Ultraviolet light absorbing substance as well as preparation method therefor and use thereof

Abstract

The present invention provides a substance represented by formula I, wherein R1 is H or Cl, A is C2 to C5 alkylene, B is C2 to C5 alkylene, m+n is an integer from 2 to 120, and none of m and n is 0. The substance can be used as an ultraviolet light absorber.

Description

Ultraviolet light absorbing material, preparation method and application thereof Technical Field

[0001] The present invention relates to a substance that can be used for ultraviolet light absorption, and in particular to a substance having a benzotriazole group and a polyol structure. The substance of the present invention can be used as an ultraviolet light absorber and can be applied to various polymer materials. Background Art

[0002] Polymer materials are widely used in various products due to their diverse structures and properties. However, some polymer materials are easily degraded by ultraviolet light. Therefore, it is conventionally known to use ultraviolet absorbers (UVA) in polymer materials to provide UV protection.

[0003] Take polyurethane, for example. It's an important polymer formed by the polymerization of polyols and isocyanates. By adjusting the raw material ratios, it can be used to manufacture materials with desired mechanical properties, such as wear resistance, temperature resistance, flexibility, and elongation. These materials include coatings, elastomers, foams, adhesives, and sealants. However, polyurethane is susceptible to degradation by UV light, and deteriorates particularly rapidly in strong outdoor light conditions. To prevent degradation caused by UV light, UV absorbers can be physically incorporated into polyurethane. Benzotriazole (BTZ) is the most widely used UV absorber.

[0004] However, physically incorporated UV absorbers are prone to migration within polyurethane materials, causing blooming or damaging the surface properties of the polyurethane material. For example, these can cause the polyurethane surface to become sticky or even cause fading in the product in which they are applied. Therefore, increasing the compatibility of UV absorbers within polyurethane materials to prevent or minimize migration has become a key issue in UV absorber development. Generally, the following two methods can be used to increase the compatibility of UV absorbers within polyurethane materials and reduce or eliminate UV absorber migration.

[0005] The first approach is to increase the molecular weight of the UV absorber, as exemplified by the techniques disclosed in US Pat. Nos. 4,853,471 and 7,381,762. Increasing the molecular weight of the UV absorber slows the migration rate of the UV absorber molecules within the polyurethane material. However, this approach only slows the migration rate and does not effectively prevent it. Furthermore, increasing the UV absorber's molecular weight also reduces its effective content, necessitating a higher UV absorber dosage to achieve adequate UV protection.

[0006] The second approach involves synthesizing the UV absorber into a reactive UV absorber. The hydroxyl groups contained in the UV absorber participate in the polymerization reaction during the polyurethane synthesis process, chemically incorporating the UV absorber into the polyurethane structure. Examples of such reactive UV absorbers include those disclosed in US Pat. No. 5,459,222 and TW1638039.

[0007] In terms of efficacy, the second approach can more effectively address the migration problem of UV absorbers. However, the reactive UV absorbers disclosed in the prior art still lack the advantages of low-temperature operation (flowability and easy dissolution and dispersion at low temperatures of 40°C to 50°C), good thermal stability, and excellent UV resistance.

[0008] Summary of the Invention

[0009] In response to the aforementioned technical problems, the present invention provides a UV-absorbing substance comprising a benzotriazole group and a polyol structure. This substance can be directly chemically bonded to the polymer structure, thereby resolving the migration problem of UV absorbers. Furthermore, this substance exhibits advantages such as low-temperature operability (flowability at temperatures as low as 40°C to 50°C and easy dissolution and dispersion, such as in polyols), excellent thermal stability, and superior UV resistance.

[0010] Therefore, one object of the present invention is to provide a substance represented by formula I,

[0011] in,

[0012] R1 is H or Cl;

[0013] A is a C2 to C5 alkylene group;

[0014] B is C2 to C5 alkylene; and

[0015] m+n is an integer from 2 to 120, and both m and n are not 0.

[0016] In some embodiments of the present invention, A and B are each independently C5 alkylene.

[0017] In some embodiments of the present invention, m and n are each independently an integer from 1 to 50.

[0018] Another object of the present invention is to provide a use of the substance of formula I as an ultraviolet light absorber.

[0019] Another object of the present invention is to provide a polymer precursor composition comprising: a polymerizable monomer; and the substance of formula I above.

[0020] In some embodiments of the present invention, the polymerizable monomer comprises a polyol and a polyisocyanate.

[0021] In some embodiments of the present invention, the polymer precursor composition further comprises an additive selected from the following groups: solvents, catalysts, antioxidants, fillers, solubilizers, flame retardants, thermal stabilizers, light stabilizers, metal deactivators, plasticizers, lubricants, emulsifiers, dyes, pigments, brighteners, antistatic agents, foaming agents, chain extenders, anti-hydrolysis agents, surfactants, crosslinking agents, photoinitiators, pH adjusters, adhesion promoters, bactericides, and combinations thereof.

[0022] Another object of the present invention is to provide a polymer comprising a structure derived from the substance of formula I above.

[0023] In some embodiments of the present invention, the polymer is selected from the group consisting of polyurethane, polyester, polycarbonate, epoxy resin, amino resin, polyamide, polyimide, liquid crystal polymer, polyoxymethylene, polysiloxane, polymethacrylate copolymer, polyacrylate copolymer, and composites thereof.

[0024] Another object of the present invention is to provide a product capable of resisting ultraviolet light, wherein the product uses the substance of formula I as an ultraviolet light absorber. In addition to the substance of formula I, the product may further use other existing ultraviolet light absorbers.

[0025] In some embodiments of the present invention, the article is selected from the group consisting of plastics, coatings, inks, displays, lamps, optical films, optical lenses, goggles, glasses, contact lenses, textiles, pressure-sensitive adhesives, and sunscreens.

[0026] In some embodiments of the present invention, the article further comprises an additive selected from the following groups: solvents, catalysts, antioxidants, fillers, solubilizers, flame retardants, thermal stabilizers, light stabilizers, metal deactivators, plasticizers, lubricants, emulsifiers, dyes, pigments, brighteners, antistatic agents, foaming agents, chain extenders, anti-hydrolysis agents, surfactants, crosslinking agents, photoinitiators, pH adjusters, adhesion promoters, bactericides, and combinations thereof.

[0027] Another object of the present invention is to provide a method for preparing a product that can resist ultraviolet light, comprising using the substance of formula I in the product.

[0028] Another object of the present invention is to provide a method for preparing the substance of formula I, which comprises reacting a compound represented by formula II with a C3 to C6 lactone compound in the presence of a ring-opening polymerization catalyst, wherein R1 is H or Cl.

[0029] In some embodiments of the present invention, the ring-opening polymerization catalyst is diphenyl phosphate.

[0030] In some embodiments of the present invention, the C3 to C6 lactone compound is selected from the group consisting of β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, and combinations thereof.

[0031] In order to make the above-mentioned objectives, technical features and advantages of the present invention more obvious and easy to understand, some specific implementation plans are described in detail below. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] FIG1 is the ultraviolet absorption spectrum of the substance synthesized in Synthesis Example 1. DETAILED DESCRIPTION

[0033] Some specific embodiments according to the present invention will be described in detail below; however, the present invention can be practiced in a variety of different forms, and the scope of protection of the present invention should not be interpreted as being limited to what is described in the description.

[0034] Unless otherwise stated, the terms "a", "an", "the" and similar terms used in this specification and claims should be understood to include both the singular and the plural.

[0035] The inventors have discovered a simple method for synthesizing a substance with a benzotriazole group and a polyol structure. This substance not only solves the migration problem of existing UV absorbers but also exhibits advantages such as low-temperature operation (flowability at temperatures as low as 40°C to 50°C and easy dissolution and dispersion, such as in polyols), excellent thermal stability, and superior UV protection. Therefore, it is suitable for use in various applications requiring UV protection. The following provides a detailed description of the disclosed substance, its preparation method, and its applications.

[0036] 1. Substance shown in formula I

[0037] In the present invention, the substance represented by Formula I has the following structure:

[0038] In Formula I, R1 is H or Cl; A is a C2 to C5 alkylene group; B is a C2 to C5 alkylene group; and m+n is an integer from 2 to 120, and both m and n are not 0.

[0039] The C2-C5 alkylene group refers to a divalent group formed by removing one hydrogen atom from each of two carbon atoms of an alkyl group. In the present invention, A and B are each independently a C2-C5 alkylene group. In embodiments where n is greater than 1, each A may be the same or different, and in embodiments where m is greater than 1, each B may be the same or different. In some embodiments of the present invention, the C2-C5 alkylene group is a C2-C5 linear alkylene group, examples of which include ethylene, propylene, butylene, and pentylene. In some embodiments of the present invention, A and B are each independently a C5 alkylene group, preferably a C5 linear alkylene group, i.e., a pentylene group.

[0040] m and n represent the number of structural units in the brackets. In the present invention, m+n is an integer from 2 to 120, and both m and n are not 0. m+n is preferably an integer from 10 to 100, for example, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55 , 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, or 100, or a range consisting of any two of the foregoing values.

[0041] As will be described below and specifically exemplified in the synthesis examples, the substance having the structure of Formula I of the present invention can be prepared by polymerizing the compound represented by Formula II below with a C3 to C6 lactone compound in the presence of a ring-opening polymerization catalyst. Under the reaction mechanism, it can be expected that m and n of Formula I can be approximately the same. 47, 48, 49, or 50, or a range between any two of the foregoing values.

[0042] The substance represented by formula I of the present invention has a benzotriazole group (ie, ) and polyol structures, particularly long-chain polyol structures. Without being limited by theory, it is believed that these structures can provide at least the following advantages: good dispersibility at low operating temperatures (e.g., 50°C); excellent hydrolysis resistance; alkalinity and excellent solubility in alcohols, allowing the compound to dissolve in alcohols at low temperatures. Polyols are the main raw materials for forming some polymers (e.g., polyurethanes), so the compound is particularly useful in such polymers; and excellent thermal stability and UV resistance.

[0043] 2. Application of the substance represented by formula I

[0044] 2.1. Use as UV absorber

[0045] The substance represented by formula I can absorb ultraviolet light and is therefore suitable for use as an ultraviolet light absorber in various fields requiring protection against ultraviolet light.

[0046] 2.2. Polymer Precursor Composition

[0047] The substance represented by Formula I can be applied to polymer materials to provide an effect of protecting against ultraviolet light. Therefore, the present invention also provides a polymer precursor composition comprising a polymerizable monomer and the substance represented by Formula I.

[0048] The polymerizable monomers are any compounds that can react with each other, and preferably with the substance represented by Formula I, to form a polymer. Preferably, the polymerizable monomers can react with the substance represented by Formula I such that the formed polymer comprises a structure derived from the substance represented by Formula I.

[0049] In some embodiments of the present invention, the polymer precursor composition is a polyurethane precursor composition, and the polymerizable monomers include a polyol and a polyisocyanate. Examples of the polyol include, but are not limited to, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, glycerol, trimethylolpropane, pentaerythritol, and lactone ring-opening products. The aforementioned polyols may be used alone or in any combination. Examples of the polyisocyanate include, but are not limited to, methylene diphenyl diisocyanate (MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), cyclohexane diisocyanate (CHDI), tetramethylxylylene diisocyanate (TMXDI), 1,3-bis(isocyanatomethyl)cyclohexane (H6XDI), isophorone diisocyanate (IPDI), and methylene bis(4-cyclohexylisocyanate) (HMDI). The aforementioned polyisocyanates may be used alone or in any combination.

[0050] In the polymer precursor composition of the present invention, the content of the polymerizable monomer and the substance represented by Formula I is not particularly limited and can be adjusted according to the desired polymer material properties, the type of polymerizable monomer used, and the desired anti-ultraviolet effect. For example, in an embodiment where the polymer precursor composition is a polyurethane precursor composition, the content of the substance represented by Formula I may be 0.1 wt % to 30 wt %, more specifically 0.5 wt % to 3 wt %, such as 0.1 wt %, 0.5 wt %, 1 wt %, 1.5 wt %, 2 wt %, 2.5 wt %, 3 wt %, 3.5 wt %, 4 wt %, 4.5 wt %, 5 wt %, 5.5 wt %, 6 wt %, 6.5 wt %, 7 wt %, 7.5 wt %, 8 wt %, 8.5 wt %, 9 wt %, 9.5 wt %, 10 wt %, 10.5 wt %, 11 wt %, 11.5 wt %, 12 wt %, 12.5 wt %. %, 13 wt %, 13.5 wt %, 14 wt %, 14.5 wt %, 15 wt %, 15.5 wt %, 16 wt %, 16.5 wt %, 17 wt %, 17.5 wt %, 18 wt %, 18.5 wt %, 19 wt %, 19.5 wt %, 20 wt %, 20.5 wt %, 21 wt %, 21.5 wt %, 22 wt %, 22.5 wt %, 23 wt %, 23.5 wt %, 24 wt %, 24.5 wt %, 25 wt %, 25.5 wt %, 26 wt %, 26.5 wt %, 27 wt %, 27.5 wt %, 28 wt %, 28.5 wt %, 29 wt %, 29.5 wt %, or 30 wt %, or in a range consisting of any two of the above values, but the present invention is not limited thereto.

[0051] Without departing from the technical principles of the present invention, the polymer precursor composition of the present invention may further comprise optional ingredients as needed to improve the processability of the polymer precursor composition during the manufacturing process, promote the polymerization reaction, or specifically improve the properties of the polymer material. Examples of the aforementioned optional ingredients include, but are not limited to, solvents, catalysts, antioxidants, fillers, solubilizers, flame retardants, thermal stabilizers, light stabilizers, metal deactivators, plasticizers, lubricants, emulsifiers, dyes, pigments, brighteners, antistatic agents, foaming agents, chain extenders, anti-hydrolysis agents, surfactants, crosslinking agents, photoinitiators, pH adjusters, adhesion promoters, and bactericides. These optional ingredients may be used alone or in any combination.

[0052] Polymers

[0053] The present invention also provides a polymer comprising the substance represented by Formula I, or comprising a structure derived from the substance represented by Formula I.

[0054] The type of polymer of the present invention is not particularly limited. Examples include, but are not limited to, polyurethane, polyester, polycarbonate, epoxy resin, amino resin, polyamide, polyimide, liquid crystal polymer, polyoxymethylene, polysiloxane, polymethacrylate copolymer, polyacrylate copolymer, or a composite thereof.

[0055] The preparation method for the polymer of the present invention is not particularly limited. For example, the polymer can be prepared by reacting the aforementioned polymer precursor composition via melt polymerization or solution polymerization. Based on the disclosure of this specification, those skilled in the art will be able to prepare the polymer using conventional methods. The preparation of polyurethane is illustrated in the accompanying Examples and will not be further elaborated here.

[0056] 2.4. Products that can resist ultraviolet light

[0057] The present invention also provides a product, wherein the substance represented by Formula I is used as an ultraviolet light absorber, thereby being able to resist ultraviolet light. The product can further use other ultraviolet light absorbers available in the art.

[0058] The UV-resistant products of the present invention can be any product that is desired to have UV-resistant properties. Examples of such products include, but are not limited to, plastics, coatings, inks, displays, lamps, optical films, optical lenses, goggles, glasses, contact lenses, textiles, pressure-sensitive adhesives, and sunscreens.

[0059] The UV-resistant product may optionally contain additional additives to improve its properties. Examples of these additives include, but are not limited to, solvents, catalysts, antioxidants, fillers, solubilizers, flame retardants, thermal stabilizers, light stabilizers, metal deactivators, plasticizers, lubricants, emulsifiers, dyes, pigments, brighteners, antistatic agents, foaming agents, chain extenders, anti-hydrolysis agents, surfactants, crosslinkers, photoinitiators, pH adjusters, adhesion promoters, and fungicides. These optional ingredients may be used individually or in any combination.

[0060] 2.5. Methods for preparing UV-resistant products

[0061] The present invention also provides a method for preparing an article capable of resisting UV light, characterized in that a substance represented by Formula I is used during the preparation process of the article to provide UV resistance. For example, a polymer material can be added as a reactive monomer during the preparation process, and the resulting polymer material can be used as the entire component of the article, or only as a component of the article (e.g., only the surface component of the article), to impart UV resistance to the article.

[0062] 3. Method for preparing the substance shown in formula I

[0063] The substance represented by formula I of the present invention can be prepared by the following method: In the presence of a ring-opening polymerization catalyst, the compound represented by formula II is reacted with a C3 to C6 lactone compound, wherein R1 is H or Cl.

[0064] The ring-opening polymerization catalyst refers to a catalyst that can catalyze the ring-opening polymerization reaction between the C3 to C6 lactone compound and a hydroxyl group. In some embodiments of the present invention, the ring-opening polymerization catalyst is diphenyl phosphate.

[0065] The C3-C6 lactone compound refers to a compound having 3 to 6 carbon atoms and an ester group in a cyclic structure. Examples of the C3-C6 lactone compound include β-propiolactone, γ-butyrolactone, δ-valerolactone, and ε-caprolactone, and these compounds can be used alone or in any combination.

[0066] The reaction conditions for the ring-opening polymerization reaction vary depending on the reactants used. For example, using diphenyl phosphate as the ring-opening polymerization catalyst and ε-caprolactone as the C3-C6 lactone compound, the ring-opening polymerization reaction can be carried out at a temperature of 25°C to 45°C for 40 minutes to 6 hours. After completion of the reaction, the product can be extracted with a solvent, and the extract can then be concentrated and dried. Specific preparation methods are described in the accompanying Examples.

[0067] 4. Examples

[0068] The present invention is further illustrated by the following specific embodiments.

[0069] 4.1. Preparation of the substance represented by Formula I

[0070] [Synthesis example 1]

[0071] Take a 1L three-necked round-bottom flask and add 50 grams of the compound represented by Formula IIa (purchased from Qiti Technology), 188 grams of ε-caprolactone (CL), and 2.75 grams of diphenyl phosphate (DPP) as a ring-opening polymerization catalyst in sequence at room temperature and stir evenly. After that, the mixture is maintained at 30°C for 5 hours to react. After confirming the completion of the reaction by high-performance liquid chromatography (HPLC), 500 grams of toluene and 50 grams of 2% sodium bicarbonate aqueous solution are added for extraction. The organic layer obtained by extraction is concentrated to dryness to obtain the substance represented by Formula Ia with a conversion rate of 99%. The reaction mechanism is shown below.

[0072] Further analysis of the substance represented by Formula Ia gave the following results:

[0073] (1) Gel Permeation Chromatography (GPC, model: Waters 1515):

[0074] The molecular weight is 2219, and after calculation, m+n is 16.

[0075] (2) Nuclear Magnetic Resonance Spectrometer Analysis (NMR, Model: VARIAN INOVA 600):

[0076] 1H NMR (CDCl3, 600MHz) δ = 11.78 (s, 1H), 8.09 ~ 8.11 (m, 1H), 7.89 ~ 7.91 (m, 2H), 7.41 ~ 7.46 ( m,2H),7.13~7.47(m,1H),4.00~4.05(m,34H),3.61(t,J=6.0Hz,4H),2.92~2.97(m,9H), 2.27(t,J=6.0Hz,33H),1.59~1.63(m,65H),1.30~1.40(m,34H),0.79~0.83(m,5H)

[0077] (3) Ultraviolet absorption spectrum:

[0078] The absorption spectrum is shown in FIG1 , with characteristic peaks at 303 nm and 343 nm.

[0079] [Synthesis example 2]

[0080] To a 1L three-necked round-bottom flask, 50g of the compound represented by Formula IIa (purchased from QiTi Technology), 2508g of ε-caprolactone, and 55g of diphenyl phosphate as a ring-opening polymerization catalyst were added in sequence at room temperature and stirred uniformly. The mixture was then maintained at 40°C for 2 hours to react. After confirming the completion of the reaction using a high-performance liquid chromatograph, 6500g of toluene and 650g of a 2% aqueous sodium bicarbonate solution were added for extraction. The organic layer obtained from the extraction was concentrated to dryness to obtain the substance represented by Formula Ia with a conversion rate of 50%. The molecular weight obtained by gel permeation chromatography analysis was 11920, and m+n was calculated to be 100.

[0081] [Synthesis example 3]

[0082] To a 1L three-necked round-bottom flask, 50g of the compound represented by Formula IIa (purchased from QiTi Technology), 940g of ε-caprolactone, and 55g of diphenyl phosphate as a ring-opening polymerization catalyst were added in sequence at room temperature and stirred uniformly. The mixture was then maintained at 40°C for 1 hour to react. After confirming the completion of the reaction using a high-performance liquid chromatograph, 1100g of toluene and 110g of a 2% aqueous sodium bicarbonate solution were added for extraction. The organic layer obtained from the extraction was concentrated to dryness to obtain the substance represented by Formula Ia with a conversion rate of 99%. The molecular weight obtained by gel permeation chromatography analysis was 8990, and the calculated m+n was 74.

[0083] [Synthesis Example 4]

[0084] To a 1L three-necked round-bottom flask, 50g of the compound represented by Formula IIa (purchased from QiTi Technology), 225g of ε-caprolactone, and 2.75g of diphenyl phosphate as a ring-opening polymerization catalyst were added in sequence at room temperature and stirred evenly. The mixture was then maintained at 30°C for 3 hours to react. After confirming the completion of the reaction using a high-performance liquid chromatograph, 600g of toluene and 60g of a 2% aqueous sodium bicarbonate solution were added for extraction. The organic layer obtained by extraction was concentrated to dryness to obtain the substance represented by Formula Ia with a conversion rate of 80%. The molecular weight obtained by gel permeation chromatography analysis was 2110, and the calculated m+n was 28.

[0085] 4.2. Solubility and dispersibility test

[0086] 100 g of polycaprolactone polyol was taken as a blank sample and observed at operating temperatures of 25°C, 50°C, and 100°C. Separately, 5 g of the compound of Formula Ia in Synthesis Example 1 or 5 g of the compound of Formula IIa was added to 100 g of polycaprolactone polyol and mixed. The dispersion was observed at operating temperatures of 25°C, 50°C, and 100°C, and the results are recorded in Table 1.

[0087] Table 1: Solubility and dispersibility of the compound of formula Ia and formula IIa in polycaprolactone polyol in Synthesis Example 1

[0088] As shown in Table 1, polycaprolactone polyol is a waxy solid at 25°C and a transparent liquid when heated to 50°C. Table 1 further shows that the polycaprolactone polyol containing the compound of Formula IIa is a liquid containing suspended particles at 50°C and must be heated to 100°C to become a transparent liquid, indicating that the compound of Formula IIa can only be uniformly dissolved and dispersed in the polycaprolactone polyol at 100°C. In contrast, the polycaprolactone polyol containing the compound of Formula Ia from Synthesis Example 1 of the present invention becomes a transparent liquid at 50°C, indicating that the compound of Formula Ia is uniformly dispersed in the polycaprolactone polyol at 50°C. This result clearly demonstrates that the compound of Formula Ia of the present invention has the advantage of low-temperature operation.

[0089] 4.3. Preparation of polymers

[0090] [Example 1]

[0091] 110 g of polycaprolactone polyol (model: PCL-3000 (230N), purchased from Daicel Chemicals, Japan), 15 g of 1,4-butanediol (purchased from Tokyo Chemical Industry), 0.2 wt% (based on the total weight of the reactants) of hindered amine light stabilizer (model: Chiguard 106, purchased from ChiTi Technology), 0.7 wt% (based on the total weight of the reactants) of antioxidant (model: Revonox 5068L, purchased from ChiTi Technology), and 4.3 g of the compound of formula Ia from Synthesis Example 1 were added to a reaction kettle, heated to 50°C, and mixed thoroughly. 20 ppm of dibutyltin dilaurate was then added to the reaction kettle, mixed thoroughly, and heated to 110°C. 52 g of methylene diphenyl diisocyanate (MDI) (available from BASF) was preheated to 110°C and added to the reaction kettle. The mixture was stirred for 1 minute to react and produce a rubber block. The block was then placed in an oven and baked at 70°C for 24 hours to cure, yielding the thermoplastic polyurethane block of Example 1, in which the content of the substance of Formula Ia was 0.5 wt%.

[0092] [Example 2]

[0093] A thermoplastic polyurethane was prepared in the same manner as in Example 1, except that the amount of the substance of Formula Ia in Synthesis Example 1 was adjusted to 8.6 g, to obtain a thermoplastic polyurethane block of Example 2, in which the content of the substance of Formula Ia was 1.0 wt %.

[0094] [Example 3]

[0095] A thermoplastic polyurethane was prepared in the same manner as in Example 1, except that the amount of polycaprolactone polyol was adjusted to 84 g and the amount of the substance of Formula Ia from Synthesis Example 1 was adjusted to 22 g, to obtain a thermoplastic polyurethane block of Example 3, in which the content of the substance of Formula Ia was 3.0 wt %.

[0096] [Comparative Example 1]

[0097] A thermoplastic polyurethane was prepared in the same manner as in Example 1, except that the amount of polycaprolactone polyol was adjusted to 120 g and the substance of Formula Ia in Synthesis Example 1 was not used, to obtain the thermoplastic polyurethane block of Comparative Example 1.

[0098] 4.4. Polymer property testing

[0099] 4.4.1. Preparation of thermoplastic polyurethane test pieces

[0100] Thermoplastic polyurethane test sheets were prepared using the thermoplastic polyurethane blocks from Examples 1, 2, and 3, as well as Comparative Example 1. First, 55 grams of the thermoplastic polyurethane block was placed in a 100°C oven for 2 hours to remove surface moisture and thoroughly dry. Next, the thermoplastic polyurethane block was placed in a 20 cm × 15 cm × 0.15 cm mold and press-formed using a hot press (purchased from Longchang Company) at 190°C for 1.5 minutes at a pressure of 20 kg / cm². The press-formed thermoplastic polyurethane was then placed in a cold press and cooled at a pressure of 50 kg / cm² for 5 to 10 minutes to produce a thermoplastic polyurethane test sheet with a thickness of 0.15 cm.

[0101] 4.4.2. Test instruments and methods

[0102] [Melt flow index (MFI) measurement]

[0103] Prepare a 5-gram thermoplastic polyurethane sample as a test sample. The initial melt index (MFI) of the thermoplastic polyurethane was measured using a melt flow meter (model: GT-7100-MI, available from GOTECH) in accordance with ASTM 1238 under the following conditions: temperature of 200°C, pressure of 5 kg, and measurement of the weight passing through a standard die (2.095 mm diameter) within 10 minutes. The MFI is expressed in grams per 10 minutes (g / 10 min).

[0104] [Hue Detection]

[0105] According to ASTM 1926-70, a spectrocolorimeter (model: ColorQuest XE, purchased from Hunter Lab) was used to measure the initial yellowness index (YI) of the thermoplastic polyurethane test piece.

[0106] [Color difference detection]

[0107] UV-Vis spectrophotometer (Varian 50, purchased from Agilent) was used to test the ΔE of thermoplastic polyurethane test pieces.

[0108] [Light aging and yellowing test (QUV340test)]

[0109] According to ISO 11341, thermoplastic polyurethane specimens were exposed to UV light in an accelerated weathering tester using a xenon lamp for 888 hours. ΔYI and ΔE values ​​were measured after 72, 240, 408, 600, and 888 hours of exposure. Lower values ​​indicate better resistance to yellowing after light aging.

[0110] 4.4.3. Test results

[0111] The properties of the thermoplastic polyurethanes of Examples 1, 2, 3 and Comparative Example 1 were measured according to the aforementioned measurement methods, including melt index (MFI), initial yellowness index (YI), ΔYI and ΔE after UV irradiation, and the results are recorded in Table 2.

[0112] Table 2: Properties of thermoplastic polyurethanes of Examples 1, 2, 3 and Comparative Example 1

[0113] As shown in Table 2, the thermoplastic polyurethane prepared in Comparative Example 1, which did not include the substance of Formula Ia of the present invention as a UV absorber, exhibited poor results in the light aging yellowing test. In contrast, the thermoplastic polyurethanes prepared in Examples 1 to 3, which used the substance of Formula Ia of the present invention as a UV absorber, exhibited excellent light aging resistance. Specifically, Example 1 demonstrates that using 0.5 wt% of the substance of Formula Ia in the preparation of the thermoplastic polyurethane significantly reduced the ΔYI and ΔE values ​​in the light aging yellowing test, demonstrating that the present invention can indeed provide thermoplastic polyurethanes with excellent light aging yellowing resistance. Furthermore, Examples 1 to 3 demonstrate that increasing the amount of the substance of Formula Ia from 0.5 wt% to 3 wt% further improves the ΔYI and ΔE performance of the resulting thermoplastic polyurethanes.

[0114] The above embodiments are intended only to illustrate the principles and efficacy of the present invention and to illustrate the technical features of the present invention, and are not intended to limit the scope of protection of the present invention. Any modifications or arrangements that can be readily accomplished by a person skilled in the art without violating the technical principles of the present invention are within the scope of the present invention.

Claims

1. A substance represented by formula I, in, R1 is H or Cl; A is C 2 To C 5 Alkylene; B is C 2 To C 5 Alkylene; and m+n is an integer from 2 to 120, and both m and n are not 0.

2. The substance according to claim 1, It is characterized in that A and B are each independently C 5 Alkyl stretching.

3. The substance according to claim 1, It is characterized in that m and n are each independently an integer from 1 to 50.

4. Use of a substance as claimed in any one of claims 1 to 3, It is characterized in that It acts as a UV light absorber.

5. A polymer precursor composition, It is characterized in that Include: A polymerizable monomer; and a substance as claimed in any one of claims 1 to 3.

6. The polymer precursor composition according to claim 5, It is characterized in that The polymerizable monomers include polyols and polyisocyanates.

7. The polymer precursor composition according to claim 5, It is characterized in that It further comprises additives selected from the following groups: solvents, catalysts, antioxidants, fillers, solubilizers, flame retardants, heat stabilizers, light stabilizers, metal deactivators, plasticizers, lubricants, emulsifiers, dyes, pigments, brighteners, antistatic agents, foaming agents, chain extenders, anti-hydrolysis agents, surfactants, crosslinking agents, photoinitiators, pH adjusters, adhesion promoters, bactericides, and combinations thereof.

8. A polymer, It is characterized in that It comprises a structure derived from a substance as claimed in any one of claims 1 to 3.

9. The polymer according to claim 8, It is characterized in that The material is selected from the following group: polyurethane, polyester, polycarbonate, epoxy resin, amino resin, polyamide, polyimide, liquid crystal polymer, polyoxymethylene, polysilicone, polymethacrylate copolymer, polyacrylate copolymer, and composites thereof.

10. A product that can resist ultraviolet light, It is characterized in that The method comprises using the substance as claimed in any one of claims 1 to 3 as an ultraviolet light absorber.

11. The article according to claim 10, It is characterized in that The article is selected from the group consisting of plastics, coatings, inks, displays, lamps, optical films, optical lenses, goggles, glasses, contact lenses, textiles, pressure-sensitive adhesives, and sunscreens.

12. The article according to claim 10, It is characterized in that The product also contains additives selected from the following groups: solvents, catalysts, antioxidants, fillers, solubilizers, flame retardants, heat stabilizers, light stabilizers, metal deactivators, plasticizers, lubricants, emulsifiers, dyes, pigments, brighteners, antistatic agents, foaming agents, chain extenders, anti-hydrolysis agents, surfactants, crosslinking agents, photoinitiators, pH adjusters, adhesion promoters, bactericides, and combinations thereof.

13. A method for preparing an article that can resist ultraviolet light, It is characterized in that The product comprises a substance as claimed in any one of claims 1 to 3.

14. A method for preparing a substance as claimed in any one of claims 1 to 3, It is characterized in that The method comprises the steps of: reacting a compound represented by formula II with C in the presence of a ring-opening polymerization catalyst; 3 To C 6 Lactone compound reaction, Wherein R1 is H or Cl.

15. The method of claim 14, It is characterized in that The ring-opening polymerization catalyst is diphenyl phosphate.

16. The method of claim 14, It is characterized in that The C 3 To C 6 The lactone compound is selected from the group consisting of β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, and combinations thereof.

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