Alcohol-resistant anti-fading ABS material and preparation method thereof
By introducing cashew phenol as a crosslinking agent into ABS resin and chemically crosslinking it with polypropylene resin, the problems of swelling and fading of ABS materials in alcohol solvents are solved, and the mechanical properties and alcohol resistance of the material are improved.
Patent Information
- Application Number
- CN202510902025.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-07-01
- Publication Date
- 2025-10-17
- Estimated Expiration
- Not applicable · inactive patent
AI Technical Summary
ABS resin is prone to swelling and fading in alcohol solvents, which affects its performance and appearance. Existing crosslinking agents have limited effect in improving this condition.
Cashew phenol is used as a crosslinking agent to chemically crosslink with ABS resin and polypropylene resin under the action of dicumyl peroxide, thereby increasing the degree of crosslinking and flexibility of the material, and improving its mechanical properties and alcohol resistance.
It improves the tensile strength and elongation at break of ABS material, inhibits the entry of alcohol solvents, and maintains the material's alcohol resistance and mechanical properties.
Smart Images
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Abstract
Description
Technical Field
[0001] The invention relates to the technical field of ABS resins, in particular to an alcohol-resistant and anti-fading ABS material and a preparation method thereof. Background Art
[0002] ABS resin is widely used in packaging containers, automotive parts, electronic appliances, machinery manufacturing, etc. However, ABS resin has poor solvent resistance and easily swells in polar chemical solvents such as alcohol, which affects its performance. When ABS resin products are disinfected with ethanol or contain alcoholic solutions, the surface of the ABS products that are in contact with them for a long time will fade, affecting the appearance of the ABS products and the normal use of the solutions. Therefore, it is necessary to improve the resistance of ABS resin to solvents such as alcohol.
[0003] Composites of ABS resin and polypropylene create alloys with improved mechanical strength, toughness, and other properties. Adding dicumyl peroxide and a crosslinking agent to materials like ABS resin and polypropylene can enhance the material's crosslinking capacity, improving mechanical properties and solvent resistance. Traditional crosslinking agents include triallyl isocyanurate, divinylbenzene, and rosin esters. The present invention utilizes cardanol, which contains acrylate groups, as a crosslinking agent to enhance the mechanical properties and alcohol resistance of the ABS / polypropylene material. Summary of the Invention
[0004] (1) Technical problems to be solved:
[0005] In view of the shortcomings of the existing technology, the present invention provides an alcohol-resistant and anti-fading ABS material and a preparation method, which solves the problems of poor resistance to solvents such as ethanol and low mechanical properties of ABS materials.
[0006] (II) Technical Solution: A method for preparing an alcohol-resistant and anti-fading ABS material:
[0007] (1) Add dichloromethane, N,N-dihydroxyethylglycine, and triethylamine to a reaction flask, place in an ice-water bath, add acryloyl chloride dropwise, and then react at 10-25°C for 6-10 hours, filter, and rotary evaporate the filtrate. The crude product is separated by column chromatography to obtain an intermediate; then add thionyl chloride, heat to 60-70°C, react for 2-3 hours, rotary evaporate to remove thionyl chloride, and dry to obtain N,N-diacrylate ethyl glycine chloride.
[0008] (2) Add dichloromethane, cardanol, and triethylamine to the reaction flask, place it in an ice-water bath, and dropwise add N,N-diacrylate ethyl glycine chloride. After the reaction, filter and rotary evaporate the filtrate. The crude product is separated by column chromatography to obtain a cardanol co-crosslinking agent.
[0009] (3) ABS resin, polypropylene resin, antioxidant, are placed in a mixer to mix, and then the material is placed in a Banbury mixer to perform a first Banbury mixing, then adding cardanol co-crosslinking agent, dicumyl peroxide, to perform a second Banbury mixing, and the material is discharged to obtain an alcohol-resistant and color-falling-resistant ABS material.
[0010] Further, the ratio of N,N-dihydroxyethyl glycine, triethylamine, and acryloyl chloride in (1) is 1 mol:(2-2.6) mol:(2-3) mol.
[0011] Further, the ratio of cardanol, triethylamine, and N,N-diacryloyl ethyl glycine chloride in (2) is 1 mol:(1-1.1) mol:(1-1.3) mol.
[0012] Further, the reaction in (2) is performed at 20-30°C for 12-18h.
[0013] Further, the ratio of ABS resin, polypropylene resin, antioxidant, cardanol co-crosslinking agent, and crosslinking agent in (3) is (65-80) g:(20-35) g:(0.2-0.3) g:(3-7) g:(0.17-0.25) g.
[0014] Further, the temperature during the first Banbury mixing in (3) is 190-200°C, and the time is 3-5 min; and the time during the second Banbury mixing is 7-10 min.
[0015] (Three) Beneficial technical effects: The cardanol co-crosslinking agent is added to the ABS resin and polypropylene resin composite system, which contains multiple active acrylate groups, and under the action of dicumyl peroxide during high-temperature Banbury mixing, the multiple acrylate groups undergo chemical crosslinking reaction with ABS resin and polypropylene, and the long carbon chain contains an unsaturated alkenyl group, which also has a certain crosslinking effect, thereby improving the crosslinking degree of ABS and polypropylene in the material, which is beneficial to improving the mechanical properties and tensile strength of the material.
[0016] The cardanol co-crosslinking agent of the present application contains a benzene ring and a long carbon chain, which can reduce the crystallinity of the polypropylene molecular chain and improve the mechanical properties, and the long carbon chain has great flexibility, which can toughen the ABS resin to some extent, thereby improving the elongation at break of the composite material.
[0017] The crosslinking degree of the ABS and polypropylene composite system of the present application is increased, and structural defects are not easily formed inside the material, which can inhibit solvents such as ethanol from entering the material matrix, and the material still has high tensile strength and elongation at break after ethanol immersion, thereby improving the alcohol resistance of the material. DETAILED DESCRIPTION
[0018] With reference to the embodiments of the present application, the technical solutions in the embodiments of the present application will be described clearly and completely. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments of the present application, all the other embodiments obtained by a person of ordinary skill in the art without creative work are within the protection scope of the present application.
[0019] Embodiment 1
[0020] (1) 120 mL of dichloromethane, 60 mmol of N,N-dihydroxyethyl glycine, 156 mmol of triethylamine were added into a reaction bottle, and the reaction bottle was placed in an ice water bath, 180 mmol of acryloyl chloride was added dropwise, and then the reaction was carried out at 10 ℃ for 10 h, filtration was performed, the filtrate was rotary evaporated, the crude product was separated by column chromatography, and elution was performed with petroleum ether and ethyl acetate solution to obtain an intermediate; then the intermediate was added into 420 mmol of sulfoxide chloride, heated to 60 ℃, and condensation reflux reaction was carried out for 3 h, rotary evaporation was performed to remove the sulfoxide chloride, and drying was performed to obtain N,N-diacryloyl ethyl glycine acyl chloride. The reaction formula is as follows:
[0021]
[0022] (2) 15 mL of dichloromethane, 70 mmol of cardanol, and 70 mmol of triethylamine were added into a reaction bottle, the reaction bottle was placed in an ice water bath, 70 mmol of N,N-diacryloyl ethyl glycine acyl chloride was added dropwise, and then the reaction was carried out at 30 ℃ for 12 h, filtration was performed, the filtrate was rotary evaporated, the crude product was separated by column chromatography, and elution was performed with petroleum ether and ethyl acetate solution to obtain a cardanol co-crosslinking agent. The reaction formula is as follows:
[0023]
[0024] (3) 8 kg of acrylonitrile-butadiene-styrene copolymer ABS resin, 2 kg of polypropylene resin, and 23 g of antioxidant 1010 were mixed in a mixer, and then the materials were placed in a banbury mixer, banburying was performed at 190 ℃ for 5 min, then 300 g of the cardanol co-crosslinking agent and 17 g of dicumyl peroxide were added, banburying was performed for 8 min, and then the materials were discharged to obtain an alcohol-resistant and color-falling-off-resistant ABS material.
[0025] Embodiment 2
[0026] (1) Into a reaction flask, 100 mL of dichloromethane, 60 mmol of N,N- dihydroxyethylglycine, 120 mmol of triethylamine were added, and the mixture was placed in an ice water bath. Then, 120 mmol of acryloyl chloride was added dropwise, and the mixture was reacted at 25°C for 6 h. The mixture was filtered, and the filtrate was rotary evaporated. The crude product was separated by column chromatography using petroleum ether and ethyl acetate solution as eluent to obtain an intermediate. Then, the intermediate was added to 600 mmol of sulfoxonium chloride, and the mixture was heated to 70°C and condensed to reflux for 2 h. The sulfoxonium chloride was removed by rotary evaporation, and the mixture was dried to obtain N,N-diallyl ethyl glycine acyl chloride.
[0027] (2) Into a reaction flask, 20 mL of dichloromethane, 70 mmol of cardanol, 77 mmol of triethylamine were added, and the mixture was placed in an ice water bath. Then, 91 mmol of N,N-diallyl ethyl glycine acyl chloride was added dropwise, and the mixture was reacted at 20°C for 18 h. The mixture was filtered, and the filtrate was rotary evaporated. The crude product was separated by column chromatography using petroleum ether and ethyl acetate solution as eluent to obtain a cardanol co-crosslinking agent.
[0028] (3) 7.5 kg of acrylonitrile-butadiene-styrene copolymer ABS resin, 2.5 kg of polypropylene resin, and 20 g of antioxidant 1010 were mixed in a mixer. Then, the mixture was placed in an internal mixer, and the mixture was mixed at 200°C for 3 min. Then, 430 g of the cardanol co-crosslinking agent and 22 g of dicumyl peroxide were added, and the mixture was mixed at 200°C for 7 min. The mixture was discharged to obtain an alcohol-resistant and color-bleeding-resistant ABS material.
[0029] Example 3
[0030] (1) The cardanol co-crosslinking agent was prepared according to the method of Example 1.
[0031] (2) 7 kg of acrylonitrile-butadiene-styrene copolymer ABS resin, 3 kg of polypropylene resin, and 30 g of antioxidant 1010 were mixed in a mixer. Then, the mixture was placed in an internal mixer, and the mixture was mixed at 190°C for 5 min. Then, 570 g of the cardanol co-crosslinking agent and 25 g of dicumyl peroxide were added, and the mixture was mixed at 190°C for 10 min. The mixture was discharged to obtain an alcohol-resistant and color-bleeding-resistant ABS material.
[0032] Example 4
[0033] (1) The cardanol co-crosslinking agent was prepared according to the method of Example 1.
[0034] (2) 6.5 kg of acrylonitrile-butadiene-styrene copolymer ABS resin, 3.5 kg of polypropylene resin, and 28 g of antioxidant 1010 were mixed in a mixer. Then, the mixture was placed in an internal mixer, and the mixture was mixed at 200°C for 4 min. Then, 700 g of the cardanol co-crosslinking agent and 20 g of dicumyl peroxide were added, and the mixture was mixed at 200°C for 8 min. The mixture was discharged to obtain an alcohol-resistant and color-bleeding-resistant ABS material.
[0035] Comparative Example 1
[0036] (1) 8 kg of acrylonitrile-butadiene-styrene copolymer ABS resin, 2 kg of polypropylene resin, 23 g of antioxidant 1010 were mixed in a mixer, and then the materials were placed in an internal mixer, and internal mixing was performed at 190°C for 5 min. Then, 17 g of dicumyl peroxide was added, and internal mixing was performed for 8 min. The material was discharged to obtain an ABS material.
[0037] Comparative Example 2
[0038] (1) 8 kg of acrylonitrile-butadiene-styrene copolymer ABS resin, 2 kg of polypropylene resin, 23 g of antioxidant 1010 were mixed in a mixer, and then the materials were placed in an internal mixer, and internal mixing was performed at 190°C for 5 min. Then, 300 g of triallyl isocyanurate and 17 g of dicumyl peroxide were added, and internal mixing was performed for 8 min. The material was discharged to obtain an ABS material.
[0039] Comparative Example 3
[0040] (1) 10 mL of dichloromethane, 15.1 g of cardanol, and 5.05 g of triethylamine were added to a reaction bottle, and after stirring, 10 mL of a dichloromethane solution containing 5.43 g of acryloyl chloride was added dropwise, and the reaction was performed for 12 h. The filtrate was rotary evaporated, and the crude product was separated by column chromatography, eluted with petroleum ether and ethyl acetate solution to obtain cardanol acrylate, and the structural formula was n is 28-31.
[0041] (2) 8 kg of acrylonitrile-butadiene-styrene copolymer ABS resin, 2 kg of polypropylene resin, 23 g of antioxidant 1010 were mixed in a mixer, and then the materials were placed in an internal mixer, and internal mixing was performed at 190°C for 5 min. Then, 300 g of cardanol acrylate and 17 g of dicumyl peroxide were added, and internal mixing was performed for 8 min. The material was discharged to obtain an ABS material.
[0042] The ABS material was molded into a test piece in a flat plate vulcanizing machine at a pressure of 10 MPa and a temperature of 180°C.
[0043] The tensile properties were tested according to the GB / T 1040.1-2018 standard. The ABS material was soaked in an ethanol solvent for 24 h, the surface solvent was wiped dry, and then the tensile properties were tested.
[0044] Table 1 Performance test of ABS
[0045]
[0046] Compared with Comparative Example 1, the cashew phenol co-crosslinking agent added in Examples 1-4 contains multiple active acrylate groups, which can react with ABS resin and polypropylene to form chemical crosslinking under the action of dicumyl peroxide, and the long carbon chain contains unsaturated alkenyl groups, which has a certain crosslinking effect although the steric hindrance is large, thereby increasing the crosslinking degree of ABS and polypropylene in the material, which is beneficial to improve the mechanical properties and tensile strength of the material. In addition, cashew phenol contains benzene ring and long carbon chain, which can reduce the crystallinity of polypropylene molecular chain and improve the mechanical properties. At the same time, the long carbon chain has great flexibility, which can play a toughening role, thereby improving the elongation at break of the material. In addition, the crosslinking degree of ABS and polypropylene is increased, and it is not easy to form structural defects in the material, which can inhibit the entry of solvents such as ethanol into the material matrix, thereby improving the alcohol resistance of the material. After ethanol immersion, the material still has high tensile strength and elongation at break.
[0047] Compared with Example 1, Comparative Example 2 uses conventional triallyl isocyanurate as a co-crosslinking agent, and the tensile strength and elongation at break of the material are lower than those of Example 1. In addition, the retention rate of the tensile strength and elongation at break of the material after ethanol immersion is low, and the alcohol resistance is poor. Comparative Example 3 uses cashew phenol acrylate as a co-crosslinking agent, which contains only one acrylate. Although the long carbon chain contains unsaturated alkenyl groups, the steric hindrance is large, and the crosslinking activity is low, which leads to lower crosslinking performance of cashew phenol acrylate with ABS resin and polypropylene than Example 1, resulting in lower tensile strength and elongation at break of the material. In addition, the retention rate of the tensile strength and elongation at break of the material after ethanol immersion is low, and the alcohol resistance is poor.
[0048] Although embodiments of the present application have been shown and described, it is to be understood that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the present application, the scope of which is defined by the appended claims and their equivalents.
Claims
1. A method for preparing an alcohol-resistant and anti-fading ABS material, characterized in that: The preparation method is: S1. Add dichloromethane, cardanol, and triethylamine to a reaction flask, place in an ice-water bath, and dropwise add N,N-diacrylate ethyl glycine chloride. After the reaction, filter, rotary evaporate the filtrate, and separate the crude product by column chromatography to obtain a cardanol co-crosslinking agent. S2. ABS resin, polypropylene resin, and antioxidant are placed in a mixer for mixing, and then the materials are placed in an internal mixer for primary internal mixing. Then, cardanol co-crosslinking agent and dicumyl peroxide are added for secondary internal mixing, and the material is discharged to obtain an alcohol-resistant and anti-fading ABS material.
2. The method for preparing the alcohol-resistant and anti-fading ABS material according to claim 1, wherein: The ratio of cardanol, triethylamine and N,N-diethylacrylate glycine chloride in S1 is 1 mol: (1-1.1) mol: (1-1.3) mol.
3. The method for preparing the alcohol-resistant and anti-fading ABS material according to claim 1, wherein: The reaction in S1 is carried out at 20-30°C for 12-18 hours.
4. The method for preparing the alcohol-resistant and anti-fading ABS material according to claim 1, wherein: The ratio of ABS resin, polypropylene resin, antioxidant, cardanol co-crosslinking agent and crosslinking agent in S2 is (65-80) g: (20-35) g: (0.2-0.3) g: (3-7) g: (0.17-0.25) g.
5. The method for preparing the alcohol-resistant and anti-fading ABS material according to claim 1, characterized in that: The temperature of the first banburying in S2 is 190-200° C. and the time is 3-5 minutes; the time of the second banburying is 7-10 minutes.
6. The method for preparing the alcohol-resistant and anti-fading ABS material according to claim 2, characterized in that: The preparation method of N,N-diacrylate ethyl glycine chloride comprises the following steps: adding dichloromethane, N,N-dihydroxyethylglycine, and triethylamine to a reaction flask, placing the flask in an ice-water bath, dropwise adding acryloyl chloride, reacting at 10-25° C. for 6-10 hours, filtering, rotary evaporating the filtrate, and separating the crude product by column chromatography to obtain an intermediate; then adding the intermediate to thionyl chloride, heating the flask to 60-70° C., reacting the flask for 2-3 hours, rotary evaporating the thionyl chloride, and drying the flask to obtain N,N-diacrylate ethyl glycine chloride.
7. The method for preparing the alcohol-resistant and anti-fading ABS material according to claim 6, characterized in that: The ratio of N,N-dihydroxyethylglycine, triethylamine and acryloyl chloride in (1) is 1 mol: (2-2.6) mol: (2-3) mol.
8. An alcohol-resistant and anti-fading ABS material obtained by the preparation method according to any one of claims 1 to 7.