Anti-ultraviolet aging additive and application thereof

Abstract

The invention provides an anti-ultraviolet aging additive and application thereof. The additive is a pyrrole derivative which is connected to boron nitride and contains an amino group and an ester group at the same time, and an additional five-membered ring or six-membered ring can be formed in an intramolecular hydrogen bond form. A five-membered ring containing an amino group and an ester group is connected to boron nitride, so that a hydrogen bond can be formed in a molecule to construct another five-membered ring or six-membered ring, and the energy of ultraviolet light is absorbed by utilizing the damage of the five-membered ring or six-membered ring formed by the hydrogen bond; meanwhile, the boron nitride can lead out heat brought by sunlight as soon as possible, and the phenomenon of hydrogen bond breakage caused by heat accumulation is avoided. According to the scheme, the ultraviolet resistance of the ABS is improved, so that the ABS has more excellent ageing resistance.

Description

Technical Field

[0001] The present invention belongs to the field of polymer materials, and particularly relates to an anti-ultraviolet aging additive and its application. Background Art

[0002] ABS plastic is a copolymer of acrylonitrile-butadiene-styrene. Due to its excellent properties and easy processing, it is widely used in various fields such as automobiles, household appliances, and office supplies. However, the free carbon-carbon double bonds in polybutadiene cause ABS to be easily aged under sunlight. The breakage of unsaturated double bonds reduces the rubber phase content and molecular weight, and at the same time, the double bonds are oxidized to form polar groups such as carboxyl or hydroxyl groups, ultimately resulting in yellowing of ABS and a sharp decline in its own toughness, thus restricting the wide application of ABS. The common way for ABS to resist ultraviolet aging is to add ultraviolet absorbers to absorb ultraviolet light energy or add substances such as titanium dioxide and zinc oxide to shield or reflect light, so as to achieve the anti-ultraviolet effect. For example, in the patent CN115572452A, a mixture of nano-titanium dioxide and carboxymethyl chitosan is used as a composite anti-ultraviolet agent, and in the patent CN115536977A, zinc titanate grafted with EMA-GMA is used to form a dense light shielding layer on the product surface to play a protective role. The above-mentioned invention patents still resist ultraviolet by absorbing ultraviolet light or shielding ultraviolet rays, but the long-term effectiveness and anti-ultraviolet ability cannot be further improved. Therefore, there is an urgent need in the art for a new type of ultraviolet absorber that can effectively improve the long-term effectiveness and significantly improve the anti-ultraviolet ability of the ultraviolet absorber. Summary of the Invention

[0003] One of the purposes of the present invention is to provide an anti-ultraviolet aging additive, which can further improve the anti-ultraviolet light ability of ABS and make it have more excellent anti-aging performance.

[0004] To achieve the above-mentioned invention purpose, the present invention adopts the following technical solutions:

[0005] An anti-ultraviolet aging additive, wherein the additive is a pyrrole derivative with an amino group and an ester group connected to boron nitride, and can form another five-membered or six-membered ring in the form of an intramolecular hydrogen bond;

[0006] Among them, the pyrrole derivative is preferably one or two of the following 2 substances:

[0007]

[0008] The inventors found that the novel ultraviolet-resistant additive can form hydrogen bonds within the molecule, and the formed hydrogen bonds will constitute relatively stable five-membered or six-membered rings. Therefore, the destruction of its hydrogen bonds can consume more ultraviolet light energy. At the same time, as a reversible cross-linking bond, hydrogen bonds can continuously break and recombine to absorb the energy of ultraviolet light repeatedly. As a lamellar structure, boron nitride can form a shielding protective layer when it constitutes an additive with the ability to absorb ultraviolet light, thereby better protecting the internal ABS molecular chains. The novel ultraviolet-resistant additive has boron nitride added compared to other ultraviolet-resistant additives. As a substance with excellent thermal conductivity, boron nitride can prevent heat accumulation and the occurrence of hydrogen bond breakage, and cooperate with the pyrrole derivatives connected to boron nitride to further improve the ability of the ultraviolet-resistant agent to absorb ultraviolet light.

[0009] Another object of the present invention is to provide a method for preparing an ultraviolet-resistant aging additive.

[0010] A method for preparing the above-mentioned ultraviolet-resistant aging additive, the method is: pyrrole-2-carboxylic acid or 3-pyrrole carboxylic acid reacts with hydroxyl-modified boron nitride to obtain the target product; preferably, the molar ratio of the hydroxyl-modified boron nitride to pyrrole-2-carboxylic acid or 3-pyrrole carboxylic acid is 1:(1 - 3).

[0011] Another object of the present invention is to provide an ABS resin with ultraviolet-resistant aging.

[0012] An ABS resin with ultraviolet-resistant aging, the ABS resin uses the above-mentioned ultraviolet-resistant aging additive, or the ultraviolet-resistant aging additive prepared by the above method, and the ABS resin is prepared from the following raw materials in parts by mass:

[0013] 20 - 40 parts of rubber powder,

[0014] 60 - 80 parts of SAN,

[0015] 0.1 - 0.2 parts of primary antioxidant,

[0016] 0.2 - 0.4 parts of secondary antioxidant,

[0017] 0.1 - 10 parts of lubricant;

[0018] 0.5 - 2 parts of ultraviolet-resistant agent.

[0019] In one embodiment of the present invention, the primary antioxidant is a hindered phenol, preferably one or more of 1076, 1010, 1024, 2246, and preferably antioxidant 1076.

[0020] In one embodiment of the present invention, the auxiliary antioxidant is phosphite, preferably one or more of 618, 168, 126, and PEPQ, and preferably antioxidant 168.

[0021] In one embodiment of the present invention, the lubricant is one or more of ethylene bisstearamide, metal soap, fatty amide, and high melting point paraffin, and preferably ethylene bisstearic acid amide.

[0022] Another object of the present invention is to provide a method for preparing an anti-ultraviolet aging ABS resin.

[0023] A method for preparing an anti-ultraviolet aging ABS resin, the preparation method uses the above-mentioned anti-ultraviolet aging additive, or the anti-ultraviolet aging additive prepared by the above method, or prepares the above-mentioned ABS resin. In the preparation method, additives are added to the rubber powder and SAN, and after mixing evenly, they are melt-extruded and granulated; preferably, melt-extrusion granulation is carried out using a twin-screw extruder; preferably, the temperature of the extruder is 80-240 °C and the rotation speed is 200-500 r / min.

[0024] Another object of the present invention is to provide a use of the anti-ultraviolet aging additive.

[0025] A use of the anti-ultraviolet aging additive, the additive is the above-mentioned anti-ultraviolet aging additive, or the anti-ultraviolet aging additive prepared by the above method. The anti-ultraviolet aging additive can be used for anti-ultraviolet aging of plastic products, preferably for anti-ultraviolet aging of ABS resin.

[0026] Another object of the present invention is to provide a use of the anti-ultraviolet aging ABS resin.

[0027] A use of the anti-ultraviolet aging ABS resin, the ABS resin is the above-mentioned ABS resin, or the ABS resin prepared by the above preparation method. The ABS resin is used in the fields of household appliances, automobiles, and construction, and preferably used in the automotive field.

[0028] Compared with the prior art, the present invention has the following positive effects:

[0029] By adding a pyrrole derivative containing an ester group and boron nitride as an anti-ultraviolet agent to ABS, the initial yellowness value of the prepared ABS is about 17. After 48 hours of ultraviolet aging, its yellowness value can still be maintained below 20, and the tensile strength is maintained above 40 MPa, further improving the anti-ultraviolet aging performance of ABS. Description of the Drawings

[0030] Figure 1 It is the characterization result of the anti-ultraviolet agent 1 prepared in Preparation Example 1;

[0031] Figure 2 Characterization results of the anti-ultraviolet agent 2 prepared in Preparation Example 2. Detailed implementation manners

[0032] The following examples further illustrate the technical solutions provided by the present invention. However, the present invention is not limited to the listed examples, and also includes any other known changes within the scope of the claims of the present invention.

[0033] The sources of the main raw materials in the examples and comparative examples of the present invention are as follows. Others are obtained from ordinary commercial channels if not otherwise specified:

[0034] Hydroxyl-modified boron nitride: purchased from Kempu New Materials Co., Ltd., purity ≥ 99%;

[0035] Pyrrole-2-carboxylic acid: purchased from Aladdin, purity 98%;

[0036] 3-Pyrrolecarboxylic acid: purchased from Aladdin, purity ≥ 95%;

[0037] Rubber powder: HR181 purchased from KUMHO ASIA PACIFIC;

[0038] Styrene-acrylonitrile copolymer (SAN): 80HF purchased from LG Chem;

[0039] Antioxidants 1076 and 168 are both purchased from BASF;

[0040] Ethylene bisstearamide: B50 purchased from CMS CHEM.

[0041] Equipment and instruments:

[0042] The high-speed mixer uses the SHR-50L high-speed mixer of Suzhou Songyuan;

[0043] The extruder uses the RXT26-900-22-58 co-rotating twin-screw extruder of Nanjing Ruia Extrusion Machinery Manufacturing Co., Ltd.;

[0044] The injection molding machine uses the MA 900Ⅲ injection molding machine of Haitian;

[0045] The tensile property test is carried out according to ASTM D638, using the Roell Z005 universal testing machine of Zwick;

[0046] The ultraviolet aging is tested by the QUV / spray aging chamber of Q-LAB;

[0047] The chromaticity test is carried out by using the HunterLab UltraScan PRO color difference meter;

[0048] The nuclear magnetic test is carried out by using the 600M nuclear magnetic resonance spectrometer of Bruker.

[0049] Preparation Example 1

[0050] 11.11 g of pyrrole-2-carboxylic acid and 2.48 g of hydroxyl-modified boron nitride were respectively added to a round-bottom flask containing deionized water, and reacted under mechanical stirring at room temperature with a rotation speed of 50 r and a time of 10 min. After filtering, washing, and drying the precipitate in the flask, the ultraviolet absorber 1 can be obtained. The NMR qualitative characterization results are shown in the attached figure.

[0051] Preparation Example 2

[0052] 33.33 g of 3-pyrrolecarboxylic acid and 2.48 g of hydroxyl-modified boron nitride were added to a round-bottom flask containing deionized water, and reacted under mechanical stirring at room temperature with a rotation speed of 100 r and a time of 5 min. After filtering, washing, and drying the precipitate in the flask, the ultraviolet absorber 2 can be obtained. The NMR qualitative characterization results are shown in the attached figure.

[0053] Example 1

[0054] 500 g of powdered rubber;

[0055] 1500 g of SAN;

[0056] 2 g of primary antioxidant 1076;

[0057] 4 g of secondary antioxidant 168;

[0058] 40 g of lubricant EBS;

[0059] 20 g of ultraviolet absorber 1;

[0060] (1) After respectively weighing primary antioxidant 1076, secondary antioxidant 168, lubricant EBS, and ultraviolet absorber 1, they were added to the mixture of powdered rubber and SAN and premixed for 10 min using a high-speed mixer;

[0061] (2) After mixing evenly, it was added to a twin-screw extruder for melt blending. The temperature of each zone of the extruder was set at 80, 140, 180, 200, 220, 220, 220, 220, 220, 220, 220, 220 °C, and the rotation speed was 500 r / min to extrude and obtain ABS particles.

[0062] Example 2

[0063] 800 g of powdered rubber;

[0064] 1200 g of SAN;

[0065] 2 g of primary antioxidant 1076;

[0066] 8 g of secondary antioxidant 168;

[0067] 200 g of lubricant EBS;

[0068] Ultraviolet absorber 1: 40 g

[0069] (1) Weigh the primary antioxidant 1076, secondary antioxidant 168, lubricant EBS, and ultraviolet absorber 1 separately, and then add them to the mixture of rubber powder and SAN, and premix for 5 minutes using a high-speed mixer.

[0070] (2) After mixing evenly, add it to a twin-screw extruder for melt blending. The temperature of each zone of the extruder is set at 80, 140, 180, 200, 220, 220, 220, 220, 220, 220, 220, 220, 220 °C, and the rotation speed is 200 r / min to obtain ABS particles by extrusion.

[0071] Example 3

[0072] Rubber powder: 400 g

[0073] SAN: 1600 g

[0074] Primary antioxidant 1076: 4 g

[0075] Secondary antioxidant 168: 8 g

[0076] Lubricant EBS: 2 g

[0077] Ultraviolet absorber 2: 10 g

[0078] (1) Weigh the primary antioxidant 1076, secondary antioxidant 168, lubricant EBS, and ultraviolet absorber 2 separately, and then add them to the mixture of rubber powder and SAN, and premix for 10 minutes using a high-speed mixer.

[0079] (2) After mixing evenly, add it to a twin-screw extruder for melt blending. The temperature of each zone of the extruder is set at 80, 140, 180, 200, 220, 220, 220, 220, 220, 220, 220, 220, 220 °C, and the rotation speed is 400 r / min to obtain ABS particles by extrusion.

[0080] Comparative Example 1

[0081] Refer to Example 1 to prepare ultraviolet-resistant ABS resin. The difference is only that boron nitride and pyrrole-2-carboxylic acid are directly added to ABS for premixing, and other operations and conditions remain unchanged, and ABS particles are obtained by extrusion.

[0082] Comparative Example 2

[0083] Refer to Example 1 to prepare ultraviolet-resistant ABS resin. The difference is only that boron nitride is replaced by calcium carbonate, and other operations and conditions remain unchanged, and ABS particles are obtained by extrusion.

[0084] Comparative Example 3

[0085] The anti-UV ABS resin was prepared with reference to Example 1, except that pyrrole-2-carboxylic acid was replaced with pyrrole, and other operations and conditions remained unchanged, and ABS particles were obtained by extrusion.

[0086] For the ABS particles prepared in Examples 1-3 and Comparative Examples 1-3, their color plates and mechanical specimens were obtained by injection molding with an injection molding machine at an injection molding temperature of 220 °C. The chromaticity and mechanical properties before and after aging were tested respectively, and the performance comparison is summarized in Table 1 below.

[0087] Table 1 Performance comparison of ABS color plates and mechanical specimens before and after aging

[0088]

[0089] According to the above experimental data, comparing the test results of Example 1 and Comparative Example 1, it shows that the anti-UV agent prepared by the reaction of hydroxyl-modified boron nitride and pyrrole-2-carboxylic acid has higher mechanical properties and lower YI value after aging when added to ABS; in Comparative Example 2, when boron nitride was replaced with calcium carbonate, the heat conduction function was lost. Although it has a certain anti-UV ability, the effect is limited; in Comparative Example 3, when the reactant was replaced with pyrrole, a five-membered or six-membered ring that absorbs ultraviolet light energy could not be formed through hydrogen bonds, resulting in the loss of anti-UV ability. Therefore, the YI value after UV aging increased significantly.

[0090] The above embodiments are only preferred specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present invention, the scope covered by the claims and other changes or substitutions that can be easily thought of should be covered within the protection scope of the present invention.

Claims

1. An anti-ultraviolet aging additive, characterized in that, The additive is a pyrrole derivative with an amino group and an ester group connected to boron nitride, and can form additional five-membered or six-membered rings through intramolecular hydrogen bonding; Among them, the pyrrole derivative is preferably one or both of the following two substances:

2. A method for preparing the anti-ultraviolet aging additive according to claim 1, characterized in that, The method is: reacting pyrrole-2-carboxylic acid or 3-pyrrolecarboxylic acid with hydroxyl-modified boron nitride to obtain the target product; Preferably, the molar ratio of the hydroxyl-modified boron nitride to pyrrole-2-carboxylic acid or 3-pyrrolecarboxylic acid is 1:(1-3).

3. An anti-ultraviolet aging ABS resin, which uses the anti-ultraviolet aging additive described in claim 1 or the anti-ultraviolet aging additive prepared by the method described in claim 2, and is characterized in that The ABS resin is prepared from the following raw materials in parts by mass: 20-40 parts of rubber powder, 60-80 parts of SAN, 0.1-0.2 part of a primary antioxidant, 0.2-0.4 part of a secondary antioxidant, 0.1-10 parts of a lubricant; 0.5-2 parts of an ultraviolet absorber.

4. The ABS resin according to claim 3, wherein, The primary antioxidant is a hindered phenol, preferably one or more of 1076, 1010, 1024, 2246, and preferably antioxidant 1076; And / or, the secondary antioxidant is a phosphite, preferably one or more of 618, 168, 126, PEPQ, and preferably antioxidant 168; And / or, the lubricant is one or more of ethylene bisstearamide, metal soap, fatty amide, high melting point paraffin, and preferably ethylene bisstearamide.

5. A method for preparing an anti-ultraviolet aging ABS resin, wherein the preparation method uses the anti-ultraviolet aging additive described in claim 1, or the anti-ultraviolet aging additive prepared by the method described in claim 2, or prepares the ABS resin described in claim 3 or 4, and is characterized in that, In the preparation method, additives are added to the rubber powder and SAN, and after mixing evenly, melt extrusion granulation is carried out; Preferably, melt extrusion granulation is carried out using a twin-screw extruder; Preferably, the temperature of the extruder is 80-240 °C and the rotation speed is 200-500 r / min.

6. Use of an anti-ultraviolet aging additive, wherein the additive is the anti-ultraviolet aging additive described in claim 1, or the anti-ultraviolet aging additive prepared by the method described in claim 2, characterized in that The anti-ultraviolet aging additive can be used for anti-ultraviolet aging of plastic products, and is preferably used for anti-ultraviolet aging of ABS resin.

7. Use of an ABS resin resistant to ultraviolet aging, wherein the ABS resin is the ABS resin described in claim 3 or 4, or the ABS resin prepared by the preparation method described in claim 5, characterized in that The ABS resin is used in the fields of household appliances, automobiles, and construction, and is preferably used in the automotive field.

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