 1:1:1, 1mol of cyanuric chloride is dissolved in 50-500mL of solvent;
step four
Slowly dripping the mixture of the phosphorus-containing diamine intermediate obtained in the step two and the acid-binding agent into the same container in the step three at the temperature of 40-50 ℃, reacting for 3-6 hours, then continuously heating to 80-130 ℃, reacting for 5-10 hours, cooling, washing and drying to obtain powdery solid, namely the phosphorus-nitrogen-silicon intumescent flame retardant containing the triazine ring and the cage structure; wherein the molar ratio of the silicon-containing monobasic substituent (CNC-Si), the phosphorus-containing intermediate and the acid-binding agent is 1:1: 2-3; 1mol of silicon-containing monobasic substituent (CNC-Si) was dissolved in 20-600mL of solvent.
In the technical scheme, the solvent is one or a mixture of acetone, acetonitrile, tetrahydrofuran, butanone, ethyl acetate, dioxane, chloroform, toluene, xylene, trimethylbenzene, tetramethylbenzene, dimethyl sulfoxide and N, N-dimethylformamide.
In the technical scheme, the acid-binding agent is one of triethylamine, triethylene diamine and pyridine.
Compared with the prior art, the invention has the advantages that:
1) the flame retardant is rich in phosphorus, can play a good role of an acid source and promotes the flame retardant to form carbon; the flame retardant contains a triazine ring structure and a cage-like structure of PEPA, has good char-forming capability, contains a silicon compound in the structure, can form a stronger char layer during combustion, and effectively combines an acid source, a carbon source and a gas source to exert an intramolecular flame-retardant synergistic effect;
2) the product is white or light yellow powder, the yield is more than 90 percent, and the decomposition temperature of 5 percent under the nitrogen atmosphere is more than 300 ℃;
3) the flame retardant has reasonable proportion of the acid source, the carbon source and the gas source, and the product has good thermal stability, char formation and flame retardant property and can form an expanded compact char layer with high strength during combustion.
Detailed Description
The following further describes the embodiments of the present invention. It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example one
The synthesis steps of the phosphorus-nitrogen-silicon intumescent flame retardant containing triazine ring and cage structure are as follows:
step one
Adding 250mL of acetonitrile into 1000mL of acetonitrile, cooling to-10 ℃, adding 153.33g (namely 1 mol) of phosphorus oxychloride (POCl 3), stirring and dispersing, gradually dropwise adding 180g (namely 1 mol) of 1-oxyphosphide-4-hydroxymethyl-2, 6, 7-trioxabicyclo [2.2.2] octane (PEPA) and 101.20g (1 mol) of triethylamine, and reacting for 4 hours to obtain a monobasic substituent (POCl 2-PEPA) containing PEPA;
step two
Adding 120.20g (2 mol) of ethylenediamine, 50mL of acetonitrile and 202.40g (2 mol) of triethylamine into another container, mixing, cooling to-10 ℃, slowly adding 296.83g (1 mol) of PEPA-containing monobasic substituent (POCl 2-PEPA) dropwise, reacting for 6 hours, and separating to obtain a phosphorus-containing diamine intermediate;
step three
Adding 184.5g (1 mol) of cyanuric chloride into a 1000mL three-neck flask provided with a reflux condenser, a stirrer and a constant pressure dropping funnel, then adding 200mL of acetonitrile, putting the three-neck flask into an oil bath, fully stirring to uniformly disperse the cyanuric chloride, dropwise adding 221.37 g (namely 1 mol) of gamma-aminopropyltriethoxysilane (KH 550) into the three-neck flask, dropwise adding 101.20g (1 mol) of triethylamine into the three-neck flask by using the constant pressure funnel, controlling the pH to be between 5 and 7, controlling the reaction temperature to be-5 ℃ and the reaction time to be 4 hours, and obtaining a silicon-containing monobasic substituent (CNC-Si) of the cyanuric chloride;
step four
344.03g (1 mol) of phosphorus-containing diamine intermediate obtained in the second step is dissolved in 200mL of acetonitrile, then the mixture is gradually dripped into a three-necked bottle containing cyanuric chloride and silicon-containing monobasic substituent (CNC-Si) in the third step, 101.20g (1 mol) of triethylamine is dripped at the same time, the reaction temperature is controlled at 40 ℃, the reaction is carried out for 6 hours, then the temperature is continuously raised to 80 ℃, 101.20g (1 mol) of triethylamine is dripped, the reaction is carried out for 10 hours, white precipitate is obtained, distilled water is washed and dried, white solid is obtained, 582.76 g of phosphorus-nitrogen-silicon intumescent flame retardant containing triazine rings and cage structures is obtained, and the yield is 91.0%.
In this embodiment, the structural formula of the phosphorus-nitrogen-silicon intumescent flame retardant containing a triazine ring and a cage structure is:
example two
The synthesis steps of the phosphorus-nitrogen-silicon intumescent flame retardant containing triazine ring and cage structure are as follows:
step one
Adding 300mL of acetonitrile into 1000mL of acetonitrile, cooling to 10 ℃, adding 153.33g (1 mol) of phosphorus oxychloride (POCl 3), stirring and dispersing, gradually dropwise adding 180g (1 mol) of 1-oxyphospho-4-hydroxymethyl-2, 6, 7-trioxabicyclo [2.2.2] octane (PEPA) and 101.20g (1 mol) of triethylamine acetonitrile solution, and reacting for 1 hour to obtain a monobasic substituent (POCl 2-PEPA) containing PEPA;
step two
Adding a mixture of 176.30g (2 mol) of butanediamine, 50mL of acetonitrile and 202.40g (2 mol) of triethylamine into another container, cooling to 10 ℃, slowly adding 296.83g (1 mol) of PEPA-containing monobasic substituent (POCl 2-PEPA) obtained in the step one dropwise, reacting for 3 hours, and separating to obtain a phosphorus-containing diamine intermediate;
step three
Adding 184.5g (1 mol) of cyanuric chloride into a 1000mL three-neck flask provided with a reflux condenser, a stirrer and a constant pressure dropping funnel, then adding 200mL of acetonitrile, putting the three-neck flask into an oil bath, fully stirring to uniformly disperse the cyanuric chloride, dropwise adding 179.3 g (namely 1 mol) of gamma-aminopropyltrimethoxysilane (KH 551) into the three-neck flask, dropwise adding 101.20g (1 mol) of triethylamine into the three-neck flask by using the constant pressure funnel, controlling the pH to be between 5 and 7, controlling the reaction temperature to be 10 ℃ and the reaction time to be 1 hour to obtain a silicon-containing monobasic substituent (CNC-Si) of the cyanuric chloride;
step four
358.03g (1 mol) of phosphorus-containing diamine intermediate obtained in the second step is dissolved in 150mL of acetonitrile, then the mixture is gradually dripped into a three-neck flask filled with a silicon-containing monobasic substituent (CNC-Si) in the third step, 101.20g (1 mol) of triethylamine is dripped at the same time, the reaction temperature is controlled at 50 ℃, the reaction is carried out for 3 hours, then the temperature is continuously raised to 130 ℃, 101.20g (1 mol) of triethylamine is dripped, the reaction is carried out for 5 hours, a white precipitate is obtained, distilled water is washed and dried, a white solid is obtained, 605.32 g of phosphorus-nitrogen-silicon intumescent flame retardant B containing triazine rings and cage structures is obtained, and the yield is 92.5%.
In this example, the structure formula of the phosphorus-nitrogen-silicon intumescent flame retardant containing triazine ring and cage structure is:
EXAMPLE III
The synthesis steps of the phosphorus-nitrogen-silicon intumescent flame retardant containing triazine ring and cage structure are as follows:
step one
Adding 300mL of acetonitrile into 1000mL of acetonitrile, cooling to 0 ℃, adding 153.33g (1 mol) of phosphorus oxychloride (POCl 3), stirring and dispersing, gradually dropwise adding 180g (1 mol) of 1-oxyphospho-4-hydroxymethyl-2, 6, 7-trioxabicyclo [2.2.2] octane (PEPA) and 101.20g (1 mol) of triethylamine, and reacting for 2.5 hours to obtain a monobasic substituent (POCl 2-PEPA) containing PEPA;
step two
Adding 120.20g (2 mol) of ethylenediamine, 50mL of acetonitrile and 202.40g (2 mol) of triethylamine into another container, mixing, cooling to 0 ℃, slowly adding a monobasic substitute (POCl 2-PEPA) containing 296.83g (1 mol) of PEPA obtained in the step one dropwise, reacting for 4.5 hours, and separating to obtain a phosphorus-containing diamine intermediate;
step three
Adding 184.5g (1 mol) of cyanuric chloride into a 1000mL three-neck flask provided with a reflux condenser, a stirrer and a constant pressure dropping funnel, then adding 200mL of acetone, putting the three-neck flask into an oil bath, fully stirring to uniformly disperse the cyanuric chloride, dropwise adding 191.34 g (1 mol) of gamma-aminopropyl methyl diethoxysilane (KH 552) into the three-neck flask, dropwise adding 101.20g (1 mol) of triethylamine into the three-neck flask by using the constant pressure funnel, controlling the pH value between 5 and 7, controlling the reaction temperature at 0 ℃ and the reaction time at 2.5 hours to obtain a silicon-containing monobasic substituent (CNC-Si) of the cyanuric chloride;
step four
344.03g (1 mol) of phosphorus-containing diamine intermediate obtained in the second step is dissolved in 250mL of acetonitrile, then the mixture is gradually dripped into a three-neck flask filled with a silicon-containing monobasic substituent (CNC-Si) in the third step, 101.20g (1 mol) of triethylamine is dripped at the same time, the reaction temperature is controlled at 45 ℃, the reaction is carried out for 4.5 hours, then the temperature is continuously raised to 105 ℃, 101.20g (1 mol) of triethylamine is dripped, the reaction is carried out for 7.5 hours, a white precipitate is obtained, distilled water is washed and dried, a white solid is obtained, 558.49g of triazine ring and cage-structured phosphorus-nitrogen-silicon intumescent flame retardant is obtained, and the yield is 91.5%.
In this example, the structure formula of the phosphorus-nitrogen-silicon intumescent flame retardant containing triazine ring and cage structure is:
structural formula 3 of phosphorus-nitrogen-silicon intumescent flame retardant C containing triazine ring and cage structure
The embodiments of the present invention have been described in detail, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention.
Claims (4)
1. A phosphorus-nitrogen-silicon intumescent flame retardant containing triazine rings and cage structures is characterized in that the structural formula is as follows:
in the formula: y is NH or O;
r1 is one of linear or branched alkylene groups containing 1 to 18 carbons, or R1 is one of p-phenyl, m-phenyl or o-phenyl;
r2 is aminosilane coupling agent which is one of gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropylmethyldiethoxysilane, aminopropylsilane hydrolysate, gamma-aminopropylmethyldimethoxysilane, N-phenyl-gamma-aminopropyltrimethoxysilane, N- β - (aminoethyl) -gamma-aminopropylmethyldimethoxysilane, N-diethylaminopropyltrimethoxysilane, N-dimethylaminopropyltrimethoxysilane, N- β - (aminoethyl) -aminopropyltrimethoxysilane, N- β - (aminoethyl) -aminopropyltriethoxysilane, gamma-divinyltriaminopropylmethyldimethoxysilane, gamma-divinyltriaminopropyltrimethoxysilane, bis- (gamma-trimethoxysilylpropyl) amine, bis- (gamma-triethoxysilylpropyl) amine, gamma-piperazinylpropylmethyldimethoxysilane, N-phenylaminomethyltriethoxysilane, gamma-diethylaminomethyltriethoxysilane or their mixture.
2. A synthetic method of a phosphorus-nitrogen-silicon intumescent flame retardant containing triazine rings and cage structures is characterized by comprising the following steps:
step one
Adding a solvent into a container, cooling to-10-10 ℃, adding phosphorus oxychloride, stirring and dispersing, gradually dropwise adding 1-oxyphosphate-4-hydroxymethyl-2, 6, 7-trioxabicyclo [2.2.2] octane and an acid-binding agent, and reacting for 1-4 hours to obtain a monobasic substitute containing PEPA; wherein the molar ratio of phosphorus oxychloride to 1-oxyphosphole-4-hydroxymethyl-2, 6, 7-trioxabicyclo [2.2.2] octane to the acid-binding agent is 1:1:1, 1mol of phosphorus oxychloride is added with 50-500mL of solvent;
step two
Adding diamine or dihydric alcohol substances, a solvent and an acid-binding agent into another container, mixing, cooling to-10-10 ℃, slowly dropwise adding the monoprotic substituent containing PEPA obtained in the step one, reacting for 3-6 hours, and separating to obtain a phosphorus-containing diamine intermediate; wherein the mole ratio of the PEPA-containing monobasic substituent, diamine or dihydric alcohol and the acid-binding agent is 1:2: 2-4; 1mol of PEPA-containing monobasic substitute is added with 50-500mL of solvent;
step three
Adding a solvent into a container provided with a reflux condenser, a stirrer and a constant-pressure dropping funnel, cooling to-10-10 ℃, adding cyanuric chloride, stirring and dispersing, gradually dropwise adding an aminosilane coupling agent and an acid-binding agent, controlling the pH to be 5-7, controlling the reaction temperature to be-5-5 ℃, and reacting for 1-4 hours to obtain a silicon-containing monobasic substituent; wherein the molar ratio of the cyanuric chloride to the aminosilane coupling agent to the acid-binding agent is 1:1:1, 1mol of the cyanuric chloride is dissolved in 50-500mL of solvent;
step four
Slowly dripping the phosphorus-containing diamine intermediate obtained in the step two into the same container in the step three at the temperature of 40-50 ℃, reacting with the mixture of the acid-binding agent for 3-6 hours, then continuously heating to 80-130 ℃, reacting for 5-10 hours, cooling, washing and drying to obtain powdery solid, namely the phosphorus-nitrogen-silicon intumescent flame retardant containing the triazine ring and the cage structure; wherein the molar ratio of the silicon-containing monobasic substituent to the phosphorus-containing intermediate to the acid-binding agent is 1:1: 2-3; 1mol of the silicon-containing monosubstituted substituent is dissolved in 20-600mL of solvent.
3. The method for synthesizing the triazine ring and cage structure containing phosphorus-nitrogen-silicon intumescent flame retardant of claim 2, wherein the solvent is one or a mixture of acetone, acetonitrile, tetrahydrofuran, butanone, ethyl acetate, dioxane, chloroform, toluene, xylene, trimethylbenzene, tetramethylbenzene, dimethyl sulfoxide and N, N-dimethylformamide.
4. The method for synthesizing the phosphorus-nitrogen-silicon intumescent flame retardant containing the triazine ring and the cage structure according to claim 2, wherein the acid-binding agent is one of triethylamine, triethylene diamine and pyridine.
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Correction item: Patentee|Address Correct: Shunde Vocational and Technical College|528300 Desheng East Road, Daliang, Shunde District, Foshan City, Guangdong Province False: Guangzhou Guangtong Technology Co.,Ltd.|510700 701, 7th Floor, Building 4, No. 20, Guanda Road, Yunpu Industrial Zone, Huangpu District, Guangzhou City, Guangdong Province Number: 17-01 Volume: 37 |