Hindered amine light stabilizer as well as preparation method and application thereof

Abstract

The invention relates to a hindered amine light stabilizer as well as a preparation method and application thereof. The hindered amine light stabilizer is mainly composed of one or more compounds shown in the formula I and / or compounds shown in the formula II. The light transmittance retention rate of the photovoltaic adhesive film in an ultraviolet and high-temperature and high-humidity environment can be remarkably improved by adding the light transmittance retention agent into the photovoltaic adhesive film, the yellowing phenomenon is effectively inhibited, and the light transmittance retention agent is suitable for various base material systems such as EVA, POE and PVB. The photovoltaic adhesive film can be used for packaging a photovoltaic module, and has excellent weather resistance and optical stability.

Description

Technical Field

[0001] This invention belongs to the field of light stabilizer technology, and relates to a hindered amine light stabilizer, its preparation method and its application. Specifically, it relates to a hindered amine light stabilizer mainly composed of one or more compounds of Formula I and / or compounds of Formula II, its preparation method and its application. Background Technology

[0002] Polymer materials, with their excellent properties such as lightweight, high plasticity, corrosion resistance, good electrical insulation, and relatively low cost, have permeated all aspects of modern life. From everyday plastic packaging, synthetic fiber clothing, car tires, and electronic product casings, to high-tech medical devices, aerospace components, building waterproofing materials, and new energy battery separators and photovoltaic cell films, polymers have an extremely wide range of applications and are indispensable. However, during long-term use, these materials are inevitably exposed to various environmental factors (such as heat, oxygen, ozone, and ultraviolet radiation), leading to polymer aging, manifested as material cracking, discoloration, loss of luster, decreased strength, and dimensional instability. This irreversible degradation of performance not only shortens the service life of polymer products, affecting their reliability and safety, but may also generate more waste due to frequent replacements, placing a burden on the environment. Hindered amine light stabilizers (HALS) have emerged as a highly efficient and innovative light stabilization system.

[0003] Specific commercially available hindered amine light stabilizer products include: bis(2,2,6,6-tetramethyl-1-piperidinyl) succinate (light stabilizer 770), a mixture of bis(1,2,2,6,6-pentamethyl-4-piperidinyl) succinate and mono(1,2,2,6,6-pentamethyl-4-piperidinyl) succinate (light stabilizer 292), etc. Among them, bis(2,2,6,6-tetramethyl-1-piperidinyl) succinate is the most widely used hindered amine light stabilizer, especially in the photovoltaic film industry, which mainly includes EVA film, POE film, EPE film and PVB film.

[0004] However, the hindered amine light stabilizer mainly used in photovoltaic films (including EVA film, POE film, EPE film and PVB film) is bis(2,2,6,6-tetramethyl-1-piperidinyl) sebacate. Films using this light stabilizer generally have problems such as increased yellowing value, decreased light transmittance and decreased adhesion under aging conditions, making it difficult to effectively protect the material as a whole during long-term outdoor use.

[0005] Meanwhile, traditional hindered amine light stabilizers mostly use sebacic acid as a single raw material, which has a low functional group ratio, limited room for improvement in light stability performance, and high raw material costs, which is not conducive to cost reduction and efficiency improvement in the photovoltaic film industry. Summary of the Invention

[0006] To address the aforementioned problems, this invention provides a hindered amine light stabilizer and its application, which can improve the light transmittance reduction of photovoltaic films after UV aging and high-temperature and high-humidity aging; it can also reduce the yellowing index after UV aging and high-temperature and high-humidity aging. Furthermore, this invention provides a method for preparing the light stabilizer, which shortens the curing time of the hindered amine light stabilizer product by controlling the proportion of mixed acid components, solving the problems of spray granulation and discharge in the production process, and realizing industrial production.

[0007] A first aspect of the present invention provides a hindered amine light stabilizer, which is mainly composed of one or more compounds of formula I and / or formula II.

[0008] in, R1 and R2 may be the same or different, and each is independently selected from H and C. 1-10 Alkyl and C 1-10 Alkoxy groups, wherein the alkyl and alkoxy groups are optionally substituted with one or more halogen atoms; R3 is selected from H and C. 1-10 Alkyl, C 3-10 Cycloalkyl and 3-10 membered heterocyclic alkyl; and n is an integer from 1 to 7.

[0009] In some embodiments, the hindered amine light stabilizer of the present invention consists of two or more compounds represented by Formula I.

[0010] A second aspect of the present invention provides a photovoltaic encapsulant film comprising the hindered amine light stabilizer described in the first aspect of the present invention.

[0011] A third aspect of the present invention provides an anti-aging composition comprising (i) the hindered amine light stabilizer described in the first aspect of the present invention and (ii) an antioxidant and / or an ultraviolet absorber.

[0012] A fourth aspect of the present invention provides a composition comprising a photovoltaic encapsulant resin matrix and the anti-aging composition described in the third aspect of the present invention.

[0013] The fifth aspect of the present invention provides the application of the hindered amine light stabilizer described in the first aspect of the present invention in photovoltaic films.

[0014] A sixth aspect of the present invention provides a photovoltaic module comprising the hindered amine light stabilizer described in the first aspect of the present invention, the photovoltaic encapsulant film described in the second aspect of the present invention, the anti-aging composition described in the third aspect of the present invention, and the composition described in the fourth aspect of the present invention.

[0015] The seventh aspect of the present invention provides the application of the hindered amine light stabilizer described in the first aspect of the present invention, the photovoltaic encapsulant film described in the second aspect of the present invention, the anti-aging composition described in the third aspect of the present invention, and the composition described in the fourth aspect of the present invention in photovoltaic modules.

[0016] An eighth aspect of the present invention provides a method for preparing the hindered amine light stabilizer of the present invention, the method comprising reacting a compound of formula a1 and / or a2 with one or more compounds of formula b under conditions sufficient for reaction to obtain the light stabilizer of the present invention.

[0017] The definitions of R1, R2, R3, and n are the same as those in Equations I and II of the first aspect.

[0018] Beneficial effects The hindered amine light stabilizer provided by this invention can improve the light transmittance of photovoltaic films after UV aging and high temperature and humidity aging when used in photovoltaic films; at the same time, it can also reduce the yellowing index after UV aging and high temperature and humidity aging. Detailed Implementation

[0019] Exemplary embodiments will now be described more fully. However, exemplary embodiments can be implemented in many forms and should not be construed as limited to the examples set forth herein; rather, these embodiments are provided to make this application more complete and comprehensive, and to fully convey the concept of exemplary embodiments to those skilled in the art. The described features, structures, or characteristics may be combined in any suitable manner in one or more embodiments. In the following description, numerous specific details are provided to give a full understanding of embodiments of this application.

[0020] definition As used in this article, "C" x-y "Having x to y carbon atoms, for example, C..." 1-10 This refers to having 1 to 10 carbon atoms, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 carbon atoms. When modified with an alkyl group, C... 1-10 Alkyl groups refer to alkyl groups having 1 to 10 carbon atoms, such as alkyl groups having 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 carbon atoms; when modified with an alkoxy group, C 1-10 Alkoxy groups refer to alkoxy groups having 1 to 10 carbon atoms, such as alkoxy groups having 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 carbon atoms; when modified with cycloalkyl groups, C 3-10 Cycloalkyl means an alkoxy group having 3 to 10 carbon atoms, such as cycloalkyl groups having 3, 4, 5, 6, 7, 8, 9, or 10 carbon atoms.

[0021] As used herein, “XY-membered” refers to a cyclic group having X to Y ring atoms. For example, 3-10-membered heterocyclic alkyl refers to a heterocyclic alkyl having 3 to 10 ring atoms, such as heterocyclic alkyl having 3, 4, 5, 6, 7, 8, 9, or 10 ring atoms, wherein the ring atoms include carbon atoms in the ring and heteroatoms in the ring.

[0022] As used herein, the term "alkyl" refers to a monovalent straight-chain or branched saturated aliphatic hydrocarbon group. Unless otherwise specified, it is an alkyl group with 1 to 10 carbon atoms, preferably an alkyl group with 1 to 8 carbon atoms, more preferably an alkyl group with 1 to 6 carbon atoms, further preferably an alkyl group with 1 to 4 carbon atoms, and even more preferably an alkyl group with 1 to 2 carbon atoms. Non-limiting examples include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, neobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, and their various branched isomers.

[0023] As used herein, the term "alkoxy" or "alkyloxy" refers to -O-alkyl, wherein the alkyl group is defined as described above with respect to alkyl groups. For example, C 1-8 Alkoxy and -OC 1-8 Alkyl groups have the same meaning. C 1-8 Non-limiting examples of alkoxy groups include, but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, n-hexoxy, n-heptoxy, n-octoxy and their various branched isomers.

[0024] As used herein, the term "cycloalkyl" refers to a fully saturated hydrocarbon ring, whether substituted or unsubstituted, which can be monocyclic, bicyclic, or polycyclic, and bicyclic or polycyclic can be fused, spirocyclic, or bridged. Non-limiting examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl.

[0025] As used herein, the term "heterocyclic alkyl" refers to a fully saturated heterocycle that, in addition to a carbon atom, contains one or more (preferably 1 to 3) heteroatoms selected from N, S, and O as ring members. Non-limiting examples of heterocyclic alkyl groups include, but are not limited to, aziridinyl, ethylene oxide, thiopropylcycloyl, aziridine, oxacyclobutyl, thiocyclobutyl, tetrahydrofuranyl, pyrrolyl, tetrahydrothiophenyl, 1,3-dioxolanecycloyl, 1,3-oxazolyl, isoxazolyl, imidazoyl, pyrazolyl, thiazoyl, piperidinyl, tetrahydropyranyl, tetrahydrothiaranyl, morpholinyl, thiomorpholinyl, piperazine, aziridine-heptyl, oxacycloheptanyl, thioheptanyl, aziridine-octyl, oxacycloheptanyl, thioheptanyl, aziridine-nonyl, oxacycloheptanyl, 1,6-diazacycloheptanyl, aziridine-decyl, oxacycloheptanyl, and 1,7-diazacycloheptanyl.

[0026] As used herein, the term "halogen atom" refers to fluorine (F), chlorine (Cl), bromine (Br), and iodine (I).

[0027] As used herein, the terms "optional" or "optionally" mean that an event or situation described subsequently may, but is not required to, occur; this description includes the possibility that the event or situation may or may not occur. For example: "C" 1-10 Alkyl and C 1-10 "The alkoxy group may be substituted by one or more halogen atoms" means that the alkyl group may, but does not have to, be substituted by halogen atoms, including cases where the alkyl group is substituted by halogen atoms and cases where the alkyl group is not substituted by halogen atoms.

[0028] As used herein, the terms "mainly composed of," "comprising," and "including" are open-ended expressions, meaning they may also contain unmentioned components, structural elements, or method steps; the term "composed of" is a closed-ended expression, meaning it does not contain unmentioned components, structural elements, or method steps. Specifically, in the context of this invention, "the hindered amine light stabilizer of the present invention is mainly composed of" is intended to indicate that the content of the mentioned components in the hindered amine light stabilizer is 70% or more, for example, 75% or more, 80% or more, 85% or more, 90% or more, or 95% or more, and the content of unmentioned components in the hindered amine light stabilizer is less than 30%, for example, less than 25%, less than 20%, less than 15%, less than 10%, or less than 5%. Those skilled in the art will understand that, in the context of this invention, unmentioned components include, but are not limited to, byproducts, intermediates, residual reactants, solvents, etc., generated during the preparation of the hindered amine light stabilizer.

[0029] In a first aspect of the invention, a hindered amine light stabilizer is provided, which is mainly composed of one or more compounds of formula I and / or formula II.

[0030] in, R1 and R2 may be the same or different, and each is independently selected from H and C. 1-10 Alkyl and C 1-10 Alkoxy groups, wherein the alkyl and alkoxy groups are optionally substituted with one or more halogen atoms; R3 is selected from H and C. 1-10 Alkyl, C 3-10 Cycloalkyl and 3-10 membered heterocyclic alkyl; and n is an integer from 1 to 7.

[0031] In some implementations, R1 and R2 may be the same or different, and each is independently selected from H and C. 1-4 Alkyl and C1-8 Alkyl group.

[0032] In some embodiments, R1 and R2 may be the same or different, and each is independently selected from H, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-hexyloxy, straight-chain and branched heptoxy, and straight-chain and branched octoxy.

[0033] In some implementations, R1 and R2 are the same and are selected from H and C. 1-4 Alkyl and C 1-8 Alkyl group.

[0034] In some embodiments, R1 and R2 are the same and are selected from H, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-hexyloxy, straight-chain and branched heptoxy, and straight-chain and branched octoxy.

[0035] In some embodiments, R1 and R2 are the same and are selected from H, methyl, and -OC8H. 17 .

[0036] In some embodiments, R1 and R2 are the same and are selected from H and methyl.

[0037] In some implementations, R3 is selected from H and C. 1-8 Alkyl, C 3-6 Cycloalkyl and 3-6 membered heterocyclic alkyl groups.

[0038] In some implementations, R3 is selected from H and C. 1-8 alkyl.

[0039] In some implementations, R3 is selected from H and C. 1-4 alkyl.

[0040] In some embodiments, R3 is selected from H and methyl.

[0041] In some implementations, n is 2, 3, 4 or 5; preferably, n is 2, 3 or 4.

[0042] In some embodiments, the compound represented by Formula I is a compound represented by Formula Ia or Formula Ib.

[0043] Wherein, n is 1, 2, 3, 4, 5, 6 or 7; preferably, n is 2, 3 or 4.

[0044] In some embodiments, the compound of formula I is selected from the compounds shown in formulas I-a1 to I-a7 and I-b1 to I-b7:

[0045] In some embodiments, the compound represented by Formula II is a compound represented by Formula II-a or Formula II-b.

[0046] Wherein, n is 1, 2, 3, 4, 5, 6 or 7; preferably, n is 2, 3 or 4.

[0047] In some embodiments, the compound of formula II is selected from the compounds shown in formulas II-a1 to II-a7 and II-b1 to II-b7:

[0048] In some embodiments, the compound represented by Formula II is an intermediate product in the synthesis of the corresponding compound represented by Formula I. For example, the compound represented by Formula II-b4 is an intermediate product in the synthesis of the compound represented by Formula I-b4.

[0049] In some embodiments, the hindered amine light stabilizer of the present invention is mainly composed of two or more compounds shown in Formula I and / or Formula II.

[0050] In some embodiments, the hindered amine light stabilizer of the present invention is mainly composed of two or more compounds of Formula I and / or Formula II, where n is 2, 3 or 4.

[0051] In some embodiments, the hindered amine light stabilizer of the present invention is mainly composed of two or more compounds shown in Formula I and / or Formula II, wherein the compound shown in Formula I is selected from the compounds shown in Formula I-a2 to I-a4 and Formula I-b2 to I-b4, and the compound shown in Formula II is selected from the compounds shown in Formula II-a2 to II-a4 and Formula II-b2 to II-b4.

[0052] In some embodiments, the hindered amine light stabilizer of the present invention is mainly composed of compounds shown in Formula I-a2, Formula I-a3, Formula II-a2 and Formula II-a3, or mainly composed of compounds shown in Formula I-a2, Formula I-a3, Formula I-a4, Formula II-a2, Formula II-a3 and Formula II-a4, or mainly composed of compounds shown in Formula I-b2, Formula I-b3, Formula II-b2 and Formula II-b3, or mainly composed of compounds shown in Formula I-b2, Formula I-b3, Formula I-b4, Formula II-b2, Formula II-b3 and Formula II-b4.

[0053] In some embodiments, the hindered amine light stabilizer of the present invention is mainly composed of two or three compounds selected from those shown in Formula I-a2, Formula I-a3, Formula I-a4, Formula I-b2, Formula I-b3, Formula I-b4, Formula II-b2, Formula II-b3 and Formula II-b4.

[0054] In some embodiments, the hindered amine light stabilizer of the present invention is mainly composed of two or more compounds of Formula I, wherein the compounds of Formula I are selected from the compounds of Formula I-a2 to I-a4 and Formula I-b2 to I-b4.

[0055] In some embodiments, the hindered amine light stabilizer of the present invention is mainly composed of two or three compounds shown in Formula I.

[0056] In some embodiments, the hindered amine light stabilizer of the present invention is mainly composed of two or three compounds of Formula I with n being 2, 3 or 4.

[0057] In some embodiments, the hindered amine light stabilizer of the present invention is mainly composed of two or three compounds of Formula I, wherein the compounds of Formula I are selected from the compounds of Formula I-a2 to I-a4 and Formula I-b2 to I-b4.

[0058] In some embodiments, the hindered amine light stabilizer of the present invention is mainly composed of two compounds shown in Formula I.

[0059] In some embodiments, the hindered amine light stabilizer of the present invention is mainly composed of two compounds of Formula I with n being 2, 3 or 4.

[0060] In some embodiments, the hindered amine light stabilizer of the present invention is mainly composed of two compounds represented by Formula I, wherein the compounds represented by Formula I are selected from the compounds represented by Formulas I-a2 to I-a4 and I-b2 to I-b4.

[0061] In some embodiments, the hindered amine light stabilizer of the present invention is mainly composed of two compounds shown in Formula I, wherein the compounds shown in Formula I are the compounds shown in Formula I-a2 and I-a3, or the compounds shown in Formula I-b2 and I-b3.

[0062] In some embodiments, the hindered amine light stabilizer of the present invention is mainly composed of two compounds represented by Formula I, wherein the compounds represented by Formula I are compounds represented by Formula I-a2 and I-a3, and the proportion of the compound represented by Formula I-a3 in the hindered amine light stabilizer of the present invention is less than 45%, for example less than 42%, 40%, 38%, 35%, 30%, 28%, 25%, 20%, 10%, 5%, and 1%; more preferably, the proportions of the compounds represented by Formula I-a2 and I-a3 in the hindered amine light stabilizer of the present invention are about 58% and about 42%, respectively.

[0063] In some embodiments, the hindered amine light stabilizer of the present invention is mainly composed of three compounds shown in Formula I.

[0064] In some embodiments, the hindered amine light stabilizer of the present invention is mainly composed of three compounds of Formula I with n being 2, 3 and 4.

[0065] In some embodiments, the hindered amine light stabilizer of the present invention is mainly composed of three compounds represented by Formula I, wherein the compounds represented by Formula I are compounds represented by Formula I-a2, I-a3 and I-a4, or compounds represented by Formula I-b2, I-b3 and I-b4.

[0066] In some embodiments, the hindered amine light stabilizer of the present invention is mainly composed of three compounds represented by Formula I, wherein the compounds represented by Formula I are compounds represented by Formula I-a2, I-a3, and I-a4, and the proportions of the compounds represented by Formula I-a2, I-a3, and I-a4 in the hindered amine light stabilizer of the present invention are 0%-35% (e.g., 5%, 10%, 15%, 20%, 25%, 30%, 35%) and 5-70% (e.g., 5%, 10%, 15%, 20%, 25%), respectively. %, 30%, 35%, 40%, 45%, 50%, 60%), 5%-95% (e.g., 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 60%, 70%, 80%, 90%), preferably 0% to 10%, 5% to 15% and 75% to 95%, more preferably 4% to 6%, 9% to 12% and 80% to 84%; even more preferably, about 6.5%, about 11% and about 82.5%.

[0067] In some embodiments, the hindered amine light stabilizer of the present invention is mainly composed of three compounds represented by Formula I, wherein the compounds represented by Formula I are compounds represented by Formula I-b2, I-b3 and I-b4, and further include compounds represented by Formula II-b2, II-b3 and II-b4.

[0068] In some embodiments, the total amount of the compounds shown in formulas I-b2, I-b3, and I-b4 in the hindered amine light stabilizer of the present invention is 70% to 100% (e.g., 70%, 75%, 80%, 85%, 90%, 95%) and 0% to 30% (e.g., 5%, 10%, 15%, 20%, 25%) of the total amount of the compounds shown in formulas II-b2, II-b3, and II-b4, respectively; preferably, 70% to 80% and 20% to 30%.

[0069] When the hindered amine light stabilizer of the present invention is mainly composed of a mixture of compounds of formula I in which n is 2, 3 and 4, the photovoltaic film prepared therefrom has a higher light transmittance retention rate after ultraviolet aging and high temperature and humidity aging.

[0070] In a second aspect of the invention, a photovoltaic film is provided, the photovoltaic film comprising the hindered amine light stabilizer of the present invention.

[0071] In some embodiments, the photovoltaic film contains 0.1% to 1%, preferably 0.1% to 0.5%, more preferably 0.1% to 0.2% (e.g., 0.1%, 0.15%, 0.2%) of the hindered amine light stabilizer of the present invention, based on the total weight of the photovoltaic film.

[0072] In some embodiments, the photovoltaic film further includes antioxidants and / or ultraviolet absorbers.

[0073] In some embodiments, the antioxidant is selected from at least one of hindered phenolic antioxidants, thioester antioxidants, and phosphite antioxidants.

[0074] In some embodiments, the hindered phenolic antioxidant is preferably a lactone group ( Hindered phenolic antioxidants (where Rc is methyl or tert-butyl).

[0075] In some embodiments, the hindered phenolic antioxidant is selected from at least one of the following: 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (isooctyl ester), 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate C7-C9 alcohol mixture, 3,5-di-tert-butyl-4-hydroxyphenylpropionate C12-C14 alcohol mixture, 3,5-di-tert-butyl-4-hydroxyphenylpropionate C13-C15 alcohol mixture, 3,5-di-tert-butyl-4-hydroxyphenylpropionate C14-C16 alcohol mixture, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate octadecyl ester, triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate] and pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].

[0076] In some embodiments, the phosphite antioxidant is, for example, tris(2,4-di-tert-butylphenyl) phosphite.

[0077] In some embodiments, the thioester antioxidant may be selected from at least one of 4,6-bis(octylthiomethyl)o-cresol and 2,4-bis(dodecylthiomethyl)-6-methylphenol.

[0078] In some embodiments, the ultraviolet absorber includes, but is not limited to, at least one of benzotriazole ultraviolet absorbers, triazine ultraviolet absorbers, and benzophenone ultraviolet absorbers.

[0079] In some embodiments, the ultraviolet absorber is selected from at least one of 2-hydroxy-4-n-octyloxybenzophenone (UV-531), 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole (UV-326), 2-(2'-hydroxy-3',5'-di-tert-pentylphenyl)benzotriazole (UV-328), 2-(2-hydroxy-5-tert-octyl)phenylbenzotriazole (UV-329), 2-(2'-hydroxy-3',5'-dicumylphenyl)benzotriazole (UV-234), and 2-[4,6-bis(2,4-xylyl)-1,3,5-triazin-2-yl]-5-octyloxyphenol (UV-1164).

[0080] In some embodiments, the photovoltaic film comprises the hindered amine light stabilizer, antioxidant, and ultraviolet absorber of the present invention.

[0081] In some embodiments, the photovoltaic film comprises the hindered amine light stabilizer, matrix material, crosslinking agent, antioxidant, and ultraviolet absorber of the present invention, as well as one or more of the co-crosslinking agent and coupling agent.

[0082] In some embodiments, the matrix material is selected from one or more of ethylene-vinyl acetate copolymer (EVA), polyolefin elastomer (POE), polyvinyl butyral (PVB), thermoplastic polyolefin (TPO), and copolymers of ethylene and acrylic monomers, wherein the acrylic monomers include at least one of acrylic acid, acrylate, methacrylic acid, and methacrylate.

[0083] In some embodiments, the matrix material is selected from one or more of ethylene-vinyl acetate copolymer (EVA), polyolefin elastomer (POE), and polyvinyl butyral (PVB). Preferably, the matrix material is ethylene-vinyl acetate copolymer (EVA) or polyolefin elastomer (POE).

[0084] In some embodiments, the vinyl acetate content of the EVA is 25%-33%, preferably 26%-30%.

[0085] In some embodiments, the POE is one or more of a copolymer of 1-butene and ethylene (1-butenyl POE) or a copolymer of 1-octene and ethylene (1-octenyl POE).

[0086] In some embodiments, the crosslinking agent is at least one selected from dicumyl peroxide, benzoyl peroxide, tert-amyl acetate peroxide, tert-amyl 3,5,5-trimethylhexanoate peroxide, di-tert-butyl peroxide, tert-butyl isopropyl peroxide, dicyclohexyl peroxide, bis(2-phenylethoxy) peroxide, di(2-ethylhexyl) peroxide, bis(4-tert-butylcyclohexyl) peroxide, and tert-butyl tert-valerate peroxide, preferably a peroxide crosslinking agent, and more preferably tert-butyl peroxide-2-ethylhexyl.

[0087] In some embodiments, the co-crosslinking agent is selected from at least one of 1,3,5-triallyl cyanurate, trimethylolpropane trimethacrylate, triallyl isocyanurate, and polytriallyl isocyanurate, preferably one or more of trimethylolpropane trimethacrylate or triallyl isocyanurate, and more preferably trimethylolpropane trimethacrylate and triallyl isocyanurate.

[0088] In some embodiments, the coupling agent is a silane coupling agent, including but not limited to at least one of 3-aminopropyltriethoxysilane, γ-(2,3-epoxypropoxy)propyltrimethoxysilane, mercaptomethyldiethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-(2,3-epoxypropoxy)propyltriethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, preferably γ-methacryloxypropyltrimethoxysilane.

[0089] In some embodiments, the photovoltaic film is composed of a matrix material, an antioxidant, an ultraviolet absorber, and the hindered amine light stabilizer of the present invention.

[0090] In some embodiments, the photovoltaic film is composed of a matrix material, a crosslinking agent, a co-crosslinking agent, a coupling agent, an antioxidant, an ultraviolet absorber, and the hindered amine light stabilizer of the present invention.

[0091] In some embodiments, the photovoltaic film is composed of a matrix material, a crosslinking agent, an antioxidant, an ultraviolet absorber, and the hindered amine light stabilizer of the present invention.

[0092] In some embodiments, the antioxidant comprises a primary antioxidant and a secondary antioxidant.

[0093] In some embodiments, the primary antioxidant is a hindered phenolic antioxidant; and the secondary antioxidant is a phosphite antioxidant.

[0094] In some embodiments, the photovoltaic film comprises, by weight, 60-110 parts (e.g., 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110 parts) of matrix material, 0-30 parts (e.g., 0, 0.1, 0.4, 0.7, 1.0, 1.3, 1.7, 2.0, 20, 22, 24, 25, 26, 28, 30 parts) of crosslinking agent, 0-2 parts (e.g., 0, 0.25, 0.5, 0.75, 1, 1.25, 1.5, 1.75, 2 parts) of co-crosslinking agent, and 0-1 part (e.g., 0, 0.25, 0.5, 0.75, 1... The mixture comprises 0.01 to 2 parts (e.g., 0.01, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.5, 2.0 parts) of coupling agent, 0.1 to 1 part (e.g., 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0 parts) of antioxidant, 0.1 to 1 part (e.g., 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0 parts) of UV absorber, and 0.01 to 1 part (e.g., 0.01, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0 parts) of hindered amine light stabilizer of the present invention.

[0095] In some embodiments, the photovoltaic film comprises, by weight, 90-110 parts (e.g., 90, 95, 100, 105, 110 parts) of matrix material, 0.1-2 parts (e.g., 0.1, 0.4, 0.7, 1.0, 1.3, 1.7, 2.0 parts) of crosslinking agent, 0.1-2 parts (e.g., 0.1, 0.25, 0.5, 0.75, 1, 1.25, 1.5, 1.75, 2 parts) of co-crosslinking agent, and 0.1-1 part (e.g., 0, 0.25, 0.5, 0.75, 1 part) of coupling agent. The product comprises 0.01 to 0.1 parts (e.g., 0.01, 0.03, 0.05, 0.07, 0.09, 0.1 parts) of an antioxidant, 0.1 to 1 part (e.g., 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0 parts) of an ultraviolet absorber, and 0.01 to 1 part (e.g., 0.01, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0 parts) of the hindered amine light stabilizer of the present invention.

[0096] In some embodiments, the photovoltaic film comprises, by weight, 60-80 parts (e.g., 60, 65, 70, 75, 80 parts) of matrix material, 20-30 parts (e.g., 20, 22, 24, 25, 26, 28, 30 parts) of crosslinking agent, 0.1-1 parts (e.g., 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0 parts) of main antioxidant, and 0.1-1 parts (e.g., 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0 parts) of [unclear - possibly a specific ingredient or component]. The composition includes 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0) auxiliary antioxidants, 0.1 to 1 part (e.g., 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0 parts) ultraviolet absorbers, and 0.01 to 1 part (e.g., 0.01, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0 parts) of the hindered amine light stabilizer of the present invention.

[0097] In a third aspect of the invention, an anti-aging composition is provided, comprising (i) the hindered amine light stabilizer of the present invention and (ii) an antioxidant and / or an ultraviolet absorber.

[0098] In some embodiments, the anti-aging composition of the present invention comprises (i) the hindered amine light stabilizer of the present invention and (ii) an antioxidant and an ultraviolet absorber.

[0099] In some embodiments, the anti-aging composition of the present invention comprises, by weight, (i) 0.1-0.5 parts of the hindered amine light stabilizer of the present invention and (ii) 0.01-2 parts of antioxidant and / or 0.1-0.5 parts of ultraviolet absorber.

[0100] In some embodiments, the anti-aging composition of the present invention comprises, by weight, (i) 0.1-0.5 parts of the hindered amine light stabilizer of the present invention and (ii) 0.01-2 parts of antioxidant and 0.1-0.5 parts of ultraviolet absorber.

[0101] In some embodiments, the anti-aging composition of the present invention comprises, by weight, (i) 0.1-0.3 parts of the hindered amine light stabilizer of the present invention and (ii) 0.05-1 parts of antioxidant and / or 0.1-0.3 parts of ultraviolet absorber.

[0102] In some embodiments, the anti-aging composition of the present invention comprises, by weight, (i) 0.1-0.3 parts of the hindered amine light stabilizer of the present invention and (ii) 0.05-1 parts of an antioxidant and 0.1-0.3 parts of an ultraviolet absorber.

[0103] In some embodiments, the anti-aging composition of the present invention comprises, by weight, (i) 0.2 parts of the hindered amine light stabilizer of the present invention and (ii) 0.05, 0.5 or 1 parts of antioxidant and / or 0.2 parts of ultraviolet absorber.

[0104] In some embodiments, the anti-aging composition of the present invention comprises, by weight, (i) 0.2 parts of the hindered amine light stabilizer of the present invention and (ii) 0.05 parts of an antioxidant and 0.2 parts of an ultraviolet absorber.

[0105] In some embodiments, the anti-aging composition of the present invention comprises, by weight, (i) 0.2 parts of the hindered amine light stabilizer of the present invention and (ii) 1 part of an antioxidant and 0.2 parts of an ultraviolet absorber.

[0106] The selection of antioxidants and ultraviolet absorbers in the anti-aging composition of the present invention is the same as that described above regarding photovoltaic films.

[0107] In some embodiments, the anti-aging composition of the present invention comprises, by weight, (i) 0.1-0.5 parts (e.g., 0.1, 0.2, 0.3, 0.5 parts) of the hindered amine light stabilizer of the present invention and (ii) 0.01-0.1 parts (0.01, 0.05, 0.1 parts) of the hindered phenolic antioxidant and 0.1-0.5 parts of the ultraviolet absorber.

[0108] In some embodiments, the anti-aging composition of the present invention comprises, by weight, (i) 0.1-0.5 parts (e.g., 0.1, 0.2, 0.3, 0.5 parts) of the hindered amine light stabilizer of the present invention and (ii) 0.1-1 parts (0.1, 0.5, 1.0 parts) of hindered phenolic antioxidant and / or phosphite antioxidant and 0.1-0.5 parts (e.g., 0.1, 0.2, 0.3, 0.5 parts) of ultraviolet absorber.

[0109] In a fourth aspect of the invention, a composition is provided comprising a photovoltaic film resin matrix and an anti-aging composition of the third aspect of the invention.

[0110] In some embodiments, the photovoltaic film resin matrix material is selected from one or more of ethylene-vinyl acetate copolymer (EVA), polyolefin elastomer (POE), polyvinyl butyral (PVB), thermoplastic polyolefin (TPO), and copolymers of ethylene and acrylic monomers, wherein the acrylic monomers include at least one of acrylic acid, acrylate, methacrylic acid, and methacrylate.

[0111] In a fifth aspect of the invention, the application of the hindered amine light stabilizer of the invention in photovoltaic films is provided.

[0112] In some embodiments, the hindered amine light stabilizer of the present invention is added as a raw material in the preparation of photovoltaic films.

[0113] In a further aspect of the invention, a method for preparing a photovoltaic encapsulant film is provided, the method comprising: S1: Mix the raw materials of photovoltaic film evenly to obtain a mixture; S2: The mixture is added to an extruder for extrusion to obtain the extruded material; S3: The extruded material is cast, cooled, drawn, and wound to obtain a photovoltaic film.

[0114] In some embodiments, step S1 involves mixing the matrix material, crosslinking agent, co-crosslinking agent, and coupling agent evenly, then adding antioxidant, ultraviolet absorber, and light stabilizer, and mixing evenly again to obtain a mixture.

[0115] In some embodiments, the extrusion method in step S2 is either blending extrusion or three-layer co-extrusion. Preferably, when the extrusion method is three-layer co-extrusion, the inner layer thickness is 0.1~0.4 mm and the outer layer thickness is 0.1~0.4 mm; more preferably, when the extrusion method is three-layer co-extrusion, the inner layer thickness is 0.2~0.3 mm and the outer layer thickness is 0.2~0.3 mm; more preferably, the inner layer thickness is 0.2 mm and the outer layer thickness is 0.3 mm.

[0116] In some embodiments, the extrusion temperature in step S2 is 80~100°C, preferably 85~95°C, and more preferably 90~95°C. In some embodiments, the extrusion temperature is 90°C, and in other embodiments, the extrusion temperature is 95°C.

[0117] In some embodiments, the thickness of the photovoltaic film obtained in step S3 is 0.4~0.6 mm, preferably 0.5 mm.

[0118] In some embodiments, the photovoltaic encapsulant film is prepared by the following steps: (1) Mix the raw materials of photovoltaic film evenly to obtain a mixture; (2) The mixture is extruded through a twin-screw vented extruder to obtain the extruded material; (3) The extruded material is extruded through a single screw extruder and hot rolled into a photovoltaic film.

[0119] In some embodiments, the mixing method in step (1) is stirring; preferably, the mixing is carried out in a high-speed mixer. The mixing temperature is 40~80℃. The mixing temperature can be 50~70℃; preferably, the mixing temperature is 60℃.

[0120] In some embodiments, the body temperature of the twin-screw vented extruder in step (2) is 90~160℃, preferably 100~150℃, more preferably 100~140℃; the die temperature is 100~160℃, preferably 110~150℃, more preferably 120~140℃.

[0121] In some embodiments, the body temperature of the single screw extruder in step (3) is 90~160°C, preferably 100~150°C, more preferably 100~140°C; the die temperature is 100~160°C, preferably 110~150°C, more preferably 120~140°C.

[0122] In a sixth aspect of the invention, a photovoltaic module is provided, comprising the hindered amine light stabilizer of the first aspect of the invention or the photovoltaic encapsulant film of the second aspect of the invention, the anti-aging composition of the third aspect of the invention, and the composition of the fourth aspect of the invention. In some embodiments, the photovoltaic module comprises a first glass, a first encapsulant film, a solar cell, a second encapsulant film, and a second glass or backsheet sequentially stacked; wherein the first encapsulant film and / or the second encapsulant film comprises or is the photovoltaic encapsulant film of the present invention.

[0123] In a seventh aspect of the invention, the application of the hindered amine light stabilizer of the first aspect of the invention or the photovoltaic film of the second aspect of the invention, the anti-aging composition of the third aspect of the invention, and the composition of the fourth aspect of the invention in photovoltaic modules is provided.

[0124] In an eighth aspect of the invention, a method for preparing the hindered amine light stabilizer of the invention is provided, the method comprising reacting a compound of formula a1 and / or a2 with one or more compounds of formula b under conditions sufficient for reaction to obtain the light stabilizer of the invention.

[0125] The definitions of R1, R2, R3, and n are the same as those in Equations I and II of the first aspect.

[0126] In some embodiments, the method for preparing the light stabilizer of the present invention includes: Step 1) Mix the compound shown in formula a1 and / or the compound shown in formula a2, one or more compounds shown in formula b, a catalyst, and a solvent to form a reaction mixture; Step 2) Nitrogen gas is introduced into the reaction mixture, and the temperature is raised to a first temperature (e.g., 100~160℃) to carry out the reaction and obtain the crude reaction product; Step 3) The obtained crude reaction product is washed with water, dehydrated, filtered, and the solvent is removed by vacuum distillation to obtain the hindered amine light stabilizer of the present invention.

[0127] In some embodiments, the method for preparing the light stabilizer of the present invention further includes: step 4) decolorizing the hindered amine light stabilizer obtained in step 3).

[0128] In some embodiments, in step 1), the compound represented by formula a1 and / or the compound represented by formula a2 is selected from 2,2,6,6-tetramethylpiperidine-4-ol or 1,2,2,6,6-pentamethylpiperidine-4-ol.

[0129] In some embodiments, in step 1), one or more compounds of formula b are dicarboxylic acids, for example, dicarboxylic acids having 3, 4, 5, 6, 7, 8 or 9 carbon atoms; preferably, the dicarboxylic acid is oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid or pimelic acid; more preferably, the dicarboxylic acid is succinic acid, glutaric acid or adipic acid.

[0130] In some embodiments, in step 1), one or more compounds of formula b are mixed dicarboxylic acids, for example, a mixture of dicarboxylic acids having 3, 4, 5, 6, 7, 8 or 9 carbon atoms; preferably, the mixed dicarboxylic acid is a mixture of two or more of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid or pimelic acid; more preferably, the mixed dicarboxylic acid is a mixture of two or three of succinic acid, glutaric acid or adipic acid.

[0131] In some embodiments, in step 1), one or more compounds of formula b are dicarboxylic acid esters, which are obtained by esterification of the above-mentioned dicarboxylic acid with an alcohol (e.g., methanol, ethanol) and distillation to obtain a dicarboxylic acid monoester or a dicarboxylic acid diester; preferably, the dicarboxylic acid ester is obtained by esterification of the above-mentioned dicarboxylic acid with methanol and distillation to obtain a dimethyl dicarboxylic acid ester.

[0132] In some embodiments, in step 1), one or more compounds of formula b are mixed dicarboxylic acid esters, which are obtained by esterification of the above-mentioned mixed dicarboxylic acid with an alcohol (e.g., methanol, ethanol) and distillation to obtain a mixed dicarboxylic acid monoester or a mixed dicarboxylic acid diester; preferably, the dicarboxylic acid ester is a dimethyl dicarboxylic acid ester obtained by esterification of the above-mentioned dicarboxylic acid with methanol and distillation.

[0133] In some embodiments, in step 1), 2,2,6,6-tetramethylpiperidin-4-ol or 1,2,2,6,6-pentamethylpiperidin-4-ol is mixed with a mixed dicarboxylic acid or a mixed dicarboxylic acid ester, a catalyst, and a solvent to form a reaction mixture.

[0134] In some embodiments, the mixed dicarboxylic acid or dicarboxylic acid ester compound is a binary or ternary system.

[0135] In some embodiments, the binary system is succinic acid or its ester (preferably dimethyl succinate) and glutaric acid or its ester (preferably dimethyl glutate).

[0136] In some embodiments, the proportion of glutaric acid or its ester in the binary system is less than 45%, for example less than 42%, 40%, 38%, 35%, 30%, 28%, 25%, 20%, 10%, 5%, or 1%; preferably, the proportions of succinic acid or its ester and glutaric acid or its ester are 55% to 90% and 10% to 45%, respectively, more preferably about 58% and about 42%, respectively.

[0137] In some embodiments, the ternary system is succinic acid or its ester (preferably dimethyl succinate), glutaric acid or its ester (preferably dimethyl glutate), and adipic acid or its ester (preferably dimethyl adipicate).

[0138] In some embodiments, the proportions of succinic acid or its ester, glutaric acid or its ester, and adipic acid or its ester in the ternary system are 0%-35% (e.g., 5%, 10%, 15%, 20%, 25%, 30%, 35%), 5-70% (e.g., 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 60%), and 5%-95% (e.g., 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 60%, 70%, 80%, 90%), preferably 0% to 10%, 5% to 15%, and 75% to 95%, more preferably 4% to 6%, 9% to 12%, and 80% to 84%, respectively; and even more preferably, about 6.5%, about 11%, and about 82.5%.

[0139] In the preparation method of the present invention, by controlling the proportion of each component in the mixed dicarboxylic acid or dicarboxylic acid ester compound, the curing time of the obtained hindered amine light stabilizer product can be shortened, and problems such as spray granulation can be solved.

[0140] In some embodiments, the mixed dicarboxylic acid or dicarboxylic acid ester compound is derived from adipic acid production byproducts. Using byproducts from adipic acid production to synthesize hindered amine light stabilizers can reduce production costs, resource waste, and environmental pollution.

[0141] In some embodiments, the molar ratio of the compound shown in formula a1 and / or the compound shown in formula a2 to one or more compounds shown in formula b is 2 to 2.5:1.

[0142] In some embodiments, in step 1), the catalyst is a commonly used catalyst, such as tetrabutyl titanate, dibutyltin dilaurate, sodium methoxide, p-toluenesulfonic acid, etc. Those skilled in the art can select a suitable catalyst and determine its addition amount based on the type and amount of piperidinol and diacid / ester used. For example, when using a diacid, those skilled in the art can select a suitable esterification catalyst; when using a diacid ester, those skilled in the art can select a suitable transesterification catalyst.

[0143] In some embodiments, in step 1), the solvent is an inert organic solvent (e.g., heptane), which can be removed by vacuum distillation after the reaction and does not remain in the product.

[0144] In some embodiments, step 2) further includes monitoring the content of the compound shown in formula a1 and / or the compound shown in formula a2 and / or one or more compounds shown in formula b in the reaction mixture and the content of the crude reaction product.

[0145] In some embodiments, in step 2), the reaction is stopped when the content of the compound shown in formula a1 and / or the compound shown in formula a2 and / or one or more compounds shown in formula b in the reaction mixture is less than 1.5%, and the content of the crude reaction product meets the requirements.

[0146] The monitoring method in step 2) is well known to those skilled in the art, and they can choose an appropriate monitoring method as needed.

[0147] Example The following embodiments are used to illustrate the present invention and are not intended to limit the scope of the invention. Unless otherwise specified, the operations involved in the embodiments are conventional techniques in the art.

[0148] The raw materials and sources of the reagents used in the following examples are as follows: EVA: Ethylene-vinyl acetate copolymer, is a resin with a vinyl acetate content of 28% (Sirbon Petrochemical, EVAUE2825); 1-Butenyl POE: A copolymer of 1-butene and ethylene (Dow Chemical, ENGAGE™ PV 8680); 1-Octenyl POE: A copolymer of 1-octene and ethylene (Dow Chemical, ENGAGE™ PV 8660); TBEC: tert-butyl percarbonate-2-ethylhexyl ester (Arkema, LUPEROX TBEC); TAEC: tert-amyl peroxide (2-ethylhexyl) carbonate (Arkema, LUPEROX TAEC); T-1: Triallyl isocyanurate (Hunan Fangruida, FARIDA TAIC); T-2: Trimethylolpropane trimethacrylate (FARIDA TMPTMA, Hunan Fangruida); H-1: Light stabilizer UV-770 (RIASORB) ® UV-770DF); H-2: Light stabilizer UV-292 (RIASORB) ® UV-292); H-3: Light stabilizer UV-622 (RIASORB) ® UV-622); AO-1: β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate n-octadecyl alcohol ester; UVT-1: 2-hydroxy-4-n-octyloxybenzophenone.

[0149] As mentioned in the following preparation examples and elsewhere in this disclosure, the percentages of each component in the mixed dicarboxylic acid / dicarboxylic acid ester refer to the percentages of each component as determined by chromatographic methods.

[0150] The chromatographic conditions used are as follows: .

[0151] It should be recognized that the proportion of each component in a mixed dicarboxylic acid is first determined by converting the dicarboxylic acid into methyl diacid ester through an esterification reaction, and then measuring the proportion.

[0152] Preparation Example 1. Preparation of HT-1 (Compound I-a4) At room temperature, 169 g of 2,2,6,6-tetramethylpiperidin-4-ol (1.08 mol), 87 g of dimethyl adipate (0.5 mol), and 400 mL of heptane were added to a 1 L four-necked flask equipped with a thermometer and a condenser. Nitrogen gas was introduced, the mixture was stirred, and the temperature was raised to 100 °C. 2.67 g of tetraisopropyl titanate was added, and the temperature was raised to 120–125 °C under normal pressure and maintained for 17 h. After the reaction was complete, the mixture was cooled to 80 °C under nitrogen protection, washed with water, dehydrated, filtered, and distilled to obtain the product, which was a solid at room temperature. The HT-1 content in the product reached 99.5%, and the yield was 97.8%.

[0153] Preparation Example 2. Preparation of HT-2 (Compound I-a2) At room temperature, 225 g of 2,2,6,6-tetramethylpiperidin-4-ol, 95 g of dimethyl succinate, and 400 mL of heptane were added to a 1 L four-necked flask equipped with a thermometer and a condenser. Nitrogen gas was introduced, the mixture was stirred, and the temperature was raised to 100 °C. 4.25 g of tetraisopropyl titanate was added, and the temperature was raised to 120–125 °C under normal pressure and maintained for 15 h. After the reaction was complete, the mixture was cooled to 80 °C under nitrogen protection, washed with water, dehydrated, filtered, and distilled to obtain the product, which was a solid at room temperature. The HT-2 content in the product reached 99.3%, and the yield was 97.5%.

[0154] Preparation Example 3. Preparation of HT-3 (a mixture of compounds I-a2, I-a3 and I-a4) At room temperature, 195 g of 2,2,6,6-tetramethylpiperidin-4-ol, 90 g of mixed dimethyl dicarboxylic acid esters (containing approximately 25% dimethyl succinate, 50% dimethyl glutarate, and 25% dimethyl adipate), and 400 mL of heptane were added to a 1 L four-necked flask equipped with a thermometer and a condenser. Nitrogen gas was introduced, the mixture was stirred, and the temperature was raised to 100 °C. 3.27 g of tetraisopropyl titanate was added, and the temperature was raised to 120–125 °C under normal pressure and maintained for 10 h. After the reaction was complete, the mixture was cooled to 80 °C under nitrogen protection, washed with water, dehydrated, filtered, and distilled to obtain the product, which was a solid at room temperature. The product contained 99.2% HT-3, with a yield of 97.2%. In this preparation example, the product obtained by distillation was poured into a tray and allowed to slowly solidify (curing time 12 h, curing conditions: room temperature).

[0155] Preparation Example 4. Preparation of HT-4 (a mixture of compounds I-b2, I-b3, and I-b4, and compounds II-b2, II-b3, and II-b4) At room temperature, 190 g of 1,2,2,6,6-pentamethylpiperidin-4-ol, 105 g of mixed dimethyl dicarboxylic acid esters (containing approximately 25% dimethyl succinate, 50% dimethyl glutarate, and 25% dimethyl adipate), and 400 mL of heptane were added to a 1 L four-necked flask equipped with a thermometer and a condenser. Nitrogen gas was introduced, the mixture was stirred, and the temperature was raised to 100 °C. 1.10 g of tetraisopropyl titanate was added, and the temperature was raised to 120-125 °C under normal pressure and maintained for 2-3 hours. After the reaction was completed, the mixture was cooled to 70 °C under nitrogen protection, washed with water, dehydrated, filtered, and distilled to obtain the product, which was a liquid at room temperature. The product contained 99.4% HT-4, and the yield was 96.5%.

[0156] Preparation Example 5. Preparation of HT-5 (a mixture of compounds I-a2, I-a3 and I-a4) At room temperature, 235 g of 2,2,6,6-tetramethylpiperidin-4-ol, 90 g of a mixed dicarboxylic acid (6.5% succinic acid, 11% glutaric acid, and 82.4% adipic acid), and 400 mL of heptane were added to a 1 L four-necked flask equipped with a thermometer and a condenser. Nitrogen gas was introduced, the mixture was stirred, and the temperature was raised to 50 °C. 5.75 g of dioctyltin oxide was added, and the temperature was raised to 140–145 °C under normal pressure and maintained for 6 hours. After the reaction was complete, the mixture was cooled to 80 °C under nitrogen protection, washed with water, dehydrated, filtered, and distilled to obtain the product. The HT-5 content in the product reached 98.7%, and the yield was 95%. In this preparation example, the product obtained after distillation was rapidly cured after being poured into a tray (curing time 34 s, curing conditions: room temperature).

[0157] Preparation Example 6. Preparation of HT-6 (a mixture of compounds I-a2 and I-a3) At room temperature, 195 g of 2,2,6,6-tetramethylpiperidin-4-ol, 90 g of mixed dimethyl dicarboxylic acid ester (of which dimethyl succinate accounted for 58.4% and dimethyl glutarate for 41.5%), and 400 mL of heptane were added to a 1 L four-necked flask equipped with a thermometer and a condenser. Nitrogen gas was introduced, the mixture was stirred, and the temperature was raised to 100 °C. 2.67 g of tetraisopropyl titanate was added, and the temperature was raised to 120-125 °C under normal pressure and maintained for 10 h. After the reaction was completed, the mixture was cooled to 80 °C under nitrogen protection, washed with water, dehydrated, filtered, and distilled to obtain the product. The HT-6 content in the product reached 99.1%, and the yield was 97%. In this preparation example, the product obtained by distillation was rapidly cured after being poured into a tray (curing time 30 s, curing conditions: room temperature).

[0158] Preparation Example 7. Preparation of HT-7 (a mixture of compounds I-a2, I-a3 and I-a4) At room temperature, 195g of 2,2,6,6-tetramethylpiperidin-4-ol, 90g of mixed dicarboxylic acid dimethyl ester (containing approximately 17.5% dimethyl succinate, 62.9% dimethyl glutarate, and 19.5% dimethyl adipate), and 400mL of solvent were added to a 1L four-necked flask equipped with a thermometer and a condenser. Nitrogen gas was introduced, the mixture was stirred, and the temperature was raised to 100°C. 2.67g of tetraisopropyl titanate was added, and the temperature was raised to 120-125°C under normal pressure and maintained for 8 hours. After the reaction was completed, the mixture was cooled to 80°C under nitrogen protection, washed with water, dehydrated, filtered, and distilled to obtain the final product. The main content of the product reached 99.4%, and the product yield was 96%. In this preparation example, the product obtained after distillation was poured into a tray and slowly cured (curing time 12 hours, curing conditions: room temperature).

[0159] Example: Preparation of photovoltaic encapsulant film 1. Raw material composition of basic formulas 1 to 5 The raw material composition of basic formula 1 is shown in Table 1.

[0160] Table 1:

[0161] The raw material composition of basic formula 2 is to replace EVA in basic formula 1 with 1-butenyl POE.

[0162] The raw material composition of basic formula 3 is to replace EVA in basic formula 1 with 1-octenyl POE.

[0163] The raw material composition of basic formula 4 is to replace EVA in basic formula 1 with EVA and 1-octenyl POE, wherein the weights of EVA and 1-octenyl POE are 60kg and 40kg, respectively.

[0164] The raw material composition of basic formula 5 is shown in Table 2.

[0165] Table 2:

[0166] Photovoltaic films 1-25 were prepared according to the basic formulation and light stabilizer as shown in Table 3 below, using the method described below.

[0167] The raw material composition of the photovoltaic films in Examples 1 to 25 is shown in Table 3.

[0168] Table 3:

[0169] Example 1 EVA, tert-butylperoxycarbonate-2-ethylhexyl ester, trimethylolpropane trimethacrylate, triallyl isocyanurate, and γ-methacryloyloxypropyltrimethoxysilane were mixed evenly. Then, β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate n-octadecyl alcohol ester, 2-hydroxy-4-n-octyloxybenzophenone, and light stabilizer HT-1 were added and mixed evenly again to obtain a mixture.

[0170] The mixture is added to an extruder for co-extrusion at an extrusion temperature of 90°C. The extruded material is then cast, cooled, drawn, and wound to obtain a photovoltaic film with a thickness of 0.5 mm.

[0171] Preparation of photovoltaic encapsulant films in Examples 2-3, 16, and 21 Compared with Example 1, the only difference is that the light stabilizer is changed from HT-1 to HT-2, HT-3, HT-4, and HT-5 respectively.

[0172] Preparation of photovoltaic encapsulant films in Examples 22 and 23 Compared with Example 1, the difference is that the light stabilizer is changed from HT-1 to HT-5, and the basic formulation is changed from basic formulation 1 to basic formulation 2 and basic formulation 3 respectively.

[0173] Preparation of photovoltaic encapsulant films in Examples 4-9, 17, and 18 Compared with Example 1, the only difference is that the basic formulation and light stabilizer have been changed, and the extrusion temperature has been changed to 95°C.

[0174] Preparation of photovoltaic encapsulant films in Examples 10-12, 19, and 24 Compared to Example 1, the difference lies in the change of the basic formulation and light stabilizer, and the preparation method adopts a three-layer co-extrusion process, with the inner layer being POE with a thickness of 0.2 mm and the outer layer being EVA with a thickness of 0.3 mm. A photovoltaic film with a thickness of 0.5 mm is obtained.

[0175] Example 13 Preparation of photovoltaic encapsulant film PVB, tert-butylperoxycarbonate-2-ethylhexyl ester, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], tris(2,4-di-tert-butylphenyl) phosphite, light stabilizer HT-1, and 2-hydroxy-4-n-octyloxybenzophenone were stirred and mixed evenly in a high-speed mixer at 60°C. After discharge, the mixture was rapidly cooled to obtain the final product.

[0176] The mixture was extruded and granulated using a twin-screw vented extruder to obtain PVB granules. The obtained PVB granules were then extruded in a single-screw extruder and hot-rolled into a photovoltaic film with a thickness of 0.5 mm.

[0177] The twin-screw vented extruder has a body temperature of 100~140℃ and a die temperature of 120~140℃; the single-screw extruder has a body temperature of 100~140℃ and a die temperature of 120~140℃.

[0178] Preparation of photovoltaic encapsulant films in Examples 14-15, 20, and 25 Compared with Example 13, the only difference is that the light stabilizer is changed from HT-1 to HT-2, HT-3, HT-4 and HT-5 respectively.

[0179] Preparation of photovoltaic films in Comparative Examples 1 to 15 The raw material composition of Comparative Examples 1 to 15 is shown in Table 4.

[0180] Table 4:

[0181] Comparative Examples 1, 6, and 11 were prepared according to the preparation method of Example 1.

[0182] Comparative Examples 2, 3, 7, 8, 12, and 13 were prepared according to the preparation method of Example 3.

[0183] Comparative Examples 4, 9, and 14 were prepared according to the preparation method of Example 7.

[0184] Comparative Examples 5, 10, and 15 were prepared according to the preparation method of Example 9.

[0185] Test Case Performance Test Sample preparation For photovoltaic films obtained using basic formulations 1, 2, 3, or 4, the sample preparation method is as follows: Take a 50 mm x 50 mm photovoltaic film and arrange it from bottom to top in the following order: front panel material, non-adhesive film, photovoltaic film, non-adhesive film, and back panel material. Place the front panel face down in a vacuum laminator and cure and crosslink according to the product's required curing temperature and time. Then, remove it and place it in a desiccator to cool to room temperature before use. The sample taken from the non-adhesive film should have flat upper and lower surfaces, uniform thickness, and a crosslinking degree of over 75%.

[0186] For the photovoltaic encapsulant film obtained using basic formulation 5, the sample preparation method is as follows: Two pieces of the obtained photovoltaic film with a size of 300 mm x 150 mm were taken and stacked from bottom to top in the following order: front panel material, front photovoltaic film, rear photovoltaic film, and back panel material. The front panel was placed face down in a vacuum laminator. The temperature was 150℃, the vacuum was drawn for 4 minutes, and the lamination was carried out for 15 minutes to obtain a laminate sample with no defects in appearance.

[0187] a) Photovoltaic film transmittance test The samples were tested according to the spectrophotometer method of GB / T2410-2008.

[0188] The wavelength range of the spectrophotometer is set to 380 nm to 1100 nm. Calculate the average transmittance from 380 nm to 1100 nm. At least three samples should be tested in each group, and the average value of the test results should be taken.

[0189] b) UV aging resistance test The samples were subjected to ultraviolet irradiation aging tests in accordance with the requirements of the International Electrotechnical Commission standard IEC61215.

[0190] The experimental procedure is as follows: Place the sample with the glass side facing the light source within the effective irradiation area of ​​the UV aging test chamber. Test conditions: Ultraviolet spectral distribution: Irradiance in the wavelength range of 280 nm to 400 nm is 54 W / m. 2 During ultraviolet irradiation, the surface temperature of the sample inside the test chamber was maintained at 60℃±2℃; Test time: 120kWh / m², calculated as the cumulative dose from the irradiation power. 2 .

[0191] After the test, the samples were removed and allowed to recover for 2 to 4 hours in an open environment at 23℃±5℃ and relative humidity less than 75%. A visual inspection was then conducted, and no visual defects were required. The yellowness index (YI) of the laminated samples before and after the test was measured according to ASTM E 313-2010.

[0192] The visible light transmittance before and after the test was measured according to GB / T 2401, and the retention rate of visible light transmittance was calculated using the following formula:

[0193] c) High-temperature and high-humidity aging performance test According to section 4.13 of EC61215-2:2021.

[0194] The test procedure is as follows: all samples were placed in a high temperature and high humidity aging test chamber. The test conditions were: temperature 85℃±2℃, relative humidity 85%±5%; test time: 1000h. The yellowness index YI of the laminated sample before and after the test was measured according to ASTM E313-2010. At least 3 points were measured for each sample. The yellowness index YI of the sample was the average value of the measured points. The difference between the yellowness index YI after aging and the yellowness index YI before aging was recorded, which is the yellowing index ΔYI.

[0195] The visible light transmittance before and after the test was measured according to GB / T 2401, and the retention rate of visible light transmittance was calculated using the following formula:

[0196] The performance test data is shown in Table 5.

[0197] Table 5:

[0198] As can be seen from the above data, the light stabilizer provided by the present invention exhibits significant advantages in light transmittance retention and anti-yellowing performance tests.

[0199] Regarding transmittance retention, the initial transmittance of all embodiments was comparable to that of the comparative example, indicating that the light stabilizer of the present invention does not affect the initial optical properties of the film. After UV aging, the transmittance retention of all embodiments was higher than that of the comparative example (for the same basic formulation); after high temperature and high humidity aging, the transmittance retention of all embodiments was higher than that of the comparative example (for the same basic formulation).

[0200] Regarding anti-yellowing properties, the light stabilizer of this invention exhibits a more significant improvement. The yellowing index (ΔYI) after UV aging and the yellowing index (ΔYI) after high-temperature and high-humidity aging are both lower than those of the comparative example. This indicates that the light stabilizer of this invention has a significant advantage in inhibiting film aging and yellowing (for the same basic formulation).

[0201] Although the present invention has been described in detail above with general descriptions, specific embodiments, and experiments, modifications or improvements can be made to it, which will be obvious to those skilled in the art. Therefore, all such modifications or improvements made without departing from the spirit of the present invention fall within the scope of protection claimed by the present invention.

Claims

1. A hindered amine light stabilizer, characterized in that, The hindered amine light stabilizer is mainly composed of one or more compounds of formula I and / or formula II. in, R1 and R2 may be the same or different, and each is independently selected from H and C. 1-10 Alkyl and C 1-10 Alkoxy groups, wherein the alkyl and alkoxy groups are optionally substituted with one or more halogen atoms; R3 is selected from H and C. 1-10 Alkyl, C 3-10 Cycloalkyl and 3-10 membered heterocyclic alkyl; and n is an integer from 1 to 7.

2. The hindered amine light stabilizer according to claim 1, characterized in that, R1 and R2 are the same, and are selected from H and C. 1-4 Alkyl and C 1-8 alkoxy group; R3 is selected from H and C. 1-4 Alkyl group, and n is 2, 3 or 4.

3. The hindered amine light stabilizer according to claim 1, characterized in that, R1 and R2 are the same, and are selected from H, methyl and -OC8H. 17 R3 is selected from H and methyl, and n is 2, 3 or 4.

4. The hindered amine light stabilizer according to any one of claims 1-3, characterized in that, The hindered amine light stabilizer is mainly composed of two or more compounds shown in Formula I and / or Formula II.

5. The hindered amine light stabilizer according to claim 4, characterized in that, The hindered amine light stabilizer is mainly composed of two or three compounds selected from the formulas I-a2, I-a3, I-a4, I-b2, I-b3, I-b4, II-b2, II-b3, and II-b4: 。 6. The hindered amine light stabilizer according to claim 5, characterized in that, The hindered amine light stabilizer is mainly composed of compounds shown in Formula I-a2 and Formula I-a3; or mainly composed of compounds shown in Formula I-a2, Formula I-a3 and Formula I-a4; or mainly composed of compounds shown in Formula I-b2, Formula I-b3 and Formula I-b4.

7. The hindered amine light stabilizer according to claim 6, characterized in that, The hindered amine light stabilizer is mainly composed of compounds shown in formulas I-a2 and I-a3, wherein the proportion of the compound shown in formula I-a3 is less than 45%; or The hindered amine light stabilizer is mainly composed of compounds shown in Formula I-a2, Formula I-a3 and Formula I-a4, wherein the proportions of compounds shown in Formula I-a2, Formula I-a3 and Formula I-a4 are 0%-35%, 5-70% and 5%-95%, respectively.

8. The hindered amine light stabilizer according to claim 6, characterized in that, The hindered amine light stabilizer is mainly composed of compounds shown in Formula I-b2, Formula I-b3 and Formula I-b4, and the hindered amine light stabilizer further contains compounds shown in Formula II-b2, Formula II-b3 and Formula II-b4.

9. The use of the hindered amine light stabilizer according to any one of claims 1-8 in photovoltaic films.

10. A photovoltaic encapsulant film, characterized in that, The photovoltaic film comprises a resin matrix material and a hindered amine light stabilizer as described in any one of claims 1-8.

11. The photovoltaic encapsulant film according to claim 10, characterized in that, The photovoltaic encapsulant film contains 0.1% to 1% of the hindered amine light stabilizer based on the total weight of the photovoltaic encapsulant film; The resin matrix material is selected from one or more of ethylene-vinyl acetate copolymer, polyolefin elastomer, polyvinyl butyral, thermoplastic polyolefin, and copolymer of ethylene and acrylic monomer, wherein the acrylic monomer includes at least one of acrylic acid, acrylate, methacrylic acid, and methacrylate.

12. The photovoltaic encapsulant film according to claim 11, characterized in that, The photovoltaic film further comprises antioxidants and / or ultraviolet absorbers; The antioxidant is selected from at least one of hindered phenolic antioxidants, thioester antioxidants, and phosphite antioxidants; The ultraviolet absorber is selected from at least one of benzotriazole ultraviolet absorbers, triazine ultraviolet absorbers, and benzophenone ultraviolet absorbers.

13. An anti-aging composition comprising, by weight, (i) 0.1-0.5 parts of the hindered amine light stabilizer according to any one of claims 1-8 and (ii) 0.01-2 parts of an antioxidant and / or 0.1-0.5 parts of an ultraviolet absorber; The antioxidant is selected from at least one of hindered phenolic antioxidants, thioester antioxidants, and phosphite antioxidants; The ultraviolet absorber is selected from at least one of benzotriazole ultraviolet absorbers, triazine ultraviolet absorbers, and benzophenone ultraviolet absorbers.

14. The anti-aging composition according to claim 13, characterized in that: The hindered phenolic antioxidant is selected from at least one of the following: 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (isooctyl ester), 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate C7~C9 alcohol mixture ester, 3,5-di-tert-butyl-4-hydroxyphenylpropionate C12~C14 alcohol mixture ester, 3,5-di-tert-butyl-4-hydroxyphenylpropionate C13~C15 alcohol mixture ester, 3,5-di-tert-butyl-4-hydroxyphenylpropionate C14~C16 alcohol mixture ester, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate octadecyl ester, triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate] and tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] pentaerythritol ester; The phosphite antioxidant is tris(2,4-di-tert-butylphenyl) phosphite; The thioester antioxidant is selected from at least one of 4,6-bis(octylthiomethyl)o-cresol and 2,4-bis(dodecylthiomethyl)-6-methylphenol; The ultraviolet absorber is selected from at least one of 2-hydroxy-4-n-octyloxybenzophenone, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-pentylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octyl)phenylbenzotriazole, 2-(2'-hydroxy-3',5'-dicumylphenyl)benzotriazole and 2-[4,6-bis(2,4-dimethylyl)-1,3,5-triazin-2-yl]-5-octyloxyphenol.

15. A composition comprising a photovoltaic encapsulant resin matrix material and the anti-aging composition of claim 13 or 14; wherein the photovoltaic encapsulant resin matrix material is selected from one or more of ethylene-vinyl acetate copolymer, polyolefin elastomer, polyvinyl butyral, thermoplastic polyolefin, and copolymer of ethylene and acrylic monomer, wherein the acrylic monomer comprises at least one of acrylic acid, acrylate, methacrylic acid, and methacrylate.

16. A photovoltaic module comprising the hindered amine light stabilizer of any one of claims 1-8, or the photovoltaic encapsulant film of any one of claims 10-12, or the anti-aging composition of claim 13 or 14, or the composition of claim 15.

17. A method for preparing a hindered amine light stabilizer, the method comprising: The compound shown in formula a1 and / or the compound shown in formula a2 is reacted with one or more compounds shown in formula b under conditions sufficient for reaction to obtain a hindered amine light stabilizer. R1 is selected from H and C. 1-10 Alkyl and C 1-10 Alkoxy groups, wherein the alkyl and alkoxy groups are optionally substituted with one or more halogen atoms; R3 is selected from H and C. 1-10 Alkyl, C 3-10 Cycloalkyl and 3-10 membered heterocyclic alkyl; and n is an integer from 1 to 7.

18. The method according to claim 17, characterized in that, The one or more compounds of formula b are a mixture of succinic acid or its ester and glutaric acid or its ester, or a mixture of succinic acid or its ester, glutaric acid or its ester, and adipic acid or its ester.

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