CN116376035A - Hyperbranched flame retardant containing MOFs and preparation method thereof - Google Patents
Hyperbranched flame retardant containing MOFs and preparation method thereof Download PDFInfo
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- CN116376035A CN116376035A CN202310284991.XA CN202310284991A CN116376035A CN 116376035 A CN116376035 A CN 116376035A CN 202310284991 A CN202310284991 A CN 202310284991A CN 116376035 A CN116376035 A CN 116376035A
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 82
- 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 77
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 13
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 claims description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- -1 diamine compound Chemical class 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- 239000003495 polar organic solvent Substances 0.000 claims description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 238000007142 ring opening reaction Methods 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 6
- 125000003277 amino group Chemical group 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 239000012716 precipitator Substances 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000013179 MIL-101(Fe) Substances 0.000 claims description 4
- 239000013206 MIL-53 Substances 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 239000013207 UiO-66 Substances 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical group CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 claims description 3
- 125000004193 piperazinyl group Chemical group 0.000 claims description 3
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- PISLZQACAJMAIO-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine Chemical compound CCC1=CC(C)=C(N)C(CC)=C1N PISLZQACAJMAIO-UHFFFAOYSA-N 0.000 claims description 2
- RLYCRLGLCUXUPO-UHFFFAOYSA-N 2,6-diaminotoluene Chemical compound CC1=C(N)C=CC=C1N RLYCRLGLCUXUPO-UHFFFAOYSA-N 0.000 claims description 2
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 claims description 2
- HVCNXQOWACZAFN-UHFFFAOYSA-N 4-ethylmorpholine Chemical compound CCN1CCOCC1 HVCNXQOWACZAFN-UHFFFAOYSA-N 0.000 claims description 2
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- 239000013177 MIL-101 Substances 0.000 claims description 2
- 239000013178 MIL-101(Cr) Substances 0.000 claims description 2
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 claims description 2
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 150000004985 diamines Chemical class 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 239000011159 matrix material Substances 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- BLPURQSRCDKZNX-UHFFFAOYSA-N 2,4,6-tris(oxiran-2-ylmethoxy)-1,3,5-triazine Chemical compound C1OC1COC(N=C(OCC1OC1)N=1)=NC=1OCC1CO1 BLPURQSRCDKZNX-UHFFFAOYSA-N 0.000 abstract 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract 1
- 239000000654 additive Substances 0.000 abstract 1
- 230000000996 additive effect Effects 0.000 abstract 1
- 230000007547 defect Effects 0.000 abstract 1
- 229910052698 phosphorus Inorganic materials 0.000 abstract 1
- 239000011574 phosphorus Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 10
- 238000012360 testing method Methods 0.000 description 7
- 239000003822 epoxy resin Substances 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229920000587 hyperbranched polymer Polymers 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000000979 retarding effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DDPRYTUJYNYJKV-UHFFFAOYSA-N 1,4-diethylpiperazine Chemical compound CCN1CCN(CC)CC1 DDPRYTUJYNYJKV-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001291 vacuum drying 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
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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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 provides a nitrogen-containing hyperbranched flame retardant containing MOFs and a preparation method thereof, wherein specific MOFs, diamino compounds and triglycidyl cyanurate are taken as hyperbranched base structures, the defects of poor compatibility between an additive flame retardant and a matrix, low flame retardant efficiency, loss in the using process and the like are overcome, and when a high polymer is flame-retardant, a small amount of MOFs-containing hyperbranched flame retardant is compounded with a phosphorus-containing flame retardant, so that a higher flame retardant effect is achieved due to the expansion type flame retardant effect and the synergistic catalysis effect.
Description
Technical Field
The invention relates to the technical field of flame retardants, in particular to a hyperbranched flame retardant containing MOFs, and a preparation method and application thereof.
Background
Triglycidyl isocyanurate (TGIC) is a heterocyclic polyepoxy compound with good heat resistance, weatherability, adhesion and excellent high temperature properties. TGIC is mainly used as a curing agent for carboxyl group-containing polyesters, carboxyl group-containing acrylic resin powder coatings, and TGIC of high purity is generally used for manufacturing adhesives, electric insulation laminates, plastic stabilizers, and the like. TGIC is widely used to prepare precursors of nitrogen-containing compounds in intumescent flame retardants due to its high nitrogen content and characteristic epoxy groups.
Metal Organic Frameworks (MOFs) are an ordered crystalline framework created by self-assembly of metal ions and organic ligands. Because of the characteristics of large specific surface area, regular pore structure, adjustable surface chemical property and the like, the porous material is widely applied to the fields of gas storage, catalysis, separation, drug delivery and the like. In recent years, MOF materials have been widely used as new flame retardants for various polymers due to their high thermal stability. MOFs have a rich variety of transition metals, flame retardant elements and potential carbon sources, and are easily tunable in structure and properties, making MOFs and their derivatives and MOF hybrids promising for flame retardant research. MOFs (metal organic framework materials) are combined with gas sources at the nanometer level based on a modification strategy of MOF, which is very beneficial for researchers to quickly grasp the latest developments in this field.
The hyperbranched polymer is a macromolecule with a high three-dimensional structure and high branching, and the hyperbranched polymer intumescent flame retardant in the prior art has the problems of low nitrogen content, weak carbon forming capability and low flame retardant efficiency, so that the MOFs structure is introduced into the hyperbranched flame retardant, and the problems of the prior flame retardant are hopeful to be solved.
Chinese patent publication No. CN104262680B discloses a hyperbranched intumescent flame retardant and a preparation method thereof, wherein AB is prepared by the reaction of phthalic anhydride, diethanolamine and the like 2 The monomer improves the flame retardant efficiency of the flame retardant, but the component arrangement does not contain MOFs and is not optimized.
Disclosure of Invention
The invention provides a hyperbranched flame retardant containing MOFs, and a preparation method and application thereof.
In order to solve the technical problems, the invention is realized by the following technical scheme:
a hyperbranched flame retardant containing MOFs, which has a structure shown in a formula I:
in the formula I, Y is-NH-or-N-, R is piperazine ring or branched chain alkylene containing 1-30 carbon atoms, aryl and polycyclic aromatic hydrocarbon,
is an extension of hyperbranched structures, ō is MOFs structure containing amino groups.
The preparation method of the hyperbranched flame retardant containing MOFs comprises the following steps:
(1) In the environment of inert gas, diamine compound is dissolved in polar organic solvent, then catalyst is added, and then the temperature is raised to 70-150 ℃.
(2) Dissolving triglycidyl isocyanurate in a polar organic solvent, slowly adding the polar organic solvent into the mixed solution obtained in the step (1), carrying out ring-opening reaction under the protection of inert gas, maintaining the ring-opening reaction temperature of 80-150 ℃, and reacting for 8-24 hours under the condition of stirring to obtain the nitrogenous hyperbranched flame retardant.
(3) Adding MOFs material containing amino into the nitrogen-containing hyperbranched flame retardant obtained in the step (2), and continuously stirring for 8-24 hours to carry out end-capping reaction; then adding a precipitator, performing solid-liquid separation, water washing and drying to obtain the MOFs hyperbranched flame retardant with the structure shown in the formula I.
Preferably, the diamine compound is one or a mixture of several of piperazine, ethylenediamine, hydroxyethyl ethylenediamine, 3-diamino diphenyl sulfone, diethyl toluene diamine, 2, 6-toluene diamine, N-amino ethyl piperazine, N-dimethyl-1, 3-propane diamine, diamino diphenyl methane or diamino diphenyl sulfone.
Preferably, the catalyst is N, N-dimethylcyclohexylamine, bis (2-dimethylaminoethyl) ether, N, N, N ', N' -tetramethylalkylenediamine, N, N-dimethylbenzylamine, triethylamine, N-ethylmorpholine, N, N '-diethylpiperazine, N, N' -dimethylpyridine or pyridine.
Preferably, the amino group-containing MOFs structure is an amino group-containing metal organic framework material, which is NH 2 -UiO-66(Zr)、NH 2 -UiO-66(Hf)、NH 2 -MIL-53(Fe)、NH 2 -MIL-101(Fe)、NH 2 -MIL-53(Al)、NH 2 -MIL-101(Al)、NH 2 MIL-101 (Cr) or NH 2 -one or more of MILs-125 (Ti); the end capping reaction is to end cap the hyperbranched flame retardant through epoxy ring-opening reaction of amino.
Preferably, the polar organic solvent is acetonitrile, dichloroethane, chloroform, dimethylformamide or dimethyl sulfoxide.
Preferably, the mol ratio of triglycidyl isocyanurate to diamine compound is (2.5-10): 1-2; the mass ratio of triglycidyl isocyanurate and diamine compound to MOFs material containing amino is (3-5): 1.
Preferably, the inert gas is one or more of nitrogen, argon or helium.
Preferably, the precipitator in the step (3) is water, a reaction product obtained by the end-capping reaction and the water are precipitated, and then solid-liquid separation, water washing and drying are sequentially carried out, so that the nitrogen-containing hyperbranched flame retardant with the structure shown in the formula I is obtained.
An application method of a hyperbranched flame retardant containing MOFs, in particular to an application of the hyperbranched flame retardant containing MOFs in the flame retardant field.
In the present invention, when the diamine compound and the MOFs are a mixture, the proportion of each substance in the mixture is not particularly limited except for the specific limitation of the present invention, and a mixture of any proportion may be used. The source of the diamine compound is not particularly limited except for the specific limitation, and commercially available products known to those skilled in the art may be used.
In the present invention, the principle of the ring-opening reaction is the following reaction equation:
in the reaction equation, Y is-NH-or-N-, R is piperazine ring or branched chain alkylene group, aryl group or polycyclic aromatic hydrocarbon group containing 1-30 carbon atoms, and ō is MOFs structure containing amino.
After the precipitation is completed, the solid-liquid separation is carried out on the precipitated system to obtain a solid product. The specific mode of the solid-liquid separation in the present invention is not particularly limited, and a solid-liquid separation mode well known to those skilled in the art may be adopted, and specifically, filtration is performed.
After the solid product is obtained, the solid product is preferably subjected to water washing to obtain a water washing product. The number of times of washing and the amount of water used in the present invention are not particularly limited.
After the aqueous product is obtained, the water washing product is preferably dried to obtain the nitrogenous hyperbranched flame retardant. The specific mode of the drying is not particularly limited, and a drying mode well known to those skilled in the art can be adopted, and specifically, the drying is preferably carried out at 50 ℃ for 2-10 hours in vacuum.
The invention also provides an application of the hyperbranched flame retardant containing MOFs in the flame retardant field, more preferably an application of the hyperbranched flame retardant containing MOFs in flame retardant resin, wherein the hyperbranched flame retardant containing MOFs is prepared by the technical scheme or the preparation method of any one of the technical scheme.
In the invention, the mass fraction of the MOFs-containing hyperbranched flame retardant in the polymer material is preferably 5-15%.
The beneficial effects of the invention are as follows:
according to the invention, the MOFs material containing amino is taken as a core newly-added structure to form the nitrogen-containing hyperbranched flame retardant containing MOFs, so that the flame retardant grade of the formed flame retardant material can basically reach V0 grade (at least over V1), the Limiting Oxygen Index (LOI) can reach more than 32, and the optimal implementation mode can reach more than 37 (the Limiting Oxygen Index (LOI) of the polyolefin material is conventionally 21), thereby greatly improving the flame retardant performance.
The preparation method specifically provided by the invention has mild reaction conditions, the preparation process is easy to realize, and meanwhile, the high polymer material can be endowed with good flame retardant property. The hyperbranched flame retardant has high nitrogen content, can be used as a good air source of an intumescent flame retardant and a synergistic flame retardant, and has high-efficiency flame retardant effect in materials such as epoxy resin, polyolefin and the like.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The MOFs-containing hyperbranched flame retardant, the preparation method and the application thereof provided by the invention are described in detail below with reference to examples, but are not to be construed as limiting the scope of the invention.
Example 1
Dissolving 0.52mol of anhydrous piperazine in 250mL of acetonitrile and adding into a 500mL three-port bottle provided with a reflux condenser, a constant pressure dropping funnel and a stirrer, adding 0.01mol of triethylamine, heating the system to 85 ℃, dissolving 0.25mol of triglycidyl isocyanurate (TAIC) in 100mL of acetonitrile and dropwise adding into the system, regulating the maintaining temperature to 85 ℃ under the protection of nitrogen and maintaining mechanical stirring for 8 hours, adding 25gNH 2 MIL-101 (Fe) continuously stirring for 8 hours, then adding 200mL of water as a precipitator, stopping stirring, carrying out suction filtration while the mixture is hot, washing the mixture with water for 3 times, and carrying out vacuum drying at 90 ℃ for 8 hours to obtain the MOFs-containing hyperbranched flame retardant.
Comparative example 1
The comparative example was not added with "NH 2 The procedure of MIL-101 (Fe) "was the same as in example 1. The results are shown in Table 2.
Example 2
Dissolving 0.5mol of ethylenediamine in 300mL of dimethyl sulfoxide, adding into a 500mL three-necked flask equipped with a reflux condenser, a constant pressure dropping funnel and a stirrer, adding 0.01mol of triethylamine, heating the system to 120 ℃, dissolving 0.20mol of triglycidyl isocyanurate (TAIC) in 100mL of dimethylformamide, dropwise adding into the system, maintaining 120 ℃ under nitrogen protection, regulating stirring for 10 hours, adding 15gNH 2 MIL-125 (Ti), stirring continuously for 10 hours, adding 100mL of water as a precipitator, stopping stirring, filtering while hot, washing with water for 6 times, and drying in vacuum at 80 ℃ for 8 hours to obtain the MOFs-containing hyperbranched flame retardant.
Comparative example 2
The comparative example was not added with "NH 2 The procedure of MIL-125 (Ti) ", and the other steps were the same as those of example 2. The results are shown in Table 2.
Example 3
Dissolving 0.5mol of diaminodiphenylmethane in 300mL of chloroform, adding the mixture into a 500mL three-necked flask equipped with a reflux condenser, a constant pressure dropping funnel and a stirrer, adding 0.01mol of N, N-dimethylcyclohexylamine, heating the system to 70 ℃, dissolving 0.25mol of triglycidyl isocyanurate in 100mL of chloroform, dropwise adding the mixture into the system, maintaining the temperature at 80 ℃ under the protection of nitrogen and stirring continuously for 8 hours, and adding 15gNH 2 MIL-125 (Ti), stirring for 10 hours, adding 150ml of water as a precipitator, stopping stirring, filtering while hot, washing with water for 4 times, and drying in vacuum at 80 ℃ for 8 hours to obtain the MOFs-containing hyperbranched flame retardant.
Comparative example 3
The comparative example was not added with "NH 2 The procedure of MIL-125 (Ti) ", and the other steps were the same as those of example 3. The results are shown in Table 2.
To examine the flame retarding effect of the MOFs-containing hyperbranched flame retardant of the invention, a flammable epoxy resin was selected as a matrix, the flame retardants prepared in example 1, example 2 and example 3 were added to the epoxy resin according to the proportions shown in Table 1, and after being mixed uniformly, they were poured into a mold and thermally cured to prepare standard samples, which were subjected to flame retarding performance tests according to UL94 test standard (SATM D3801-10) and LOI test standard (ASRM D2863-06A), the test results of which are shown in Table 1.
TABLE 1
In the typical preparation process of comparative example 1, comparative example 2 and comparative example 3, the preparation step of adding MOFs flame retardant was not included, resulting in a conventional nitrogen-containing hyperbranched flame retardant containing no MOFs. The flame retardants prepared in comparative examples 1, 2 and 3 were added to epoxy resins in the same proportions as in Table 1 (corresponding proportions to Table 1) in the same proportions as in Table 2, and after being uniformly mixed, they were poured into a mold and thermally cured to prepare standard samples, which were subjected to flame retardant property tests according to UL94 test standards (SATM D3801-10) and LOI test standards (ASRM D2863-06A), and the test results are shown in Table 2.
TABLE 2
As can be seen from tables 1 and 2, the flame retardant prepared by the invention has mild reaction conditions, simple and easy preparation process and can endow high polymer materials with good flame retardant property. Compared with the flame retardant material formed by mixing the hyperbranched flame retardant containing MOFs with APP in a mode of 1:2 and 2:1 in each embodiment, the LOI values of the hyperbranched flame retardant containing MOFs added to the flame retardant material in the same proportion are higher than the LOI values of the flame retardant material without MOFs added in table 2, which shows that the flame retardant is improved by adding the proper MOFs material to the flame retardant.
Claims (10)
1. The hyperbranched flame retardant containing MOFs is characterized by having a structure shown in a formula I:
in the formula I, Y is-NH-or-N-, R is piperazine ring or branched chain alkylene containing 1-30 carbon atoms, aryl and polycyclic aromatic hydrocarbon,
is an extension of hyperbranched structures, ō is MOFs structure containing amino groups.
2. A method for preparing a hyperbranched flame retardant containing MOFs, which is characterized in that the hyperbranched flame retardant containing MOFs is the hyperbranched flame retardant containing MOFs according to claim 1, and comprises the following steps:
(1) Dissolving diamine compound in polar organic solvent in inert gas environment, adding catalyst, and heating to 70-150 deg.c;
(2) Dissolving triglycidyl isocyanurate in a polar organic solvent, slowly adding the polar organic solvent into the mixed solution obtained in the step (1), carrying out ring-opening reaction under the protection of inert gas, maintaining the ring-opening reaction temperature of 80-150 ℃, and reacting for 8-24 hours under the condition of stirring to obtain the nitrogenous hyperbranched flame retardant;
(3) Adding MOFs material containing amino into the nitrogen-containing hyperbranched flame retardant obtained in the step (2), and continuously stirring for 8-24 hours to carry out end-capping reaction; then adding a precipitator, performing solid-liquid separation, water washing and drying to obtain the MOFs hyperbranched flame retardant with the structure shown in the formula I.
3. The method according to claim 2, wherein the diamine compound is one or a mixture of several of piperazine, ethylenediamine, hydroxyethylethylenediamine, 3-diaminodiphenyl sulfone, diethyltoluenediamine, 2, 6-toluenediamine, N-aminoethylpiperazine, N-dimethyl-1, 3-propylenediamine, diaminodiphenylmethane, and diaminodiphenyl sulfone.
4. The process according to claim 2, wherein the catalyst is N, N-dimethylcyclohexylamine, bis (2-dimethylaminoethyl) ether, N, N, N ', N' -tetramethylalkylene diamine, N-dimethylbenzylamine, triethylamine, N-ethylmorpholine, N '-diethylpiperazine, N' -dimethylpyridine or pyridine.
5. The method according to claim 2, wherein the amino group-containing MOFs structure is an amino group-containing metal organic framework material, which is NH 2 -UiO-66(Zr)、NH 2 -UiO-66(Hf)、NH 2 -MIL-53(Fe)、NH 2 -MIL-101(Fe)、NH 2 -MIL-53(Al)、NH 2 -MIL-101(Al)、NH 2 MIL-101 (Cr) or NH 2 -one or more of MILs-125 (Ti); the end capping reaction is to end cap the hyperbranched flame retardant through epoxy ring-opening reaction of amino.
6. The method according to claim 2, wherein the polar organic solvent is acetonitrile, dichloroethane, chloroform, dimethylformamide, dimethylsulfoxide, or the like.
7. The method according to claim 2, wherein the molar ratio of triglycidyl isocyanurate to diamine compound is (2.5-10): 1-2; the mass ratio of triglycidyl isocyanurate and diamine compound to MOFs material containing amino is (3-5): 1.
8. The method of claim 2, wherein the inert gas is one or more of nitrogen, argon, or helium.
9. The preparation method of claim 2, wherein the precipitant in the step (3) is water, the reaction product obtained by the end-capping reaction and the water are precipitated, and then solid-liquid separation, water washing and drying are sequentially carried out, so that the MOFs-containing hyperbranched flame retardant with the structure shown in the formula I is obtained.
10. An application method of the nitrogen-containing hyperbranched flame retardant is characterized in that the hyperbranched flame retardant containing MOFs as set forth in claim 1 or the application of the hyperbranched flame retardant containing MOFs prepared by the preparation method as set forth in any one of claims 2 to 9 in the flame retardant field.
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