CN114573874A - Modified fullerene, anti-aging and antistatic ABS composite material and preparation method thereof - Google Patents
Modified fullerene, anti-aging and antistatic ABS composite material and preparation method thereof Download PDFInfo
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- CN114573874A CN114573874A CN202210414530.5A CN202210414530A CN114573874A CN 114573874 A CN114573874 A CN 114573874A CN 202210414530 A CN202210414530 A CN 202210414530A CN 114573874 A CN114573874 A CN 114573874A
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- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 230000003712 anti-aging effect Effects 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229910003472 fullerene Inorganic materials 0.000 claims abstract description 47
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 42
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000002156 mixing Methods 0.000 claims abstract description 29
- ZXUKNOGFRSOORK-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyl chloride Chemical compound CC(C)(C)C1=CC(CCC(Cl)=O)=CC(C(C)(C)C)=C1O ZXUKNOGFRSOORK-UHFFFAOYSA-N 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229940126062 Compound A Drugs 0.000 claims abstract description 14
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 21
- 238000001914 filtration Methods 0.000 claims description 19
- 230000035484 reaction time Effects 0.000 claims description 9
- 238000001125 extrusion Methods 0.000 claims description 4
- 238000005469 granulation Methods 0.000 claims description 4
- 230000003179 granulation Effects 0.000 claims description 4
- 239000002861 polymer material Substances 0.000 abstract description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 64
- 238000005303 weighing Methods 0.000 description 21
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 239000007800 oxidant agent Substances 0.000 description 8
- 230000001590 oxidative effect Effects 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 230000032683 aging Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 150000001263 acyl chlorides Chemical group 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- -1 3, 5-di-tert-butyl-4-hydroxyphenyl Chemical group 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229910002249 LaCl3 Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/045—Fullerenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
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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)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Carbon And Carbon Compounds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a modified fullerene and anti-aging and anti-static ABS composite material and a preparation method thereof, belonging to the technical field of high polymer materials. The modified fullerene is prepared by the following steps: 1) mixing fullerene and Ce (NO)3)3Mixing the solution with water, and reacting to obtain a compound A; 2) mixing the compound A and hydrogen peroxide, and reacting to obtain hydroxylated fullerene; 3) and mixing the hydroxylated fullerene, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride, triethylamine and acetone, and reacting to obtain the modified fullerene.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a modified fullerene and anti-aging and anti-static ABS composite material and a preparation method thereof.
Background
ABS plastic is a terpolymer of acrylonitrile (A) -butadiene (B) -styrene (S). The ABS plastic integrates the performances of three components, the characteristics of the three components enable the ABS plastic to become thermoplastic plastic with good comprehensive performances of 'hardness, toughness and rigidity', but the ageing resistance and antistatic property of the ABS are general, so that the application of the ABS material in some specific fields is limited.
Patent CN108794972A adds fullerene to ABS to improve the antistatic property of ABS, but the compatibility between fullerene and ABS is poor, which affects the physical property of ABS composite material, and a compatibilizer needs to be added additionally for improvement.
Disclosure of Invention
The invention provides a modified fullerene and anti-aging and anti-static ABS composite material and a preparation method thereof. The modified fullerene provided by the invention has good compatibility with ABS, and the prepared ABS composite material has excellent ageing resistance and antistatic property.
In order to achieve the purpose, the invention provides a modified fullerene which is prepared by the following steps:
1) mixing fullerene and Ce (NO)3)3Mixing the solution with water, and reacting to obtain a compound A;
2) mixing the compound A and hydrogen peroxide, and reacting to obtain hydroxylated fullerene;
3) and mixing the hydroxylated fullerene, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride, triethylamine and acetone, and reacting to obtain the modified fullerene.
Preferably, in the step 1), the reaction temperature is 20-30 ℃ and the reaction time is 4-6 h;
in the step 2), the reaction temperature is 40-60 ℃ and the reaction time is 4-6 h;
in the step 3), the reaction temperature is 50-70 ℃ and the reaction time is 6-8 h.
Preferably, Ce (NO) in the step 1)3)3Solution of Ce (NO)3)3·6H2O and acetone, the Ce (NO)3)3·6H2The mass ratio of O to acetone is (30-50): (120-160).
Preference is given toThe fullerene and Ce (NO) in the step 1)3)3The mass ratio of the solution to the water is (40-50): (40-60): (120-160).
Preferably, the mass ratio of the compound A to the hydrogen peroxide in the step 2) is (30-40): (60-80).
Preferably, the mass ratio of the hydroxylated fullerene, the beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride, the triethylamine and the acetone in the step 3) is (20-30): (1.6-2): (0.3-0.5): (80-100).
Preferably, the steps 1), 2) and 3) are respectively filtered, washed and dried after the reaction is completed; the drying temperatures are independently 80-100 ℃.
The invention also provides an anti-aging and antistatic ABS composite material, which comprises the following components in parts by weight:
80-100 parts of ABS and 10-16 parts of modified fullerene;
the modified fullerene is the modified fullerene according to any one of the above embodiments.
The invention also provides a preparation method of the anti-aging and antistatic ABS composite material, which comprises the following steps:
1) mixing ABS and modified fullerene to obtain a mixture;
2) and extruding and granulating the mixture to obtain the anti-aging and anti-static ABS composite material.
Preferably, the extrusion granulation is performed in a twin-screw extruder, and the twin-screw extruder adopts six temperature zones arranged in sequence during extrusion granulation, which are respectively: the temperature of the first area is 200-210 ℃, the temperature of the second area is 210-220 ℃, the temperature of the third area is 210-220 ℃, the temperature of the fourth area is 210-220 ℃, the temperature of the fifth area is 210-220 ℃, and the temperature of the sixth area is 210-220 ℃; the head temperature of the double-screw extruder is 210-220 ℃, and the screw rotating speed is 200-280 r/min.
Compared with the prior art, the invention has the advantages and positive effects that:
the modified fullerene provided by the invention adopts rare earth ion Ce3+Treating the fullerene to make the surface of the fullerene more adherentContaining oxygen-reactive radicals, rare-earth Ce3+As an intermediate medium, chemical bond connection between the fullerene surface and the ABS matrix is promoted, the interface bonding force between the fullerene and the ABS matrix is improved, and the compatibility between the fullerene and the ABS matrix is improved.
Meanwhile, the acyl chloride group of the beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) is reacted with the hydroxyl on the hydroxylated fullerene, so that the beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride is grafted to the fullerene, and the fullerene serving as a filler has aging resistance, and the aging resistance of the ABS is improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a modified fullerene, which is prepared by the following steps:
1) mixing fullerene and Ce (NO)3)3Mixing the solution with water, and reacting to obtain a compound A;
2) mixing the compound A and hydrogen peroxide, and reacting to obtain hydroxylated fullerene;
3) and mixing the hydroxylated fullerene, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride, triethylamine and acetone, and reacting to obtain the modified fullerene.
The invention adds Ce (NO)3)3The solution and water are mixed and reacted to obtain compound A. In the present invention, the Ce (NO) is3)3The solution is preferably made of Ce (NO)3)3·6H2O and acetone, the Ce (NO)3)3·6H2The mass ratio of O to acetone is (30-50): (120-160). It will be appreciated that one skilled in the art can select an appropriate reaction ratio within the above preferred ranges, such as 30:120, 50:160 or 40:130, etc. In the present invention, the reaction temperature is preferably 20 to 30 ℃ and the reaction time is preferably 4 to 6 hours. In the present invention, it is preferable to sequentially perform filtration, washing and drying after the completion of the reaction; the washing is preferably carried out with water. The temperature of the drying is preferably 80 to 100 ℃.
After the compound A is obtained, the compound A and hydrogen peroxide are mixed and react to obtain the hydroxylated fullerene. In the invention, the mass ratio of the compound A to the hydrogen peroxide is preferably (30-40): (60-80). It will be appreciated that one skilled in the art can select an appropriate reaction ratio within the above-mentioned preferred ratio range, such as 30:60, 40:80 or 35: 70. In the present invention, the reaction temperature is preferably 40 to 60 ℃ and the reaction time is preferably 4 to 6 hours. In the present invention, it is preferable to sequentially perform filtration, washing and drying after the completion of the reaction; the washing is preferably carried out with water. The temperature of the drying is preferably 80 to 100 ℃.
After obtaining the hydroxylated fullerene, the invention mixes the hydroxylated fullerene, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride, triethylamine and acetone for reaction to obtain the modified fullerene. In the present invention, the mass ratio of the hydroxylated fullerene, the beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride, the triethylamine and the acetone is preferably (20-30): (1.6-2): (0.3-0.5): (80-100). It will be appreciated that one skilled in the art can select an appropriate reaction ratio within the above preferred ratio ranges, such as 30:60, 1.6:0.3:80, or 20:2:0.3:100, etc. In the present invention, the reaction temperature is preferably 50 to 70 ℃ and the reaction time is preferably 6 to 8 hours. In the present invention, it is preferable to sequentially perform filtration, washing and drying after the completion of the reaction; the washing is preferably carried out with water. The temperature of the drying is preferably 80 to 100 ℃.
The invention passes rare earth ion Ce3+Treating fullerene to attach more oxygen-containing active groups, rare earth Ce3+As an intermediate medium, chemical bond connection between the fullerene surface and the ABS matrix is promoted, the interface bonding force between the fullerene and the ABS matrix is improved, and the compatibility between the fullerene and the ABS matrix is improved.
Beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride has oxidation resistance, and an acyl chloride group of the beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride is utilized to react with hydroxyl on hydroxylated fullerene, so that the beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride is grafted on the fullerene and has aging resistance as a filler, and the beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride is used for modifying ABS to improve the aging resistance of ABS.
The fullerene has excellent conductive performance, and the ABS modified by the fullerene also improves the antistatic performance of the ABS composite material.
The invention also provides an anti-aging and antistatic ABS composite material, which comprises the following components in parts by weight:
80-100 parts of ABS and 10-16 parts of modified fullerene;
the modified fullerene is the modified fullerene according to any one of the above embodiments.
The anti-aging and antistatic ABS composite material provided by the invention comprises ABS. Including 80-100 parts by weight, it is understood that the ABS content may be 80, 81, 90, 95, 100 parts, or any value within the above ranges. The source of the ABS is not particularly limited in the invention, and the ABS can be obtained by adopting conventional commercial products in the field.
The anti-aging and antistatic ABS composite material provided by the invention comprises modified fullerene. Including 10-16 parts by weight, it is understood that the ABS content may be 10, 11, 12, 13, 14, 15, 16 parts or any value within the above range.
The invention also provides a preparation method of the anti-aging and antistatic ABS composite material, which comprises the following steps:
1) mixing ABS and modified fullerene to obtain a mixture;
2) and extruding and granulating the mixture to obtain the anti-aging and anti-static ABS composite material.
In the present invention, the extrusion granulation is preferably performed in a twin-screw extruder. The double-screw extruder preferably adopts six temperature zones which are sequentially arranged when extruding and granulating, and the six temperature zones sequentially respectively comprise: the temperature of the first area is 200-210 ℃, the temperature of the second area is 210-220 ℃, the temperature of the third area is 210-220 ℃, the temperature of the fourth area is 210-220 ℃, the temperature of the fifth area is 210-220 ℃, and the temperature of the sixth area is 210-220 ℃; the head temperature of the double-screw extruder is 210-220 ℃, and the screw rotating speed is 200-280 r/min.
In order to further illustrate the present invention, the following embodiments are described in detail, but they should not be construed as limiting the scope of the present invention.
The raw materials used in the following examples are as follows:
ABS (model 757K), qimei chemical; ce (NO)3)3·6H2O, new materials, shandong desheng ltd; acetone, south beijing sincerity chemical limited; fullerene, Jiangsu Xiancheng nanomaterial science and technology ltd; hydrogen peroxide, denna kunfeng chemical limited; beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride, Daqing institute of Petroleum chemical and chemical industry; triethylamine, Shandong Rui chemical Co., Ltd; deionized water, chemical Limited, Jinan Hai Ruibao.
Example 1
(1) Weighing 80 parts of ABS and 10 parts of modified fullerene M1, mixing and uniformly stirring to obtain a mixture;
(2) and (3) extruding and granulating the mixture obtained in the step (1) from an extruder to obtain the ABS composite material P1.
Wherein the temperature and the screw rotating speed of each zone of the double-screw extruder are respectively as follows: the temperature of the first zone is 210 ℃, the temperature of the second zone is 220 ℃, the temperature of the third zone is 220 ℃, the temperature of the fourth zone is 220 ℃, the temperature of the fifth zone is 220 ℃, the temperature of the sixth zone is 220 ℃, the temperature of the machine head is 220 ℃, and the rotating speed of the screw is 200 r/min.
The modified fullerene M1 is prepared by the following steps:
(1) weighing 300g Ce (NO)3)3·6H2O, 1.2kg of acetone, adding Ce (NO)3)3·6H2Adding O into acetone to obtain Ce (NO)3)3A solution;
(2) 400g of fullerene and 400g of Ce (NO)3)3Putting the solution into a beaker filled with 1.2kg of deionized water, reacting for 4 hours at normal temperature, filtering, washing,Drying to obtain the fullerene A.
(3) Weighing 300g of fullerene A and 600g of oxidant hydrogen peroxide, placing the fullerene A and the oxidant hydrogen peroxide in a reaction vessel, reacting for 4 hours at 40 ℃, filtering, washing and drying to obtain hydroxylated fullerene B.
(4) Weighing 200g of hydroxylated fullerene B, 16g of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride, 3g of catalyst triethylamine and 800g of acetone, placing the mixture in a reaction vessel, reacting for 6 hours at 50 ℃, filtering, washing and drying to obtain the modified fullerene M1.
Example 2
(1) Weighing 100 parts of ABS and 16 parts of modified fullerene M2, mixing and uniformly stirring to obtain a mixture;
(2) and (2) extruding and granulating the mixture obtained in the step (1) from an extruder to obtain the ABS composite material P2.
Wherein the temperature and the screw rotating speed of each area of the double-screw extruder are respectively as follows: the temperature of the first zone is 210 ℃, the temperature of the second zone is 220 ℃, the temperature of the third zone is 220 ℃, the temperature of the fourth zone is 220 ℃, the temperature of the fifth zone is 220 ℃, the temperature of the sixth zone is 220 ℃, the temperature of the machine head is 220 ℃, and the rotating speed of the screw is 200 r/min.
The modified fullerene M2 is prepared by the following steps:
(1) 500g of Ce (NO) are weighed3)3·6H2O, 1.6kg of acetone, adding Ce (NO)3)3·6H2Adding O into acetone to obtain Ce (NO)3)3A solution;
(2) 500g of fullerene and 600g of Ce (NO)3)3And putting the solution into a beaker filled with 1.6kg of deionized water, reacting for 6 hours at normal temperature, filtering, washing and drying to obtain the fullerene A.
(3) Weighing 400g of fullerene A and 800g of oxidant hydrogen peroxide, placing the fullerene A and the oxidant hydrogen peroxide in a reaction vessel, reacting for 6 hours at the temperature of 60 ℃, filtering, washing and drying to obtain the hydroxylated fullerene B.
(4) Weighing 300g of hydroxylated fullerene B, 20g of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride, 5g of catalyst triethylamine and 1.0kg of acetone, placing the mixture in a reaction vessel, reacting for 8 hours at 70 ℃, filtering, washing and drying to obtain the modified fullerene M2.
Example 3
(1) Weighing 90 parts of ABS and 13 parts of modified fullerene M3, mixing and uniformly stirring to obtain a mixture;
(2) and (3) extruding and granulating the mixture obtained in the step (1) from an extruder to obtain the ABS composite material P3.
Wherein the temperature and the screw rotating speed of each area of the double-screw extruder are respectively as follows: the temperature of the first zone is 210 ℃, the temperature of the second zone is 220 ℃, the temperature of the third zone is 220 ℃, the temperature of the fourth zone is 220 ℃, the temperature of the fifth zone is 220 ℃, the temperature of the sixth zone is 220 ℃, the temperature of the machine head is 220 ℃, and the rotating speed of the screw is 200 r/min.
The modified fullerene M3 is prepared by the following steps:
(1) weighing 400g Ce (NO)3)3·6H2O, 1.4kg of acetone, adding Ce (NO)3)3·6H2Adding O into acetone to obtain Ce (NO)3)3A solution;
(2) 450g of fullerene and 500g of Ce (NO)3)3And putting the solution into a beaker filled with 1.4kg of deionized water, reacting for 5 hours at normal temperature, filtering, washing and drying to obtain the fullerene A.
(3) Weighing 350g of fullerene A and 700g of oxidant hydrogen peroxide, placing the fullerene A and the oxidant hydrogen peroxide in a reaction vessel, reacting for 5 hours at 50 ℃, filtering, washing and drying to obtain hydroxylated fullerene B.
(4) Weighing 250g of hydroxylated fullerene B, 18g of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride, 4g of catalyst triethylamine and 900g of acetone, placing the materials in a reaction vessel, reacting for 7 hours at 60 ℃, filtering, washing and drying to obtain the modified fullerene M3.
Example 4
(1) Weighing 95 parts of ABS and 11 parts of modified fullerene M4, mixing and uniformly stirring to obtain a mixture;
(2) and (3) extruding and granulating the mixture obtained in the step (1) from an extruder to obtain the ABS composite material P4.
Wherein the temperature and the screw rotating speed of each area of the double-screw extruder are respectively as follows: the temperature of the first zone is 200 ℃, the temperature of the second zone is 210 ℃, the temperature of the third zone is 210 ℃, the temperature of the fourth zone is 210 ℃, the temperature of the fifth zone is 210 ℃, the temperature of the sixth zone is 210 ℃, the temperature of the head is 210 ℃ and the screw rotating speed is 200 r/min.
The modified fullerene M4 is prepared by the following steps:
(1) weighing 380g Ce (NO)3)3·6H2O, 1.45kg of acetone, and adding Ce (NO)3)3·6H2Adding O into acetone to obtain Ce (NO)3)3A solution;
(2) 480g of fullerene, 550g of Ce (NO)3)3And putting the solution into a beaker filled with 1.35kg of deionized water, reacting for 6 hours at normal temperature, filtering, washing and drying to obtain the fullerene A.
(3) 395g of fullerene A and 695g of hydrogen peroxide serving as an oxidant are weighed and placed in a reaction vessel to react for 6 hours at 55 ℃, and then the hydroxylated fullerene B is obtained after filtration, washing and drying.
(4) 285g of hydroxylated fullerene B, 19g of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride, 4.5g of catalyst triethylamine and 950g of acetone are weighed, placed in a reaction vessel, reacted for 7 hours at 65 ℃, filtered, washed and dried to obtain modified fullerene M4.
Example 5
(1) Weighing 95 parts of ABS and 15 parts of modified fullerene M5, mixing and uniformly stirring to obtain a mixture;
(2) and (3) extruding and granulating the mixture obtained in the step (1) from an extruder to obtain the ABS composite material P5.
Wherein the temperature and the screw rotating speed of each area of the double-screw extruder are respectively as follows: the temperature of the first zone is 210 ℃, the temperature of the second zone is 220 ℃, the temperature of the third zone is 220 ℃, the temperature of the fourth zone is 220 ℃, the temperature of the fifth zone is 220 ℃, the temperature of the sixth zone is 220 ℃, the temperature of the machine head is 220 ℃, and the rotating speed of the screw is 200 r/min.
The modified fullerene M5 is prepared by the following steps:
(1) weighing 380g Ce (NO)3)3·6H2O, 1.55kg of acetone, adding Ce (NO)3)3·6H2Adding O into acetone to obtain Ce (NO)3)3A solution;
(2) 475g of fullerene, 465g of Ce (NO)3)3Putting the solution into a beaker filled with 1.15kg of deionized water, reacting for 5 hours at normal temperature, filtering, washing and drying,obtaining the fullerene A.
(3) 375g of fullerene A and 665g of oxidant hydrogen peroxide are weighed and placed in a reaction vessel to react for 5 hours at 55 ℃, and then the hydroxylated fullerene B is obtained after filtration, washing and drying.
(4) 225g of hydroxylated fullerene B, 18g of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride, 3.9g of catalyst triethylamine and 995g of acetone are weighed and placed in a reaction vessel to react for 7 hours at 65 ℃, and then the modified fullerene M5 is obtained by filtering, washing and drying.
Comparative example 1
95 parts of ABS were weighed out of the extruder and pelletized, denoted D1.
Wherein the temperature and the screw rotating speed of each area of the double-screw extruder are respectively as follows: the temperature of the first zone is 210 ℃, the temperature of the second zone is 220 ℃, the temperature of the third zone is 220 ℃, the temperature of the fourth zone is 220 ℃, the temperature of the fifth zone is 220 ℃, the temperature of the sixth zone is 220 ℃, the temperature of the machine head is 220 ℃, and the rotating speed of the screw is 200 r/min.
Comparative example 2
(1) Weighing 95 parts of ABS and 15 parts of fullerene, mixing and uniformly stirring to obtain a mixture;
(2) and (3) extruding and granulating the mixture obtained in the step (1) from an extruder to obtain the ABS composite material, and recording the ABS composite material as D2.
Wherein the temperature and the screw rotating speed of each area of the double-screw extruder are respectively as follows: the temperature of the first zone is 210 ℃, the temperature of the second zone is 220 ℃, the temperature of the third zone is 220 ℃, the temperature of the fourth zone is 220 ℃, the temperature of the fifth zone is 220 ℃, the temperature of the sixth zone is 220 ℃, the temperature of the machine head is 220 ℃, and the rotating speed of the screw is 200 r/min.
Comparative example 3
(1) Weighing 95 parts of ABS, 15 parts of fullerene and 3 parts of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride, mixing and uniformly stirring to obtain a mixture;
(2) and (3) extruding and granulating the mixture obtained in the step (1) from an extruder to obtain the ABS composite material, and recording the ABS composite material as D3.
Wherein the temperature and the screw rotating speed of each area of the double-screw extruder are respectively as follows: the temperature of the first zone is 210 ℃, the temperature of the second zone is 220 ℃, the temperature of the third zone is 220 ℃, the temperature of the fourth zone is 220 ℃, the temperature of the fifth zone is 220 ℃, the temperature of the sixth zone is 220 ℃, the temperature of the machine head is 220 ℃, and the rotating speed of the screw is 200 r/min.
Comparative example 4
The difference from example 5 is that, unlike the preparation method of modified fullerene, the modified fullerene is modified by the method of example 1 in patent CN108794972A, and the other operation steps are exactly the same as those in example 5. The specific scheme is as follows:
(1) weighing 95 parts of ABS and 15 parts of modified fullerene M5, mixing and uniformly stirring to obtain a mixture;
(2) and (3) extruding and granulating the mixture obtained in the step (1) from an extruder to obtain the ABS composite material D4.
Wherein the temperature and the screw rotating speed of each area of the double-screw extruder are respectively as follows: the temperature of the first zone is 210 ℃, the temperature of the second zone is 220 ℃, the temperature of the third zone is 220 ℃, the temperature of the fourth zone is 220 ℃, the temperature of the fifth zone is 220 ℃, the temperature of the sixth zone is 220 ℃, the temperature of the machine head is 220 ℃, and the rotating speed of the screw is 200 r/min.
The modified fullerene is prepared by the following steps:
(1) weighing 200g of nano TiO21.6kg of absolute ethyl alcohol, and mixing the nano TiO2Placing in anhydrous alcohol, and ultrasonic oscillating for 8 min.
(2) Drying, and then drying the nano TiO2Placing into a plasma chamber, introducing argon plasma, and reacting for 20min to obtain modified nanometer TiO2。
(3) Weighing 400g of modified nano TiO22.0kg of deionized water, 200g of LaCl3·7H2O and 100g of polyacrylamide, and placing the materials into an ultrasonic oscillator to oscillate for 3 hours to obtain a solution A.
(4) Weighing 300g of fullerene and 80g of ZnCl3Grinding fullerene into powder with 1kg deionized water, and mixing fullerene powder with ZnCl3And (3) putting the solution and deionized water into an ultrasonic oscillator for oscillation for 4 hours, filtering and drying to obtain the zinc-loaded fullerene.
(5) Adding the zinc-loaded fullerene into the solution A, adding HCl solution to adjust the pH value to be neutral, stirring and reacting for 3 hours at 60 ℃, and performing suction filtration, drying and grinding to obtain the modified fullerene.
Performance testing
The properties of the ABS composite materials prepared in the examples and comparative examples were measured, and the specific results are shown in table 1.
TABLE 1 Performance data of ABS composites
As can be seen from Table 1, the physical properties, aging resistance and antistatic properties of examples 1 to 5 are better than those of comparative examples 1 to 4 in combination.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered as the protection scope of the present invention.
Claims (10)
1. The modified fullerene is characterized by being prepared by the following steps:
1) mixing fullerene and Ce (NO)3)3Mixing the solution with water, and reacting to obtain a compound A;
2) mixing the compound A and hydrogen peroxide, and reacting to obtain hydroxylated fullerene;
3) and mixing the hydroxylated fullerene, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride, triethylamine and acetone, and reacting to obtain the modified fullerene.
2. The modified fullerene according to claim 1, wherein in the step 1), the reaction temperature is 20-30 ℃ and the reaction time is 4-6 h;
in the step 2), the reaction temperature is 40-60 ℃ and the reaction time is 4-6 h;
in the step 3), the reaction temperature is 50-70 ℃ and the reaction time is 6-8 h.
3. The modified fullerene according to claim 1, wherein Ce (NO) in step 1)3)3Solution of Ce (NO)3)3·6H2O and acetone, the Ce (NO)3)3·6H2The mass ratio of O to acetone is (30-50): (120-160).
4. The modified fullerene of claim 3, wherein the fullerene, Ce (NO) in step 1)3)3The mass ratio of the solution to the water is (40-50): (40-60): (120-160).
5. The modified fullerene of claim 1, wherein the mass ratio of the compound A to the hydrogen peroxide in the step 2) is (30-40): (60-80).
6. The modified fullerene according to claim 1, wherein the mass ratio of hydroxylated fullerene, β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride, triethylamine and acetone in step 3) is (20-30): (1.6-2): (0.3-0.5): (80-100).
7. The modified fullerene according to claim 1, wherein the steps 1), 2) and 3) are carried out by filtering, washing and drying, respectively, after the reaction is completed; the drying temperatures are independently 80-100 ℃.
8. The anti-aging and antistatic ABS composite material is characterized by comprising the following components in parts by weight:
80-100 parts of ABS and 10-16 parts of modified fullerene;
the modified fullerene according to any one of claims 1 to 7.
9. The preparation method of the anti-aging and anti-static ABS composite material as claimed in claim 8, characterized by comprising the following steps:
1) mixing ABS and modified fullerene to obtain a mixture;
2) and extruding and granulating the mixture to obtain the anti-aging and anti-static ABS composite material.
10. The preparation method according to claim 9, wherein the extrusion granulation is performed in a twin-screw extruder, and the twin-screw extruder employs six temperature zones arranged in sequence, which are respectively: the temperature of the first zone is 200-210 ℃, the temperature of the second zone is 210-220 ℃, the temperature of the third zone is 210-220 ℃, the temperature of the fourth zone is 210-220 ℃, the temperature of the fifth zone is 210-220 ℃, and the temperature of the sixth zone is 210-220 ℃; the head temperature of the double-screw extruder is 210-220 ℃, and the screw rotating speed is 200-280 r/min.
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Application publication date: 20220603 Assignee: Haike Technology Innovation Service (Jiangsu) Co.,Ltd. Assignor: Shandong Haike Innovation Research Institute Co.,Ltd. Contract record no.: X2023980046100 Denomination of invention: Modified fullerene and anti-aging and anti-static ABS composites and their preparation methods Granted publication date: 20230516 License type: Common License Record date: 20231110 |