CN114573874B - 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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- CN114573874B CN114573874B CN202210414530.5A CN202210414530A CN114573874B CN 114573874 B CN114573874 B CN 114573874B CN 202210414530 A CN202210414530 A CN 202210414530A CN 114573874 B CN114573874 B CN 114573874B
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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 121
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 230000003712 anti-aging effect Effects 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 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 43
- 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 28
- 238000002156 mixing Methods 0.000 claims abstract description 23
- 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 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229940126062 Compound A Drugs 0.000 claims abstract description 13
- 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 13
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 14
- 238000001125 extrusion Methods 0.000 claims description 6
- 238000005469 granulation Methods 0.000 claims description 6
- 230000003179 granulation Effects 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000002861 polymer material Substances 0.000 abstract description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 59
- 238000005303 weighing Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000001914 filtration Methods 0.000 description 7
- 230000032683 aging Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 239000007800 oxidant agent Substances 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- -1 rare earth ions Chemical class 0.000 description 3
- 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000843 powder Substances 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
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical group CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 150000001263 acyl chlorides Chemical group 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 230000008092 positive effect Effects 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)
- Carbon And Carbon Compounds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a modified fullerene, anti-aging and antistatic ABS composite material and a preparation method thereof, and belongs to the technical field of high polymer materials. The modified fullerene is prepared by the following steps: 1) Fullerene, ce (NO) 3 ) 3 Mixing the solution with water, and reacting to obtain a compound A; 2) Mixing the compound A with 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, anti-aging and antistatic ABS composite material and a preparation method thereof.
Background
ABS plastic is a terpolymer of acrylonitrile (A) -butadiene (B) -styrene (S). The three-component ABS plastic is a thermoplastic plastic with good combination of 'hard quality, toughness and rigidity', but the ABS has general ageing resistance and antistatic property, which limits the application of the ABS material in some specific fields.
The patent CN108794972a adds fullerene into ABS to improve the antistatic property of ABS, but the compatibility of fullerene and ABS is poor, which affects the physical properties of ABS composite material, and requires additional addition of compatilizer for improvement.
Disclosure of Invention
The invention provides a modified fullerene, anti-aging and antistatic 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 above purpose, the invention provides a modified fullerene prepared by the following steps:
1) Fullerene, ce (NO) 3 ) 3 Mixing the solution with water, and reacting to obtain a compound A;
2) Mixing the compound A with 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 4-6h;
in the step 2), the reaction temperature is 40-60 ℃ and the reaction time is 4-6h;
in the step 3), the reaction temperature is 50-70 ℃ and the reaction time is 6-8h.
Preferably, in the step 1), ce (NO 3 ) 3 The solution is composed of Ce (NO) 3 ) 3 ·6H 2 Formulated with O and acetone, the Ce (NO 3 ) 3 ·6H 2 The mass ratio of O to acetone is (30-50): (120-160).
Preferably, the fullerene, ce (NO) in the step 1) 3 ) 3 The mass ratio of the solution to the water is (40-50): (40-60): (120-160).
Preferably, in the step 2), the mass ratio of the compound A to the hydrogen peroxide 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, in the steps 1), 2) and 3), filtration, washing and drying are performed after the reaction is completed, respectively; the drying temperature is 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 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 antistatic ABS composite material.
Preferably, the extrusion granulation is performed in a twin-screw extruder, and six temperature areas sequentially arranged are adopted in the extrusion granulation of the twin-screw extruder, and the six temperature areas are respectively in sequence: 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 temperature of the head of the double-screw extruder is 210-220 ℃, and the rotating speed of the screw 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 ions Ce 3+ The fullerene is treated to enable the surface of the fullerene to be attached with more oxygen-containing active groups and rare earth Ce 3+ As an intermediate medium, the chemical bond connection between the surface of the fullerene and the ABS substrate is promoted, the interfacial binding force between the fullerene and the ABS substrate is improved, and the compatibility of the fullerene and the ABS substrate is improved.
Meanwhile, the invention utilizes the acyl chloride group of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) to react with the hydroxyl on the hydroxylated fullerene, thereby grafting beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride on the fullerene, and enabling the beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride to have ageing resistance as a filler, thereby improving the ageing resistance of ABS.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a modified fullerene, which is prepared by the following steps:
1) Fullerene, ce (NO) 3 ) 3 Mixing the solution with water, and reacting to obtain a compound A;
2) Mixing the compound A with 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 uses Ce (NO) 3 ) 3 The solution is mixed with water to react, and the compound A is obtained. In the present invention, the Ce (NO 3 ) 3 The solution is preferably composed of Ce (NO) 3 ) 3 ·6H 2 Formulated with O and acetone, the Ce (NO 3 ) 3 ·6H 2 The mass ratio of O to acetone is (30-50): (120-160). It will be appreciated that the skilled artisan can select the appropriate reaction ratios within the preferred ratios described above, such as 30:120, 50:160 or 40:130, etc. In the present invention, the temperature of the reaction is preferably 20 to 30℃and the time is preferably 4 to 6 hours. In the present invention, the filtration, washing and drying are preferably performed sequentially after the completion of the reaction; the washing is preferably performed with water. The drying temperature is preferably 80-100 ℃.
After the compound A is obtained, the compound A and hydrogen peroxide are mixed for reaction to obtain the hydroxylated fullerene. In the invention, the mass ratio of the compound A to the hydrogen peroxide is (30-40): (60-80). It will be appreciated that the skilled artisan can select the appropriate reaction ratios within the preferred ratios described above, such as 30:60, 40:80, or 35:70, etc. In the present invention, the temperature of the reaction is preferably 40 to 60℃and the time is preferably 4 to 6 hours. In the present invention, the filtration, washing and drying are preferably performed sequentially after the completion of the reaction; the washing is preferably performed with water. The drying temperature is preferably 80-100 ℃.
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, β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride, triethylamine and acetone is preferably (20-30): (1.6-2): (0.3-0.5): (80-100). It will be appreciated that the skilled artisan can select a suitable reaction ratio within the preferred ranges described above, such as 30:60, 1.6:0.3:80, or 20:2:0.3:100, etc. In the present invention, the temperature of the reaction is preferably 50 to 70℃and the time is preferably 6 to 8 hours. In the present invention, the filtration, washing and drying are preferably performed sequentially after the completion of the reaction; the washing is preferably performed with water. The drying temperature is preferably 80-100 ℃.
The invention uses rare earth ion Ce 3+ The fullerene is treated to enable the surface of the fullerene to be attached with more oxygen-containing active groups and rare earth Ce 3+ As an intermediate medium, the chemical bond connection between the surface of the fullerene and the ABS substrate is promoted, the interfacial binding force between the fullerene and the ABS substrate is improved, and the compatibility of the fullerene and the ABS substrate is improved.
Beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride has oxidation resistance, and the acid 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 beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride is grafted to the fullerene, and the beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride is used as a filler to have ageing resistance, and the anti-ageing property of ABS is improved by using the beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride to modify ABS.
Fullerene has excellent conductivity, and the modified ABS has improved antistatic performance.
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 according to any one of the above embodiments.
The anti-aging and antistatic ABS composite material provided by the invention comprises ABS. 80-100 parts by weight, it being 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, and the ABS can be obtained by adopting products which are conventionally and commercially available in the field.
The anti-aging and antistatic ABS composite material provided by the invention comprises modified fullerene. It is understood that the ABS may be present in an amount of 10 to 16 parts by weight, 10, 11, 12, 13, 14, 15, 16 parts by weight, or any value within the above ranges.
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 antistatic ABS composite material.
In the present invention, the extrusion granulation is preferably performed in a twin screw extruder. The twin-screw extruder preferably adopts six temperature areas of arranging in order when carrying out extrusion granulation, is respectively in proper order: 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 temperature of the head of the double-screw extruder is 210-220 ℃, and the rotating speed of the screw is 200-280 r/min.
The technical solutions provided by the present invention are described in detail below in conjunction with examples for further illustrating the present invention, 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), odd-beauty chemical industry; ce (NO) 3 ) 3 ·6H 2 O, shandong Desheng New Material Co., ltd; acetone, nanjing sincerity chemical industry Co., ltd; fullerene, jiangsu Xianfeng nano materials science and technology Co., ltd;hydrogen peroxide, jinan kunfeng chemical industry Co., ltd; beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride, daqing institute of chemical industry, college of petroleum; triethylamine, shandong Rui Kong chemical Co., ltd; deionized water, jinan Hai Ruibao chemical Co., ltd.
Example 1
(1) Weighing 80 parts of ABS and 10 parts of modified fullerene M1, mixing and stirring uniformly to obtain a mixture;
(2) 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 area is 210 ℃, the temperature of the second area is 220 ℃, the temperature of the third area is 220 ℃, the temperature of the fourth area is 220 ℃, the temperature of the fifth area is 220 ℃, the temperature of the sixth area is 220 ℃, the temperature of the machine head is 220 ℃, and the rotating speed of the screw is 200r/min.
Wherein the modified fullerene M1 is prepared by the following steps:
(1) 300g Ce (NO) was weighed 3 ) 3 ·6H 2 O, 1.2kg acetone, ce (NO 3 ) 3 ·6H 2 Adding O into acetone to obtain Ce (NO) 3 ) 3 A solution;
(2) 400g of fullerene, 400g of Ce (NO 3 ) 3 The solution is put into a beaker containing 1.2kg of deionized water, reacted for 4 hours at normal temperature, filtered, washed and dried to obtain fullerene A.
(3) 300g of fullerene A and 600g of oxidant hydrogen peroxide are weighed, placed in a reaction vessel for reaction for 4 hours at 40 ℃, filtered, washed and dried to obtain hydroxylated fullerene B.
(4) 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 are weighed, placed in a reaction vessel, reacted for 6 hours at 50 ℃, filtered, washed and dried to obtain 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) 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 zone of the double-screw extruder are respectively as follows: the temperature of the first area is 210 ℃, the temperature of the second area is 220 ℃, the temperature of the third area is 220 ℃, the temperature of the fourth area is 220 ℃, the temperature of the fifth area is 220 ℃, the temperature of the sixth area is 220 ℃, the temperature of the machine head is 220 ℃, and the rotating speed of the screw is 200r/min.
Wherein the modified fullerene M2 is prepared by the following steps:
(1) 500g Ce (NO) was weighed 3 ) 3 ·6H 2 O, 1.6kg acetone, ce (NO 3 ) 3 ·6H 2 Adding O into acetone to obtain Ce (NO) 3 ) 3 A solution;
(2) 500g of fullerene, 600g of Ce (NO) 3 ) 3 The solution is put into a beaker containing 1.6kg of deionized water, reacted for 6 hours at normal temperature, filtered, washed and dried to obtain fullerene A.
(3) 400g of fullerene A and 800g of oxidant hydrogen peroxide are weighed, placed in a reaction vessel, reacted for 6 hours at 60 ℃, filtered, washed and dried to obtain hydroxylated fullerene B.
(4) 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 are weighed, placed in a reaction vessel for reaction for 8 hours at 70 ℃, filtered, washed and dried to obtain 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) 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 zone of the double-screw extruder are respectively as follows: the temperature of the first area is 210 ℃, the temperature of the second area is 220 ℃, the temperature of the third area is 220 ℃, the temperature of the fourth area is 220 ℃, the temperature of the fifth area is 220 ℃, the temperature of the sixth area is 220 ℃, the temperature of the machine head is 220 ℃, and the rotating speed of the screw is 200r/min.
Wherein the modified fullerene M3 is prepared by the following steps:
(1) 400g Ce (NO) was weighed 3 ) 3 ·6H 2 O, 1.4kg acetone, ce (NO 3 ) 3 ·6H 2 Adding O into acetone to obtain Ce (NO) 3 ) 3 A solution;
(2) 450g of fullerene, 500g of Ce (NO) 3 ) 3 The solution is put into a beaker containing 1.4kg of deionized water, reacted for 5 hours at normal temperature, filtered, washed and dried to obtain fullerene A.
(3) Weighing 350g of fullerene A and 700g of oxidant hydrogen peroxide, placing the mixture into a reaction vessel for reaction 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 mixture into a reaction vessel, reacting for 7h at 60 ℃, filtering, washing and drying to obtain modified fullerene M3.
Example 4
(1) Weighing 95 parts of ABS and 11 parts of modified fullerene M4, mixing and stirring uniformly to obtain a mixture;
(2) 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 zone of the double-screw extruder are respectively as follows: the temperature of the first area is 200 ℃, the temperature of the second area is 210 ℃, the temperature of the third area is 210 ℃, the temperature of the fourth area is 210 ℃, the temperature of the fifth area is 210 ℃, the temperature of the sixth area is 210 ℃, the temperature of the machine head is 210 ℃, and the rotating speed of the screw is 200r/min.
Wherein the modified fullerene M4 is prepared by the following steps:
(1) 380g Ce (NO) was weighed 3 ) 3 ·6H 2 O, 1.45kg acetone, ce (NO 3 ) 3 ·6H 2 Adding O into acetone to obtain Ce (NO) 3 ) 3 A solution;
(2) 480g of fullerene, 550g of Ce (NO) 3 ) 3 The solution is put into a beaker containing 1.35kg of deionized water, reacted for 6 hours at normal temperature, filtered, washed and dried to obtain fullerene A.
(3) 395g of fullerene A and 695g of oxidant hydrogen peroxide are weighed, placed in a reaction vessel for reaction for 6 hours at 55 ℃, filtered, washed and dried to obtain hydroxylated fullerene B.
(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 for reaction 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) 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 zone of the double-screw extruder are respectively as follows: the temperature of the first area is 210 ℃, the temperature of the second area is 220 ℃, the temperature of the third area is 220 ℃, the temperature of the fourth area is 220 ℃, the temperature of the fifth area is 220 ℃, the temperature of the sixth area is 220 ℃, the temperature of the machine head is 220 ℃, and the rotating speed of the screw is 200r/min.
Wherein the modified fullerene M5 is prepared by the following steps:
(1) 380g Ce (NO) was weighed 3 ) 3 ·6H 2 O, 1.55kg acetone, ce (NO 3 ) 3 ·6H 2 Adding O into acetone to obtain Ce (NO) 3 ) 3 A solution;
(2) 475g of fullerene, 465g of Ce (NO) 3 ) 3 The solution is put into a beaker containing 1.15kg of deionized water, reacted for 5 hours at normal temperature, filtered, washed and dried to obtain fullerene A.
(3) 375g of fullerene A and 665g of oxidant hydrogen peroxide are weighed, placed in a reaction vessel for reaction for 5 hours at 55 ℃, filtered, washed and dried to obtain hydroxylated fullerene B.
(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, placed in a reaction vessel for reaction for 7 hours at 65 ℃, filtered, washed and dried to obtain modified fullerene M5.
Comparative example 1
95 parts of ABS are weighed out and extruded from an extruder to form granules, which are designated as D1.
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 area is 210 ℃, the temperature of the second area is 220 ℃, the temperature of the third area is 220 ℃, the temperature of the fourth area is 220 ℃, the temperature of the fifth area is 220 ℃, the temperature of the sixth area is 220 ℃, the temperature of the machine head is 220 ℃, and the rotating speed of the screw is 200r/min.
Comparative example 2
(1) Weighing 95 parts of ABS and 15 parts of fullerene, mixing and stirring uniformly to obtain a mixture;
(2) Extruding and granulating the mixture obtained in the step (1) from an extruder to obtain the ABS composite material, which is marked as D2.
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 area is 210 ℃, the temperature of the second area is 220 ℃, the temperature of the third area is 220 ℃, the temperature of the fourth area is 220 ℃, the temperature of the fifth area is 220 ℃, the temperature of the sixth area is 220 ℃, the temperature of the machine head is 220 ℃, and the rotating speed of the screw is 200r/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 stirring uniformly to obtain a mixture;
(2) Extruding and granulating the mixture obtained in the step (1) from an extruder to obtain the ABS composite material, which is marked as D3.
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 area is 210 ℃, the temperature of the second area is 220 ℃, the temperature of the third area is 220 ℃, the temperature of the fourth area is 220 ℃, the temperature of the fifth area is 220 ℃, the temperature of the sixth area is 220 ℃, the temperature of the machine head is 220 ℃, and the rotating speed of the screw is 200r/min.
Comparative example 4
The difference from example 5 is that the modified fullerene was modified by the method of example 1 in patent CN108794972a, and the other steps are exactly the same as 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) 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 zone of the double-screw extruder are respectively as follows: the temperature of the first area is 210 ℃, the temperature of the second area is 220 ℃, the temperature of the third area is 220 ℃, the temperature of the fourth area is 220 ℃, the temperature of the fifth area is 220 ℃, the temperature of the sixth area is 220 ℃, the temperature of the machine head is 220 ℃, and the rotating speed of the screw is 200r/min.
Wherein the modified fullerene is prepared by the following steps:
(1) 200g of nano TiO is weighed 2 1.6kg of absolute ethyl alcohol, and nano TiO 2 Placing in absolute ethanol, and ultrasonic oscillating for 8min.
(2) Drying the nano TiO 2 Placing the mixture into a plasma chamber, introducing argon plasma, and reacting for 20min to obtain modified nano TiO 2 。
(3) 400g of modified nano TiO is weighed 2 2.0kg deionized water, 200g LaCl 3 ·7H 2 O, 100g polyacrylamide, and putting them into an ultrasonic oscillator to oscillate for 3 hours to obtain a solution A.
(4) Weighing 300g of fullerene and 80g of ZnCl 3 Grinding fullerene into powder, grinding fullerene powder and ZnCl into powder 3 And (5) putting the solution and deionized water into an ultrasonic oscillator for oscillating for 4 hours, filtering and drying to obtain the zinc-loaded fullerene.
(5) Adding 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 carrying out suction filtration, drying and grinding to obtain the modified fullerene.
Performance testing
The properties of the ABS composite materials prepared in examples and comparative examples were tested, and the specific results are shown in table 1.
TABLE 1 Performance data for 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 merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The modified fullerene is characterized by being prepared by the following steps:
1) Fullerene, ce (NO) 3 ) 3 Mixing the solution with water, and reacting to obtain a compound A;
2) Mixing the compound A with 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 ℃ for 4-6 hours;
in the step 2), the reaction temperature is 40-60 ℃ and the reaction time is 4-6h;
in the step 3), the reaction temperature is 50-70 ℃ and the reaction time is 6-8h.
3. The modified fullerene according to claim 1, wherein Ce (NO 3 ) 3 The solution is composed of Ce (NO) 3 ) 3 ·6H 2 Formulated with O and acetone, the Ce (NO 3 ) 3 ·6H 2 The mass ratio of O to acetone is (30-50): (120-160).
4. A modified fullerene according to claim 3, wherein the fullerene, ce (NO 3 ) 3 The mass ratio of the solution to the water is (40-50): (40-60): (120-160).
5. The modified fullerene according to claim 1, wherein in the step 2), the mass ratio of the compound a to the hydrogen peroxide is (30-40): (60-80).
6. The modified fullerene according to claim 1, wherein the mass ratio of the hydroxylated fullerene, β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride, triethylamine and acetone in the 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 respectively filtered, washed and dried after the completion of the reaction; the drying temperature is independently 80-100 ℃.
8. An 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 method for preparing the anti-aging and antistatic ABS composite material according to claim 8, which is 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 antistatic 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 adopts six temperature areas which are sequentially arranged when the extrusion granulation is performed, and the six temperature areas are sequentially and 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 temperature of the head of the double-screw extruder is 210-220 ℃, and the rotating speed of the screw 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 |