A polymeric hindered amine and its preparation method and application

Abstract

The present invention provides a polymeric hindered amine, comprising the following general formula I structure: The compound of the present invention has the advantages of high anti-aging performance, high molecular weight, not easy to migrate out in polymer material products, thermal stability, good compatibility, etc.; The NOR amine ether type polymer compound obtained by selecting a specific monomer containing a NOR amine ether structure for polymerization reaction has the advantages of low alkalinity and flame retardancy. The present invention also provides a preparation method thereof, which has simple steps, is low-carbon and environmentally friendly.

Description

Technical Field

[0001] The invention relates to the field of polymer technology, and in particular to a polymeric hindered amine and a preparation method and application thereof. Background Art

[0002] Polymer materials play an increasingly important role in people's daily lives. During the use of polymer materials, they are often damaged by factors such as light, heat, and oxygen, causing them to powder, crack, and yellow, which further affects their appearance, performance, and life. In order to avoid such phenomena, some stabilizers are usually added during the processing of polymer materials.

[0003] In recent years, hindered amine light stabilizers (HALS) have been actively researched and developed in today's society due to their outstanding application performance, and are the focus of light stabilizer research and development. Among them, piperidine derivative series of light stabilizers are the top priority, such as 770, 938, 2020(EP782994), HS-950, 783, 379, HS-625, 393, NOR116, etc. Among them, low molecular weight hindered amine light stabilizer products have defects such as easy volatility and easy migration during the processing of films, fibers and other products, so their scope of use is restricted; in comparison, high molecular weight hindered amine light stabilizer products have significant advantages in this regard.

[0004] In addition, in certain specific polymer material application scenarios, additives are required to have the characteristics and functions of low alkalinity and flame retardancy. Therefore, NOR amine ether type hindered amine products are increasingly attracting the attention of the market and researchers, especially polymerized NOR amine ether type hindered amine products.

[0005] Patent document CN113354813A discloses a preparation method of a low-alkalinity hindered amine light stabilizer NOR371, and synthesizes the low-alkalinity hindered amine light stabilizer NOR371 in an electrocatalytic manner. Patent CN111303481B discloses an oligomeric hindered amine light stabilizer and a preparation method thereof, using commercially available light stabilizer 944 as a starting material, and obtaining a low-alkalinity, acid-resistant, and oligomeric hindered amine light stabilizer containing an alkoxy structure through end-capping, free radicalization, and alkoxylation; Patent CN100384826C introduces a preparation method using Chimassorb 2020 to undergo a nucleophilic substitution reaction with allyl bromide, followed by an oxidative rearrangement with peracetic acid, and finally hydrogenation reduction to generate NOR371. However, there are few polymeric hindered amine light stabilizers in the prior art that take into account the low alkalinity, flame retardancy, stability, and compatibility of the product, and the preparation method is simple in steps and economical and environmentally friendly. Summary of the invention

[0006] In order to overcome the deficiencies of the prior art, the present invention provides a polymeric hindered amine and a preparation method and application thereof.

[0007] In a first aspect of the present invention, a polymeric hindered amine is provided, having the following structure:

[0008]

[0009] in,

[0010] A n , B n For different unit structures, A n Contains at least two hindered amine structures, B n Contains at least two grafting sites A n With B n By grafting site End to end;

[0011] The * is a grafting site;

[0012] R′ is selected from the group consisting of any one or more of the following groups: hydrogen, alkyl, cycloalkyl, heterocycloalkyl, heteroalkyl, or alkyl interrupted by one or more first spacer groups;

[0013] The first spacer group includes any one or more combinations of the following groups: heteroatoms, -C(=O)O-, amine groups, -OC(=O)O-, alkenyl groups, alkynyl groups, -C(=S)O-, amide groups, urea groups, arylene groups, heteroalkylene groups, heteroarylene groups, alkylene groups substituted by one or more first substituents, heteroalkylene groups substituted by one or more first substituents, and cycloalkylene groups substituted by one or more first substituents;

[0014] The first substituent is selected from the group consisting of any one or more of the following groups: hydroxy, halogen, aryl, cycloalkyl, hydroxyalkyl, alkoxy, thioalkoxy, nitro, cyano, amino, heteroaryl, heterocycloalkyl, aryloxycarbonyl, heteroaryloxycarbonyl, alkoxycarbonyl, heteroalkoxycarbonyl, alkoxythiocarbonyl, acyloxy, alkanoyloxy, aroyloxy, heteroaroyloxy, cycloalkanoyloxy, heteroalkanoyloxy, alkanoyl, aminoacyl, alkylaminoacyl, alkylsulfonyl, aroyl, alkyl interrupted by one or more heteroatoms, alkyl interrupted by one or more second spacer groups;

[0015] The second spacer group is selected from one or more combinations of the following structures: heteroatom, -C(=O)O-, -OC(=O)O-, -C(=O)-, -C(=S)O-, amide, urea, arylene, alkenyl, alkynyl, amine, heteroalkylene, heteroarylene;

[0016] m1, m2...m n is the degree of polymerization of each repeating unit, which is an integer between 1 and 20 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20); n is an integer between 1 and 20; n represents the degree of polymerization;

[0017] Preferably, the m1+m2+...+m n ≥3;

[0018] n is an integer of 1-20 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20); n represents the degree of polymerization;

[0019] A1, A2, A3...A n Can be the same or different; B1, B2, B3...B n It can be the same or different;

[0020] RT1 and RT2 are the same or different terminal groups;

[0021] Specifically, in Formula I, one or more (possibly present) identical or different For example, when n=4, ----- represents When n=5, ----- represents etc.

[0022] Specifically, RT 1 , RT 2 is any suitable capping group, which may carry a latently reactive group, or be an inert capping group.

[0023] Preferably, RT 1 , RT 2 Independently selected from any one or more of the following structures: hydrogen, alkyl, cycloalkyl, heterocycloalkyl, heteroalkyl, alkyl spaced by one or more second spacer groups, alkyl substituted by one or more substituents, heteroalkyl substituted by one or more first substituents, cycloalkyl substituted by one or more first substituents.

[0024] In some embodiments of the present invention, n is 1, and the polymeric hindered amine has the following structure:

[0025]

[0026] In some embodiments of the present invention, n is an integer greater than 2, for example 2, and the polymeric hindered amine has the following structure:

[0027]

[0028] Furthermore, the hindered amine structure of the present invention has the following general formula II:

[0029]

[0030] Wherein, E1, E2, and E3 are independently selected from: or Any of , a1 is 0, 1 or 2;

[0031] Preferably, the hindered amine structure can be selected from one or more of the following structures:

[0032]

[0033] In some embodiments of the present invention, the hindered amine structure has the following structure:

[0034]

[0035] Furthermore, the A1, A2, ..., A n Can be independently selected from one or more of the following general structural formulas AI to AV:

[0036]

[0037] in,

[0038] X 1 , X 2 independently selected from the group consisting of one or more of the following groups: a single bond, -O-, -NH-, -alkylene-, -O-alkylene-, -NH-alkylene, -C(O)- or -C(O)-alkylene;

[0039] Preferably, X 1 , X 2 independently selected from -O- or -alkylene-;

[0040] Y 1 , Y 2 independently selected from the group consisting of one or more of the following groups: single bond, -O-, -NH-, -alkylene-, -O-alkylene-, -NH-alkylene, -C(O)-, -C(O)-alkylene;

[0041] Preferably, Y 1 , Y 2 are independently selected from -O-, -alkylene-;

[0042] Z 1 , Z 2 Independently selected from the group consisting of one or more of the following groups: -alkylidene-, -O-alkylidene-, -NH-alkylidene, alkylidene substituted by one or more alkyl, hydroxy, halogen or alkoxy groups;

[0043] Preferably, Z 1 , Z 2 Selected from -C-, -alkylidene-;

[0044] X 3 , X 4 Independently selected from the following groups: -O-, -NH-, -N(R 13 The group consisting of any one or more of )-, -S-, -alkylene-, alkylene interrupted by one or more heteroatoms, or alkylene substituted by one or more second substituents.

[0045] Preferably, X 3 , X 4 Independently selected from: -O-, -NH-, -N(R 13 )-, -O-alkylene-, or -alkylene-.

[0046] The R 13 It is selected from: alkylene, alkylene interrupted by one or more heteroatoms or alkylene substituted by one or more second substituents.

[0047] The second substituent is selected from the group consisting of one or more of the following groups: alkyl, hydroxy, alkenyl, halogen, aryl, arylene, cycloalkyl, alkoxy, thioalkoxy, nitro, cyano, amino, heteroaryl, heterocycloalkyl, hydroxyalkyl, alkoxycarbonyl, aryloxycarbonyl, heteroaryloxycarbonyl, heteroalkoxycarbonyl, alkoxythiocarbonyl, acyloxy, alkanoyloxy, aroyloxy, heteroaroyloxy, cycloalkanoyloxy, heteroalkanoyloxy, alkanoyl, aminoacyl, alkylaminoacyl, alkylsulfonyl, alkyl separated by one or more second spacer groups; the second spacer group is selected from one or more of the following groups: heteroatom, -C(=O)O-, -OC(=O)O-, -C(=O)-, -C(=S)O-, -S(=O)-, -S(=O)2-, amide, urea, arylene, alkenyl, alkynyl, heteroalkylene or heteroarylene;

[0048] Specifically, Y 3 , Y 4 independently selected from the group consisting of one or more of the following groups: a single bond (-), -O-, -NH-, -alkylene-, -O-alkylene-, -NH-alkylene, or an alkylene substituted with one or more second substituents;

[0049] Preferably, Y 3 , Y 4 are independently selected from: a single bond, -alkylene-, or -NH-;

[0050] Specifically, X 5 , X 6 Independently selected from the following groups: -O-, -NH-, -N(R 13 )-、-N(R 14 )-, -C(═O)-, -C(S)-, -C(═O)O-, -OC(═O)-, -alkylene-, alkylene interrupted by one or more heteroatoms or substituted by one or more substituents;

[0051] More preferably, X 5 , X 6 Independently selected from: -alkylene-, -NH-, -NH-alkylene-

[0052] More specifically, the R 14 Selected from: alkyl, alkyl interrupted by one or more heteroatoms, alkyl substituted by one or more second substituents.

[0053] Specifically, R 1 , R 2Independently selected from the group consisting of one or more of the following groups: single bond (-), -alkylene, -cycloalkylene, -heterocyclylene, alkylene or arylene interrupted by one or more heteroatoms, alkylene substituted by one or more second substituents;

[0054] When R 1 When Z is a single bond (-), 1 , Z 2 Directly connected is a spiral ring structure, and the AI ​​structure is:

[0055]

[0056] Preferably, R 1 , R 2 independently selected from: a single bond (-), -alkylene-, -arylene-, -OC(=O)O-, -OC(=O)-, -C(=O)O-, -C(=O)-, -O-, -NH-, -N(R 14 )-、 A group consisting of any one or more groups;

[0057] Preferably, the R 14 Selected from: alkyl;

[0058] Specifically, X 7 , X 8 , X 9 Independently selected from the group consisting of one or more of the following groups: single bond (-), -alkylene-, imino, nitrilo, -N(R 14 )-, -NH-alkylene-, -cycloalkylene-, -heterocyclylene-, -O-, or -S-;

[0059] R 3 , R 3” independently selected from the group consisting of one or more of the following groups: hydrogen, -NH-alkyl, -cycloalkyl, -heterocyclyl, -O-cycloalkyl, cycloalkyl interrupted by one or more heteroatoms, cycloalkyl substituted by one or more alkyl groups, cycloalkyl substituted by one or more alkyl groups and heteroatoms;

[0060] Preferably, R 3 , R 3 " is independently selected from hydrogen, -alkyl, -NH-alkyl, or

[0061] Preferably, X 7 , X 8 , X 9 independently selected from single bonds (-), -alkylene-, -imino-, -nitro-, -N(R 14)-, -NH-alkylene-, or -S-.

[0062] Furthermore, the B1, B2, B3, B4, B5...B n Selected from independently selected structures selected from general formula BI to BV-II:

[0063]

[0064] in,

[0065] a, b, c, e, f, g, h represent B respectively n The number of grafting sites in ; a, b, c, e, f, g, h are selected from 1 or 2;

[0066] Preferably, a+b≥2; c≥2; e+f≥2; g≥2; h≥2;

[0067] R 3 'Independently selected from the group consisting of any one or more of the following groups: hydrogen, -alkylene-, -NH-alkylene, -cycloalkylene, -heterocyclylene, -O-cycloalkylene, cycloalkylene interrupted by one or more heteroatoms, cycloalkylene substituted by one or more alkyl groups, cycloalkylene substituted by one or more alkyl groups and interrupted by one or more heteroatoms;

[0068] Preferably, R 3’ is -alkylene or

[0069] R 4 , R 11 、 R 12 , R 15 , R 16 independently selected from the group consisting of any one or more of the following groups: H, alkyl, cycloalkyl, heterocycloalkyl, alkyl spaced by one or more third spacer groups, wherein the third spacer group is selected from the group consisting of any one or more of the following groups: heteroatom, -C(=O)O-, heteroalkylene, alkenyl, alkynyl, -C(=O)-, -C(=S)O-, amide, urea, -OC(=O)O-, alkylene substituted by a third substituent, or heterocycloalkylene substituted by a third substituent;

[0070] Preferably, R 15 , R 16 is H or alkyl;

[0071] The third substituent is selected from the group consisting of any one or more of the following groups: hydroxy, cycloalkyl, alkoxy, thioalkoxy, nitro, cyano, amine, heterocycloalkyl, alkoxycarbonyl, alkoxycarbonyl, heteroalkoxycarbonyl, alkoxythiocarbonyl, acyloxy, alkanoyloxy, cycloalkanoyloxy, heteroalkanoyloxy, alkanoyl, aminoacyl, alkylaminoacyl, alkylsulfonyl, or alkyl substituted with one or more fourth substituents;

[0072] The fourth substituent is selected from the group consisting of one or more of the following groups: a heteroatom, -C(=O)O-, -OC(=O)O-, -C(=O)-, -C(=S)O-, an amide group, a urea group, an alkenyl group, an alkynyl group, or a heteroalkylene group;

[0073] Preferably, R 4 Selected from: H or alkyl;

[0074] More preferably, R 4 Selected from: H or -CH3;

[0075] R 5 , R 6 , R 8 independently selected from a single bond (-), an alkylene group, a cycloalkylene group, a heterocycloalkylene group, or an alkylene group interrupted by one or more fourth spacer groups;

[0076] R 7 , R 10 , R 15’ independently selected from alkylene, cycloalkylene, heterocycloalkylene, alkylene interrupted by one or more fourth spacer groups;

[0077] Preferably, R 7 is a C7-C22 alkylene group;

[0078] Preferably, R 12 Selected from: H, alkyl or -C(=O)-;

[0079] Preferably, R 15’ is an alkylene group;

[0080] R7 in B-II and R in B-IV 10 There are two or more active sites on it, and these two grafting sites are connected to A. Preferably, R7 in B-Ⅱ and R in B-Ⅳ 10 is a long-chain carbon, more preferably, the long carbon chain is a C8-C22 alkylene group;

[0081] The fourth spacer is selected from the group consisting of one or more of the following groups: alkyl, imino, -C(=O)O-, heteroalkylene, arylene, alkenyl, alkynyl, -C(=O)-, -C(=S)O-, amide, urea or -OC(=O)O-alkyl;

[0082] Preferably, R 5 , R 6 , R 8 Selected from: H or -alkylene-;

[0083] More preferably, R 5 and R 6 It is a C8-C22 alkylene group.

[0084] Preferably, R 7 Selected from: any one of H, alkylene, -NH-alkylene-;

[0085] Preferably, R 5 , R 6 , R 7 , R 8 is a long-chain alkyl group selected from C8-C22 alkylene groups, including but not limited to C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C21 or C22 alkylene groups;

[0086] R 9 independently selected from alkylene, cycloalkylene, heterocycloalkylene, alkylene interrupted by one or more fifth spacer groups;

[0087] The fifth spacer is selected from the group consisting of one or more of the following groups: heteroatoms, -C(=O)O-, heteroalkylene, arylene, alkenyl, alkynyl, -C(=O)-, -C(=S)O-, amide, urea, -OC(=O)O-, alkylene substituted by a fifth substituent, heterocycloalkylene substituted by one or more fifth substituents;

[0088] The fifth substituent is selected from the group consisting of one or more of the following groups: hydroxy, cycloalkyl, alkoxy, thioalkoxy, nitro, cyano, amine, heterocycloalkyl, alkoxycarbonyl, alkoxycarbonyl, heteroalkoxycarbonyl, alkoxythiocarbonyl, acyloxy, alkanoyloxy, cycloalkanoyloxy, heteroalkanoyloxy, alkanoyl, aminoacyl, alkylaminoacyl, alkylsulfonyl, alkylene interrupted by one or more sixth spacer groups;

[0089] The sixth spacer group is selected from one or more of the following groups: heteroatom, -C(=O)O-, -OC(=O)O-, -C(=O)-, -C(=S)O-, amide, urea, alkenyl, alkynyl, heteroalkylene;

[0090] Preferably, R 9 Selected from: single bond (-), alkylene, -O-;

[0091] Preferably, R 10 Selected from: alkylene;

[0092] The X 8’ , X 10 , X 11 , X 12 , X 13 , X 14 independently selected from the group consisting of any one or more of the following groups: a single bond (-), -O-, -NH-, -NH-C(=O)-, -N(R 14 )-、-NH(R 13 )-, -S-, -alkylene-, or alkylene substituted by one or more sixth substituents;

[0093] The sixth substituent is selected from the group consisting of one or more of the following groups: heteroatom, hydroxyl, cycloalkyl, alkoxy, thioalkoxy, nitro, cyano, amine, heterocycloalkyl, carbonyl, alkoxycarbonyl, heteroalkoxycarbonyl, alkoxythiocarbonyl, acyloxy, alkanoyloxy, cycloalkanoyloxy, heteroalkanoyloxy, alkanoyl, aminoacyl, alkylaminoacyl, alkylsulfonyl, alkyl spaced by one or more seventh spacer groups;

[0094] The seventh spacer group includes one or more combinations of the following groups: heteroatoms, -C(=O)O-, -OC(=O)O-, -C(=O)-, -C(=S)O-, amides, urea groups, alkenyl groups, alkynyl groups, and heteroalkylene groups;

[0095] Preferably, X 8’ Selected from: -alkylene- or -NH-;

[0096] Preferably, X 10 Selected from: -O-, -NH- or -alkylene-;

[0097] Preferably, X 11 Selected from: -alkylene-, -NH-C(=O)-, -NH-, -N(R 14 )-、-NH(R 13 )-or-O;

[0098] Preferably, X 12 , X 13 are independently selected from: a single bond (-), -alkylene-, -NH- or -NH-alkylene-;

[0099] More preferably, X 12 is -alkylene- or -NH-;

[0100] X 15 , X 16 , Y 5 , Y 6 are independently selected from -O-, -N-, -alkylene-, -O-alkylene-, -N-alkylene or carbonyl;

[0101] Preferably, X 16 Selected from -N-, -alkylene-;

[0102] Z 3 An alkylene group independently selected from -alkylene-, -O-alkylene-, -N-alkylene substituted with one or more substituents, wherein the substituents are independently selected from: alkyl, cycloalkyl, hydroxy, halogen or alkoxy;

[0103] Z 4 Independently selected from -alkylene-, cycloalkyl, cycloalkylene, alkylene, cycloalkylene or cycloalkylene substituted with one or more seventh substituents.

[0104] Preferably, Z 4 is selected from alkylene substituted by cycloalkyl.

[0105] Furthermore, AI can be independently selected from the following structures:

[0106]

[0107]

[0108] wherein i is an integer from 1 to 22, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22;

[0109] * is the available grafting site for grafting A-Ⅰ and B;

[0110] Preferably, i is an integer of 1-12, more preferably an integer of 1-8;

[0111] A-II is independently selected from the following structures:

[0112]

[0113]

[0114]

[0115] wherein j is an integer from 1 to 22, specifically, j can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22;

[0116] Preferably, j is an integer of 1-12, more preferably, j is an integer of 1-8;

[0117] * is the available grafting site for A-Ⅱ and B grafting.

[0118] A-III can be independently selected from the following structures:

[0119]

[0120] wherein k is an integer from 1 to 22, specifically, k can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22;

[0121] * is the available grafting site for A-Ⅲ and B grafting.

[0122] A-IV can be independently selected from the following structures:

[0123]

[0124]

[0125]

[0126]

[0127]

[0128]

[0129]

[0130] A-V are independently selected from the following structures:

[0131]

[0132] Wherein O is an integer of 1-22, specifically, O can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22;

[0133] * is the available grafting site for A-V and B grafting.

[0134] Preferably, O is an integer of 8-22, more preferably an integer of 8-12.

[0135] Further, in some embodiments of the present invention, B-I is independently selected from the following structures:

[0136]

[0137] wherein x and x' are independently selected from integers of 8-22; and * is an available grafting site for grafting B-I with A.

[0138] B-II is independently selected from the following structures:

[0139]

[0140] wherein y is an integer from 5 to 22, for example, y may be 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22;

[0141] Preferably, y is an integer from 8 to 22;

[0142] * is the available grafting site for B-Ⅱ and A.

[0143] B-III is independently selected from the following structures:

[0144]

[0145] Wherein, p is an integer from 1 to 22, for example, p can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22;

[0146] Preferably, p is an integer from 1 to 8;

[0147] q is an integer from 0 to 22, for example, q can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22;

[0148] Preferably, q is an integer from 1 to 8;

[0149] r is an integer from 0 to 22, for example, r can be 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22;

[0150] Preferably, r is an integer from 0 to 8;

[0151] * is the available grafting site for B-Ⅲ and A. Only when q>1, there is an available grafting site.

[0152] B-IV is independently selected from the following structures:

[0153]

[0154]

[0155] BVI is independently selected from the following structures:

[0156]

[0157] BV-II is independently selected from the following structures:

[0158]

[0159] Wherein, z is an integer of 8-22, for example, z can be 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22;

[0160] Preferably, z is an integer of 12-22, more preferably, z is an integer of 12-16; * is an available grafting site for grafting B-IV, BVI, BV-II and A.

[0161] The second aspect of the present invention provides a method for preparing a polymeric hindered amine, which comprises the steps of polymerizing a monomer under the action of a catalyst and a hydroperoxide;

[0162] The monomers include monomer A and monomer B, both monomer A and monomer B include hindered amine structures, monomer A includes at least two hindered amine structures, and monomer B includes two grafting site structures;

[0163] The polymerization reaction can be carried out in a solvent, which can be selected from the group consisting of tetrahydrofuran, 2-methyltetrahydrofuran, halogenated hydrocarbons (such as dichloromethane, dichloroethane, carbon tetrachloride, etc.), acetonitrile, propionitrile, butyronitrile, aromatic hydrocarbons (such as benzene, toluene, xylene, chlorobenzene, dichlorotoluene, etc.), aliphatic hydrocarbons (such as petroleum ether, n-hexane, n-heptane, cyclohexane, n-octane, etc.), alcohols (such as methanol, ethanol, propanol, ethylene glycol, diethylene glycol, ethylene glycol methyl ether), dimethyl sulfoxide, N,N-dimethylamide, diphenyl ether, and one or more thereof. Preferably, the solvent can be selected from the group consisting of toluene, chlorobenzene, xylene, cyclohexane, n-heptane, and dichloromethane.

[0164] The catalyst may be selected from one of catalysts based on tungsten, molybdenum, and ruthenium,

[0165] The catalyst may be a homogeneous catalyst or a solid / supported catalyst.

[0166] The catalyst is preferably molybdenum or ruthenium, and more preferably, the catalyst is molybdenum trioxide, dichloro[o-isopropoxybenzylidene][1,3-bis(2,4,6-trimethylphenyl)-2-imidazolinylidene]ruthenium;

[0167] The hydroperoxide is an inorganic hydroperoxide or an organic hydroperoxide;

[0168] The inorganic hydroperoxide includes H2O2; the organic hydroperoxide includes alkyl hydroperoxide and aryl hydroperoxide. Preferably, the alkyl hydroperoxide includes tert-alkyl hydroperoxide (such as tert-butyl hydroperoxide, tert-amyl hydroperoxide, tert-hexyl hydroperoxide, tert-octyl hydroperoxide), and the aryl hydroperoxide includes ethylbenzene hydroperoxide, tetralin peroxide or isopropylbenzene hydroperoxide.

[0169] Preferably, the hydroperoxide is selected from any one of H2O2, tert-amyl hydroperoxide or cumene hydroperoxide.

[0170] The amount of the peroxide is 1-20 molar equivalents, preferably 1-10 molar equivalents, more preferably 1-5 molar equivalents, based on the molar equivalents of the polymerizable monomer;

[0171] The amount of the catalyst used is 0.0001-0.6 molar equivalent, preferably 0.01-0.3 molar equivalent, and more preferably 0.01-0.15 molar equivalent.

[0172] Further, the molar ratio of the catalyst to the monomer is 5:100 to 1:100000 (e.g., 1:100, 1:200, 1:400, 1:500, 1:600, 1:800, 1:1000, 1:2000, 1:4000, 1:5000, 1:6000, 1:8000, 1:10000, 1:50000, 1:100000), especially 1:100 to 1:10000.

[0173] And / or, the reaction temperature of the polymerization reaction is 0-150°C, preferably 120-150°C (e.g., 120, 125, 130, 135, 140, 145, 150°C).

[0174] And / or, the polymerization reaction pressure is -0.099 MPa to 0.1 MPa, preferably -0.099 MPa to 0.02 MPa (e.g., -0.1, -0.001, -0.005, 0.01, 0.02 MPa).

[0175] The polymerization reaction is carried out in a protective gas, which can be a chemically inactive inert gas, such as argon or nitrogen. Preferably, the protective gas includes: one or both of argon and nitrogen;

[0176] Preferably, the pressure of the preparation method is 0.5-30 bar, preferably 0.5-20 bar, more preferably 0.5-10 bar. The preparation method can also be carried out under atmospheric pressure.

[0177] Furthermore, the monomer A in the above polymerization reaction includes at least two hindered amine structures (as described in the first aspect of the present invention) and the monomer B includes two grafting sites. The structure of monomer A and monomer B is grafted through the grafting site Connect end to end.

[0178] Further, in some embodiments of the present invention, the monomer A comprises or

[0179] (Free radicals).

[0180] More specifically, the monomer is selected from the structures of AI to AV, and the monomer A-I is independently selected from one or more of the following structures:

[0181]

[0182]

[0183]

[0184] wherein i is an integer from 1 to 22 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22); preferably, an integer from 1 to 12, more preferably, an integer from 1 to 8;

[0185] Monomer A-II is independently selected from one or more of the following structures:

[0186]

[0187]

[0188]

[0189] Wherein j is an integer from 1 to 22 (for example, j can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22), preferably an integer from 1 to 12, and more preferably an integer from 1 to 8.

[0190] The monomer A-III is selected from one or more of the following structures:

[0191]

[0192] Monomers A-IV are independently selected from the following structures:

[0193]

[0194]

[0195]

[0196]

[0197]

[0198]

[0199]

[0200]

[0201]

[0202]

[0203]

[0204]

[0205]

[0206] The monomers A-V are selected from one or more of the following structures:

[0207]

[0208] Wherein O is an integer of 1-22 (such as 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22), preferably, O is an integer of 8-22, more preferably an integer of 8-12.

[0209] Specifically, in some embodiments of the present invention, monomer B-I is selected from one or more of the following structures:

[0210]

[0211]

[0212] wherein x and x' are independently selected from integers of 8-22 (e.g., 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22). 。

[0213] Monomer B-II is independently selected from one or more of the following structures:

[0214]

[0215] y is an integer of 5-22, for example, y can be 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22, preferably, y is an integer of 8-22, more preferably, y is an integer of 8-12;

[0216] Monomer B-III is independently selected from the following structures:

[0217]

[0218]

[0219] Wherein, p is an integer from 1 to 22, for example, p can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22;

[0220] Preferably, p is an integer from 1 to 8;

[0221] q is an integer from 0 to 22, for example, q can be 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22;

[0222] Preferably, q is an integer from 1 to 8;

[0223] r is an integer from 0 to 22, for example, r can be 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22;

[0224] Preferably, r is an integer from 0 to 8;

[0225] The monomer B-IV is independently selected from one or more of the following structures:

[0226]

[0227] The monomer BVI or BV-II is selected from one or more of the following structures:

[0228]

[0229] Wherein z is an integer of 8-22, for example, z can be 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22, preferably, z is an integer of 12-22.

[0230] Specifically, the above monomers can be directly used as commercial products, or can be prepared according to methods known in the art.

[0231] The third aspect of the present invention provides a use of a monomer A and a monomer B in the preparation of a polymeric hindered amine light stabilizer I, wherein the monomer A comprises at least two hindered amine structures, and the monomer B comprises two grafting sites. The structure of monomer A and monomer B is grafted through the grafting site Connect end to end.

[0232] In the fourth aspect of the present invention, a polymer auxiliary agent is provided, which comprises the polymeric hindered amine and additives described in the first aspect of the present invention. The polymer auxiliary agent can be used as a light stabilizer and / or flame retardant in the production, processing and use of polymer products to delay or prevent the aging of polymer products and improve the performance and service life of polymer products.

[0233] Specifically, the additives include: one or more of antioxidants, UV absorbers, hindered amine light stabilizers, reinforcing agents, fillers, flame retardants, plasticizers, lubricants, emulsifiers, pigments, rheological additives, catalysts, flow control agents, optical brighteners, fire retardants, antistatic agents and foaming agents.

[0234] Preferably, the antioxidant can be selected from: one or more of phenolic and / or amine antioxidants, phosphites or thioesters, for example, antioxidant 1010, antioxidant 1076, antioxidant 1098, antioxidant 168, etc.

[0235] Preferably, the UV absorber can be selected from: one or more of salicylates, benzoates, benzophenones, benzotriazoles or triazines.

[0236] Preferably, the hindered amine light stabilizer is selected from: hindered amine light stabilizers having a structure different from the polymeric hindered amine compound or a mixture thereof described in the first aspect of the present invention, such as bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate, a polymer of succinic acid and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol, Chimassorb944, Chimassorb2020, UV-3346, UV-3529, Tinuvin770, Tinuvin622LD, Tinuvin292, HS-625 or HS-950 and other hindered amine light stabilizers.

[0237] Preferably, the filler and reinforcing agent can be selected from: any one or more of calcium carbonate, silicate, glass fiber, glass beads, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood powder and flour or other natural product fibers or synthetic fibers;

[0238] Preferably, the auxiliary agent also includes an organic substance that is sensitive to light, heat or oxidation;

[0239] Preferably, the organic substance sensitive to light, heat or oxidation includes one or more of the following substances: a combination of one or more of polyolefins, acrylonitrile / butadiene / styrene, polyvinyl chloride, polymethyl methacrylate, polyacetal, polyamide, polyimide, epoxy resin, polyurethane, polycarbonate, polyurethane, polyester, polysulfone, polyurea, polystyrene, and thermoplastic elastomer.

[0240] In a fifth aspect of the present invention, a composition is provided, comprising the polymeric hindered amine described in the first aspect, and one or more organic substances that are sensitive to light, heat or oxidation.

[0241] Preferably, the organic substance sensitive to light, heat or oxidation includes the following substances: one or a combination of two or more of polyolefin, acrylonitrile / butadiene / styrene, polyvinyl chloride, polymethyl methacrylate, polyacetal, polyamide, polyimide, epoxy resin, polyurethane, polycarbonate, polyurethane, polyester, polysulfone, polyurea, polystyrene or thermoplastic elastomer.

[0242] Furthermore, the amount of the polymeric hindered amine is determined by the nature of the organic substance, the final use and the additives, and the polymeric hindered amine can be used in various proportions.

[0243] Preferably, in the composition, the amount of the polymeric hindered amine can be 0.01%-5%, for example 0.01%, 0.05%, 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, 0.5%, 1%, 2%, 3%, 4% or 5%.

[0244] More preferably, the amount of the polymeric hindered amine light stabilizer of the general formula I is 0.05%-2% by weight of the organic substance;

[0245] Particularly preferably, the amount of the polymeric hindered amine light stabilizer of the general formula I is 0.05%-1% by weight of the organic substance;

[0246] Particularly preferably, the amount of the high molecular weight polymeric hindered amine light stabilizer of general formula I is 0.05%-0.5% by weight of the organic substance.

[0247] Furthermore, the polyolefin is obtained by polymerizing or copolymerizing α-olefin or cycloolefin alone;

[0248] The α-olefin is selected from one or more of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene or 4-methyl-1-pentene;

[0249] The polyolefin may be polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, polyvinyl chloride, ethylene-vinyl acetate copolymer, etc.

[0250] and / or, the polyacetal is selected from one or more of polyoxymethylene, polyoxymethylene containing ethylene oxide as a comonomer, polyacetal modified with thermoplastic polyurethane, polyacetal modified with acrylate or polyacetal modified with MBS;

[0251] Preferably, the polyoxymethylene is a polyoxymethylene containing ethylene oxide as a comonomer;

[0252] And / or, the polyamide is selected from: polyamides and copolyamides derived from diamines and dicarboxylic acids and / or aminocarboxylic acids or corresponding lactams, such as polyamide 4, polyamide 6, polyamide 66, polyamide 610, polyamide 69, polyamide 612, polyamide 46, polyamide 1212, polyamide 11, polyamide 12, aromatic polyamides obtained from meta-xylene diamine and adipic acid; one or more polyamides obtained from hexamethylene and isophthalic acid and / or terephthalic acid in the presence or absence of an elastomer as a modifier.

[0253] And / or, the polyester is selected from: polyesters prepared from dicarboxylic acids and diols and / or from hydroxycarboxylic acids or their corresponding lactones, such as polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dihydroxymethylcyclohexane terephthalate and polyhydroxybenzoates, as well as block copolyether esters of hydroxy-terminated polyether derivatives, and polyesters modified with polycarbonate or MBS.

[0254] And / or, the thermoplastic elastomer is selected from: polyolefin thermoplastic elastomer and block copolymer polystyrene thermoplastic elastomer.

[0255] Preferably, the polyolefin thermoplastic elastomer comprises 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.

[0256] Preferably, 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, a blend of a polyolefin elastomer and a polystyrene elastomer may also be used as the thermoplastic elastomer of the present invention. The method for combining soft segments and hard segments in a thermoplastic elastomer can be roughly divided into simple blending, implantation by copolymerization, and dynamic crosslinking. The combination of polystyrene thermoplastic elastomer segments includes a hydrogenated polymer of any one of SBS, SIS, SEBS, SEPS, these four copolymers, a hydrogenated polymer of SBR (HSBR), and a blend of polypropylene and one or more arbitrary members selected from these polymers.

[0257] Preferably, the composition may also include one or more of antioxidants, UV absorbers, hindered amine light stabilizers, reinforcing agents, fillers, flame retardants, plasticizers, lubricants, emulsifiers, pigments, rheological additives, catalysts, flow control agents, optical brighteners, fire retardants, antistatic agents or foaming agents.

[0258] Preferably, the antioxidant can be selected from: one or more of phenol and / or amine antioxidants, phosphites, thioesters or other types of antioxidants, including but not limited to antioxidant 1010, antioxidant 1076, antioxidant 1098, antioxidant 168, etc.

[0259] Preferably, the UV absorber is selected from: one or more of salicylates, benzoates, benzophenones, benzotriazoles, and triazines.

[0260] Preferably, the hindered amine light stabilizer is selected from: hindered amine light stabilizers having a different structure from the polymeric hindered amine or its mixture described in the first aspect of the present invention, such as bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate, a polymer of succinic acid and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol, Chimassorb944, Chimassorb2020, UV-3346, UV-3529, Tinuvin770, Tinuvin622LD, Tinuvin292, HS-625 or HS-950 and other hindered amine light stabilizers.

[0261] Specifically, the filler and reinforcing agent can be selected from: one or more of calcium carbonate, silicate, glass fiber, glass beads, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood powder and flour or other natural product fibers, synthetic fibers.

[0262] In a sixth aspect of the present invention, there is provided use of the polymeric hindered amine described in the first aspect or the polymeric hindered amine prepared by the method described in the second aspect in the preparation of a light stabilizer and / or a flame retardant.

[0263] Specifically, the light stabilizer and flame retardant are used in the production, processing and use of polymer products to delay or prevent the aging of polymer products and improve the performance and service life of polymer products.

[0264] In the seventh aspect of the present invention, there is provided use of the polymeric hindered amine described in the first aspect and the polymer auxiliary agent described in the fourth aspect in the preparation of polymer material products.

[0265] Specifically, the polymer material product can be: plastic, rubber, fiber, coating, adhesive or composite material, etc.;

[0266] The application includes: using the polymer material product in the fields of automobile interior or exterior decoration materials, floating devices, road traffic devices, agricultural products, electrical appliances, furniture, shoes, sanitary products or health care products.

[0267] Specifically, the plastic can be manufactured by any method known to those skilled in the art, including but not limited to extrusion, extrusion blow molding, film casting, calendering, injection molding, blow molding, compression molding, thermoforming, spin molding, blow extrusion and rotational casting.

[0268] Beneficial effects of the present invention:

[0269] In the present invention, a monomer A containing two hindered amine structures and a monomer containing two grafting sites are formed. The monomer B is polymerized to generate a high molecular weight hindered amine light stabilizer. The polymerized hindered amine light stabilizer provided by the present invention has the advantages of high anti-aging performance, high molecular weight, not easy to migrate out in polymer material products, good thermal stability, etc., and can also be made to have good compatibility with different types of polymer materials by changing the substituents; the NOR amine ether type polymer compound obtained by selecting a specific monomer containing a NOR amine ether structure for polymerization reaction has the advantages of low alkalinity and flame retardancy. Compared with the prior art, the preparation method provided by the present invention is simpler, low-carbon and environmentally friendly. DETAILED DESCRIPTION

[0270] Unless otherwise defined, all scientific and technical terms used in the present invention have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention relates.

[0271] The term "alkyl" as used herein may be a straight chain or branched chain alkyl. The alkyl group described herein contains 1 to 22 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22) carbon atoms (e.g., C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, C7 alkyl, C8 alkyl, C9 alkyl, C10 alkyl, C11 alkyl, C12 alkyl, C13 alkyl, C14 alkyl, C15 alkyl, C16 alkyl, C17 alkyl, C18 alkyl, C19 alkyl, C20 alkyl, C21 alkyl, C22 alkyl, C23 alkyl, C24 alkyl, C25 alkyl, C26 alkyl, C27 alkyl, C28 alkyl, C29 alkyl, C30 alkyl, C31 alkyl, C32 alkyl, C33 alkyl, C34 alkyl, C35 alkyl, C36 alkyl, C37 alkyl, C38 alkyl, C39 alkyl, C40 alkyl, C41 alkyl, C42 alkyl, C43 alkyl, C44 alkyl, C45 alkyl, C46 alkyl, C47 alkyl, C48 alkyl, C49 alkyl, C50 alkyl, C51 alkyl, C52 alkyl, C53 alkyl, C54 alkyl, C55 alkyl, C56 alkyl, C57 alkyl, C58 alkyl, C59 alkyl, C60 alkyl, C61 alkyl, C62 alkyl, C63 alkyl, C64 alkyl, C65 alkyl, C66 alkyl, C11 alkyl, C12 alkyl, C13 alkyl, C14 alkyl, C15 alkyl, C16 alkyl, C17 alkyl, C18 alkyl, C19 alkyl, C20 alkyl, C21 alkyl, C22 alkyl), can be selected from C1-8 alkyl, C1-6 alkyl, C1-3 alkyl, including but not limited to: methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, n-dodecyl, n-octadecyl.

[0272] The term "halogen" as used herein includes the following atoms: fluorine (F), chlorine (Cl), bromine (Br), and iodine (I).

[0273] The "alkoxy" of the present invention contains 1 to 22 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22) carbon atoms, i.e., C1-22 alkoxy (e.g., C1 alkoxy, C2 alkoxy, C3 alkoxy, C4 alkoxy, C5 alkoxy, C6 alkoxy, C7 alkoxy, C8 alkoxy, C9 alkoxy, C10 alkoxy, C11 alkoxy, C12 alkoxy oxy, C13 alkoxy, C14 alkoxy, C15 alkoxy, C16 alkoxy, C17 alkoxy, C18 alkoxy, C19 alkoxy, C20 alkoxy, C21 alkoxy, C22 alkoxy), can be selected from: C1-18 alkoxy, C1-8 alkoxy, C1-6 alkoxy, C1-3 alkoxy, further, including but not limited to: methoxy, ethoxy, isopropoxy, propoxy, butoxy, hexyloxy, octyloxy, n-dodecyloxy, n-octadecyloxy. The alkoxy group of the present invention may be substituted, and the substituent may be halogen, aryl, hydroxyl, cyano, nitro, C1-22 alkoxy and C1-22 alkylamino (for example, C1 alkylamino, C2 alkylamino, C3 alkylamino, C4 alkylamino, C5 alkylamino, C6 alkylamino, C7 alkylamino, C8 alkylamino, C9 alkylamino, C10 alkylamino, C11 alkylamino, C12 alkylamino, C13 alkylamino, C14 alkylamino, C15 alkylamino, C16 alkylamino, C17 alkylamino, C18 alkylamino, C19 alkylamino, C20 alkylamino, C21 alkylamino, C22 alkylamino); the alkoxy group of the present invention may be spaced by a spacer group, and the spacer group is oxygen, nitrogen, sulfur, arylene, heteroalkylene, -C(=O)-, or -C(=O)O-.

[0274] The term "cycloalkyl" appearing in the present invention includes substituted or unsubstituted cycloalkyl and unsaturated cycloalkyl. The cycloalkyl described in the present invention contains 1 to 10 carbon atoms, i.e., C1-10 cycloalkyl, for example, C3-6 cycloalkyl (for example: C1 cycloalkyl, C2 cycloalkyl, C3 cycloalkyl, C4 cycloalkyl, C5 cycloalkyl, C6 cycloalkyl, C7 cycloalkyl, C8 cycloalkyl, C9 cycloalkyl, C10 cycloalkyl, C11 cycloalkyl, C12 cycloalkyl, C13 cycloalkyl, C14 cycloalkyl, C15 cycloalkyl, C16 cycloalkyl, C17 cycloalkyl, C18 cycloalkyl, C19 cycloalkyl, C20 cycloalkyl, C21 cycloalkyl, C22 cycloalkyl). The cycloalkyl described in the present invention includes, but is not limited to, cyclopentyl, cyclopropyl, and cyclohexyl.

[0275] The term "alkylene" in the present invention may be a linear or branched alkylene. The alkylene described in the present invention contains 1 to 22 carbon atoms, i.e., C1-22 alkylene, such as C1-18 alkylene, C1-12 alkylene, C1-8 alkylene, C1-6 alkylene, C1-3 alkylene (e.g., C1 alkylene, C2 alkylene, C3 alkylene, C4 alkylene, C5 alkylene, C6 alkylene, C7 alkylene, C8 alkylene, C9 alkylene, C10 alkylene, C11 alkylene, C12 alkylene, C13 alkylene, C14 alkylene, C15 alkylene, C16 alkylene, C17 alkylene, C18 alkylene, C19 alkylene, C20 alkylene, C21 alkylene, C22 alkylene). In some embodiments of the present invention, the alkylene may be methylene, ethylene, propylene, butylene, etc.

[0276] If an alkylene group is substituted with a cycloalkyl group, it is correspondingly a "cycloalkylenealkyl" group;

[0277] If an alkylene group is substituted with an aryl group, then it is correspondingly an "arylenealkyl";

[0278] If an alkylene group is substituted by a heterocyclyl group, it is correspondingly a "heterocyclylenealkyl group".

[0279] The term "aryl" in the present invention includes C6-C18 aryl (e.g., C6 aryl, C7 aryl, C8 aryl, C9 aryl, C10 aryl, C11 aryl, C12 aryl, C13 aryl, C14 aryl, C15 aryl, C16 aryl, C17 aryl, C18 aryl), such as benzene ring and naphthalene ring aryl, especially benzene ring aryl. The aryl may be substituted by one or more alkyl, halogen, C3-C8 cycloalkyl, C3-C8 cycloalkyloxy, C1-C18 alkoxy;

[0280] The "heteroaryl" of the present invention refers to an aromatic monocyclic or polycyclic ring system containing 5-18 ring atoms (such as 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18 ring atoms), preferably 5-10 ring atoms, wherein one or more ring atoms are not carbon atoms, but are, for example, nitrogen, sulfur, oxygen, phosphorus, silicon, especially oxygen, nitrogen, and the remaining ring atoms are carbon atoms. The heteroaryl of the present invention may be substituted by a substituent, wherein the substituent may be an alkyl, cyano, nitro, alkoxy, hydroxyl, halogen, amino, alkylamino, aroyl, alkanoyl, arylsulfonyloxy, alkaneamide or alkanesulfonamido. Examples of the heteroaryl of the present invention are benzotriazole and 1,3,5-triazine.

[0281] The term "arylene" described in the present invention includes C6-C18 arylene, for example: C6 arylene, C7 arylene, C8 arylene, C9 arylene, C10 arylene, C11 arylene, C12 arylene, C13 arylene, C14 arylene, C15 arylene, C16 arylene, C17 arylene, C18 arylene.

[0282] The term "heteroalkyl" appearing in the present invention refers to an alkyl group in which one or more carbon atoms in the C1-22 alkyl group as defined above (such as C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, C7 alkyl, C8 alkyl, C9 alkyl, C10 alkyl, C11 alkyl, C12 alkyl, C13 alkyl, C14 alkyl, C15 alkyl, C16 alkyl, C17 alkyl, C18 alkyl, C19 alkyl, C20 alkyl, C21 alkyl, C22 alkyl) are replaced by one or more atoms other than carbon, and the atoms other than carbon include any one or more of nitrogen, sulfur, oxygen, phosphorus, and silicon.

[0283] The term "heterocyclyl" as used herein includes heteroaryl and heterocycloalkyl groups containing 1 to 3 single and / or condensed rings and 3 to about 18 ring atoms.

[0284] The term "heterocycloalkyl" in the present invention includes a monocyclic or polycyclic ring system containing 5-18 ring atoms (such as 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18 ring atoms), preferably 5-10 ring atoms, wherein one or more ring atoms are not carbon atoms, but for example: nitrogen, sulfur, oxygen, phosphorus, silicon, especially oxygen, nitrogen, and the remaining ring atoms are carbon atoms. The heterocycloalkyl of the present invention includes but is not limited to: pyrrolidine, piperidine, morpholine, tetrahydrofuran, piperidone, piperazinone, imidazoline, imidazolinone, 1,3,5-triazinane or piperazine. The heterocycloalkyl of the present invention may also be substituted by a substituent, and the substituent may be an alkyl, hydroxyalkyl, halogen, hydroxyl, alkoxy, aroyl, alkanoyl, nitro, cyano, amino or alkylamino.

[0285] In the present invention, the terms "alkoxycarbonyl", "heteroalkoxycarbonyl", "alkoxythiocarbonyl", "alkanoyloxy", "cycloalkanoyloxy", "heteroalkanoyloxy", "alkanoyl", "alkylaminoacyl", "alkylsulfonyl" include carbon atoms of 1-22 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22)

[0286] In the present invention, the aryl group in the term "aryloxycarbonyl", "heteroaryloxycarbonyl", "aroyl", "aroyloxy" and "heteroaroyloxy" contains 6-18 carbon atoms (for example: 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18)

[0287] The term "halogen" appearing in the present invention refers to bromine, chlorine, iodine or fluorine.

[0288]

[00136] Various publications, patents, and published patent specifications are cited herein, the disclosures of which are incorporated by reference in their entireties.

[0289] The polymerizable monomers shown above are known in the art, some of which are commercially available, or can be synthesized according to methods known in the art.

[0290] The solvent used in the method of the present invention is a commonly used organic solvent such as aromatic hydrocarbons (such as benzene, xylene, chlorobenzene, etc.), halogenated hydrocarbons, alcohols (such as methanol, ethanol, ethylene glycol or methyl ether) or water.

[0291] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only some embodiments of the present invention, not all. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0292] Example 1

[0293] Monomer 1-1:

[0294] Monomer 1-2:

[0295] In a 1L round-bottom flask, 110g of monomer 1 and 100g of monomer 2 were dissolved in 500mL of xylene, 0.8g of molybdenum trioxide was added, and the mixture was heated to 140°C. Then, 90g of tert-amyl hydroperoxide (70% aqueous solution) was slowly added dropwise and stirred for 18h. After complete reaction, an excess of saturated sodium sulfite solution was added, stirred, phase separated, filtered, and the organic phase was concentrated to obtain 195.2g of the target product P1-EX1.

[0296] Molecular weight: 3179.5

[0297] Viscosity (100℃): 962cps

[0298] Example 2

[0299] Monomer 2-1:

[0300] Monomer 2-2:

[0301] In a 1L round-bottom flask, 135g of monomer 1 and 106g of monomer 2 were dissolved in 500mL of xylene, 0.6g of molybdenum trioxide was added, and the mixture was heated to 130°C. Then 90g of cumene hydroperoxide (70% aqueous solution) was slowly added dropwise and stirred for 12h. After complete reaction, an excess of saturated sodium sulfite solution was added, stirred, phase separated, filtered, and the organic phase was concentrated to obtain 214g of the target product P1-EX2.

[0302] Molecular weight: 2263.43

[0303] Viscosity (100℃): 695cps

[0304] Example 3

[0305] Monomer 3-1:

[0306] Monomer 3-2:

[0307] In a 1000mL round-bottom flask, 125g of monomer 3-1 and 208g of monomer 3-2 were dissolved in 500mL of dichloromethane, 1g of molybdenum trioxide was added, and the mixture was heated to 150°C. Then 100g of isopropylbenzene hydroperoxide (70% aqueous solution) was slowly added dropwise and stirred for 16h. After complete reaction, an excess of saturated sodium sulfite solution was added, stirred, phase separated, filtered, and the organic phase was concentrated to obtain 266g of the target product P1-EX3.

[0308] Molecular weight: 1028.57

[0309] Viscosity (100℃): 423cps

[0310] Example 4

[0311] Monomer 4-1:

[0312] Monomer 4-2:

[0313] In a 1000 mL round-bottom flask, 160 g of monomer 4-1 and 202 g of monomer 4-2 were dissolved in 500 mL of chlorobenzene, 2.8 g of dichloro[o-isopropoxybenzylidene][1,3-bis(2,4,6-trimethylphenyl)-2-imidazolineylidene]ruthenium was added, heated to 130°C, and then 120 g of tert-amyl hydroperoxide (70% aqueous solution) was slowly added dropwise and stirred for 18 h. After complete reaction, an excess of saturated sodium sulfite solution was added, stirred, phase separated, filtered, and the organic phase was concentrated to obtain 293.2 g of the target product P1-EX4.

[0314] Molecular weight: 2178.82

[0315] Viscosity (100℃): 695cps

[0316] Example 5

[0317] Monomer 5-1:

[0318] Monomer 5-2:

[0319] In a 1000mL round-bottom flask, 270g of monomer 5-1 and 149g of monomer 5-2 were dissolved in 600mL of dichloromethane, 0.5g of molybdenum trioxide was added, and the mixture was heated to 140°C. Then 100g of tert-amyl hydroperoxide (70% aqueous solution) was slowly added dropwise and stirred for 18h. After complete reaction, an excess of saturated sodium sulfite solution was added, stirred, phase separated, filtered, and the organic phase was concentrated to obtain 162g of the target product P1-EX5.

[0320] Molecular weight: 2584.58

[0321] Viscosity: 846cps (100℃)

[0322] Example 6

[0323] Monomer 6-1:

[0324] Monomer 6-2:

[0325] In a 2000mL round-bottom flask, 280g of monomer 6-1 and 211g of monomer 6-2 were dissolved in 800mL of xylene. After argon replacement, 0.5g of catalyst molybdenum trioxide was added, heated to 140°C, and then 100g of tert-amyl hydroperoxide (70% aqueous solution) was slowly added dropwise and stirred for 18h. After complete reaction, an excess of saturated sodium sulfite solution was added, stirred, phase separated, filtered, and the organic phase was concentrated to obtain 370.4g of the target product P1-EX6.

[0326] Molecular weight: 2939.5

[0327] Viscosity: 1029cps (100℃)

[0328] Example 7

[0329] Monomer 7-1:

[0330] Monomer 7-2:

[0331] In a 2000mL round-bottom flask, 233g of monomer 7-1 and 196g of monomer 7-2 were dissolved in 600mL of xylene. After nitrogen replacement, 5g of catalyst dichloro[o-isopropoxybenzylidene][1,3-bis(2,4,6-trimethylphenyl)-2-imidazolineylidene]ruthenium was added, heated to 140°C, and then 180g of isopropylbenzene hydroperoxide (70% aqueous solution) was slowly added dropwise and stirred for 18h. After complete reaction, an excess of saturated sodium sulfite solution was added, stirred, phase separated, filtered, and the organic phase was concentrated to obtain 370.4g of the target product P1-EX7.

[0332] Molecular weight: 2639

[0333] Viscosity: 1023cps (100℃)

[0334] Example 8

[0335] Monomer 8-1:

[0336] Monomer 8-2:

[0337] In a 2000mL round-bottom flask, 306g of monomer 8-1 and 217g of monomer 8-2 were dissolved in 800mL of xylene. After argon replacement, 3.8g of catalyst dichloro[o-isopropoxybenzylidene][1,3-bis(2,4,6-trimethylphenyl)-2-imidazolineylidene]ruthenium was added, heated to 135°C, and then 130g of tert-amyl hydroperoxide (70% aqueous solution) was slowly added dropwise and stirred for 16h. After complete reaction, an excess of saturated sodium sulfite solution was added, stirred, phase separated, filtered, and the organic phase was concentrated to obtain 516.8g of the target product P1-EX8.

[0338] Molecular weight: 3131.38

[0339] Viscosity: 916cps (100℃)

[0340] Example 9

[0341] Monomer 9-1:

[0342] Monomer 9-2:

[0343] In a 2000mL round-bottom flask, 192g of monomer 9-1 and 184g of monomer 9-2 were dissolved in 500mL of dichloromethane. After nitrogen replacement, 3.8g of catalyst dichloro[o-isopropoxybenzylidene][1,3-bis(2,4,6-trimethylphenyl)-2-imidazolineylidene]ruthenium was added, heated to 135°C, and then 130g of tert-amyl hydroperoxide (70% aqueous solution) was slowly added dropwise and stirred for 12h. After complete reaction, an excess of saturated potassium sulfite solution was added, stirred, phase separated, filtered, and the organic phase was concentrated to obtain 346.1g of the target product P1-EX9.

[0344] Molecular weight: 2320.51

[0345] Viscosity: 843cps (100℃)

[0346] Example 10

[0347] Monomer 10-1:

[0348] Monomer 10-2:

[0349] In a 2000mL round-bottom flask, 196g of monomer 10-1 and 297g of monomer 10-2 were dissolved in 600mL of xylene. After nitrogen replacement, 0.8g of catalyst molybdenum trioxide was added, heated to 140°C, and then 130g of hydrogen peroxide (40% aqueous solution) was slowly added dropwise and stirred for 12h. After complete reaction, an excess of saturated sodium sulfite solution was added, stirred, phase separated, filtered, and the organic phase was concentrated to obtain 396.7g of the target product P1-EX10.

[0350] Molecular weight: 3935.4

[0351] Viscosity: 1210cps (100℃)

[0352] Embodiment 11

[0353] Monomer 11-1:

[0354] Monomer 11-2:

[0355] In a 2000mL round-bottom flask, 205g of monomer 11-1 and 296g of monomer 11-2 were dissolved in 600mL of xylene. After nitrogen replacement, 4.8g of catalyst dichloro[o-isopropoxybenzylidene][1,3-bis(2,4,6-trimethylphenyl)-2-imidazolineylidene]ruthenium was added, heated to 140°C, and then 120g of tert-amyl hydroperoxide (70% aqueous solution) was slowly added dropwise and stirred for 13h. After complete reaction, an excess of saturated sodium sulfite solution was added, stirred, phase separated, filtered, and the organic phase was concentrated to obtain 396.7g of the target product P1-EX11.

[0356] Molecular weight: 2047.84

[0357] Viscosity: 897cps (100℃)

[0358] Example 12

[0359] Monomer 12-1:

[0360] Monomer 12-2:

[0361] In a 2000mL round-bottom flask, 314.4g of monomer 12-1 and 275g of monomer 12-2 were dissolved in 500mL of xylene. After nitrogen replacement, 0.8g of catalyst molybdenum trioxide was added, heated to 140°C, and then 150g of hydrogen peroxide (40% aqueous solution) was slowly added dropwise and stirred for 14h. After complete reaction, an excess of saturated sodium sulfite solution was added, stirred, phase separated, filtered, and the organic phase was concentrated to obtain 483g of the target product P1-EX12.

[0362] Molecular weight: 3575.8

[0363] Viscosity: 1321cps (100℃)

[0364] Example 13

[0365] Monomer 13-1:

[0366] Monomer 13-2:

[0367] In a 2000mL round-bottom flask, 328.5g of monomer 13-1 and 275.5g of monomer 13-2 were dissolved in 600mL of xylene. After nitrogen replacement, 0.8g of molybdenum trioxide catalyst was added, heated to 130°C, and then 130g of hydrogen peroxide (40% aqueous solution) was slowly added dropwise and stirred for 12h. After complete reaction, an excess of saturated sodium sulfite solution was added, stirred, phase separated, filtered, and the organic phase was concentrated to obtain 496.7g of the target product P1-EX13.

[0368] Molecular weight: 2458

[0369] Viscosity: 1021cps (100℃)

[0370] Embodiment 14

[0371] Monomer 14-1:

[0372] Monomer 14-2:

[0373] In a 2000mL round-bottom flask, 275g of monomer 14-1 and 283.5g of monomer 14-2 were dissolved in 600mL of xylene. After nitrogen replacement, 4.8g of catalyst dichloro[o-isopropoxybenzylidene][1,3-bis(2,4,6-trimethylphenyl)-2-imidazolineylidene]ruthenium was added, heated to 135°C, and then 140g of hydrogen peroxide (40% aqueous solution) was slowly added dropwise and stirred for 12h. After complete reaction, an excess of saturated sodium sulfite solution was added, stirred, phase separated, filtered, and the organic phase was concentrated to obtain 457g of the target product P1-EX14.

[0374] Molecular weight: 4558

[0375] Viscosity: 2013cps (100℃)

[0376] Embodiment 15

[0377] Monomer 15-1:

[0378] Monomer 15-2:

[0379] In a 2000mL round-bottom flask, 286g of monomer 15-1 and 253.5g of monomer 15-2 were dissolved in 500mL of xylene. After argon replacement, 0.9g of molybdenum trioxide was added, and the mixture was heated to 150°C. Then 80g of hydrogen peroxide (40% aqueous solution) was slowly added dropwise and stirred for 12h. After complete reaction, an excess of saturated sodium sulfite solution was added, stirred, phase separated, filtered, and the organic phase was concentrated to obtain 456.7g of the target product P1-EX15.

[0380] Molecular weight: 3310

[0381] Viscosity: 1763cps (100℃)

[0382] Example 16

[0383] Monomer 16-1:

[0384] Monomer 16-2:

[0385] In a 2000mL round-bottom flask, 363.5g of monomer 16-1 and 205g of monomer 16-2 were dissolved in 500mL of xylene. After nitrogen replacement, 0.8g of catalyst molybdenum trioxide was added, heated to 130°C, and then 90g of hydrogen peroxide (40% aqueous solution) was slowly added dropwise and stirred for 12h. After complete reaction, an excess of saturated sodium sulfite solution was added, stirred, phase separated, filtered, and the organic phase was concentrated to obtain 456.7g of the target product P1-EX16.

[0386] Molecular weight: 3301

[0387] Viscosity: 1763cps (100℃)

[0388] Embodiment 17

[0389] Monomer 17-1:

[0390] Monomer 17-2:

[0391] In a 2000mL round-bottom flask, 309g of monomer 17-1 and 350g of monomer 17-2 were dissolved in 700mL of xylene. After nitrogen replacement, 0.8g of catalyst molybdenum trioxide was added, heated to 150°C, and then 100g of hydrogen peroxide (40% aqueous solution) was slowly added dropwise and stirred for 12h. After complete reaction, an excess of saturated sodium sulfite solution was added, stirred, phase separated, filtered, and the organic phase was concentrated to obtain 557.7g of the target product P1-EX17.

[0392] Molecular weight: 2678

[0393] Viscosity: 861cps (100℃)

[0394] Embodiment 18

[0395] Monomer 18-1:

[0396] Monomer 18-2:

[0397] In a 2000mL round-bottom flask, 236g of monomer 18-1 and 302g of monomer 18-2 were dissolved in 500mL of xylene. After nitrogen replacement, 0.8g of catalyst molybdenum trioxide was added, heated to 140°C, and then 70g of hydrogen peroxide (40% aqueous solution) was slowly added dropwise and stirred for 15h. After complete reaction, an excess of saturated sodium sulfite solution was added, stirred, phase separated, filtered, and the organic phase was concentrated to obtain 486g of the target product P1-EX18.

[0398] Molecular weight: 3297

[0399] Viscosity: 1065cps (100℃)

[0400] Example 19: Experiment on stabilizing polypropylene material

[0401] Basic recipe:

[0402] Standard polymer: 79.8wt% thermoplastic polypropylene; 20wt% hydrotalcite; 0.20wt% antioxidant (AO-1010);

[0403] 1# is 100wt% standard polymer;

[0404] 2# is 99.7wt% standard polymer, 0.3wt% polymeric hindered amine light stabilizer P1-EX1 (Example 1);

[0405] 3# is 99.7wt% standard polymer, 0.3wt% polymeric hindered amine light stabilizer P1-EX2 (Example 2);

[0406] 4# is 99.7wt% standard polymer, 0.3wt% polymeric hindered amine light stabilizer P1-EX3 (Example 3);

[0407] 5# is 99.7wt% standard polymer, 0.3wt% polymeric hindered amine light stabilizer P1-EX4 (Example 4);

[0408] 6# is 99.7wt% standard polymer, 0.3wt% polymeric hindered amine light stabilizer P1-EX5 (Example 5);

[0409] 7# is 99.7wt% standard polymer, 0.3wt% polymeric hindered amine light stabilizer P1-EX6 (Example 6);

[0410] 8# is 99.7wt% standard polymer, 0.3wt% polymeric hindered amine light stabilizer P1-EX7 (Example 7);

[0411] 9# is 99.7wt% standard polymer, 0.3wt% polymeric hindered amine light stabilizer P1-EX8 (Example 8);

[0412] 10# is 99.7wt% standard polymer, 0.3wt% polymeric hindered amine light stabilizer P1-EX9 (Example 9);

[0413] 11# is 99.7wt% standard polymer, 0.3wt% polymeric hindered amine light stabilizer P1-EX10 (Example 10);

[0414] 12# is 99.7wt% standard polymer, 0.3wt% polymeric hindered amine light stabilizer P1-EX11 (Example 11);

[0415] 13# is 99.7wt% standard polymer, 0.3wt% polymeric hindered amine light stabilizer P1-EX12 (Example 12);

[0416] 14# is 99.7wt% standard polymer, 0.3wt% polymeric hindered amine light stabilizer P1-EX13 (Example 13);

[0417] 15# is 99.7wt% standard polymer, 0.3wt% polymeric hindered amine light stabilizer P1-EX14 (Example 14);

[0418] 16# is 99.7wt% standard polymer, 0.3wt% polymeric hindered amine light stabilizer P1-EX15 (Example 15);

[0419] 17# is 99.7wt% standard polymer, 0.3wt% polymeric hindered amine light stabilizer P1-EX16 (Example 16);

[0420] 18# is 99.7wt% standard polymer, 0.3wt% polymeric hindered amine light stabilizer P1-EX17 (Example 17);

[0421] 19# is 99.7wt% standard polymer and 0.3wt% polymeric hindered amine light stabilizer P1-EX18 (Example 18).

[0422] Preparation of test samples:

[0423] The components were pre-mixed in a mixer, and then extruded and granulated on a twin-screw extruder at 220°C. Drying was performed at 80°C for 8 hours, and then injection molding was performed using an injection molding machine at 240°C. Finally, the samples were subjected to a xenon lamp aging test according to the SAEJ2527 standard. The test results are shown in Table 1:

[0424] Table 1 △E* of samples after xenon lamp aging (low value is required)

[0425]

[0426] Example 20: Stabilized Thermoplastic Polyethylene Test

[0427] Basic recipe:

[0428] Standard polymer: 79.8wt% thermoplastic polyethylene; 20wt% calcium carbonate; 0.20wt% antioxidant (AO-1010);

[0429] 1# is 100wt% standard polymer;

[0430] 2# is 99.6wt% standard polymer, 0.4wt% polymeric hindered amine light stabilizer P1-EX1 (Example 1);

[0431] 3# is 99.6wt% standard polymer, 0.4wt% polymeric hindered amine light stabilizer P1-EX2 (Example 2);

[0432] 4# is 99.6wt% standard polymer, 0.4wt% polymeric hindered amine light stabilizer P1-EX3 (Example 3);

[0433] 5# is 99.6wt% standard polymer, 0.4wt% polymeric hindered amine light stabilizer P1-EX4 (Example 4);

[0434] 6# is 99.6wt% standard polymer, 0.4wt% polymeric hindered amine light stabilizer P1-EX5 (Example 5);

[0435] 7# is 99.6wt% standard polymer, 0.4wt% polymeric hindered amine light stabilizer P1-EX6 (Example 6);

[0436] 8# is 99.6wt% standard polymer, 0.4wt% polymeric hindered amine light stabilizer P1-EX7 (Example 7);

[0437] 9# is 99.6wt% standard polymer, 0.4wt% polymeric hindered amine light stabilizer P1-EX8 (Example 8);

[0438] 10# is 99.6wt% standard polymer, 0.4wt% polymeric hindered amine light stabilizer P1-EX9 (Example 9);

[0439] 11# is 99.6wt% standard polymer, 0.4wt% polymeric hindered amine light stabilizer P1-EX10 (Example 10);

[0440] 12# is 99.7wt% standard polymer, 0.3wt% polymeric hindered amine light stabilizer P1-EX11 (Example 11);

[0441] 13# is 99.7wt% standard polymer, 0.3wt% polymeric hindered amine light stabilizer P1-EX12 (Example 12);

[0442] 14# is 99.7wt% standard polymer, 0.3wt% polymeric hindered amine light stabilizer P1-EX13 (Example 13);

[0443] 15# is 99.7wt% standard polymer, 0.3wt% polymeric hindered amine light stabilizer P1-EX14 (Example 14);

[0444] 16# is 99.7wt% standard polymer, 0.3wt% polymeric hindered amine light stabilizer P1-EX15 (Example 15);

[0445] 17# is 99.7wt% standard polymer, 0.3wt% polymeric hindered amine light stabilizer P1-EX16 (Example 16);

[0446] 18# is 99.7wt% standard polymer, 0.3wt% polymeric hindered amine light stabilizer P1-EX17 (Example 17);

[0447] 19# is 99.7wt% standard polymer and 0.3wt% polymeric hindered amine light stabilizer P1-EX18 (Example 18).

[0448] Preparation of test samples:

[0449] The components were pre-mixed in a mixer, and then extruded and granulated on a twin-screw extruder at 190°C. Drying was performed at 80°C for 8 hours, and then blow molding was performed using a film blowing machine at 200°C. Finally, the samples were subjected to an artificial xenon lamp accelerated aging test according to GB / T16422.2-2014 standard. The test results are shown in Table 2:

[0450] Table 2 Tensile strength retention rate %

[0451]

[0452]

[0453] Example 21: Test of Stabilized Thermoplastic Polyvinyl Chloride

[0454] Basic recipe:

[0455] Standard polymers:

[0456] 65.5wt% thermoplastic polyvinyl chloride; 31.5wt% plasticizer; 1.6wt% epoxidized soybean oil; 1.4wt% calcium zinc stabilizer;

[0457] 1# is 100wt% standard polymer;

[0458] 2# is 99.5wt% standard polymer, 0.25wt% UV-531; 0.25wt% polymeric hindered amine light stabilizer P1-EX1 (Example 1);

[0459] 3# is 99.5wt% standard polymer, 0.25wt% UV-531; 0.25wt% polymeric hindered amine light stabilizer P1-EX4 (Example 4);

[0460] 4# is 99.5wt% standard polymer, 0.25wt% UV-531; 0.25wt% polymeric hindered amine light stabilizer P1-EX6 (Example 6);

[0461] 5# is 99.5wt% standard polymer, 0.25wt% UV-531; 0.25wt% polymeric hindered amine light stabilizer P1-EX8 (Example 8).

[0462] Preparation of test samples:

[0463] The components were pre-mixed in a mixer, and then kneaded on a double-roll mill at 165°C for 7 minutes to obtain the desired sample. Finally, the sample was subjected to a xenon lamp aging test according to GB / T16422.2-2014 standard. The test results are shown in Table 3:

[0464] Table 3 Retention rate of elongation at break %

[0465]

[0466] Example 22: Test on Stabilized Thermoplastic Polyamide 6

[0467] Basic recipe:

[0468] Standard polymer: 79.8wt% thermoplastic polyamide 6; 20wt% calcium carbonate; 0.20wt% antioxidant (AO-1098);

[0469] 1# is 100wt% standard polymer;

[0470] 2# is 99.6wt% standard polymer, 0.4wt% polymeric hindered amine light stabilizer P1-EX1 (Example 1);

[0471] 3# is 99.6wt% standard polymer, 0.4wt% polymeric hindered amine light stabilizer P1-EX4 (Example 4);

[0472] 4# is 99.6wt% standard polymer, 0.4wt% polymeric hindered amine light stabilizer P1-EX6 (Example 6);

[0473] 5# is 99.6wt% standard polymer, 0.4wt% polymeric hindered amine light stabilizer P1-EX7 (Example 7);

[0474] 6# is 99.6wt% standard polymer and 0.4wt% polymeric hindered amine light stabilizer P1-EX18 (Example 18).

[0475] Preparation of test samples:

[0476] The components were pre-mixed in a mixer, then extruded and granulated on a twin-screw extruder at 260°C, dried at 80°C for 12 hours, and then injection molded using an injection molding machine at 265°C. Finally, the samples were subjected to a xenon lamp aging test in accordance with standard GB / T16422.2-2014, and the test results are shown in Table 4:

[0477] Table 4 △E* of samples after xenon lamp aging (low value is required)

[0478]

[0479] Example 23: Performance test as flame retardant in PP film

[0480] Basic recipe:

[0481] Standard polymer: 99.65wt% thermoplastic polypropylene; 0.05wt% calcium stearate; 0.30wt% antioxidant (AO-1010:AO-168=1:1);

[0482] 1# is 100wt% standard polymer;

[0483] 2# is 99.6wt% standard polymer, 0.4wt% polymeric hindered amine light stabilizer P1-EX1 (Example 1);

[0484] 3# is 99.6wt% standard polymer, 0.4wt% polymeric hindered amine light stabilizer P1-EX2 (Example 2);

[0485] 4# is 99.6wt% standard polymer, 0.4wt% polymeric hindered amine light stabilizer P1-EX6 (Example 6);

[0486] 5# is 99.6wt% standard polymer and 0.4wt% polymeric hindered amine light stabilizer P1-EX9 (Example 9).

[0487] Preparation of test samples:

[0488] The components were pre-mixed in a mixer, and then extruded and granulated on a twin-screw extruder at 220°C. Drying was performed at 80°C for 8 hours, and then compression molding was performed in a hot press. Finally, the samples were tested for flame retardancy according to DIN4102-B2 standard. The test results are shown in Table 5:

[0489] Table 5 Flame retardant properties of samples

[0490]

[0491] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

[0492] The aforementioned embodiments and methods described in the present invention may be varied based on the ability, experience and preference of those skilled in the art.

[0493] In the present invention, merely listing the steps of the method in a certain order does not constitute any limitation on the order of the method steps.

Claims

1. A polymeric hindered amine, characterized in that: Contains the following general formula I structure: Among them, A n , B n For different unit structures, A n Contains at least two hindered amine structures, B n Contains at least two grafting sites A n With B n By grafting site connect; R′ is selected from the group consisting of any one or more of the following groups: hydrogen, alkyl, cycloalkyl, heterocycloalkyl, heteroalkyl, or alkyl interrupted by one or more first spacer groups; The first spacer group includes any one or more combinations of the following groups: heteroatoms, -C(=O)O-, amine groups, -OC(=O)O-, alkenyl groups, alkynyl groups, -C(=S)O-, amide groups, urea groups, arylene groups, heteroalkylene groups, heteroarylene groups, alkylene groups substituted by one or more first substituents, heteroalkylene groups substituted by one or more first substituents, and cycloalkylene groups substituted by one or more first substituents; The first substituent is selected from the group consisting of any one or more of the following groups: hydroxy, halogen, aryl, cycloalkyl, hydroxyalkyl, alkoxy, thioalkoxy, nitro, cyano, amino, heteroaryl, heterocycloalkyl, aryloxycarbonyl, heteroaryloxycarbonyl, heteroalkoxycarbonyl, alkoxythiocarbonyl, acyloxy, alkanoyloxy, aroyl, aroyloxy, heteroaroyloxy, cycloalkanoyloxy, heteroalkanoyloxy, alkanoyl, aminoacyl, alkylaminoacyl, alkylsulfonyl, aroyl, alkyl interrupted by one or more heteroatoms, alkyl interrupted by one or more second spacer groups; The second spacer group is selected from one or more combinations of the following structures: heteroatom, -C(=O)O-, -OC(=O)O-, -C(=O)-, -C(=S)O-, amide, urea, arylene, alkenyl, alkynyl, amine, heteroalkylene or heteroarylene; m1, m2...m n is the degree of polymerization of each repeating unit, which is an integer between 1 and 20; n is an integer between 1 and 20; the m n ≥3; RT1 and RT2 are terminal groups; RT 1 , RT 2 independently selected from any one or more of the following structures: hydrogen, alkyl, cycloalkyl, heterocycloalkyl, heteroalkyl, alkyl separated by one or more second spacer groups, alkyl substituted by one or more substituents, heteroalkyl substituted by one or more first substituents, cycloalkyl substituted by one or more first substituents, A1, A2, ..., A n The structure is independently selected from one or more of the following general structural formulas AI to AV: Wherein, E1, E2, and E3 are independently selected from: -O-, Any of , where a1 is 0, 1 or 2; X 1 , X 2 independently selected from the group consisting of one or more of the following groups: a single bond, -O-, -NH-, -alkylene-, -O-alkylene-, -NH-alkylene, -C(O)- or -C(O)-alkylene; Y 1 , Y 2 independently selected from the group consisting of one or more of the following groups: single bond, -O-, -NH-, -alkylene-, -O-alkylene-, -NH-alkylene, -C(O)-, -C(O)-alkylene; Z 1 , Z 2 X is independently selected from the group consisting of one or more of the following groups: -alkylidene-, -O-alkylidene-, -NH-alkylidene, alkylidene substituted by one or more alkyl, hydroxyl, halogen or alkoxy groups; 3 , X 4 Independently selected from the following groups: -O-, -NH-, -N(R 13 )-, -S-, -alkylene-, alkylene interrupted by one or more heteroatoms, or alkylene substituted by one or more second substituents; The R 13 Selected from: alkylene, alkylene interrupted by one or more heteroatoms, alkylene substituted by one or more second substituents; The second substituent is selected from the group consisting of one or more of the following groups: alkyl, hydroxy, alkenyl, halogen, aryl, arylene, cycloalkyl, alkoxy, thioalkoxy, nitro, cyano, amino, heteroaryl, heterocycloalkyl, hydroxyalkyl, alkoxycarbonyl, aryloxycarbonyl, heteroaryloxycarbonyl, heteroalkoxycarbonyl, alkoxythiocarbonyl, acyloxy, alkanoyloxy, aroyloxy, heteroaroyloxy, cycloalkanoyloxy, heteroalkanoyloxy, alkanoyl, aminoacyl, alkylaminoacyl, alkylsulfonyl, alkyl spaced by one or more second spacer groups, the second spacer groups being selected from one or more of the following groups: heteroatom, -C(=O)O-, -OC(=O)O-, -C(=O)-, -C(=S)O-, -S(=O)-, -S(=O)2-, amide, urea, arylene, alkenyl, alkynyl, heteroalkylene or heteroarylene; Y 3 , Y 4 independently selected from the group consisting of one or more of the following groups: a single bond (-), -O-, -NH-, -alkylene-, -O-alkylene-, -NH-alkylene, or an alkylene substituted with one or more second substituents; X 5 , X 6 Independently selected from the following groups: -O-, -NH-, -N(R 14 )-、-N(R 13 )-, -C(=O)-, -C(S)-, -C(=O)O-, -OC(=O)-, -alkylene-, alkylene interrupted by one or more heteroatoms or alkylene substituted by one or more second substituents; The R 14 Independently selected from: alkyl, alkyl interrupted by one or more heteroatoms, alkyl substituted by one or more second substituents; R 1 , R 2 Independently selected from the group consisting of one or more of the following groups: single bond (-), -alkylene-, -cycloalkylene-, -arylene-, -heterocyclylene-, alkylene or arylene interrupted by one or more heteroatoms, alkylene substituted by one or more second substituents; X 7 , X 8 , X 9 Independently selected from the following groups: single bond (-), -alkylene-, -imino-, -nitro-, -N(R 14 )-, -NH-alkylene-, -cycloalkylene-, -heterocyclylene-, -O-, or -S-; R 3 , R 3” Independently selected from the group consisting of one or more of the following groups: hydrogen, -alkyl, -NH-alkyl, -cycloalkyl, -heterocyclyl, -O-cycloalkyl, cycloalkyl interrupted by one or more heteroatoms, cycloalkyl substituted by one or more alkyl groups, cycloalkyl substituted by one or more alkyl groups and heteroatoms.

2. The polymeric hindered amine according to claim 1, characterized in that R 1 , R 2 independently selected from: a single bond (-), -alkylene-, -arylene-, -OC(=O)O-, -OC(=O)-, -C(=O)O-, -C(=O)-, -O-, -NH-, -N(R 14 )-、 Any one or more groups in a group.

3. The polymeric hindered amine according to claim 1, characterized in that The R 14 Selected from: alkyl.

4. The polymeric hindered amine according to claim 1, characterized in that R 3 , R 3” are independently selected from hydrogen, -alkyl, -NH-alkyl, 5. The polymeric hindered amine according to claim 1, characterized in that B1, B2, B3, B4, B5...B n The structure is independently selected from the structure of general formula BI to BV-II: Among them, a, b, c, e, f, g, and h represent B n The number of grafting sites in , a, b, c, e, f, g, h is selected from 1 or 2; R 3’ independently selected from the group consisting of any one or more of the following groups: hydrogen, -alkylene-, -NH-alkylene, -cycloalkylene, -heterocyclylene, -O-cycloalkylene, cycloalkylene interrupted by one or more heteroatoms or substituted by one or more alkyl groups, cycloalkylene substituted by one or more alkyl groups and interrupted by one or more heteroatoms; R 4 , R 11 , R 12 , R 15 , R 16 independently selected from the group consisting of any one or more of the following groups: H, alkyl, cycloalkyl, heterocycloalkyl, alkyl spaced by one or more third spacer groups, wherein the third spacer group is selected from the group consisting of any one or more of the following groups: heteroatom, -C(=O)O-, heteroalkylene, alkenyl, alkynyl, -C(=O)-, -C(=S)O-, amide, urea, -OC(=O)O-, alkylene substituted by a third substituent, or heterocycloalkylene substituted by a third substituent; The third substituent is selected from the group consisting of any one or more of the following groups: hydroxy, cycloalkyl, alkoxy, thioalkoxy, nitro, cyano, amine, heterocycloalkyl, alkoxycarbonyl, alkoxycarbonyl, heteroalkoxycarbonyl, alkoxythiocarbonyl, acyloxy, alkanoyloxy, cycloalkanoyloxy, heteroalkanoyloxy, alkanoyl, aminoacyl, alkylaminoacyl, alkylsulfonyl, or alkyl substituted with one or more fourth substituents; The fourth substituent is selected from the group consisting of one or more of the following groups: a heteroatom, -C(=O)O-, -OC(=O)O-, -C(=O)-, -C(=S)O-, an amide group, a urea group, an alkenyl group, an alkynyl group, or a heteroalkylene group; R 5 , R 6 , R 8 independently selected from a single bond (-), an alkylene group, a cycloalkylene group, a heterocycloalkylene group, an alkylene group interrupted by one or more fourth spacer groups; R 7 , R 10 , R 15’ independently selected from alkylene, cycloalkylene, heterocycloalkylene, alkylene interrupted by one or more fourth spacer groups; The fourth spacer is selected from the group consisting of one or more of the following groups: alkylene, imino, -C(=O)O-, heteroalkylene, arylene, alkenyl, alkynyl, -C(=O)-, -C(=S)O-, amide, urea or -OC(=O)O-alkyl; R 9 independently selected from alkylene, cycloalkylene, heterocycloalkylene, alkylene interrupted by one or more fifth spacer groups; The fifth spacer is selected from the group consisting of one or more of the following groups: heteroatom, -C(=O)O-, heteroalkylene, arylene, alkenyl, alkynyl, -C(=O)-, -C(=S)O-, amide, urea, -OC(=O)O-, alkylene substituted by a fifth substituent, heterocycloalkylene substituted by one or more fifth substituents, the fifth substituent is selected from the group consisting of one or more of the following groups: hydroxyl, cycloalkyl, alkoxy, thioalkoxy, nitro, cyano, amine, heterocycloalkyl, alkoxycarbonyl, alkoxycarbonyl, heteroalkoxycarbonyl, alkoxythiocarbonyl, acyloxy, alkanoyloxy, cycloalkanoyloxy, heteroalkanoyloxy, alkanoyl, aminoacyl, alkylaminoacyl, alkylsulfonyl, alkylene spaced by one or more sixth spacer groups; The sixth spacer group is selected from one or more of the following groups: heteroatom, -C(=O)O-, -OC(=O)O-, -C(=O)-, -C(=S)O-, amide, urea, alkenyl, alkynyl, heteroalkylene; the X 8’ , X 10 , X 11 , X 12 , X 13 , X 14 independently selected from the group consisting of any one or more of the following groups: a single bond, -O-, -NH, -NH-C(=O)-, -N(R 14 )-、-NH(R 13 )-, -S-, -alkylene-, or alkylene substituted by one or more sixth substituents; The sixth substituent is selected from the group consisting of one or more of the following groups: heteroatom, hydroxyl, cycloalkyl, alkoxy, thioalkoxy, nitro, cyano, amine, heterocycloalkyl, carbonyl, alkoxycarbonyl, heteroalkoxycarbonyl, alkoxythiocarbonyl, acyloxy, alkanoyloxy, cycloalkanoyloxy, heteroalkanoyloxy, alkanoyl, aminoacyl, alkylaminoacyl, alkylsulfonyl, alkyl spaced by one or more seventh spacer groups; The seventh spacer group includes one or more combinations of the following groups: heteroatoms, -C(=O)O-, -OC(=O)O-, -C(=O)-, -C(=S)O-, amides, urea groups, alkenyl groups, alkynyl groups, and heteroalkylene groups; X 15 , X 16 , Y 5 , Y 6 are independently selected from -O-, -N-, -alkylene-, -O-alkylene-, -N-alkylene, carbonyl; Z 3 An alkylidene group independently selected from -alkylidene-, -O-alkylidene-, -N-alkylidene substituted by one or more seventh substituents, wherein the seventh substituent is independently selected from: alkyl, cycloalkyl, hydroxy, halogen or alkoxy; Z 4 Independently selected from -alkylene-, cycloalkyl, cycloalkylene, alkylene, cycloalkylene or cycloalkylene substituted with one or more seventh substituents.

6. The polymeric hindered amine according to claim 5, characterized in that a+b≥2; c≥2; e+f≥2; g≥2; h≥2.

7. The polymeric hindered amine according to claim 5, characterized in that R 9 Selected from: a single bond (-), an alkylene group, and -O-.

8. The polymeric hindered amine according to claim 5, characterized in that R 10 It is an alkylene group.

9. The polymeric hindered amine according to claim 5, characterized in that X 11 Selected from: -alkylene-, -NH-C(=O)-, -NH-, -N(R 14 )-、-NH(R 13 )-or-O-.

10. The polymeric hindered amine according to claim 5, characterized in that X 12 , X 13 Independently selected from: single bond (-), -alkylene-, -NH-, -NH-alkylene-.

11. The polymeric hindered amine according to claim 1, characterized in that The AI ​​is independently selected from the following structures: Wherein i is an integer of 1-22, * is the grafting site of A-Ⅰ and B; A-Ⅱ is independently selected from the following structures: Wherein j is an integer from 1 to 22, and * is the grafting site of A-Ⅱ and B; A-III is independently selected from the following structures: Wherein k is an integer of 1-22, * is the grafting site of A-Ⅲ and B; A-Ⅳ is independently selected from the following structures: A-V are independently selected from the following structures: Wherein O is an integer of 1-22, and * is the grafting site where A-V and B are grafted.

12. The polymeric hindered amine according to claim 5, characterized in that The B-I is independently selected from the following structures: Wherein x and x' are independently selected from integers of 8-22; * is the grafting site of B-Ⅰ and A; B-Ⅱ is independently selected from the following structures: Where y is an integer from 5 to 22; * is the grafting site of B-Ⅱ and A; B-III is independently selected from the following structures: Wherein, p is an integer from 1 to 22; q is an integer from 0 to 22; r is an integer from 0 to 22; * is the grafting site of B-Ⅲ and A. When q>1, there is a grafting site; B-Ⅳ is independently selected from the following structures: BVI is independently selected from the following structures: BV-II is independently selected from the following structures: Wherein z is an integer of 8-22, and * is the grafting site of B-Ⅳ, BVI, BV-II and A.

13. The method for preparing a polymeric hindered amine according to claim 1, characterized in that: The method comprises the steps of polymerizing the monomers under the action of a catalyst and a hydroperoxide; The monomers include monomer A and monomer B, both monomer A and monomer B include hindered amine structures, monomer A includes at least two hindered amine structures, and monomer B includes two grafting site structures; The polymerization reaction is carried out in a solvent, and the solvent is selected from one or more of tetrahydrofuran, 2-methyltetrahydrofuran, halogenated hydrocarbons, acetonitrile, propionitrile, butyronitrile, aromatic hydrocarbons, aliphatic hydrocarbons, alcohols, dimethyl sulfoxide, N,N-dimethylamide, and diphenyl ether; The catalyst is selected from one of catalysts based on tungsten, molybdenum, and ruthenium; The hydroperoxide is an inorganic hydroperoxide or an organic hydroperoxide; The inorganic hydroperoxide is H2O2; the organic hydroperoxide is alkyl hydroperoxide and aryl hydroperoxide.

14. The preparation method according to claim 13, characterized in that: The amount of the peroxide used is 1-20 molar equivalents.

15. The preparation method according to claim 13, characterized in that: The amount of the catalyst used is 0.0001-0.6 molar equivalent.

16. The preparation method according to claim 13, characterized in that: The molar ratio of the catalyst to the monomer is 5:100 to 1:100000; and / or, the polymerization reaction temperature is 0-150°C; and / or, the polymerization reaction pressure is -0.099Mpa to 0.1Mpa; And / or, the polymerization reaction is carried out in a protective gas, and the protective gas includes: one or both of argon and nitrogen.

17. The preparation method according to claim 13, characterized in that: The pressure of the preparation method is: 0.5-30 bar.

18. The preparation method according to claim 13, characterized in that: The monomer A structure comprises 19. The preparation method according to claim 18, characterized in that: The monomer is selected from the structures of AI to AV, and the monomer A-I is independently selected from one or more of the following structures: Where i is an integer from 1 to 22; The monomer A-II is selected from one or more of the following structures: Where j is an integer from 1 to 22; The monomer A-III is selected from one or more of the following structures: Wherein, k is an integer from 1 to 22; The monomer A-IV is selected from one or more of the following structures: The monomers A-V are selected from one or more of the following structures: Wherein O is an integer from 1 to 22.

20. The preparation method according to claim 13, characterized in that: The monomer B-I is independently selected from one or more of the following structures: Wherein x and x' are independently selected from integers of 8-22; monomer B-II is selected from one or more of the following structures: y is an integer from 5 to 22; Monomer B-III is selected from one or more of the following structures: Wherein, p is an integer from 1 to 22; q is an integer from 0 to 22; r is an integer from 0 to 22; The monomer B-IV is selected from one or more of the following structures: The monomer BVI or BV-II is selected from one or more of the following structures: Wherein z is an integer from 8 to 22.

21. A polymer auxiliary agent, characterized in that: Comprising the polymeric hindered amine according to claim 1 and additives; The additives include: one or more of antioxidants, UV absorbers, hindered amine light stabilizers, reinforcing agents, fillers, flame retardants, plasticizers, lubricants, emulsifiers, pigments, rheological additives, catalysts, flow control agents, optical brighteners, fire retardants, antistatic agents and foaming agents.

22. The polymer auxiliary agent according to claim 21, characterized in that The antioxidant is selected from: one or more of phenol and / or amine antioxidants, phosphites or thioesters.

23. The polymer auxiliary agent according to claim 21, characterized in that The UV absorber is selected from one or more of salicylate, benzoate, benzophenone, benzotriazole or triazine ultraviolet absorbers.

24. The polymer auxiliary agent according to claim 21, characterized in that The hindered amine light stabilizer is selected from: a hindered amine light stabilizer having a different structure from the polymeric hindered amine described in claim 1.

25. The polymer auxiliary agent according to claim 21, characterized in that The filler and reinforcing agent are selected from: calcium carbonate, silicate, glass fiber, glass beads, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood powder and flour or any one or more of other natural product fibers or synthetic fibers.

26. The polymer auxiliary agent according to claim 21, characterized in that The additives also include organic substances that are sensitive to light, heat or oxidation.

27. The polymer auxiliary agent according to claim 26, characterized in that The organic substance that is sensitive to light, heat or oxidation includes one or more of the following substances: a combination of one or more of polyolefins, acrylonitrile / butadiene / styrene, polyvinyl chloride, polymethyl methacrylate, polyacetal, polyamide, polyimide, epoxy resin, polyurethane, polycarbonate, polyester, polysulfone, polyurea, polystyrene, and thermoplastic elastomer.

28. A composition, characterized in that The invention comprises the polymeric hindered amine according to claim 1 and one or more organic substances sensitive to light, heat or oxidation.

29. The composition of claim 28, wherein The organic material sensitive to light, heat or oxidation includes the following: one or more combinations of polyolefins, acrylonitrile / butadiene / styrene, polyvinyl chloride, polymethyl methacrylate, polyacetal, polyamide, polyimide, epoxy resin, polyurethane, polycarbonate, polyester, polysulfone, polyurea, polystyrene or thermoplastic elastomers.

30. The composition of claim 28, wherein The mass range of the polymeric hindered amine is: 0.01-5wt%.

31. The composition of claim 29, wherein The polyolefin is obtained by polymerizing or copolymerizing α-olefin or cycloolefin alone; The α-olefin is selected from one or more of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene or 4-methyl-1-pentene; And / or, the polyacetal is selected from: one or more of polyoxymethylene, polyacetal modified with thermoplastic polyurethane, polyacetal modified with acrylate, or polyacetal modified with MBS; And / or, the polyamide is selected from: polyamides and copolyamides derived from diamines and dicarboxylic acids and / or aminocarboxylic acids or corresponding lactams, aromatic polyamides obtained from meta-xylene diamine and adipic acid; polyamides obtained from hexamethylene and isophthalic acid and / or terephthalic acid in the presence or absence of an elastomer as a modifier; And / or, the polyester is selected from: one or more of polyesters prepared from dicarboxylic acids and diols and / or from hydroxycarboxylic acids or their corresponding lactones, block copolyether esters of hydroxyl-terminated polyether derivatives, and polyesters modified with polycarbonate or MBS; And / or, the thermoplastic elastomer is selected from: polyolefin thermoplastic elastomer and block copolymer polystyrene thermoplastic elastomer.

32. The composition of claim 28, wherein The composition may further include one or more of an antioxidant, a UV absorber, a hindered amine light stabilizer, a reinforcing agent, a filler, a flame retardant, a plasticizer, a lubricant, an emulsifier, a pigment, a rheological additive, a catalyst, a flow control agent, an optical brightener, a fire retardant, an antistatic agent or a foaming agent.

33. The composition of claim 32, wherein The antioxidant is selected from: one or more of phenol and / or amine antioxidants, phosphites, and thioesters.

34. The composition of claim 32, wherein The UV absorber is selected from one or more of salicylates, benzoates, benzophenones, benzotriazoles, and triazines.

35. The composition of claim 32, wherein The hindered amine light stabilizer is selected from: a hindered amine light stabilizer having a different structure from the polymeric hindered amine described in claim 1.

36. The composition of claim 35, wherein The hindered amine light stabilizer is selected from: bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, a polymer of succinic acid and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol, Chimassorb 944, Chimassorb 2020, UV-3346, UV-3529, Tinuvin 770, Tinuvin 622LD, Tinuvin 292, HS-625 or HS-950.

37. The composition of claim 32, wherein The filler and reinforcing agent are selected from: calcium carbonate, silicate, glass fiber, glass beads, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood powder and flour or other natural product fibers, synthetic fibers or one or more thereof.

38. Use of the polymeric hindered amine described in any one of claims 1 to 12 and / or the polymeric hindered amine prepared by the method described in claims 13 to 20, and / or the polymer auxiliary agent described in claims 21 to 27, and / or the composition described in claims 28 to 37 in the preparation of polymer material products.

39. The use according to claim 38, characterized in that The polymer material product is selected from one or more of the following: plastic, rubber, fiber, coating, adhesive or composite material; The application includes: using the polymer material product in the fields of automobile interior or exterior decoration materials, floating devices, road traffic devices, agricultural products, electrical appliances, furniture, shoes, sanitary products, and health care products.

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