TWI633079B - Ultraviolet absorber and plastic article having the ultraviolet absorber - Google Patents

Abstract

The invention relates to an ultraviolet absorber and a plastic product having the ultraviolet absorber, wherein the ultraviolet absorber is an ultraviolet absorber not containing N-methylaniline residue, and the plastic product having the ultraviolet absorber does not release toxic N-methylaniline. By converting harmful ultraviolet energy into harmless heat release, it can prevent or slow down the aging and degradation of plastic products caused by ultraviolet radiation, thus maintaining the color stability and mechanical property maintenance rate of plastic products, thereby prolonging the plastic products. Durability.

Description

Ultraviolet absorber and plastic product having the same

The present invention relates to an ultraviolet absorber, and more particularly to an ultraviolet absorber for a plastic article.

Photodegradation often occurs in organic synthetic resin products, natural resin products and polymerizable organic polymer products (hereinafter collectively referred to as "plastic products") exposed to light, especially ultraviolet radiation, which easily causes yellowing and physicality of the plastic products. The phenomenon of deterioration of performance affects the durability of the plastic product, among which, in particular, some plastic products of light-sensitive organic materials, such as polyurethane, polystyrene, etc., the photodegradation causes discoloration and/or discoloration of the product and makes Product properties are declining. In order to solve the above problems, a UV absorber is added during the manufacturing process or processing of various plastic products to achieve the effect of inhibiting photodegradation and slowing down the deterioration of plastic products.

A variety of compounds related to the formamidine ultraviolet absorber are known today. For example, U.S. Patent 4,041,471 discloses a formamidine compound as a UV absorber, the most well known in the art is Givsorb UV-1 [N-(Ethoxycarbonylphenyl)-N'-methyl-N'-phenylformamidine. ; N-(ethoxycarbonylphenyl)-N'-methyl-N'-phenylformamidine; CAS No.: 57834-33-0], because UV-1 is a viscous liquid at normal temperature, operation It is very convenient to use and measure, so it is often used in the polyurethane industry. However, UV-1 has the following disadvantages. Firstly, because the high-purity UV-1 melting point is about 28~30°C, it is easy to cause crystallization solidification after long-term storage, so it is still used before use. It must be preheated into a liquid before it can be conveniently used. Secondly, since one of the raw materials for synthesizing UV-1 is N-methylaniline, in addition to the trace amount of N-methylaniline remaining in the synthesized UV-1, UV is -1 is added to the plastic product, no matter in the synthesis reaction stage or the processing stage of the plastic product, a small amount of N-methylaniline is released, resulting in the N-methylaniline exceeding the standard in the final formed plastic product, for some For the limited application of N-methylaniline, UV-1 cannot be used as a UV absorber. In particular, the Toy Directive (2009/EC/48) issued by the European Union has expressly restricted N-methylaniline and N-ethylaniline. Used in children's toys. In view of the above defects of UV-1 remaining N-methylaniline, the present invention discloses an ultraviolet absorber completely free of N-methylaniline, and also does not produce N-methylaniline for the plastic article. UV absorber.

The present invention provides a compound represented by the formula (1), In the formula (1), R ₁ represents a C _1-6 alkoxycarbonyl group; R ₂ represents a hydrogen atom, a C _1-6 alkyl group, an N,N'-dimethylamino group, a halogen atom, a C _1-6 alkane Alkoxycarbonyl; A and B respectively represent a hydrogen atom, a chlorine atom, a methoxy group; X represents an oxygen atom or a nitrogen atom; R ₃ represents a linear or branched C _1-5 alkyl group; and R ₄ represents a hydrogen atom. , formazan, C _1-12 alkylcarbonyl, Wherein R ₅ is a hydrogen atom, a C _1-2 alkoxy group or a halogen atom.

The compound represented by the formula (1) can be added during the synthesis of the material, or added during the processing of the latter product, and used as a UV absorber in a plastic product.

The present invention further provides a plastic article comprising the compound represented by the formula (1) as an ultraviolet absorber. The plastic product of the present invention contains the compound represented by the formula (1), so that the plastic article has high ultraviolet resistance and increases its durability in the need of exposure to ultraviolet rays, and does not release toxic N-methyl groups. Aniline can therefore extend the use of the ultraviolet absorber and the plastic article containing the ultraviolet absorber.

The embodiments of the present invention are described by way of specific examples, and those skilled in the art can readily understand the advantages and functions of the present invention from the disclosure. The present invention may be embodied or applied by other different embodiments, and the various details of the present invention may be variously modified and changed without departing from the spirit and scope of the invention.

The present invention provides a compound represented by the formula (1), In the formula (1), R ₁ represents a C _1-6 alkoxycarbonyl group; R ₂ represents a hydrogen atom, a C _1-6 alkyl group, an N,N'-dimethylamino group, a halogen atom, a C _1-6 alkane Alkoxycarbonyl; A and B respectively represent a hydrogen atom, a chlorine atom, a methoxy group; X represents an oxygen atom or a nitrogen atom; R ₃ represents a linear or branched C _1-5 alkyl group; and R ₄ represents a hydrogen atom. , formazan, C _1-12 alkylcarbonyl, Wherein R ₅ is a hydrogen atom, a C _1-2 alkoxy group or a halogen atom.

The compound of the formula (1) of the present invention is synthesized by the following synthetic route: Wherein R ₁ , R ₂ , A, B, X, R ₃ , R ₄ and R ₅ are the same as the formula (1).

In a specific embodiment, in the compound of the formula (1), R ₁ is an ethoxycarbonyl group, R ₂ , A and B are each a hydrogen atom, X is an oxygen atom, and R ₃ is an ethyl group.

For example, the compound of the formula (1) of the present invention has the structures of the following formulas (A-1) to (A-5):

In one embodiment, in the compound of the formula (1), R ₁ is an ethoxycarbonyl group, R ₂ , A and B are each a hydrogen atom, X is a nitrogen atom, and R ₃ is an ethyl group. For example, the compound of the formula (1) of the present invention has the structures of the following formulas (B-1) to (B-3):

In one embodiment, in the compound of the formula (1), R ₁ is an ethoxycarbonyl group, R ₂ , A and B are each a hydrogen atom, X is an oxygen atom, and R ₃ is an isopropyl group. For example, the compound of the formula (1) of the present invention has a structure of the following formula (C-1) to (C-5):

In a specific embodiment, in the compound of the formula (1), R ₁ is an ethoxycarbonyl group, R ₂ , A and B are each a hydrogen atom, X is an oxygen atom, and R ₃ is a n-propyl group. For example, the compound of the formula (1) of the present invention has the structures of the following formulas (D-1) to (D-4):

In a specific embodiment, in the compound of the formula (1), R ₁ represents a methoxycarbonyl group, R ₂ , A and B are a hydrogen atom, X is an oxygen atom, and R ₃ is an ethyl group. For example, the compound of the formula (1) of the present invention has a structure of the following formulas (E-1) to (E-5):

In a specific embodiment, in the compound of the formula (1), R ₁ represents a methoxycarbonyl group, R ₂ , A and B are a hydrogen atom, X is an oxygen atom, and R ₃ is an isopropyl group. For example, the compound of the formula (1) of the present invention has a structure of the following formulas (F-1) to (F-5):

In a specific embodiment, in the compound of the formula (1), R ₁ represents a methoxycarbonyl group, R ₂ , A and B are a hydrogen atom, X is an oxygen atom, and R ₃ is a n-propyl group. For example, the compound of the formula (1) of the present invention has a structure of the following formulas (G-1) to (G-4):

In a specific embodiment, in the compound of the formula (1), R ₁ represents a methoxycarbonyl group, R ₂ , A and B are a hydrogen atom, X is an oxygen atom, and R ₃ is an ethyl group. For example, the compound of the formula (1) of the present invention has a structure of the following formulas (H-1) to (H-9):

In a specific embodiment, in the compound of the formula (1), R ₁ represents a methoxycarbonyl group, R ₄ , A and B are a hydrogen atom, X is an oxygen atom, and R ₃ is an ethyl group. For example, the compound of the formula (1) of the present invention has a structure of the following formulas (I-1) to (I-5):

In a specific embodiment, in the compound of the formula (1), R ₁ represents a methoxycarbonyl group, R ₄ and R ₂ are a hydrogen atom, A and B are chlorine atoms, X is an oxygen atom, and R ₃ is Ethyl. For example, the compound of the formula (1) of the present invention has the structure i of the following formula (J-1) to (J-4)

In a specific embodiment, in the compound of the formula (1), R ₁ represents a methoxycarbonyl group, R ₄ and R ₂ are a hydrogen atom, A is a methoxy group, B is a chlorine atom, and X is an oxygen atom. And R ₃ is an ethyl group. For example, the compound of the formula (1) of the present invention has a structure of the following formula (K-1) to (K-4):

In a specific embodiment, in the compound of the formula (1), R ₁ and R ₂ are an ethoxycarbonyl group, both A and B are a hydrogen atom, X is an oxygen atom, and R ₃ is an ethyl group. For example, the compound of the formula (1) of the present invention has a structure of the following formula (L-1) to (L-5):

The present invention further provides a plastic article comprising the compound represented by the formula (1) as an ultraviolet absorber. The plastic article can be a product made of polyurethane (PU). The method of adding the ultraviolet absorber may be added during material synthesis or added to the plastic product during processing of the latter product. In the plastic product provided by the present invention, the ultraviolet absorber is added in an amount of 0.1 to 10.0% by weight based on the entire plastic product.

The plastic product of the present invention contains the compound represented by the formula (1), so that the plastic product has high ultraviolet resistance and increases its durability in the need of exposure to ultraviolet rays, and the plastic product having the ultraviolet absorbent does not The release of toxic N-methylaniline can increase the value of the plastic product.

Synthesis Example 1: Synthesis of N-(ethoxycarbonylphenyl)-N'-(2'-hydroxyethyl)-N'-phenylformamidine (HEMP)

6.41 g of N-(2-hydroxyethyl)aniline and 10.34 g of ethyl 4-((ethoxymethylene)aminobenzoate, hereinafter referred to as NE) Into the reaction flask, the temperature was slowly raised to 65 ° C, the temperature was reacted for 16 hours, and the mixture was cooled under reduced pressure, and then separated by a column to obtain 7.00 g of pale yellow solid, yield 48%.

¹ H-NMR (CDCl ₃ , 300 MHz) δ: 1.36 (t, 3H, J = 7.2 Hz), 3.39 (t, 2H, J = 6.0 Hz), 4.09 (t, 2H, J = 6.0 Hz), 4.31 ( q, 2H, J = 7.2 Hz), 4.61 (br s, 1H), 6.50 (d, 2H, J = 8.7 Hz), 7.16 (d, 2H, J = 7.2 Hz), 7.30-7.45 (m, 3H) , 7.84 (d, 2H, J = 8.7 Hz), 8.41 (s, 1H)

Synthesis Example 2: Synthesis of N-(ethoxycarbonylphenyl)-N'-(2'-acetoxyethyl)-N'-phenylformamidine (AEMP)

8.37 g of N-(2-acetoxyethyl)aniline and 10.34 g of NE were added to the reaction flask, and the temperature was slowly raised to 65 ° C. The reaction was held for 16 hours under temperature, and the mixture was cooled under reduced pressure and then separated by a column. 15.39 g of light yellow oil in 93% yield.

¹ H-NMR (CDCl ₃ , 300 MHz) δ: 1.38 (t, 3H, J = 7.2 Hz), 1.91 (s, 1H), 3.96 (t, 2H, J = 5.7 Hz), 4.24 (t, 2H, J =5.7 Hz), 4.40 (q, 2H, J = 6.9 Hz), 7.03 (d, 2H, J = 8.4 Hz) 7.15-7.25 (m, 3H), 7.35-7.43 (m, 2H), 7.98 (d, 2H, J = 8.4Hz), 8.00(s, 1H)

Synthesis Example 3: Synthesis of N-(ethoxycarbonylphenyl)-N'-(2'-benzomethoxyethyl)-N'-phenylformamidine (Formula 2-3) (BEMP)

11.27 g of N-(2-phenoxyethyl)aniline and 10.34 g of NE were added to the reaction flask, and the temperature was slowly raised to 65 ° C, and the reaction was held for 16 hours under temperature, and the mixture was cooled under reduced pressure and then separated by a column. 17.12 g of light yellow oil in 88% yield.

¹ H-NMR (CDCl ₃ , 300 MHz) δ: 1.39 (t, 3H, J = 7.2 Hz), 4.36 (t, 2H, J = 7.2 Hz), 4.45 (t, 2H, J = 5.4 Hz), 4.67 ( t, 2H, J = 5.4 Hz), 7.02 (d, 2H, J = 8.4 Hz), 7.19 (m, 1H), 7.25 (d, 2H, J = 7.5 Hz), 7.32-7.40 (m, 4H), 7.52 (t, 1H, J = 7.5 Hz), 7.82 (d, 2H, J = 7.2 Hz), 7.98 (d, 2H, J = 8.7 Hz), 8.04 (s, 1H)

Synthesis Example 4: Synthesis of N-(ethoxycarbonylphenyl)-N'-(2'-acetamidoethyl)-N'-phenylformamidine (N-AEMP)

8.35 g of N-(2-acetamidoethyl)aniline and 10.34 g of NE were added to the reaction flask, and the temperature was slowly raised to 65 ° C, and the reaction was held for 16 hours under temperature, and the mixture was cooled under reduced pressure and then separated by a column. 14.86 g of light yellow oil in 90% yield.

¹ H-NMR (CDCl ₃ , 300 MHz) δ: 1.39 (t, 3H, J = 7.2 Hz), 1.94 (s, 1H), 3.58 (t, 2H, J = 6.0 Hz), 4.20 (t, 2H, J =6.0 Hz), 4.36 (q, 2H, J = 7.2 Hz), 7.02 (br s, 1H), 7.03 (d, 2H, J = 8.4 Hz) 7.15-7.25 (m, 3H), 7.35-7.45 (m , 2H), 8.00 (d, 2H, J = 8.4 Hz), 8.06 (s, 1H)

Synthesis Example 5: Synthesis of N-(4-ethoxycarbonylphenyl)-N'-(2'-hydroxyethyl)-N'-(4'-ethoxycarbonylphenyl)formamidine (HEET) )

9.78 g of N-(2'-hydroxyethyl)-N'-(4-ethoxycarbonyl)aniline and 10.34 g of NE were added to the reaction flask, and the temperature was slowly raised to 65 ° C, and the reaction was held for 16 hours while maintaining the temperature. After concentration under reduced pressure, a white solid was obtained.

¹ H-NMR (CDCl ₃ , 300 MHz) δ: 1.38 (m, 6H), 3.42 (t, 2H, J = 6.0 Hz), 4.13 (t, 2H, J = 6.0 Hz), 4.31 (t, 2H, J =6.9 Hz), 4.39 (q, 2H, J = 6.9 Hz), 6.50 (d, 2H, J = 8.7 Hz), 7.21 (d, 2H, J = 8.7 Hz), 7.85 (d, 2H, J = 8.7) Hz), 8.08 (d, 2H, J = 8.7 Hz), 8.52 (s, 1H)

Test Example 1: Yellowing resistance test of polyurethane foam

The ultraviolet absorbers of the above Synthesis Examples 1 to 4 were added to a polyurethane foam while being combined with N-(ethoxycarbonylphenyl)-N'-methyl-N'-phenylformamidine (NEMP, and New Chemicals). And the blank group without adding any ultraviolet absorber is compared, and the yellowing resistance test of the polyurethane foam is carried out by the same preparation method, and the relevant test steps and results are described below.

1. Polyurethane foam formula ratio (as shown in Table 1):

2. Polyurethane foam production steps:

2-1 6.1 g of toluene diisocyanate (TDI-80) and 12 g of polyol (PP-3000) were placed in two A, B beakers, respectively.

2-2 Take 0.02 g of diamine catalyst (33LV), 0.04 g of organic tin catalyst (T-9), 0.12 g of foam stabilizer (SZ-580), 0.48 g of distilled water and 0.188 g of UV absorber. Add to the B beaker.

2-3 Adjust the speed of the high-speed mixer at 3000 rpm, stir the mixture of the B beaker with the rotor, and stir for 30 seconds before stopping the stirring.

2-4 Pour the toluene di-isocyanate in the A beaker into the B beaker, adjust the high-speed mixer rotation speed to 3000 rpm, stir for 15 seconds, stop the stirring, and quickly pour the mixture into the mold to naturally foam.

2-5 After standing at room temperature for 24 hours, the polyurethane foam was taken out to prepare a foam test piece having a thickness of 20 mm and a diameter of 60 mm for the yellowing resistance test.

3. Yellowing resistance test:

The above test pieces were placed in an accelerated aging test box (QUV instrument, ASTM G154 only irradiation, Q-Lab, Q-Basic; light source: UVB-313; temperature: 60 ° C) for aging test, taken after 12 hours , test for yellowness (Yi) and yellowing index (ΔYi). The results obtained are shown in Table 2:

The smaller the value of ΔYi shown in Table 2, the better the case where the polyurethane test piece is resistant to yellowing. The urethane foam test piece comprising the ultraviolet absorbing agent of the present invention has a ΔYi value lower than that of the blank group of the urethane foam test piece, indicating that the ultraviolet absorbing agent of the present invention can significantly enhance the anti-yellowing effect of the urethane. .

Test Example 2: Yellowing resistance test of thermoplastic polyurethane film

The ultraviolet absorbers of the above Synthesis Examples 1 to 4 were added to a thermoplastic polyurethane film while being combined with N-(ethoxycarbonylphenyl)-N'-methyl-N'-phenylformamidine (NEMP, and New Chemicals). And the blank group without adding any ultraviolet absorber is compared, and the yellowing resistance test of the thermoplastic polyurethane film is carried out by the same preparation method, and the relevant test steps and results are described below.

1. Manufacturing steps of thermoplastic polyurethane (TPU) film:

1-1 TPU plastic (Bayer, Desmopan-385SX) was dissolved in dimethylformamide and a 10% w/w TPU solution was prepared under the control of 45 °C.

1-2 Take 30 g of the above solution, add 1.0% w/w UV absorber, and mix well.

1-3 The solution prepared in the step (2) was applied to a glass plate by an applicator and the wet film thickness of the applicator was set to 1 mm.

1-4 After coating, the wet film of step (3) is dried in a hot air circulating oven at 80 ° C for 30 minutes, and a film having a thickness of about 15 μm is obtained after the solvent is volatilized.

2. Yellowing resistance test:

The above test pieces were placed in an accelerated aging test box (QUV instrument, ASTM G154 only irradiation, Q-Lab, Q-Basic; light source: UVB-313; temperature: 60 ° C) for aging test, which lasted 24 hours and 48 hours. After taking out, the yellowness (Yi) and yellowing index (ΔYi) tests were performed. The results obtained are shown in Table 3.

The longer the test time, the more energy the test piece receives, and the effect on the yellowing is more obvious. As can be seen from the results of Table 3, the thermoplastic polyurethane film test piece comprising the ultraviolet absorbent of the present invention has a ΔYi value lower than that of the blank thermoplastic thermoplastic film test piece, indicating that the ultraviolet absorbent added by the present invention can be significantly improved. The anti-yellowing effect of polyurethane.

Test Example 3: N-methylaniline (NMA) residue test

Each 50 g of AEMP, N-AEMP and N-(ethoxycarbonylphenyl)-N'-methyl-N'-phenylformamidine (NEMP, and New Chemical) were placed in separate beakers and placed in separate beakers. Into the hot air circulation oven for 90 ° C aging, aging time of 36 hours, After the extraction, the mixture was uniformly stirred, and the sample was subjected to gas chromatography (GC) to detect the residue of N-methylaniline. The relevant test procedures and results are described below.

1. Gas chromatograph analysis method:

Use solvents and instruments:

2. Inspection process:

2-1 Preparation of N-methylaniline standard: Separately weighed 50 mg, 100 mg, and 200 mg of N-methylaniline, respectively, and added 100 mL of cyanide to prepare a concentration of 500 ppm, 1000 ppm, and 2000 ppm.

2-2 The fixed standard injection volume is 10 μL (μL) for testing.

2-3 Perform linear regression analysis of the three standard results on the calibration curve, the X-axis is the concentration, and the Y-axis is the integrated area; and check whether the linear correlation coefficient value (R ² ) is above 0.995 (if this standard is not met) Must be reconstituted).

2-4 Take 1 g of each of NEMP, AEMP and N-AEMP samples and add 10 mL of cyanamide.

2-5 The N-methylaniline content of each sample was analyzed (injection amount was 3.0 μl).

2-6 The linear regression formula of the obtained result is placed in the calibration curve to determine the residual concentration.

3. Detection steps:

3-1 Check the spectral baseline: Is there any instability and noise generation (stability ± 1 mAU).

3-2 Test blank test.

3-3 Detect the sample and test it three times in succession. The average value of the three times is averaged. The relative standard deviation (RSD) of the absorption area must be less than 2.0%.

Table 4 shows the results obtained by gas chromatography to detect N-methylaniline residues as described below.

As can be seen in Table 4, NEMP will produce N- in normal temperature. Methyl aniline, therefore, the long-term high temperature aging test shows that the content of the N-methylaniline is significantly improved. Compared with the NEMP product, the ultraviolet absorbing agent provided by the present invention does not have N-methyl even after high temperature aging. The formation of aniline can therefore meet the EU requirements for N-methylaniline restrictions.

Test Example 4: UV absorption rate test

Each sample in Table 5 (the ultraviolet absorber of the above Synthesis Examples 1 to 5; N-(ethoxycarbonylphenyl)-N'-methyl-N'-phenylformamidine (NEMP, and New Chemicals) The same weight was dissolved in dichloromethane and diluted to prepare a solution of 2.0 mg / liter, using a UV spectrometer (Shimadzu, UV-1700, measuring the width of the dish: 1 cm; scanning range: 200 to 800 nm; temperature: The UV absorbance test was carried out at 25 degrees. The results obtained are shown in Table 5.

As can be seen in Table 5, the ultraviolet absorber provided by the present invention has an absorption effect in the near ultraviolet region (wavelength of 200 to 380 nm), showing the present invention. The ultraviolet absorbing agent provided is added to the plastic product. Since the ultraviolet absorbing agent absorbs the ultraviolet light energy, the durability of the plastic product in the ultraviolet environment can be improved.

In summary, the plastic article of the present invention contains the compound of the formula (1), so that the plastic article has high ultraviolet resistance and increases its durability in the need of exposure to ultraviolet rays, and has the ultraviolet absorber. The plastic product does not release toxic N-methylaniline, thereby expanding the use of the ultraviolet absorber and the plastic article containing the ultraviolet absorber.

Claims (15)

a compound of the formula (1), Wherein R ₁ represents a C _1-6 alkoxycarbonyl group; R ₂ represents a hydrogen atom, a C _1-6 alkyl group, an N,N'-dimethylamino group, a halogen atom or a C _1-6 alkoxycarbonyl group; A and B respectively represent a hydrogen atom, a chlorine atom or a methoxy group; X represents an oxygen atom or NH; R ₃ represents a linear or branched C _1-5 alkyl group; and R ₄ represents a hydrogen atom, a methyl group, C _1-12 alkylcarbonyl or Wherein R ₅ is a hydrogen atom, a C _1-2 alkoxy group or a halogen atom. The compound according to claim 1, wherein R ₁ represents an ethoxycarbonyl group; R ₂ , A and B are a hydrogen atom; X is an oxygen atom; and R ₃ is an ethyl group. The compound according to item 2 of the patent application is selected from one of the following structural formulas: The compound of claim 1, wherein R ₁ represents an ethoxycarbonyl group; R ₂ , A and B are a hydrogen atom; X is NH and R ₃ is an ethyl group. A compound according to claim 4, which is selected from one of the following structural formulae: The compound according to claim 1, wherein R ₁ represents an ethoxycarbonyl group; R ₂ , A and B are a hydrogen atom; X is an oxygen atom; and R ₃ is a stretching propyl group. A compound as described in claim 6 is selected from one of the following structural formulae: The compound of claim 1, wherein R ₁ represents a methoxycarbonyl group; R ₂ , A and B are a hydrogen atom; X is an oxygen atom; and R ₃ is an ethyl group. A compound as described in claim 8 is selected from one of the following structural formulae: The compound according to claim 1, wherein R ₁ represents a methoxycarbonyl group; R ₂ , A and B are a hydrogen atom; X is an oxygen atom; and R ₃ is a stretching propyl group. A compound according to claim 10, which is selected from one of the following structural formulae: The compound according to claim 1, wherein R ₁ and R ₂ represent an ethoxycarbonyl group; A and B are a hydrogen atom; X is an oxygen atom; and R ₃ is an ethyl group. A compound according to claim 12, which is selected from one of the following structural formulae: A plastic article comprising the compound of any one of claims 1 to 13 as a UV absorber. For example, the plastic product described in claim 14 is a polyurethane plastic product.