CN117844167B - ABS antistatic plastic based on graphene modification and preparation process thereof - Google Patents
ABS antistatic plastic based on graphene modification and preparation process thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 46
- 229920003023 plastic Polymers 0.000 title claims abstract description 39
- 239000004033 plastic Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000012986 modification Methods 0.000 title claims abstract description 18
- 230000004048 modification Effects 0.000 title claims abstract description 18
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims abstract description 80
- 239000002253 acid Substances 0.000 claims abstract description 26
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 26
- 239000004417 polycarbonate Substances 0.000 claims abstract description 26
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 25
- 239000012948 isocyanate Substances 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 7
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 7
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims abstract 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 39
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 30
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 29
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 28
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 27
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 23
- -1 pyridine ketoacid Chemical class 0.000 claims description 22
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 13
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical class C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 11
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 11
- 239000005062 Polybutadiene Substances 0.000 claims description 11
- 229960004543 anhydrous citric acid Drugs 0.000 claims description 11
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims description 11
- 235000018417 cysteine Nutrition 0.000 claims description 11
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 11
- 229920002857 polybutadiene Polymers 0.000 claims description 11
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 claims description 9
- 229910017073 AlLi Inorganic materials 0.000 claims description 8
- AHLBNYSZXLDEJQ-FWEHEUNISA-N orlistat Chemical compound CCCCCCCCCCC[C@H](OC(=O)[C@H](CC(C)C)NC=O)C[C@@H]1OC(=O)[C@H]1CCCCCC AHLBNYSZXLDEJQ-FWEHEUNISA-N 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 claims description 7
- 229960002479 isosorbide Drugs 0.000 claims description 7
- LVWZTYCIRDMTEY-UHFFFAOYSA-N metamizole Chemical compound O=C1C(N(CS(O)(=O)=O)C)=C(C)N(C)N1C1=CC=CC=C1 LVWZTYCIRDMTEY-UHFFFAOYSA-N 0.000 claims description 7
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 claims description 6
- 238000007605 air drying Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000004090 dissolution Methods 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims 1
- 230000008018 melting Effects 0.000 claims 1
- 238000001125 extrusion Methods 0.000 abstract description 5
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 35
- 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 27
- IRJGZWIEFFOYJN-UHFFFAOYSA-N copper;pyridine Chemical compound [Cu].C1=CC=NC=C1 IRJGZWIEFFOYJN-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 10
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 6
- YIJYFLXQHDOQGW-UHFFFAOYSA-N 2-[2,4,6-trioxo-3,5-bis(2-prop-2-enoyloxyethyl)-1,3,5-triazinan-1-yl]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCN1C(=O)N(CCOC(=O)C=C)C(=O)N(CCOC(=O)C=C)C1=O YIJYFLXQHDOQGW-UHFFFAOYSA-N 0.000 description 5
- CFXCGWWYIDZIMU-UHFFFAOYSA-N Octyl-3,5-di-tert-butyl-4-hydroxy-hydrocinnamate Chemical group CCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 CFXCGWWYIDZIMU-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- ZCUQLZTWMFRJAH-UHFFFAOYSA-N C(C(O)C)(=O)O.C(CCC)N1CN(C=C1)C Chemical compound C(C(O)C)(=O)O.C(CCC)N1CN(C=C1)C ZCUQLZTWMFRJAH-UHFFFAOYSA-N 0.000 description 3
- HXBPYFMVGFDZFT-UHFFFAOYSA-N allyl isocyanate Chemical group C=CCN=C=O HXBPYFMVGFDZFT-UHFFFAOYSA-N 0.000 description 3
- 229960004643 cupric oxide Drugs 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical group OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229940081066 picolinic acid Drugs 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 238000010561 standard procedure Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- SZDVDUDLIIZMKX-UHFFFAOYSA-N copper;pyridine Chemical compound [Cu].C1=CC=NC=C1.C1=CC=NC=C1.C1=CC=NC=C1.C1=CC=NC=C1.C1=CC=NC=C1.C1=CC=NC=C1 SZDVDUDLIIZMKX-UHFFFAOYSA-N 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000012546 transfer 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
- C08L2201/04—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)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to the technical field of antistatic plastics, in particular to an ABS antistatic plastic based on graphene modification and a preparation process thereof. The method comprises the following steps: step 1: preparing modified graphene by using isocyanate ABS and pyridonic acid to modify graphene oxide; step 2: preparation of ABS antistatic plastic: drying and uniformly mixing ABS resin, polycarbonate, modified graphene, a compatilizer, a cross-linking agent and an antioxidant to obtain a raw material; and (3) carrying out melt extrusion on the raw materials in a screw extruder to obtain the ABS antistatic plastic. The ABS antistatic plastic comprises the following raw materials: 100 parts of ABS resin, 25-35 parts of polycarbonate, 6-8 parts of modified graphene, 6-9 parts of compatilizer, 0.5-0.8 part of cross-linking agent and 0.2-0.5 part of antioxidant. In the scheme, the prepared ABS antistatic plastic has excellent antistatic property and impact resistance.
Description
Technical Field
The invention relates to the technical field of antistatic plastics, in particular to an ABS antistatic plastic based on graphene modification and a preparation process thereof.
Background
ABS (acrylonitrile-butadiene-styrene) is engineering plastic with very common application, and has good processability and good mechanical properties; is widely applied to a plurality of fields such as automobiles, electronic communication, aerospace, national defense and the like. However, ABS resins have some drawbacks: the surface resistivity of the material is 4× 15 Ω, and the material has high insulation and poor antistatic property, so that the application of the material in some fields is limited. On the other hand, it has a problem of poor heat resistance, and impact resistance is also required to be further improved in some application fields.
In the prior art, antistatic agents such as graphene and the like are generally introduced to improve the antistatic performance of ABS plastic, but when the introduced amount of the inorganic filler is less than 5wt%, the antistatic performance is limited, and when the introduced amount exceeds 5wt%, the dispersibility of the graphene in ABS resin is poor due to the agglomeration problem, so that the mechanical performance is obviously reduced. On the other hand, amorphous thermoplastic resin polycarbonate and ABS resin are generally introduced to complement each other, so that the heat resistance and the shock resistance of the ABS plastic are improved; however, there is a compatibility problem between the two, resulting in a decrease in mechanical properties.
In summary, the preparation of the graphene-based modified ABS antistatic plastic has important significance in solving the problems.
Disclosure of Invention
The invention aims to provide an ABS antistatic plastic based on graphene modification and a preparation process thereof, so as to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
The preparation process of the ABS antistatic plastic based on graphene modification comprises the following steps:
Step 1: preparation of modified graphene:
S11: (1) Adding 2, 4-toluene diisocyanate into a reaction bottle, heating to 40-60 ℃ in a nitrogen atmosphere, dropwise adding hydroxyethyl acrylate, reacting for 4-6 hours, and cooling to obtain modified isocyanate; (2) Adding ABS resin into toluene, heating to 120-125 ℃ in nitrogen atmosphere, adding toluene mixed solution containing modified isocyanate and dicumyl peroxide, reacting for 4-5 hours, precipitating with methanol, and purifying to obtain isocyanato ABS;
S12: sequentially adding anhydrous citric acid and cysteine into deionized water for dissolution to obtain a mixed solution; placing the mixed solution in a forced air drying oven, drying at 130-140 ℃ for 12-24 hours, and purifying to obtain pyridine ketoacid;
s13: dispersing graphene oxide in chloroform by ultrasonic waves, sequentially adding triethylamine, hexamethylene diisocyanate and pyridine copper acid in a nitrogen atmosphere, and reacting for 2-4 hours at 40-50 ℃; adding an isocyanato ABS-chloroform solution, heating to 60-65 ℃, reacting for 6-8 hours, cooling, and purifying to obtain modified graphene;
Step 2: preparation of ABS antistatic plastic: drying and uniformly mixing ABS resin, polycarbonate, modified graphene, a compatilizer, a cross-linking agent and an antioxidant to obtain a raw material; and (3) carrying out melt extrusion on the raw materials in a screw extruder to obtain the ABS antistatic plastic.
In a further scheme, the ABS antistatic plastic comprises the following raw materials: 100 parts of ABS resin, 25-35 parts of polycarbonate, 6-8 parts of modified graphene, 6-9 parts of compatilizer, 0.5-0.8 part of cross-linking agent and 0.2-0.5 part of antioxidant.
In a further scheme, in S11 of the step 1, the molar ratio of the 2, 4-toluene diisocyanate to the hydroxyethyl acrylate in the modified isocyanate is 1 (0.8-1); in the isocyanato ABS, the mass ratio of the ABS resin to the modified isocyanate to the dicumyl peroxide is 2.5 (0.4-0.45) to 0.05-0.075.
In a further scheme, in S12 of the step 1, the molar ratio of anhydrous citric acid to cysteine in the pyridine copper acid is 1:1.
In a further scheme, in step S13 of step 1, the raw materials of the modified graphene include the following components: according to the weight portions, 5 portions of graphene oxide, 4.5 to 5 portions of triethylamine, 3 to 4 portions of hexamethylene diisocyanate, 2 to 2.5 portions of pyridine copper acid and 2.5 to 3.5 portions of isocyanato ABS.
In a further embodiment, the process for preparing the polycarbonate comprises the steps of:
s21: adding pyridine copper acid into tetrahydrofuran, setting the temperature to be minus 10 ℃ to minus 5 ℃, slowly adding H 4 AlLi, and stirring and reacting for 8-10 hours in a nitrogen atmosphere; adding 12-15 wt% of NaOH solution, continuously stirring for 30-40 minutes, and extracting and purifying by using ethyl acetate to obtain pyridine copper alcohol;
S22: sequentially adding diphenyl carbonate, isosorbide, cupric pyridine alcohol, tetraethylene glycol and double-end hydroxyl polybutadiene into a reaction kettle at room temperature, adding a catalyst under a nitrogen atmosphere, reacting for 2-3 hours at 110-120 ℃, gradually heating to 220-240 ℃, reducing the pressure to 30-50 pa, continuing to react for 25-35 minutes, and cooling to obtain the polycarbonate.
In a further embodiment, the polycarbonate comprises the following raw materials: 18-20 parts of diphenyl carbonate, 6-8 parts of isosorbide, 1-2 parts of cupric pyridine alcohol, 3-4 parts of tetraethylene glycol and 0.4-0.6 part of double-end hydroxyl polybutadiene.
In the further scheme, in the pyridine copper alcohol, the mass ratio of pyridine copper acid to H 4 AlLi is 1 (0.5-0.6); the ratio of the pyridine copper acid to the NaOH solution is 1mg (0.6-0.8 mL).
In a further scheme, the rotating speed of the screw extruder is 200-250 rpm, the temperature of each temperature zone is 200-210 ℃, 220-240 ℃, 240-250 ℃, 250-260 ℃, 260-270 ℃ and the feeding rotating speed is 30-60 rpm.
In a further scheme, the ABS antistatic plastic is prepared based on the preparation process of the graphene modified ABS antistatic plastic.
Compared with the prior art, the application has the following beneficial effects:
(1) The modified graphene with the weight percent of more than 5 percent is introduced as the antistatic agent, so that the dispersibility and the compatibility in the raw materials of the ABS antistatic plastic are ensured, and the antistatic property and the mechanical property of the ABS antistatic plastic are improved.
In the scheme, the modified graphene is prepared by modifying the surface of graphene oxide with double substances on the basis of the reaction of isocyanate and carboxyl by using isocyanate ABS and pyridonic acid. The modified isocyanate containing unsaturated bonds is prepared by utilizing one isocyanate group in 2, 4-toluene diisocyanate to react with hydroxyl in hydroxyethyl acrylate, and then grafting ABS resin under the initiation of dicumyl peroxide by utilizing the unsaturated bonds.
In the previous step of modification by using isocyanate ABS, pi-pi accumulation exists between the pyridine keto acid and the graphene oxide by using two isocyanate groups of hexamethylene diisocyanate, so that the pyridine keto acid is effectively spliced on the graphene oxide, pi conjugation is contained in the pyridine keto acid, and pi-pi accumulation interaction can be generated between the pyridine keto acid and the graphene oxide, and the conductivity of the graphene oxide is improved; on the other hand, the structure of the graphene oxide contains sulfur atoms, has strong electrophilicity, and the pyridonic acid is modified to oxidize the graphene, so that the charge density of the surface of the graphene can be increased, and the antistatic performance of the graphene is further improved. In addition, the grafting of the small molecule pyridine ketoacid is favorable for the intercalation of the large molecular weight isocyanate ABS.
(2) Further introduces polycarbonate containing copper pyridine alcohol and double-end hydroxyl polybutadiene, and further improves the antistatic property and the shock resistance of the ABS antistatic plastic.
In the scheme, pyridone acid is catalyzed by H 4 AlLi to form pyridone alcohol, and the pyridone alcohol is introduced into polycarbonate, so that charge transfer is effectively promoted, and the antistatic performance is improved. Meanwhile, the compatibility with the modified graphene is improved, so that the physical effect of the modified graphene oxide is utilized, the compatible interface effect of the polycarbonate and the ABS resin is promoted, and the dispersibility is improved. On the other hand, double-end hydroxyl polybutadiene is introduced, similar compatibility with ABS resin is promoted by using similar chain segments, and meanwhile, the toughness of the double-end hydroxyl polybutadiene can be increased by toughness. Thus, compared with the common polycarbonate, the polycarbonate has higher compatibility, antistatic property and impact resistance.
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 following parts are by mass, and the manufacturers of all the raw materials according to the present invention include, without any particular limitation: 584-84-9 CAS number of 2, 4-toluene diisocyanate, 818-61-1 CAS number of hydroxyethyl acrylate, 77-92-9 CAS number of anhydrous citric acid, 52-90-4 CAS number of cysteine, 822-06-0 CAS number of hexamethylene diisocyanate, 112-60-7 CAS number of tetraethylene glycol; the CAS number of the tris (2-acryloyloxyethyl) isocyanurate is 40220-08-4; the average molecular weight of the double-end hydroxyl polybutadiene is 5000, and the brand is a new macro-element material; the antioxidant is antioxidant 1135, brand Hengchang; the compatilizer is SMA compatilizer, and the brand is star origin chemical; the brand of the graphene oxide is aochuang, and the product number is 777676; the brand of the ABS resin is PA-757, and the brand of the ABS resin is Qimei.
Example 1: the preparation process of the ABS antistatic plastic based on graphene modification comprises the following steps:
Step 1: s11: (1) Adding 2, 4-toluene diisocyanate into a reaction bottle, heating to 55 ℃ in a nitrogen atmosphere, dropwise adding hydroxyethyl acrylate, reacting for 6 hours, and cooling to obtain modified isocyanate; the molar ratio of the 2, 4-toluene diisocyanate to the hydroxyethyl acrylate is 1:1; (2) Adding 2.5 parts of ABS resin into 50 parts of toluene, heating to 120 ℃ in nitrogen atmosphere, adding toluene mixed solution containing modified isocyanate and dicumyl peroxide (0.42 part of modified isocyanate, 0.06 part of dicumyl peroxide and 30 parts of toluene), reacting for 5 hours, precipitating and purifying by using methanol to obtain isocyanato ABS;
S12: sequentially adding anhydrous citric acid and cysteine into deionized water for dissolution to obtain a mixed solution; placing the mixed solution in a forced air drying oven, drying at 130 ℃ for 18 hours, and purifying to obtain pyridine ketoacid; the molar ratio of the anhydrous citric acid to the cysteine is 1:1;
s13: dispersing 5 parts of graphene oxide in 50 parts of chloroform by ultrasonic, sequentially adding 5 parts of triethylamine, 3.5 parts of hexamethylene diisocyanate and 2.5 parts of pyridine copper acid in a nitrogen atmosphere, and reacting for 4 hours at 50 ℃; adding an isocyanato ABS-chloroform solution (3 parts of isocyanato ABS and 10 parts of chloroform), heating to 60 ℃, reacting for 6 hours, cooling, and purifying to obtain modified graphene;
Step 2: s21: adding 10 parts of pyridine copper acid into 50 parts of tetrahydrofuran, setting the temperature to-10 ℃, slowly adding 5 parts of H 4 AlLi, and stirring for reaction for 10 hours under the nitrogen atmosphere; adding a 14wt% NaOH solution (the ratio of the NaOH solution to the cupric pyridine acid is 1mg:0.6 mL), continuously stirring for 30 minutes, and extracting and purifying by using ethyl acetate to obtain cupric pyridine alcohol;
S22: at room temperature, sequentially adding 20 parts of diphenyl carbonate, 7 parts of isosorbide, 1.5 parts of cupric oxide, 3 parts of tetraethylene glycol and 0.5 part of double-end hydroxyl polybutadiene into a reaction kettle, adding 1-butyl-3-methylimidazole lactate (accounting for 0.005mol percent of the diphenyl carbonate) in a nitrogen atmosphere, reacting for 2 hours at 120 ℃, gradually heating to 220 ℃, reducing the pressure to 50pa, continuously reacting for 30 minutes, and cooling to obtain polycarbonate;
Step 3: 100 parts of ABS resin, 30 parts of polycarbonate, 8 parts of modified graphene, 8 parts of SMA compatilizer, 0.5 part of tris (2-acryloyloxyethyl) isocyanurate and 0.5 part of antioxidant 1135 are dried and then uniformly mixed to obtain a raw material; the raw materials are placed in a screw extruder, the rotating speed of the screw extruder is set to be 250rpm, the temperature of each temperature zone is 200 ℃, 220 ℃, 240 ℃, 250 ℃, 260 ℃ and the feeding rotating speed is 50rpm, and the ABS antistatic plastic is obtained through melt extrusion.
Example 2: the preparation process of the ABS antistatic plastic based on graphene modification comprises the following steps:
Step 1: s11: (1) Adding 2, 4-toluene diisocyanate into a reaction bottle, heating to 55 ℃ in a nitrogen atmosphere, dropwise adding hydroxyethyl acrylate, reacting for 6 hours, and cooling to obtain modified isocyanate; the molar ratio of the 2, 4-toluene diisocyanate to the hydroxyethyl acrylate is 1:1; (2) Adding 2.5 parts of ABS resin into 50 parts of toluene, heating to 120 ℃ in nitrogen atmosphere, adding toluene mixed solution containing modified isocyanate and dicumyl peroxide (0.42 part of modified isocyanate, 0.06 part of dicumyl peroxide and 30 parts of toluene), reacting for 5 hours, precipitating and purifying by using methanol to obtain isocyanato ABS;
S12: sequentially adding anhydrous citric acid and cysteine into deionized water for dissolution to obtain a mixed solution; placing the mixed solution in a forced air drying oven, drying at 130 ℃ for 18 hours, and purifying to obtain pyridine ketoacid; the molar ratio of the anhydrous citric acid to the cysteine is 1:1;
s13: dispersing 5 parts of graphene oxide in 50 parts of chloroform by ultrasonic, sequentially adding 5 parts of triethylamine, 3 parts of hexamethylene diisocyanate and 2 parts of pyridine copper acid in a nitrogen atmosphere, and reacting for 4 hours at 50 ℃; adding an isocyanato ABS-chloroform solution (3.5 parts of isocyanato ABS and 10 parts of chloroform), heating to 60 ℃, reacting for 6 hours, cooling, and purifying to obtain modified graphene;
Step 2: s21: adding 10 parts of pyridine copper acid into 50 parts of tetrahydrofuran, setting the temperature to-10 ℃, slowly adding 5 parts of H 4 AlLi, and stirring for reaction for 10 hours under the nitrogen atmosphere; adding a 14wt% NaOH solution (the ratio of the NaOH solution to the cupric pyridine acid is 1mg:0.6 mL), continuously stirring for 30 minutes, and extracting and purifying by using ethyl acetate to obtain cupric pyridine alcohol;
S22: at room temperature, sequentially adding 20 parts of diphenyl carbonate, 7 parts of isosorbide, 1.5 parts of cupric oxide, 3 parts of tetraethylene glycol and 0.5 part of double-end hydroxyl polybutadiene into a reaction kettle, adding 1-butyl-3-methylimidazole lactate (accounting for 0.005mol percent of the diphenyl carbonate) in a nitrogen atmosphere, reacting for 2 hours at 120 ℃, gradually heating to 220 ℃, reducing the pressure to 50pa, continuously reacting for 30 minutes, and cooling to obtain polycarbonate;
step 3: 100 parts of ABS resin, 25 parts of polycarbonate, 8 parts of modified graphene, 6 parts of SMA compatilizer, 0.5 part of tris (2-acryloyloxyethyl) isocyanurate and 0.2 part of antioxidant 1135 are dried and then uniformly mixed to obtain a raw material; the raw materials are placed in a screw extruder, the rotating speed of the screw extruder is set to be 250rpm, the temperature of each temperature zone is 200 ℃, 220 ℃, 240 ℃, 250 ℃, 260 ℃ and the feeding rotating speed is 50rpm, and the ABS antistatic plastic is obtained through melt extrusion.
Example 3: the preparation process of the ABS antistatic plastic based on graphene modification comprises the following steps:
Step 1: s11: (1) Adding 2, 4-toluene diisocyanate into a reaction bottle, heating to 55 ℃ in a nitrogen atmosphere, dropwise adding hydroxyethyl acrylate, reacting for 6 hours, and cooling to obtain modified isocyanate; the molar ratio of the 2, 4-toluene diisocyanate to the hydroxyethyl acrylate is 1:1; (2) Adding 2.5 parts of ABS resin into 50 parts of toluene, heating to 120 ℃ in nitrogen atmosphere, adding toluene mixed solution containing modified isocyanate and dicumyl peroxide (0.42 part of modified isocyanate, 0.06 part of dicumyl peroxide and 30 parts of toluene), reacting for 5 hours, precipitating and purifying by using methanol to obtain isocyanato ABS;
S12: sequentially adding anhydrous citric acid and cysteine into deionized water for dissolution to obtain a mixed solution; placing the mixed solution in a forced air drying oven, drying at 130 ℃ for 18 hours, and purifying to obtain pyridine ketoacid; the molar ratio of the anhydrous citric acid to the cysteine is 1:1;
S13: dispersing 5 parts of graphene oxide in 50 parts of chloroform by ultrasonic, sequentially adding 4.5 parts of triethylamine, 4 parts of hexamethylene diisocyanate and 2.5 parts of pyridine copper acid in a nitrogen atmosphere, and reacting for 4 hours at 50 ℃; adding an isocyanato ABS-chloroform solution (2.5 parts of isocyanato ABS and 10 parts of chloroform), heating to 60 ℃, reacting for 6 hours, cooling, and purifying to obtain modified graphene;
Step 2: s21: adding 10 parts of pyridine copper acid into 50 parts of tetrahydrofuran, setting the temperature to-10 ℃, slowly adding 5 parts of H 4 AlLi, and stirring for reaction for 10 hours under the nitrogen atmosphere; adding a 14wt% NaOH solution (the ratio of the NaOH solution to the cupric pyridine acid is 1mg:0.6 mL), continuously stirring for 30 minutes, and extracting and purifying by using ethyl acetate to obtain cupric pyridine alcohol;
S22: at room temperature, sequentially adding 20 parts of diphenyl carbonate, 7 parts of isosorbide, 1.5 parts of cupric oxide, 3 parts of tetraethylene glycol and 0.5 part of double-end hydroxyl polybutadiene into a reaction kettle, adding 1-butyl-3-methylimidazole lactate (accounting for 0.005mol percent of the diphenyl carbonate) in a nitrogen atmosphere, reacting for 2 hours at 120 ℃, gradually heating to 220 ℃, reducing the pressure to 50pa, continuously reacting for 30 minutes, and cooling to obtain polycarbonate;
Step 3: 100 parts of ABS resin, 35 parts of polycarbonate, 6 parts of modified graphene, 9 parts of SMA compatilizer, 0.8 part of tris (2-acryloyloxyethyl) isocyanurate and 0.5 part of antioxidant 1135 are dried and then uniformly mixed to obtain a raw material; the raw materials are placed in a screw extruder, the rotating speed of the screw extruder is set to be 250rpm, the temperature of each temperature zone is 200 ℃, 220 ℃, 240 ℃, 250 ℃, 260 ℃ and the feeding rotating speed is 50rpm, and the ABS antistatic plastic is obtained through melt extrusion.
Comparative example 1: based on example 1, graphene oxide was modified with 3-isocyanatopropylene, specifically modified as: s13: dispersing 5 parts of graphene oxide in 50 parts of chloroform in an ultrasonic manner, sequentially adding 5 parts of triethylamine and 5.5 parts of 3-isocyanatopropylene in a nitrogen atmosphere, heating to 60 ℃, reacting for 6 hours, cooling, and purifying to obtain modified graphene; the remainder was the same as in example 1.
Comparative example 2: based on example 1, graphene oxide was modified with picolinic acid alone, specifically modified as: s13: dispersing 5 parts of graphene oxide in 50 parts of chloroform in an ultrasonic manner, sequentially adding 5 parts of triethylamine, 3.5 parts of hexamethylene diisocyanate and 5.5 parts of pyridine copper acid in a nitrogen atmosphere, heating to 60 ℃, reacting for 6 hours, cooling and purifying to obtain modified graphene; the remainder was the same as in example 1.
Comparative example 3: based on example 1, graphene oxide was modified with isocyanate ABS alone, specifically modified as: s13: dispersing 5 parts of graphene oxide in 50 parts of chloroform in an ultrasonic manner, sequentially adding a mixed solution of 5 parts of triethylamine and 5.5 parts of isocyanato ABS-10 parts of chloroform in a nitrogen atmosphere, heating to 60 ℃, reacting for 6 hours, cooling, and purifying to obtain modified graphene; the remainder was the same as in example 1.
Comparative example 4: the polycarbonate was replaced by polycarbonate-CD 402, branded Bayer Germany, and the remainder was the same as in example 1.
Experiment 1: performing performance test on the ABS antistatic plastics prepared in the examples 1-3 and the comparative examples 1-4;
(1) The tensile strength was tested at a tensile rate of 10mm/min with reference to the standard method of GB/T1040.1;
(2) With reference to the standard method of GB/T1410, a sample having a sample size of 10cm 1mm is left at 23℃for a period of time under a humidity of 33%, and its volume resistivity is measured using a volume surface resistivity meter; the data obtained are shown below:
Conclusion: the data of examples 1-3 show that: according to the scheme, the dispersibility of the graphene in the ABS antistatic plastic is effectively enhanced by modifying the graphene, and the antistatic performance is effectively enhanced on the basis of ensuring the mechanical property. Comparing the data of example 1 with comparative examples 1-4, the data shows that: when the graphene oxide in comparative example 1 is modified by 3-isocyanatopropylene, although the propylene can generate reaction crosslinking, the problem of dispersibility still exists, so that the mechanical property is reduced, and meanwhile, the antistatic property is obviously reduced due to the fact that the graphene oxide does not contain conjugated pyridonic acid; in comparative example 2, the dispersibility was lowered and the mechanical properties were lowered due to the single use of the picolinic acid modified graphene; in comparative example 3, the antistatic property was lowered due to the single use of the isocyanate group ABS modification; meanwhile, the effect with the polycarbonate is weakened, so that the mechanical property is reduced; in comparative example 4, since polycarbonate-CD 402 was used, the compatibility was lowered, resulting in a decrease in mechanical properties.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. The preparation process of the ABS antistatic plastic based on graphene modification is characterized by comprising the following steps of: the method comprises the following steps:
Step 1: preparation of modified graphene:
S11: (1) Adding 2, 4-toluene diisocyanate into a reaction bottle, heating to 40-60 ℃ in a nitrogen atmosphere, dropwise adding hydroxyethyl acrylate, reacting for 4-6 hours, and cooling to obtain modified isocyanate; (2) Adding ABS resin into toluene, heating to 120-125 ℃ in nitrogen atmosphere, adding toluene mixed solution containing modified isocyanate and dicumyl peroxide, reacting for 4-5 hours, precipitating with methanol, and purifying to obtain isocyanato ABS;
S12: sequentially adding anhydrous citric acid and cysteine into deionized water for dissolution to obtain a mixed solution; placing the mixed solution in a forced air drying oven, drying at 130-140 ℃ for 12-24 hours, and purifying to obtain pyridine ketoacid;
S13: dispersing graphene oxide in chloroform by ultrasonic waves, sequentially adding triethylamine, hexamethylene diisocyanate and pyridonic acid in a nitrogen atmosphere, and reacting for 2-4 hours at 40-50 ℃; adding an isocyanato ABS-chloroform solution, heating to 60-65 ℃, reacting for 6-8 hours, cooling, and purifying to obtain modified graphene;
Step 2: preparation of polycarbonate:
S21: adding pyridonic acid into tetrahydrofuran, setting the temperature to be minus 10 ℃ to minus 5 ℃, slowly adding H 4 AlLi, and stirring and reacting for 8-10 hours in a nitrogen atmosphere; adding 12-15 wt% NaOH solution, continuously stirring for 30-40 minutes, extracting and purifying by using ethyl acetate to obtain pyridone alcohol;
S22: sequentially adding diphenyl carbonate, isosorbide, pyridone alcohol, tetraethylene glycol and double-end hydroxyl polybutadiene into a reaction kettle at room temperature, adding a catalyst under a nitrogen atmosphere, reacting for 2-3 hours at 110-120 ℃, gradually heating to 220-240 ℃, reducing the pressure to 30-50 pa, continuing to react for 25-35 minutes, and cooling to obtain polycarbonate;
Step 3: preparation of ABS antistatic plastic: drying and uniformly mixing ABS resin, polycarbonate, modified graphene, a compatilizer, a cross-linking agent and an antioxidant to obtain a raw material; melting and extruding the raw materials in a screw extruder to obtain ABS antistatic plastic;
The ABS antistatic plastic comprises the following raw materials: 100 parts of ABS resin, 25-35 parts of polycarbonate, 6-8 parts of modified graphene, 6-9 parts of compatilizer, 0.5-0.8 part of cross-linking agent and 0.2-0.5 part of antioxidant;
The raw materials of the modified graphene comprise the following components: according to parts by weight, 5 parts of graphene oxide, 4.5-5 parts of triethylamine, 3-4 parts of hexamethylene diisocyanate, 2-2.5 parts of pyridonic acid and 2.5-3.5 parts of isocyanato ABS;
The raw materials of the polycarbonate comprise the following components: 18-20 parts of diphenyl carbonate, 6-8 parts of isosorbide, 1-2 parts of pyridone alcohol, 3-4 parts of tetraethylene glycol and 0.4-0.6 part of double-end hydroxyl polybutadiene.
2. The preparation process of the ABS antistatic plastic based on graphene modification, which is described in claim 1, is characterized in that: in the step S11 of the step 1, the molar ratio of the 2, 4-toluene diisocyanate to the hydroxyethyl acrylate in the modified isocyanate is 1 (0.8-1); in the isocyanato ABS, the mass ratio of the ABS resin to the modified isocyanate to the dicumyl peroxide is 2.5 (0.4-0.45) to 0.05-0.075.
3. The preparation process of the ABS antistatic plastic based on graphene modification, which is described in claim 1, is characterized in that: in step S12 of step 1, the molar ratio of anhydrous citric acid to cysteine in the pyridonic acid is 1:1.
4. The preparation process of the ABS antistatic plastic based on graphene modification, which is described in claim 1, is characterized in that: in the pyridone alcohol, the mass ratio of the pyridonic acid to the H 4 AlLi is 1 (0.5-0.6); the ratio of the pyridine keto acid to the NaOH solution is 1mg (0.6-0.8 mL).
5. The preparation process of the ABS antistatic plastic based on graphene modification, which is described in claim 1, is characterized in that: the rotation speed of the screw extruder is 200-250 rpm, the temperature of each temperature zone is 200-210 ℃, 220-240 ℃, 240-250 ℃, 250-260 ℃, 260-270 ℃ and the feeding rotation speed is 30-60 rpm.
6. The ABS antistatic plastic prepared by the preparation process of the graphene-modified-based ABS antistatic plastic according to any one of claims 1-5.
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