A rABS / rHIPS blend modified with a rABS-g-SAG-g-rHIPS dual-layer compatibilizer and its preparation method

Abstract

This invention relates to the field of waste plastic modification in polymer materials, specifically to an rABS / rHIPS blend modified with a dual-compatibilizer, rABS-g-SAG-g-rHIPS, and its preparation method. SAG, rHIPS, and rABS are dried and then melt-blended in a torque rheometer to obtain rABS-g-SAG-g-rHIPS, which is then added to the rABS / rHIPS blend to obtain rABS / rHIPS / rABS-g-SAG-g-rHIPS blend. The notched impact strength of the blend provided by this invention is increased from 6.06 kJ / m² to 20.91 kJ / m², a 245% increase compared to the rABS / rHIPS blend. The elongation at break is increased from 9.74% to 26.28%, a 270% increase, and the ductility is significantly improved. The blend and preparation method of this invention have high market value.

Description

Technical Field

[0001] This invention relates to the field of waste plastic modification in polymer materials, specifically to an rABS / rHIPS blend modified with a rABS-g-SAG-g-rHIPS dual-component compatibilizer and its preparation method. Background Technology

[0002] Acrylonitrile-butadiene-styrene (ABS) and high-impact polystyrene (HIPS) are two common general-purpose plastics widely used in various manufacturing industries. ABS has high hardness and good toughness, possessing good impact strength, hardness, thermal stability, and corrosion resistance. HIPS is known for its excellent processability, ease of molding, and dimensional stability similar to general-purpose polystyrene (PS), while exhibiting superior impact strength and rigidity. These two plastics are not only primary materials for producing various electronic devices but are also widely used in automotive manufacturing and office supplies.

[0003] During the aging process, ABS materials are primarily affected by light and heat, leading to the decomposition and oxidation of acrylonitrile and styrene monomers. Furthermore, the unsaturation of butadiene also accelerates ABS aging; for example, under ultraviolet light irradiation, butadiene undergoes a photo-oxidation reaction, generating peroxides, which in turn degrades the material's properties. HIPS aging is mainly due to the decomposition of polystyrene. Under ultraviolet light irradiation, polystyrene undergoes photodegradation, generating free radicals. These free radicals initiate chain breakage and cross-linking reactions, resulting in a decrease in the material's mechanical properties. All of these aging processes cause a decline in the mechanical properties of both ABS and HIPS, particularly a significant reduction in impact strength.

[0004] The method of recycling waste acrylonitrile / butadiene / styrene (rABS) and waste high-impact polystyrene (rHIPS) through direct melt blending cannot improve the impact strength, and may even reduce it compared to the single component. Summary of the Invention

[0005] This invention addresses the technical problem of low impact strength in rABS / rHIPS blends by providing an rABS-g-SAG-g-rHIPS compatibilizer-modified rABS / rHIPS blend. Based on the large number of carboxyl groups generated during molecular chain breakage and thermo-oxidative degradation, the addition of the rABS-g-SAG-g-rHIPS compatibilizer to the rABS / rHIPS blend improves the compatibility between rABS (waste acrylonitrile-styrene-butadiene copolymer) and rHIPS (waste high-impact polystyrene) to a certain extent, and also increases the impact strength of the blend.

[0006] To solve the above-mentioned technical problems, the technical solution adopted by the present invention is as follows: a rABS / rHIPS blend modified with rABS-g-SAG-g-rHIPS dual-composite compatibilizer, which is made from the following raw materials in parts by weight: 4-7.5 parts of rABS-g-SAG-g-rHIPS compatibilizer, 42.5-52.5 parts of rABS, and 42.5-52.5 parts of rHIPS.

[0007] As a further limitation of the technical solution of the present invention, it is made from the following raw materials in parts by weight: 5 parts of rABS-g-SAG-g-rHIPS compatibilizer, 47.5 parts of rABS, and 47.5 parts of rHIPS.

[0008] As a further limitation of the technical solution of the present invention, the preparation method of the rABS-g-SAG-g-rHIPS compatibilizer is as follows: melt blending is carried out in a torque rheometer. First, 40 parts of rHIPS are added at a temperature of 180°C and a rotation speed of 50 r / min for 15 minutes. Then, 40 parts of SAG (styrene-acrylonitrile-glycidyl methacrylate copolymer) are added at the same temperature and rotation speed for 15 minutes. Finally, 20 parts of rABS are added, the temperature is increased to 210°C, the rotation speed is kept constant, and the mixing time is 15 minutes to obtain the rABS-g-SAG-g-rHIPS compatibilizer.

[0009] As a further limitation of the technical solution of the present invention, the rABS melt index is 3.58 g / 10 min.

[0010] As a further limitation of the technical solution of the present invention, the rHIPS melt index is 10.89 g / 10 min.

[0011] As a further limitation of the technical solution of the present invention, the epoxy equivalent of the SAG is 400-850 g / mol.

[0012] The present invention also provides a method for preparing a rABS / rHIPS blend modified with a dual-component compatibilizer, comprising the following steps: drying rABS and rHIPS and then melt-blending them with rABS-g-SAG-g-rHIPS in a torque rheometer to obtain the rABS / rHIPS / rABS-g-SAG-g-rHIPS blend.

[0013] By using the above blending sequence, the rABS-g-SAG-g-rHIPS compatibilizer reacts with the rABS / rHIPS aging groups, and the rABS-g-SAG-g-rHIPS compatibilizer can be used as a chain extender to repair broken molecular chains.

[0014] As a further limitation of the technical solution of the present invention, the conditions for melt blending in the torque rheometer are as follows: first, rHIPS is added at a temperature of 180°C and a rotation speed of 50 r / min for 15 minutes; then, rABS-g-SAG-g-rHIPS compatibilizer is added at the same temperature and rotation speed for 15 minutes; finally, rABS is added, the temperature is increased to 210°C, the rotation speed is kept constant, and the mixing time is 15 minutes.

[0015] Compared with the prior art, the present invention has the following beneficial effects:

[0016] This invention uses rABS-g-SAG-g-rHIPS compatibilizer to compatibilize rABS / rHIPS blends. The market price of rABS plastic is below 8000 RMB / ton, while the market price of ABS is 15000-20000 RMB / ton; the market price of rHIPS plastic is below 8000 RMB / ton, while the market price of HIPS is 14800 RMB / ton. This invention prepares rABS / rHIPS / rABS-g-SAG-g-rHIPS blends with good mechanical properties, significantly reducing preparation costs. Experimental results show that the notched impact strength of the rABS / rHIPS / rABS-g-SAG-g-rHIPS material provided by this invention is 6.06 kJ / m. 2 Increased to 20.91 kJ / m 2 This represents a 245% improvement over the rABS / rHIPS blend. The elongation at break increased from 9.74% to 26.28%, a 270% increase. Attached Figure Description

[0017] Figure 1 Scanning electron microscope image of rABS-g-SAG-g-rHIPS compatibilizer without the addition of rABS-g-SAG-g-rHIPS. rABS / rHIPS (50 / 50) form a blend with a two-phase incompatible "sea-island" structure.

[0018] Figure 2 Scanning electron microscope image of the blend with 5 parts rABS-g-SAG-g-rHIPS compatibilizer and 47.5 parts rABS and 47.5 parts rHIPS added by melt blending.

[0019] Figure 3 The images show the proton NMR spectra of rABS-g-SAG-g-rHIPS compatibilizer and SAG. Detailed Implementation

[0020] The present invention will be further described below with reference to specific embodiments.

[0021] The SAG brand used in the following examples is SAG-002, manufactured by Jia Yi Rong Compatibilizer Jiangsu Co., Ltd., with an epoxy equivalent of 400-850 g / mol.

[0022] The rABS used in the following examples is manufactured by Yangzhou Ningda Precious Metals Co., Ltd., with a melt flow index of 3.58 g / 10 min.

[0023] The rABS used in the following examples is manufactured by Yangzhou Ningda Precious Metals Co., Ltd., with a melt flow index of 10.89 g / 10 min.

[0024] In the following examples, the torque rheometer was provided by Guangzhou Putong Experimental Analytical Instrument Co., Ltd., model: RTOI-20 / 10;

[0025] Example 1

[0026] Weigh 50g of rHIPS, 100g of SAG, and 50g of rABS. Dry them in a constant temperature drying oven at 80℃ for 8 hours. In a torque rheometer, first add rHIPS at 180℃ and 50 rpm for 15 minutes. Then add SAG, maintaining the same temperature and speed, and mix for 15 minutes. Finally, add rABS, raising the temperature to 210℃ while maintaining the same speed, and mix for 15 minutes to obtain rABS-g-SAG-g-rHIPS.

[0027] Weigh 10g of rABS-g-SAG-g-rHIPS and dry it in a constant temperature forced-air drying oven at 80℃ for 8 hours. Set aside for later use. Weigh 95g of rABS and 95g of rHIPS and dry them in a constant temperature forced-air drying oven at 80℃ for 8 hours. First, add rHIPS to a torque rheometer at 180℃ and 50 rpm for 15 minutes. Then add the rABS-g-SAG-g-rHIPS compatibilizer, maintaining the same temperature and speed for 15 minutes. Finally, add rABS, raise the temperature to 210℃, and maintain the same speed for 15 minutes.

[0028] Example 2

[0029] Weigh 40g of rHIPS, 80g of SAG, and 80g of rABS. Dry them in a constant temperature drying oven at 80℃ for 8 hours. First, add rHIPS to a torque rheometer at 180℃ and 50 rpm for 15 minutes. Then add SAG, maintaining the same temperature and speed, and mix for 15 minutes. Finally, add rABS, raising the temperature to 210℃ while maintaining the same speed, and mix for 15 minutes to obtain rABS-g-SAG-g-rHIPS.

[0030] Weigh 10g of rABS-g-SAG-g-rHIPS and dry it in a constant temperature forced-air drying oven at 80℃ for 8 hours. Set aside for later use. Weigh 95g of rABS and 95g of rHIPS and dry them in a constant temperature forced-air drying oven at 80℃ for 8 hours. First, add rHIPS to a torque rheometer at 180℃ and 50 rpm for 15 minutes. Then add the rABS-g-SAG-g-rHIPS compatibilizer, maintaining the same temperature and speed for 15 minutes. Finally, add rABS, raise the temperature to 210℃, and maintain the same speed for 15 minutes.

[0031] Example 3

[0032] Weigh 80g of rHIPS, 80g of SAG, and 40g of rABS. Dry them in a constant temperature drying oven at 80℃ for 8 hours. Then, add rHIPS to a torque rheometer at 180℃ and 50 rpm for 15 minutes. Next, add SAG while maintaining the same temperature and speed for 15 minutes. Finally, add rABS, raise the temperature to 210℃, and mix for 15 minutes to obtain rABS-g-SAG-g-rHIPS.

[0033] Weigh 10g of rABS-g-SAG-g-rHIPS and dry it in a constant temperature forced-air drying oven at 80℃ for 8 hours. Set aside for later use. Weigh 95g of rABS and 95g of rHIPS and dry them in a constant temperature forced-air drying oven at 80℃ for 8 hours. First, add rHIPS to a torque rheometer at 180℃ and 50 rpm for 15 minutes. Then add the rABS-g-SAG-g-rHIPS compatibilizer, maintaining the same temperature and speed for 15 minutes. Finally, add rABS, raise the temperature to 210℃, and maintain the same speed for 15 minutes.

[0034] Example 4

[0035] Weigh 80g of rHIPS, 80g of SAG, and 40g of rABS. Dry them in a constant temperature drying oven at 80℃ for 8 hours. Then, add rHIPS to a torque rheometer at 180℃ and 50 rpm for 15 minutes. Next, add SAG while maintaining the same temperature and speed for 15 minutes. Finally, add rABS, raise the temperature to 210℃, and mix for 15 minutes to obtain rABS-g-SAG-g-rHIPS.

[0036] Weigh 8g of rABS-g-SAG-g-rHIPS and dry it in a constant-temperature forced-air drying oven at 80℃ for 8 hours. Set aside for later use. Weigh 85g of rABS and 105g of rHIPS and dry them in a constant-temperature forced-air drying oven at 80℃ for 8 hours. First, add rHIPS to a torque rheometer at 180℃ and 50 rpm for 15 minutes. Then add the rABS-g-SAG-g-rHIPS compatibilizer, maintaining the same temperature and speed for 15 minutes. Finally, add rABS, raise the temperature to 210℃, and maintain the same speed for 15 minutes.

[0037] Example 5

[0038] Weigh 80g of rHIPS, 80g of SAG, and 40g of rABS. Dry them in a constant temperature drying oven at 80℃ for 8 hours. Then, add rHIPS to a torque rheometer at 180℃ and 50 rpm for 15 minutes. Next, add SAG while maintaining the same temperature and speed for 15 minutes. Finally, add rABS, raise the temperature to 210℃, and mix for 15 minutes to obtain rABS-g-SAG-g-rHIPS.

[0039] Weigh 15g of rABS-g-SAG-g-rHIPS and dry it in a constant temperature forced-air drying oven at 80℃ for 8 hours. Set aside for later use. Weigh 105g of rABS and 85g of rHIPS and dry them in a constant temperature forced-air drying oven at 80℃ for 8 hours. First, add rHIPS to a torque rheometer at 180℃ and 50 rpm for 15 minutes. Then add the rABS-g-SAG-g-rHIPS compatibilizer, maintaining the same temperature and speed for 15 minutes. Finally, add rABS, raise the temperature to 210℃, and maintain the same speed for 15 minutes.

[0040] Comparative Example 1

[0041] Weigh 100g of rABS and 100g of rHIPS, and dry them in a constant temperature drying oven at 80℃ for 8 hours. First, add rHIPS to the torque rheometer at 180℃ and 50r / min for 15 minutes of melting; then add rABS, raise the temperature to 210℃, keep the speed constant, and mix for 15 minutes.

[0042] The rABS and rHIPS used in Comparative Example 1 are the same as those used in Examples 1-3.

[0043] Test results:

[0044] The notched impact strength and tensile strength of the modified materials prepared in Examples 1, 2, 3, and Comparative Example 1 were tested respectively. The notched impact strength was tested according to the standard test method GB1843-80; the tensile strength was tested according to the standard test method GB / T1040-92. The average of the three experimental data was taken as the impact strength and tensile strength of the sample. The test results are shown in Table 1. Figure 1 Scanning electron microscope image of the sample without rABS-g-SAG-g-rHIPS compatibilizer. Figure 2 Scanning electron microscope images of melt blends modified with 5 parts rABS-g-SAG-g-rHIPS, 47.5 parts rABS, and 47.5 parts rHIPS.

[0045] As shown in Table 1, Examples 1 to 3 demonstrate that the present invention provides a method for preparing rABS / rHIPS blends modified with rABS-g-SAG-g-rHIPS. Comparative Example 1 shows that after adding 5 parts of rABS-g-SAG-g-rHIPS, the impact strength of the rABS / rHIPS blend increased from only 6.06 kJ / m². 2 Increased to 20.91 kJ / m 2 The elongation at break increased from 9.74% to 26.28%, an increase of 270%.

[0046] Table 1: Test Results of Mechanical Properties of rABS / rHIPS Modified rABS-g-SAG-g-rHIPS Materials

[0047] project Comparative Example 1 Example 1 Example 2 Example 3 Example 4 Example 5 <![CDATA[Izod impact strength (KJ / m 2 )]]> 6.06 13.04 12.70 20.91 11.46 16.39 Elongation at break (%) 9.74 9.02 6.20 26.28 12.85 7.07

[0048] From the table above and appendix Figure 1 As can be seen, using the modification method provided by this invention, 50 parts of rABS and 50 parts of rHIPS are melt-blended to form a blend with a two-phase incompatible "sea-island" structure. Due to uneven dispersion, irregular shape, and large particle size, the rABS / rHIPS exhibits poor compatibility, thus affecting the mechanical properties of rABS / rHIPS.

[0049] From the table above and the appendix Figure 2 As can be seen, compared with Comparative Example 1, the compatibility of the blend was improved after adding rABS-g-SAG-g-rHIPS, the interfacial tension between the two phases was reduced, the adhesion was enhanced, the distribution of the dispersed phase became more uniform, and the shape became more regular. From the perspective of mechanical properties, the impact strength of the blend was significantly improved. This invention improves the impact resistance of the blend while also improving the elongation at break of the blend.

[0050] Depend on Figure 1 and Figure 2 The comparison shows that after adding 5 parts of rABS-g-SAG-g-rHIPS, the dispersed phase of the rABS / rHIPS / rABS-g-SAG-g-rHIPS blend is more uniformly distributed, the particle size is smaller, and the cross-section is smoother. This improves the interfacial adhesion between the two phases and achieves the purpose of phase repair, which is consistent with the result of improved impact resistance from a macroscopic perspective.

[0051] Depend on Figure 3 It can be seen that, compared with SAG, the compatibilizer has a new resonance signal peak at 5.37 ppm, which is the resonance signal peak of the hydroxyl hydrogen of the alcohol, indicating that the grafting was successful. The resonance signal peak at 1.55 ppm represents the resonance signal peak of the rABS graft, and the one at 7.08 ppm represents the resonance signal peak of the rHIPS graft. After grafting rABS and rHIPS onto SAG, the original peak intensity will decrease. This is because during the blending process, the epoxy group of SAG reacts with the carboxyl group of rABS and rHIPS to form a new chemical bond, resulting in a change in the chemical environment of the benzene ring hydrogen, thus reducing the intensity. Furthermore, calculations show that the grafting rate of rABS in the rABS-g-SAG-g-rHIPS compatibilizer provided by this invention is 18.36%, and the grafting rate of rHIPS is 19.50%, indicating that the grafting was successful and the double-comb type compatibilizer was successfully prepared.

[0052] Experimental results show that the notched impact strength of the rABS / rHIPS / rABS-g-SAG-g-rHIPS material provided by this invention is 245% higher than that of the rABS / rHIPS blend, and the elongation at break is increased from 9.74% to 26.28%, an increase of 270%, with significantly improved ductility. The preparation method of this invention allows for the melt modification and granulation of rABS / rHIPS plastics for separate reuse, giving it high market value.

[0053] The above description is merely a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. A rABS / rHIPS blend modified with a rABS-g-SAG-g-rHIPS dual-layer compatibilizer, characterized in that, It is made from the following raw materials in parts by weight: 5 parts rABS-g-SAG-g-rHIPS compatibilizer, 47.5 parts rABS, and 47.5 parts rHIPS; The preparation method of the rABS-g-SAG-g-rHIPS compatibilizer is as follows: a melt blending reaction is carried out in a torque rheometer. First, 40 parts of rHIPS are added at 180℃ and 50 r / min for 15 minutes. Then, 40 parts of SAG are added at the same temperature and speed for 15 minutes. Finally, 20 parts of rABS are added, the temperature is increased to 210℃, the speed is kept constant, and the mixing time is 15 minutes to obtain the rABS-g-SAG-g-rHIPS compatibilizer. The preparation method of the rABS / rHIPS blend includes the following steps: drying rABS and rHIPS and then melting and blending them with rABS-g-SAG-g-rHIPS in a torque rheometer to obtain the rABS / rHIPS / rABS-g-SAG-g-rHIPS blend. The conditions for melt blending in the torque rheometer are as follows: first, add rHIPS at a temperature of 180℃ and a speed of 50 r / min for 15 minutes; then add rABS-g-SAG-g-rHIPS compatibilizer at the same temperature and speed for 15 minutes; finally, add rABS, raise the temperature to 210℃, keep the speed constant, and mix for 15 minutes.

2. The rABS / rHIPS blend modified with a dual-layer compatibilizer according to claim 1, characterized in that, The rABS melt index is 3.58 g / 10 min.

3. The rABS / rHIPS blend modified with a dual-layer compatibilizer according to claim 1, characterized in that, The rHIPS melt index is 10.89 g / 10 min.

4. The rABS / rHIPS blend modified with a dual-layer compatibilizer according to claim 1, characterized in that, The melt flow index of the rABS / rHIPS is 4.10 g / 10 min.

5. The rABS / rHIPS blend modified with a dual-layer compatibilizer according to claim 1, characterized in that, The epoxy equivalent of the SAG is 400-850 g / mol.

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