Uvioresistant abs material, its preparation method and packing bottle

Abstract

The application relates to the technical field of ABS packaging bottles, and more specifically to an ultraviolet-resistant ABS material, a preparation method thereof and a packaging bottle. An ultraviolet-resistant ABS material comprises the following raw materials in parts by weight: 50-80 parts of styrene, 14-26 parts of acrylonitrile, 12-18 parts of a benzotriazole ultraviolet-resistant absorber, 8-14 parts of butadiene, 0.1-0.9 parts of benzoyl peroxide, 0.1-0.5 parts of tertiary dodecyl mercaptan and 40-60 parts of toluene; the benzotriazole ultraviolet-resistant absorber comprises the following raw materials in mole: 1-3 parts of hydroxyethyl methacrylate, 2-4 parts of toluene-3,5-diisocyanate and 1-3 parts of a polyhydroxy-containing ultraviolet-resistant absorber. The ultraviolet-resistant ABS material has excellent ultraviolet-resistant performance and migration resistance.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of ABS packaging bottles, and more particularly to an ultraviolet-resistant ABS material, a preparation method thereof and a packaging bottle. BACKGROUND

[0002] ABS plastic is a terpolymer of acrylonitrile, butadiene and styrene, so that the ABS plastic has the high elasticity and high toughness of butadiene, the excellent processing performance of styrene, and the chemical corrosion resistance, heat resistance and hardness of acrylonitrile, thereby facilitating the ABS plastic to be widely applied in the manufacturing industries of machinery, textiles and handicrafts and the chemical industry.

[0003] However, the ultraviolet resistance of the ABS plastic is quite limited, and when the ABS material is exposed to the ultraviolet environment for a long time, the ABS plastic is prone to discoloration, brittleness and cracking. At present, in order to improve the ultraviolet resistance of the ABS plastic, an ultraviolet absorber is generally added to the ABS base.

[0004] Common ultraviolet absorbers include benzophenone, triazine and benzotriazole, among which the benzotriazole ultraviolet absorber has a wide absorption wavelength, a wide variety and a wide application range, and is therefore widely applied. However, most benzotriazole ultraviolet absorbers have poor anti-migration performance, so that when the ABS material packaging bottle stores other substances, the migration of the benzotriazole ultraviolet absorber will affect the properties of the stored substances, and therefore there is an urgent need for an ABS material with excellent ultraviolet resistance and anti-migration performance. SUMMARY

[0005] In order to improve the defect that the common ultraviolet absorber has poor anti-migration performance, the application provides an ultraviolet-resistant ABS material, a preparation method thereof and a packaging bottle.

[0006] In a first aspect, the application provides an ultraviolet-resistant ABS material, which adopts the following technical scheme:

[0007] An ultraviolet-resistant ABS material comprises the following raw materials in parts by weight: 50-80 parts of styrene, 14-26 parts of acrylonitrile, 12-18 parts of a benzotriazole ultraviolet absorber, 8-14 parts of butadiene, 0.1-0.9 parts of benzoyl peroxide, 0.1-0.5 parts of tertiary dodecyl mercaptan and 40-60 parts of toluene.

[0008] The benzotriazole ultraviolet absorber comprises the following raw materials in mole parts: 1-3 parts of hydroxyethyl methacrylate, 2-4 parts of toluene-3,5-diisocyanate and 1-3 parts of a polyhydroxy-containing ultraviolet absorber.

[0009] Preferably, the polyhydroxyl-containing anti-ultraviolet light absorbing agent comprises the following raw materials by weight: 14-18 parts of diisopropanolamine, 100-130 parts of toluene, 0.3-0.8 parts of lithium hydroxide, and 8-12 parts of 3-(2-benzotriazolyl)-4-hydroxy-5-tert-butylbenzene propionic acid.

[0010] Preferably, the method for preparing the polyhydroxyl-containing anti-ultraviolet light absorbing agent comprises the following steps: mixing diisopropanolamine, toluene, and lithium hydroxide, then refluxing and dehydrating for 2 hours, then cooling to 50°C, adding half of the 3-(2-benzotriazolyl)-4-hydroxy-5-tert-butylbenzene propionic acid, then stirring at 80°C for 1 hour, adding the remaining 3-(2-benzotriazolyl)-4-hydroxy-5-tert-butylbenzene propionic acid, continuing to stir for 8 hours, then stopping the reaction, adding glacial acetic acid to the reaction solution to a pH of 5-6, then washing and evaporating the toluene, and finally cooling to room temperature to obtain the polyhydroxyl-containing anti-ultraviolet light absorbing agent.

[0011] Preferably, the method for preparing the benzotriazole anti-ultraviolet light absorbing agent comprises the following steps: first adding hydroxyethyl methacrylate, the polyhydroxyl-containing anti-ultraviolet light absorbing agent, and toluene-3, 5-diisocyanate into N, N-dimethylformamide, then continuously stirring at a temperature of 60-80°C, adding dibutyltin dilaurate during the stirring process, then reacting for 6-8 hours, then filtering and washing after the reaction is completed, and finally obtaining the benzotriazole anti-ultraviolet light absorbing agent.

[0012] When diisopropanolamine, 3-(2-benzotriazolyl)-4-hydroxy-5-tert-butylbenzene propionic acid, and lithium hydroxide are mixed, acid-amine reactions occur between diisopropanolamine and 3-(2-benzotriazolyl)-4-hydroxy-5-tert-butylbenzene propionic acid, thereby connecting hydroxyl groups to 3-(2-benzotriazolyl)-4-hydroxy-5-tert-butylbenzene propionic acid. When hydroxyethyl methacrylate, the polyhydroxyl-containing anti-ultraviolet light absorbing agent, and toluene-3, 5-diisocyanate are mixed, the hydroxyl groups on hydroxyethyl methacrylate and the polyhydroxyl-containing anti-ultraviolet light absorbing agent react with and connect to the two isocyanate groups on toluene-3, 5-diisocyanate under the catalysis of dibutyltin dilaurate, thereby causing hydroxyethyl methacrylate and the polyhydroxyl-containing anti-ultraviolet light absorbing agent to be on the same main chain.

[0013] When styrene, acrylonitrile, and butadiene undergo copolymerization, because hydroxyethyl methacrylate also has a double bond, hydroxyethyl methacrylate can be connected to the main chain of the ABS matrix as a grafting segment, thereby also connecting the polyhydroxyl-containing anti-ultraviolet light absorbing agent to the main chain of the ABS matrix. In this way, the anti-ultraviolet light absorbing agent in the anti-ultraviolet light ABS material has excellent anti-migration performance while not affecting the anti-ultraviolet light performance of the anti-ultraviolet light ABS material.

[0014] Preferably, the UV-resistant ABS material further includes 3-7 parts of a shielding UV absorber, wherein the shielding UV absorber includes 1-3 parts of 3-butenetriethoxysilane and 2-4 parts of palm fiber-rutile titanium dioxide composite.

[0015] Preferably, the preparation method of the palm fiber-rutile titanium dioxide complex is as follows: first, the palm fiber is crushed into powder, and then palm pulp is prepared by acid hydrolysis; then, 4-6 kg of palm pulp is ultrasonically dispersed in 100 L of deionized water for 20-40 min, and then 3 L of titanium tetrachloride is slowly added dropwise at a temperature of 20-30℃ for 0.5-1.5 h. After the reaction is completed, the mixture is centrifuged, washed, dried and ground to obtain the palm fiber-rutile titanium dioxide complex.

[0016] Titanium dioxide possesses excellent UV resistance properties, exhibiting superior UV absorption, reflection, and scattering characteristics. It exists in rutile, anatase, and plate-type forms, with rutile titanium dioxide exhibiting the most stable thermodynamic properties and the best refractive index. Furthermore, rutile titanium dioxide demonstrates excellent dispersibility; therefore, materials using rutile titanium dioxide exhibit more pronounced UV resistance.

[0017] Palm fiber contains abundant cellulose and lignin. Cellulose, upon acid hydrolysis, forms nanocellulose. Because nanocellulose contains numerous hydroxyl groups on its surface, it can form hydrogen bonds with hydroxyl groups on the surface of inorganic particles, thereby inducing the nucleation and growth of these particles under low-temperature conditions, thus promoting rutile titanium dioxide formation. Furthermore, palm fiber lignin possesses excellent ultraviolet absorption and shielding properties, further enhancing the UV resistance of rutile titanium dioxide.

[0018] 3-Butenetriethoxysilane is a silane coupling agent with double bonds. Therefore, it can act as a bridge to connect palm fiber-rutile titanium dioxide copolymer with ABS matrix. Moreover, due to the presence of double bonds, 3-butenetriethoxysilane can also be attached to ABS matrix as a grafting segment, causing palm fiber-rutile titanium dioxide copolymer to exist in solid phase in ABS matrix. This synergistically pulls on benzotriazole UV absorbers, further improving the anti-migration performance of benzotriazole UV absorbers in UV-resistant ABS materials.

[0019] Secondly, this application provides a method for preparing an anti-ultraviolet ABS material, which adopts the following technical solution: A method for preparing an anti-ultraviolet ABS material includes the following steps: First, toluene, styrene, acrylonitrile and butadiene are mixed, then a benzotriazole anti-ultraviolet absorber is added and mixed, then benzoyl peroxide and tert-dodecyl mercaptan are added, and the mixture is mixed and reacted at 80-140℃ for 2-3 hours. After the reaction is completed, vacuum devolatilization is performed to obtain the anti-ultraviolet ABS material.

[0020] A method for preparing an anti-ultraviolet ABS material includes the following steps: First, 3-butenetriethoxysilane and palm fiber-rutile titanium dioxide copolymer are mixed to obtain a shielding anti-ultraviolet absorber; then, toluene, styrene, acrylonitrile and butadiene are mixed, and then the shielding anti-ultraviolet absorber and benzotriazole anti-ultraviolet absorber are added and mixed; then, benzoyl peroxide and tert-dodecyl mercaptan are added, and the mixture is mixed and reacted at 80-140℃ for 2-3 hours. After the reaction is completed, vacuum devolatilization is performed to obtain the anti-ultraviolet ABS material.

[0021] Thirdly, this application provides a packaging bottle, which adopts the following technical solution:

[0022] A packaging bottle made from the aforementioned UV-resistant ABS material.

[0023] In summary, this application has the following beneficial effects:

[0024] 1. Under lithium hydroxide catalysis, diisopropanolamine undergoes an acid amination reaction with 3-(2-benzotriazolyl)-4-hydroxy-5-tert-butylphenylpropionic acid, thereby attaching a hydroxyl group to 3-(2-benzotriazolyl)-4-hydroxy-5-tert-butylphenylpropionic acid. Under the catalysis of dibutyltin dilaurate, the hydroxyl groups on hydroxyethyl methacrylate and the hydroxyl groups on the polyhydroxyl-containing UV absorber react with and attach to the two isocyanate groups on toluene-3,5-diisocyanate, thus ensuring that hydroxyethyl methacrylate and the polyhydroxyl-containing UV absorber remain on the same main chain.

[0025] When styrene, acrylonitrile, and butadiene undergo copolymerization, hydroxyethyl methacrylate can be grafted onto the main chain of the ABS matrix as a graft segment. Consequently, the polyhydroxyl-containing UV absorber is also attached to the main chain of the ABS matrix. Without affecting the UV resistance of the UV-resistant ABS material, the UV absorber in the UV-resistant ABS material also has excellent anti-migration properties.

[0026] 2. Rutile titanium dioxide has the most stable thermodynamic properties and the best optical refractive index. At the same time, rutile titanium dioxide also has excellent dispersibility. Therefore, materials using rutile titanium dioxide have more outstanding UV resistance.

[0027] 3. Palm fiber contains a large amount of cellulose and lignin. Cellulose, upon acid hydrolysis, forms nanocellulose, which induces the nucleation and growth of rutile titanium dioxide under low-temperature conditions. Furthermore, palm fiber lignin possesses excellent UV absorption and shielding properties, further enhancing the UV resistance of rutile titanium dioxide. Detailed Implementation

[0028] The present application will be further described in detail below with reference to Examples 1-12 and Comparative Examples 1-3.

[0029] raw material

[0030] Styrene CAS: 100-42-5; Acrylonitrile CAS: 107-13-1; Butadiene CAS: 106-99-0; Benzoyl peroxide CAS: 94-36-0; Tert-dodecyl mercaptan CAS: 25103-58-6; Toluene CAS: 108-88-3; Hydroxyethyl methacrylate CAS: 868-77-9; Toluene-3,5-diisocyanate CAS: 26471-62-5; Diisopropanolamine CAS: 110-97-4; Lithium hydroxide CAS: 1310-66 -3; 3-(2-benzotriazolyl)-4-hydroxy-5-tert-butylphenylpropionic acid CAS: 84268-36-0; glacial acetic acid CAS: 64-19-7; N,N-dimethylformamide CAS: 68-12-2; dibutyltin dilaurate CAS: 77-58-7; 3-butenetriethoxysilane CAS: 57813-67-9; titanium tetrachloride CAS: 7550-45-0; cellulose CAS: 70225-79-5; methyltrimethoxysilane CAS: 1185-55-3.

[0031] Example

[0032] Example 1

[0033] An anti-ultraviolet ABS material comprises the following raw materials by weight: 65 kg styrene, 20 kg acrylonitrile, 15 kg benzotriazole anti-ultraviolet absorber, 11 kg butadiene, 0.5 kg benzoyl peroxide, 0.3 kg tert-dodecyl mercaptan, and 50 kg toluene.

[0034] The preparation method of UV-resistant ABS material includes the following steps: First, toluene, styrene, acrylonitrile and butadiene are mixed, then benzotriazole UV absorber is added and mixed, then benzoyl peroxide and tert-dodecyl mercaptan are added, and the mixture is mixed and reacted at 110°C for 2.5 h. After the reaction is completed, vacuum devolatilization is performed to obtain UV-resistant ABS material.

[0035] Benzotriazole UV absorbers consist of the following raw materials in molar amounts: 2 mol hydroxyethyl methacrylate, 3 mol toluene-3,5-diisocyanate, and 2 mol polyhydroxyl-containing UV absorbers.

[0036] The preparation method of benzotriazole UV absorbers is as follows: First, 2 mol of hydroxyethyl methacrylate, 2 mol of polyhydroxyl UV absorber and 3 mol of toluene-3,5-diisocyanate are added to 300 ml of N,N-dimethylformamide. Then, the mixture is continuously stirred at a temperature of 60-80℃. During the stirring process, 3 g of dibutyltin dilaurate is added. The reaction is then carried out for 6-8 hours. After the reaction is completed, the mixture is filtered and washed to obtain the benzotriazole UV absorber.

[0037] The polyhydroxyl-containing UV absorber comprises the following raw materials in parts by weight: 16 kg diisopropanolamine, 115 kg toluene, 0.55 kg lithium hydroxide and 10 kg 3-(2-benzotriazolyl)-4-hydroxy-5-tert-butylphenylpropionic acid.

[0038] The preparation method of the polyhydroxyl-containing UV absorber is as follows: 16 kg of diisopropanolamine, 115 kg of toluene, and 0.55 kg of lithium hydroxide are mixed and then refluxed for 2 h to remove water. After cooling to 50 °C, 5 kg of 3-(2-benzotriazolyl)-4-hydroxy-5-tert-butylphenylpropionic acid is added. Then, the mixture is stirred at 80 °C for 1 h and 5 kg of 3-(2-benzotriazolyl)-4-hydroxy-5-tert-butylphenylpropionic acid is added. The mixture is stirred for another 8 h and then the reaction is stopped. Glacial acetic acid is added until the pH of the reaction solution is between 5 and 6. Finally, the toluene is washed off and the mixture is cooled to room temperature to obtain the polyhydroxyl-containing UV absorber.

[0039] Example 2-3

[0040] The difference from Example 1 is that the amount of each component added to the UV-resistant ABS material is different, as shown in Table 1.

[0041] Table 1. Amount of each component added to the UV-resistant ABS material in Examples 1-3 (kg)

[0042]

[0043] Examples 4-5

[0044] The difference from Example 1 is that the amount of each component added to the benzotriazole UV absorber is different, as shown in Table 2.

[0045] Table 2. Dosage of each component added to the benzotriazole UV absorbers in Examples 1 and 4-5 (mol)

[0046] Example 1 Example 4 Example 5 hydroxyethyl methacrylate 2 1 3 toluene-3,5-diisocyanate 3 2 4 polyhydroxyl-containing ultraviolet light absorbing agent 2 3 1

[0047] Examples 6-7

[0048] The difference from Example 1 is that the amount of each component containing the polyhydroxyl UV absorber added is different, as shown in Table 3.

[0049] Table 3. Dosage of each component in Examples 1 and 6-7 containing polyhydroxyl UV absorbers (kg)

[0050]

[0051] Example 8

[0052] The difference from Example 1 is that the UV-resistant ABS material also includes 5 kg of shielding UV absorber, which is obtained by mixing 2 kg of 3-butenetriethoxysilane and 3 kg of palm fiber-rutile titanium dioxide composite.

[0053] The preparation method of palm fiber-rutile titanium dioxide complex is as follows: First, palm fiber is crushed into powder, and then palm pulp is prepared by sulfuric acid hydrolysis. Then, 5g of palm pulp is ultrasonically dispersed in 100ml of deionized water for 30min. Then, 3ml of titanium tetrachloride is slowly added dropwise at 25℃ for 1h. After the reaction is completed, the mixture is centrifuged, washed, dried and ground to obtain palm fiber-rutile titanium dioxide complex.

[0054] Examples 9-10

[0055] The difference from that obtained in Example 8 is that the amount of each component added to the shielding UV absorber is different, as shown in Table 4.

[0056] Table 4. Dosage of each component added to the shielding-type UV absorber in Examples 8-10 (kg)

[0057]

[0058] Example 11

[0059] The difference from Example 8 is that the palm fiber is replaced with the same amount of cellulose.

[0060] Example 12

[0061] The difference from Example 8 is that 3-butenetriethoxysilane is replaced with the same amount of methyltrimethoxysilane.

[0062] Comparative Example

[0063] Comparative Example 1

[0064] The difference from Example 1 is that benzotriazole UV absorbers are no longer added.

[0065] Comparative Example 2

[0066] The difference from Example 1 is that the benzotriazole UV absorber is replaced with the same amount of 3-(2-benzotriazole)-4-hydroxy-5-tert-butylphenylpropionic acid.

[0067] Comparative Example 3

[0068] The difference from Example 1 is that the polyhydroxyl-containing UV absorber is replaced with the same amount of 3-(2-benzotriazolyl)-4-hydroxy-5-tert-butylphenylpropionic acid.

[0069] Performance testing

[0070] Detection methods

[0071] I. UV Resistance Test

[0072] Three samples were taken from Examples 1-12 and Comparative Examples 1-3 respectively. Then, according to the fluorescent ultraviolet lamp exposure test method of GB / T 14522-2008 "Artificial Climate Aging Test Method for Plastics, Coatings and Rubber Materials for Mechanical Industry Products - Fluorescent Ultraviolet Lamp", each sample was made into a pattern of specified size. The irradiation intensity was 0.68W / m2×nm, continuous light exposure for 700h, blackboard temperature 63℃, and no spraying conditions. The impact strength of the pattern before and after aging was tested and recorded, and the impact strength reduction rate was calculated. Impact strength reduction rate = impact strength after aging / impact strength before aging × 100%.

[0073] II. Anti-migration performance test

[0074] Three samples were taken from Examples 1-12 and Comparative Examples 1-3 respectively, and then packaging bottles were prepared by injection molding. Vitamin C essence was then injected into the packaging bottles. After 90 days, the content of 3-(2-benzotriazolyl)-4-hydroxy-5-tert-butylphenylpropionic acid in the vitamin C essence was measured by liquid chromatography and the average value was taken.

[0075] The test data are shown in Table 5.

[0076] Table 5. Detection data of Examples 1-12 and Comparative Examples 1-3

[0077]

[0078] Referring to Comparative Examples 1-3 and Table 5, it can be seen that the impact strength reduction rate of Comparative Example 2 is significantly lower than that of Comparative Example 1. Furthermore, the impact strength reduction rate of Comparative Example 3 is even lower than that of Comparative Example 2, and the migration content of Comparative Example 3 is also significantly lower. This indicates that the benzotriazole-based UV absorber system can effectively improve the UV resistance and migration resistance of UV-resistant ABS materials.

[0079] The reason for this is that when hydroxyethyl methacrylate, a polyhydroxyl-containing UV absorber, and toluene-3,5-diisocyanate are mixed, under the catalysis of dibutyltin dilaurate, the hydroxyl groups on hydroxyethyl methacrylate and the polyhydroxyl-containing UV absorber react with and connect with the two isocyanate groups on toluene-3,5-diisocyanate, thereby ensuring that hydroxyethyl methacrylate and the polyhydroxyl-containing UV absorber are always on the same main chain.

[0080] When styrene, acrylonitrile, and butadiene undergo copolymerization, hydroxyethyl methacrylate (HME) also carries double bonds. Therefore, HME can be grafted onto the main chain of the ABS matrix as a graft segment. Consequently, polyhydroxyl-containing UV absorbers are also attached to the main chain of the ABS matrix. Without affecting the UV resistance of the UV-resistant ABS material, the UV absorbers in the UV-resistant ABS material also have excellent anti-migration properties.

[0081] Referring to Example 1 and Comparative Example 3 and in conjunction with Table 5, it can be seen that, compared to Comparative Example 3, the impact strength reduction rate of Example 1 is slightly lower, and the migration content is significantly lower. This indicates that the system containing polyhydroxyl UV absorbers has better anti-migration performance.

[0082] The reason for this is that when diisopropanolamine, 3-(2-benzotriazolyl)-4-hydroxy-5-tert-butylphenylpropionic acid and lithium hydroxide are mixed, diisopropanolamine undergoes an acid amination reaction with 3-(2-benzotriazolyl)-4-hydroxy-5-tert-butylphenylpropionic acid, thereby attaching more hydroxyl groups to 3-(2-benzotriazolyl)-4-hydroxy-5-tert-butylphenylpropionic acid, thus obtaining more connection sites and improving the anti-migration performance of UV-resistant ABS materials.

[0083] Referring to Examples 1-3 and Table 5, it can be seen that the impact strength of Examples 2-3 is slightly improved compared to Example 1, and the migration content of Examples 2-3 is also slightly improved. This indicates that when the components of the UV-resistant ABS material are prepared in the proportions of Example 1, the resulting UV-resistant ABS material has better UV resistance and migration resistance.

[0084] Referring to Examples 1, 4-5, and Table 5, it can be seen that compared to Example 1, the impact strength reduction rate of Example 4 is slightly lower, but the migration content of Example 4 is significantly higher. Compared to Example 1, the impact strength reduction rate of Example 5 is significantly higher, but the migration content of Example 5 is also significantly lower.

[0085] Example 4 exhibits superior UV resistance, but slightly inferior anti-migration properties. Example 5 demonstrates excellent anti-migration properties, but relatively poor UV resistance. Considering all factors, when the components of the benzotriazole UV absorber are formulated in the proportions of Example 1, the resulting UV-resistant ABS material possesses both excellent UV resistance and anti-migration properties.

[0086] Referring to Examples 1, 6-7, and Table 5, it can be seen that compared to Example 1, the impact strength reduction rate of Example 6 is significantly increased, but the migration content of Example 6 is also significantly decreased. Compared to Example 1, the impact strength reduction rate of Example 7 is slightly decreased, but the migration content of Example 7 is significantly increased.

[0087] Example 6 exhibits excellent anti-migration properties, but poor UV resistance. Example 7 demonstrates even better UV resistance, but slightly weaker anti-migration properties. Considering all factors, when the components containing the polyhydroxyl-containing UV absorber are formulated in the proportions of Example 1, the resulting UV-resistant ABS material possesses both excellent UV resistance and anti-migration properties.

[0088] Referring to Examples 1 and 8 and in conjunction with Table 5, it can be seen that, compared to Example 1, the rate of decrease in impact strength of Example 8 is significantly lower, and the migration content of Example 8 is also significantly lower. This indicates that the addition of a shielding type UV absorber has the advantage of improving the UV resistance and migration resistance of UV-resistant ABS materials.

[0089] Referring to Examples 8-10 and Table 5, it can be seen that, compared with Example 8, the rate of decrease in impact strength of Examples 9-10 is slightly improved, and the migration content of Examples 9-10 is also slightly improved. This indicates that when the components of the shielding UV absorber are formulated in the proportions of Example 8, the prepared UV-resistant ABS material has better UV resistance and migration resistance.

[0090] Referring to Examples 8 and 11 and in conjunction with Table 5, it can be seen that the migration content in Example 11 is basically unchanged compared to Example 8, but the impact strength obtained in Example 11 is slightly improved. This indicates that, compared to cellulose, using palm fiber to induce rutile titanium dioxide can result in UV-resistant ABS materials exhibiting superior UV resistance.

[0091] The reason lies in the fact that palm fiber contains a large amount of cellulose and lignin. Cellulose, after acid hydrolysis, forms nanocellulose. Since nanocellulose contains a large number of hydroxyl groups on its surface, it can form hydrogen bonds with the hydroxyl groups on the surface of inorganic particles, thereby inducing the nucleation and growth of inorganic particles under low-temperature conditions, thus promoting rutile titanium dioxide. Furthermore, palm fiber lignin has excellent ultraviolet absorption and shielding properties, further enhancing the UV resistance of rutile titanium dioxide.

[0092] Referring to Examples 8 and 12 and in conjunction with Table 5, it can be seen that, compared to Example 8, the rate of decrease in impact strength in Example 12 is slightly higher, and the migration content in Example 12 is also significantly higher. This indicates that, compared to methyltrimethoxysilane, 3-butenetriethoxysilane can promote UV-resistant ABS materials to have better anti-migration properties.

[0093] The reason for this is that 3-butenetriethoxysilane is a silane coupling agent with double bonds. Therefore, it can act as a bridge to connect the palm fiber-rutile titanium dioxide composite with the ABS matrix. Moreover, due to the presence of double bonds, 3-butenetriethoxysilane can also be attached to the ABS matrix as a grafting segment, causing the palm fiber-rutile titanium dioxide composite to exist in the solid phase within the ABS matrix. This synergistically pulls on the benzotriazole UV absorbers, further improving the anti-migration performance of the benzotriazole UV absorbers in the UV-resistant ABS material.

[0094] This specific embodiment is merely an explanation of this application and is not intended to limit it. After reading this specification, those skilled in the art can make modifications to this embodiment without contributing any inventive step, but such modifications are protected by patent law as long as they fall within the scope of the claims of this application.

Claims

1. A UV-resistant ABS material, characterized in that, The raw materials include the following parts by weight: 50-80 parts styrene, 14-26 parts acrylonitrile, 12-18 parts benzotriazole UV absorber, 8-14 parts butadiene, 0.1-0.9 parts benzoyl peroxide, 0.1-0.5 parts tert-dodecyl mercaptan, and 40-60 parts toluene; wherein the benzotriazole UV absorber includes the following molar parts of raw materials: 1-3 parts hydroxyethyl methacrylate, 2-4 parts toluene-3,5-diisocyanate, and 1-3 parts polyhydroxyl-containing UV absorber; The polyhydroxyl-containing UV absorber comprises the following raw materials in parts by weight: 14-18 parts diisopropanolamine, 100-130 parts toluene, 0.3-0.8 parts lithium hydroxide, and 8-12 parts 3-(2-benzotriazolyl)-4-hydroxy-5-tert-butylphenylpropionic acid; The preparation method of the polyhydroxyl-containing UV absorber is as follows: diisopropanolamine, toluene, and lithium hydroxide are mixed, then refluxed for 2 hours to remove water, and then cooled to 50°C. Half of the 3-(2-benzotriazolyl)-4-hydroxy-5-tert-butylphenylpropionic acid is added. After stirring at 80°C for 1 hour, the remaining 3-(2-benzotriazolyl)-4-hydroxy-5-tert-butylphenylpropionic acid is added. The reaction is stopped after stirring for another 8 hours. Glacial acetic acid is added until the pH of the reaction solution is between 5 and 6. Finally, toluene is washed off and the solution is cooled to room temperature to obtain the polyhydroxyl-containing UV absorber. The preparation method of the benzotriazole UV absorber is as follows: First, hydroxyethyl methacrylate, a polyhydroxy UV absorber and toluene-3,5-diisocyanate are added to N,N-dimethylformamide, and then the mixture is continuously stirred at a temperature of 60-80°C. During the stirring process, dibutyltin dilaurate is added, and the reaction is carried out for 6-8 hours. After the reaction is completed, the mixture is filtered and washed to obtain the benzotriazole UV absorber.

2. The UV-resistant ABS material according to claim 1, characterized in that: The UV-resistant ABS material also includes 3-7 parts of a shielding UV absorber, which includes 1-3 parts of 3-butenetriethoxysilane and 2-4 parts of palm fiber-rutile titanium dioxide composite.

3. The UV-resistant ABS material according to claim 2, characterized in that, The preparation method of the palm fiber-rutile titanium dioxide complex is as follows: First, the palm fiber is crushed into powder, and then palm pulp is prepared by acid hydrolysis. Then, 4-6 kg of palm pulp is ultrasonically dispersed in 100 L of deionized water for 20-40 min. Then, 3 L of titanium tetrachloride is slowly added dropwise at a temperature of 20-30℃ for 0.5-1.5 h. After the reaction is completed, the mixture is centrifuged, washed, dried and ground to obtain the palm fiber-rutile titanium dioxide complex.

4. A method for preparing the UV-resistant ABS material according to claim 1, characterized in that, The process includes the following steps: First, toluene, styrene, acrylonitrile, and butadiene are mixed. Then, a benzotriazole-based UV absorber is added and mixed again. After that, benzoyl peroxide and tert-dodecyl mercaptan are added and mixed and reacted at 80-140°C for 2-3 hours. After the reaction is complete, the mixture is vacuum devolatilized to obtain UV-resistant ABS material.

5. A method for preparing the UV-resistant ABS material according to any one of claims 2-3, characterized in that, Includes the following steps: First, 3-butenetriethoxysilane and palm fiber-rutile titanium dioxide composite are mixed to obtain a shielding UV absorber. Then, toluene, styrene, acrylonitrile and butadiene are mixed, and then the shielding UV absorber and benzotriazole UV absorber are added and mixed. Then, benzoyl peroxide and tert-dodecyl mercaptan are added and mixed and reacted at 80-140℃ for 2-3 hours. After the reaction is completed, vacuum devolatilization is performed to obtain UV-resistant ABS material.

6. The application of the UV-resistant ABS material according to any one of claims 1-3, characterized in that, The UV-resistant ABS material is used to manufacture packaging bottles.

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