RABS / rHIPS blend modified by rABS-g-SAG-g-rHIPS double-splicing compatilizer and preparation method of rABS / rHIPS blend

Abstract

The invention relates to the field of modification of waste plastics in high polymer materials, in particular to an rABS / rHIPS blend modified by an rABS-g-SAG-g-rHIPS double-splicing compatilizer and a preparation method of the rABS / rHIPS blend. The preparation method comprises the following steps: drying SAG, rHIPS and rABS, carrying out melt blending in a torque rheometer to obtain rABS-g-SAG-g-rHIPS, and adding the rABS-g-SAG-g-rHIPS into the rABS / rHIPS blend to obtain an rABS / rHIPS / rABS-g-SAG-g-rHIPS blend; the notch impact strength of the blending material provided by the invention is improved to 20.91 kJ / m from 6.06 kJ / m, and is improved by 245% compared with that of an rABS / rHIPS blend. And the elongation at break is improved from 9.74% to 26.28% and is improved by 270%, and the ductility is greatly improved. The blend and the preparation method have high market value.

Description

Technical Field

[0001] The invention relates to the field of waste plastic modification in polymer materials, and in particular to a rABS-g-SAG-g-rHIPS double-splicing compatibilizer-modified rABS / rHIPS blend and a preparation method thereof. Background Art

[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, and has good impact strength, hardness, thermal stability and corrosion resistance. HIPS is known for its excellent processing performance, easy molding, dimensional stability of general-purpose polystyrene (PS), and better performance in impact strength and rigidity. These two plastics are not only the main materials for the production of various electronic devices, but are also widely used in fields such as automobile manufacturing and office supplies.

[0003] During the aging process, ABS materials are mainly affected by light and heat, which leads to the decomposition and oxidation of acrylonitrile and styrene monomers. In addition, the unsaturation of butadiene also accelerates the aging of ABS. For example, under ultraviolet light, butadiene undergoes photooxidation to generate peroxides, which in turn degrades the material performance. The aging of HIPS is mainly due to the decomposition of polystyrene. Under ultraviolet light, polystyrene undergoes photodegradation to generate free radicals. These free radicals trigger chain breakage and cross-linking reactions, resulting in a decrease in the mechanical properties of the material. The above aging processes will cause the mechanical properties of ABS and HIPS to deteriorate, especially the significant decrease in impact strength.

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

[0005] The present invention is to solve the technical problem of low impact strength of rABS / rHIPS blends, and provides a rABS-g-SAG-g-rHIPS compatibilizer-modified rABS / rHIPS blend. Based on the breakage of molecular chains and a large number of carboxyl groups generated by thermal oxidative aging degradation, after adding the rABS-g-SAG-g-rHIPS compatibilizer to the rABS / rHIPS blend, the compatibility of rABS (waste acrylonitrile-styrene-butadiene copolymer) and rHIPS (waste high-impact polystyrene) is improved to a certain extent, and the impact strength of the blend is improved.

[0006] In order to solve the above technical problems, the technical solution adopted by the present invention is: a rABS / rHIPS blend modified by a rABS-g-SAG-g-rHIPS double-spliced ​​compatibilizer is made of 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 of 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 to operate in a torque rheometer by melt blending, first adding 40 parts of rHIPS, the temperature is 180°C, the speed is 50r / min, and the melting time is 15 minutes; then adding 40 parts of SAG (styrene-acrylonitrile-methacrylate copolymer), the temperature and speed remain unchanged, and the mixing time is 15 minutes; finally, adding 20 parts of rABS, the temperature is raised to 210°C, the speed remains unchanged, and the mixing time is 15 minutes, so as 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 the above-mentioned rABS / rHIPS blend modified by a rABS-g-SAG-g-rHIPS double-spliced ​​compatibilizer, comprising the following steps: drying rABS and rHIPS and melt-blending them with rABS-g-SAG-g-rHIPS in a torque rheometer to obtain a rABS / rHIPS / rABS-g-SAG-g-rHIPS blend.

[0013] Through the above blending sequence, the rABS-g-SAG-g-rHIPS compatibilizer is used to react with the aged groups of rABS / rHIPS, and the rABS-g-SAG-g-rHIPS compatibilizer can be used as a chain extender to repair the broken molecular chains.

[0014] As a further limitation of the technical solution of the present invention, the conditions for running melt blending in the torque rheometer are: first add rHIPS, the temperature is 180°C, the speed is 50r / min, and the melting time is 15 minutes; then add rABS-g-SAG-g-rHIPS compatibilizer, keep the temperature and speed unchanged, and mix for 15 minutes; finally add rABS, increase the temperature to 210°C, keep the speed unchanged, and mix for 15 minutes.

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

[0016] The present invention uses rABS-g-SAG-g-rHIPS compatibilizer to increase the volume of rABS / rHIPS blends. The market price of rABS plastic is less than 8,000 yuan / ton, and the market price of ABS is 15,000-20,000 yuan / ton; the market price of rHIPS plastic is less than 8,000 yuan / ton, and the market price of HIPS is 14,800 yuan / ton. The present invention prepares rABS / rHIPS / rABS-g-SAG-g-rHIPS blends with good mechanical properties, greatly reducing the preparation cost. Experimental results show that the notched impact strength of the rABS / rHIPS / rABS-g-SAG-g-rHIPS material provided by the present invention is increased from 6.06 kJ / m 2 Increased to 20.91 kJ / m 2 , which is 245% higher than that of rABS / rHIPS blends. The elongation at break increased from 9.74% to 26.28%, an increase of 270%. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 This is a scanning electron micrograph of rABS-g-SAG-g-rHIPS without adding a compatibilizer. The blend morphology of rABS / rHIPS (50 / 50) is a "sea-island" structure in which the two phases are incompatible.

[0018] Figure 2 Scanning electron micrograph of a blend of 47.5 parts of rABS and 47.5 parts of rHIPS with 5 parts of rABS-g-SAG-g-rHIPS compatibilizer added for the melt blending process.

[0019] Figure 3 This is the nuclear magnetic resonance hydrogen spectrum of rABS-g-SAG-g-rHIPS compatibilizer and SAG. DETAILED DESCRIPTION

[0020] The present invention is further described below in conjunction with specific embodiments.

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

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

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

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

[0025] Example 1

[0026] Weigh 50g of rHIPS, 100g of SAG, and 50g of rABS, and dry them in a constant temperature blast drying oven for 8 hours at 80°C. After drying, set aside. First add rHIPS to the torque rheometer, the temperature of the torque rheometer is 180°C, the speed is 50r / min, and the melting time is 15 minutes; then add SAG, keep the temperature and speed unchanged, and mix for 15 minutes; finally add rABS, raise the temperature to 210°C, keep the speed unchanged, and mix for 15 minutes to obtain rABS-g-SAG-g-rHIPS.

[0027] Weigh 10g of rABS-g-SAG-g-rHIPS, dry it in a constant temperature blast drying oven for 8 hours at 80℃, and set it aside after drying. Weigh 95g of rABS and 95g of rHIPS, dry them in a constant temperature blast drying oven for 8 hours at 80℃. First add rHIPS to the torque rheometer, the temperature is 180℃, the speed is 50r / min, and the melting time is 15 minutes; then add rABS-g-SAG-g-rHIPS compatibilizer, keep the temperature and speed unchanged, and mix for 15 minutes; finally add rABS, raise the temperature to 210℃, keep the speed unchanged, and mix for 15 minutes.

[0028] Example 2

[0029] Weigh 40g of rHIPS, 80g of SAG, and 80g of rABS, and dry them in a constant temperature blast drying oven for 8 hours at 80°C. After drying, set aside. First add rHIPS to the torque rheometer, the temperature of the torque rheometer is 180°C, the speed is 50r / min, and the melting time is 15 minutes; then add SAG, keep the temperature and speed unchanged, and mix for 15 minutes; finally add rABS, raise the temperature to 210°C, keep the speed unchanged, and mix for 15 minutes to obtain rABS-g-SAG-g-rHIPS.

[0030] Weigh 10g of rABS-g-SAG-g-rHIPS, dry it in a constant temperature blast drying oven for 8 hours at 80℃, and set it aside after drying. Weigh 95g of rABS and 95g of rHIPS, dry them in a constant temperature blast drying oven for 8 hours at 80℃. First add rHIPS to the torque rheometer, the temperature is 180℃, the speed is 50r / min, and the melting time is 15 minutes; then add rABS-g-SAG-g-rHIPS compatibilizer, keep the temperature and speed unchanged, and mix for 15 minutes; finally add rABS, raise the temperature to 210℃, keep the speed unchanged, and mix for 15 minutes.

[0031] Example 3

[0032] Weigh 80g of rHIPS, 80g of SAG, and 40g of rABS, and dry them in a constant temperature blast drying oven for 8 hours at 80°C. After drying, set aside. First add rHIPS to the torque rheometer, the temperature of the torque rheometer is 180°C, the speed is 50r / min, and the melting time is 15 minutes; then add SAG, keep the temperature and speed unchanged, and mix for 15 minutes; finally add rABS, raise the temperature to 210°C, keep the speed unchanged, and mix for 15 minutes to obtain rABS-g-SAG-g-rHIPS.

[0033] Weigh 10g of rABS-g-SAG-g-rHIPS, dry it in a constant temperature blast drying oven for 8 hours at 80℃, and set it aside after drying. Weigh 95g of rABS and 95g of rHIPS, dry them in a constant temperature blast drying oven for 8 hours at 80℃. First add rHIPS to the torque rheometer, the temperature is 180℃, the speed is 50r / min, and the melting time is 15 minutes; then add rABS-g-SAG-g-rHIPS compatibilizer, keep the temperature and speed unchanged, and mix for 15 minutes; finally add rABS, raise the temperature to 210℃, keep the speed unchanged, and mix for 15 minutes.

[0034] Example 4

[0035] Weigh 80g of rHIPS, 80g of SAG, and 40g of rABS, and dry them in a constant temperature blast drying oven for 8 hours at 80°C. After drying, set aside. First add rHIPS to the torque rheometer, the temperature of the torque rheometer is 180°C, the speed is 50r / min, and the melting time is 15 minutes; then add SAG, keep the temperature and speed unchanged, and mix for 15 minutes; finally add rABS, raise the temperature to 210°C, keep the speed unchanged, and mix for 15 minutes to obtain rABS-g-SAG-g-rHIPS.

[0036] Weigh 8g of rABS-g-SAG-g-rHIPS, dry it in a constant temperature blast drying oven for 8 hours at 80°C, and set it aside after drying. Weigh 85g of rABS and 105g of rHIPS, dry them in a constant temperature blast drying oven for 8 hours at 80°C. First add rHIPS to the torque rheometer, the temperature is 180°C, the speed is 50r / min, and the melting time is 15 minutes; then add rABS-g-SAG-g-rHIPS compatibilizer, keep the temperature and speed unchanged, and mix for 15 minutes; finally add rABS, raise the temperature to 210°C, keep the speed unchanged, and mix for 15 minutes.

[0037] Example 5

[0038] Weigh 80g of rHIPS, 80g of SAG, and 40g of rABS, and dry them in a constant temperature blast drying oven for 8 hours at 80°C. After drying, set aside. First add rHIPS to the torque rheometer, the temperature of the torque rheometer is 180°C, the speed is 50r / min, and the melting time is 15 minutes; then add SAG, keep the temperature and speed unchanged, and mix for 15 minutes; finally add rABS, raise the temperature to 210°C, keep the speed unchanged, and mix for 15 minutes to obtain rABS-g-SAG-g-rHIPS.

[0039] Weigh 15g of rABS-g-SAG-g-rHIPS, dry it in a constant temperature blast drying oven for 8 hours at 80°C, and set it aside after drying. Weigh 105g of rABS and 85g of rHIPS, dry them in a constant temperature blast drying oven for 8 hours at 80°C. First add rHIPS to the torque rheometer, the temperature is 180°C, the speed is 50r / min, and the melting time is 15 minutes; then add rABS-g-SAG-g-rHIPS compatibilizer, keep the temperature and speed unchanged, and mix for 15 minutes; finally add rABS, raise the temperature to 210°C, keep the speed unchanged, and mix for 15 minutes.

[0040] Comparative Example 1

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

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

[0043] Test results:

[0044] The notched impact strength and tensile strength of the modified materials of Example 1, Example 2, Example 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 values ​​of the three experimental data were taken as the impact strength and tensile strength of the sample, and the test results are shown in Table 1. Figure 1 This is a scanning electron micrograph of rABS-g-SAG-g-rHIPS without adding a compatibilizer. Figure 2 Scanning electron micrograph of a blend of 5 parts rABS-g-SAG-g-rHIPS and 47.5 parts rABS and 47.5 parts rHIPS added for melt blending modification.

[0045] As can be seen from Table 1, from Examples 1 to 3, it can be concluded that the present invention provides a method for preparing a rABS / rHIPS blend by using rABS-g-SAG-g-rHIPS. From Comparative Example 1, it can be concluded 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 / m 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: Mechanical properties test results 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[Notched 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 above table and attached Figure 1 It can be seen that by using the modification method provided by the present invention, 50 parts of rABS and 50 parts of rHIPS are melt-blended to form a blend with a "sea-island" structure in which the two phases are incompatible. Due to uneven dispersion, irregular shape, and large particle size, the compatibility of rABS / rHIPS is poor, thereby affecting the mechanical properties of rABS / rHIPS.

[0049] From the above table and attached Figure 2 It can be seen that compared with the rABS / rHIPS blend, in Comparative Example 1, after adding rABS-g-SAG-g-rHIPS, the compatibility is improved, the interfacial tension between the two phases is reduced, the adhesion is enhanced, the distribution of the dispersed phase becomes more uniform, and the shape becomes more and more regular. From the perspective of mechanical properties, the impact strength of the blend is 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 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 evenly distributed, the particle size becomes smaller, the cross-section is relatively smooth, the interfacial adhesion of the two phases is improved, and the purpose of phase repair is achieved, 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 5.37ppm, which is the resonance signal peak of alcohol hydroxyl hydrogen, indicating that the grafting is successful; the resonance signal peak at 1.55ppm represents the resonance signal peak of rABS grafting, and 7.08ppm represents the resonance signal peak of rHIPS grafting. After SAG is grafted with rABS and rHIPS, the original peak intensity will weaken. 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, thereby reducing the intensity. And it is calculated that the grafting rate of rABS in the rABS-g-SAG-g-rHIPS compatibilizer provided by the present invention is 18.36%, and the grafting rate of rHIPS is 19.50%, indicating that the grafting is successful and the double-spliced ​​comb-type compatibilizer is successfully prepared.

[0052] The experimental results show that the notched impact strength of the rABS / rHIPS / rABS-g-SAG-g-rHIPS material provided by the present 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%, and the ductility is greatly improved. The preparation method of the present invention can be used for rABS / rHIPS plastic melt modification granulation and reuse separately, and has a high market value.

[0053] The above is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art can easily think of changes or substitutions within the technical scope disclosed by the present invention, which should be included in the protection scope of the present invention. Therefore, the protection scope of the present invention should be based on the protection scope of the claims.

Claims

1. A rABS-g-SAG-g-rHIPS double-splicing compatibilizer-modified rABS / rHIPS blend, characterized in that: The invention is prepared 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.

2. The rABS / rHIPS blend modified by a rABS-g-SAG-g-rHIPS double-splicing compatibilizer according to claim 1, characterized in that: It is made of 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.

3. The rABS / rHIPS blend modified by a rABS-g-SAG-g-rHIPS double-splicing compatibilizer according to claim 1, characterized in that: The preparation method of the rABS-g-SAG-g-rHIPS compatibilizer is to operate the melt blending reaction in a torque rheometer, first add 40 parts of rHIPS, the temperature is 180°C, the rotation speed is 50r / min, and the melting time is 15 minutes; then add 40 parts of SAG, keep the temperature and rotation speed unchanged, and mix for 15 minutes; finally add 20 parts of rABS, increase the temperature to 210°C, keep the rotation speed unchanged, and mix for 15 minutes, so as to obtain the rABS-g-SAG-g-rHIPS compatibilizer.

4. The rABS / rHIPS blend modified by a rABS-g-SAG-g-rHIPS double-splicing compatibilizer according to claim 1, characterized in that: The rABS melt index is 3.58 g / 10 min.

5. The rABS / rHIPS blend modified by a rABS-g-SAG-g-rHIPS double-splicing compatibilizer according to claim 1, characterized in that: The rHIPS melt index is 10.89 g / 10 min.

6. The rABS / rHIPS blend modified by a rABS-g-SAG-g-rHIPS double-splicing compatibilizer according to claim 1, characterized in that: The rABS / rHIPS melt index is 4.10 g / 10 min.

7. The rABS / rHIPS blend modified by a rABS-g-SAG-g-rHIPS double-splicing compatibilizer according to claim 3, characterized in that: The epoxy equivalent of the SAG is 400-850 g / mol.

8. The method for preparing a rABS / rHIPS blend modified by a rABS-g-SAG-g-rHIPS double-splicing compatibilizer according to any one of claims 1 to 7, characterized in that: The following steps are involved: After drying, rABS and rHIPS are melt-blended with rABS-g-SAG-g-rHIPS in a torque rheometer to obtain rABS / rHIPS / rABS-g-SAG-g-rHIPS blends.

9. The method for preparing a rABS / rHIPS blend modified by a rABS-g-SAG-g-rHIPS double-splicing compatibilizer according to claim 8, characterized in that: The conditions for melt blending in the torque rheometer are as follows: first add rHIPS, temperature 180°C, rotation speed 50r / min, melting time 15 minutes; then add rABS-g-SAG-g-rHIPS compatibilizer, keep the temperature and rotation speed unchanged, and mix for 15 minutes; finally add rABS, increase the temperature to 210°C, keep the rotation speed unchanged, and mix for 15 minutes.

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