TWI518058B - Ultraviolet absorber and plastic article having the ultraviolet absorber - Google Patents

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.

In general, photodegradation caused by exposure to ultraviolet light deteriorates the physical properties of many synthetic resin products, natural resin products, and polymerizable polymeric products (hereinafter collectively referred to as "plastic products"), thereby making plastics The durability of the product deteriorates rapidly. In particular, the photodegradation produced in plastic products induces discoloration and/or discoloration of the product and may result in a decrease in the physical properties of the product, thereby affecting the inability of the plastic product to function properly. In order to solve the above problems, ultraviolet absorbers are added during the manufacturing process or processing of various plastic products to alleviate the deterioration of plastic products.

A variety of compounds related to ultraviolet absorbers are known. Chinese Patent No. 100509765C discloses a benzylformamidine compound as an ultraviolet absorber. However, in view of the fact that most plastic articles must be processed and processed at a high temperature, there is a strong demand for ultraviolet absorbers having not only high ultraviolet absorbing properties but also excellent heat stability. In order to meet this need, still need other Ultraviolet absorber with high UV absorption and thermal stability.

The present invention provides a compound represented by the formula (1), In formula (1), Represents a C _6-12 aliphatic ring or a C _6-12 aromatic hydrocarbon; R ₁ represents a C _1-6 alkyl group; and R ₂ represents a group represented by the formula (2), In the formula (2), * indicates The position of the bond; R ₃ represents a C _1-6 alkoxycarbonyl group or a C _1-6 alkylaminocarbonyl group; m is an integer from 0 to 3; and n is an integer from 1 to 3, with the proviso that only When it is benzene and n is 1, R ₃ in the formula (2) is a C _1-6 alkylaminocarbonyl group.

The compound of the formula (1) can be used as a UV absorber in a plastic product which requires high-temperature processing or an additive which requires excellent thermal stability.

The present invention further provides a plastic article comprising the compound represented by the formula (1) as an ultraviolet absorber. 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 light.

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 formula (1), Represents a C _6-12 aliphatic ring or a C _6-12 aromatic hydrocarbon; R ₁ represents a C _1-6 alkyl group; and R ₂ represents a group represented by the formula (2), In the formula (2), * indicates The position of the bond; R ₃ represents a C _1-6 alkoxycarbonyl group or a C _1-6 alkylaminocarbonyl group; m is an integer from 0 to 3; and n is an integer from 1 to 3, with the proviso that when When it is benzene and n is 1, R ₃ in the formula (2) is a C _1-6 alkylaminocarbonyl group.

In a specific embodiment, in the compound represented by the formula (1) Is biphenyl, m is 0, and n is 2.

For example, the compound of the formula (1) of the present invention has the structure of the following formula (A):

In a specific embodiment, in the compound represented by the formula (1), Is benzene, R ₁ is a methyl group, and R ₃ represents a C _1-4 alkylaminocarbonyl group.

In a specific embodiment, in the compound represented by the formula (1), Is benzene, m is 0, n is 2, and the group represented by formula (2) is bonded to the ortho, meta or para position of the benzene.

For example, the compound of the formula (1) of the present invention has the structures of the following formulas (B) to (G):

In a specific embodiment, in the compound represented by the formula (1), Is benzene, R ₁ is a methyl group, m is 3, and n is 3.

For example, the compound of the formula (1) of the present invention has a structure of the following formula (H):

The invention further provides a plastic product comprising the compound represented by the formula (1) As a UV absorber. The plastic article may be a product made of polyethylene (PE), polypropylene (PP), polyester (PBT, PET), polycarbonate (PC), polyamine (PA) or polyurethane (PU).

In one embodiment, the plastic article is a polyurethane plastic article.

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 light.

Example Synthesis of 1-N,N'-bis(4-ethoxycarbonylphenyl)formamidine (NET)

50.0 g of ethyl 4-aminobenzoate and 25.0 g of triethyl orthoformate were dissolved in 80 ml of ethanol, stirred uniformly, and then heated to reflux for 9 hours. After cooling to room temperature, the solid was collected by filtration, and the solid was 40 ml of ethanol. After washing completely, it was dried to obtain 41.7 g of a NET product as a white solid with a yield of 91.4%.

Synthesis Example 2-Synthesis of 1,4-bis(N,N'-bis(4-ethoxycarbonylphenyl)methanemethyl)benzene (XNEPA)

11.8 g of 1,4-bis(chloromethyl)benzene was dissolved in 160 ml of N,N-dimethylformamide, and the temperature was raised to 40 to 45 ° C, then 23.3 g of anhydrous potassium carbonate was added in one portion, and the mixture was stirred for 10 minutes. After 47.1 g of NET was added slowly, the mixture was stirred at 43 to 48 ° C for 48 hours, cooled to room temperature, and the solid was collected by filtration. The solid was dissolved in dichloromethane (dichloromethane) and washed twice with 150 ml of water, and then the organic layer was separated and concentrated. The crude product was obtained as a dry solid, and crude material was recrystallized from ethanol to give 49.5 g of XNEPA product as a white solid with a yield of 93.8%.

¹ H-NMR (CDCl ₃ , 400 MHz) δ: 1.34~1.39 (m, 12H), 4.31~4.37 (m, 8H), 5.31 (s, 4H), 7.04 (d, 4H, J = 7.6 Hz), 7.15 (d, 4H, J = 8.4 Hz), 7.25 (s, 4H), 7.96 to 7.99 (m, 8H), 8.32 (s, 2H)

Synthesis Example 3-1, Synthesis of 2-bis(N,N'-bis(4-ethoxycarbonylphenyl)methanemethyl)benzene (ONEPA)

11.8 g of 1,2-bis(chloromethyl)benzene was dissolved in 160 ml of N,N-dimethylformamide, and the temperature was raised to 40 to 45 ° C, then 23.3 g of anhydrous potassium carbonate was added in one portion, and the mixture was stirred for 10 minutes. After 47.1 g of NET was added slowly, the mixture was stirred at 43 to 48 ° C for 24 hours. After cooling to room temperature, the solid was collected by filtration. The solid was dissolved in 400 ml of dichloromethane and washed twice with 150 ml of water. The crude product was obtained as a dry solid, and crude material was recrystallized from ethanol to give 44.3 g of ONEPA as a white solid, yield 83.9%.

¹ H-NMR (CDCl ₃ , 400 MHz) δ: 1.33~1.38 (m, 12H), 4.30~4.36 (m, 8H), 5.45 (s, 4H), 7.00 (d, 4H, J = 12 Hz), 7.15 ( s, 4H), 7.19 (d, 4H, J = 8.0 Hz), 7.94 to 7.98 (m, 8H), 8.36 (s, 2H)

Synthesis Example 4-Synthesis of 1,3-bis(N,N'-bis(4-ethoxycarbonylphenyl)methanemethyl)benzene (MNEPA)

11.8 g of 1,3-bis(chloromethyl)benzene was dissolved in 160 ml of N,N-dimethylformamide, and the temperature was raised to 40 to 45 ° C, and then 23.3 g of anhydrous potassium carbonate was added at a time, and the mixture was stirred for 10 minutes. After slowly adding 47.1 g of NET, the mixture was stirred at 43 to 48 ° C for 22 hours, cooled to room temperature, and the solid was collected by filtration. The solid was dissolved in 400 ml of dichloromethane and washed twice with 150 ml of water. The crude product was obtained as a dry solid, and crude material was recrystallized from ethanol to give 44.8 g of MNEPA product as a white solid with a yield of 84.9%.

¹ H-NMR (CDCl ₃ , 400 MHz) δ: 1.34~1.39 (m, 12H), 4.30~4.36 (m, 8H), 5.27 (s, 4H), 6.92 (d, 4H, J = 8.4 Hz), 7.05 (d, 4H, J = 8.4 Hz), 7.15 (d, 2H, J = 8.0 Hz), 7.23 to 7.27 (m, 2H), 7.90 to 7.94 (m, 8H), 8.23 (s, 2H)

Synthesis Example 5-4, 4'-bis(N,N-bis(4-ethoxycarbonylphenyl)methanemethyl)-1,1'-biphenyl (BNEPA)

15.0 g of 4,4'-bis(chloromethyl)-1,1'-biphenyl was dissolved in 150 ml of N,N-dimethylformamide, and the temperature was raised to 40 to 45 ° C, and then 21.3 g of anhydrous carbonic acid was added at a time. Potassium, stirring for 10 minutes, slowly adding 41.7 g of NET, stirring at 43 to 48 ° C for 44 hours, cooling to room temperature, collecting solids by filtration, solid dissolved in 400 ml of dichloromethane, each washed with 50 ml of water The organic layer was separated and concentrated to dryness to give a crude material. The crude material was recrystallized from ethanol to give 46.2 g of BNEPA product as a white solid, yield 90.0%.

¹ H-NMR (CDCl ₃ , 400 MHz) δ: 1.33~1.39 (m, 12H), 4.30~4.37 (m, 8H), 5.38 (s, 4H), 7.07 (d, 4H, J = 8.0 Hz), 7.18 (d, 4H, J = 8.8 Hz), 7.32 (d, 4H, J = 8.4 Hz), 7.47 (d, 4H, J = 8.4 Hz), 7.97 to 8.00 (m, 8H), 8.35 (s, 2H)

Synthesis of 6-N,N'-bis(4-butoxycarbonylphenyl)formamidine (NBT)

23.6 g of butyl 4-aminobenzoate and 15.0 g of triethyl orthoformate were dissolved in 30 ml of ethanol, stirred uniformly, and heated to reflux for 20 hours. The solid was collected by filtration after cooling to room temperature, and the solid was washed with 20 ml of ethanol and then dried to give 19.0 g of the NBT product as a white solid, yield 78.8%.

Synthesis of 7-1,4-bis(N,N'-bis(4-butoxycarbonylphenyl)methylmethyl)benzene (XNBPA)

12.0 g of 1,4-bis(chloromethyl)benzene was dissolved in 160 ml of N,N-dimethylformamide, and the temperature was raised to 40 to 45 ° C, and then 28.5 g of anhydrous potassium carbonate was added thereto, and the mixture was stirred for 10 minutes. After slowly adding 57.0 g of NBT, the mixture was stirred at 43 to 48 ° C for 32 hours, cooled to room temperature, and the solid was collected by filtration. The solid was dissolved in 400 ml of dichloromethane and washed twice with 150 ml of water, and the organic layer was separated and concentrated. The crude product was obtained as a dry solid, and crude material was recrystallized from ethanol to give 55.5 g of XNBPA product as a white solid with a yield of 90.4%.

¹ H-NMR (CDCl ₃ , 400 MHz) δ: 0.93 to 0.98 (m, 12H), 1.41 to 1.49 (m, 8H), 1.67 to 1.75 (m, 8H), 4.26 to 4.30 (m, 8H), 5.30 ( s, 4H), 7.03 (d, 4H, J = 8.0 Hz), 7.15 (d, 4H, J = 8.4 Hz), 7.24 (s, 4H), 7.95 to 7.98 (m, 8H), 8.33 (s, 2H) )

Synthesis of 8-N,N'-bis(4-methoxycarbonylphenyl)formamidine (NMT)

50.0 g of methyl 4-aminobenzoate and 60.0 g of triethyl orthoformate were dissolved in 80 ml of ethanol, stirred uniformly, and then heated to reflux for 9 hours. After cooling to room temperature, the solid was collected by filtration, and the solid was 40 ml of ethanol. After washing completely, it was dried to obtain 33.5 g of a NMT product as a white solid in a yield of 65.0%.

Synthesis Example 9- Synthesis of 1,4-bis(N,N'-bis(4-methoxycarbonylphenyl)methanemethyl)benzene (XNMPA)

10.8 g of 1,4-bis(chloromethyl)benzene was dissolved in 160 ml of N,N-dimethylformamide, and the temperature was raised to 40 to 45 ° C, then 24.0 g of anhydrous potassium carbonate was added in one portion, and the mixture was stirred for 10 minutes. After slowly adding 26.8 g of NET, the mixture was stirred at 43 to 48 ° C for 48 hours, cooled to room temperature, and the solid was collected by filtration. The solid was dissolved in 400 ml of dichloromethane and washed twice with 150 ml of water, and the organic layer was separated and concentrated. Dry to obtain crude product, the crude product was recrystallized from ethanol to give 34.8 g The finished product of XNMPA was a white solid with a yield of 77.3%.

¹ H-NMR (CDCl ₃ , 400 MHz) δ: 3.87 (d, 12H, J = 4.0 Hz), 5.30 (s, 4H), 7.02 (d, 4H, J = 8.0 Hz), 7.14 (d, 4H, J =8.8Hz), 7.22(s,4H), 7.95~7.98(m,8H),8.32(s,2H)

Synthesis Example 10-1,3,5-Tris(methyl)-2,4,6-paran (N,N'-bis(4-ethoxycarbonylphenyl)methylmethyl)benzene (TBTMNEPA) synthesis

5.0 g of 1,3,5-tris(bromomethyl)-2,4,6-trimethylbenzene and 12.8 g of NET were dissolved in 60 ml of cyanomethane, and 10.4 g of anhydrous potassium carbonate was added in one portion, and the mixture was uniformly stirred. The temperature was raised to reflux for 17 hours, cooled to room temperature and then filtered off. The filtrate was concentrated to dryness and then purified by column to yield 7.4 g of TBTMNEPA product as a white solid, yield 50.1%.

¹ H-NMR (CDCl ₃ , 400 MHz) δ : 7.98 (d, 6H, J = 8.8 Hz), 7.89 (s, 4H), 7.79 (d, 6H, J = 8.8 Hz), 7.03 (d, 6H, J) = 8.4 Hz), 6.76 (d, 6H, J = 8.4 Hz), 5.18 (s, 6H), 4.40 to 4.30 (m, 12H), 2.18 (s, 9H), 1.42 to 1.33 (m, 18H).

Synthesis of 11-N,N'-bis(4-methylaminocarbonylphenyl)formamidine (NNDMT)

10.0 g of dimethylammonium 4-aminobenzoate and 5.86 g of triethyl orthoformate were dissolved in 60 ml of toluene, stirred uniformly, and heated to reflux for 26 hours. After cooling to room temperature, the solid was collected by filtration and solid. After washing with 30 ml of dichloromethane, it was completely dried, and 3.0 g of the NNDMT product was obtained as a white solid, yield 29.1%.

Synthesis Example 12- Synthesis of 1,4-bis(N,N'-bis(4-methylaminocarbonylphenyl)mercaptomethyl)benzene (XNNDMPA)

0.37 g of 1,4-bis(chloromethyl)benzene was dissolved in 20 ml of N,N-dimethylformamide, and the temperature was raised to 40 to 45 ° C, then 1.2 g of anhydrous potassium carbonate was added in one portion, and the mixture was stirred for 10 minutes. After slowly adding 1.5 g of NNDMT, stirring at 43 to 48 ° C for 53 hours, cooling to room temperature, collecting solid by filtration, and dissolving the solid The organic layer was separated into 50 ml of methylene chloride. The organic layer was separated and evaporated to dryness.

¹ H-NMR (CDCl ₃ , 400 MHz) δ: 2.97~3.05 (m, 24H), 5.24 (s, 4H), 6.99 (d, 4H, J = 8.4 Hz), 7.11 (d, 4H, J = 8.4 Hz ), 7.23 (s, 4H), 7.35~7.38 (m, 8H), 8.24 (s, 2H)

Synthesis Example 13-N,N'-bis(4-ethoxycarbonylphenyl)-N'-benzylformamidine (NEPA)

37.5 g of benzyl chloride was dissolved in 15 ml of N,N-dimethylformamide, and the temperature was raised to 40 to 45 degrees, then 47 g of anhydrous potassium carbonate was added at a time, and after stirring for 10 minutes, slowly adding 69 g of NET was carried out at 43 After stirring for 48 hours, the mixture was stirred for 24 hours. After cooling to room temperature, the solid was collected by filtration. The solid was dissolved in 200 ml of dichloromethane, and then washed twice with 100 ml of water. The organic layer was separated and concentrated to dryness. 69.8 g of NEPA finished product was obtained as a white solid in a yield of 80.0%.

¹ H-NMR (CDCl ₃ , 400 MHz) δ : 1.33~1.39 (m, 6H), 4.30~4.37 (m, 4H), 5.29 (s, 2H), 7.04~7.40 (m, 9H), 7.95~8.02 ( m, 4H), 8.34 (s, 1H)

Test Example 1 - UV Absorption Rate Test

Each sample in Table 1 (Tinuvin series and Uvinul 3030 are BASF products; Cyasorb series is Cytec products; Hostavin B-CAP is Klein products); the same weight of samples are dissolved in dichloromethane and diluted to prepare A solution of 2.0 mg/liter was subjected to a UV absorbance test by a UV spectrometer (Shimadzu, UV-1700, measuring dish width: 1 cm; scanning range: 200 to 800 nm; temperature: 25 degrees). The results obtained are shown in Table 1.

Test Example 2 - Thermal Stability Test

The samples in Table 2 (Tinuvin series and Uvinul 3030 are BASF products; Cyasorb series is Cytec products; Hostavin B-CAP is Klein products) 5.0 mg by thermogravimetric analyzer (PerkinElmer, Pyris 6, test conditions: The air stability test was carried out by air, 50-800 ° C, heating rate: 10 ° C / min. The results obtained are shown in Table 2.

Test Example 3 - Yellowing resistance test

100 parts of TPU polyester (Desmopan 385S, purchased from Bayer) were added to the various UV absorbers in Table 3 (Tinuvin series and Uvinul 3030 are BASF products; Cyasorb series is Cytec products; Hostavin B-CAP is Klein) Company products), antioxidants (Irganox 1010 and Irgafos 168, for BASF products) and processing oil (Sunpar 2280), with twin-screw extruder (PSM30A Φ=31.2mm, L/D=40, test conditions: processing temperature: 190 to 200 ° C; extruding machine tube temperature: 200 ° C; extruder mold temperature: 20 to 30 ° C) to test each test piece. The test pieces were placed in an accelerated aging test box (QUV instrument, ASTM G154 only irradiation, Q-Lab, Q-Basic; light source: UVA-340; temperature: 60 ° C) for aging test, lasting 96 After 480 hours, it was taken out and tested for yellowness (YI) and yellowing index (△YI). The results obtained are shown in Table 3.

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 light.

Claims (10)

a compound of the formula (1), In formula (1), Represents a C _6-12 aliphatic ring or a C _6-12 aromatic hydrocarbon; R ₁ represents a C _1-6 alkyl group; and R ₂ represents a group represented by the formula (2), In the formula (2), * indicates The position of the bond; R ₃ represents a C _1-6 alkoxycarbonyl group or a C _1-6 alkylaminocarbonyl group; m is an integer of 0 to 3; and n is an integer of 2 or 3. Such as the compound described in claim 1, wherein Is biphenyl, m is 0, and n is 2. A compound as described in claim 2, which is a compound of the formula: Such as the compound described in claim 1, wherein Is benzene, R ₁ is a methyl group, and R ₃ represents a C _1-4 alkylaminocarbonyl group. Such as the compound described in claim 1, wherein Is benzene, m is 0, n is 2, and the group represented by formula (2) is bonded to the ortho, meta or para position of the benzene. A compound according to claim 5, which is selected from one of the following structural formulae: Such as the compound described in claim 1, wherein Is benzene, R ₁ is a methyl group, m is 3, and n is 3. A compound as described in claim 7 is a compound of the formula: A plastic product comprising the compound of claim 1 as a UV absorber. For example, the plastic product described in claim 9 is a polyurethane plastic product.