CN115785069A - Preparation method of hindered amine flame retardant NOR116 - Google Patents
Preparation method of hindered amine flame retardant NOR116 Download PDFInfo
- Publication number
- CN115785069A CN115785069A CN202211418917.4A CN202211418917A CN115785069A CN 115785069 A CN115785069 A CN 115785069A CN 202211418917 A CN202211418917 A CN 202211418917A CN 115785069 A CN115785069 A CN 115785069A
- Authority
- CN
- China
- Prior art keywords
- compound
- flame retardant
- organic solvent
- nor116
- hindered amine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 24
- 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 19
- 150000001412 amines Chemical class 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 30
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- 239000003960 organic solvent Substances 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 15
- 239000007800 oxidant agent Substances 0.000 claims description 13
- 230000001590 oxidative effect Effects 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 229940125782 compound 2 Drugs 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 10
- 229940125904 compound 1 Drugs 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- -1 (3-aminopropyl) ethyl Chemical group 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-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
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 5
- 229960000583 acetic acid Drugs 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 5
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 5
- 229940045803 cuprous chloride Drugs 0.000 claims description 5
- 239000012362 glacial acetic acid Substances 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- WIVXEZIMDUGYRW-UHFFFAOYSA-L copper(i) sulfate Chemical compound [Cu+].[Cu+].[O-]S([O-])(=O)=O WIVXEZIMDUGYRW-UHFFFAOYSA-L 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N monoethyl amine Natural products CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims 2
- 229960002089 ferrous chloride Drugs 0.000 claims 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims 1
- 229910001629 magnesium chloride Inorganic materials 0.000 claims 1
- 239000011592 zinc chloride Substances 0.000 claims 1
- 235000005074 zinc chloride Nutrition 0.000 claims 1
- IVKFHHPNCASANI-UHFFFAOYSA-N n'-(3-aminopropyl)-n'-butan-2-ylpropane-1,3-diamine Chemical compound NCCCN(C(C)CC)CCCN IVKFHHPNCASANI-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000706 filtrate Substances 0.000 description 8
- 238000001914 filtration Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 230000004224 protection Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 3
- KVFDZFBHBWTVID-UHFFFAOYSA-N cyclohexanecarbaldehyde Chemical compound O=CC1CCCCC1 KVFDZFBHBWTVID-UHFFFAOYSA-N 0.000 description 2
- 125000002933 cyclohexyloxy group Chemical group C1(CCCCC1)O* 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000010413 gardening Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- YULZYCFPHFYDNP-UHFFFAOYSA-N 2-n,4-n-dibutyl-6-chloro-2-n,4-n-bis(2,2,6,6-tetramethylpiperidin-4-yl)-1,3,5-triazine-2,4-diamine Chemical compound N=1C(Cl)=NC(N(CCCC)C2CC(C)(C)NC(C)(C)C2)=NC=1N(CCCC)C1CC(C)(C)NC(C)(C)C1 YULZYCFPHFYDNP-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Images
Abstract
The invention discloses a preparation method of a hindered amine flame retardant NOR116, which comprises the steps of reacting 2-chloro-4, 6-di (N-butyl-2, 6-tetramethyl-4-piperidylamino) -1,3, 5-triazine with hydrogen peroxide to synthesize nitroxide radicals, reacting with cyclohexane to synthesize 2-chloro-4, 6-di (N-butyl-1-cyclohexyloxy-2, 6-tetramethyl-4-piperidylamino) -1,3, 5-triazine, and finally grafting N, N-di (3-aminopropyl) ethyl ethylamine to obtain a product NOR-116 compound.
Description
Technical Field
The invention belongs to the field of high polymer material modification auxiliary agents, and particularly relates to a preparation method of a hindered amine flame retardant NOR 116.
Background
The amine NOR flame retardant is a monomolecular N-alkoxy amine hindered stabilizer (NOR HAS) which is used in polyolefin and simultaneously plays the roles of a halogen-free flame retardant and a halogen-free flame retardant synergist, the flametab NOR116 with the content of 0.5 percent can show good halogen-free flame retardant effect in transparent polypropylene PP films, polypropylene fibers, thin sheets and narrow tapes, the addition ratio is recommended to be optimized based on parameters such as thickness, orientation degree (such as traction and sedimentation ratio), structure (co-extrusion/non-woven fabrics and textiles) and processing conditions, the addition range is generally recommended to be 1.0-2.0 percent, the European Union building material fireproof standard (B2) can be achieved, the amine NOR flame retardant also HAS excellent long-term light stability and thermal stability, and the advantage of no reaction with residual pesticide and acidic components of the halogen-containing flame retardant, and the amine NOR flame retardant HAS the advantages of weather resistance, flame retardance, environmental protection, good lighting, multifunctional transparent PP films, transparent PP sheets, polyolefin fabrics and the like which are increasingly applied to building of gardening greenhouses, gardening ecotopes, hot spring, ecological villages, leaky grounds, stadium seats, high-speed trains and high-speed railway and the like. NOR-116 has the advantages of good transparency, low addition amount, high flame retardant efficiency, no halogen and phosphorus, environmental protection, and ultraviolet resistance.
According to domestic and foreign documents and patent reports, at present, the research method of the product mainly uses 2-chloro-4,6-di (N-butyl-2,2,6,6-tetramethyl-4-piperidylamino) -1,3,5-triazine and tert-butyl hydroperoxide to synthesize a key intermediate NOR compound by using cyclohexane as a solvent under the catalysis of molybdenum trioxide through a one-pot method, but the route has low raw material conversion rate, more impurities, multiple refining and low yield; in another route, the key intermediate NOR compound is synthesized by using more expensive raw materials of cyclohexane formaldehyde and 2-chloro-4, 6-di (N-butyl-2, 6-tetramethyl-4-piperidylamino) -1,3, 5-triazine, so that the cost of the raw materials is too high, and the cyclohexane formaldehyde is not produced on a large scale and is not suitable for industrial production.
Disclosure of Invention
In order to solve the problems, the invention discloses a preparation method of a hindered amine flame retardant NOR 116.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the structural formula of the hindered amine flame retardant NOR116 is shown as follows:
a preparation method of a hindered amine flame retardant NOR116 comprises the following synthetic process route:
a preparation method of a hindered amine flame retardant NOR116 specifically comprises the following steps:
step (1): taking a compound 1 shown in a formula 1, a catalyst, water and an oxidant as raw materials, heating up and carrying out reflux reaction in the presence of an organic solvent, and oxidizing to obtain a compound 2 shown in a formula 2;
step (2): heating and refluxing a compound 2 shown in a formula 2, cyclohexane, a catalyst and an oxidant in an organic solvent for reaction, washing after the reaction is finished, and concentrating to obtain a NOR-intermediate compound shown in a formula 3;
and (3): the final product NOR-116 compound is prepared by synthesizing a NOR-intermediate compound shown in formula 3 and an acid binding agent in an organic solvent under the conditions of high temperature and high pressure, washing the obtained material after the reaction is finished, and carrying out reduced pressure distillation.
Further, the compound 1 is 2-chloro-4, 6-bis (N-butyl-2, 6-tetramethyl-4-piperidinylamino) -1,3, 5-triazine, the compound 2 is an intermediate nitroxide radical, and the NOR-intermediate compound is 2-chloro-4, 6-bis (N-butyl-1-cyclohexyloxy-2, 6-tetramethyl-4-piperidinylamino) -1,3, 5-triazine.
Further, the molar ratio of the compound 1 to the oxidizing agent in step (1) of the present invention is 1:4 to 5;
further, the molar ratio of the compound 1 to the catalyst in step (1) of the present invention is 1:0.05 to 0.15.
Further, the mass ratio of the compound 1 to the organic solvent in the step (1) of the present invention is 1:2 to 3.
Further, in the step (1) of the present invention, the organic solvent is any one of methanol, ethanol, isopropanol, acetone, acetonitrile, and glacial acetic acid.
Further, in the step (1), the oxidant is any one of hydrogen peroxide, tert-butyl hydroperoxide and peroxyacetic acid.
Further, in the step (1), the catalyst is any one or more of sodium tungstate, phosphotungstic acid, cuprous chloride, ferrous sulfate, cuprous sulfate and manganese dioxide.
Further, in the step (1) of the present invention, the reaction temperature is from 30 to 80 ℃, preferably from 40 to 65 ℃.
Further, the molar ratio of the compound 2 to the oxidant in the step (2) of the present invention is 4 to 5.
Further, in step (2) of the present invention, the molar ratio of the compound 2 to the catalyst is 1.
Further, in step (2) of the present invention, the mass ratio of the compound 2 to the organic solvent is 1:2 to 3.
Further, in the step (2), the oxidant is one or more of hydrogen peroxide, tert-butyl hydroperoxide and peroxyacetic acid.
Further, in step (2) of the present invention, the solvent is any one or more of methanol, ethanol, ethyl acetate, dichloromethane, cyclohexane and petroleum ether.
Further, in the step (2) of the present invention, the reaction temperature is from 20 to 100 ℃, preferably from 45 to 75 ℃.
Further, the molar ratio of the NOR-intermediate compound to the N-bis (3-aminopropyl) ethylethylamine in step (3) of the present invention is 1:0.25 to 0.4.
Further, in step (3) of the present invention, the molar ratio of the NOR-intermediate compound to the acid scavenger is 1:1 to 1.2.
Further, the mass ratio of the NOR-intermediate compound to the organic solvent in step (3) of the present invention is 1:2 to 3.
Further, in the step (3), the organic solvent is any one of toluene, xylene, chlorobenzene, and N, N-dimethylformamide.
Further, in the step (3), the acid-binding agent is any one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and triethylamine.
Further, the reaction temperature in the step (3) of the present invention is 120 to 200 ℃, preferably 160 to 200 ℃.
Further, in the step (3), the reaction time is 12 to 24h, and the initial pressure is 0.5 to 1 MPa.
The beneficial effects of the invention are as follows:
according to the method, firstly, the nitroxide free radicals are generated, then a mixed double-oxidant method is adopted, and a proper amount of hydrogen peroxide is added under the condition of tert-butyl hydroperoxide to promote the reaction, so that the reaction rate is improved, the reaction is carried out more efficiently, cyclohexane is used as a solvent and a reaction raw material, and a higher yield is obtained.
Drawings
FIG. 1 is a liquid phase spectrum of the nitroxide radical (formula 2) synthesized in example 1 of the present invention;
FIG. 2 is a liquid phase diagram of the synthesis of NOR-intermediate compound (formula 3) of example 5 of the present invention;
FIG. 3 is a nuclear magnetic spectrum of a synthetic NOR-intermediate compound (formula 3) of example 5 of the present invention;
FIG. 4 is an IR spectrum of synthetic NOR-flame retardant 116 of example 7 of the present invention;
FIG. 5 is a GPC chart of synthetic NOR-flame retardant 116 of example 7 of the present invention.
Detailed Description
The present invention will be further illustrated with reference to the accompanying drawings and specific embodiments, which are to be understood as merely illustrative of the invention and not as limiting the scope of the invention.
The following examples were set at room temperature from 20 to 25 ℃.
Example 1
15g of raw material 2-chloro-4, 6-bis (N-butyl-2, 6-tetramethyl-4-piperidinylamino) -1,3, 5-triazine (0.028 mol) and 50ml of methanol are put into a four-neck reaction flask with stirring, 1g of sodium tungstate (0.0034 mol) and 3ml of pure water are added, the mixture is stirred and heated to 45 to 50 ℃, 9.5g (0.126 mol) of 45% hydrogen peroxide is dripped, the mixture is dripped for 1 hour, the mixture is kept warm and reacted for 8 hours, the raw materials are controlled to react completely, concentrated and cooled to 10 to 15 ℃, filtered, 14.33g of dried orange solid powder is obtained, the yield is 90.6%, and the results are shown in a figure 1.
Example 2
10g of raw material 2-chloro-4, 6-bis (N-butyl-2, 6-tetramethyl-4-piperidinylamino) -1,3, 5-triazine (0.019 mol) and 30ml of isopropanol are added into a four-neck reaction flask with a stirrer, 0.4g of sodium tungstate (0.0014 mol), 0.1g of manganese dioxide (0.001 mol) and 5ml of pure water are added, the temperature is raised to 60 to 65 ℃ by stirring, 6.5g (0.086 mol) of 45% hydrogen peroxide is added dropwise for 1 hour, the dropping is finished, the heat preservation reaction is carried out for 8 hours, the medium-controlled raw materials are completely reacted, the mixture is concentrated, cooled and filtered, and dried orange solid powder is 8.15g, and the yield is 79.1 percent.
Example 3
Adding 5.65g of intermediate nitroxide free radical (0.01 mol) and 12ml of methanol into a four-neck reaction flask with a stirring and refluxing device, stirring and dissolving, then sequentially adding 5ml of cyclohexane, 0.3g (0.001 mol) of ferrous sulfate heptahydrate and 0.5g (0.008 mol) of glacial acetic acid, heating to 50-55 ℃, starting to dropwise add 2g (0.016 mol) of 70% tert-butyl hydroperoxide, then dropwise adding 2.5g (0.033 mol) of 45% hydrogen peroxide, finishing the dropwise addition, keeping the temperature for reaction for 6 hours, controlling the reaction until the raw materials are completely reacted, cooling to room temperature, filtering, extracting the filtrate by using 75ml of 3 dichloromethane, combining dichloromethane layers, washing by using 0.5% hydrochloric acid and washing once, then adding 0.2g of 500-mesh active carbon and 0.2g of 300-mesh active clay, mixing and stirring for half an hour, filtering, concentrating the filtrate under negative pressure to obtain 6.1g of a product, wherein the yield is 83.3%,
example 4
Adding 11.3g of intermediate nitroxide free radical (0.02 mol) into a four-mouth reaction flask with a stirring and refluxing device, adding 30ml of cyclohexane, 0.2g (0.002 mol) of cuprous chloride and 0.5g (0.008 mol) of glacial acetic acid, heating to 50-55 ℃, starting to dropwise add 2g (0.016 mol) of 70% tert-butyl hydroperoxide and 5g (0.066 mol) of 45% hydrogen peroxide, finishing dropping, keeping the temperature for reaction for 8 hours, controlling the reaction time until the raw materials are completely reacted, cooling to room temperature, filtering, extracting filtrate by using 75ml of 3 dichloromethane, combining dichloromethane layers, washing by using 0.5% hydrochloric acid and washing once by using water, then adding 0.2g of 500-mesh active carbon and 0.2g of 300-mesh active clay, mixing and stirring for half an hour, filtering, concentrating the filtrate under negative pressure to obtain 6.8g of a product, wherein the yield is 92.8%, and the result is shown in figure 2.
Example 5
Adding 11.3g of intermediate nitroxide free radical (0.02 mol) into a four-mouth reaction flask with a stirring and refluxing device, adding 30ml of cyclohexane, 0.3g (0.003 mol) of cuprous chloride and 1g (0.016 mol) of glacial acetic acid, heating to 65-70 ℃, starting to dropwise add 2g (0.016 mol) of 70% tert-butyl hydroperoxide and 10.2g (0.09 mol) of 30% hydrogen peroxide, finishing dropping, keeping the temperature for reaction for 8 hours, controlling the reaction to be complete, cooling to room temperature, filtering, extracting filtrate by using 75ml of 3 dichloromethane, combining dichloromethane layers, washing by using 0.5% hydrochloric acid and washing by using water, then adding 0.2g of 500-mesh active carbon and 0.2g of 300-mesh active clay, mixing and stirring for half an hour, filtering, concentrating the filtrate under negative pressure to obtain 7.05g of a product, wherein the yield is 96.3%, and the result is shown in figure 3.
Example 6
18 g (0.025 mol) of cyclohexyloxy intermediate, 50ml of xylene, 1.15g (0.029 mol) of sodium hydroxide, 10g of water, 1.53g (0.0088 mol) of N, N-bis (3-aminopropyl) ethyl ethylamine and three times of nitrogen replacement are added into a stainless steel autoclave, the initial pressure is 0.5 MPa, the stirring is started, the reaction is carried out for 8 hours at 180 ℃, the temperature is cooled to 60 ℃, the mixture is layered, washed by water and filtered, the filtrate is distilled under reduced pressure to obtain 7.3g of white-like solid, and the product yield is 82.3%.
Example 7
27 g (0.036 mol) of the cyclohexyloxy intermediate, 70ml of toluene, 1.7g (0.042 mol) of sodium hydroxide, 10g of water, 1.87g (0.011 mol) of N, N-bis (3-aminopropyl) ethyl ethylamine, three times of nitrogen substitution, initial pressure of 0.6MPa, stirring, reaction at 180 ℃ for 8 hours, cooling to 50 ℃, layering, washing with water, filtering, and reduced pressure distillation of the filtrate to obtain 7.9g of an off-white solid with a product yield of 89.0%, with reference to the results shown in FIGS. 4 and 5.
It should be noted that the above-mentioned contents only illustrate the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and it is obvious to those skilled in the art that several modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations fall within the protection scope of the claims of the present invention.
Claims (10)
1. A preparation method of a hindered amine flame retardant NOR116 is characterized in that the synthesis process route is as follows:
2. the method for preparing the hindered amine flame retardant NOR116 of claim 1, which comprises the following steps:
step (1): taking a compound 1 shown in a formula 1, a catalyst, water and an oxidant as raw materials, stirring and heating the raw materials in the presence of an organic solvent until the raw materials are dissolved and reacted, and oxidizing the raw materials to obtain a compound 2 shown in a formula 2;
step (2): heating a compound 2 shown in a formula 2, cyclohexane, a catalyst and an oxidant in an organic solvent for reflux reaction, washing after the reaction is finished, and concentrating to obtain a NOR-intermediate compound shown in a formula 3;
and (3): the method comprises the steps of synthesizing a NOR-intermediate compound shown in a formula 3, N-di (3-aminopropyl) ethyl amine and an acid binding agent in an organic solvent under the conditions of high temperature and high pressure, washing the obtained material after the reaction is finished, and carrying out reduced pressure distillation on the obtained material to obtain a final product NOR-116 compound.
3. The method of claim 2, wherein the compound 1 is 2-chloro-4, 6-bis (N-butyl-2, 6-tetramethyl-4-piperidinylamino) -1,3, 5-triazine, the compound 2 is an intermediate nitroxide radical, and the NOR-intermediate compound is 2-chloro-4, 6-bis (N-butyl-1-cyclohexyloxy-2, 6-tetramethyl-4-piperidinylamino) -1,3, 5-triazine.
4. The method of claim 2, wherein the molar ratio of compound 1 to the oxidant in step (1) is 1:4 to 5; the molar ratio of the compound 1 to the catalyst is 1:0.05 to 0.15; the mass ratio of the compound 1 to the organic solvent is 1:2 to 3.
5. The method for preparing the hindered amine flame retardant NOR116 of claim 2, wherein in the step (1), the organic solvent is any one of methanol, ethanol, isopropanol, acetone, acetonitrile and glacial acetic acid, the oxidant is any one of hydrogen peroxide, tert-butyl hydroperoxide and peroxyacetic acid, and the catalyst is any one or more of sodium tungstate, phosphotungstic acid, cuprous chloride, ferrous sulfate, cuprous sulfate and manganese dioxide.
6. The method of claim 2, wherein the molar ratio of compound 2 to the oxidant in step (2) is 1:4 to 5, wherein the molar ratio of the compound 2 to the catalyst is 1:0.05 to 0.15; the mass ratio of the compound 2 to the organic solvent is 1:2 to 3.
7. The method for preparing the hindered amine flame retardant NOR116 of claim 2, wherein the oxidant in step (2) is any one or more of hydrogen peroxide, tert-butyl hydroperoxide and peracetic acid, and the solvent is any one or more of methanol, ethanol, ethyl acetate, dichloromethane, cyclohexane and petroleum ether; the catalyst is any one or more of ferrous sulfate, cuprous chloride, cuprous sulfate, magnesium chloride, ferrous chloride and zinc chloride.
8. The method of claim 2, wherein the molar ratio of the NOR-intermediate compound to the N, N-bis (3-aminopropyl) ethyl amine in step (3) is 1:0.25 to 0.4, wherein the molar ratio of the NOR-intermediate compound to the acid-binding agent is 1:1 to 1.2, wherein the mass ratio of the NOR-intermediate compound to the organic solvent is 1:2 to 3.
9. The method for preparing the hindered amine flame retardant NOR116 of claim 2, wherein the organic solvent in step (3) is any one of toluene, xylene, chlorobenzene and N, N-dimethylformamide, and the acid-binding agent is any one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and triethylamine.
10. The method for preparing a hindered amine flame retardant NOR116 of claim 2, wherein the reaction temperature is 30-80 ℃ in the step (1), 20-100 ℃ in the step (2), 120-200 ℃ in the step (3), 12-24h in the step (3), and 0.5-1 MPa in the initial pressure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211418917.4A CN115785069A (en) | 2022-11-14 | 2022-11-14 | Preparation method of hindered amine flame retardant NOR116 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211418917.4A CN115785069A (en) | 2022-11-14 | 2022-11-14 | Preparation method of hindered amine flame retardant NOR116 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115785069A true CN115785069A (en) | 2023-03-14 |
Family
ID=85437313
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211418917.4A Pending CN115785069A (en) | 2022-11-14 | 2022-11-14 | Preparation method of hindered amine flame retardant NOR116 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115785069A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1823042A (en) * | 2003-07-14 | 2006-08-23 | 西巴特殊化学品控股有限公司 | Hydrogen peroxide catalyzed process for the preparation of sterically hindered n-hydrocarbyloxyamines |
| CN101484423A (en) * | 2006-07-05 | 2009-07-15 | 西巴控股有限公司 | Process for the preparation of sterically hindered nitroxyl ethers |
| CN112250668A (en) * | 2020-10-10 | 2021-01-22 | 利安隆凯亚(河北)新材料有限公司 | Preparation method of N-alkoxy hindered amine light stabilizer and intermediate thereof |
-
2022
- 2022-11-14 CN CN202211418917.4A patent/CN115785069A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1823042A (en) * | 2003-07-14 | 2006-08-23 | 西巴特殊化学品控股有限公司 | Hydrogen peroxide catalyzed process for the preparation of sterically hindered n-hydrocarbyloxyamines |
| CN101484423A (en) * | 2006-07-05 | 2009-07-15 | 西巴控股有限公司 | Process for the preparation of sterically hindered nitroxyl ethers |
| CN112250668A (en) * | 2020-10-10 | 2021-01-22 | 利安隆凯亚(河北)新材料有限公司 | Preparation method of N-alkoxy hindered amine light stabilizer and intermediate thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108794745B (en) | Schiff base charring agent containing triazine ring and synthesis method thereof | |
| CN113248831A (en) | Efficient PP flame-retardant master batch and preparation method thereof | |
| CN110643066B (en) | Phosphorus-nitrogen flame retardant and preparation method thereof | |
| WO2013134900A1 (en) | Phosphorus-silicon synergic flame retardant, and preparation method and application thereof | |
| CN107434787A (en) | A kind of preparation, structure and the photoluminescent property of benzimidazole perchlorate | |
| CN115785069A (en) | Preparation method of hindered amine flame retardant NOR116 | |
| JP2013163767A (en) | Fluorescent substance and its use | |
| CN113150386A (en) | Modified ammonium polyphosphate intumescent flame retardant and preparation method and application thereof | |
| CN112028819B (en) | Organic ligand compound of tetraphenyl ethylene terpyridine, coordination supermolecule, preparation and application thereof | |
| KR20130104551A (en) | Water-soluble perylene compounds having light interception and shift wavelength and process for producing the same | |
| JP2008195674A (en) | Rare earth metal complex graft-copolymerizable with eva resin and method for producing the same | |
| CN115160588A (en) | Full-spectrum luminescent nanoscale zirconium-based metal organic framework material and preparation method thereof | |
| CN109320528B (en) | Triheteroaryl free radical capable of stably emitting light at room temperature, and preparation method and application thereof | |
| CN110734375B (en) | Preparation method of bilastine intermediate | |
| CN114539620A (en) | Nitrogen-phosphorus synergistic flame retardant and preparation method and application thereof | |
| CN110845371B (en) | Method for synthesizing o-sulfobenzaldehyde under normal pressure | |
| CN111635427A (en) | Antibacterial silane coupling agent and preparation method thereof | |
| CN114456375B (en) | Polyhydroxy triazine charring agent and preparation method and application thereof | |
| KR101115576B1 (en) | Method for preparing sulfonium salt and sulfonium salt prepared by the same | |
| CN109438377A (en) | A kind of method of Long carbon chain triazine-based ultraviolet absorbent of the low temperature process preparation containing ehter bond | |
| CN110734392A (en) | Azobenzene side chain polymerizable monomer based on modified cis-5-norbornene-2, 3-dicarboxylic anhydride and application thereof | |
| CN117304149A (en) | Synthesis method of 4-phenylacetylene phthalic anhydride | |
| CN117186393B (en) | Sulfonate flame retardant applied to polycarbonate and synthesis method | |
| KR20210000936A (en) | Method For Manufacturing Triazine Compound | |
| CN108383870B (en) | Glufosinate-ammonium salt intermediate and synthetic method of glufosinate-ammonium salt |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20230314 |
|
| RJ01 | Rejection of invention patent application after publication |