A polymer, its preparation and use

Abstract

This invention relates to the field of light stabilizer technology, specifically to a polymer, its preparation method, and its applications. The polymer of this invention comprises piperidine structural units, functionalized residue units, and polyoxyethylene chains. The polymer provided by this invention has a liquid state at room temperature and can be used as a liquid hindered amine light stabilizer. Using this polymer as a light stabilizer exhibits both good aqueous compatibility and good anti-photoaging effects, showing promising application prospects, and is particularly suitable for high-end applications requiring high compatibility and weather resistance.

Description

Technical Field

[0001] This invention relates to the field of hindered amine light stabilizers, and more particularly to a polymer, its preparation method, and its application. Background Technology

[0002] Polymer materials are widely used in various fields related to national economy and people's livelihood, occupying a fundamental, even crucial, position in modern society. However, a significant limiting factor for polymer materials is their aging characteristics. Especially when polymers are used outdoors, ultraviolet rays in sunlight damage the covalent bonds of the polymers, triggering degradation reactions. Aged polymer materials suffer severe deterioration in both color, appearance, and performance, ultimately failing to meet their intended use. Currently, preventing outdoor photoaging is mainly addressed by adding light stabilizers. The main types of light stabilizers are ultraviolet absorbers and hindered amine light stabilizers. Ultraviolet absorbers absorb or shield ultraviolet rays that can damage polymers, while hindered amine light stabilizers scavenge free radicals that lead to polymer degradation. These two types of light stabilizers have different functional focuses; hindered amine light stabilizers significantly alleviate the aging process of polymer materials and are an important product category in the field of polymer anti-aging.

[0003] Hindered amine light stabilizers are available in solid and liquid forms depending on the application requirements. Many polymer material systems use fluid raw materials during processing, and liquid forms are preferred for ease of mixing and subsequent application. Currently, most mainstream liquid light stabilizers are developed for solvent-based polymer systems, such as UV-292 and UV-123. With increasingly stringent environmental regulations, solvent-based polymer systems are facing stricter restrictions due to VOC emissions, leading to rapid development of corresponding environmentally friendly technologies to replace them. Among these technologies, water-based technologies are particularly favored. Water-based technologies have been successfully used in many fields such as coatings, adhesives, and polyurethane elastomers. However, a complete solution to the anti-aging problem of water-based polymer systems remains elusive. Currently, water-based stabilizers are mainly prepared or added using two methods: one is to dissolve the light stabilizer in a co-solvent first, and then add the dissolved light stabilizer to the water-based system. This method is only suitable for systems containing a large amount of co-solvent, which still contributes to VOC emissions. With technological upgrades and stricter regulations, cosolvents will inevitably become increasingly scarce, rendering solvent-based light stabilizers unsuitable for this approach. The second method involves using water-based resins or emulsifiers as carriers. This involves modifying the original solvent-based light stabilizer, then uniformly mixing the water-based resin prepolymer with the light stabilizer, additives, and water to produce a water-dispersible light stabilizer. This technical approach is more complex, more expensive, and has a very low effective content. Furthermore, it is affected by the stability of the water-based resin or emulsion, requiring stringent storage conditions and having a short shelf life. In addition, the additional carriers (water-based resins or emulsifiers) are often not needed by the original material system and may even cause compatibility issues or affect the properties of the polymer itself.

[0004] Therefore, developing novel liquid hindered amine light stabilizers that can meet the requirements of both traditional solvent-based systems and new aqueous systems has become a technical challenge for the industry. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of the prior art and provide a polymer with both good aqueous compatibility and good anti-photoaging effect, as well as its preparation method and application.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows: In a first aspect, the present invention provides a polymer, The polymer comprises the following structural units: (A) Piperidine structural unit, which is derived from piperidine compounds as shown in formula (I): ; In formula (I), R is selected from any one of hydrogen, hydroxyethyl, hydroxypropyl, hydroxyisopropyl, amino, or -NHR6; preferably, R is hydrogen or hydroxyethyl. R3 and R4 are each independently selected from hydrogen, substituted or unsubstituted C. 1-6 Any of the alkyl groups, wherein the substitution refers to C 1-6 At least one hydrogen atom on a carbon atom in the alkyl group is independently replaced by a substituent; preferably, R3 is hydrogen, and / or R4 is hydrogen; R5 is selected from any one of hydroxyl, amino, or -NHR6; The R6 in -NHR6 is independently selected from linear or branched substituted or unsubstituted C. 1-22 Any one of the alkyl groups; the substitution refers to C 1-22 At least one hydrogen atom on a carbon atom in an alkyl group is independently replaced by a substituent; (B) Functionalized residue units derived from a component containing at least one reactive functional group; said reactive functional group being a group capable of reacting with a hydroxyl, amino, or said NHR6; Preferably, the component containing at least one reactive functional group is selected from at least one of trialkyl orthoformate, dialkyl carbonate, polybasic acid, polybasic acid ester, polyisocyanate, polybasic acid anhydride, or polybasic acyl compound. And (C) a polyoxyethylene chain derived from one or more of the following epoxy compounds: ethylene oxide, propylene oxide or butane oxide; preferably, the epoxy compound is ethylene oxide.

[0007] Preferably, the polymer satisfies at least one of the following (i)-(iii): (i) The number average molecular weight of the polymer is 500-2000; preferably, the number average molecular weight of the polymer is 800-1800; more preferably, the number average molecular weight of the polymer is 800-1400. (ii) The polymer contains 20%-50% by weight of piperidine groups; preferably, the polymer contains 25%-50% by weight of piperidine groups; more preferably, the polymer contains 30%-50% by weight of piperidine groups. (iii) The dispersibility index of the polymer is 1.9-5.1, preferably 1.9-2.1.

[0008] Preferably, in the piperidine compound, R is hydrogen or hydroxyethyl, and R3 and R4 are both hydrogen; preferably, the piperidine compound is 2,2,6,6-tetramethyl-4-piperidineol or 1-(2'-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidineol.

[0009] Preferably, the component containing at least one reactive functional group satisfies at least one of the following (i)-(v): (i) The trialkyl orthoformate is selected from tri-C orthoformate. 1-6 At least one of alkyl esters; preferably, the trialkyl orthoformate is trimethyl orthoformate; (ii) The dialkyl carbonate is selected from dicarbonate. 1-6 At least one of alkyl esters; preferably, the dialkyl carbonate is dimethyl carbonate; (iii) The polyester is a C-type polyacid. 1-10 Alkyl esters, wherein the polyacid in the polyacid ester or the polyacid is selected from C 2-12 dicarboxylic acids, C 3-12 Tricarboxylic acids or C 4-12 The dicarboxylic acid is selected from at least one of succinic acid, glutaric acid, adipic acid, sebacic acid, or 1,2-cyclohexanedicarboxylic acid; the tricarboxylic acid is selected from at least one of triglyceride, cis-aconitine, trans-aconitine, citric acid, or tribenzoic acid; and the tetracarboxylic acid is selected from at least one of butanetetracarboxylic acid or pyromellitic acid; preferably, the polycarboxylic acid ester is selected from succinic acid dicarboxylic acid. 1-6 Alkyl esters, di-C glutaric acid 1-6 Alkyl esters, di-C adipic acid 1-6 Alkyl esters, di-C sebacate 1-6 Alkyl esters, tricarboxylic acid 1-6 Alkyl esters, trans-aconitine tri-C 1-6 Alkyl esters or tetracarboxylic acids of butane tetracarboxylic acid tetraC 1-6 At least one of the alkyl esters; (iv) The polyisocyanate is at least one of aromatic polyisocyanate or aliphatic polyisocyanate; preferably, the polyisocyanate is selected from at least one of toluene diisocyanate, diphenylmethane diisocyanate, tetramethylmethylene diisocyanate, phenylmethylene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate or isophorone diisocyanate; (v) The polyacid anhydride is at least one of maleic anhydride, phthalic anhydride or trimellitic anhydride.

[0010] Preferably, the component containing at least one reactive functional group is selected from at least one of dimethyl succinate, dimethyl glutarate, dimethyl adipate, trimethyl trans-aconitate, trimethyl orthoformate, tetramethyl butanetetracarboxylate, 1,6-hexamethylenediisocyanate, or maleic anhydride.

[0011] Preferably, the piperidine compound is 2,2,6,6-tetramethyl-4-piperidinol; the component containing at least one reactive functional group is dimethyl succinate, dimethyl glutarate, dimethyl adipate, trimethyl trans-aconitate, trimethyl orthoformate, or a mixture thereof; and the epoxide compound is ethylene oxide. Alternatively, the piperidine compound is 1-(2'-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol; the component containing at least one reactive functional group is tetramethyl butanetetracarboxylate, 1,6-hexanediisocyanate, maleic anhydride, dimethyl succinate, dimethyl glutarate, dimethyl adipate, or a mixture thereof; and the epoxy compound is ethylene oxide.

[0012] Preferably, the raw materials for preparing the polymer also include a catalyst; the catalyst is an acidic catalyst or a basic catalyst; preferably, the catalyst is a titanate catalyst, a sodium alkoxide catalyst, an organotin catalyst or a bimetallic cyanide.

[0013] Secondly, the present invention provides a method for preparing the above-mentioned polymer, which includes the following steps: S1. A piperidine compound and a component containing at least one reactive functional group are reacted under the action of a catalyst to obtain a first reaction intermediate; S2. Add an epoxy compound to the reaction system obtained in step S1 and continue the polymerization reaction to obtain the polymer. Preferably, the method for preparing the polymer includes the following steps: S1. A piperidine compound, a component containing at least one reactive functional group, and a catalyst are reacted in an organic solvent at a temperature of 90-160°C. The reaction is stopped when the content of the component containing at least one reactive functional group in the reaction solution is less than 1.5%, and a first reaction intermediate is obtained. S2. Add an epoxy compound to the reaction system obtained in step S1, and continue the polymerization reaction under a protective atmosphere at a temperature of 90-120°C. Stop the reaction when the number average molecular weight of the reaction product is 500-2000 to obtain the polymer.

[0014] Thirdly, the present invention provides another method for preparing the above-mentioned polymer, which includes the following steps: polymerizing a first prepolymer having the structure shown in formula (II) with a component containing at least one reactive functional group to obtain the polymer; ; In formula (II), p = an integer from 0 to 30, q = an integer from 0 to 30, and p+q>5, p+q≤50; preferably, 6≤p+q≤25.

[0015] Fourthly, the present invention provides another method for preparing the above-mentioned polymer, the method comprising the following steps: S1. The piperidine compound and the epoxy compound are reacted in the presence of a catalyst to obtain the first prepolymer; S2. Add a component containing at least one reactive functional group to the reaction system obtained in step S1, and continue the polymerization reaction to obtain the polymer.

[0016] More preferably, the method for preparing the polymer includes the following steps: S1. The piperidine compound, epoxide compound and catalyst are reacted in an organic solvent at a temperature of 80-160℃ until the number average molecular weight of the reaction product is 450-7269, at which point the reaction is stopped to obtain the first prepolymer. S2. Add a component containing at least one reactive functional group to the reaction system obtained in step S1, and continue the polymerization reaction to obtain the polymer.

[0017] Fifthly, the present invention provides the use of the above-mentioned polymer as a light stabilizer.

[0018] In a sixth aspect, the present invention provides an additive composition comprising the above-mentioned polymer and an additive selected from at least one of other hindered amine light stabilizers, antioxidants, fillers, binders, wetting agents, rheology modifiers, ultraviolet absorbers, flame retardants, anti-hydrolysis agents, defoamers, leveling agents, slip agents, substrate wetting agents, free radical scavengers, biocides, or coalescing agents.

[0019] Preferably, the ultraviolet absorber is selected from one or more of triazine ultraviolet absorbers, benzotriazole ultraviolet absorbers, benzophenone ultraviolet absorbers, cyanopropionate ultraviolet absorbers, and oxaloaniline ultraviolet absorbers. More preferably, the ultraviolet absorber is a liquid ultraviolet absorber.

[0020] Preferably, the antioxidant is selected from one or more of hindered phenolic antioxidants, phosphite antioxidants, thioester antioxidants, aromatic amine antioxidants, or compound antioxidants.

[0021] In a seventh aspect, the present invention provides a polymer material comprising: (a) the polymer or the additive composition described above; and (b) A polymer, wherein the polymer is at least one of polyolefins, polyurethanes, polyesters, polyamides, polycarbonates, polyester carbonates, polyoxymethylene, fluoropolymers, polyphenylene ethers or thioethers, epoxy resins and their modified resins, phenolic resins, amino resins, alkyd resins, vinyl ester resins, cyanate ester resins, polyimides, silane-modified resins, polycyanoacrylates, polyacrylates, ethylene / acrylic acid copolymers, acid cellulose and its derivatives, polyvinyl alcohol, polymethyl methacrylate, and aliphatic isocyanates.

[0022] Eighthly, the present invention provides a polymer material article comprising the above-mentioned polymer or the above-mentioned additive composition; the polymer material article is a plastic, rubber, coating, elastomer, sponge, ink or adhesive.

[0023] In a ninth aspect, the present invention provides a coating comprising a resin matrix and the aforementioned polymer or the aforementioned additive composition; wherein the resin matrix is ​​selected from one or more of polyurethane materials, amino resin materials, acrylic resin materials, polyester resin materials, silane-modified resins, alkyd resin materials and epoxy resin materials; and / or, the weight of the polymer is 0.1%-5% of the weight of the resin matrix.

[0024] Preferably, the coating is a water-based coating, and the coating is a water-based coating system, a solvent-based coating system, a powder coating system, or a solvent-free coating system; and / or, the coating is a transparent coating or a pigment-containing coating.

[0025] Compared with the prior art, the beneficial technical effects of the present invention are as follows: (1) This invention provides a novel polymer that can be used as a hindered amine light stabilizer. The polymer of this invention is in liquid form at room temperature, which facilitates its addition.

[0026] (2) The polymer of the present invention, as a hindered amine light stabilizer (HALS), can be directly used in water-based systems such as water-based coatings and water-based adhesives, and has excellent aqueous dispersion stability. At the same time, the HALS has better water extraction resistance, achieving a balance between water compatibility and water resistance.

[0027] (3) As a new liquid HALS, the polymer of the present invention can also be applied to traditional solvent-based systems, with stronger compatibility and its anti-photoaging performance is comparable to that of traditional HALS products.

[0028] (4) The polymer of the present invention, as a new liquid HALS, can also be used in combination with ultraviolet absorbers, antioxidants, heat stabilizers and various additives to achieve better protection effects, or to solve the problems of heat stability and light stability at the same time. Attached Figure Description

[0029] To more clearly illustrate the technical solutions in this invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of this invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0030] Figure 1 The GPC spectrum of the product of Embodiment 1 of the present invention; Figure 2 The GPC spectrum of the product in Embodiment 2 of the present invention; Figure 3 The GPC spectrum of the product in Embodiment 3 of the present invention; Figure 4 The GPC spectrum of the product in Embodiment 4 of the present invention; Figure 5 The GPC spectrum of the product in Embodiment 5 of the present invention; Figure 6 The GPC spectrum of the product in Embodiment 6 of the present invention; Figure 7 This is the GPC map of the product in Embodiment 7 of the present invention. Detailed Implementation

[0031] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some, not all, of the embodiments of this invention. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.

[0032] Terminology definition: In this application, unless otherwise stated, the scientific and technical terms used herein have meanings commonly understood by those skilled in the art. Furthermore, the relevant terms and laboratory procedures used herein are widely used terms and routine procedures in the respective fields. To better understand this disclosure, definitions and explanations of relevant terms are provided below.

[0033] As used herein, the term alkyl refers to a noncyclic saturated aliphatic group, including those of the general formula C1. n H 2n+1 The alkyl group represents a straight-chain or branched alkyl saturated hydrocarbon group, where n is the number of carbon atoms 1, 2, 3, 4, etc. In some embodiments, alkyl refers to a straight-chain, unsubstituted C14 group. 1-22Alkyl groups may be selected from the group consisting of: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, nonadecanyl, eicosyl, dodecyl, and docosyl. In some embodiments, alkyl refers to an unsubstituted branched C14. 3-22 Alkyl groups may be selected from the group consisting of: 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 1-methylheptyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methylheptyl, 1-methyloctyl, 2-methyloctyl, 3-methyloctyl, 4-methyloctyl 5-Methyloctyl, 6-Methyloctyl, 7-Methyloctyl, 1-Methylnonyl, 2-Methylnonyl, 3-Methylnonyl, 4-Methylnonyl, 5-Methylnonyl, 6-Methylnonyl, 7-Methylnonyl, 8-Methylnonyl, 1-Methyldecyl, 2-Methyldecyl, 3-Methyldecyl, 4-Methyldecyl, 5-Methyldecyl, 6-Methyldecyl, 7-Methyldecyl, 8-Methyldecyl, 9-Methyldecyl, 1-Methylundecyl, 2-Methylundecyl, 3-Methylundecyl, 4-Methylundecyl, 5-Methylundecyl, 6- Methylundecyl, 7-methylundecyl, 8-methylundecyl, 9-methylundecyl, 10-methylundecyl, 1-methyldodecyl, 2-methyldodecyl, 3-methyldodecyl, 4-methyldodecyl, 5-methyldodecyl, 6-methyldodecyl, 7-methyldodecyl, 8-methyldodecyl, 9-methyldodecyl, 10-methyldodecyl, 11-methyldodecyl, 1-methyltridecyl, 2-methyltridecyl, 3-methyltridecyl, 4-methyltridecyl, 5-methyltridecyl 6-Methyltetrazyl, 7-Methyltetrazyl, 8-Methyltetrazyl, 9-Methyltetrazyl, 10-Methyltetrazyl, 11-Methyltetrazyl, 12-Methyltetrazyl, 1-Methyltetradecyl, 2-Methyltetradecyl, 3-Methyltetradecyl, 4-Methyltetradecyl, 5-Methyltetradecyl, 6-Methyltetradecyl, 7-Methyltetradecyl, 8-Methyltetradecyl, 9-Methyltetradecyl, 10-Methyltetradecyl, 11-Methyltetradecyl, 12-Methyltetradecyl, 13-Methyltetradecyl, etc.

[0034] As used in this article, "C" 1-10"Alkyl" can include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isopropyl, tert-butyl, 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 1 -Methylheptyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methylheptyl, 1-methyloctyl, 2-methyloctyl, 3-methyloctyl, 4-methyloctyl, 5-methyloctyl, 6-methyloctyl, 7-methyloctyl, 1-methylnonyl, 2-methylnonyl, 3-methylnonyl, 4-methylnonyl, 5-methylnonyl, 6-methylnonyl, 7-methylnonyl, 8-methylnonyl, tert-amyl, etc.

[0035] As used herein and unless otherwise stated, the terms “comprising,” “including,” “having,” “containing,” and their grammatical equivalents, including their grammatical equivalents, should generally be understood as open-ended and non-restrictive, e.g., not excluding other unlisted elements or steps.

[0036] Existing hindered amine light stabilizers suffer from poor convenience in aqueous systems (e.g., poor compatibility, poor dispersion performance), or while some products solve the dispersion or dissolution problems in aqueous systems, their anti-aging efficiency needs further improvement. To address these shortcomings, this invention first provides a polymer comprising the following structural units: (A) Piperidine structural unit, which is derived from piperidine compounds as shown in formula (I): ; In the formula (I), R is selected from any one of hydrogen, hydroxyethyl, hydroxypropyl, hydroxyisopropyl, amino, or -NHR6; R3 and R4 are each independently selected from hydrogen, substituted or unsubstituted C. 1-6 Any of the alkyl groups, wherein the substitution refers to C 1-6 At least one hydrogen atom on a carbon atom in an alkyl group is independently replaced by a substituent; R5 is selected from any one of hydroxyl, amino, or -NHR6; The R6 in -NHR6 is independently selected from linear or branched substituted or unsubstituted C1- 22 Any one of the alkyl groups; the substitution refers to C 1-22 At least one hydrogen atom on a carbon atom in an alkyl group is independently replaced by a substituent; (B) Functionalized residue units derived from a component containing at least one reactive functional group; said reactive functional group being a group capable of reacting with a hydroxyl, amino, or -NHR6; And (C) a polyoxyethylene chain derived from one or more of the following epoxy compounds: ethylene oxide, propylene oxide or butane oxide.

[0037] The polymer of this invention uses a piperidine ring structure as its functional core, endowing it with photostability. Simultaneously, hydrophilic groups, such as nonionic polyethylene oxide chains or polypropylene glycol segments, are introduced onto the side chains of the piperidine ring structure. This not only achieves broader compatibility and addresses the convenience of downstream aqueous systems, such as solvent decomposition and dispersion in aqueous phases, but also considers both traditional solvent-based and aqueous systems. It maintains applicability in solvent-based systems, controls the hydrophilic groups on the side chains within a reasonable range, thus increasing water solubility while ensuring water resistance. Furthermore, it maintains the appropriate proportion of the piperidine ring functional group in the entire molecular chain, thereby preserving its performance while reducing alkalinity.

[0038] The polymers of this invention link two or more host structures together through multifunctional molecules capable of reacting with terminal hydroxyl groups. Due to the increase in overall molecular weight, migration and water extraction within the matrix are significantly improved. Simultaneously, the increased proportion of the HALS core functional group (piperidinyl) also results in stronger resistance to photoaging.

[0039] The polymer of this invention possesses a piperidine ring structure as the functional host, hydrophilic groups, and linking groups, exhibiting not only excellent aqueous compatibility but also effective resistance to photoaging. The polymer is liquid at room temperature, and when used as a liquid hindered amine light stabilizer, its photoaging protection effect on materials is consistent with traditional products. Furthermore, the polymer of this invention has a wider range of applications, covering both traditional solvent-based and solvent-free fluid materials, and can be directly added to aqueous systems without the need for organic solvents, resulting in improved safety.

[0040] In some embodiments, the number-average molecular weight of the polymer is 500-2000; for example, the number-average molecular weight of the polymer is 500, 906, 1065, 1035, 1107, 1197, 1252, 1465, 1504, 1516, 1630, or 2000. The number-average molecular weight is determined by GPC.

[0041] More preferably, the number average molecular weight of the polymer is 800-1800; even more preferably, the number average molecular weight of the polymer is 800-1400; the number average molecular weight of the polymer is particularly preferably 800-1000, 1000-1200 or 1300-1400.

[0042] In some embodiments, the weight percentage of piperidine groups in the polymer is 20%-50%; for example, the weight percentage of piperidine groups in the polymer is 20.70%, 27.32%, 28.75%, 29.31%, 32.98%, 33.73%, 36.68%, 37.74%, 42%, or 50%. The piperidine content is calculated as the percentage of piperidine molecular weight in the total molecular weight, i.e., the number of piperidine groups multiplied by the molecular weight (141) divided by the total molecular weight. A piperidine group content within this range in the polymer ensures an anti-aging effect.

[0043] In some preferred embodiments, the polymer contains 25%-50% by weight of piperidine groups; more preferably, the polymer contains 30%-50% by weight of piperidine groups. Such polymers have the following advantages: the product has low alkalinity, low viscosity, good compatibility with coatings, low cost, and color stability.

[0044] In some embodiments, the polymer has a number average molecular weight of 500-2000; and the polymer contains 20%-50% by weight of piperidine groups.

[0045] In some embodiments, the polymer has a dispersibility index of 1.9-5.1. For example, dispersibility indices are 1.9, 2.1, 2.3, 2.5, 2.7, 2.9, 3.1, 3.5, 4.0, 4.5, 4.8, and 5.1. The polymer of the present invention is a liquid product and is water-soluble.

[0046] In some embodiments, R in formula (I) is hydrogen; in other embodiments, R in formula (I) is hydroxyethyl.

[0047] In some embodiments, in formula (I), R3 is hydrogen, and / or R4 is hydrogen.

[0048] In some preferred embodiments, R in the piperidine compound is hydrogen or hydroxyethyl, and R3 and R4 are both hydrogen; more preferably, the piperidine compound is 2,2,6,6-tetramethyl-4-piperidineol or 1-(2'-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidineol.

[0049] In some embodiments, the epoxy compound is ethylene oxide.

[0050] In this invention, the term "reactive functional group" refers to a functional group capable of reacting with hydroxyl, amino, or -NHR6 groups, such as carboxyl, ester, isocyanate, anhydride, amide, ether, siloxy, or acyl groups. "A component containing at least one reactive functional group" refers to a substance containing at least one functional group capable of reacting with hydroxyl, amino, or -NHR6 groups, which may be a carboxylic acid, carboxylic acid ester, isocyanate, carbamate, amide, ether, siloxy, or anhydride. In some embodiments, the component "containing at least one reactive functional group" described in this application typically has at least two reactive functional groups, particularly at least two hydroxyl reactive functional groups. Specifically, the component containing at least one reactive functional group may be selected from one, two, three, or more of the following: trialkyl orthoformate, dialkyl carbonate, polybasic acid, polybasic acid ester, polyisocyanate, polybasic anhydride, or polyacryl compound.

[0051] In some embodiments, the trialkyl orthoformate is selected from tri-C orthoformate. 1-6 At least one of alkyl esters; preferably, the trialkyl orthoformate is trimethyl orthoformate.

[0052] In some embodiments, the dialkyl carbonate is selected from dicarbonate. 1-6 At least one of alkyl esters; preferably, the dialkyl carbonate is dimethyl carbonate; In some embodiments, the component containing at least one reactive functional group is selected from polybasic acids or their esters. In some embodiments, the polybasic acid or its ester is C 2-12 dicarboxylic acids or their C 1-10 Alkyl esters, such as the polyacids or their esters, are selected from succinic acid or its C4 esters. 1-10 Alkyl esters, glutaric acid or their C 1-10 Alkyl esters, adipic acid or their C4 esters 1-10 Alkyl esters, sebacic acid or their C 1-10 Alkyl esters, 1,2-cyclohexanedicarboxylic acids or their C4 esters 1-10 At least one of the alkyl esters; preferably, the polyacid or its ester is C. 2-12 dicarboxylic acids or their C 1-6 Alkyl esters, such as the polybasic acid or its ester succinic acid or its C4 ester. 1-6 Alkyl esters, adipic acid or their C4 esters 1-6 Alkyl esters or sebacic acid or its C 1-6 At least one of alkyl esters.

[0053] In some embodiments, the polyacid or its ester is C 3-12 Tricarboxylic acids or their C 1-10 Alkyl esters, for example, the polyacid or its ester selected from tricornioic acid or its C4 ester. 1-10Alkyl esters, cis-aconitine or their C4 esters 1-10 Alkyl esters, trans-aconitic acid or its C 1-10 Alkyl esters, citric acid or their C 1-10 Alkyl esters, benzotricarboxylic acid or their C 1-10 At least one of the alkyl esters; preferably, the polyacid or its ester is C. 3-12 Tricarboxylic acids or their C 1-6 Alkyl esters, such as the polyacid or its esters, are selected from tricornioic acid or its C-esters. 1-6 Alkyl esters, cis-aconitine or their C4 esters 1-6 Alkyl esters, trans-aconitic acid or its C 1-6 Alkyl esters, citric acid or their C 1-6 Alkyl esters, benzotricarboxylic acid or their C 1-6 At least one of alkyl esters.

[0054] In some embodiments, the polyacid or its ester is C 4-12 tetracarboxylic acids or their C 1-10 Alkyl esters, for example, the polyacid or its ester selected from butanetetracarboxylic acid or its C4 ester. 1-10 Alkyl esters, pyromellitic acid or their C4 esters 1-10 One or more of the alkyl esters; preferably, the polyacid or its ester is C. 4-12 tetracarboxylic acids or their C 1-6 Alkyl esters, for example, the polyacid or its ester selected from butanetetracarboxylic acid or its C4 ester. 1-6 Alkyl esters, pyromellitic acid or their C4 esters 1-6 At least one of alkyl esters.

[0055] In some embodiments, the polyacid or its ester is di(C) succinate. 1-6 Alkyl esters (e.g., dimethyl esters), di-C glutaric acid 1-6 Alkyl esters, di-C adipic acid 1-6 Alkyl esters, di-C sebacate 1-6 Alkyl esters, tricarboxylic acid 1-6 Alkyl esters (e.g., trimethyl esters), trans-aconitine trimethyl esters 1-6 Alkyl esters (e.g., trimethyl esters), tetramethyl butanetetracarboxylic acid 1-6 Alkyl esters (e.g., tetramethyl esters), etc. More preferably, the polyacid or its ester is selected from at least one of dimethyl succinate, dimethyl adipate, dimethyl sebacate, trimethyl trans-aconitate, trimethyl orthoformate, and tetramethyl butanetetracarboxylate.

[0056] In some embodiments, the polyisocyanate is at least one of aromatic polyisocyanate or aliphatic polyisocyanate; preferably, the polyisocyanate is selected from at least one of toluene diisocyanate, diphenylmethane diisocyanate, tetramethylmethylene diisocyanate, phenylmethylene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate or isophorone diisocyanate.

[0057] In some embodiments, the polybasic anhydride is at least one of maleic anhydride, phthalic anhydride, or trimellitic anhydride.

[0058] In some preferred embodiments, the component containing at least one reactive functional group is selected from at least one of dimethyl succinate, dimethyl glutarate, dimethyl adipate, trimethyl trans-aconitate, trimethyl orthoformate, tetramethyl butanetetracarboxylate, 1,6-hexamethylenediisocyanate, or maleic anhydride.

[0059] In some preferred embodiments, the piperidine compound is 2,2,6,6-tetramethyl-4-piperidinol; the component containing at least one reactive functional group is dimethyl succinate, dimethyl glutarate, dimethyl adipate, trimethyl trans-aconitate, trimethyl orthoformate, or a mixture thereof; and the epoxy compound is ethylene oxide.

[0060] In some other preferred embodiments, the piperidine compound is 1-(2'-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol; the component containing at least one reactive functional group is tetramethyl butanetetracarboxylate, 1,6-hexanediisocyanate, maleic anhydride, or dimethyl succinate, dimethyl glutarate, dimethyl adipate, or a mixture thereof; and the epoxy compound is ethylene oxide.

[0061] The preparation process of the polymer of this invention can be completed under the action of a catalyst, which can be either an acidic catalyst or a basic catalyst. The catalyst can be any catalyst known in the art; in some embodiments, the catalyst is a titanate catalyst, a sodium alkoxide catalyst, an organotin catalyst, or a dimetallic cyanide (DMC). For example, sodium alkoxide catalysts can be potassium tert-butoxide, sodium methoxide, sodium hydride, etc.

[0062] The polymer of this invention is a reaction product of a piperidine compound, a component containing at least one reactive functional group, and an epoxy compound. Its preparation method can involve the simultaneous reaction of the piperidine compound, the component containing at least one reactive functional group, and the epoxy compound, or the reaction of an intermediate product obtained after reacting two of the reactants with another reactant. Different reaction sequences result in polymers with different structures, and all polymers with these structures are within the scope of protection of this application.

[0063] In some embodiments, the present invention provides a method for preparing the above-mentioned polymer, wherein the method first reacts a component containing at least one reactive functional group with a piperidine compound to obtain a first reaction intermediate, and then reacts it with ethylene oxide to introduce a polyoxyethylene chain to form the final polymer. Specifically, the method for preparing the polymer includes the following steps: S1. A piperidine compound and a component containing at least one reactive functional group are reacted under the action of a catalyst to obtain a first reaction intermediate; S2. Add an epoxy compound to the reaction system obtained in step S1 and continue the reaction to obtain the polymer. Preferably, the method for preparing the polymer includes the following steps: S1. A piperidine compound, a component containing at least one reactive functional group, and a catalyst are reacted in an organic solvent at a temperature of 90-160°C. The reaction is stopped when the content of the component containing at least one reactive functional group in the reaction solution is less than 1.5%, and a first reaction intermediate is obtained. S2. Add an epoxy compound to the reaction system obtained in step S1, and react under a protective atmosphere at a temperature of 90-120°C. Stop the reaction when the number average molecular weight of the reaction product is 500-2000 to obtain the polymer.

[0064] The organic solvent used in step S1 can be a solvent known in the art, such as petroleum ether; the reaction temperature in step S1 is preferably 90-160°C, for example, the reaction temperature is 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C or 160°C.

[0065] In step S2 above, the polyoxyethylene chain can be introduced into the polymer by reacting with ethylene oxide gas. For example, the first reaction intermediate is placed in an autoclave, purged with nitrogen, and then heated to 90-120°C (e.g., the reaction temperature is 90°C, 100°C, 110°C, or 120°C), before ethylene oxide gas is introduced. The degree of polymerization of the polyoxyethylene chain in the polymer of the present invention is typically 3-10, for example 3-8, etc. Specifically, the degree of polymerization of the polyoxyethylene chain in the polymer of the present invention can be 3, 4, 5, 6, 7, 8, 9, or 10.

[0066] In the above embodiments, preferably, R, R3, and R4 in the piperidine compound are hydrogen.

[0067] In a preferred embodiment, the piperidine compound is 2,2,6,6-tetramethyl-4-piperidinol; the component containing at least one reactive functional group is dimethyl succinate, dimethyl glutarate, dimethyl adipate, trimethyl trans-aconitate, trimethyl orthoformate, or a mixture thereof; and the epoxy compound is ethylene oxide.

[0068] In other embodiments, the present invention provides another method for preparing the above-mentioned polymer, which includes the following steps: polymerizing a first prepolymer having the structure shown in formula (II) with a component containing at least one reactive functional group to obtain the polymer; ; In equation (II), p = an integer from 0 to 30, q = an integer from 0 to 30, and p + q > 5, p + q ≤ 50; for example, p + q can be 6, 7, 8, 9, 10, 11, 12, 15, 18, 20, 21, 23, 24, 25, 26, 30, 35, 40, 45, 49, 50, etc. Preferably, 6 ≤ p + q ≤ 25, more preferably 6 ≤ p + q ≤ 12.

[0069] The first prepolymer with the structure shown in formula (II) of this invention can be obtained by reacting a piperidine compound with an epoxy compound under the action of a catalyst, or it can be purchased. This first prepolymer also contains a piperidine ring structure, and a polyoxyethylene chain is attached to both the N atom and / or the C atom at the 4-position of the piperidine ring. The polyoxyethylene chain is hydroxyl-terminated. By reacting this prepolymer with a component containing at least one hydroxyl reactive functional group, a piperidine ring structure with a polyoxyethylene chain attached to both the N atom and / or the C atom at the 4-position can be introduced into the polymer of this invention. This allows the polymer of this invention to have low basicity and contain a hydrophilic polyether structure, avoiding reproductive toxicity and overcoming the problems of strong basicity and reproductive toxicity of the existing light stabilizer 292.

[0070] In some embodiments, the number-average molecular weight of the first prepolymer is 400-2200, for example, 420, 450, 480, 500, 530, 560, 590, 620, 650, 680, 730, 800, 900, 1000, 1500, or 2000; preferably 450-800; more preferably 450-480 or 553-729. When the number-average molecular weight of the first prepolymer is within this range, it has the following advantages: it ensures that the polymer has appropriate water solubility and is suitable for solvent-based systems; moreover, the viscosity of this product is moderate, which will not be too high and cause inconvenience in transportation and use; and it can ensure that the functional group weight percentage of the final product is in the range of 30%-50%. After obtaining the first prepolymer, the reactants can be subjected to simple post-treatment to remove unreacted ethylene oxide and piperidine compounds. Then, the subsequent reaction process begins.

[0071] In some embodiments, the component containing at least one reactive functional group described in this invention typically has at least two reactive functional groups, which facilitates the linking of at least two first prepolymers through the component containing at least one reactive functional group, thereby forming a polymer with multiple piperidine rings. Such a polymer has the following advantages: having multiple effective piperidine ring groups improves the application performance of the product. The overall polymer structure results in good stability and resistance to water extraction, making it suitable not only for aqueous polymer systems but also for solvent-based polymer systems and UV / electron beam curing systems.

[0072] In some embodiments, the polymer is prepared by first reacting a piperidine compound with ethylene oxide to obtain a first prepolymer, which is then reacted with a component containing at least one reactive functional group to form the final polymer. Specifically, the polymer preparation method includes the following steps: S1. The piperidine compound and the epoxy compound are reacted in the presence of a catalyst to obtain the first prepolymer; S2. Add a component containing at least one reactive functional group to the reaction system obtained in step S1, and continue the polymerization reaction to obtain the polymer.

[0073] In the above preparation method, the piperidine ring of the piperidine compound contains a hydroxyl group and optionally a hydroxyethyl group. Therefore, it can react with an epoxide compound in the presence of a catalyst, thereby introducing a polyethylene oxide chain onto the piperidine ring. This reaction is generally carried out in the presence of a basic catalyst (such as potassium tert-butoxide, sodium hydride, etc.) or a bimetallic cyanide (DMC) catalyst.

[0074] In some preferred embodiments, the method for preparing the polymer includes the following steps: S1. The piperidine compound, epoxide compound and catalyst are reacted in an organic solvent at a temperature of 80-160℃ until the number average molecular weight of the reaction product is 450-729, at which point the reaction is stopped to obtain the first prepolymer. S2. Add a component containing at least one reactive functional group to the reaction system obtained in step S1, and continue the polymerization reaction to obtain the polymer.

[0075] In step S1 of the above preparation method, the organic solvent can be a solvent known in the art, such as toluene, xylene, petroleum ether, ethylene glycol dimethyl ether, etc.

[0076] The reaction temperature can be 80-160℃, for example, 80℃, 90℃, 100℃, 110℃, 120℃, 130℃, 140℃, 150℃ or 160℃, preferably 100-140℃. The molecular weight (degree of polymerization) of the first prepolymer can be controlled by controlling reaction conditions such as temperature and reaction time, for example, controlling p+q to 6, 7, 8, 9, 10, 11, 12, 15, 18, 20, 21, 23, 24, 25, 26, 30, 35, 40, 45, 49, 50, etc.

[0077] More preferably, in the piperidine compound, R is hydroxyethyl, and R3 and R4 are both hydrogen.

[0078] In a preferred embodiment, the piperidine compound is 1-(2'-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol; the component containing at least one reactive functional group is tetramethyl butanetetracarboxylate, 1,6-hexanediisocyanate, maleic anhydride, dimethyl succinate, dimethyl glutarate, dimethyl adipate, or a mixture thereof; and the epoxy compound is ethylene oxide.

[0079] In a more preferred embodiment, the piperidine compound is 1-(2'-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol, the component containing at least one reactive functional group is dimethyl succinate, and the epoxy compound is ethylene oxide; the molar ratio of the first prepolymer to dimethyl succinate is (1.5~2.5):1. Preferably, the molar ratio of the first prepolymer to dimethyl succinate is 2:1.

[0080] The polymer of this invention is in liquid form and exhibits good aqueous compatibility and resistance to photoaging, as well as water resistance, making it suitable for use as a light stabilizer. Therefore, this invention also provides the use of the above-mentioned polymer as a light stabilizer.

[0081] Furthermore, the present invention provides an additive composition comprising at least one polymer of the present invention. Preferably, the additive composition comprises the above-described polymer and an additive selected from at least one of other hindered amine light stabilizers, antioxidants, fillers, binders, wetting agents, rheology modifiers, ultraviolet absorbers, flame retardants, anti-hydrolysis agents, defoamers, leveling agents, slip agents, substrate wetting agents, free radical scavengers, biocides, or coalescing agents; more preferably, the additive is an ultraviolet absorber. These additives can utilize various components conventional in the art.

[0082] The novel HALS structure, when used in combination with a UV absorber, achieves better anti-photoaging effects than using a UV absorber or hindered amine light stabilizer alone. Preferably, the UV absorber is selected from one or more of triazine UV absorbers, benzotriazole UV absorbers, benzophenone UV absorbers, cyanopropionate UV absorbers, and oxaloylaniline UV absorbers. More preferably, the UV absorber is a liquid UV absorber, such as a mixture of 2-[4-(2-hydroxy-3-tetaneoxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-[4-(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine (UV- 400 (CAS No.: 153519-44-9), 2-[2-hydroxy-4-[3-(2-ethylhexyloxy)-2-hydroxypropoxy]phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine (UV405, CAS No.: 137658-79-8), UV-477 (triazine, 2-[4-[4-[2,4-bis[(1-octyloxy-1-oxopropyl-2-yl) [Oxy]phenyl]-6-[2-hydroxy-4-(1-octyloxy-1-oxoprop-2-yl)oxyphenyl]-1,3,5-triazin-2-yl]-3-hydroxyphenoxy]octyl propionate, CAS No.: 348144-63-8), methyl 3-(3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl)propionate and PEG 300 reaction product (UV-1130, benzotriazole, CAS No.: 104810-48-2), 2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol (UV-571, CAS: 125304-04-3) ), 95% phenylpropionic acid, 3-benzotriazole-5-tert-butyl-4-hydroxyphenylpropionate reacting with C7-C9 alcohols, propylene glycol methyl ether acetate (benzotriazole, UV384-2, CAS No.: 127519-17-9; 108-65-6), 2-(2'-hydroxy-3'-cumyl-5'-tert-octylphenyl)benzotriazole (UV-928, CAS No.: 73936-91-1), 2-(2′-hydroxy-3′,5′-dicumylphenyl)-2H-benzotriazole (UV-234, CAS No.: 70321-86-7), 2-2-(2′-hydroxy-3′,5′-ditert-pentylphenyl)benzotriazole (UV-328, CAS No.: At least one of 25973-55-1) or UV-3039 (cyanopropionate, CAS No.: 6197-30-4).

[0083] For applications requiring simultaneous solutions to both light and heat aging, such as adhesives, elastomers, and polyurethanes, hindered amine light stabilizers, UV absorbers, antioxidants, heat stabilizers, and pigments and fillers can be combined in optimized proportions to achieve better results with lower dosage.

[0084] In a preferred embodiment, the antioxidant is selected from one or more of hindered phenolic antioxidants, phosphite antioxidants, thioester antioxidants, aromatic amine antioxidants, or compound antioxidants. More preferably, the hindered phenolic antioxidants include, but are not limited to, at least one of 2,6-di-tert-butyl-p-cresol (BHT), pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (1010), octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (1076), octyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (1135), and isooctyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (1135R); the phosphite antioxidants include, but are not limited to, tris(2,4-di-tert-butylphenyl) phosphite (168) or bis(2,4-di-tert-butylphenyl) At least one of pentaerythritol diphosphite (626); the thioester antioxidant is selected from at least one of dilauryl thiodipropionate (DLTDP) or distearate thiodipropionate (DSTDP).

[0085] As a preferred embodiment, the other hindered amine light stabilizers include, but are not limited to, a mixture of bis(1,2,2,6,6,-pentamethyl-4-piperidinyl) sebacate and mono(1,2,2,6,6,-pentamethyl-4-piperidinyl) sebacate (UV-292), bis(1-octoxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate (CAS: 129757-67-1 UV-123), and bis(2,2,6,6-tetramethyl-1-undecyloxypiperidin-4-yl) carbonate 2-[2,2,6,6-tetramethyl-4-(3,5,5-trimethyl-hexanoyloxy)piperidinyl]-3,5 5-Trimethylhexanoate ethyl ester (CAS: 1445870-18-7), 2,2,6,6-Tetramethyl-4-piperidine stearate (CAS: 1420448-49-2).

[0086] Furthermore, the present invention also provides a polymeric material comprising the above-described polymer or the above-described additive composition, and an organic material susceptible to degradation induced by oxygen, heat, or light. Preferably, the polymeric material comprises: (a) the polymer or the additive composition described above; and (b) A polymer, wherein the polymer is at least one of polyolefins, polyurethanes, polyesters, polyamides, polycarbonates, polyester carbonates, polyoxymethylene, fluoropolymers, polyphenylene ethers or thioethers, epoxy resins and their modified resins, phenolic resins, amino resins, alkyd resins, vinyl ester resins, cyanate ester resins, polyimides, silane-modified resins, polycyanoacrylates, polyacrylates, ethylene / acrylic acid copolymers, acid cellulose and its derivatives, polyvinyl alcohol, polymethyl methacrylate, and aliphatic isocyanates.

[0087] In a preferred embodiment, the polyolefin is selected from at least one of polyvinyl chloride, polystyrene and its derivatives.

[0088] In addition, the present invention also provides a polymer material article comprising the above-mentioned polymer or the above-mentioned additive composition; the polymer material article is a plastic, rubber, coating, elastomer, sponge, ink or adhesive.

[0089] In addition, the present invention provides a coating comprising a resin matrix and the above-mentioned polymer or the above-mentioned additive composition; wherein the resin matrix is ​​selected from one or more of polyurethane materials, amino resin materials, acrylic resin materials, polyester resin materials, silane-modified resins, alkyd resin materials and epoxy resin materials.

[0090] Preferably, the weight of the polymer is 0.01%-5% of the weight of the resin matrix; for example, the weight of the polymer is 0.01%, 0.05%, 0.1%, 0.2%, 0.5%, 1%, 2%, 3%, 4%, or 5% of the weight of the resin matrix. More preferably, the weight of the polymer is 0.1%-5% of the total weight of the resin matrix; further, the weight of the polymer is 0.2%-5% of the total weight of the resin matrix.

[0091] In some embodiments, the coating further includes a liquid diluent and a curing agent / crosslinking agent; preferably, the liquid diluent is water or an organic solvent, and the organic solvent includes one or more of alcohols, ethers, alcohol ethers, esters, ketones, and aromatics. The alcohol solvent is ethanol, n-butanol, isopropanol, benzyl alcohol, etc.; the ether solvent is selected from diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, 1,4-dioxane, etc.; the alcohol ether is, for example, ethylene glycol ethyl ether, ethylene glycol butyl ether, propylene glycol butyl ether (PNB), diethylene glycol monoethyl ether, etc.; the ester solvent is, for example, ethyl acetate, butyl acetate, amyl acetate, etc.; the ketone solvent is, for example, acetone, methyl ethyl ketone (MEK), cyclohexanone, methyl isobutyl ketone, etc.; the aromatic solvent is, for example, benzene, toluene, xylene, No. 200 coal tar solvent, No. 200 solvent gasoline, kerosene, turpentine, etc.

[0092] The curing agent (or crosslinking agent) is a functional resin, oligomer, or other organic compound that undergoes a crosslinking reaction with the main resin matrix of the coating. These include isocyanates, amino resins, epoxy resins, amines, and acid anhydrides. Examples of isocyanates include aromatic TDI-TMP adducts and MDI prepolymers; aliphatic HDI trimers, HDI biuret, IPDI adducts, and HDI-IPDI mixed trimers; and blocked IPDI or HDI blocked with butanone oxime, ε-caprolactam, etc. Examples of amino resins include butylated melamine-formaldehyde (HMMM), partially methylated melamine, urea-formaldehyde resin, and phenyl melamine. The amines mentioned include, for example, aliphatic amines such as ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), hexamethylenediamine, and m-phenylenediamine; alicyclic amines such as isophorone diamine (IPDA), methylcyclohexanediamine, and 4,4′-diamino-3,3′-dimethyldicyclohexylmethane; aromatic amines such as m-phenylenediamine, diaminodiphenylmethane (DDM), and diaminodiphenyl sulfone (DDS); and polyamides formed by the condensation of dimer acids and polyamines. The anhydrides mentioned include, for example, phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, pyromellitic dianhydride, 647 anhydride, and tung oil anhydride (308). It should be noted that liquid diluents, curing agents / crosslinking agents, and various additives can all be various substances conventional in the art, which will not be elaborated here.

[0093] The coating is prepared by dispersing a fine particulate solid material in a liquid diluent in the presence of the polymer of the present invention. The coating further comprises additives. Dispersion is achieved using conventional techniques such as high-speed mixing, ball milling, sand milling, grinding, or two-roll or three-roll milling.

[0094] In some embodiments, the coating is a water-based coating system, a solvent-based coating system, a powder coating system, or a solvent-free coating system; in other embodiments, the coating is a transparent coating system or a coating system containing pigments or fillers. When the polymer of the present invention is used in water-based coatings, it exhibits particularly superior application performance.

[0095] The present invention also provides an adhesive comprising a resin matrix and the above-described polymer or the above-described additive composition; wherein the resin matrix is ​​selected from at least one of polyurethane, polyvinyl acetate, silane-modified resin, polyvinyl chloride resin, cyanoacrylate, epoxy resin, acrylate, phenolic resin, and urea-formaldehyde resin.

[0096] The present invention will be further described below through specific embodiments.

[0097] In the following examples, the weight-average molecular weight of the polymer ( Mw ) and number average molecular weight (M n The determination was performed by gel permeation chromatography (GPC) using THF as the eluent (1 mL / min) and polystyrene as the standard resin, according to DIN 55672-1.

[0098] The GPC detection methods used in the embodiments are shown in Table 1 below: Table 1

[0099] The raw materials used in the examples are as follows: UV-292: Bis(1,2,2,6,6-pentamethylpiperidinol) sebacate (CAS No.: 41556-26-7). 1-(2'-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol (CAS No.: 52722-86-8); Tetramethylpiperidine, also known as 2,2,6,6-tetramethyl-4-piperidine (CAS No.: 2403-88-5).

[0100] Example 1 At room temperature, 95 g of dimethyl succinate, 170 g of 2,2,6,6-tetramethyl-4-piperidinol (molar ratio of 2,2,6,6-tetramethyl-4-piperidinol to dimethyl succinate was added to a 1 L four-necked flask, along with 1.2 g of catalyst (potassium tert-butoxide) and 500 mL of solvent (toluene). The temperature was raised to 110-150 °C and maintained for reaction to obtain an intermediate. The intermediate was then subjected to polymerization under a nitrogen atmosphere using ethylene oxide. The reaction ended when the number average molecular weight of the product reached 1065. The final product was obtained by distillation, with a yield of 95% and a transmittance of 97.6% at 425 nm.

[0101] The GPC spectrum of the product in Example 1 is as follows: Figure 1 As shown.

[0102] Example 2 At room temperature, 95 g of trimethyl trans-aconitate, 170 g of 2,2,6,6-tetramethyl-4-piperidinol, 1.2 g of catalyst (potassium tert-butoxide), and 500 mL of solvent (toluene) were added to a 1 L four-necked flask. The temperature was raised to 110-150 °C and maintained for reaction to obtain an intermediate. The intermediate was then subjected to polymerization in ethylene oxide under a nitrogen atmosphere. The reaction ended when the number average molecular weight of the product reached 1516. The product was then distilled to obtain the final product with a yield of 97% and a transmittance of 96.8% at 425 nm.

[0103] The GPC profile of the product in Example 2 is as follows: Figure 2 As shown.

[0104] Example 3 At room temperature, 45 g of trimethyl orthoformate, 170 g of 2,2,6,6-tetramethyl-4-piperidinol, 1.2 g of catalyst (potassium tert-butoxide), and 500 mL of solvent (toluene) were added to a 1 L four-necked flask. The temperature was raised to 110-150 °C and maintained for reaction to obtain an intermediate. The intermediate was then subjected to polymerization in ethylene oxide under a nitrogen atmosphere. The reaction ended when the number average molecular weight of the product reached 1035. The final product was obtained by distillation, with a yield of 93% and a transmittance of 97.3% at 425 nm.

[0105] The GPC spectrum of the product in Example 3 is as follows: Figure 3 As shown.

[0106] Example 4 At room temperature, 95 g of dimethyl succinate, 170 g of 2,2,6,6-tetramethyl-4-piperidinol, 1.2 g of catalyst (potassium tert-butoxide), and 500 mL of solvent (xylene) were added to a 1 L four-necked flask. The temperature was raised to 120 °C and maintained for reaction to obtain an intermediate. The intermediate was then subjected to polymerization in ethylene oxide under a nitrogen atmosphere. The reaction ended when the number average molecular weight of the product reached 1197. The product was then distilled to obtain the final product with a yield of 96% and a transmittance of 98.1% at 425 nm.

[0107] The GPC profile of the product in Example 4 is as follows: Figure 4 As shown.

[0108] The physicochemical property test results of the products in Examples 1-4 are shown in Table 2 below.

[0109] Table 2. Test results of the physicochemical properties of the products in Examples 1-4

[0110] Note: Piperidin content calculation method: the proportion of piperidin molecular weight in the total molecular weight, that is, the number of piperidin groups multiplied by the molecular weight (141) divided by the total molecular weight.

[0111] Example 5 50g of 1-(2'-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol was mixed with 200mL of xylene, and 0.4g of potassium tert-butoxide catalyst was added. The mixture was heated to 100~140℃ and ethylene oxide was introduced. As the reaction proceeded, the molecular weight increased continuously. When the number average molecular weight of the reaction system reached 450~480, the reaction was stopped to obtain the first prepolymer. Add 20.3g of tetramethyl butanetetracarboxylate to the first prepolymer, heat to 140~150℃, keep warm for 7-8h to stop the reaction, and obtain the finished product by vacuum distillation of the solvent.

[0112] The GPC spectrum of the product in Example 5 is as follows: Figure 5 As shown.

[0113] Example 6 Mix 50g of 1-(2'-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol with 200mL of xylene, add 0.4g of potassium tert-butoxide catalyst, heat to 100~140℃, and introduce ethylene oxide. As the reaction proceeds, the molecular weight continuously increases. When the number average molecular weight of the reaction system reaches 450~480, the reaction is stopped to obtain the first prepolymer.

[0114] Add 21.84 g of 1,6-hexamethylene diisocyanate to the first prepolymer, heat to 140-150°C, keep warm for 3-4 hours, stop the reaction, and obtain the finished product by vacuum distillation of the solvent.

[0115] The GPC spectrum of the product in Example 6 is as follows: Figure 6 As shown.

[0116] Example 7 Mix 50g of 1-(2'-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol with 200mL of xylene, add 0.4g of potassium tert-butoxide catalyst, heat to 100~140℃, and introduce ethylene oxide. As the reaction proceeds, the molecular weight continuously increases. When the number average molecular weight of the reaction system reaches 450~480, the reaction is stopped, and the first prepolymer is obtained.

[0117] Add 12.74g of maleic anhydride to the first prepolymer, heat to 80~100℃, keep warm for 3~4h, stop the reaction, and obtain the finished product by vacuum distillation of the solvent.

[0118] The GPC spectrum of the product in Example 7 is as follows: Figure 7 As shown.

[0119] Example 8 50g of 1-(2'-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol was mixed with 200mL of xylene, and 0.4g of potassium tert-butoxide catalyst was added. The mixture was heated to 100-140℃, and ethylene oxide was introduced. As the reaction proceeded, the molecular weight continuously increased. The reaction was stopped when the number average molecular weight of the reaction system reached 553-729, yielding the first prepolymer. The number of repeating p+q units in ethylene oxide is 8-12.

[0120] Add 18.8g of dimethyl succinate to the first prepolymer, heat to 80~100℃, keep warm for 3~4h, stop the reaction, and obtain the finished product by vacuum distillation of the solvent.

[0121] Example 9 The product of the reaction between the first prepolymer obtained in Example 8 and 20g of sebacic acid ester, liquid, with a molecular weight Mn=1104.

[0122] Example 10 50g of 1-(2'-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol was mixed with 200mL of xylene, and 0.4g of potassium tert-butoxide catalyst was added. The mixture was heated to 100-140℃, and ethylene oxide was introduced. As the reaction proceeded, the molecular weight continuously increased. The reaction was stopped when the number average molecular weight of the reaction system reached 350-420, yielding the first prepolymer. The number of repeating p+q units in ethylene oxide is approximately four.

[0123] Add 20.3g of dimethyl succinate to the first prepolymer, heat to 80~100℃, keep warm for 3~4h, stop the reaction, and obtain the finished product by vacuum distillation of the solvent.

[0124] Example 11 50 g of 1-(2'-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol was mixed with 200 mL of xylene, and 0.4 g of potassium tert-butoxide catalyst was added. The mixture was heated to 100-140 °C, and ethylene oxide was introduced. As the reaction proceeded, the molecular weight continuously increased. The reaction was stopped when the number average molecular weight of the reaction system reached 2300-2400, yielding the first prepolymer. The number of repeating p+q units in ethylene oxide is approximately 54.

[0125] Add 20.3g of dimethyl succinate to the first prepolymer, heat to 80~100℃, keep warm for 3~4h, stop the reaction, and obtain the finished product by vacuum distillation of the solvent.

[0126] The physicochemical property test results of the products in Examples 5-11 are shown in Table 3 below.

[0127] Table 3. Test results of physicochemical properties of products in Examples 5-11

[0128] Application effect test The light stabilizers used in the test are as follows: HA-1: Riasorb UV-292, CAS number: 41556-26-7&82919-37-7; HA-2: Riasorb UV-123, CAS number: 129757-67-1; HA-3: The first prepolymer obtained in Example 8; HA-4: The finished product obtained in Example 10; HA-5: The finished product obtained in Example 11; LHA-1: The finished product obtained in Example 1; LHA-2: The finished product obtained in Example 2; LHA-3: The finished product obtained in Example 3; LHA-4: The finished product obtained in Example 4; NHA-1: The finished product obtained in Example 8; NHA-2: The finished product obtained in Example 9; NHA-3: The finished product obtained in Example 5.

[0129] I. Compatibility Experiment in Aqueous Phase 1.1 The water dispersibility of the product itself In a 30mL cylindrical glass bottle, add 16g of deionized water, then add 4g of each of the different HALS products. Shake for 10 minutes to mix thoroughly. After standing for 15 minutes, observe the compatibility of each group of HALS in pure water. The results are shown in Table 4 below: Table 4. Product compatibility test in aqueous phase.

[0130] The compatibility tests above show that, compared to traditional HALS products, hindered amine light stabilizers with the introduction of hydrophilic polyoxyethylene chains exhibit improved aqueous compatibility to a certain extent. Furthermore, in the HALS structure linked by multiple functional groups, the repeating structure of the polyoxyethylene chains exhibits the best aqueous compatibility within the preferred range.

[0131] 1.2 Dispersion stability in aqueous systems Solvent-based systems were among the earliest application systems in many industries, such as coatings, adhesives, and inks. However, solvent-based systems emit large amounts of VOCs (volatile organic compounds), making water-based systems a more environmentally friendly technology and a key development direction for the industry. In water-based coatings, the dispersion medium is changed from traditional organic solvents to water, resulting in a significant reduction in VOC emissions. The following are representative products of water-based wood coatings (the main paint composition of water-based wood coatings is shown in Table 5), where HALS in the experimental group represents the structures listed above: Table 5. Composition of the base coating for water-based wood coatings

[0132] NeoCryl XK-12 was purchased from Covestro in Germany; R595 titanium dioxide was purchased from DuPont, USA. AMP-95 and Acrysol RM-8W were purchased from Dow Chemical Company, USA. Tego Foamex 810 and Tego WET 270 were acquired from Evonik Group of France; The curing agent composition is: Bayhydur XP 2655 : propylene glycol methyl ether acetate = 80:20.

[0133] When using this wood coating, mix the base paint and hardener at a ratio of 4:1, and spray it onto the wood surface to be coated immediately after mixing.

[0134] Different hindered amine light stabilizers (HA-1, HA-2, HA-3, HA-4, HA-5, NHA-1, NHA-2, or NHA-3) were added to blank wood coatings (base coat) in the above proportions, and stirred for 20 minutes until uniformly dispersed in the system. The coating samples were then placed at room temperature, and the stability of the different hindered amine light stabilizers in the water-based coatings was observed after 2 months. The results are shown in Table 6 below. Table 6 Storage stability test of water-based wood coatings

[0135] Compared to traditional HALS products, the new HALS, which introduces hydrophilic polyoxyethylene chains, exhibits good compatibility and long-term stability in waterborne coatings.

[0136] II. Weather Resistance Test (1) Test board fabrication Preparation: Select a smooth, undefect-free beechwood board and sand it down with 240-grit sandpaper to remove burrs. Spray a commercially available two-component primer sealer, bake at 60 degrees Celsius for 20 minutes, and then wait for 3 days. Sand the sealed board smooth with 400-grit sandpaper, and prepare to spray the above-mentioned water-based wood coating containing different hindered amine light stabilizers (HA-3, HA-4, HA-5, LHA-1, LHA-2, LHA-3, LHA-4, NHA-1, NHA-2, or NHA-3).

[0137] Spraying: The composition of the experimental group coatings is shown in Table 5. Due to the precipitation of HA-1 and HA-2, they were not included in the weather resistance test. The remaining experimental group coatings were mixed with the base paint and hardener according to the usage method described above, and then sprayed onto the prepared beechwood test board surface. The wet film thickness of the coatings was uniformly controlled at 120-130 micrometers. The boards were baked at 60 degrees Celsius for 20 minutes, and then left at room temperature for 7 days before testing.

[0138] (2) QUV photoaging test The test panels were placed in a QUV ultraviolet aging chamber (model: Q-Lab QUV / Spray ultraviolet fluorescence aging test chamber), and the test standard was based on GB / T 23983-2009 "Test Method for Yellowing Resistance of Wood Coatings". The test panels were removed at regular intervals to measure the gloss at 20 degrees. Gloss meter: BYK micro-TRI-gloss. The test results are shown in Table 7 below.

[0139] Table 7 QUV photoaging test

[0140] The QUV test results above indicate that the new HALS linked by multifunctional groups has a better anti-photoaging effect than the unlinked HA-3. The optimized range of hydrophilic side chains in the HALS (NHA 1-3) ensures that waterborne coatings have a better anti-photoaging effect.

[0141] III. Water Resistance Test While the hydrophilic polyoxyethylene chains enhance compatibility in the aqueous phase, excessive hydrophilicity can lead to the HALS product being washed away by water (such as rainwater) or lost through extraction by water in the usage environment. This loss of HALS results in insufficient protection of the material's long-term weather resistance.

[0142] Silicone-modified resin systems are commonly used in adhesives / sealants and coatings, especially in building sealants where a certain tolerance to rainwater runoff is required. The composition of the adhesive used in the water resistance test is shown in Table 8 below, where HALS selects the aforementioned structural components: Table 8. Adhesive Components Table

[0143] The Kaneka S303H was purchased from Kaneka Corporation in Japan. Silquest A-171 and A-1120 were purchased from Momentive Performance Materials, USA. The prepared adhesive containing each HALS product was coated into a 2mm film. The film was cured at room temperature for one week, and then fully cured at 85% humidity and 60 degrees Celsius to produce the final product sample.

[0144] All gel samples were placed in 60°C hot water and removed at intervals. 0.5g of gel sample was cut from each group. The gel samples were cut into very fine particles and then extracted by immersion in 20mL of tetrahydrofuran solvent. The extraction solution system was sonicated for 20 minutes, and the extract was filtered. The content of HALS in the extract was determined by GPC (Gas-Cured Liquid Chromatography). Instrument: Agilent 1260. The HALS retention rate was calculated as: Retention rate = Peak area of ​​the intermittent extract GPC / Peak area of ​​the initial extract GPC × 100%. The HALS retention rates under different hot water extraction times are shown in Table 9 below. Table 9 HALS Retention Rate

[0145] NHA-1, NHA-2, and NHA-3 exhibit significantly better water resistance than unlinked HA-3; by optimizing the segment range, even better water-resistant extraction results can be achieved.

[0146] IV. Applications in Water-Based Adhesives Hindered amine light stabilizers containing polyethylene glycol segments also exhibit good compatibility in waterborne adhesives, imparting excellent weather resistance. Their weather resistance is further enhanced when used in combination with UV absorbers possessing certain water-emulsifying properties, such as Riasorb UV-1130. Table 10 below shows the composition of component A in waterborne two-component polyurethane adhesives: Table 10. Component A of Waterborne Polyurethane Adhesives

[0147] Adwel 1630B and Aquolin 161 were purchased from Wanhua Chemical Group; Acrysol RM-12W was purchased from Dow Chemical Company in the United States. Tego Foamex 810 and Tego WET 270 were acquired from Evonik Group of France; Riasorb UV-1130 is produced by Tianjin Lialong New Materials Co., Ltd.

[0148] Component B of the water-based adhesive is Aquolin 161. During application, mix components A and B thoroughly at a mass ratio of 100:8.

[0149] (1) Test board fabrication Preparation: Mix component A of the blank group and component A of the adhesive containing the hindered amine light stabilizer of this application with the same component B in the specified ratio. After mixing evenly, apply the mixture to form a 2mm thick film. After drying at room temperature for 30 minutes, bake in a 60℃ oven for 30 minutes. Then let it stand for 7 days to allow the film to fully cure. Cut the film into multiple strips using a dumbbell cutter.

[0150] (2) QUV photoaging test The test strips from the blank and experimental groups were placed in a QUV ultraviolet aging chamber (model: Q-Lab QUV / Spray ultraviolet fluorescence aging test chamber), and the test standard was based on ASTM G154-06 cylce 1. The tensile strength was tested at regular intervals. Tensile strength tester: Universal testing machine. The test results are shown in Table 11 below: Table 11 Tensile strength test results after QUV aging

[0151] V. Application in Solvent-Based Coatings Hindered amine light stabilizers containing polyethylene glycol segments are applied to solvent-based polymer systems such as coatings, for example, in solvent-based automotive clear coats (whose composition is shown in Table 12 below).

[0152] Table 12 shows the composition formulations of typical single-component solvent-based varnishes.

[0153] Setalux 1766, Setalux 1795, Setalux 91795, Setal 168: Hydroxyacrylate resin, anti-sagging resin, purchased from Zhanxin Resin (China) Co., Ltd. Cymel 303 and Cymel 1168: amino resins, purchased from Changxin Resin (Guangdong) Co., Ltd. BYK 378 and BYK 306: silicone leveling agents, purchased from BYK Additives (Shanghai) Co., Ltd. Nacure 5225: an acid catalyst, purchased from King Industries Inc., USA.

[0154] Based on the above single-component solvent-based clear varnish formulation, three groups of test coating samples were obtained by adding different types of light stabilizers. The coating test samples were prepared by spraying as follows: The substrate was a uniform steel plate with an electrophoretic coating (purchased from ACT, USA). A solvent-based intermediate coat and a solvent-based solid white base coat (Nippon Paint automotive paint) were uniformly sprayed on. The intermediate coat film thickness was 30 micrometers. Leveling was allowed at room temperature for 10 minutes, followed by baking in a 140°C oven for 30 minutes. After the white base coat was sprayed, leveling was allowed at room temperature for 10 minutes, followed by spraying the above three groups of clear varnishes to a film thickness of 40 micrometers. Leveling was allowed at room temperature for 10 minutes, followed by baking in a 140°C oven for 30 minutes.

[0155] The xenon lamp testing conditions were as follows: The test panel was placed in a xenon lamp aging test chamber (model: Atlas Ci4400 xenon lamp aging test chamber), and the test standard referred to ISO 11341 (2004). The test panel was removed at regular intervals to measure a gloss level of 20 degrees. Gloss meter: BYK micro-TRI-gloss. The test results are shown in Table 13 below.

[0156] Table 13 Xenon Lamp Aging Test Results

[0157] The novel multi-chain HALS (NHA-1, NHA-2, NHA-3) linked by multiple functional groups exhibits significantly improved anti-photoaging performance compared to the single-chain hindered amine light stabilizer (HA-3). Their anti-photoaging performance is almost identical to that of the traditional hindered amine light stabilizer (UV-123), indicating that they remain suitable for traditional solvent-based coating systems.

[0158] VI. Product-based complexes Multi-chain hindered amine light stabilizers containing polyethylene glycol segments can be used in combination with many other types of additives to form synergistic complexes. These additives include, but are not limited to, one or more of ultraviolet absorbers, antioxidants, flame retardants, and hydrolysis inhibitors. These complexes can be used in coatings, adhesives, inks, elastomers, foaming materials, and other fields.

[0159] Complex with UV absorbers: The new HALS structure, when used in combination with UV absorbers, can achieve better anti-photoaging effects than using UV absorbers or hindered amine light stabilizers alone. Common types of UV absorbers include triazine UV absorbers, benzotriazole UV absorbers, benzophenone UV absorbers, and cyanopropionate UV absorbers. Preferred liquid UV absorbers include: UV-400 (triazine, CAS No.: 153519-44-9), UV-477 (triazine), UV-1130 (benzotriazole, CAS No.: 104810-48-2 & 104810-47-1), UV 384-2 (benzotriazole, CAS No.: 127519-17-9), and UV-3039 (cyanopropionate, CAS No.: 6197-30-4).

[0160] A two-component acrylic polyurethane clear varnish coating system that cures with isocyanate was selected. This system can be used in plastic coatings, automotive refinish coatings, and other fields. The formulation of component A is shown in Table 14 below.

[0161] Table 14 Two-component acrylic polyurethane clear varnish coating, Component A

[0162] 1. Desmodur N3300: An aliphatic polyisocyanate based on hexamethylene diisocyanate (HDI), purchased from Covestro Polymers (China) Co., Ltd. 2. Setalux 1274 BA-70: Hydroxyacrylate resin, purchased from Zhanxin Resin (China) Co., Ltd.; 3. BYK 378: Silicone leveling agent, purchased from BYK Additives (Shanghai) Co., Ltd.; 4. Riasorb UV-1130 is from Tianjin Lianlong New Materials Co., Ltd.; 5. DBTDL: Dibutyltin dilaurate, catalyst, purchased from Tianjin Xiens Biotechnology Co., Ltd.

[0163] Component B is Desmodur N3300 (Covestro), and by weight, the ratio of component A to component B is 100:20.45.

[0164] The following method was used to prepare the coating test samples: The substrate was galvanized steel sheet, sanded, and wiped clean with isopropyl alcohol. Solvent-based epoxy primer, solvent-based isocyanate acrylic intermediate coat, and solvent-based solid white base coat were uniformly sprayed (coatings provided by Yatu High-Tech Materials Co., Ltd.). The primer film thickness was 25 microns, leveled at room temperature for 10 minutes, and then baked in a 60°C oven for 30 minutes. The intermediate coat film thickness was 30 microns, leveled at room temperature for 10 minutes, and then baked in an 80°C oven for 30 minutes. After spraying the white base coat, leveled at room temperature for 10 minutes, followed by spraying the above four groups of clear coats to a film thickness of 35 microns, leveling at room temperature for 10 minutes, and then baking in a 120°C oven for 25 minutes. QUV testing began 7 days after surface conditioning.

[0165] The test panel was placed in a QUV ultraviolet aging chamber (model: Q-Lab QUV / Spray ultraviolet fluorescence aging test chamber), and the test standard was based on ASTM G154-06 cylce 1. The test panel was removed and its color measured at regular intervals. An X-rite MA5 spectrophotometer was used. The test results are shown in Table 15 below.

[0166] Table 15 Comparison of Xenon Lamp Aging Tests for Compositions

[0167] Combination of multiple stabilizers: For applications requiring simultaneous solutions to both photoaging and thermal aging, such as adhesives, elastomers, and polyurethanes, hindered amine light stabilizers, UV absorbers, antioxidants, heat stabilizers, and pigments and fillers can be combined in optimized proportions to achieve better results with lower dosage.

[0168] The following are application examples in building sealants, with resin systems including polyurethane and silane-modified resins. The resin used in this experiment is silane-modified polyether, and its composition is shown in Table 16.

[0169] Table 16 Composition of Silane-Modified Sealants

[0170] 1. Kerilin 200D: Silane-modified polyether polymer, purchased from Jiangsu Ruiyang Antai New Material Technology Co., Ltd.; 2. Titanium dioxide R595, purchased from DuPont, USA; 3. Fumed silica AEROSIL R972, purchased from Evonik Specialty Chemicals (Shanghai) Co., Ltd.; 4. Coupling agent KH-792, purchased from Nanjing Pinning Coupling Agent Co., Ltd.; 5. DBTDL: Dibutyltin dilaurate, catalyst, purchased from Tianjin Xinsheng Biotechnology Co., Ltd.; 6. Riasorb UV-571 and Rianox 1135 are from Tianjin Lialong New Materials Co., Ltd.

[0171] Sample preparation: The four sealant samples were coated into 2mm thick films and left to cure at 35℃ and 80% humidity for 7 days. Once fully cured, the films were cut into 6cm x 6cm pieces.

[0172] Thermal aging test: The sample films were placed in a 110℃ oven and heated. The yellowing index of the film was tested at intervals, and surface changes were observed. The test results are shown in Table 17 below: Table 17 Thermal Aging Test of Silane-Modified Sealants

[0173] As shown in the table above, the composition containing NHA-2 has a better anti-heat aging effect than the addition of antioxidant (AO-1135) alone.

[0174] Photoaging test: The samples were placed in a QUV ultraviolet aging chamber (model: Q-Lab QUV / Spray ultraviolet fluorescence aging test chamber), and the test standard was based on ASTM G154-06 cylce 1. The color of the test samples was measured periodically. An X-rite MA5 spectrophotometer was used. The results are shown in Table 18 below: Table 18 QUV light aging test of silane-modified sealants

[0175] As shown in the table above, the composition containing NHA-2 has a better anti-heat aging effect than the composition containing only UV absorber (UV-571) and hindered amine light stabilizer (Example 2).

[0176] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A polymer, characterized in that, The polymer comprises the following structural units: (A) Piperidine structural unit, which is derived from piperidine compounds as shown in formula (I): ； In the formula (I), R is selected from any one of hydrogen, hydroxyethyl, hydroxypropyl, hydroxyisopropyl, amino, or -NHR6; R3 and R4 are each independently selected from hydrogen, substituted or unsubstituted C. 1-6 Any of the alkyl groups, wherein the substitution refers to C 1-6 At least one hydrogen atom on a carbon atom in an alkyl group is independently replaced by a substituent; R5 is selected from any one of hydroxyl, amino, or -NHR6; The R6 in -NHR6 is independently selected from linear or branched substituted or unsubstituted C. 1-22 Any one of the alkyl groups; the substitution refers to C 1-22 At least one hydrogen atom on a carbon atom in an alkyl group is independently replaced by a substituent; (B) Functionalized residue units derived from a component containing at least one reactive functional group; said reactive functional group being a group capable of reacting with a hydroxyl, amino, or said -NHR6; And (C) a polyoxyethylene chain derived from one or more of the following epoxy compounds: ethylene oxide, propylene oxide or butane oxide.

2. The polymer according to claim 1, characterized in that, The polymer satisfies at least one of the following (i)-(iii): (i) The number-average molecular weight of the polymer is 500-2000; (ii) The weight percentage of piperidine groups in the polymer is 20%-50%; (iii) The dispersibility index of the polymer is 1.9-5.

1.

3. The polymer according to claim 1 or 2, characterized in that, The polymer satisfies at least one of the following (i)-(iv): (i) R is hydrogen or hydroxyethyl; (ii) R3 is hydrogen; (iii) R4 is hydrogen; (iv) The component containing at least one reactive functional group is selected from at least one of trialkyl orthoformate, dialkyl carbonate, polybasic acid, polybasic acid ester, polyisocyanate, polybasic acid anhydride or polybasic acyl compound.

4. The polymer according to claim 3, characterized in that, The component containing at least one reactive functional group satisfies at least one of the following (i)-(v): (i) The trialkyl orthoformate is selected from tri-C orthoformate. 1-6 At least one of the alkyl esters; (ii) The dialkyl carbonate is selected from dicarbonate. 1-6 At least one of the alkyl esters; (iii) The polyester is a C-type polyacid. 1-10 Alkyl esters, wherein the polyacid in the polyacid ester or the polyacid is selected from C 2-12 dicarboxylic acids, C 3-12 Tricarboxylic acids or C 4-12 At least one of the tetracarboxylic acids; (iv) The polyisocyanate is at least one of aromatic polyisocyanate or aliphatic polyisocyanate; (v) The polyacid anhydride is at least one of maleic anhydride, phthalic anhydride or trimellitic anhydride.

5. The polymer according to claim 4, characterized in that, The component containing at least one reactive functional group is selected from at least one of dimethyl succinate, dimethyl glutarate, dimethyl adipate, trimethyl trans-aconitate, trimethyl orthoformate, tetramethyl butanetetracarboxylate, 1,6-hexamethylenediisocyanate, or maleic anhydride.

6. The polymer according to claim 5, characterized in that, The piperidine compound is 1-(2'-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol; the component containing at least one reactive functional group is tetramethyl butanetetracarboxylate, 1,6-hexanediisocyanate, maleic anhydride, dimethyl succinate, dimethyl glutarate, dimethyl adipate, or a mixture thereof; the epoxy compound is ethylene oxide.

7. A method for preparing the polymer according to any one of claims 1-6, characterized in that, Includes the following steps: The polymer is obtained by polymerizing a first prepolymer having the structure shown in formula (II) with a component containing at least one reactive functional group. ； In equation (II), p = an integer from 0 to 30, q = an integer from 0 to 30, and p+q>5, p+q≤50.

8. A method for preparing the polymer according to any one of claims 1-6, characterized in that, Includes the following steps: S1. The piperidine compound and the epoxy compound are reacted in the presence of a catalyst to obtain the first prepolymer; S2. Add a component containing at least one reactive functional group to the reaction system obtained in step S1, and continue the polymerization reaction to obtain the polymer.

9. Use of the polymer according to any one of claims 1-6 as a light stabilizer.

10. An adjuvant composition, characterized in that, The invention comprises the polymer and additives described in any one of claims 1-6, wherein the additives are selected from at least one of other hindered amine light stabilizers, antioxidants, fillers, binders, wetting agents, rheology modifiers, ultraviolet absorbers, flame retardants, anti-hydrolysis agents, defoamers, leveling agents, slip agents, substrate wetting agents, free radical scavengers, biocides, or coalescing agents.

11. A polymer material, characterized in that, include: (a) The polymer according to any one of claims 1-6 or the additive composition according to claim 10; as well as (b) A polymer, wherein the polymer is at least one of polyolefins, polyurethanes, polyesters, polyamides, polycarbonates, polyester carbonates, polyoxymethylene, fluoropolymers, polyphenylene ethers or thioethers, epoxy resins and their modified resins, phenolic resins, amino resins, alkyd resins, vinyl ester resins, cyanate ester resins, polyimides, silane-modified resins, polycyanoacrylates, polyacrylates, ethylene / acrylic acid copolymers, acid cellulose and its derivatives, polyvinyl alcohol, polymethyl methacrylate, and aliphatic isocyanates.

12. A polymer material product, characterized in that, Includes the polymer of any one of claims 1-6 or the additive composition of claim 10; the polymer material article is a plastic, rubber, coating, elastomer, sponge, ink or adhesive.

13. A coating, characterized in that, The coating comprises a resin matrix and the polymer of any one of claims 1-6 or the additive composition of claim 10; the resin matrix is ​​selected from one or more of polyurethane materials, amino resin materials, acrylic resin materials, polyester resin materials, silane-modified resins, alkyd resin materials and epoxy resin materials; and / or, the weight of the polymer is 0.1%-5% of the weight of the resin matrix.

14. The coating according to claim 13, characterized in that, The coating is a water-based coating system, a solvent-based coating system, a powder coating system, or a solvent-free coating system; and / or, the coating is a transparent coating or a pigment-containing coating.

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