CN109942549A - A kind of low alkalinity polymerized hindered amine light stabilizer and preparation method thereof - Google Patents

A kind of low alkalinity polymerized hindered amine light stabilizer and preparation method thereof Download PDF

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CN109942549A
CN109942549A CN201811266705.2A CN201811266705A CN109942549A CN 109942549 A CN109942549 A CN 109942549A CN 201811266705 A CN201811266705 A CN 201811266705A CN 109942549 A CN109942549 A CN 109942549A
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compound
methyl
butyl
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李靖
周彦博
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BEIJIN TIANGANG AUXILIARY Co Ltd
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BEIJIN TIANGANG AUXILIARY Co Ltd
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Priority to PCT/CN2019/111386 priority patent/WO2020088249A1/en
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    • 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • 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
    • 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
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors

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Abstract

The present invention provides the compounds that a kind of general formula is I, the compound can be used to prepare low alkalinity polymerized hindered amine light stabilizer, the light stablizing effect of such hindered amine light stabilizer is excellent, molecular weight is big, resistant to extraction, alkalinity is low, and compatibility is good and has a wide range of application, and the present invention also provides a kind of preparation method and applications of low alkalinity polymerized hindered amine light stabilizer.

Description

A kind of low alkalinity polymerized hindered amine light stabilizer and preparation method thereof
Technical field
The present invention relates to polymeric material field, in particular to a kind of low alkalinity polymerized hindered amine light stabilizer and its system Preparation Method.
Background technique
High molecular material such as plastics, fiber and rubber etc., are chronically exposed under daylight, due to absorbing ultraviolet energy and Auto-oxidation reaction is caused, the degradation of polymer is resulted in；So that material discoloration, embrittlement, performance decline, so that can not It continues to use, this process is referred to as photo aging process.Light stabilizer is one of most common high molecular material additive, it It can prevent or excellent properties that delaying aging keeps its original are to prolong its service life.
Currently, light stabilizer is various in style, photomask agent, ultraviolet absorbing agent, quencher can be divided by its mechanism of action And radical scavenger.Wherein, hindered amine light stabilizer (HALS) be the 1970s mid-term by Japan three altogether companies The new and effective light stabilizer of one kind of development, light stablizing effect is 2~4 times of conventional suction type light stabilizer, is One of widest light stabilizer is studied at present.Although the ratio of this kind of light stabilizer exploitation is later, quickly grow.In early days Although hindered amine light stabilizer kind light stability it is excellent, but still the defects of that there is molecular weight is low, and alkalinity is higher, Make its narrow scope of application.Therefore, it is to develop at present that design synthesis, which has the hindered amine light stabilizer of high molecular weight and low alkalinity, The main direction of studying of such light stabilizer.
In the prior art, patent CN102827148A provides a kind of hindered amine compound, using blocking group to GW- Amino on 944 piperidine rings is protected, and necleophilic reaction leading-in end alkenyl group is then utilized.As high molecular polymer When light stabilizer, since the end alkenyl group containing unsaturated bond technology can be grafted on macromolecular chain via radiation, shape At carbon-carbon bond, therefore hindered amine compound not readily dissolves precipitation, photostability enhancing.Patent CN104725361A is disclosed Light stabilizer 3346 and preparation method thereof, light stabilizer 3346 is polymerized hindered amine light stabilizer, more demanding to weatherability Coloured or colourless polyolefin articles protection it is especially effective, and it is special be suitable for agricultural film, fiber and moulding article etc., in addition to Have the characteristics that fabulous photostability, with the fabulous compatibility of resin, outside color is shallow, nontoxic and high-temperature volatile is low, also has Good hot oxygen protective performance.
The hindered amine light stabilizer disclosed in above-mentioned patent still has the higher problem of alkalinity, limits it and sets with acidity The synergistic stability effect of rouge, halogen containing flame-retardant and phenolic antioxidant.To overcome the shortcomings of existing technologies, it invents in the present invention People's design has synthesized a kind of low alkalinity polymerized hindered amine light stabilizer product.
Summary of the invention
It is poly- using the low alkalinity it is an object of the invention to design to synthesize a kind of low alkalinity polymerized hindered amine light stabilizer Mould assembly hindered amine light stabilizer fights the problem of decomposing organic materials caused by light, heat or oxidation；A present invention also purpose It is to provide a kind of preparation method of low alkalinity polymerized hindered amine light stabilizer.
The present invention provides a kind of compound that general formula is I:
R1、R2And R3It is independent to be selected from: C1-20Alkyl or C3-12Naphthenic base；
Preferably, the C1-20Alkyl is selected from: methyl, ethyl, propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, Tert-butyl, 2- ethyl-butyl, n-pentyl, isopentyl, 1- methyl amyl, 1,3- dimethylbutyl, n-hexyl, 1- methylhexyl, N-heptyl, different heptyl, 1,1,3,3- tetramethyl butyl, 1- methylheptyl, 3- methylheptyl, n-octyl, 2- ethylhexyl, 1, 1,3- trimethyl, 1,1,3,3- tetramethyl amyl, nonyl, decyl, undecyl, 1- methylundecyl, dodecane Base, 1,1,3,3,5,5- hexamethyl hexyl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, 18 Alkyl and eicosyl；
It is furthermore preferred that the C1-20Alkyl is selected from: methyl, ethyl, propyl, isopropyl, normal-butyl, sec-butyl, isobutyl Base, tert-butyl, 2- ethyl-butyl, n-pentyl, isopentyl, 1- methyl amyl, 1,3- dimethylbutyl, n-hexyl, 1- methyl oneself Base, n-heptyl, different heptyl, 1,1,3,3- tetramethyl butyl, 1- methylheptyl, 3- methylheptyl, n-octyl, 2- ethylhexyl, 1,1,3- trimethyl, 1,1,3,3- tetramethyl amyl, nonyl, decyl.
Preferably, the C3-12Naphthenic base is the monovalent monocyclic alkyl of saturation, is selected from: cyclopropyl, cyclobutyl, methyl ring fourth Base, cyclopenta, methylcyclopentyl, dimethylcyclopentyl, front three cyclopentyl, ethylcyclopentyl, propyl cyclopenta, isopropyl It is cyclopenta, cyclohexyl, methylcyclohexyl, Dimethylcyclohexyl, trimethylcyclohexyl, ethylcyclohexyl, propylcyclohexyl, different Propylcyclohexyl, butylcyclohexyl, isobutyl butylcyclohexyl, tert-butylcyclohexyl, suberyl, methylcycloheptyl, dimethyl cycloheptyl Base, front three cycloheptyl, ethylcyclohexyl, propyl suberyl, isopropyl cycloheptyl, butyl suberyl, isobutyl cycloheptyl, Tert-butyl suberyl, cyclooctyl, methylcyclooctyl, dimethylcyclooctyl, trimethyl cyclooctyl, ethyl cyclooctyl, propyl ring are pungent Base, isopropyl cyclooctyl, butyl cyclooctyl, isobutyl group cyclooctyl, tert-butyl cyclooctyl, cyclononyl, methyl cyclononyl, diformazan Basic ring nonyl, trimethyl cyclononyl, ethyl cyclononyl, propyl cyclononyl, isopropyl cyclononyl, cyclodecyl, methyl cyclodecyl, Dimethyl cyclodecyl, ethyl cyclodecyl；
It is furthermore preferred that the C3-12Naphthenic base is selected from: cyclopropyl, cyclobutyl, methyl-cyclobutyl, cyclopenta, methyl ring penta Base, dimethylcyclopentyl, front three cyclopentyl, ethylcyclopentyl, propyl cyclopenta, isopropyl cyclopentyl, cyclohexyl, methyl Cyclohexyl, Dimethylcyclohexyl, ethylcyclohexyl, suberyl, methylcycloheptyl, cyclooctyl.
R4It is selected from: C1-10Alkyl；
Preferably, the R4It is selected from: methyl, ethyl, propyl, normal-butyl, n-pentyl, isopentyl, n-hexyl, 1- methyl Hexyl；
In a preferred embodiment of the invention, R4For normal-butyl.
R5And R6It is independent to be selected from: C1-10Alkyl or C3-8Naphthenic base；
Preferably, the R5And R6It is independent to be selected from: methyl, ethyl, propyl, isopropyl, normal-butyl, sec-butyl, isobutyl Base, n-pentyl, isopentyl, n-hexyl, 1- methylhexyl, n-heptyl, different heptyl, n-octyl, cyclopropyl, cyclobutyl, methyl ring Butyl, cyclopenta, methylcyclopentyl or cyclohexyl；
In a preferred embodiment of the invention, R5And R6It is independent to be selected from: normal-butyl.
Z is selected from the C of straight chain or branching2-20Straight chain that alkylidene or at least one C atom are replaced by oxygen or sulphur or branching C2-20Alkylidene chain；
In a preferred embodiment of the invention, Z is selected from: hexylidene.
N is 2-12.
In a preferred embodiment of the invention, the structural formula of generalformulaⅰcompound is as follows:
The present invention provides a kind of preparation method of generalformulaⅰcompound, and steps are as follows:
(1)Obtain II compound of formula；
Obtain III compound of formula；
(3)Obtain IV chemical combination of formula Object；
The formula of obtaining V compound；
(5) II compound of formula that step (1) obtains is reacted with V compound of formula that step (4) obtains, and is obtained
R1-R6, Z it is as defined above；
Preferably, in the step (1)In molar ratio it is 2:1-3:1 with Cyanuric Chloride, adds alkali, the alkali Be selected from: sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide or triethylamine, alkali withMolar ratio be 1:1-1.5:1, Reaction temperature is 30-60 DEG C, and reaction dissolvent is selected from: acetone, methylene chloride, toluene or dimethylbenzene；
Preferably, the reaction time is 5-12h in the step (2), and the catalyst is selected from: molybdenum trioxide, five oxidations two The molar ratio of the hindered amine piperidine structure unit of vanadium, chromium trioxide, tungstic acid or manganese dioxide, catalyst and addition is 0.02:1-0.2:1, the alkylating reagent are selected from: halogenated hydrocarbons, sulfuric ester, aromatic sulfonic acid ester, alcohol, ether, olefines, formaldehyde, first The combination of one or more of acid；
Preferably, in the step (3)With the molar ratio 1:1-1:1.5 of Cyanuric Chloride, add alkali, the alkali Be selected from: sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide or triethylamine, alkali withMolar ratio be 1:1-1.5: 1, reaction temperature is -10-10 DEG C, and reaction time 1-12h, the catalyst is selected from: molybdenum trioxide, vanadic anhydride, three The molar ratio of the hindered amine piperidine structure unit of chromium oxide, tungstic acid or manganese dioxide, catalyst and addition is 0.02:1- 0.2:1, the alkylating reagent are selected from: halogenated hydrocarbons, sulfuric ester, aromatic sulfonic acid ester, alcohol, ether, olefines, formaldehyde, one in formic acid Kind or two or more combinations, reaction dissolvent are selected from: acetone, methylene chloride, toluene, dimethylbenzene or tetrahydrofuran；
Preferably, the molar ratio of III compound of step (4) Chinese style and IV compound of formula is 2:1-3:1, adds alkali, described Alkali be selected from: the molar ratio of sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide or triethylamine, alkali and IV compound of formula is 1: 1-1.5:1, reaction temperature are 150-200 DEG C, reaction time 3-12h, and reaction dissolvent is selected from toluene, chlorobenzene, dichloro-benzenes or two Toluene, reaction carry out in autoclave；
Preferably, the molar ratio of II compound of step (5) Chinese style and V compound of formula is 2:1-3:1, adds alkali, described Alkali is selected from: sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide or triethylamine, and the molar ratio of alkali and V compound of formula is 1:1- 1.5:1, reaction temperature are 100-150 DEG C, reaction time 3-12h, and reaction carries out in autoclave.
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common Technical staff's every other embodiment obtained without creative efforts belongs to what the present invention protected Range.
The preparation of 1 low alkalinity hindered amine light stabilizer A of embodiment
18.4g Cyanuric Chloride is dissolved in 120mL toluene, after being cooled to 0 DEG C, 25.8g di-n-butylamine (trimerization is slowly added dropwise The molar ratio of chlorine cyanogen and di-n-butylamine is 1:2), after dripping, 40 DEG C are warming up to, 4g NaOH is added, after stirring 2h, filtering, Filtrate water washing, organic phase are concentrated to give II compound of formula.
150mL iodomethane will be added in 39.5g hexamethylene diamine piperidines, 0.5g tungstic acid stirs 12h in 50C, is cooled to room Excessive saturation NaHSO is added to filtrate in temperature, filtering3Solution stirs, and separation, organic phase is concentrated to give III compound of formula.
18.4g Cyanuric Chloride is dissolved in 300mL acetone, after being cooled to 0 DEG C, sequentially adds 21.2g N- (2,2,6,6- tetra- Methyl -4- piperidyl) n-butylamine (molar ratio of Cyanuric Chloride and N- (2,2,6,6- tetramethyl -4- piperidyl) n-butylamine is 1: And 13.8g K 1)2CO3, 1h, filtering are stirred, filtrate water washs, then 150mL will be added in organic phase concentration in concentrate Iodomethane, 0.5g tungstic acid are cooled to room temperature in 50 DEG C of stirring 12h, filtering, and excessive saturation NaHSO is added to filtrate3It is molten Liquid stirs, and separation, organic phase is concentrated to give IV compound of formula.
III compound of 24.7g formula, IV compound of 8.8g formula and 150mL dimethylbenzene are put into 300mL autoclave, are sealed, Use N2It replaces in kettle air 3 times, is then warming up to 80 DEG C of reaction 2h, cool down, open kettle, 2.4g NaOH is added, N is used in sealing2It sets Air 3 times in kettle are changed, stirs, is then heated to 190 DEG C of reaction 5h.Cooling is deflated, and kettle, reaction solution filtering, filtrate water are opened Solution washing, organic phase are concentrated to give V compound of formula.
II compound of 18.4g formula, V compound of formula, 150mL dimethylbenzene and 2.4g NaOH are put into 300mL autoclave, Sealing, uses N2It replaces in kettle air 3 times, is then heated to 150 DEG C of reaction 5h.Cooling is deflated, and kettle, reaction solution filtering, filter are opened Liquid is washed with aqueous solution, and organic phase is concentrated to get low alkalinity light stabilizer A, yield 90%.
The preparation of 2 low alkalinity hindered amine light stabilizer A of embodiment
18.4g Cyanuric Chloride is dissolved in 120mL toluene, after being cooled to 0 DEG C, 25.8g di-n-butylamine (trimerization is slowly added dropwise The molar ratio of chlorine cyanogen and di-n-butylamine is 1:2), after dripping, 40 DEG C are warming up to, 4g NaOH is added, after stirring 2h, filtering, Filtrate water washing, organic phase are concentrated to give II compound of formula.
150mL dimethyl suflfate will be added in 39.5g hexamethylene diamine piperidines, 0.5g molybdenum trioxide is cold in 50 DEG C of stirring 12h To room temperature, excessive saturation NaHSO is added to filtrate in filtering3Solution stirs, and separation, organic phase is concentrated to give III compound of formula.
18.4g Cyanuric Chloride is dissolved in 300mL acetone, after being cooled to 0 DEG C, sequentially adds 21.2g N- (2,2,6,6- tetra- Methyl -4- piperidyl) n-butylamine (molar ratio of Cyanuric Chloride and N- (2,2,6,6- tetramethyl -4- piperidyl) n-butylamine is 1: And 13.8g K 1)2CO3, 1h, filtering are stirred, filtrate water washs, then 150mL will be added in organic phase concentration in concentrate Dimethyl suflfate, 0.5g molybdenum trioxide are cooled to room temperature in 50 DEG C of stirring 12h, filtering, and excessive saturation is added to filtrate NaHSO3Solution stirs, and separation, organic phase is concentrated to give IV compound of formula.
III compound of 24.7g formula, IV compound of 8.8g formula and 150mL dimethylbenzene are put into 300mL autoclave, are sealed, Use N2It replaces in kettle air 3 times, is then warming up to 80 DEG C of reaction 2h, cool down, open kettle, 2.4g NaOH is added, N is used in sealing2It sets Air 3 times in kettle are changed, stirs, is then heated to 190 DEG C of reaction 5h.Cooling is deflated, and kettle, reaction solution filtering, filtrate water are opened Solution washing, organic phase are concentrated to give V compound of formula.
II compound of 18.4g formula, V compound of formula, 150mL dimethylbenzene and 2.4g NaOH are put into 300mL autoclave, Sealing, uses N2It replaces in kettle air 3 times, is then heated to 170 DEG C of reaction 5h.Cooling is deflated, and kettle, reaction solution filtering, filter are opened Liquid is washed with aqueous solution, and organic phase is concentrated to get low alkalinity light stabilizer A, yield 92%.
The preparation of 3 low alkalinity hindered amine light stabilizer A of embodiment
18.4g Cyanuric Chloride is dissolved in 120mL toluene, after being cooled to 0 DEG C, 25.8g di-n-butylamine (trimerization is slowly added dropwise The molar ratio of chlorine cyanogen and di-n-butylamine is 1:2), after dripping, 40 DEG C are warming up to, 4g NaOH is added, after stirring 2h, filtering, Filtrate water washing, organic phase are concentrated to give II compound of formula.
150mL dimethyl carbonate will be added in 39.5g hexamethylene diamine piperidines, 0.5g molybdenum trioxide is cold in 50 DEG C of stirring 12 h To room temperature, excessive saturation NaHSO is added to filtrate in filtering3Solution stirs, and separation, organic phase is concentrated to give III compound of formula.
18.4g Cyanuric Chloride is dissolved in 300mL acetone, after being cooled to 0 DEG C, sequentially adds 21.2g N- (2,2,6,6- tetra- Methyl -4- piperidyl) n-butylamine (molar ratio of Cyanuric Chloride and N- (2,2,6,6- tetramethyl -4- piperidyl) n-butylamine is 1: And 13.8g K 1)2CO3, 1h, filtering are stirred, filtrate water washs, then 150mL carbon will be added in organic phase concentration in concentrate Dimethyl phthalate, 0.5g molybdenum trioxide are cooled to room temperature in 50 DEG C of stirring 12h, filtering, and excessive saturation NaHSO is added to filtrate3 Solution stirs, and separation, organic phase is concentrated to give IV compound of formula.
III compound of 36.1g formula, IV compound of 8.8g formula and 150mL dimethylbenzene are put into 300mL autoclave, are sealed, Use N2It replaces in kettle air 3 times, is then warming up to 80 DEG C of reaction 2h, cool down, open kettle, 2.4g NaOH is added, N is used in sealing2It sets Air 3 times in kettle are changed, stirs, is then heated to 190 DEG C of reaction 5h.Cooling is deflated, and kettle, reaction solution filtering, filtrate water are opened Solution washing, organic phase are concentrated to give V compound of formula.
II compound of 18.4g formula, V compound of formula, 150mL dimethylbenzene and 2.4g NaOH are put into 300mL autoclave, Sealing, uses N2It replaces in kettle air 3 times, is then heated to 170 DEG C of reaction 5h.Cooling is deflated, and kettle, reaction solution filtering, filter are opened Liquid is washed with aqueous solution, and organic phase is concentrated to get low alkalinity light stabilizer A, yield 95%.
The preparation of 4 low alkalinity hindered amine light stabilizer B of embodiment
18.4g Cyanuric Chloride is dissolved in 120mL toluene, after being cooled to 0 DEG C, 25.8g di-n-butylamine (trimerization is slowly added dropwise The molar ratio of chlorine cyanogen and di-n-butylamine is 1:2), after dripping, 40 DEG C are warming up to, 4g NaOH is added, after stirring 2h, filtering, Filtrate water washing, organic phase are concentrated to give II compound of formula.
150mL bromo propane will be added in 39.5g hexamethylene diamine piperidines, 0.5g molybdenum trioxide is cooled in 50 DEG C of stirring 12h Excessive saturation NaHSO is added to filtrate in room temperature, filtering3Solution stirs, and separation, organic phase is concentrated to give III compound of formula.
18.4g Cyanuric Chloride is dissolved in 300mL acetone, after being cooled to 0 DEG C, sequentially adds 21.2g N- (2,2,6,6- tetra- Methyl -4- piperidyl) n-butylamine (molar ratio of Cyanuric Chloride and N- (2,2,6,6- tetramethyl -4- piperidyl) n-butylamine is 1: And 13.8g K 1)2CO3, 1h, filtering are stirred, filtrate water washs, then 150mL bromine will be added in organic phase concentration in concentrate For propane, 0.5g molybdenum trioxide is cooled to room temperature in 50 DEG C of stirring 12h, filtering, and excessive saturation NaHSO is added to filtrate3It is molten Liquid stirs, and separation, organic phase is concentrated to give IV compound of formula.
III compound of 24.7g formula, IV compound of 8.8g formula and 150mL dimethylbenzene are put into 300mL autoclave, are sealed, Use N2It replaces in kettle air 3 times, is then warming up to 80 DEG C of reaction 2h, cool down, open kettle, 3g NaOH is added, N is used in sealing2Displacement Air 3 times in kettle, stirring, are then heated to 190 DEG C of reaction 5h.Cooling is deflated, and kettle is opened, and reaction solution filters, and filtrate water is molten Liquid washing, organic phase are concentrated to give V compound of formula.
II compound of 18.4g formula, V compound of formula, 150mL dimethylbenzene and 3g NaOH are put into 300mL autoclave, Sealing, uses N2It replaces in kettle air 3 times, is then heated to 170 DEG C of reaction 5h.Cooling is deflated, and kettle, reaction solution filtering, filter are opened Liquid is washed with aqueous solution, and organic phase is concentrated to get low alkalinity light stabilizer B, yield 93%.
The preparation of 5 low alkalinity hindered amine light stabilizer B of embodiment
18.4g Cyanuric Chloride is dissolved in 120mL toluene, after being cooled to 0 DEG C, 25.8g di-n-butylamine (trimerization is slowly added dropwise The molar ratio of chlorine cyanogen and di-n-butylamine is 1:2), after dripping, 40 DEG C are warming up to, 4g NaOH is added, after stirring 2h, filtering, Filtrate water washing, organic phase are concentrated to give II compound of formula.
Three propyl ester of 150mL carbonic acid will be added in 39.5g hexamethylene diamine piperidines, 0.5g tungstic acid is cold in 50 DEG C of stirring 12 h To room temperature, excessive saturation NaHSO is added to filtrate in filtering3Solution stirs, and separation, organic phase is concentrated to give III compound of formula.
18.4g Cyanuric Chloride is dissolved in 300mL acetone, after being cooled to 0 DEG C, sequentially adds 21.2g N- (2,2,6,6- tetra- Methyl -4- piperidyl) n-butylamine (molar ratio of Cyanuric Chloride and N- (2,2,6,6- tetramethyl -4- piperidyl) n-butylamine is 1: And 13.8g K 1)2CO3, 1h, filtering are stirred, filtrate water washs, then 150mL alkane will be added in organic phase concentration in concentrate Base reagent, 0.5g tungstic acid are cooled to room temperature in 50 DEG C of stirring 12h, filtering, and excessive saturation NaHSO is added to filtrate3 Solution stirs, and separation, organic phase is concentrated to give IV compound of formula.
III compound of 24.7g formula, IV compound of 8.8g formula and 150mL dimethylbenzene are put into 300mL autoclave, are sealed, Use N2It replaces in kettle air 3 times, is then warming up to 80 DEG C of reaction 2h, cool down, open kettle, 2.4g NaOH is added, N is used in sealing2It sets Air 3 times in kettle are changed, stirs, is then heated to 190 DEG C of reaction 5h.Cooling is deflated, and kettle, reaction solution filtering, filtrate water are opened Solution washing, organic phase are concentrated to give V compound of formula.
II compound of 24.7g formula, V compound of formula, 150mL dimethylbenzene and 2.4g NaOH are put into 300mL autoclave, Sealing, uses N2It replaces in kettle air 3 times, is then heated to 190 DEG C of reaction 5h.Cooling is deflated, and kettle, reaction solution filtering, filter are opened Liquid is washed with aqueous solution, and organic phase is concentrated to get low alkalinity light stabilizer B, yield 91%.
The preparation of 6 low alkalinity hindered amine light stabilizer C of embodiment
18.4g Cyanuric Chloride is dissolved in 120mL toluene, after being cooled to 0 DEG C, 25.8g di-n-butylamine (trimerization is slowly added dropwise The molar ratio of chlorine cyanogen and di-n-butylamine is 1:2), after dripping, 40 DEG C are warming up to, 4g NaOH is added, after stirring 2h, filtering, Filtrate water washing, organic phase are concentrated to give II compound of formula.
150mL bromocyclohexane will be added in 39.5g hexamethylene diamine piperidines, 0.5g molybdenum trioxide is cold in 50 DEG C of stirring 12 h To room temperature, excessive saturation NaHSO is added to filtrate in filtering3Solution stirs, and separation, organic phase is concentrated to give III compound of formula.
18.4g Cyanuric Chloride is dissolved in 300mL acetone, after being cooled to 0 DEG C, sequentially adds 21.2g N- (2,2,6,6- tetra- Methyl -4- piperidyl) n-butylamine (molar ratio of Cyanuric Chloride and N- (2,2,6,6- tetramethyl -4- piperidyl) n-butylamine is 1: And 13.8g K 1)2CO3, 1h, filtering are stirred, filtrate water washs, then 150mL bromine will be added in organic phase concentration in concentrate For hexamethylene, 0.5g molybdenum trioxide is cooled to room temperature in 50 DEG C of stirring 12h, filtering, and excessive saturation NaHSO is added to filtrate3 Solution stirs, and separation, organic phase is concentrated to give IV compound of formula.
III compound of 24.7g formula, IV compound of 8.8g formula and 150mL dimethylbenzene are put into 300mL autoclave, are sealed, Use N2It replaces in kettle air 3 times, is then warming up to 80 DEG C of reaction 2h, cool down, open kettle, 4.8g NaOH is added, N is used in sealing2It sets Air 3 times in kettle are changed, stirs, is then heated to 190 DEG C of reaction 5h.Cooling is deflated, and kettle, reaction solution filtering, filtrate water are opened Solution washing, organic phase are concentrated to give V compound of formula.
II compound of 18.4g formula, V compound of formula, 150mL dimethylbenzene and 4.8g NaOH are put into 300mL autoclave, Sealing, uses N2It replaces in kettle air 3 times, is then heated to 170 DEG C of reaction 5h.Cooling is deflated, and kettle, reaction solution filtering, filter are opened Liquid is washed with aqueous solution, and organic phase is concentrated to get low alkalinity light stabilizer C, yield 92%.
The preparation of 7 low alkalinity hindered amine light stabilizer D of embodiment
18.4g Cyanuric Chloride is dissolved in 120mL toluene, after being cooled to 0 DEG C, 25.8g di-n-butylamine (trimerization is slowly added dropwise The molar ratio of chlorine cyanogen and di-n-butylamine is 1:2), after dripping, 40 DEG C are warming up to, 4g NaOH is added, after stirring 2h, filtering, Filtrate water washing, organic phase are concentrated to give II compound of formula.
150mL iodomethane will be added in 38.1g pentanediamine piperidines, 0.5g tungstic acid stirs 12h in 50C, is cooled to room Excessive saturation NaHSO is added to filtrate in temperature, filtering3Solution stirs, and separation, organic phase is concentrated to give III compound of formula.
18.4g Cyanuric Chloride is dissolved in 300mL acetone, after being cooled to 0 DEG C, sequentially adds 21.2g N- (2,2,6,6- tetra- Methyl -4- piperidyl) n-butylamine (molar ratio of Cyanuric Chloride and N- (2,2,6,6- tetramethyl -4- piperidyl) n-butylamine is 1: And 13.8g K 1)2CO3, 1h, filtering are stirred, filtrate water washs, then 150mL will be added in organic phase concentration in concentrate Iodomethane, 0.5g tungstic acid are cooled to room temperature in 50 DEG C of stirring 12h, filtering, and excessive saturation NaHSO is added to filtrate3It is molten Liquid stirs, and separation, organic phase is concentrated to give IV compound of formula.
III compound of 24.7g formula, IV compound of 8.8g formula and 150mL dimethylbenzene are put into 300mL autoclave, are sealed, Use N2It replaces in kettle air 3 times, is then warming up to 80 DEG C of reaction 2h, cool down, open kettle, 2.4g NaOH is added, N is used in sealing2It sets Air 3 times in kettle are changed, stirs, is then heated to 190 DEG C of reaction 5h.Cooling is deflated, and kettle, reaction solution filtering, filtrate water are opened Solution washing, organic phase are concentrated to give V compound of formula.
II compound of 18.4g formula, V compound of formula, 150mL dimethylbenzene and 2.4g NaOH are put into 300mL autoclave, Sealing, uses N2It replaces in kettle air 3 times, is then heated to 150 DEG C of reaction 5h.Cooling is deflated, and kettle, reaction solution filtering, filter are opened Liquid is washed with aqueous solution, and organic phase is concentrated to get low alkalinity light stabilizer D, yield 90%.
Detain canopy experiment in 8 thermoplastic polyethylene farmland of embodiment
Basic components:
Standard polymers: 79.8wt% thermoplastic polyethylene；20wt% calcium carbonate；0.20wt% antioxidant (AO-1010)；
Prepare test sample:
1# is 100wt% standard polymers；
2# is 99.7wt% standard polymers, 0.4wt% compound A；
3# is 99.7wt% standard polymers, 0.4wt% compound B；
4# is 99.7wt% standard polymers, 0.4wt% compound C；
5# is 99.7wt% standard polymers, 0.4wt% compound D；
It is pre-mixed each component in mixing machine, then squeezed out at 190 DEG C, be granulated on double screw extruder.80 Dry 8h, then uses inflation film manufacturing machine blow molding at 200 DEG C at DEG C.Sample progress grape is finally buckled into canopy test, test knot Fruit is as shown in table 1:
1 tensile strength retention rate % of table
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above Detail, within the scope of the technical concept of the present invention, can with various simple variants of the technical solution of the present invention are made, These simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance It in the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention is to various No further explanation will be given for possible combination.

Claims (5)

1. the compound that a kind of general formula is I:
R1、R2And R3It is independent to be selected from: C1-20Alkyl or C3-12Naphthenic base；
R4It is selected from: C1-10Alkyl；
R5And R6It is independent to be selected from: C1-10Alkyl or C3-8Naphthenic base；
Z is selected from the C of straight chain or branching2-20Alkylidene or at least one C atom straight chain replaced by oxygen or sulphur or the C of branching2-20 Alkylidene chain；
N is 2-12.
2. compound according to claim 1, which is characterized in that R1、R2And R3It is independent to be selected from: methyl, ethyl, propyl, Isopropyl, normal-butyl, sec-butyl, isobutyl group, tert-butyl, 2- ethyl-butyl, n-pentyl, isopentyl, 1- methyl amyl, 1,3- bis- Methyl butyl, n-hexyl, 1- methylhexyl, n-heptyl, different heptyl, 1,1,3,3- tetramethyl butyl, 1- methylheptyl, 3- methyl Heptyl, n-octyl, 2- ethylhexyl, 1,1,3- trimethyl, 1,1,3,3- tetramethyl amyl, nonyl, decyl, hendecane Base, 1- methylundecyl, dodecyl, 1,1,3,3,5,5- hexamethyl hexyl, tridecyl, myristyl, pentadecyl, Cetyl, heptadecyl, octadecyl and eicosyl, cyclopropyl, cyclobutyl, methyl-cyclobutyl, cyclopenta, methyl ring penta Base, dimethylcyclopentyl, front three cyclopentyl, ethylcyclopentyl, propyl cyclopenta, isopropyl cyclopentyl, cyclohexyl, methyl ring Hexyl, Dimethylcyclohexyl, trimethylcyclohexyl, ethylcyclohexyl, propylcyclohexyl, isopropylcyclohexyl, butylcyclohexyl, Isobutyl butylcyclohexyl, tert-butylcyclohexyl, suberyl, methylcycloheptyl, dimethyl-cyclopentyl, front three cycloheptyl, ethyl ring Heptyl, propyl suberyl, isopropyl cycloheptyl, butyl suberyl, isobutyl cycloheptyl, tert-butyl suberyl, cyclooctyl, methyl Cyclooctyl, dimethylcyclooctyl, trimethyl cyclooctyl, ethyl cyclooctyl, propyl cyclooctyl, isopropyl cyclooctyl, butyl ring are pungent Base, isobutyl group cyclooctyl, tert-butyl cyclooctyl, cyclononyl, methyl cyclononyl, dimethyl cyclononyl, trimethyl cyclononyl, ethyl Cyclononyl, propyl cyclononyl, isopropyl cyclononyl, cyclodecyl, methyl cyclodecyl, dimethyl cyclodecyl or ethyl cyclodecyl；
R4It is selected from: methyl, ethyl, propyl, normal-butyl, n-pentyl, isopentyl, n-hexyl or 1- methylhexyl；
R5And R6It is independent to be selected from: methyl, ethyl, propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, n-pentyl, isopentyl, N-hexyl, 1- methylhexyl, n-heptyl, different heptyl, n-octyl, cyclopropyl, cyclobutyl, methyl-cyclobutyl, cyclopenta, methyl ring Amyl or cyclohexyl.
3. compound according to claim 2, which is characterized in that the compound is such as flowering structure:
Wherein, R1、R2And R3It is independent to be selected from: methyl, ethyl, propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, tertiary fourth Base, 2- ethyl-butyl, n-pentyl, isopentyl, 1- methyl amyl, 1,3- dimethylbutyl, n-hexyl, 1- methylhexyl, positive heptan Base, different heptyl, 1,1,3,3- tetramethyl butyl, 1- methylheptyl, 3- methylheptyl, n-octyl, 2- ethylhexyl, 1,1,3- tri- Methylhexyl, 1,1,3,3- tetramethyl amyl, nonyl, decyl, cyclopropyl, cyclobutyl, methyl-cyclobutyl, cyclopenta, methyl ring Amyl, dimethylcyclopentyl, front three cyclopentyl, ethylcyclopentyl, propyl cyclopenta, isopropyl cyclopentyl, cyclohexyl, methyl Cyclohexyl, Dimethylcyclohexyl, ethylcyclohexyl, suberyl, methylcycloheptyl, cyclooctyl.
4. the preparation method of compound described in claim 1, steps are as follows:
(1)Obtain II compound of formula；
(2)Obtain III compound of formula；
(3)Obtain IV compound of formula；
(4)Obtain V compound of formula；
(5) II compound of formula that step (1) obtains is reacted with V compound of formula that step (4) obtains, and is obtained
R1-R6, Z definition such as right It is required that described in 1.
5. the preparation method according to claim 4, which is characterized in that in the step (1)It is pressed with Cyanuric Chloride Molar ratio is 2:1-3:1, adds alkali, and the alkali is selected from: sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide or triethylamine, alkali WithMolar ratio be 1:1-1.5:1, reaction temperature be 30-60 DEG C, reaction dissolvent is selected from: acetone, methylene chloride, first Benzene or dimethylbenzene；
The reaction time is 5-12h in the step (2), and the catalyst is selected from: molybdenum trioxide, vanadic anhydride, chromium trioxide, The molar ratio of the hindered amine piperidine structure unit of tungstic acid or manganese dioxide, catalyst and addition is 0.02:1-0.2:1, institute It states alkylating reagent to be selected from: one or both of halogenated hydrocarbons, sulfuric ester, aromatic sulfonic acid ester, alcohol, ether, olefines, formaldehyde, formic acid Above combination；
In the step (3)With the molar ratio 1:1-1:1.5 of Cyanuric Chloride, add alkali, the alkali is selected from: sodium carbonate, Potassium carbonate, sodium hydroxide, potassium hydroxide or triethylamine, alkali withMolar ratio be 1:1-1.5:1, reaction temperature be- 10-10 DEG C, reaction time 1-12h, the catalyst is selected from: molybdenum trioxide, vanadic anhydride, chromium trioxide, tungstic acid Or manganese dioxide, the molar ratio of the hindered amine piperidine structure unit of catalyst and addition are 0.02:1-0.2:1, the alkylation Reagent is selected from: the group of one or more of halogenated hydrocarbons, sulfuric ester, aromatic sulfonic acid ester, alcohol, ether, olefines, formaldehyde, formic acid It closes, reaction dissolvent is selected from: acetone, methylene chloride, toluene, dimethylbenzene or tetrahydrofuran；
The molar ratio of III compound of step (4) Chinese style and IV compound of formula is 2:1-3:1, adds alkali, the alkali is selected from: carbon The molar ratio of sour sodium, potassium carbonate, sodium hydroxide, potassium hydroxide or triethylamine, alkali and IV compound of formula is 1:1-1.5:1, reaction Temperature is 150-200 DEG C, reaction time 3-12h, and reaction dissolvent is selected from toluene, chlorobenzene, dichloro-benzenes or dimethylbenzene, is reacted in height It is carried out in pressure kettle；
The molar ratio of II compound of step (5) Chinese style and V compound of formula is 2:1-3:1, adds alkali, the alkali is selected from: carbonic acid The molar ratio of sodium, potassium carbonate, sodium hydroxide, potassium hydroxide or triethylamine, alkali and V compound of formula is 1:1-1.5:1, reaction temperature Degree is 100-150 DEG C, reaction time 3-12h, and reaction carries out in autoclave.
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