CN109134928B - N-substituted triazine hindered amine light stabilizer, and preparation method and application thereof - Google Patents

N-substituted triazine hindered amine light stabilizer, and preparation method and application thereof Download PDF

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CN109134928B
CN109134928B CN201811285139.XA CN201811285139A CN109134928B CN 109134928 B CN109134928 B CN 109134928B CN 201811285139 A CN201811285139 A CN 201811285139A CN 109134928 B CN109134928 B CN 109134928B
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陈炜
安晶晶
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Tianji Chemical Auxiliary Agent Cangzhou Co ltd
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    • 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
    • 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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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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
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    • 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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Abstract

The invention discloses a compound with a general formula I, which can be used as a stabilizer and a flame retardant for organic substances, wherein the stabilizer and the flame retardant are sensitive to degradation caused by light, heat or oxidation; the invention also discloses a preparation method of the compound with the general formula I. In addition, the invention discloses a composition comprising the compound with the general formula I and application of the composition.

Description

N-substituted triazine hindered amine light stabilizer, and preparation method and application thereof
Technical Field
The invention relates to the field of high polymer materials, and particularly relates to a polymeric hindered amine light stabilizer, a preparation method and application thereof.
Background
With the continuous improvement of the quality of human life and the production technology level, the polymer materials have been widely applied to various fields of human social life. However, the physical, chemical and mechanical properties of the polymer materials are generally deteriorated during the processing, storage and use. Yellowing, embrittlement and cracking of plastics, for example; the tackiness, hardening, cracking and insulation properties of the rubber are reduced. Discoloration, fading, strength reduction, breakage and the like of the fiber product. These phenomena are collectively referred to as aging or degradation of the polymer material. The aging of the polymer material is caused by many factors, and the influence of oxygen, light and heat is most significant. Therefore, in order to prevent or retard aging and prolong the service life, chemical additives with specific functions are usually added into the polymer material. Among them, the light stabilizer is a kind of compound which can intervene in the physical and chemical process of light-induced degradation of polymer materials, and is one of the most common and important polymer material additives.
The current varieties of light stabilizers mainly include ultraviolet absorbers, quenchers, radical scavengers and light-shielding agents. The free radical trapping agent can trap active free radicals generated in the polymer, so that the photooxidation process is inhibited, and the purpose of light stability is achieved. The main type of the free radical scavenger is hindered amine light stabilizer, and the hindered amine light stabilizer is widely concerned due to the excellent light stabilizing effect and is the most actively studied light stabilizer at home and abroad for two to thirty years. Although such light stabilizers are developed relatively late, they are developed rapidly. The hindered amine light stabilizer in the light stabilizer applied abroad at present accounts for about 60 percent. In China, the proportion of the hindered amine light stabilizer is higher, about 80%.
The hindered amine light stabilizers are: piperidine derivatives, imidazolone derivatives, and azacycloalkanone derivatives. The piperidine derivatives have more researches and fastest development, and a plurality of varieties are supplied to the market. Patent document CN105636954A discloses a triazine, piperidine and pyrrolidinyl hindered amine light stabilizer, which can be added into organic substances sensitive to degradation caused by light, heat or oxidation, but the pyrrolidine monomer for synthesizing the light stabilizer is flammable and toxic, and the vapor and air can form explosive mixtures, so there is a great risk in the process of preparing triazine, piperidine and pyrrolidinyl hindered amine light stabilizers.
In the present invention, the inventors provide a compound which is useful as a stabilizer and a flame retardant for organic substances containing an organic substance susceptible to degradation by light, heat or oxidation, and which is simple to prepare and safe to handle.
Disclosure of Invention
The invention aims to provide an N-substituted triazine hindered amine light stabilizer; it is another object of the present invention to provide the use of an N-substituted triazine hindered amine light stabilizer. It is another object of the present invention to provide a composition comprising an N-substituted triazine hindered amine light stabilizer; it is also an object of the present invention to provide a use of the above composition.
A compound of formula I, having the formula:
Figure BDA0001848856900000021
R1and R2Independently selected from: -H, -O.cndot., -OH, -CH2CN、C1-22Alkyl radical, C3-12Cycloalkyl radical, C1-18Alkoxy, C substituted by hydroxy2-18Alkoxy radical, C3-12Cycloalkoxy, C3-6Alkylene radical, C3-6Alkenyloxy radical, C1-8Acyl, unsubstituted or substituted on phenyl by 1-3C1-4Alkyl substituted C7-9Phenylalkyl, or a group of formula Ia:
Figure BDA0001848856900000022
n is an integer of 2 to 10.
Preferably, said R is1And R2Independently selected from: -H, C1-10Alkyl radical, C3-8Cycloalkyl radical, C1-18Alkoxy radical, C3-12Cycloalkoxy or
Figure BDA0001848856900000023
n is an integer of 2 to 10.
In a preferred embodiment of the present invention, R is1And R2Independently selected from: -H, -CH3、
Figure BDA0001848856900000024
Figure BDA0001848856900000025
R3And R4Independently selected from: c1-22Alkyl or a group of formula lb:
Figure BDA0001848856900000026
R0selected from: -H, -O.cndot., -OH, -CH2CN、C1-22Alkyl, C substituted by hydroxy2-18Alkoxy radical, C3-12Cycloalkyl radical, C1-18Alkoxy radical, C3-12Cycloalkoxy, C3-6Alkylene radical, C3-6Alkenyloxy radical, C1-8Acyl, unsubstituted or substituted on phenyl by 1-3C1-4Alkyl substituted C7-9PhenylalkanesOr a group of formula Ia:
Figure BDA0001848856900000031
n is an integer of 2 to 10.
Preferably, said R is3And R4Independently selected from: c1-10Alkyl or (Ib).
Preferably, said R is0Selected from: -H, C1-22Alkyl, C substituted by hydroxy2-18Alkoxy radical, C3-12Cycloalkyl radical, C1-18Alkoxy radical, C3-12Cycloalkoxy, C3-6Alkylene radical, C3-6Alkenyloxy radical, C1-8Acyl, unsubstituted or substituted on phenyl by 1-3C1-4Alkyl substituted C7-9Phenylalkyl, or a group of formula Ia:
Figure BDA0001848856900000032
n is an integer of 2 to 10.
In a preferred embodiment of the present invention, R is3And R4Independently selected from:
Figure BDA0001848856900000033
R5and R6Independently selected from: -H, C1-12Alkyl, unsubstituted or substituted by 1-3C1-4Alkyl substituted C3-12Cycloalkyl, unsubstituted or substituted by 1-3-OH and C1-10Phenyl substituted by alkyl radicals, unsubstituted or by phenyl substituted by 1-3-OH and C1-10C substituted by alkyl radicals7-9Phenylalkyl, (Ib) group or R5And R6Form a morpholino group with N therebetween;
in a preferred embodiment of the present invention, R is5And R6Independently selected from:
Figure BDA0001848856900000034
or R5And R6With formation of N therebetween
Figure BDA0001848856900000035
R7And R8Independently selected from: -H, C1-8Alkyl or benzyl.
Preferably, said R is7And R8Independently selected from: -H, C1-6Alkyl or benzyl.
In a preferred embodiment of the present invention, R is7And R8Independently selected from: -CH3。
C according to the invention1-22The alkyl group is selected from: methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1, 3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,3, 3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1, 3-trimethylhexyl, 1,3, 3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1,3,3,5, 5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl and eicosyl.
C according to the invention3-12Cycloalkyl is selected from: cyclopropyl, cyclobutyl, methylcyclobutyl, cyclopentyl, methylcyclopentyl, dimethylcyclopentyl, trimethylcyclopentyl, ethylcyclopentyl, propylcyclopentyl, isopropylcyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, ethylcyclohexyl, cycloheptyl, methylcycloheptyl, cyclooctyl.
C according to the invention1-18Alkoxy is selected from: methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, 2-ethylbutoxy, n-pentyloxy, isopentyloxy, 1-methylpentyloxy, 1, 3-dimethylbutyloxy, n-hexyloxy, 1-methylhexyloxy, n-heptyloxy, isoheptyloxy, 1,3, 3-tetramethylbutoxy, 1-methylheptyloxy, 3-methylheptyloxy, n-octyloxy, 2-ethylhexyloxy, 1, 3-trimethylhexyloxy, 1,3, 3-tetramethylpentyloxy, nonyloxy, decyloxy, undecyloxy, 1-methylundecyloxy, n-butyloxy, n-pentyloxy, n-,Dodecyloxy, 1,3,3,5, 5-hexamethylhexyloxy, tetradecyloxy, hexadecyloxy, and octadecyloxy.
C according to the invention3-12The cycloalkoxy group is selected from: cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, cyclooctyloxy, cyclodecyloxy and cyclododecyloxy.
C according to the invention3-6The alkylene group is selected from: allyl, 2-methylallyl, butenyl, pentenyl and hexenyl.
C according to the invention3-6The alkenyloxy group is selected from: 1-propenyloxy and 2-propenyloxy.
C according to the invention1-8The acyl group is selected from: formyl, acetyl, propionyl, butyryl, pentanoyl, hexanoyl, heptanoyl, octanoyl, acryloyl, methacryloyl, and benzoyl.
C according to the invention7-9Phenylalkyl groups are preferably benzyl and 2-phenylethyl.
The compound of the invention consists of 1-3C1-4Alkyl substituted C7-9Phenylalkyl, preferably methylbenzyl, dimethylbenzyl, trimethylbenzyl or tert-butylbenzyl.
The hydrogen on any carbon atom of the alkoxy group of the present invention may be substituted by a hydroxyl group, preferably a 2-hydroxyethoxy group.
In a specific embodiment of the invention, there are provided specific compounds of the following structure:
Figure BDA0001848856900000051
Figure BDA0001848856900000061
the invention provides a preparation method of a compound with a general formula I, which comprises the following steps:
Figure BDA0001848856900000062
Figure BDA0001848856900000071
preferably, the molar ratio of the reactants in the step (1) is 1 (2-3).
Preferably, the molar ratio of the reactants in the step (2) is 1 (1-2). Preferably, the reaction solvent in steps (1), (2) and (3) is selected from: acetone, dichloromethane, toluene or xylene, xylene or tetrahydrofuran;
preferably, a base is added in the steps (1) and (2), and the base is selected from the group consisting of: sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide or triethylamine.
Preferably, the base is reacted with
Figure BDA0001848856900000072
The molar ratio of (A) to (B) is: (1-1.5):1.
Preferably, the base is reacted with the compound in the step (2)
Figure BDA0001848856900000073
The molar ratio of (A) to (B) is: (1-1.5):1.
Preferably, the alkylating agent in step (3) is selected from: halogenated hydrocarbon, sulfate, aryl sulfonate, alcohol, ether, olefin, formaldehyde and formic acid.
Preferably, the step (3) is performed by adding a catalyst selected from the group consisting of: molybdenum trioxide, vanadium pentoxide, chromium trioxide, tungsten trioxide or manganese dioxide, catalyst and additive
Figure BDA0001848856900000074
The molar ratio of (0.02-0.2) to (1).
Preferably, if R is selected from: -O.C1-18Alkoxy, C substituted by hydroxy2-18Alkoxy radical, C3-12Cycloalkoxy, C3-6Alkenyloxy radical, C1-8An acyl group, wherein in step (3) a hydroperoxide is added, said hydroperoxide being selected from the group consisting of: tert-butyl hydroperoxide, peracetic acid, hydrogen peroxide solution, etcHydroperoxides with addition of
Figure BDA0001848856900000075
The molar ratio of (2-10) to (1).
The invention provides the use of a compound of general formula (I) as a stabiliser for organic substances which are sensitive to degradation by light, heat or oxidation.
The invention provides application of a compound with a general formula I as an organic matter flame retardant.
The present invention provides a composition comprising a compound of formula i and an organic material which contains a moiety susceptible to degradation by light, heat or oxidation.
Preferably, the composition further comprises an antioxidant, a UV absorber, a hindered amine light stabilizer, a filler, a reinforcing agent, or other additives.
The amount of the compound of formula I depends on the nature of the organic material, the end use and additives, and the amount of the compound of formula I can be used in various proportions.
Preferably, the mass fraction of the compound with the general formula I is 0.01-5% of the weight of the organic substances;
more preferably, the mass fraction of the compound with the general formula I is 0.05-2% of the weight of the organic substances;
most preferably, the mass fraction of the compound of formula I is 0.05% to 1% of the weight of the organic substance.
The organic substance is selected from: a thermoplastic polymer.
The thermoplastic polymer is selected from: polyolefin, acrylonitrile/butadiene/styrene, polyvinyl chloride, polymethyl methacrylate, polyformaldehyde, polyamide, polyurethane, polycarbonate, polyurethane, polyester, polystyrene, thermoplastic elastomer and ethylene-vinyl acetate copolymer.
Preferably, the thermoplastic polymer is selected from: polyolefins, thermoplastic elastomers.
The thermoplastic elastomer comprises polyolefin thermoplastic elastomer and block copolymer type polystyrene thermoplastic elastomer. The polyolefin thermoplastic elastomer includes a polyolefin resin such as polyethylene and polypropylene serving as a hard segment and a rubber composition such as ethylene-propylene-diene Elastomer (EPDM) serving as a soft segment. The block copolymer type polystyrene thermoplastic elastomer comprises polystyrene serving as a hard segment and a polydiene (such as polybutadiene or polyisoprene) serving as a soft segment. Alternatively, blends of polyolefin elastomers and polystyrene elastomers may also be used as the thermoplastic elastomer of the present invention. The methods for combining the soft segment and the hard segment in the thermoplastic elastomer can be roughly classified into simple blending, implantation by copolymerization, and dynamic crosslinking. Combinations of polystyrene thermoplastic elastomer segments include SBS, SIS, SEBS, SEPS, hydrogenated polymers of any of these four copolymers, non-SBR hydrogenated polymers (HSBR), and blends of polypropylene with one or more of any of these polymers.
The polyolefin is selected from: polyethylene or polypropylene containing a rubbery phase based on ethylene and/or propylene.
The antioxidant is selected from: antioxidant 1010, antioxidant 1076, antioxidant 1098 and antioxidant 168.
The UV absorber is selected from: salicylates, benzoates, benzophenones, benzotriazoles, triazines.
The hindered amine light stabilizer is selected from: hindered amine light stabilizers which are different from the compounds of the general formula I and have the structure (Ib), such as bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate, polymers of succinic acid and 4-hydroxy-2, 2,6, 6-tetramethyl-1-piperidineethanol, Chimassorb 944 and Chimassorb 2020.
The filler and reinforcing agent are selected from: calcium carbonate, silicates, glass fibres, glass beads, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and flour or other natural product fibres, synthetic fibres.
The other additives are selected from: plasticizers, lubricants, emulsifiers, pigments, rheology additives, catalysts, flow control agents, optical brighteners, flameproofing agents, antistatic agents and blowing agents.
The invention provides the use of said composition for the preparation of any plastic product selected from the group consisting of: interior or exterior finishing materials for automobiles, floating devices, road traffic devices, agricultural products, electric appliances, furniture, footwear, sanitary products, health products, and the like.
The plastic product may be made by any method known to those of ordinary skill in the art including, but not limited to, extrusion blow molding, film casting, calendering, injection molding, blow molding, compression molding, thermoforming, spin forming, blow extrusion, and rotational casting.
Detailed Description
EXAMPLE 1 Synthesis of Compound (1)
Figure BDA0001848856900000091
36.9g of cyanuric chloride is dissolved in 300mL of xylene, the solution is cooled to 10 ℃, 84.8g of 84.8g N- (2,2,6, 6-tetramethyl-4-piperidyl) N-butylamine (the molar ratio of cyanuric chloride to N- (2,2,6, 6-tetramethyl-4-piperidyl) N-butylamine is 1:2) and stirred for 1h, 50g of aqueous sodium hydroxide solution (30%) is added and stirred for 3h at 60 ℃, the phases are separated, and then 17.5g of morpholine (the molar ratio of cyanuric chloride to morpholine is 1:1) is added and the stirring is continued for 3 h. After completion of the reaction, the phases were separated and the organic phase was washed several times with water, then the organic phase was separated and concentrated under reduced pressure to obtain 53.3g of compound (1). (91% of theory)
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).
EXAMPLE 2 Synthesis of Compound (2)
Figure BDA0001848856900000101
50.0g of the compound (1) prepared in example 1 was dissolved in 300mL of xylene, and then 150mL of formaldehyde and 1.5g of tungsten trioxide were added, and stirred at 50 ℃ for 12 hours, followed byCooling to room temperature, filtering, and adding an excess of saturated NaHSO to the filtrate3The solution is stirred, separated and the organic phase is concentrated to obtain the compound (2). Compound (2) is prepared from1H-NMR analysis revealed that the N-H group on the piperidyl group of the compound (1) was converted into the corresponding N-CH3Thereby forming compound (2).
EXAMPLE 3 Synthesis of Compound (3)
Figure BDA0001848856900000102
50.0g of the compound (1) prepared in example 1 was dissolved in 300mL of xylene, 150mL of cyclohexane, 1.5g of tungsten trioxide and 50g of a 70% aqueous solution of t-butyl hydroperoxide were added, stirred at 50 ℃ for 12 hours, then cooled to room temperature, filtered, and an excess of saturated NaHSO was added to the filtrate3The solution is stirred, separated and the organic phase is concentrated to obtain the compound (3). Compound (3) is prepared from1H-NMR analysis revealed that the N-H group on the piperidyl group of the compound (1) was converted into the corresponding N-cyclohexyloxy group, thereby forming a compound (3).
EXAMPLE 4 Synthesis of Compound (4)
Figure BDA0001848856900000111
50.0g of the compound (1) prepared in example 1 was dissolved in 300mL of xylene, 50g of 2-ethylhexanal and 1.5g of tungsten trioxide were added and stirred at 20 ℃ for 2 hours, then 40g of 30% aqueous hydrogen peroxide was added and stirred at 50 ℃ for 12 hours, then cooled to room temperature, filtered, and an excess of saturated NaHSO was added to the filtrate3The solution is stirred, separated and the organic phase is concentrated to obtain the compound (4). Compound (4) is prepared from1H-NMR analysis revealed that the N-H group on the piperidyl group of the compound (1) was converted into the corresponding N-alkoxy group, thereby forming a compound (4).
EXAMPLE 5 Synthesis of Compound (5)
Figure BDA0001848856900000112
Figure BDA0001848856900000121
140.0g of polyethylene glycol methyl ether, 133.6g of ethyl bromoacetate, 2.0g of p-toluenesulfonic acid monohydrate, 400mL of xylene were added to a 1000mL three-necked flask, and the mixture was stirred at reflux temperature for 20 h. The solution was then concentrated under vacuum and filtered to give compound (a).
50.0g of the compound (1) prepared in example 1 was dissolved in 300mL of xylene, and then 25.0g of the compound (A), 34.5g of potassium carbonate and 6.9g of potassium iodide were added, stirred at reflux temperature for 20 hours, cooled to room temperature after completion of the reaction, filtered, water was added to the filtrate, stirred, the organic phase was separated and concentrated in vacuo. The concentrate was washed with ethanol, then water and finally dried to give compound (5). Compound (5) is prepared from1H-NMR analysis revealed that the N-H group on the piperidyl group of the compound (1) was converted into the corresponding N-alkyl group, thereby forming a compound (5).
EXAMPLE 6 Synthesis of Compound (6)
Figure BDA0001848856900000122
36.9g of cyanuric chloride is dissolved in 300mL of xylene, the solution is cooled to 10 ℃, 84.8g of 84.8g N- (2,2,6, 6-tetramethyl-4-piperidyl) N-butylamine (the molar ratio of cyanuric chloride to N- (2,2,6, 6-tetramethyl-4-piperidyl) N-butylamine is added at 1:2), the mixture is stirred for 1h, 50g of aqueous sodium hydroxide solution (30%) is added, the mixture is stirred for 3h at 60 ℃, the phases are separated, then 25.8g of di-N-butylamine (the molar ratio of cyanuric chloride to di-N-butylamine is 1:1) is added, and the stirring is continued for 3 h. After completion of the reaction, the phases were separated and the organic phase was washed several times with water, then the organic phase was separated and concentrated under reduced pressure to obtain 58.4g of compound (6). (93% of theory)
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).
EXAMPLE 7 Synthesis of Compound (7)
Figure BDA0001848856900000131
50.0g of the compound (6) prepared in example 6 was dissolved in 300mL of xylene, 150mL of formaldehyde and 1.5g of tungsten trioxide were then added, and the mixture was stirred at 50 ℃ for 12 hours, then cooled to room temperature, filtered, and an excess of saturated NaHSO was added to the filtrate3The solution was stirred, separated and the organic phase was concentrated to give compound (7). Compound (7) is prepared from1H-NMR analysis revealed that the N-H group on the piperidyl group of the compound (6) was converted into the corresponding N-CH3Thereby forming compound (7).
EXAMPLE 8 Synthesis of Compound (8)
Figure BDA0001848856900000132
50.0g of the compound (6) prepared in example 6 was dissolved in 300mL of xylene, and then 150mL of cyclohexane, 1.5g of tungsten trioxide and 50g of a 70% aqueous solution of t-butyl hydroperoxide were added, stirred at 50 ℃ for 12 hours, then cooled to room temperature, filtered, and an excess of saturated NaHSO was added to the filtrate3The solution was stirred, separated and the organic phase was concentrated to give compound (8). Compound (8) is prepared from1H-NMR analysis revealed that the N-H group on the piperidyl group of the compound (6) was converted into the corresponding N-cyclohexyloxy group, thereby forming a compound (8).
EXAMPLE 9 Synthesis of Compound (9)
Figure BDA0001848856900000141
50.0g of the compound (6) prepared in example 6 was dissolved in 300mL of xylene, 50g of 2-ethylhexanal and 1.5g of tungsten trioxide were added and stirred at 20 ℃ for 2 hours, then 40g of 30% aqueous hydrogen peroxide was added and stirred at 50 ℃ for 12 hours, then cooled to room temperature, filtered, and an excess of saturated NaHSO was added to the filtrate3The solution was stirred, separated and the organic phase was concentrated to give compound (9). Compound (9) is prepared from1H-NMR analysis revealed that the N-H group on the piperidinyl group of compound (6) was converted to the corresponding N-Alkoxy group, thereby forming compound (9).
EXAMPLE 10 preparation of Compound (10)
Figure BDA0001848856900000142
50.0g of the compound (6) prepared in example 6 was dissolved in 300mL of xylene, and then 25.0g of the compound (A), 34.5g of potassium carbonate and 6.9g of potassium iodide were added, stirred at reflux temperature for 20 hours, cooled to room temperature after completion of the reaction, filtered, water was added to the filtrate, stirred, the organic phase was separated and concentrated in vacuo. The concentrate was washed with ethanol, then water and finally dried to give compound (10). Compound (10) is prepared from1H-NMR analysis revealed that the N-H group on the piperidyl group of the compound (6) was converted into the corresponding N-alkyl group, thereby forming a compound (10).
Example 11 stabilized thermoplastic Polypropylene test
The basic formula is as follows:
standard polymer: 79.8 wt% of thermoplastic polypropylene; 20 wt% hydrotalcite; 0.20 wt% of an antioxidant (AO-1010);
1# is 100 wt% standard polymer;
# 2 is 99.7% by weight of standard polymer, 0.3% by weight of compound (1);
no. 3 is 99.7% by weight of a standard polymer, 0.3% by weight of the compound (6);
preparation of test samples:
the components are mixed in advance in a mixer, and then extruded and granulated on a double-screw extruder at 220 ℃. Dried at 80 ℃ for 8h and then injection molded using an injection molding machine at 240 ℃. Finally, xenon lamp aging test is carried out on the sample according to SAE J2527 standard, and the test result is shown in Table 1:
TABLE 1 △ E of the xenon aged samples (low value is desired)
Figure BDA0001848856900000151
Example 12 stabilized thermoplastic polyethylene test
The basic formula is as follows:
standard polymer: 79.8 wt% of a thermoplastic polyethylene; 20 wt% calcium carbonate; 0.20 wt% of an antioxidant (AO-1010);
1# is 100 wt% standard polymer;
# 2 is 99.6% by weight of standard polymer, 0.4% by weight of compound (1);
# 3 is 99.6% by weight of standard polymer, 0.4% by weight of compound (2);
no. 4 is 99.6% by weight of the standard polymer, 0.4% by weight of the compound (3);
# 5 is 99.6% by weight of standard polymer, 0.4% by weight of compound (8);
preparation of test samples:
the components are mixed in advance in a mixer, and then extruded and granulated on a double-screw extruder at 190 ℃. Dried at 80 ℃ for 8h and then blow molded at 200 ℃ using a film blowing machine. Finally, the sample is subjected to an actual greenhouse buckling test, and the test results are shown in tables 2-1 and 2-2:
TABLE 2-1 tensile Strength Retention% (Farmland)
Figure BDA0001848856900000161
TABLE 2-2 tensile Strength Retention% (flowers)
Figure BDA0001848856900000162
Example 13 test for stabilization of thermoplastic polyvinyl chloride
The basic formula is as follows:
standard polymer:
65.5 wt% thermoplastic polyvinyl chloride; 31.5 wt% plasticizer; 1.6 wt% epoxidized soybean oil; 1.4 wt% calcium zinc stabilizer;
1# is 100 wt% standard polymer;
no. 2 is 99.5 wt% of standard polymer, 0.25 wt% of UV-531; 0.25 wt% of Compound (8)
No. 3 is 99.5 wt% of standard polymer, 0.25 wt% of UV-531; 0.25 wt% of Compound (9)
Preparation of test samples:
the components were premixed in a mixer and then kneaded on a two-roll mill at 165 ℃ for 7 minutes to obtain the desired sample. Finally, the sample is subjected to xenon lamp aging test according to the GB/T16422.2-2014 standard, and the test result is shown in Table 3:
TABLE 3 retention of elongation at break%
Figure BDA0001848856900000171
EXAMPLE 14 stabilized thermoplastic Acrylonitrile/butadiene/styrene (ABS) test
The basic formula is as follows:
standard polymer: 96 wt% of a thermoplastic ABS resin; 3 wt% titanium dioxide; 1 wt% of a slip agent;
1# is 100 wt% standard polymer;
no. 2 is 99.65 wt% standard polymer, 0.1 wt% paraffin oil; 0.25 wt% of Compound (3)
No. 3 is 99.65 wt% standard polymer, 0.1 wt% paraffin oil; 0.25 wt% of Compound (8)
Preparation of test samples:
the components are mixed in advance in a mixer, and then extruded and granulated on a double-screw extruder at 220 ℃. Dried at 80 ℃ for 8h and then injection molded using an injection molding machine at 240 ℃. Finally, the sample is subjected to xenon lamp aging test according to the GB/T16422.2-2014 standard, and the test result is shown in Table 4:
TABLE 4 Delta E of the xenon aged samples (low value is desired)
Figure BDA0001848856900000172
Figure BDA0001848856900000181
Example 15 Performance testing as flame retardant in PP film
The basic formula is as follows:
standard polymer: 99.65 wt% thermoplastic polypropylene; 0.05 wt% calcium stearate; 0.30 wt% antioxidant (AO-1010: AO-168 ═ 1: 1);
1# is 100 wt% standard polymer;
2# 99.6 wt% Standard Polymer, 0.5 wt% Compound (4)
No. 3 is 99.6% by weight of a standard polymer, 0.5% by weight of a compound (9)
Preparation of test samples:
the components are mixed in advance in a mixer, and then extruded and granulated on a double-screw extruder at 220 ℃. Drying at 80 deg.C for 8 hr, and compression molding in hot press. Finally, the samples were subjected to flame retardancy tests in accordance with DIN 4102-B2, the test results being shown in Table 5:
TABLE 5 sample flame retardance
Sample (I) Weight loss/%) Length of combustion/mm Burning dropping liquid Pass/fail
1# 100 190 Is that Fail to be qualified
2# 8.7 105 Is that Qualified
3# 8 102 Is that Qualified

Claims (9)

1. A compound of formula I as a stabilizer and/or as a flame retardant for organic materials containing organic materials susceptible to degradation by light, heat or oxidation, which compound has the formula:
Figure FDA0002310219660000011
R1and R2Is a radical of the formula Ia:
Figure FDA0002310219660000012
n is an integer of 2 to 10;
R3and R4Is C1-22An alkyl group;
R5and R6Is composed of
Figure FDA0002310219660000013
Or, R5And R6Form a morpholino group with N therebetween;
R7and R8Independently selected from: -H, C1-8Alkyl or benzyl.
2. The compound of claim 1,
the R is3And R4Is C1-10An alkyl group.
3. The compound according to claim 1 or 2,
the R is3And R4Is composed of
Figure FDA0002310219660000014
The R is7And R8is-CH3。
4. The compound of claim 3, wherein the compound has the structure:
Figure FDA0002310219660000015
or
Figure FDA0002310219660000021
5. Use of a compound according to any one of claims 1 to 4 as a stabiliser for organic materials which are susceptible to degradation by light, heat or oxidation and/or as a flame retardant for organic materials.
6. A composition comprising a compound according to any one of claims 1 to 4 and an organic material susceptible to degradation by light, heat or oxidation.
7. The composition of claim 6, further comprising an antioxidant, a UV absorber, a hindered amine light stabilizer, a filler, a reinforcing agent, or other additives.
8. The composition as claimed in claim 6, wherein the mass fraction of the compound of formula I is 0.01% to 5% by weight of the organic substance.
9. Use of the composition of claim 6 for the preparation of a plastic product selected from the group consisting of: the fields of automobile interior or exterior decorative materials, floating devices, road traffic devices, agricultural products, electric appliances, furniture, shoes, sanitary products and health-care products.
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