CN114907665A - Toughened yellowing-resistant ABS reclaimed material and preparation method thereof - Google Patents
Toughened yellowing-resistant ABS reclaimed material and preparation method thereof Download PDFInfo
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- CN114907665A CN114907665A CN202210613073.2A CN202210613073A CN114907665A CN 114907665 A CN114907665 A CN 114907665A CN 202210613073 A CN202210613073 A CN 202210613073A CN 114907665 A CN114907665 A CN 114907665A
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- 239000000463 material Substances 0.000 title claims abstract description 50
- 238000004383 yellowing Methods 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 35
- 239000004970 Chain extender Substances 0.000 claims abstract description 23
- 239000004593 Epoxy Substances 0.000 claims abstract description 18
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 claims abstract description 15
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 14
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 13
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 12
- 238000007599 discharging Methods 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 5
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 4
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims 1
- 229910045601 alloy Inorganic materials 0.000 claims 1
- 229920006132 styrene block copolymer Polymers 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000004048 modification Effects 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 4
- 229920003023 plastic Polymers 0.000 abstract description 4
- 239000004033 plastic Substances 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 38
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 37
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 37
- 230000000052 comparative effect Effects 0.000 description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- XOFYZVNMUHMLCC-ZPOLXVRWSA-N prednisone Chemical compound O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 XOFYZVNMUHMLCC-ZPOLXVRWSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a toughened yellowing-resistant ABS reclaimed material and a preparation method thereof, and belongs to the technical field of modification of waste recycled plastics. The toughened yellowing-resistant ABS reclaimed material is prepared by firstly carrying out melt blending on an ABS reclaimed material, styrene butadiene styrene block copolymer grafted maleic anhydride and 2, 4-dihydroxy benzophenone, then adding an epoxy chain extender and a catalyst for melt blending, and finally adding an antioxidant for melt blending. The ABS reclaimed material prepared by the invention has higher tensile strength and impact strength, higher elongation at break and more excellent yellowing resistance, is mainly used for manufacturing electric appliance shells, and has remarkable economic value and social benefit.
Description
Technical Field
The invention belongs to the technical field of modification of waste recycled plastics, and particularly relates to a toughened yellowing-resistant ABS recycled material and a preparation method thereof.
Background
Acrylonitrile-butadiene-styrene (ABS) copolymer has excellent electrical properties, mechanical properties, abrasion resistance, dimensional stability, chemical resistance, surface gloss, etc., and is widely used for making housings of electric appliances such as washing machines, televisions, refrigerators, computers, mobile phones, etc. When the electric appliances are eliminated, the ABS plastic for manufacturing the electric appliance shell can be crushed again to form an ABS reclaimed material which is recycled. In the early use process of the ABS reclaimed materials, the molecular chains are broken due to aging reaction under the action of light, heat and oxygen, so that the toughness of the ABS reclaimed materials is very poor, and most of the ABS reclaimed materials can only be used for manufacturing plastic products with low added values at present.
Disclosure of Invention
The invention provides a toughened yellowing-resistant ABS reclaimed material and a preparation method thereof, aiming at the problems that the traditional ABS reclaimed material has poor toughness and can only be used for manufacturing plastic products with low added values. The ABS reclaimed material prepared by the invention has higher tensile strength and impact strength, higher elongation at break and more excellent yellowing resistance, is mainly used for manufacturing electric appliance shells, and has remarkable economic value and social benefit.
In order to achieve the purpose, the invention adopts the following technical scheme:
the toughening yellowing-resistant ABS reclaimed material is prepared by firstly carrying out melt blending on the ABS reclaimed material, styrene butadiene styrene block copolymer grafted maleic anhydride and 2, 4-dihydroxy benzophenone, then adding an epoxy chain extender and a catalyst for melt blending, and finally adding an antioxidant for melt blending.
The preparation method of the toughened yellowing-resistant ABS reclaimed material specifically comprises the following steps:
sequentially adding 60-100 g of ABS reclaimed materials, 6-20 g of styrene butadiene styrene block copolymer grafted maleic anhydride and 0.5-2 g of 2, 4-dihydroxy benzophenone into an internal mixer, and internally mixing for 2-4 min at the temperature of 180-200 ℃ and the pressure of 0.2-0.4 MPa; then adding 0.1-0.5 g of epoxy chain extender and 0.02-0.2 g of catalyst into the internal mixer, and continuously carrying out internal mixing for 8-12 min at the temperature of 200-220 ℃ and the pressure of 0.3-0.6 MPa; finally, 0.5-1.5 g of antioxidant is added into the internal mixer, and internal mixing is carried out for 3-6 min at the temperature of 170-190 ℃ and the pressure of 0.1-0.3 MPa; and discharging after banburying, and crushing at room temperature to obtain a finished product, namely the toughened yellowing-resistant ABS reclaimed material.
The epoxy chain extender is any one of an epoxy chain extender ADR4400 and an epoxy chain extender ADR 4468.
The catalyst is any one of triethylamine, triethylene diamine or triethylene diamine.
The antioxidant is a compound system of an antioxidant 1010 and an antioxidant 168, wherein the weight ratio of the antioxidant 1010 to the antioxidant 168 is 1: 1.
The invention has the following remarkable advantages:
(1) the invention takes a polyepoxy compound ADR as a chain extender, and utilizes the reaction of hydroxyl and carboxyl on ABS reclaimed material molecules and epoxy groups of ADR chain extender molecules to increase the molecular weight of the ABS reclaimed material and improve the tensile strength of the ABS reclaimed material.
(2) According to the invention, a polyepoxy compound ADR is used as a chain extender, carboxyl of a styrene butadiene styrene block copolymer grafted maleic anhydride molecule reacts with epoxy of an ADR chain extender molecule, and the styrene butadiene styrene block copolymer is grafted on an ABS reclaimed material molecule, so that the dispersion stability of the styrene butadiene styrene block copolymer in the ABS reclaimed material is improved. Meanwhile, the styrene butadiene styrene block copolymer with excellent toughness can improve the impact strength and the elongation at break of the ABS reclaimed material.
(3) According to the invention, a polyepoxy compound ADR is used as a chain extender, and the 4-phenolic hydroxyl group of a 2, 4-dihydroxy benzophenone molecule is reacted with the epoxy group of the ADR chain extender molecule to graft the 2, 4-dihydroxy benzophenone on the ABS reclaimed material molecule, so that the dispersion stability of the 2, 4-dihydroxy benzophenone in the ABS reclaimed material is improved. Meanwhile, the 2, 4-dihydroxy benzophenone can endow the ABS reclaimed material with excellent light stability.
(4) The ABS recycled material prepared by the invention has high tensile strength and impact strength, high elongation at break and excellent yellowing resistance, the tensile strength is 47.3-58.9 MPa, the elongation at break is 28.5-35.5%, and the impact strength is 22.1-25.5 kJ/m 2 And the surface color difference delta E is 3.42-4.16, and the method is mainly used for manufacturing the shell of the electric appliance and has obvious economic value and social benefit.
Detailed Description
The advantages and effects of the preparation method of the recycled toughened yellowing-resistant ABS material in this embodiment are further illustrated by three groups of examples and three groups of comparative examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
Sequentially adding 80g of ABS reclaimed materials, 10 g of styrene butadiene styrene block copolymer grafted maleic anhydride and 1g of 2, 4-dihydroxy benzophenone into an internal mixer, and internally mixing for 3min at the temperature of 190 ℃ and the pressure of 0.3 MPa; then 0.3g of epoxy chain extender ADR4400 and 0.1g of triethylamine are added into the internal mixer, and the internal mixing is continued for 10 min at the temperature of 210 ℃ and the pressure of 0.5 MPa; finally, adding 1g of antioxidant into an internal mixer, and internally mixing for 4min at the temperature of 180 ℃ and the pressure of 0.2 MPa; and discharging after banburying, and crushing at room temperature to obtain a finished product, namely the toughened yellowing-resistant ABS reclaimed material.
Example 2
Sequentially adding 60 g of ABS reclaimed materials, 6g of styrene butadiene styrene block copolymer grafted maleic anhydride and 0.5g of 2, 4-dihydroxy benzophenone into an internal mixer, and internally mixing for 4min at the temperature of 180 ℃ and the pressure of 0.4 MPa; then 0.1g of epoxy chain extender ADR4468 and 0.02 g of triethylene diamine are added into the internal mixer, and the internal mixing is continued for 12 min at the temperature of 200 ℃ and the pressure of 0.6 MPa; finally, 0.5g of antioxidant is added into the internal mixer, and internal mixing is carried out for 6min at the temperature of 170 ℃ and the pressure of 0.3 MPa; discharging after banburying is finished, and crushing at room temperature to obtain a finished product, namely the toughened yellowing-resistant ABS reclaimed material.
Example 3
Sequentially adding 100g of ABS reclaimed materials, 20 g of styrene butadiene styrene block copolymer grafted maleic anhydride and 2g of 2, 4-dihydroxy benzophenone into an internal mixer, and internally mixing for 2 min at the temperature of 200 ℃ and the pressure of 0.2 MPa; then 0.5g of epoxy chain extender ADR4400 and 0.2g of triethylene diamine are added into the internal mixer, and the internal mixing is continued for 8 min at the temperature of 220 ℃ and the pressure of 0.3 MPa; finally, adding 1.5g of antioxidant into an internal mixer, and internally mixing for 3min at the temperature of 190 ℃ and the pressure of 0.1 MPa; discharging after banburying is finished, and crushing at room temperature to obtain a finished product, namely the toughened yellowing-resistant ABS reclaimed material.
Comparative example 1
Sequentially adding 80g of ABS reclaimed materials and 1g of 2, 4-dihydroxy benzophenone into an internal mixer, and internally mixing for 3min at the temperature of 190 ℃ and the pressure of 0.3 MPa; then 0.3g of epoxy chain extender ADR4400 and 0.1g of triethylamine are added into the internal mixer, and the internal mixing is continued for 10 min at the temperature of 210 ℃ and the pressure of 0.5 MPa; finally, adding 1g of antioxidant into an internal mixer, and internally mixing for 4min at the temperature of 180 ℃ and the pressure of 0.2 MPa; discharging after banburying, and crushing at room temperature to obtain the finished product.
Comparative example 2
Sequentially adding 80g of ABS reclaimed materials and 10 g of styrene butadiene styrene block copolymer grafted maleic anhydride into an internal mixer, and internally mixing for 3min at the temperature of 190 ℃ and the pressure of 0.3 MPa; then 0.3g of epoxy chain extender ADR4400 and 0.1g of triethylamine are added into the internal mixer, and the internal mixing is continued for 10 min at the temperature of 210 ℃ and the pressure of 0.5 MPa; finally, adding 1g of antioxidant into an internal mixer, and internally mixing for 4min at the temperature of 180 ℃ and the pressure of 0.2 MPa; discharging after banburying, and crushing at room temperature to obtain the finished product.
Comparative example 3
Sequentially adding 80g of ABS reclaimed materials, 10 g of styrene butadiene styrene block copolymer grafted maleic anhydride and 1g of 2, 4-dihydroxybenzophenone into an internal mixer, and internally mixing for 3min at the temperature of 190 ℃ and the pressure of 0.3 MPa; adding 1g of antioxidant into the internal mixer, and internally mixing for 4min at the temperature of 180 ℃ and the pressure of 0.2 MPa; discharging after banburying, and crushing at room temperature to obtain the finished product.
The products prepared in the three groups of examples and the three groups of comparative examples are tested for tensile strength and elongation at break according to GB/T1040-.
Table 1 results of performance testing
| Tensile Strength (MPa) | Elongation at Break (%) | Impact Strength (kJ/m) 2 ） | Surface color difference Δ E | |
| Unmodified ABS reclaimed material | 25.8 | 9.26 | 14.6 | 12.3 |
| Example 1 | 58.9 | 33.4 | 25.5 | 3.53 |
| Example 2 | 47.3 | 28.5 | 22.1 | 4.16 |
| Example 3 | 56.6 | 35.5 | 24.8 | 3.42 |
| Comparative example 1 | 66.0 | 10.2 | 18.3 | 3.38 |
| Comparative example 2 | 55.4 | 34.6 | 26.7 | 11.6 |
| Comparative example 3 | 20.4 | 16.4 | 20.9 | 5.41 |
From the test results of the three groups of examples and the three groups of comparative examples, the strength, toughness and yellowing resistance of the finished products prepared by the three groups of examples are obviously superior to those of the finished products prepared by the three groups of comparative examples, and are far superior to those of unmodified ABS reclaimed materials, which shows that the ABS reclaimed materials, styrene butadiene styrene block copolymer grafted maleic anhydride and 2, 4-dihydroxy benzophenone are firstly subjected to melt blending, then epoxy chain extenders and catalysts are added for melt blending, and finally antioxidants are added for melt blending to prepare the ABS reclaimed materials with higher tensile strength and impact strength, larger elongation at break and more excellent yellowing resistance.
While the foregoing description shows and describes the preferred embodiments of the present invention, it is to be understood that the invention is not limited to the forms disclosed herein, but is not to be construed as excluding other embodiments and is capable of use in various other combinations, modifications, and environments and is capable of changes within the scope of the inventive concept as described herein, commensurate with the above teachings, or the skill or knowledge of the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (4)
1. The toughened yellowing-resistant ABS reclaimed material is characterized by comprising the following components in parts by weight: firstly, carrying out melt blending on an ABS reclaimed material, styrene butadiene styrene block copolymer grafted maleic anhydride and 2, 4-dihydroxy benzophenone, then adding an epoxy chain extender and a catalyst for melt blending, and finally adding an antioxidant for melt blending to prepare the ABS/styrene block copolymer modified ABS alloy; the method specifically comprises the following steps:
sequentially adding 60-100 g of ABS reclaimed materials, 6-20 g of styrene butadiene styrene block copolymer grafted maleic anhydride and 0.5-2 g of 2, 4-dihydroxy benzophenone into an internal mixer, and internally mixing for 2-4 min at the temperature of 180-200 ℃ and the pressure of 0.2-0.4 MPa; then adding 0.1-0.5 g of epoxy chain extender and 0.02-0.2 g of catalyst into the internal mixer, and continuously carrying out internal mixing for 8-12 min at the temperature of 200-220 ℃ and the pressure of 0.3-0.6 MPa; finally, 0.5-1.5 g of antioxidant is added into the internal mixer, and internal mixing is carried out for 3-6 min at the temperature of 170-190 ℃ and the pressure of 0.1-0.3 MPa; discharging after banburying is finished, and crushing at room temperature to obtain a finished product, namely the toughened yellowing-resistant ABS reclaimed material.
2. The preparation method of the toughened yellowing-resistant ABS recycled material as claimed in claim 1, wherein the preparation method comprises the following steps: the epoxy chain extender is any one of an epoxy chain extender ADR4400 and an epoxy chain extender ADR 4468.
3. The preparation method of the toughened yellowing-resistant ABS recycled material as claimed in claim 1, wherein the preparation method comprises the following steps: the catalyst is any one of triethylamine, triethylene diamine and triethylene diamine.
4. The preparation method of the toughened yellowing-resistant ABS recycled material as claimed in claim 1, wherein the preparation method comprises the following steps: the antioxidant is a compound system of an antioxidant 1010 and an antioxidant 168, wherein the weight ratio of the antioxidant 1010 to the antioxidant 168 is 1: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210613073.2A CN114907665B (en) | 2022-06-01 | 2022-06-01 | Toughened yellowing-resistant ABS reclaimed material and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210613073.2A CN114907665B (en) | 2022-06-01 | 2022-06-01 | Toughened yellowing-resistant ABS reclaimed material and preparation method thereof |
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| CN114907665A true CN114907665A (en) | 2022-08-16 |
| CN114907665B CN114907665B (en) | 2024-01-12 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104629315A (en) * | 2013-11-07 | 2015-05-20 | 殷培花 | Regenerated PC/ABS blending alloy |
| CN106867223A (en) * | 2017-03-01 | 2017-06-20 | 深圳市博富隆新材料科技有限公司 | A kind of recyclable casing material of glass fiber reinforcement and preparation method thereof |
| US20220017742A1 (en) * | 2018-12-06 | 2022-01-20 | South China University Of Technology | rABS/PBT/ASG Composite Material and Preparation Method Thereof |
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2022
- 2022-06-01 CN CN202210613073.2A patent/CN114907665B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104629315A (en) * | 2013-11-07 | 2015-05-20 | 殷培花 | Regenerated PC/ABS blending alloy |
| CN106867223A (en) * | 2017-03-01 | 2017-06-20 | 深圳市博富隆新材料科技有限公司 | A kind of recyclable casing material of glass fiber reinforcement and preparation method thereof |
| US20220017742A1 (en) * | 2018-12-06 | 2022-01-20 | South China University Of Technology | rABS/PBT/ASG Composite Material and Preparation Method Thereof |
Non-Patent Citations (1)
| Title |
|---|
| 王嘉: "环氧树脂含量对废旧ABS塑料性能的影响", 《高分子材料科学与工程》, pages 134 - 135 * |
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