Ultraviolet light absorbing substance and preparation method and application thereof

Abstract

The invention provides a substance shown in the following formula I, in which R1 is H or Cl, A is C2-C5 alkyl, and B is C2-C5 alkyl. M + n is an integer from 2 to 120, and both m and n are not 0. The substance can be used as an ultraviolet absorber. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a substance that can be used for ultraviolet light absorption, and particularly 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 prone to degradation under ultraviolet light irradiation. Therefore, it has been conventionally known to use an ultraviolet light absorber (UVA) in combination with polymer materials to provide protection against ultraviolet light.

[0003] Taking polyurethane as an example, it is an important polymer formed by the polymerization of polyols and isocyanates. By adjusting the ratio of raw materials, materials with desired mechanical properties such as abrasion resistance, temperature resistance, flexibility, extensibility, etc. can be manufactured, such as coatings, elastomers, foamed materials, adhesives, sealants, etc. However, polyurethane materials are prone to degradation under ultraviolet light irradiation, so they deteriorate particularly rapidly in an environment with strong outdoor light. To avoid the degradation caused by ultraviolet light, an ultraviolet light absorber can be physically mixed into the polyurethane. Among them, benzotriazole (BTZ)-type ultraviolet light absorbers are the most widely used.

[0004] However, the physically mixed ultraviolet light absorber is prone to migration in the polyurethane material, which may cause blooming of the polyurethane material or damage the surface properties of the polyurethane material. For example, it may make the surface of the polyurethane material sticky or even cause fading of the applied product. Therefore, how to improve the compatibility of the ultraviolet light absorber in the polyurethane material to avoid or reduce migration has become an important issue in the development of ultraviolet light absorbers. Generally speaking, the compatibility of the ultraviolet light absorber in the polyurethane material can be improved in the following two ways to reduce or avoid the migration of the ultraviolet light absorber.

[0005] The first way is to increase the molecular weight of the ultraviolet light absorber. For example, the technologies disclosed in US 4,853,471 and US 7,381,762 slow down the migration rate of the ultraviolet light absorber molecules in the polyurethane material by increasing the molecular weight of the ultraviolet light absorber molecules. However, this method can only slow down the migration rate and cannot effectively avoid migration. Moreover, increasing the molecular weight of the ultraviolet light absorber will correspondingly reduce the effective content of the ultraviolet light absorber, so the dosage of the ultraviolet light absorber must be increased to provide a comparable anti-ultraviolet effect.

[0006] The second method is to synthesize the ultraviolet light absorber into a reactive ultraviolet light absorber. Through the hydroxyl groups contained therein participating in the polymerization reaction during the synthesis of polyurethane, the ultraviolet light absorber is incorporated into the polyurethane structure in a chemical bonding manner. Examples of such reactive ultraviolet light absorbers include those disclosed in US 5,459,222 and TW I638039.

[0007] In terms of efficacy, the second method can more effectively solve the migration problem of the ultraviolet light absorber. However, the reactive ultraviolet light absorbers disclosed in the prior art still cannot have the advantages of being operable at low temperatures (flowable and easily soluble and dispersible at low temperatures of 40°C to 50°C), having good thermal stability, and excellent ultraviolet light absorption effect. SUMMARY OF THE INVENTION

[0008] In view of the foregoing technical problems, the present invention provides a substance capable of absorbing ultraviolet light, which has a benzotriazole group and a polyol structure. The substance can be directly bonded to the polymer structure in a chemical bonding manner, so the migration problem of the ultraviolet light absorber can be solved. In addition, the substance has the advantages of being operable at low temperatures (flowable and easily soluble and dispersible at low temperatures of 40°C to 50°C, for example, easily soluble and dispersible in polyols), having good thermal stability, and excellent ultraviolet light absorption effect.

[0009] Therefore, an object of the present invention is to provide a substance represented by Formula I,

[0010]

[0011] wherein,

[0012] R1 is H or Cl;

[0013] A is C 2 to C 5 alkylene;

[0014] B is C 2 to C 5 alkylene; and

[0015] m + n is an integer from 2 to 120, and neither m nor n is 0.

[0016] In some embodiments of the present invention, A and B are each independently C 5 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 above-mentioned 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 additives selected from the group consisting of: 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, hydrolysis inhibitors, surfactants, crosslinking agents, photoinitiators, pH regulators, adhesion promoters, fungicides, 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: polyurethanes, polyesters, polycarbonates, epoxy resins, amino resins, polyamides, polyimides, liquid crystal polymers, polyacetals, polysiloxanes, polymethacrylate copolymers, polyacrylate copolymers, and composites thereof.

[0024] Another object of the present invention is to provide an article resistant to ultraviolet light, which uses the substance of formula I above as an ultraviolet light absorber. In addition to the substance of formula I, the article 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 additives selected from the group consisting of: 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, hydrolysis inhibitors, surfactants, crosslinking agents, photoinitiators, pH regulators, adhesion promoters, fungicides, and combinations thereof.

[0027] Another object of the present invention is to provide a method for preparing an article resistant to ultraviolet light, which comprises using the substance of formula I above in the article.

[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 C in the presence of a ring-opening polymerization catalyst 3 to C6 Reaction of lactone compounds, where R1 is H or Cl.

[0029]

[0030] In some embodiments of the present invention, the ring-opening polymerization catalyst is diphenyl phosphate.

[0031] In some embodiments of the present invention, the C 3 to C 6 The lactone compounds are selected from the group consisting of: β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, and combinations thereof.

[0032] To make the above objects, technical features and advantages of the present invention more obvious and understandable, the following will be described in detail with some specific embodiments. Brief Description of the Drawings

[0033] Figure 1 It is the ultraviolet absorption spectrum of the substance synthesized in Synthesis Example 1. Detailed Description of the Embodiments

[0034] The following will specifically describe some specific embodiments according to the present invention; however, the present invention can be practiced in many different forms and should not be construed as limited to what is stated in the specification.

[0035] Unless otherwise specified, the terms "a", "the" and similar terms used in this specification and claims should be understood to include both singular and plural forms.

[0036] The inventors of the present invention have found that a substance having a structure of benzotriazole group and polyol can be synthesized by a simple method. In addition to solving the migration problem of existing ultraviolet absorbers, this substance also has the advantages of being operable at low temperature (it can flow and be easily dissolved and dispersed at a low temperature of 40 °C to 50 °C, for example, it is easily dissolved and dispersed in polyol), good thermal stability, excellent ultraviolet resistance effect, etc. Therefore, it is suitable for various fields that need to resist ultraviolet light. The following provides a detailed description of the substance of the present invention, its preparation method and application.

[0037] 1. The substance represented by Formula I

[0038] In the present invention, the substance represented by Formula I has the following structure:

[0039]

[0040] In Formula I, R1 is H or Cl; A is C 2 to C 5 alkylene; B is C 2 to C 5An alkylene group; and m + n is an integer from 2 to 120, and neither m nor n is 0.

[0041] The C 2 to C 5 The alkylene group refers to a divalent group formed by removing one hydrogen atom from each of two carbons of an alkyl group. In the present invention, A and B are each independently a C 2 to C 5 alkylene group, and in the case where n > 1, each A may be the same or different, and in the case where m > 1, each B may be the same or different. In some embodiments of the present invention, the C 2 to C 5 alkylene group is a C 2 to C 5 linear alkylene group, and examples thereof include ethylene, propylene, butylene, and pentylene. In some embodiments of the present invention, A and B are each independently a C 5 alkylene group, preferably a C 5 linear alkylene group, namely pentylene.

[0042] m and n respectively represent the number of structural units in the parentheses. In the present invention, m + n is an integer from 2 to 120, and neither m nor n is 0. m + n is preferably an integer from 10 to 100, such as 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 within the range formed by any two of the foregoing values.

[0043] 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 obtained by reacting a compound represented by the following formula II with C 3 to C 6The lactone compound is prepared by polymerization in the presence of a ring-opening polymerization catalyst. Under this reaction mechanism, it is expected that m and n in Formula I can be substantially the same. Therefore, in some embodiments of the present invention, m and n are each independently an integer from 1 to 60, preferably each independently an integer from 1 to 50, such as 1, 2, 3, 4, 5, 6, 7, 8, 9, 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, or 50, or within the range formed by any two of the foregoing values.

[0044]

[0045] The substance represented by Formula I of the present invention has a benzotriazole group (i.e., ) and the structure of a polyol, especially a long-chain polyol structure. Without being limited by theory, it is believed that these structures can provide at least the following advantages: good dispersibility can be achieved at low operating temperatures (e.g., at 50 °C); excellent hydrolysis resistance can be provided; alkalinity and excellent solubility in alcohols can be provided, enabling the substance to dissolve in alcohols at low temperatures. Moreover, since the polyol is a main raw material for forming some polymers (such as polyurethanes), this compound is particularly applicable to such polymers; excellent thermal stability and anti-ultraviolet effect can be provided.

[0046] 2. Applications of the Substance Represented by Formula I

[0047] 2.1. Use as an Ultraviolet Light Absorbent

[0048] The substance represented by Formula I can absorb ultraviolet light and is therefore suitable for use as an ultraviolet light absorbent in various fields that require protection against ultraviolet light.

[0049] 2.2. Polymer Precursor Composition

[0050] 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, which comprises a polymerizable monomer and the substance represented by Formula I.

[0051] The polymerizable monomer refers to any compound that can react with each other and preferably can react with the substance represented by Formula I to form a polymer. Preferably, the polymerizable monomer can react with the substance represented by Formula I such that the formed polymer contains a structure derived from the substance represented by Formula I.

[0052] In some embodiments of the present invention, the polymer precursor composition is a polyurethane precursor composition, and the polymerizable monomer comprises a polyol and a polyisocyanate. Examples of the polyol include, but are not limited to, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, glycerol, trimethylolpropane, pentaerythritol, and ring-opening products of lactones. The foregoing polyols can be used alone or in any combination. Examples of the polyisocyanate include, but are not limited to, methylene diphenyldiisocyanate (MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), cyclohexane diisocyanate (CHDI), tetramethylxylylene diisocyanate (TMXDI), 1,3-bis(isocyanatomethyl)cyclohexane (H 6 XDI), isophorone diisocyanate (IPDI), and methylene bis(4-cyclohexylisocyanate) (HMDI). The foregoing polyisocyanates can be used alone or in any combination.

[0053] In the polymer precursor composition of the present invention, the contents of the polymerizable monomer and the substance represented by Formula I are not particularly limited and can be adjusted according to the properties of the desired polymer material, the type of polymerizable monomer used, and the desired ultraviolet light resistance effect. For example, in an embodiment where the above polymer precursor composition is a polyurethane precursor composition, based on the total weight of the polymerizable monomer (including polyol, polyisocyanate) and the substance represented by Formula I, the content of the substance represented by Formula I can be 0.1% by weight to 30% by weight, more specifically 0.5% by weight to 3% by weight, such as 0.1% by weight, 0.5% by weight, 1% by weight, 1.5% by weight, 2% by weight, 2.5% by weight, 3% by weight, 3.5% by weight, 4% by weight, 4.5% by weight, 5% by weight, 5.5% by weight, 6% by weight, 6.5% by weight, 7% by weight, 7.5% by weight, 8% by weight, 8.5% by weight, 9% by weight, 9.5% by weight, 10% by weight, 10.5% by weight, 11% by weight, 11.5% by weight, 12% by weight, 12.5% by weight, 13% by weight, 13.5% by weight, 14% by weight, 14.5% by weight, 15% by weight, 15.5% by weight, 16% by weight, 16.5% by weight, 17% by weight, 17.5% by weight, 18% by weight, 18.5% by weight, 19% by weight, 19.5% by weight, 20% by weight, 20.5% by weight, 21% by weight, 21.5% by weight, 22% by weight, 22.5% by weight, 23% by weight, 23.5% by weight, 24% by weight, 24.5% by weight, 25% by weight, 25.5% by weight, 26% by weight, 26.5% by weight, 27% by weight, 27.5% by weight, 28% by weight, 28.5% by weight, 29% by weight, 29.5% by weight, or 30% by weight, or within the range formed by any two of the above values, but the present invention is not limited thereto.

[0054] Without departing from the technical principle of the present invention, the polymer precursor composition of the present invention can further include optional components as needed to improve the processability of the polymer precursor composition during the manufacturing process, or to promote the polymerization reaction, or to specifically improve the properties of the polymer material. Examples of the aforementioned optional components include, but are not limited to, 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, hydrolysis inhibitors, surfactants, crosslinking agents, photoinitiators, pH regulators, adhesion promoters, and fungicides. These optional components can be used alone or in any combination.

[0055] 2.3. Polymer

[0056] The present invention also provides a polymer that includes the substance represented by Formula I, or includes a structure derived from the substance represented by Formula I.

[0057] There are no special restrictions on the types of polymers of the present invention. Examples thereof include, but are not limited to, polyurethanes, polyesters, polycarbonates, epoxy resins, amino resins, polyamides, polyimides, liquid crystal polymers, polyoxymethylenes, polysiloxanes, polymethacrylate copolymers, polyacrylate copolymers, or composites of the foregoing.

[0058] There are no special restrictions on the preparation method of the polymers of the present invention. For example, the polymer precursor composition described above can be reacted by methods such as melt polymerization or solution polymerization to obtain the polymers. Those skilled in the art to which the present invention pertains can prepare the polymers using existing methods based on the disclosure of the present specification. The preparation of polyurethanes will be illustrated in the appended examples and will not be elaborated herein.

[0059] 2.4. Articles Resistant to Ultraviolet Light

[0060] The present invention also provides an article in which the substance represented by Formula I is used as an ultraviolet light absorber, so it can resist ultraviolet light. The article can further use other existing ultraviolet light absorbers in the art.

[0061] The types of articles of the present invention that can resist ultraviolet light can be any articles that are expected to have the performance of resisting ultraviolet light. Examples of such articles include, but are not limited to, plastics, coatings, inks, displays, lamps, optical films, optical lenses, goggles, glasses, contact lenses, textiles, pressure-sensitive adhesives, and sunscreen products.

[0062] The articles that can resist ultraviolet light can optionally further contain existing additives to specifically improve the properties of the articles. Examples of the foregoing additives include, but are not limited to, 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, hydrolysis inhibitors, surfactants, crosslinking agents, photoinitiators, pH regulators, adhesion promoters, and fungicides. These selected components can be used alone or in any combination.

[0063] 2.5. Method for Preparing Articles Resistant to Ultraviolet Light

[0064] The present invention also provides a method for preparing an article resistant to ultraviolet light, which is characterized in that the substance represented by Formula I is used in the preparation process of the article to provide the function of resisting ultraviolet light. Taking polymer materials as an example, the substance represented by Formula I can be added as a reaction monomer during the preparation process, and then the obtained polymer material can be used as all the constituent materials of the article, or only part of the constituent materials (for example, only the constituent materials on the surface of the article) to endow the article with the function of resisting ultraviolet light.

[0065] 3. Method for Preparing the Substance Represented by Formula I

[0066] The substance of formula I according to the present invention can be prepared by the following method. In the presence of a ring-opening polymerization catalyst, a compound of formula II is reacted with a C 3 to C 6 lactone compound, wherein R1 is H or Cl.

[0067]

[0068] The ring-opening polymerization catalyst refers to a catalyst capable of catalyzing the ring-opening polymerization reaction between the C 3 to C 6 lactone compound and the hydroxyl group. In some embodiments of the present invention, the ring-opening polymerization catalyst is diphenyl phosphate.

[0069] The C 3 to C 6 lactone compound refers to a compound having 3 to 6 carbons and an ester group in the cyclic structure. Examples of the C 3 to C 6 lactone compound include β-propiolactone, γ-butyrolactone, δ-valerolactone, and ε-caprolactone, and these compounds can be used alone or in any combination.

[0070] The reaction conditions of the ring-opening polymerization reaction depend on the reactants used. Taking diphenyl phosphate as the ring-opening polymerization catalyst and the C 3 to C 6 lactone compound being ε-caprolactone as an example, 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 the reaction is completed, extraction can be carried out with a solvent, and then the extract is concentrated and dried. The specific preparation method is shown in the attached examples.

[0071] 4. Examples

[0072] The present invention will now be further illustrated by the following specific embodiments.

[0073] 4.1. Preparation of the substance of formula I

[0074] [Synthesis Example 1]

[0075] Take a 1 L three-necked round-bottom flask and sequentially add 50 g of the compound shown in Formula IIa (purchased from Qitai Technology), 188 g of ε-caprolactone (CL), and 2.75 g of diphenyl phosphate (DPP) as a ring-opening polymerization catalyst at room temperature, and stir evenly. Then, maintain the mixture at 30 °C for 5 hours to carry out the reaction. After confirming the completion of the reaction by High Performance Liquid Chromatography (HPLC), add 500 g of toluene and 50 g of 2% aqueous sodium bicarbonate solution for extraction. Concentrate the obtained organic layer to dryness to obtain the substance shown in Formula Ia, with a conversion rate of 99%. The reaction mechanism is as shown below.

[0076]

[0077] Further analysis of the substance shown in Formula Ia gave the following results:

[0078] (1) Gel Permeation Chromatography (GPC, model: Waters1515):

[0079] The molecular weight was 2219. After calculation, m + n was 16.

[0080] (2) Nuclear Magnetic Resonance (NMR, model: VARIAN INOVA 600):

[0081] 1H NMR (CDCl 3 , 600 MHz) δ = 11.78 (s, 1H), 8.09 - 8.11 (m, 1H),

[0082] 7.89 - 7.91 (m, 2H), 7.41 - 7.46 (m, 2H), 7.13 - 7.47 (m, 1H),

[0083] 4.00 - 4.05 (m, 34H), 3.61 (t, J = 6.0 Hz, 4H), 2.92 - 2.97 (m, 9H),

[0084] 2.27 (t, J = 6.0 Hz, 33H), 1.59 - 1.63 (m, 65H), 1.30 - 1.40 (m,

[0085] 34H), 0.79 - 0.83 (m, 5H)

[0086] (3) Ultraviolet absorption spectrum:

[0087] The absorption spectrum is as Figure 1 shown, with characteristic peaks at 303 nm and 343 nm.

[0088] [Synthesis Example 2]

[0089] Take a 1 L three-necked round-bottom flask and sequentially add 50 g of the compound shown in Formula IIa (purchased from Qitai Technology), 2508 g of ε-caprolactone, and 55 g of diphenyl phosphate as a ring-opening polymerization catalyst at room temperature, and stir evenly. Then, maintain the mixture at 40 °C for 2 hours to carry out the reaction. After confirming the completion of the reaction by high-performance liquid chromatography, add 6500 g of toluene and 650 g of 2% sodium bicarbonate aqueous solution for extraction. Concentrate the obtained organic layer to dryness to obtain the substance shown in Formula Ia, with a conversion rate of 50%. The molecular weight analyzed by gel permeation chromatography is 11920, and after calculation, m + n is 100.

[0090] [Synthesis Example 3]

[0091] Take a 1 L three-necked round-bottom flask and sequentially add 50 g of the compound shown in Formula IIa (purchased from Qitai Technology), 940 g of ε-caprolactone, and 55 g of diphenyl phosphate as a ring-opening polymerization catalyst at room temperature, and stir evenly. Then, maintain the mixture at 40 °C for 1 hour to carry out the reaction. After confirming the completion of the reaction by high-performance liquid chromatography, add 1100 g of toluene and 110 g of 2% sodium bicarbonate aqueous solution for extraction. Concentrate the obtained organic layer to dryness to obtain the substance shown in Formula Ia, with a conversion rate of 99%. The molecular weight analyzed by gel permeation chromatography is 8990, and after calculation, m + n is 74.

[0092] [Synthesis Example 4]

[0093] Take a 1 L three-necked round-bottom flask and sequentially add 50 g of the compound shown in Formula IIa (purchased from Qitai Technology), 225 g of ε-caprolactone, and 2.75 g of diphenyl phosphate as a ring-opening polymerization catalyst at room temperature, and stir evenly. Then, maintain the mixture at 30 °C for 3 hours to carry out the reaction. After confirming the completion of the reaction by high-performance liquid chromatography, add 600 g of toluene and 60 g of 2% sodium bicarbonate aqueous solution for extraction. Concentrate the obtained organic layer to dryness to obtain the substance shown in Formula Ia, with a conversion rate of 80%. The molecular weight analyzed by gel permeation chromatography is 2110, and after calculation, m + n is 28.

[0094] 4.2. Dissolution and Dispersion Test

[0095] 100 g of polycaprolactone polyol was taken as a blank sample and observed at operating temperatures of 25 °C, 50 °C, and 100 °C. Additionally, 5 g of the compound of Formula Ia of Synthesis Example 1 or 5 g of the compound of Formula IIa was added to 100 g of polycaprolactone polyol and mixed, and the dispersion was observed at operating temperatures of 25 °C, 50 °C, and 100 °C, and the results were recorded in Table 1.

[0096] Table 1: Solubility and Dispersion of the Compound of Formula Ia of Synthesis Example 1 and the Compound of Formula IIa in Polycaprolactone Polyol

[0097]

[0098] As shown in Table 1, polycaprolactone polyol was a waxy solid at 25 °C and a transparent liquid when heated to 50 °C. Table 1 further shows that the polycaprolactone polyol with the addition of the compound of Formula IIa was a liquid containing suspended particles at 50 °C and became a transparent liquid only when heated to 100 °C, indicating that the compound of Formula IIa could be uniformly dissolved and dispersed in polycaprolactone polyol only at 100 °C. In contrast, the polycaprolactone polyol with the addition of the compound of Formula Ia of Synthesis Example 1 of the present invention was a transparent liquid at 50 °C, indicating that the compound of Formula Ia was uniformly dispersed in polycaprolactone polyol at 50 °C. This result fully shows that the compound represented by Formula Ia of the present invention has the advantage of being operable at low temperatures.

[0099] 4.3. Preparation of Polymer

[0100] [Example 1]

[0101] 110 g of polycaprolactone polyol (Model: PCL - 3000(230N), purchased from Daicel Chemical Industries, Ltd., 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 Qitai Technology), 0.7 wt% (based on the total weight of the reactants) of antioxidant (Model: Revonox 5068L, purchased from Qitai Technology), and 4.3 g of the compound of Formula Ia of Synthesis Example 1 were added to a reaction iron tank, heated to 50 °C and mixed evenly. Then, 20 ppm of dibutyltin dilaurate was added to the reaction iron tank and mixed evenly, and heated to 110 °C. Additionally, 52 g of methylenediphenyl diisocyanate (MDI) (purchased from BASF) was preheated to 110 °C and then added to the reaction iron tank and stirred for 1 minute to carry out the reaction to obtain a rubber block. Thereafter, the rubber block was placed in an oven and baked at 70 °C for 24 hours for aging to obtain the thermoplastic polyurethane rubber block of Example 1, wherein the content of the compound of Formula Ia was 0.5 wt%.

[0102] [Example 2]

[0103] The 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, and a thermoplastic polyurethane rubber block of Example 2 was obtained, wherein the content of the substance of Formula Ia was 1.0% by weight.

[0104] [Example 3]

[0105] The 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 in Synthesis Example 1 was adjusted to 22 g, and a thermoplastic polyurethane rubber block of Example 3 was obtained, wherein the content of the substance of Formula Ia was 3.0% by weight.

[0106] [Comparative Example 1]

[0107] The 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, and a thermoplastic polyurethane rubber block of Comparative Example 1 was obtained.

[0108] 4.4. Properties testing of polymers

[0109] 4.4.1. Preparation of thermoplastic polyurethane specimens

[0110] Thermoplastic polyurethane specimens were prepared using the thermoplastic polyurethane rubber blocks of Example 1, 2, 3 and Comparative Example 1, respectively. First, 55 g of the thermoplastic polyurethane rubber block was placed in an oven at 100 °C for 2 hours to remove surface moisture and was thoroughly dried. Then, the thermoplastic polyurethane rubber block was placed in a mold of 20 cm × 15 cm × 0.15 cm, and hot pressing was carried out using a hot press (purchased from Longchang Company) at a pressure of 20 kg / cm² at 190 °C for 1.5 minutes. Then, the hot-pressed thermoplastic polyurethane was placed in a cold press and cooled at a pressure of 50 kg / cm² for 5 to 10 minutes to obtain a thermoplastic polyurethane specimen with a thickness of 0.15 cm.

[0111] 4.4.2. Testing instruments and methods

[0112] [Measurement of melt flow index (MFI)]

[0113] Prepare 5 grams of thermoplastic polyurethane as a test sample. According to ASTM-1238, use a melt flow rate tester (model: GT-7100-MI, purchased from GOTECH) to measure the initial melt flow index MFI of the thermoplastic polyurethane under the following conditions: the temperature is 200 °C, the pressure is 5 kilograms, and measure the weight passing through a standard orifice (diameter 2.095 mm) within 10 minutes. The unit of the melt flow index MFI is grams per 10 minutes (g / 10min).

[0114] [Hue detection]

[0115] According to ASTM 1926-70, use a spectrophotometric colorimeter (model: ColorQuest XE, purchased from Hunter Lab) to test the initial yellow index (yellow index, YI) of the thermoplastic polyurethane test piece.

[0116] [Color difference detection]

[0117] Use an ultraviolet-visible spectrophotometer (UV-Vis spectrophotometer) (model: Varian 50, purchased from Agilent) to test the ΔE of the thermoplastic polyurethane test piece.

[0118] [Lightfastness yellowing test (QUV340 test)]

[0119] According to ISO 11341, use a xenon lamp to expose the thermoplastic polyurethane test piece to an artificial accelerated aging test machine and irradiate it with ultraviolet light for 888 hours, and measure the ΔYI value and ΔE value of the thermoplastic polyurethane test piece after 72 hours, 240 hours, 408 hours, 600 hours, and 888 hours of irradiation respectively. The lower the value, the better the lightfastness yellowing performance.

[0120] 4.4.3. Test results

[0121] Measure the properties of the thermoplastic polyurethanes of Examples 1, 2, 3 and Comparative Example 1 according to the measurement methods described above, including the melt flow index MFI, the initial yellow index YI, ΔYI and ΔE after ultraviolet light irradiation, and record the results in Table 2.

[0122] Table 2: Properties of the thermoplastic polyurethanes of Examples 1, 2, 3 and Comparative Example 1

[0123]

[0124] As shown in Table 2, in Comparative Example 1, the compound of formula Ia of the present invention was not added as an ultraviolet light absorber, and the light aging yellowing test results of the prepared thermoplastic polyurethane were not good; in contrast, in Examples 1 to 3, the compound of formula Ia of the present invention was used as an ultraviolet light absorber, and the prepared thermoplastic polyurethane had excellent light aging resistance. Specifically, Example 1 showed that when 0.5% by weight of the compound of formula Ia was used in the preparation of thermoplastic polyurethane, the ΔYI and ΔE of the light aging yellowing test could be significantly reduced, indicating that the present invention can indeed provide the advantage of good light aging yellowing resistance for thermoplastic polyurethane. In addition, Examples 1 to 3 showed that as the addition amount of the compound of formula Ia increased from 0.5% by weight to 3% by weight, the prepared thermoplastic polyurethane could further have better ΔYI and ΔE performance.

[0125] The above examples are only illustrative of the principles and effects of the present invention and illustrate the technical features of the present invention, rather than limiting the protection scope of the present invention. Any changes or arrangements that can be easily completed by those skilled in the art without departing from the technical principles of the present invention fall within the scope claimed by the present invention.

Claims

1. A substance represented by formula I, in, R1 is H or Cl; A is a C2 to C5 alkylene group; B is C2 to C5 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, characterized in that A and B are each independently C5 alkylene.

3. The substance according to claim 1, 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, characterized in that It acts as a UV light absorber.

5. A polymer precursor composition, 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, characterized in that The polymerizable monomers include polyols and polyisocyanates.

7. The polymer precursor composition according to claim 5, 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, 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, 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 capable of resisting ultraviolet light, 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, 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, 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 a product that can resist ultraviolet light, 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, characterized in that The method 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.

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

16. The method according to claim 14, characterized in that The C3 to C6 lactone compound is selected from the following group: β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, and combinations thereof.

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