CN115322173B - Multifunctional hindered amine light stabilizer and preparation method thereof - Google Patents
Multifunctional hindered amine light stabilizer and preparation method thereof Download PDFInfo
- Publication number
- CN115322173B CN115322173B CN202211013533.4A CN202211013533A CN115322173B CN 115322173 B CN115322173 B CN 115322173B CN 202211013533 A CN202211013533 A CN 202211013533A CN 115322173 B CN115322173 B CN 115322173B
- Authority
- CN
- China
- Prior art keywords
- triazine
- light stabilizer
- tetramethyl
- butyl
- 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.)
- Active
Links
- 239000004611 light stabiliser Substances 0.000 title claims abstract description 41
- 150000001412 amines Chemical class 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- MLRVZFYXUZQSRU-UHFFFAOYSA-N 1-chlorohexane Chemical compound CCCCCCCl MLRVZFYXUZQSRU-UHFFFAOYSA-N 0.000 claims abstract description 12
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 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
- 239000003054 catalyst Substances 0.000 claims description 8
- 239000007810 chemical reaction solvent Substances 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Substances ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- MVPPADPHJFYWMZ-IDEBNGHGSA-N chlorobenzene Chemical group Cl[13C]1=[13CH][13CH]=[13CH][13CH]=[13CH]1 MVPPADPHJFYWMZ-IDEBNGHGSA-N 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 32
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 abstract description 8
- 239000001257 hydrogen Substances 0.000 abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 238000006266 etherification reaction Methods 0.000 abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- 238000010534 nucleophilic substitution reaction Methods 0.000 abstract description 3
- 150000003254 radicals Chemical class 0.000 abstract description 3
- 238000006467 substitution reaction Methods 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
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 36
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 27
- 239000004698 Polyethylene Substances 0.000 description 10
- 230000032683 aging Effects 0.000 description 10
- 229920000573 polyethylene Polymers 0.000 description 10
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- -1 polyethylene Polymers 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 4
- 239000012043 crude product Substances 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
- 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
- 125000000524 functional group Chemical group 0.000 description 3
- 239000005457 ice water 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
- 238000001228 spectrum 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
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000012512 characterization 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
- OKKJLVBELUTLKV-VMNATFBRSA-N methanol-d1 Chemical compound [2H]OC OKKJLVBELUTLKV-VMNATFBRSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 125000003944 tolyl 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
- 239000003795 chemical substances by application Substances 0.000 description 1
- DHQCYXIOLBXVDE-UHFFFAOYSA-N chlorobenzene;hydrate Chemical compound O.ClC1=CC=CC=C1 DHQCYXIOLBXVDE-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000009977 dual effect Effects 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
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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: 2-chloro-4, 6-di- [ N-N-butyl-N- (2, 6-tetramethyl-4-piperidyl) amino ] -1,3, 5-triazine is synthesized by nucleophilic substitution by taking N-N-butyl-2, 6-tetramethyl-4-piperidylamine and 2,4, 6-trichloro-1, 3, 5-triazine as raw materials; step S2: synthesizing 2- (2 ',4' -dihydroxybenzene) -4, 6-bis [ N-N-butyl-N- (2, 6-tetramethyl-4-piperidyl) amino ] -1,3, 5-triazine through substitution reaction; step S3: 2- (2 ',4' -dihydroxybenzene) -4, 6-bis [ N-N-butyl-N- (2, 6-tetramethyl-4-piperidyl) amino ] -1,3, 5-triazine and 1-chlorohexane are subjected to etherification reaction to obtain a multifunctional hindered amine light stabilizer UH; according to the invention, an internal hydrogen bond structure is introduced and one hydroxyl group is etherified on the basis of the 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.
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 process of using and processing polymer materials, the polymer materials are inevitably aged to different degrees due to light, oxygen, heat and the like, and in order to prevent the materials from being aged prematurely during processing and use and shortening the service life, a series of anti-aging aids with different functions are researched, and a light stabilizer is one of important aids.
Hindered Amine Light Stabilizers (HALS) are currently the most widely used class of light stabilizers with the highest market share. With the development and in-depth of research on hindered amine light stabilizers, how to develop novel light stabilizers with excellent properties becomes an increasingly troublesome problem. The commercially available HALS, whether monomeric or polymeric, have represented a number of structural possibilities, and attempts have been made to introduce new functional groups. From the action mechanism of the hindered amine light stabilizer, the light stability of the hindered amine light stabilizer is shown in the hindered amine group, and the function of the functional group is particularly outstanding. Therefore, by introducing functional groups with other functions, on the basis of not affecting the action of hindered amine, by means of the intramolecular self-synergistic effect, not only is a new structure type developed, but also a new functional hindered amine light stabilizer is combined, and the novel functional hindered amine light stabilizer 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, which are used for solving the problem of poor compatibility between the multifunctional light stabilizer and different polymers 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 steps:
further, the method comprises the following steps:
step S1: 2-chloro-4, 6-di- [ N-N-butyl-N- (2, 6-tetramethyl-4-piperidyl) amino ] -1,3, 5-triazine is synthesized by nucleophilic substitution by taking N-N-butyl-2, 6-tetramethyl-4-piperidylamine and 2,4, 6-trichloro-1, 3, 5-triazine as raw materials;
step S2:2- (2 ',4' -dihydroxybenzene) -4, 6-bis- [ N-N-butyl-N- (2, 6-tetramethyl-4-piperidyl) amino ] -1,3, 5-triazine and resorcinol are used as raw materials, and are synthesized into 2- (2 ',4' -dihydroxybenzene) -4, 6-bis- [ N-N-butyl-N- (2, 6-tetramethyl-4-piperidyl) amino ] -1,3, 5-triazine through substitution reaction;
step S3: and carrying out etherification reaction on 2- (2 ',4' -dihydroxybenzene) -4, 6-bis [ N-N-butyl-N- (2, 6-tetramethyl-4-piperidinyl) amino ] -1,3, 5-triazine and 1-chlorohexane 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 2:1;
in step S2: the molar ratio of the 2-chloro-4, 6-di- [ N-N-butyl-N- (2, 6-tetramethyl-4-piperidyl) amino ] -1,3, 5-triazine to resorcinol is 1:1.1-1.3;
in step S3: the molar ratio of the 2- (2 ',4' -dihydroxybenzene) -4, 6-bis [ N-N-butyl-N- (2, 6-tetramethyl-4-piperidyl) amino ] -1,3, 5-triazine to the 1-chlorohexane is 1:1.1-1.4.
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-piperidylamine, 2,4, 6-trichloro-1, 3, 5-triazine and 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 the 2-chloro-4, 6-di- [ 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;
the molar ratio of 2- (2 ',4' -dihydroxybenzene) -4, 6-bis [ N-N-butyl-N- (2, 6-tetramethyl-4-piperidinyl) amino ] -1,3, 5-triazine, 1-chlorohexane, sodium hydroxide/potassium hydroxide is 1:1.1-1.4:1-1.3.
The beneficial effects of the invention are as follows: resorcinol and 1-chlorohexane are used as substituents, 2-chloro-4, 6-di- [ N-N-butyl-N- (2, 6-tetramethyl-4-piperidinyl) amino ] -1,3, 5-triazine is modified, an internal hydrogen bond structure is introduced on the basis of a triazine structure light stabilizer, and one hydroxyl group is etherified, so that the prepared compound has two functions of ultraviolet absorption and free radical capturing, and simultaneously has better compatibility with different materials, the problem that the compatibility of a multifunctional light stabilizer and different polymers in the prior art is poor is solved, and the compound has the advantages of one agent with multiple purposes and better compatibility; the invention takes 2-chloro-4, 6-di- [ N-N-butyl-N- (2, 6-tetramethyl-4-piperidyl) amino ] -1,3, 5-triazine as a raw material, forms an internal hydrogen bond structure after resorcinol is accessed, and is modified by taking 1-chlorohexane as a substituent group, the compound has the internal hydrogen bond and a hindered amine structure, so that the compound has the dual functions of ultraviolet absorption and free radical capture, and simultaneously has good compatibility in different materials by etherifying one hydroxyl group, thus having important application prospect in the anti-aging field of plastic products.
Drawings
FIG. 1 is a diagram showing the structural characterization of 2-chloro-4, 6-bis- [ N-N-butyl-N- (2, 6-tetramethyl-4-piperidinyl) amino ] -1,3, 5-triazine according to 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-piperidinyl) 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-piperidinyl) amino ] -1,3, 5-triazine;
FIG. 2 is a structural representation of 2- (2 ',4' -dihydroxybenzene) -4, 6-bis [ N-N-butyl-N- (2, 6-tetramethyl-4-piperidinyl) amino ] -1,3, 5-triazine according to the 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-piperidinyl) amino ] -1,3, 5-triazine;
FIG. 2 (b) is a nuclear magnetic resonance hydrogen spectrum of 2- (2 ',4' -dihydroxybenzene) -4, 6-bis [ N-N-butyl-N- (2, 6-tetramethyl-4-piperidinyl) amino ] -1,3, 5-triazine;
FIG. 3 is a diagram showing the structural characterization of a multifunctional hindered amine light stabilizer, namely a compound UH, in the present invention;
FIG. 3 (a) is a high resolution mass spectrum of a multifunctional hindered amine light stabilizer;
FIG. 3 (b) is a nuclear magnetic resonance hydrogen spectrum of a multifunctional hindered amine light stabilizer;
FIG. 4 is a graph showing the aging comparison of films of the doping compound UH and blank PE films at different aging times;
FIG. 5 is a graph showing the mechanical properties of the aged polyethylene film;
FIG. 5 (a) is a graph showing the relationship between the tensile strength retention of films and the aging time;
FIG. 5 (b) is a graph showing the relationship between the aging time and the elongation at break retention of the film.
Detailed Description
The invention will be described in detail below with reference to the drawings and the detailed description.
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: 2-chloro-4, 6-di- [ N-N-butyl-N- (2, 6-tetramethyl-4-piperidyl) amino ] -1,3, 5-triazine is synthesized by nucleophilic substitution by taking N-N-butyl-2, 6-tetramethyl-4-piperidylamine and 2,4, 6-trichloro-1, 3, 5-triazine as raw materials;
step S2:2- (2 ',4' -dihydroxybenzene) -4, 6-bis- [ N-N-butyl-N- (2, 6-tetramethyl-4-piperidyl) amino ] -1,3, 5-triazine and resorcinol are used as raw materials, and are synthesized into 2- (2 ',4' -dihydroxybenzene) -4, 6-bis- [ N-N-butyl-N- (2, 6-tetramethyl-4-piperidyl) amino ] -1,3, 5-triazine through substitution reaction;
step S3: and carrying out etherification reaction on 2- (2 ',4' -dihydroxybenzene) -4, 6-bis [ N-N-butyl-N- (2, 6-tetramethyl-4-piperidinyl) amino ] -1,3, 5-triazine and 1-chlorohexane 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 2:1;
in step S2: the molar ratio of the 2-chloro-4, 6-di- [ N-N-butyl-N- (2, 6-tetramethyl-4-piperidyl) amino ] -1,3, 5-triazine to resorcinol is 1:1.1-1.3;
in step S3: the molar ratio of the 2- (2 ',4' -dihydroxybenzene) -4, 6-bis [ N-N-butyl-N- (2, 6-tetramethyl-4-piperidyl) amino ] -1,3, 5-triazine to the 1-chlorohexane is 1:1.1-1.4.
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 and 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 the 2-chloro-4, 6-di- [ 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;
the molar ratio of 2- (2 ',4' -dihydroxybenzene) -4, 6-bis [ N-N-butyl-N- (2, 6-tetramethyl-4-piperidinyl) amino ] -1,3, 5-triazine, 1-chlorohexane, sodium hydroxide/potassium hydroxide is 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-piperidinyl) amino ] -1,3, 5-triazine
In a 500mL three-necked flask, 200mL of methanol was added, 2,4, 6-trichloro-1, 3, 5-triazine (18.44 g,100 mmol) was dissolved therein, N-N-butyl-2, 6-tetramethyl-4-piperidylamine (42.42 g,200 mmol) was slowly added under ice-water bath, and reacted for 2 hours; 35% NaOH solution was added to a 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 a pale yellow solid is obtained through desolventizing, the yield is about 48.8g, and the yield is 91%.
The product 2-chloro-4, 6-bis- [ N-N-butyl-N- (2, 6-tetramethyl-4-piperidinyl) amino ] -1,3, 5-triazine was detected 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-piperidinyl) amino ] -1,3, 5-triazine
Into a 500mL three-necked flask, 2-chloro-4, 6-bis- [ N-N-butyl-N- (2, 6-tetramethyl-4-piperidinyl) amino ] -1,3, 5-triazine (16.0 g,30.0 mmol) and 120mL of chlorobenzene were stirred, anhydrous aluminum trichloride (4.0 g,30.0 mmol) was added under ice-water bath, and after stirring in ice-water bath for 30min, resorcinol (3.96 g,36.0 mmol) was added to the flask and reacted at 80℃for 4 hours. 120mL of 2% diluted hydrochloric acid was slowly added dropwise to the reaction flask, the chlorobenzene-water azeotrope was recovered by atmospheric distillation, and the temperature was raised to 100 ℃. The crude product is filtered by suction while the crude product is hot, and washed by dilute hydrochloric acid, water and dichloromethane for several times, so that white solid is obtained, 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-piperidinyl) amino ] -1,3, 5-triazine was detected 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] + 。
step S3: preparation of multifunctional hindered amine light stabilizer UH
0.7g (17.5 mmol) of sodium hydroxide solid and 100mM of LDMF are added into a three-necked flask, heated and stirred for dissolution, then 10.0g (16.4 mmol) of intermediate is added, the temperature is raised to 80 ℃, a mixed solution of 1-chlorohexane (2.9 mL,21.3 mmol) and DMF (6.0 mL) is dropwise added while the reaction is carried out, the constant temperature continues to be carried out within 2min, after the reaction is carried out for 6-7h to reach the end point, the reaction solution is cooled, the crude product is obtained by suction filtration, the crude product is dried after washing by water, and the light yellow solid is obtained by crystallization by DMF, the yield is about 7.96g, and the yield is 70.1%.
The UH detection result of the multifunctional hindered amine light stabilizer is 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 was doped in a Polyethylene (PE) film, and an aging performance test was performed, and the test results are shown in the left side of fig. 4, the film added with the compound UH is shown in the left side of fig. 4, and the blank film is shown in the right side of fig. 4, and it is obvious from fig. 4 that the PE film without the compound UH has obvious cracks after aging for 400 hours in an ultraviolet aging machine, and the PE film after the light stabilizer UH is added is also basically intact after aging for 800 hours.
After the multifunctional hindered amine light stabilizer prepared in the embodiment is doped in the PE film, the mechanical properties of the aged polyethylene film are tested, and the test results are shown in figure 5. It can be seen from figure 5 that under different aging times, the tensile strength retention (figure 5 a) and the elongation at break retention (figure 5 b) of the polyethylene film added with the light stabilizer UH are always better than those of the polyethylene film without UH after different aging times. Thus, the light stabilizer UH does have excellent anti-aging properties.
Example 2
This example is identical to the procedure of example 1, except that:
in step S1, N-N-butyl-2, 6-tetramethyl-4-piperidinamine was added in an amount of (46.66 g,220 mmol) and NaOH solution was 25%, with a final yield of about 47.1g, 88%.
In step S2, the solvent chlorobenzene was replaced with o-dichlorobenzene, and anhydrous aluminum trichloride (4.8 g,36.0 mmol) was added, the diluted hydrochloric acid was 3% diluted hydrochloric acid, and the yield was about 16.4g, and the yield was 90%.
The amount of 1-chlorohexane added in step S3 was 3.1mL,23.0mmol, and the catalyst sodium hydroxide (0.7 g,17.5 mmol) was replaced with potassium hydroxide (0.98 g,17.5 mmol), resulting in a final yield of about 7.83g and a yield of 69%.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (4)
1. A multifunctional hindered amine light stabilizer is characterized by having the following structural formula:
。
2. a preparation method of a multifunctional hindered amine light stabilizer is characterized in that the reaction equation is as follows:
。
3. the method for preparing a multifunctional hindered amine light stabilizer according to claim 2, wherein,
in step S1: the molar ratio of the compound (1) to the compound (2) is 2:1;
in step S2: the mol ratio of the compound (3) to the resorcinol is 1:1.1-1.3;
in step S3: the molar ratio of the compound (5) to the 1-chlorohexane is 1:1.1-1.4.
4. A method for preparing a multifunctional hindered amine light stabilizer according to claim 3, 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 the compound (3), resorcinol and anhydrous aluminum trichloride is 1:1.1-1.3:1-1.2.
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 CN115322173A (en) | 2022-11-11 |
| CN115322173B true 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 |
|---|---|
| CN115322173A (en) | 2022-11-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102212150A (en) | Polymerizable thioxanthone photoinitiator containing auxiliary initiator amine and preparation method thereof | |
| US10005886B2 (en) | Hydroxide-stable ionenes | |
| CN106279104B (en) | A kind of process modification method preparing amber love song Ge Lieting | |
| CN108623567A (en) | Ao Si replaces the preparation method of Buddhist nun | |
| CN109867733A (en) | The cyclodextrine derivatives and preparation method thereof of a kind of ferulic acid modification | |
| KR102132087B1 (en) | Method for preparing azoxystrobin | |
| CN115322173B (en) | Multifunctional hindered amine light stabilizer and preparation method thereof | |
| CN103896935B (en) | The preparation method of 3-[(4-amino-5-pyrimidine base) methyl]-5-(2-ethoxy)-4-methylthiazol nitrate | |
| CN111018782B (en) | Preparation method of 9-aminoacridine and derivatives thereof | |
| CN109810235B (en) | Ethylene glycol modified melamine formaldehyde resin and preparation method thereof | |
| CN102796141A (en) | Phosphor series benzoxazine and preparation method | |
| CN113620968A (en) | Rigid bio-based diol monomer with cyclic acetal structure, and preparation method and application thereof | |
| JP5670871B2 (en) | Cyclic macromonomer and method for producing the same | |
| JPH1045728A (en) | Production of bis(2-hydroxyphenyl-3-benzotriazole) methanes | |
| CN102584610B (en) | Bisphenol 2 (m-amino p-hydroxy phenyl) ether hydrochloride and preparation method and application thereof | |
| TWI500627B (en) | Phenol-containing multifunctional epoxy curing agents and their derivatives, preparation and use | |
| CN114516807B (en) | Nitro-containing poly-substituted aromatic diamine monomer and preparation method thereof | |
| CN111647153B (en) | Preparation method of complex color-developing polyamide | |
| CN116178346A (en) | Polypiperidine light stabilizer and preparation method thereof | |
| CN109575275B (en) | High-solubility polyaramid containing di-tert-butyl benzene and dimethyl structure simultaneously and preparation method and application thereof | |
| CN111704604B (en) | Preparation method of pyridine quinazoline | |
| CN115505099B (en) | Epoxy resin containing carbazole structure, and preparation method and application thereof | |
| CN1045438C (en) | 4H carbazoleone Mannich base and its synthesizing method and application | |
| JPS6136270A (en) | Manufacture of 2_alkyl_4,5_dihydroxymethylimidazole | |
| CN116283681B (en) | Method for industrially producing octabromos ether |
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 |