CN115322173A - Multifunctional hindered amine light stabilizer and preparation method thereof - Google Patents
Multifunctional hindered amine light stabilizer and preparation method thereof Download PDFInfo
- Publication number
- CN115322173A CN115322173A CN202211013533.4A CN202211013533A CN115322173A CN 115322173 A CN115322173 A CN 115322173A CN 202211013533 A CN202211013533 A CN 202211013533A CN 115322173 A CN115322173 A CN 115322173A
- Authority
- CN
- China
- Prior art keywords
- triazine
- tetramethyl
- butyl
- light stabilizer
- piperidyl
- 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.)
- Granted
Links
- 239000004611 light stabiliser Substances 0.000 title claims abstract description 44
- 150000001412 amines Chemical class 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 40
- MLRVZFYXUZQSRU-UHFFFAOYSA-N 1-chlorohexane Chemical compound CCCCCCCl MLRVZFYXUZQSRU-UHFFFAOYSA-N 0.000 claims abstract description 14
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims abstract description 4
- 238000006467 substitution reaction Methods 0.000 claims abstract description 4
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 39
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 17
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 10
- 239000007810 chemical reaction solvent Substances 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Substances ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- MVPPADPHJFYWMZ-IDEBNGHGSA-N chlorobenzene Chemical group Cl[13C]1=[13CH][13CH]=[13CH][13CH]=[13CH]1 MVPPADPHJFYWMZ-IDEBNGHGSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000006266 etherification reaction Methods 0.000 claims description 3
- 125000003944 tolyl group Chemical group 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 abstract description 9
- 239000001257 hydrogen Substances 0.000 abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- 150000003254 radicals Chemical class 0.000 abstract description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 abstract description 2
- 239000004698 Polyethylene Substances 0.000 description 9
- 229920000573 polyethylene Polymers 0.000 description 9
- 230000032683 aging Effects 0.000 description 8
- -1 polyethylene Polymers 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000003712 anti-aging effect Effects 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- OKKJLVBELUTLKV-VMNATFBRSA-N methanol-d1 Chemical compound [2H]OC OKKJLVBELUTLKV-VMNATFBRSA-N 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- DHQCYXIOLBXVDE-UHFFFAOYSA-N chlorobenzene;hydrate Chemical compound O.ClC1=CC=CC=C1 DHQCYXIOLBXVDE-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34926—Triazines also containing heterocyclic groups other than triazine groups
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Hydrogenated Pyridines (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The invention discloses a multifunctional hindered amine light stabilizer and a preparation method thereof, wherein the preparation method comprises the following steps: step S1: N-N-butyl-2, 6-tetramethyl-4-piperidylamine and 2,4, 6-trichloro-1, 3, 5-triazine are taken as raw materials to synthesize 2-chloro-4, 6-di- [ N-N-butyl-N- (2, 6-tetramethyl-4-piperidyl) amino ] -1,3, 5-triazine by nucleophilic substitution; step S2: synthesizing 2- (2 ',4' -dihydroxy benzene) -4, 6-di [ N-N-butyl-N- (2, 6-tetramethyl-4-piperidyl) amino ] -1,3, 5-triazine by substitution reaction; and step S3: etherifying 2- (2 ',4' -dihydroxy benzene) -4, 6-di [ N-N-butyl-N- (2, 6-tetramethyl-4-piperidyl) amino ] -1,3, 5-triazine and 1-chlorohexane to obtain a multifunctional hindered amine light stabilizer UH; according to the invention, an internal hydrogen bond structure is introduced on the basis of the triazine structure light stabilizer, and one hydroxyl group is etherified, so that the prepared compound has two functions of ultraviolet absorption and free radical capture, and simultaneously has good compatibility with different materials.
Description
Technical Field
The invention belongs to the field of light stabilizers, and particularly relates to a multifunctional hindered amine light stabilizer and a preparation method thereof.
Background
In the use and processing of polymer materials, aging of different degrees caused by light, oxygen, heat and the like is inevitable, and in order to prevent the material from being aged prematurely during processing and use to shorten the service life, a series of anti-aging aids with different functions are researched, and a light stabilizer is an important aid.
Hindered Amine Light Stabilizers (HALS) are the most widely used light stabilizers with the highest market share. With the development and progress of hindered amine light stabilizers, it is becoming more and more difficult to develop novel light stabilizers with excellent properties. The commercially available HALS, whether monomeric or polymeric, already represent a number of structural possibilities, and attempts are being made to introduce new functional groups. As can be known from the action mechanism of the hindered amine light stabilizer, the light stability of the hindered amine light stabilizer lies in hindered amine groups, and the action of functional groups is particularly remarkable. Therefore, by introducing functional groups with other functions, a new structural type and a new functional hindered amine light stabilizer are developed by virtue of intramolecular self-synergistic effect on the basis of not influencing the function of hindered amine, and the introduction of functional groups with other functions becomes one of the main trends of the development of HALS at present.
Disclosure of Invention
The invention aims to provide a multifunctional hindered amine light stabilizer and a preparation method thereof, and aims to solve the problem that the compatibility of the multifunctional light stabilizer and different polymers is poor in the prior art.
The invention adopts the following technical scheme: a multifunctional hindered amine light stabilizer has the following structural formula:
a preparation method of a multifunctional hindered amine light stabilizer comprises the following reaction formula:
further, the method comprises the following steps:
step S1: N-N-butyl-2, 6-tetramethyl-4-piperidylamine and 2,4, 6-trichloro-1, 3, 5-triazine are taken as raw materials to synthesize 2-chloro-4, 6-di- [ N-N-butyl-N- (2, 6-tetramethyl-4-piperidyl) amino ] -1,3, 5-triazine by nucleophilic substitution;
step S2: synthesizing 2- (2 ',4' -dihydroxybenzene) -4, 6-di [ N-N-butyl-N- (2, 6-tetramethyl-4-piperidyl) amino ] -1,3, 5-triazine and resorcinol by substitution reaction by using 2-chloro-4, 6-di- [ N-N-butyl-N- (2, 6-tetramethyl-4-piperidyl) amino ] -1,3, 5-triazine as raw materials;
and step S3: 2- (2 ',4' -dihydroxybenzene) -4, 6-di [ N-N-butyl-N- (2, 6-tetramethyl-4-piperidyl) amino ] -1,3, 5-triazine and 1-chlorohexane are subjected to etherification reaction to obtain the multifunctional hindered amine light stabilizer UH.
Further, in step S1: the molar ratio of N-N-butyl-2, 6-tetramethyl-4-piperidylamine to 2,4, 6-trichloro-1, 3, 5-triazine is 2;
in step S2: 2-chloro-4, 6-bis- [ N-butyl-N- (2, 6-tetramethyl-4-piperidyl) amino ] -1,3, 5-triazine to resorcinol in a molar ratio of 1.1 to 1.3;
in step S3: the molar ratio of 2- (2 ',4' -dihydroxybenzene) -4, 6-bis [ N-N-butyl-N- (2, 6-tetramethyl-4-piperidyl) amino ] -1,3, 5-triazine and 1-chlorohexane is 1.1 to 1.4.
Further, in step S1:
the reaction solvent is toluene, the catalyst is 10-30% sodium hydroxide/potassium hydroxide aqueous solution, and the reaction condition is 60-90 ℃; the reaction time is 6-14h;
N-N-butyl-2, 6-tetramethyl-4-piperidinamine, 2,4, 6-trichloro-1, 3, 5-triazine, sodium hydroxide/potassium hydroxide in a molar ratio of 2-2.4:1:2-2.5.
Further, in step S2:
the reaction solvent is chlorobenzene/o-dichlorobenzene, the catalyst is anhydrous aluminum trichloride, and the reaction condition is 60-90 ℃; the reaction time is 4-12h;
the molar ratio of 2-chloro-4, 6-bis- [ N-N-butyl-N- (2, 6-tetramethyl-4-piperidyl) amino ] -1,3, 5-triazine, resorcinol and anhydrous aluminum trichloride is 1:1.1-1.3:1-1.2.
Further, in step S3:
the reaction solvent is DMF, the catalyst is sodium hydroxide/potassium hydroxide, and the reaction temperature is 80-120 ℃; the reaction time is 6-10h;
2- (2 ',4' -dihydroxybenzene) -4, 6-bis [ N-N-butyl-N- (2, 6-tetramethyl-4-piperidyl) amino ] -1,3, 5-triazine, 1-chlorohexane, sodium hydroxide/potassium hydroxide in a molar ratio of 1:1.1-1.4:1-1.3.
The invention has the beneficial effects that: the invention adopts resorcinol and 1-chlorohexane as substituent groups to modify 2-chloro-4, 6-di- [ N-N-butyl-N- (2, 6-tetramethyl-4-piperidyl) amino ] -1,3, 5-triazine, and introduces an internal hydrogen bond structure and etherifies a hydroxyl group on the basis of a triazine structure light stabilizer, so that the prepared compound has two functions of ultraviolet absorption and free radical capture, and simultaneously has better compatibility with different materials, solves the problem of poor compatibility of a multifunctional light stabilizer and different polymers in the prior art, and has the advantage of one dose of multi-use and better compatibility; the compound is obtained by taking 2-chloro-4, 6-di- [ N-N-butyl-N- (2, 6-tetramethyl-4-piperidyl) amino ] -1,3, 5-triazine as a raw material, inoculating resorcinol to form an internal hydrogen bond structure, and modifying with 1-chlorohexane as a substituent group, wherein the compound has the internal hydrogen bond and hindered amine structure, so that the compound has double functions of ultraviolet absorption and free radical capture, and meanwhile, the compound has good compatibility in different materials by etherifying one hydroxyl group, and has important application prospect in the field of anti-aging of plastic products.
Drawings
FIG. 1 is a diagram showing the structural representation of 2-chloro-4, 6-bis- [ N-N-butyl-N- (2, 6-tetramethyl-4-piperidyl) amino ] -1,3, 5-triazine in the present invention;
FIG. 1 (a) is a high resolution mass spectrum of 2-chloro-4, 6-bis- [ N-N-butyl-N- (2, 6-tetramethyl-4-piperidyl) amino ] -1,3, 5-triazine;
FIG. 1 (b) is a nuclear magnetic resonance hydrogen spectrum of 2-chloro-4, 6-bis- [ N-N-butyl-N- (2, 6-tetramethyl-4-piperidyl) amino ] -1,3, 5-triazine;
FIG. 2 is a diagram showing the structural representation of 2- (2 ',4' -dihydroxybenzene) -4, 6-bis [ N-N-butyl-N- (2, 6-tetramethyl-4-piperidyl) amino ] -1,3, 5-triazine in the present invention;
FIG. 2 (a) is a high resolution mass spectrum of 2- (2 ',4' -dihydroxybenzene) -4, 6-bis [ N-N-butyl-N- (2, 6-tetramethyl-4-piperidyl) amino ] -1,3, 5-triazine;
FIG. 2 (b) is a hydrogen nuclear magnetic resonance spectrum of 2- (2 ',4' -dihydroxybenzene) -4, 6-bis [ N-N-butyl-N- (2, 6-tetramethyl-4-piperidyl) amino ] -1,3, 5-triazine;
FIG. 3 is a structural representation of the multifunctional hindered amine light stabilizer of the present invention, compound UH;
FIG. 3 (a) is a high resolution mass spectrum of a multifunctional hindered amine light stabilizer;
FIG. 3 (b) is the hydrogen nuclear magnetic resonance spectrum of the multifunctional hindered amine light stabilizer;
FIG. 4 is a graph comparing the aging of films doped with a compound UH and blank PE films at different aging times;
FIG. 5 is a mechanical property test chart of the aged polyethylene film;
FIG. 5 (a) is a graph of tensile strength retention of films versus aging time;
FIG. 5 (b) is a graph of differential aging time versus elongation at break retention of the film.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The invention discloses a multifunctional hindered amine light stabilizer, which has the following structural formula:
the invention also discloses a preparation method of the multifunctional hindered amine light stabilizer, and the reaction equation is as follows:
a preparation method of a multifunctional hindered amine light stabilizer comprises the following steps:
step S1: N-N-butyl-2, 6-tetramethyl-4-piperidylamine and 2,4, 6-trichloro-1, 3, 5-triazine are taken as raw materials to synthesize 2-chloro-4, 6-bis- [ N-N-butyl-N- (2, 6-tetramethyl-4-piperidyl) amino ] -1,3, 5-triazine by nucleophilic substitution;
step S2: synthesizing 2- (2 ',4' -dihydroxy benzene) -4, 6-di [ N-N-butyl-N- (2, 6-tetramethyl-4-piperidyl) amino ] -1,3, 5-triazine and resorcinol by substitution reaction by using 2-chloro-4, 6-di- [ N-N-butyl-N- (2, 6-tetramethyl-4-piperidyl) amino ] -1,3, 5-triazine as raw materials;
and step S3: the multifunctional hindered amine light stabilizer UH is obtained by etherification reaction of 2- (2 ',4' -dihydroxy benzene) -4, 6-di [ N-N-butyl-N- (2, 6-tetramethyl-4-piperidyl) amino ] -1,3, 5-triazine and 1-chlorohexane.
Further, in step S1: the molar ratio of N-N-butyl-2, 6-tetramethyl-4-piperidinamine to 2,4, 6-trichloro-1, 3, 5-triazine is 2;
in step S2: 2-chloro-4, 6-bis- [ N-butyl-N- (2, 6-tetramethyl-4-piperidinyl) amino ] -1,3, 5-triazine and resorcinol in a molar ratio of 1.1 to 1.3;
in step S3: the molar ratio of 2- (2 ',4' -dihydroxybenzene) -4, 6-bis [ N-N-butyl-N- (2, 6-tetramethyl-4-piperidyl) amino ] -1,3, 5-triazine and 1-chlorohexane is 1.1 to 1.4.
In step S1:
the reaction solvent is toluene, the catalyst is 10-30% sodium hydroxide/potassium hydroxide aqueous solution, and the reaction condition is 60-90 ℃; the reaction time is 6-14h;
N-N-butyl-2, 6-tetramethyl-4-piperidylamine, 2,4, 6-trichloro-1, 3, 5-triazine, sodium hydroxide/potassium hydroxide in a molar ratio of 2-2.4:1:2-2.5.
In step S2:
the reaction solvent is chlorobenzene/o-dichlorobenzene, the catalyst is anhydrous aluminum trichloride, and the reaction condition is 60-90 ℃; the reaction time is 4-12h;
the molar ratio of 2-chloro-4, 6-bis- [ N-N-butyl-N- (2, 6-tetramethyl-4-piperidyl) amino ] -1,3, 5-triazine, resorcinol and anhydrous aluminum trichloride is 1:1.1-1.3:1-1.2.
In step S3:
the reaction solvent is DMF, the catalyst is sodium hydroxide/potassium hydroxide, and the reaction temperature is 80-120 ℃; the reaction time is 6-10h;
2- (2 ',4' -dihydroxybenzene) -4, 6-bis [ N-N-butyl-N- (2, 6-tetramethyl-4-piperidyl) amino ] -1,3, 5-triazine, 1-chlorohexane, sodium hydroxide/potassium hydroxide in a molar ratio of 1:1.1-1.4:1-1.3.
Example 1
Step S1: preparation of 2-chloro-4, 6-bis- [ N-N-butyl-N- (2, 6-tetramethyl-4-piperidyl) amino ] -1,3, 5-triazine
In a 500mL three-necked flask, 200mL of methanol was added, 2,4, 6-trichloro-1, 3, 5-triazine (18.44g, 100mmol) was dissolved therein, N-N-butyl-2, 6-tetramethyl-4-piperidinamine (42.42g, 200mmol) was slowly added under an ice-water bath, and reacted for 2 hours; 35% NaOH solution was added to the three-necked flask and reacted at 70 ℃ for 14 hours. After the reaction is finished, 200mL of water is added, extraction is carried out, an organic phase is separated, anhydrous sodium sulfate is dried, and desolventizing is carried out to obtain a light yellow solid, wherein the yield is about 48.8g, and the yield is 91%.
The detection result of the product 2-chloro-4, 6-bis- [ N-N-butyl-N- (2, 6-tetramethyl-4-piperidyl) amino ] -1,3, 5-triazine is as follows:
1 H NMR(400MHz,CDCl 3 )δ5.15(m,2H),3.33(s,4H),1.60(ddd,J＝26.5,14.3,9.4Hz,9H),1.30(m,22H),1.18(s,12H),0.94(ddd,J＝17.4,10.9,5.4Hz,6H)。MS(ESI),m/z:536.3893[M+H] + 。
step S2: preparation of 2- (2 ',4' -dihydroxybenzene) -4, 6-bis [ N-N-butyl-N- (2, 6-tetramethyl-4-piperidyl) amino ] -1,3, 5-triazine
2-chloro-4, 6-bis- [ N-N-butyl-N- (2, 6-tetramethyl-4-piperidyl) amino ] -1,3, 5-triazine (16.0 g,30.0 mmol) and 120mL of chlorobenzene were added to a 500mL three-necked flask and stirred, and anhydrous aluminum trichloride (4.0 g,30.0 mmol) was added in an ice-water bath, and after stirring for 30 minutes in an ice bath, resorcinol (3.96g, 36.0 mmol) was added to the reaction flask and reacted at 80 ℃ for 4 hours. 120mL of 2% dilute hydrochloric acid is slowly dropped into the reaction bottle, the chlorobenzene-water azeotrope is recovered by atmospheric distillation, and the temperature is raised to 100 ℃. The crude product is filtered by suction when the crude product is hot, and is washed for a plurality of times by using dilute hydrochloric acid, water and dichloromethane respectively to obtain a white solid, the yield is about 16.8g, and the yield is 92%.
The product 2- (2 ',4' -dihydroxybenzene) -4, 6-bis [ N-N-butyl-N- (2, 6-tetramethyl-4-piperidyl) amino ] -1,3, 5-triazine was examined and the results were as follows:
1 H NMR(400MHz,MeOD)δ7.46(m,1H),6.38(d,J＝6.5Hz,1H),5.45(s,1H),5.24(s,2H),3.59(s,4H),2.05(ddd,J＝17.8,15.8,6.8Hz,9H),1.70(s,16H),1.65(s,13H),1.51(dd,J＝14.1,6.8Hz,4H),1.10(t,J＝7.1Hz,6H)。MS(ESI),m/z:610.4783[M+H] + 。
and step S3: preparation of multifunctional hindered amine light stabilizer UH
Adding 0.7g (17.5 mmol) of sodium hydroxide solid and 100mL of DMF (dimethyl formamide) into a three-neck flask, heating, stirring and dissolving, then adding 10.0g (16.4 mmol) of intermediate, heating to 80 ℃, dropwise adding a mixed solution of 1-chlorohexane (2.9mL, 21.3mmol) and DMF (6.0 mL) while reacting, completing dropwise addition within 2min, continuing at constant temperature, cooling the reaction solution after the reaction is finished for 6-7h, performing suction filtration to obtain a crude product, washing with water, drying, crystallizing with DMF to obtain a light yellow solid, wherein the yield is about 7.96g, and the yield is 70.1%.
The results of the UH detection of the multifunctional hindered amine light stabilizer are as follows:
1 H NMR(400MHz,MeOD)δ7.37–7.26(m,1H),6.25(d,J＝7.3Hz,1H),5.43–5.24(m,1H),5.11(s,2H),3.42(dd,J＝20.2,8.2Hz,6H),2.05–1.82(m,12H),1.58(s,18H),1.52(d,J＝4.9Hz,14H),1.38(dd,J＝14.7,7.4Hz,6H),0.97(q,J＝7.4Hz,9H)。MS(ESI),m/z:694.5629[M+H] + 。
the multifunctional hindered amine light stabilizer prepared in this example is doped in a Polyethylene (PE) film, and an aging performance test is performed, and the test result is shown in the left side of fig. 4, the left side of fig. 4 is a film with a compound UH added, and the right side of fig. 4 is a blank film, as is apparent from fig. 4, the UH film without being added exhibits obvious cracks after being aged for 400 hours in an ultraviolet aging machine, and the PE film with the light stabilizer UH added also exhibits substantially perfect and undamaged performance after being aged for 800 hours.
After the multifunctional hindered amine light stabilizer prepared in this example is doped in a PE film, mechanical properties of the aged polyethylene film are tested, and the test results are shown in fig. 5, and it can be seen from fig. 5 that, under different aging times, the retention rate of tensile strength (fig. 5 a) and the retention rate of elongation at break (fig. 5 b) of the polyethylene film with the added light stabilizer UH are always better than those of the polyethylene film without the added UH. The light stabilizer UH therefore does have excellent anti-ageing properties.
Example 2
This example is the same as example 1 except that:
the N-N-butyl-2, 6-tetramethyl-4-piperidinamine was added in step S1 in an amount (46.66g, 220mmol) and the NaOH solution in an amount of 25%, resulting in a final yield of about 47.1g and 88%.
In step S2, the solvent chlorobenzene was replaced with o-dichlorobenzene, and anhydrous aluminum trichloride (4.8g, 36.0mmol) was added in a yield of about 16.4g and 90% in the form of 3% dilute hydrochloric acid.
In step S3, 1-chlorohexane was added in an amount of (3.1mL, 23.0mmol) and the catalyst sodium hydroxide (0.7g, 17.5mmol) was replaced with potassium hydroxide (0.98g, 17.5mmol), resulting in a final yield of about 7.83g and a yield of 69%.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (7)
1. A multifunctional hindered amine light stabilizer is characterized in that the structural formula is as follows:
2. the preparation method of the multifunctional hindered amine light stabilizer is characterized in that the reaction equation is as follows:
3. the method for preparing the multifunctional hindered amine light stabilizer according to claim 2, which comprises the following steps:
step S1: N-N-butyl-2, 6-tetramethyl-4-piperidylamine and 2,4, 6-trichloro-1, 3, 5-triazine are taken as raw materials to synthesize 2-chloro-4, 6-di- [ N-N-butyl-N- (2, 6-tetramethyl-4-piperidyl) amino ] -1,3, 5-triazine by nucleophilic substitution;
step S2: synthesizing 2- (2 ',4' -dihydroxybenzene) -4, 6-di [ N-N-butyl-N- (2, 6-tetramethyl-4-piperidyl) amino ] -1,3, 5-triazine and resorcinol by substitution reaction by using 2-chloro-4, 6-di- [ N-N-butyl-N- (2, 6-tetramethyl-4-piperidyl) amino ] -1,3, 5-triazine as raw materials;
and step S3: the multifunctional hindered amine light stabilizer UH is obtained by etherification reaction of 2- (2 ',4' -dihydroxy benzene) -4, 6-di [ N-N-butyl-N- (2, 6-tetramethyl-4-piperidyl) amino ] -1,3, 5-triazine and 1-chlorohexane.
4. The method for preparing a multifunctional hindered amine light stabilizer according to claim 3,
in step S1: the molar ratio of N-N-butyl-2, 6-tetramethyl-4-piperidinamine to 2,4, 6-trichloro-1, 3, 5-triazine is 2;
in step S2: 2-chloro-4, 6-bis- [ N-butyl-N- (2, 6-tetramethyl-4-piperidyl) amino ] -1,3, 5-triazine to resorcinol in a molar ratio of 1.1 to 1.3;
in step S3: the molar ratio of 2- (2 ',4' -dihydroxybenzene) -4, 6-bis [ N-N-butyl-N- (2, 6-tetramethyl-4-piperidyl) amino ] -1,3, 5-triazine and 1-chlorohexane is 1.1 to 1.4.
5. The method for preparing a multifunctional hindered amine light stabilizer according to claim 4, wherein in step S1:
the reaction solvent is toluene, the catalyst is 10-30% sodium hydroxide/potassium hydroxide aqueous solution, and the reaction condition is 60-90 ℃; the reaction time is 6-14h;
N-N-butyl-2, 6-tetramethyl-4-piperidylamine, 2,4, 6-trichloro-1, 3, 5-triazine, sodium hydroxide/potassium hydroxide in a molar ratio of 2-2.4:1:2-2.5.
6. The method for preparing a multifunctional hindered amine light stabilizer according to claim 4, wherein in step S2:
the reaction solvent is chlorobenzene/o-dichlorobenzene, the catalyst is anhydrous aluminum trichloride, and the reaction condition is 60-90 ℃; the reaction time is 4-12h;
the molar ratio of 2-chloro-4, 6-bis- [ N-N-butyl-N- (2, 6-tetramethyl-4-piperidyl) amino ] -1,3, 5-triazine, resorcinol and anhydrous aluminum trichloride is 1:1.1-1.3:1-1.2.
7. The method for preparing a multifunctional hindered amine light stabilizer according to claim 4, wherein in step S3:
the reaction solvent is DMF, the catalyst is sodium hydroxide/potassium hydroxide, and the reaction temperature is 80-120 ℃; the reaction time is 6-10h;
2- (2 ',4' -dihydroxybenzene) -4, 6-bis [ N-N-butyl-N- (2, 6-tetramethyl-4-piperidyl) amino ] -1,3, 5-triazine, 1-chlorohexane, sodium hydroxide/potassium hydroxide in a molar ratio of 1:1.1-1.4:1-1.3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211013533.4A CN115322173B (en) | 2022-08-23 | 2022-08-23 | Multifunctional hindered amine light stabilizer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211013533.4A CN115322173B (en) | 2022-08-23 | 2022-08-23 | Multifunctional hindered amine light stabilizer and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115322173A true CN115322173A (en) | 2022-11-11 |
| CN115322173B CN115322173B (en) | 2023-11-28 |
Family
ID=83926942
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211013533.4A Active CN115322173B (en) | 2022-08-23 | 2022-08-23 | Multifunctional hindered amine light stabilizer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115322173B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4530950A (en) * | 1982-02-10 | 1985-07-23 | Apital Produzioni Industriali S.P.A. | Piperidine derivatives and use thereof as stabilizers for polymers |
| CN110452223A (en) * | 2019-07-29 | 2019-11-15 | 宿迁联盛科技股份有限公司 | A kind of preparation method of composite light stabilizer |
| CN110606984A (en) * | 2019-07-29 | 2019-12-24 | 宿迁联盛科技股份有限公司 | Light stabilizer and preparation method thereof |
-
2022
- 2022-08-23 CN CN202211013533.4A patent/CN115322173B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4530950A (en) * | 1982-02-10 | 1985-07-23 | Apital Produzioni Industriali S.P.A. | Piperidine derivatives and use thereof as stabilizers for polymers |
| CN110452223A (en) * | 2019-07-29 | 2019-11-15 | 宿迁联盛科技股份有限公司 | A kind of preparation method of composite light stabilizer |
| CN110606984A (en) * | 2019-07-29 | 2019-12-24 | 宿迁联盛科技股份有限公司 | Light stabilizer and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115322173B (en) | 2023-11-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| FR2725204A1 (en) | 2-HYDROXYPHENYLTRIAZINES AS PHOTOSTABILIZING AGENTS | |
| CN102212150A (en) | Polymerizable thioxanthone photoinitiator containing auxiliary initiator amine and preparation method thereof | |
| EP3131951B1 (en) | Hydroxide-stable ionenes | |
| CN112920408B (en) | Polysulfonamide polymer and preparation method thereof | |
| CN115322173B (en) | Multifunctional hindered amine light stabilizer and preparation method thereof | |
| CN114957898B (en) | Reversible stress response material and preparation method and application thereof | |
| CN113149963B (en) | Benzotriazole-hindered amine composite light stabilizer and preparation process thereof | |
| CN112341372B (en) | Reactive anti-aging agent without extraction and preparation method thereof | |
| CN109810235B (en) | Ethylene glycol modified melamine formaldehyde resin and preparation method thereof | |
| CN111018782B (en) | Preparation method of 9-aminoacridine and derivatives thereof | |
| CN113620968A (en) | Rigid bio-based diol monomer with cyclic acetal structure, and preparation method and application thereof | |
| CN110283289B (en) | Preparation method and application of phosphorus-containing benzoxazine resin with high flame retardance | |
| CN114292411A (en) | Organic rare earth luminescent material and preparation method and application thereof | |
| CN111647153B (en) | Preparation method of complex color-developing polyamide | |
| CN111944145A (en) | Thermosetting polytriazole ester resin, composite material thereof and preparation method thereof | |
| RU2453562C1 (en) | Method of producing n-phenyl-substituted acyclic polyimides | |
| TWI836319B (en) | Polycarbonate and preparation method thereof | |
| CN113861168B (en) | Polymeric hindered amine light stabilizer and preparation method thereof | |
| CN117263926B (en) | Tripterenyl-containing benzoxazine derivative, polymer, preparation method and application thereof | |
| RU2261873C2 (en) | Method for preparing vinylnitrotriazole polymers | |
| CN116178346A (en) | Polypiperidine light stabilizer and preparation method thereof | |
| CN1045438C (en) | 4H carbazoleone Mannich base and its synthesizing method and application | |
| KR100514345B1 (en) | Glycidyl dinitropropyl formal, poly(glycidyl dinitropropyl formal) and preparation method thereof | |
| KR101921484B1 (en) | Norbornene-based compound and method of preparing the norbornene-based compound | |
| CN110627779A (en) | Preparation method of maleimide biphenyl diphenol type benzoxazine monomer |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |