CN109134928A - The triazine hindered amine light stabilizer and its preparation method and application that N- replaces - Google Patents
The triazine hindered amine light stabilizer and its preparation method and application that N- replaces Download PDFInfo
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- CN109134928A CN109134928A CN201811285139.XA CN201811285139A CN109134928A CN 109134928 A CN109134928 A CN 109134928A CN 201811285139 A CN201811285139 A CN 201811285139A CN 109134928 A CN109134928 A CN 109134928A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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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
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- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The present invention discloses a kind of compound that general formula is I, can be used as stabilizer and organic substance fire retardant containing the organic substance sensitive to degradation caused by light, heat or oxidation and uses；The invention also discloses the preparation methods for the compound that general formula is I.In addition, the invention discloses the purposes of a kind of composition of compound for being I including general formula and composition.
Description
Technical field
The present invention relates to polymeric material field, in particular to a kind of polymerized hindered amine light stabilizer, preparation method and
It is applied.
Background technique
With the continuous improvement of human life quality and production technology level, high molecular material has been widely applied to people
The every field of class social life.But high molecular material is during processing, storage and use, and generally existing its is physical
The phenomenon that matter, chemical property and mechanical property can gradually be deteriorated.Such as jaundice, embrittlement and the cracking of plastics；Rubber it is tacky, hard
Change, cracking and decreasing insulating.Phenomena such as discoloration of fibre, colour fading, strength reduction, fracture.These phenomenons are referred to as
The aging or degradation of high molecular material.Cause the factor of macromolecule material aging very much, wherein with oxygen, light and heat influence most
It is significant.So in order to prevent or delaying its aging, prolong its service life, people are usually by some changes with specific function
Auxiliary agent is learned to be added in high molecular material.Wherein, light stabilizer is exactly that one kind can intervene high molecular material photoinduction degradation product
It is also one of most important high molecular material additive that the compound of Physicochemical process, which is the most frequently used,.
The kind of light stabilizer mainly includes ultraviolet absorbing agent, quencher, radical scavenger and photomask agent at present.
Radical scavenger can capture living radical generated in macromolecule, to inhibit photo-oxidation process, reach light and stablize mesh
's.Radical scavenger main Types are hindered amine light stabilizers, hindered amine light stabilizer because its excellent light stablizing effect by
It is to study most active a kind of light stabilizer over nearly two, 30 years both at home and abroad to extensive concern.Although this kind of light stabilizer is opened
The ratio of hair is later, but quickly grows.Hindered amine light stabilizer has accounted for 60% or so in the light stabilizer of foreign applications at present.
At home, hindered amine light stabilizer proportion is higher, and about 80% or so.
Hindered amine light stabilizer has: piperidine derivative, imidazolone derivatives and azacycloalkyl ketone derivatives etc. are serial.Piperidines
Derivative is studied relatively more, and development is also most fast, has many kind supplies market.Patent document CN105636954A is disclosed
A kind of triazine, piperidines and pyrrolidinyl hindered amine light stabilizer are added to containing to the degradation caused by light, heat or oxidation
Stabilization can be played in sensitive organic substance, but the pyrrole alkane for synthesizing the light stabilizer is inflammable, toxic, steam
Explosive mixture can be formed with air, so depositing during preparation triazine, piperidines and pyrrolidinyl hindered amine light stabilizer
In biggish risk.
In the present invention, inventor provides a kind of compound, can be used as containing sensitive to degradation caused by light, heat or oxidation
Organic substance stabilizer and organic substance fire retardant, and prepare simple, safe operation.
Summary of the invention
The object of the present invention is to provide the triazine hindered amine light stabilizers that a kind of N- replaces；Another object of the present invention is to mention
For a kind of purposes of N- triazine hindered amine light stabilizer replaced.It is a further object to provide one kind to replace comprising N-
Triazine hindered amine light stabilizer composition；The present invention, which a further object is, provides a kind of purposes of above-mentioned composition.
A kind of compound that general formula is I, general formula are as follows:
R1And R2It is independent to be selected from :-H ,-O ,-OH ,-CH2CN、C1-22Alkyl, C3-12Naphthenic base, C1-18Alkoxy, by hydroxyl
The C that base replaces2-18Alkoxy, C3-12Cycloalkyloxy, C3-6Alkylene, C3-6Alkenyloxy group, C1-8Acyl group is unsubstituted or on phenyl
By 1-3 C1-4Alkyl-substituted C7-9The group of I a of phenylalkyl or formula:n
For the integer of 2-10.
Preferably, the R1And R2It is independent to be selected from :-H, C1-10Alkyl, C3-8Naphthenic base, C1-18Alkoxy, C3-12Cycloalkanes oxygen
Base orN is the integer of 2-10.
In a preferred embodiment of the invention, the R1And R2It is independent to be selected from :-H ,-CH3、
R3And R4It is independent to be selected from: C1-22The group of I b of alkyl or formula:
R0It is selected from :-H ,-O ,-OH ,-CH2CN、C1-22Alkyl, the C replaced by hydroxyl2-18Alkoxy, C3-12Naphthenic base,
C1-18Alkoxy, C3-12Cycloalkyloxy, C3-6Alkylene, C3-6Alkenyloxy group, C1-8Acyl group is unsubstituted or on phenyl by 1-3
C1-4Alkyl-substituted C7-9The group of I a of phenylalkyl or formula:N is the whole of 2-10
Number.
Preferably, the R3And R4It is independent to be selected from: C1-10Alkyl or (I b) group.
Preferably, the R0It is selected from :-H, C1-22Alkyl, the C replaced by hydroxyl2-18Alkoxy, C3-12Naphthenic base, C1-18Alkane
Oxygroup, C3-12Cycloalkyloxy, C3-6Alkylene, C3-6Alkenyloxy group, C1-8Acyl group is unsubstituted or on phenyl by 1-3 C1-4Alkane
The C that base replaces7-9The group of I a of phenylalkyl or formula:N is the integer of 2-10.
In a preferred embodiment of the invention, the R3And R4It is independent to be selected from:
R5And R6It is independent to be selected from :-H, C1-12Alkyl is unsubstituted or by 1-3 C1-4Alkyl-substituted C3-12Naphthenic base,
It is unsubstituted or by 1-3-OH and C1-10Phenyl that the group of alkyl replaces is unsubstituted or phenyl is by 1-3-OH and C1-10
The C that the group of alkyl replaces7-9Phenylalkyl, (I b) group or R5And R6Morpholino group is formed with the N between it；
In a preferred embodiment of the invention, the R5And R6It is independent to be selected from:
Or R5And R6It is formed with the N between it
R7And R8It is independent to be selected from :-H, C1-8Alkyl or benzyl.
Preferably, the R7And R8It is independent to be selected from :-H, C1-6Alkyl or benzyl.
In a preferred embodiment of the invention, the R7And R8It is independent to be selected from :-CH3。
C of the present invention1-22Alkyl 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, dodecyl, 1,
1,3,3,5,5- hexamethyl hexyl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, octadecyl and
Eicosyl.
C of the present invention3-12Naphthenic base is selected from: cyclopropyl, cyclobutyl, methyl-cyclobutyl, cyclopenta, methyl ring penta
Base, dimethylcyclopentyl, front three cyclopentyl, ethylcyclopentyl, propyl cyclopenta, isopropyl cyclopentyl, cyclohexyl, methyl ring
Hexyl, Dimethylcyclohexyl, ethylcyclohexyl, suberyl, methylcycloheptyl, cyclooctyl.
C of the present invention1-18Alkoxy is selected from: methoxyl group, ethyoxyl, propoxyl group, isopropoxy, n-butoxy, secondary
Butoxy, isobutoxy, tert-butoxy, 2- ethyl-butoxy, n-pentyloxy, isoamoxy, 1- methyl amoxy, 1,3- diformazan
Base butoxy, positive hexyloxy, 1- methylhexyloxy, positive oxygroup in heptan, different oxygroup in heptan, 1,1,3,3- tetramethyl butoxy, 1- methyl
Heptan oxygroup, 3- methyl heptyl, n-octyloxy, 2- ethyl hexyl oxy, 1,1,3- trimethyl hexyloxy, 1,1,3,3- tetramethyl penta
Oxygroup, nonyl epoxide, decyloxy, hendecane epoxide, 1- methylundecane oxygroup, dodecyloxy, 1,1,3,3,5,5- hexamethyl
Hexyloxy, tetradecyloxyaniline, hexadecane epoxide and octadecane epoxide.
C of the present invention3-12Cycloalkyloxy is selected from: cyclopropyl oxygroup, cyclobutoxy group, cyclopentyloxy, cyclohexyloxy, cycloheptyl
Oxygroup, ring octyloxy, ring decyloxy and cyclododecane oxygroup.
C of the present invention3-6Alkylene is selected from: allyl, 2- methacrylic, cyclobutenyl, pentenyl and hexenyl.
C of the present invention3-6Alkenyloxy group is selected from: 1- propenyloxy group and 2- propenyloxy group.
C of the present invention1-8Acyl group is selected from: formoxyl, acetyl group, propiono, bytyry, valeryl, caproyl, heptan
Acyl group, caprylyl, acryloyl group, methylacryloyl and benzoyl.
C of the present invention7-9Phenylalkyl is preferably benzyl and 2- phenethyl.
It is of the present invention by 1-3 C1-4Alkyl-substituted C7-9Phenylalkyl, preferably methylbenzyl, dimethyl benzene
Methyl, trimethylbenzene methyl or ter .- butylbenzyl.
Hydrogen in alkoxy of the present invention on any carbon atom can be optionally substituted by a hydroxyl group, preferably 2- hydroxyl-oxethyl.
In a specific embodiment of the present invention, the particular compound such as flowering structure is provided:
The present invention provides a kind of preparation method of compound that general formula is I, includes the following steps:
Preferably, the molar ratio of reactant is 1:(2-3 in the step (1)).
Preferably, reactant molar ratio is 1:(1-2 in the step (2)).Preferably, the step (1), (2) and (3)
Middle reaction dissolvent is selected from: acetone, methylene chloride, toluene or dimethylbenzene, dimethylbenzene or tetrahydrofuran；
Preferably, add alkali in the step (1) and (2), the alkali is selected from: sodium carbonate, potassium carbonate, sodium hydroxide, hydrogen
Potassium oxide or triethylamine.
Preferably, in the step (1) alkali withMolar ratio are as follows: (1-1.5): 1.
Preferably, in the step (2) alkali withMolar ratio are as follows: (1-1.5): 1.
Preferably, alkylating reagent is selected from the step (3): halogenated hydrocarbons, sulfuric ester, aromatic sulfonic acid ester, alcohol, ether, alkene
The combination of one or more of class, formaldehyde, formic acid.
Preferably, catalyst is added in the step (3), the catalyst is selected from: molybdenum trioxide, vanadic anhydride, three oxygen
Change chromium, tungstic acid or manganese dioxide, catalyst and additionMolar ratio be (0.02-0.2): 1.
Preferably, if R is selected from :-O, C1-18Alkoxy, the C replaced by hydroxyl2-18Alkoxy, C3-12Cycloalkyloxy, C3-6
Alkenyloxy group, C1-8Acyl group, in the step (3) plus hydroperoxides, the hydroperoxides are selected from: tert-butyl hydroperoxide, mistake
Fluoroacetic acid, hydrogen peroxide etc., hydroperoxides and additionMolar ratio be (2-10): 1.
The present invention provides the compound that a kind of general formula is I and is used as containing having to degradation sensitivity caused by light, heat or oxidation
The purposes of the stabilizer of machine substance.
The present invention provides a kind of purposes of the compound that general formula is I as organic substance fire retardant.
The present invention provides a kind of composition, and the composition includes the compound and contain to light, heat or oxidation that general formula is I
The sensitive organic substance of caused degradation.
Preferably, the composition further includes antioxidant, UV absorbent, hindered amine light stabilizer, filler, reinforcing agent
Or other additives.
Depending on the amount for the compound that the general formula is I is by the property, final use and additive of organic substance, general formula I
The amount of compound can use in various proportions.
Preferably, the mass fraction for the compound that the general formula is I is the 0.01%-5% of organic substance weight；
It is furthermore preferred that the mass fraction for the compound that the general formula is I is the 0.05%-2% of organic substance weight；
Most preferably, the mass fraction for the compound that the general formula is I is the 0.05%-1% of organic substance weight.
The organic substance is selected from: thermoplastic polymer.
The thermoplastic polymer is selected from: polyolefin, acrylonitrile/butadiene/styrene, polyvinyl chloride, poly- methyl-prop
E pioic acid methyl ester, polyformaldehyde, polyamide, polyurethane, polycarbonate, polyurethane, polyester, polystyrene, thermoplastic elastomer (TPE), second
One or more of alkene-acetate ethylene copolymer.
Preferably, the thermoplastic polymer is selected from: polyolefin, thermoplastic elastomer (TPE).
The thermoplastic elastomer (TPE) includes polyolefin thermoplastic elastomer and block copolymer type thermoplastic polystyrene
Elastomer.Polyolefin thermoplastic elastomer includes polyolefin resin (such as serving as the polyethylene and polypropylene of hard segment) and rubber group
It closes object (such as serving as the Ethylene-Propylene-Diene elastomer (EPDM) of soft chain segment).Block copolymer type thermoplastic polystyrene elasticity
Body is comprising serving as the polystyrene of hard segment and serving as the polydiene (such as polybutadiene or polyisoprene) of soft chain segment.Alternatively,
The admixture of polyolefin elastomer and polystyrene elastomers also can be used as thermoplastic elastomer (TPE) of the invention.For by soft chain segment
And hard segment is combined in the method in thermoplastic elastomer (TPE) and can be roughly divided into simple blending, implantation is carried out by copolymerization and is dynamically handed over
Connection.The combination of thermoplastic polystyrene elastomer segment is including any in SBS, SIS, SEBS, SEPS, these four copolymers
Hydropolymer, the one or more without the hydropolymer (HSBR) and polypropylene for returning SBR and selected from these polymer are any
The admixture of member.
The polyolefin is selected from: containing polyethylene or polypropylene based on ethylene and/or the rubber phase of propylene.
The antioxidant is selected from: antioxidant 1010, antioxidant 1076, antioxidant 1098, irgasfos 168.
The UV absorbent is selected from: salicylic acid esters, benzoates, benzophenone, stupid and triazole type, triazines.
The hindered amine light stabilizer is selected from: it is different from the compound that general formula is I, and the hindered amine light with (I b) structure
Stabilizer, such as bis- (2,2,6,6- tetramethyl -4- piperidyl) sebacate, succinic acid and 4- hydroxyls -2,2,6,6- tetramethyl -1-
Condensate, Chimassorb 944, the Chimassorb 2020 of piperidine ethanol.
The filler and reinforcing agent are selected from: calcium carbonate, silicate, glass fibre, bead, asbestos, talcum, kaolinite
Soil, mica, barium sulfate, metal oxide and hydroxide, carbon black, graphite, wood powder and flour or other natural products fibers close
At fiber.
Other described additives are selected from: plasticiser, lubricant, emulsifier, pigment, rheologic additive, catalyst, flowing control
Preparation, optical brightener, fire-proofing chemical, antistatic agent and foaming agent.
The present invention provides the application that a kind of composition is used to prepare in any plastic product, the plastic product choosing
From: automotive interior or external decorative material, floating installation, Road traffic devices, agricultural articles, electric appliance, furniture, footwear, health
Product, health-care products etc..
Any method manufacture that the plastic product can be known by those of ordinary skill in the art, including but it is unlimited
In extrusion, extrusion-blown modling, film casting, calendering, injection molding, blow molding, compression moulding, thermoforming, rotary press modelling, blow crowded and rotational casting.
Specific embodiment
The synthesis of 1 compound of embodiment (1)
36.9g Cyanuric Chloride is dissolved in 300mL dimethylbenzene, after being cooled to 10 DEG C, 84.8g N- (2,2,6,6- tetramethyls are added
Base -4- piperidyl) n-butylamine (molar ratio of Cyanuric Chloride and N- (2,2,6,6- tetramethyl -4- piperidyl) n-butylamine is 1:2),
1h is stirred, is added 50g sodium hydrate aqueous solution (30%), in 60 DEG C of stirring 3h, then 17.5g morpholine (three polychlorostyrene are added in split-phase
The molar ratio of cyanogen and morpholine is 1:1), continue to stir 3h.Completely after reaction, is mutually separated and washed organic phase with water several
It is secondary, then organic phase is separated and is concentrated under reduced pressure, obtains the compound (1) of 53.3g.(for the 91% of theoretical value)
1H-NMR (400MHz, chloroform-d): 5.17 (2H, m), 3.78 (4H, dd), 3.65 (4H, dd), 3.18 (4H,
dd),2.0(2H,s),1.67-1.50(12H,m),1.37-1.22(4H,m),1.16(12H,s),1.10(12H,s),0.96-
0.86(6H,m)。
The synthesis of 2 compound of embodiment (2)
Compound prepared by 50.0g embodiment 1 (1) is dissolved in 300mL dimethylbenzene, 150mL formaldehyde, 1.5g is then added
Tungstic acid is then cooled to room temperature in 50 DEG C of stirring 12h, filtering, and excessive saturation NaHSO is added to filtrate3Solution stirs
It mixes, separates, organic phase is concentrated to give compound (2).By compound (2) by1H-NMR analysis discloses on the piperidyl of compound (1)
N-H group be converted to corresponding N-CH3, compound (2) are consequently formed.
The synthesis of 3 compound of embodiment (3)
Compound prepared by 50.0g embodiment 1 (1) is dissolved in 300mL dimethylbenzene, then be added 150mL hexamethylene,
70% aqueous solution of 1.5g tungstic acid and 50g tert-butyl hydroperoxide then cools to room temperature, mistake in 50 DEG C of stirring 12h
Excessive saturation NaHSO is added to filtrate in filter3Solution stirs, and separation, organic phase is concentrated to give compound (3).By compound (3)
By1The N-H group that H-NMR analysis discloses on the piperidyl of compound (1) is converted to corresponding N- cyclohexyloxy, being consequently formed
It closes object (3).
The synthesis of 4 compound of embodiment (4)
Compound prepared by 50.0g embodiment 1 (1) is dissolved in 300mL dimethylbenzene, 50g 2- ethyl hexyl is then added
Then in 20 DEG C of stirring 2h 30% aqueous hydrogen peroxide solution of 40g is added, in 50 DEG C of stirring 12h, then in aldehyde, 1.5g tungstic acid
It is cooled to room temperature, filters, excessive saturation NaHSO is added to filtrate3Solution stirs, and separation, organic phase is concentrated to give compound
(4).By compound (4) by1The N-H group that H-NMR analysis discloses on the piperidyl of compound (1) is converted to corresponding N- alcoxyl
Compound (4) are consequently formed in base.
The synthesis of 5 compound of embodiment (5)
By 140.0g polyethylene glycol monomethyl ether, 133.6g bromoacetate, 2.0g p-methyl benzenesulfonic acid monohydrate, 400mL
Dimethylbenzene is added in the three-necked flask of 1000mL, which is stirred 20h at a reflux temperature.Then by the solution in vacuum
Lower thickening filtration obtains compound (A).
Compound prepared by 50.0g embodiment 1 (1) is dissolved in 300mL dimethylbenzene, 25.0g compound is then added
(A), 34.5g potassium carbonate and 6.9g potassium iodide are cooled to room temperature after reaction completely, filter in stirred under reflux temperature 20h, to
Water is added in filtrate, and organic phase is separated and be concentrated in vacuo by stirring.Concentrate first uses ethanol washing, then water washing, finally dries
Obtain compound (5).By compound (5) by1The N-H group that H-NMR analysis discloses on the piperidyl of compound (1) is converted to pair
Compound (5) are consequently formed in the N- alkyl answered.
Embodiment 6 synthesizes the synthesis of compound (6)
36.9g Cyanuric Chloride is dissolved in 300mL dimethylbenzene, after being cooled to 10 DEG C, 84.8g N- (2,2,6,6- tetramethyls are added
Base -4- piperidyl) n-butylamine (molar ratio of Cyanuric Chloride and N- (2,2,6,6- tetramethyl -4- piperidyl) n-butylamine is 1:2),
1h is stirred, is added 50g sodium hydrate aqueous solution (30%), in 60 DEG C of DEG C of stirring 3h, then 25.8g di-n-butylamine is added in split-phase
(molar ratio of Cyanuric Chloride and di-n-butylamine is 1:1), continues to stir 3h.Completely after reaction, is mutually separated and will be had with water
Machine mutually washs several times, and then organic phase is separated and is concentrated under reduced pressure, and obtains the compound (6) of 58.4g.(for theoretical value
93%)
1H-NMR (400MHz, chloroform-d): 5.17 (2H, m), 3.78 (4H, dd), 2.0 (2H, s), 1.67-1.50
(16H,m),1.37-1.22(8H,m),1.16(12H,s),1.10(12H,s),0.96-0.86(12H,m)。
The synthesis of 7 compound of embodiment (7)
Compound prepared by 50.0g embodiment 6 (6) is dissolved in 300mL dimethylbenzene, 150mL formaldehyde, 1.5g is then added
Tungstic acid is then cooled to room temperature in 50 DEG C of stirring 12h, filtering, and excessive saturation NaHSO is added to filtrate3Solution stirs
It mixes, separates, organic phase is concentrated to give compound (7).By compound (7) by1H-NMR analysis discloses on the piperidyl of compound (6)
N-H group be converted to corresponding N-CH3, compound (7) are consequently formed.
The synthesis of 8 compound of embodiment (8)
Compound prepared by 50.0g embodiment 6 (6) is dissolved in 300mL dimethylbenzene, then be added 150mL hexamethylene,
70% aqueous solution of 1.5g tungstic acid and 50g tert-butyl hydroperoxide then cools to room temperature, mistake in 50 DEG C of stirring 12h
Excessive saturation NaHSO is added to filtrate in filter3Solution stirs, and separation, organic phase is concentrated to give compound (8).By compound (8)
By1The N-H group that H-NMR analysis discloses on the piperidyl of compound (6) is converted to corresponding N- cyclohexyloxy, being consequently formed
It closes object (8).
The synthesis of 9 compound of embodiment (9)
Compound prepared by 50.0g embodiment 6 (6) is dissolved in 300mL dimethylbenzene, 50g 2- ethyl hexyl is then added
Then in 20 DEG C of stirring 2h 30% aqueous hydrogen peroxide solution of 40g is added, in 50 DEG C of stirring 12h, then in aldehyde, 1.5g tungstic acid
It is cooled to room temperature, filters, excessive saturation NaHSO is added to filtrate3Solution stirs, and separation, organic phase is concentrated to give compound
(9).By compound (9) by1The N-H group that H-NMR analysis discloses on the piperidyl of compound (6) is converted to corresponding N- alcoxyl
Compound (9) are consequently formed in base.
The preparation of 10 compound of embodiment (10)
Compound prepared by 50.0g embodiment 6 (6) is dissolved in 300mL dimethylbenzene, 25.0g compound is then added
(A), 34.5g potassium carbonate and 6.9g potassium iodide are cooled to room temperature after reaction completely, filter in stirred under reflux temperature 20h, to
Water is added in filtrate, and organic phase is separated and be concentrated in vacuo by stirring.Concentrate first uses ethanol washing, then water washing, finally dries
Obtain compound (10).By compound (10) by1The N-H group that H-NMR analysis discloses on the piperidyl of compound (6) is converted to
Compound (10) are consequently formed in corresponding N- alkyl.
Embodiment 11 stablizes thermoplastic polypropylene test
Basic components:
Standard polymers: 79.8wt% thermoplastic polypropylene；20wt% hydrotalcite；0.20wt% antioxidant (AO-1010)；
1# is 100wt% standard polymers；
2# is 99.7wt% standard polymers, 0.3wt% compound (1)；
3# is 99.7wt% standard polymers, 0.3wt% compound (6)；
Prepare test sample:
It is pre-mixed each component in mixing machine, then squeezed out at 220 DEG C, be granulated on double screw extruder.80
Dry 8h, then uses injection molding machine injection molding at 240 DEG C at DEG C.Sample is finally subjected to xenon according to 2527 standard of SAE J
Lamp burn-in test, test result are as shown in table 1:
The △ E* of sample after 1 xenon lamp aging of table (low value is required)
Embodiment 12 stablizes thermoplastic polyethylene's test
Basic components:
Standard polymers: 79.8wt% thermoplastic polyethylene；20wt% calcium carbonate；0.20wt% antioxidant (AO-1010)；
1# is 100wt% standard polymers；
2# is 99.6wt% standard polymers, 0.4wt% compound (1)；
3# is 99.6wt% standard polymers, 0.4wt% compound (2)；
4# is 99.6wt% standard polymers, 0.4wt% compound (3)；
5# is 99.6wt% standard polymers, 0.4wt% compound (8)；
Prepare test sample:
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 is finally carried out practical canopy of buckleing to test, test knot
Fruit is as shown in table 2-1 and 2-2:
Table 2-1 tensile strength retention rate % (farmland)
Table 2-2 tensile strength retention rate % (flowers)
Embodiment 13 stablizes thermoplastic polyvinyl chloride's test
Basic components:
Standard polymers:
65.5wt% thermoplastic polyvinyl chloride；31.5wt% plasticiser；1.6wt% epoxidized soybean oil；1.4wt% calcium zinc is steady
Determine agent；
1# is 100wt% standard polymers；
2# is 99.5wt% standard polymers, 0.25wt%UV-531；0.25wt% compound (8)
3# is 99.5wt% standard polymers, 0.25wt%UV-531；0.25wt% compound (9)
Prepare test sample:
It is pre-mixed each component in mixing machine China, is then kneaded 7 minutes on end runner mill at 165 DEG C, obtains institute
Need sample.Sample is finally subjected to xenon lamp aging test according to GB/T 16422.2-2014 standard, test result is as shown in table 3:
3 reserved elongation at break % of table
Embodiment 14 stablizes thermoplastic acrylonitrile/Butadiene/Styrene (ABS) test
Basic components:
Standard polymers: 96wt% thermoplastic ABS resin；3wt% titanium dioxide；1wt% slipping agent；
1# is 100wt% standard polymers；
2# is 99.65wt% standard polymers, 0.1wt% paraffin oil；0.25wt% compound (3)
3# is 99.65wt% standard polymers, 0.1wt% paraffin oil；0.25wt% compound (8)
Prepare test sample:
It is pre-mixed each component in mixing machine, then squeezed out at 220 DEG C, be granulated on double screw extruder.80
Dry 8h, then uses injection molding machine injection molding at 240 DEG C at DEG C.Finally sample is marked according to GB/T 16422.2-2014
Standard carries out xenon lamp aging test, and test result is as shown in table 4:
The △ E* of sample after 4 xenon lamp aging of table (low value is required)
Performance test as fire retardant of the embodiment 15 in PP film
Basic components:
Standard polymers: 99.65wt% thermoplastic polypropylene；0.05wt% calcium stearate；0.30wt% antioxidant (AO-
1010:AO-168=1:1)；
1# is 100wt% standard polymers；
2# is 99.6wt% standard polymers, 0.5wt% compound (4)
3# is 99.6wt% standard polymers, 0.5wt% compound (9)
Prepare test sample:
It is pre-mixed each component in mixing machine, then squeezed out at 220 DEG C, be granulated on double screw extruder.80
Dry 8h at DEG C, then in hot press prepared by compression moulding.Sample is finally subjected to the fire-retardant of sample according to DIN 4102-B2 standard
Property test, test result is as shown in table 5:
5 sample flame retardant property of table
| Sample | Weight loss/% | Burning length/mm | Burn dropping liquid | It is qualified/unqualified |
| 1# | 100 | 190 | It is | It is unqualified |
| 2# | 8.7 | 105 | It is | It is qualified |
| 3# | 8 | 102 | It is | It is qualified |
Claims (10)
1. the compound that a kind of general formula is I, general formula are as follows:
R1And R2It is independent to be selected from :-H ,-O ,-OH ,-CH2CN、C1-22Alkyl, C3-12Naphthenic base, C1-18Alkoxy is taken by hydroxyl
The C in generation2-18Alkoxy, C3-12Cycloalkyloxy, C3-6Alkylene, C3-6Alkenyloxy group, C1-8Acyl group is unsubstituted or on phenyl by 1-
3 C1-4Alkyl-substituted C7-9The group of I a of phenylalkyl or formula:N is 2-
10 integer；
R3And R4It is independent to be selected from: C1-22The group of I b of alkyl or formula:R0Be selected from :-H ,-O ,-OH ,-
CH2CN、C1-22Alkyl, the C replaced by hydroxyl2-18Alkoxy, C3-12Naphthenic base, C1-18Alkoxy, C3-12Cycloalkyloxy, C3-6Alkene
Alkyl, C3-6Alkenyloxy group, C1-8Acyl group is unsubstituted or on phenyl by 1-3 C1-4Alkyl-substituted C7-9Phenylalkyl or formula
The group of I a:N is the integer of 2-10；
R5And R6It is independent to be selected from :-H, C1-12Alkyl is unsubstituted or by 1-3 C1-4Alkyl-substituted C3-12Naphthenic base, without
Replace or by 1-3-OH and C1-10Phenyl that the group of alkyl replaces is unsubstituted or phenyl is by 1-3-OH and C1-10Alkyl
Group replace C7-9Phenylalkyl, (I b) group or R5And R6Morpholino group is formed with the N between it；
R7And R8It is independent to be selected from :-H, C1-8Alkyl or benzyl.
2. compound according to claim 1, which is characterized in that the R1And R2It is independent to be selected from :-H, C1-10Alkyl,
C3-8Naphthenic base, C1-18Alkoxy, C3-12Cycloalkyloxy orN is the integer of 2-10；
The R0It is selected from :-H, C1-22Alkyl, the C replaced by hydroxyl2-18Alkoxy, C3-12Naphthenic base, C1-18Alkoxy, C3-12Ring
Alkoxy, C3-6Alkylene, C3-6Alkenyloxy group, C1-8Acyl group is unsubstituted or on phenyl by 1-3 C1-4Alkyl-substituted C7-9
The group of I a of phenylalkyl or formula:N is the integer of 2-10；
The R3And R4It is independent to be selected from: C1-10Alkyl or (I b) group；
The R5And R6It is independent to be selected from :-H, C1-12Alkyl is unsubstituted or by 1-3 C1-4Alkyl-substituted C3-12Naphthenic base,
It is unsubstituted or by 1-3-OH and C1-10Phenyl that the group of alkyl replaces is unsubstituted or phenyl is by 1-3-OH and C1-10
The C that the group of alkyl replaces7-C9The group of phenylalkyl or formula (I b)；Or R5And R6That nitrogen connected to them shape together
At morpholino group；
The R7And R8It is independent to be selected from :-H, C1-6Alkyl or benzyl.
3. compound according to claim 1 or 2, which is characterized in that the R1And R2It is independent to be selected from :-H ,-CH3、
The R3And R4It is independent to be selected from:
The R5And R6It is independent to be selected from:Or R5And R6It is formed with the N between it
The R7And R8It is independent to be selected from :-CH3。
4. compound according to claim 3, which is characterized in that the compound structure is as follows:
5. the preparation method for the compound that general formula described in claim 1 is I, includes the following steps:
(1)
(2)
(3)
6. general formula described in claim 1 be I compound be used as containing to light, heat or oxidation caused by degradation sensitivity it is organic
The purposes of the stabilizer of substance and/or purposes as organic substance fire retardant.
7. a kind of composition, the composition include the compound that general formula described in claim 1 is I and containing to light, heat or
The sensitive organic substance of degradation caused by oxidation.
8. composition according to claim 7, which is characterized in that the composition further include antioxidant, UV absorbent,
Hindered amine light stabilizer, filler, reinforcing agent or other additives.
9. composition according to claim 7, which is characterized in that the mass fraction for the compound that the general formula is I is to have
The 0.01%-5% of machine substance weight.
10. composition as claimed in claim 7 is used to prepare the purposes of plastic product, the plastic product is selected from: automotive interior
Or external decorative material, floating installation, Road traffic devices, agricultural articles, electric appliance, furniture, footwear, hygienic articles, health care system
Product field.
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| CN201811285139.XA CN109134928B (en) | 2018-10-31 | 2018-10-31 | N-substituted triazine hindered amine light stabilizer, and preparation method and application thereof |
| PCT/CN2018/114196 WO2020087551A1 (en) | 2018-10-31 | 2018-11-06 | N-substituted triazine hindered amine light stabilizer, preparation method therefor and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN112126060A (en) * | 2019-06-25 | 2020-12-25 | 北京天罡助剂有限责任公司 | Polymeric high-molecular steric hindrance amine and preparation method thereof |
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| CN112126060A (en) * | 2019-06-25 | 2020-12-25 | 北京天罡助剂有限责任公司 | Polymeric high-molecular steric hindrance amine and preparation method thereof |
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| CN112126060B (en) * | 2019-06-25 | 2022-05-31 | 北京天罡助剂有限责任公司 | Polymeric high-molecular steric hindrance amine and preparation method thereof |
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| 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 |
| CN110452223B (en) * | 2019-07-29 | 2021-06-08 | 宿迁联盛科技股份有限公司 | Preparation method of composite light stabilizer |
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| Publication number | Publication date |
|---|---|
| WO2020087551A1 (en) | 2020-05-07 |
| CN109134928B (en) | 2020-05-19 |
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