CN115011088A - Color master batch for carbon black coloring polyethylene glycol terephthalate and preparation method thereof - Google Patents
Color master batch for carbon black coloring polyethylene glycol terephthalate and preparation method thereof Download PDFInfo
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- CN115011088A CN115011088A CN202210880488.6A CN202210880488A CN115011088A CN 115011088 A CN115011088 A CN 115011088A CN 202210880488 A CN202210880488 A CN 202210880488A CN 115011088 A CN115011088 A CN 115011088A
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- carbon black
- polyethylene glycol
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- glycol terephthalate
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- 239000006229 carbon black Substances 0.000 title claims abstract description 83
- 239000002202 Polyethylene glycol Substances 0.000 title claims abstract description 52
- 229920001223 polyethylene glycol Polymers 0.000 title claims abstract description 52
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 title claims abstract description 52
- 239000004595 color masterbatch Substances 0.000 title claims abstract description 36
- 238000004040 coloring Methods 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 150000001721 carbon Chemical class 0.000 claims abstract description 36
- 239000002994 raw material Substances 0.000 claims abstract description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 47
- 238000002156 mixing Methods 0.000 claims description 36
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 33
- 239000008367 deionised water Substances 0.000 claims description 32
- 229910021641 deionized water Inorganic materials 0.000 claims description 32
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 31
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 31
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 28
- 239000012065 filter cake Substances 0.000 claims description 27
- -1 polyethylene terephthalate Polymers 0.000 claims description 27
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 25
- 238000001816 cooling Methods 0.000 claims description 23
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 22
- 238000001914 filtration Methods 0.000 claims description 22
- OITNBJHJJGMFBN-UHFFFAOYSA-N 4-(chloromethyl)benzoic acid Chemical compound OC(=O)C1=CC=C(CCl)C=C1 OITNBJHJJGMFBN-UHFFFAOYSA-N 0.000 claims description 18
- 239000000706 filtrate Substances 0.000 claims description 17
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000010410 layer Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 14
- 239000012044 organic layer Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 10
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 10
- KJJPLEZQSCZCKE-UHFFFAOYSA-N 2-aminopropane-1,3-diol Chemical compound OCC(N)CO KJJPLEZQSCZCKE-UHFFFAOYSA-N 0.000 claims description 9
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 9
- 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 9
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 238000005453 pelletization Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000009833 condensation Methods 0.000 abstract description 4
- 230000005494 condensation Effects 0.000 abstract description 4
- 238000005054 agglomeration Methods 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 3
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 3
- 150000003242 quaternary ammonium salts Chemical group 0.000 abstract description 3
- 238000013329 compounding Methods 0.000 abstract description 2
- 229920001558 organosilicon polymer Polymers 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 229910017604 nitric acid Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical group ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- 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
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
-
- 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
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
Abstract
The invention discloses a color master batch for carbon black coloring polyethylene glycol terephthalate and a preparation method thereof, wherein the color master batch comprises the following raw materials in parts by weight: 6-8 parts of modified carbon black, 40-50 parts of modified polyethylene glycol terephthalate and 3-5 parts of antistatic synergist; modified carbon black, modified polyethylene glycol terephthalate and an antistatic synergist are subjected to hydrolytic condensation under an alkaline condition, so that the modified carbon black and the antistatic synergist are connected to a molecular chain of the modified polyethylene glycol terephthalate, the modified carbon black and the antistatic synergist can be uniformly dispersed in the modified polyethylene glycol terephthalate, the agglomeration phenomenon of the modified carbon black is avoided, meanwhile, a side chain contains an organic silicon polymer long chain, the mechanical property of the color master batch can be greatly improved by compounding the modified carbon black and the carbon black, meanwhile, the surface of the color master batch also has a large number of quaternary ammonium salt structures, an antistatic film can be formed on the surface of the color master batch, and the film is connected with a main chain of a color master batch molecule, so that the problem that the antistatic film falls off is avoided.
Description
Technical Field
The invention relates to the technical field of preparation of high polymer materials, in particular to a color master batch for coloring polyethylene glycol terephthalate by carbon black and a preparation method thereof.
Background
PET, namely polyethylene terephthalate, is a crystalline polyester, has excellent mechanical properties, insulating properties and weather resistance, and the application range comprises fibers, films, engineering plastics and the like, but PET material products can generate an aging phenomenon under the irradiation of sunlight and shorten the service life of the PET products, carbon black is a supplement and a reinforcing agent commonly used in the rubber industry and is more and more widely applied in the non-rubber industrial field, and the carbon black added in the PET material can be used as a toner and a light stabilizer for absorbing ultraviolet rays because the carbon black has good physical shielding effect on the ultraviolet rays and can also absorb and remove free radicals generated in a photo-oxidation reaction;
the existing polyethylene terephthalate has general mechanical strength, is easy to break and generate static electricity in the use process due to low self-pull strength, is not beneficial to use in special environments, improves the antistatic effect of the polyethylene terephthalate by adding an antistatic agent in part of materials, has obvious effect in a short time, and separates out and separates the antistatic component after being used for a period of time, so that the polyethylene terephthalate cannot meet the antistatic requirement;
in view of the above technical drawbacks, a solution is proposed.
Disclosure of Invention
The invention aims to provide a color master batch for carbon black coloring polyethylene glycol terephthalate and a preparation method thereof, and solves the problems of poor carbon black dispersing effect, poor polyethylene glycol terephthalate mechanical effect and easy generation of static electricity of the carbon black coloring color master batch at the present stage through modified carbon black, modified polyethylene glycol terephthalate and an antistatic synergist.
The purpose of the invention can be realized by the following technical scheme:
the color master batch for coloring polyethylene glycol terephthalate by carbon black comprises the following raw materials in parts by weight: 6-8 parts of modified carbon black, 40-50 parts of modified polyethylene glycol terephthalate and 3-5 parts of antistatic synergist;
further, the modified carbon black is prepared by the following steps:
dispersing modified carbon black, modified polyethylene glycol terephthalate and an antistatic synergist in deionized water, adjusting the pH value of a reaction solution to 10-11, stirring for 3-5h at the rotation speed of 300-90 r/min and the temperature of 70-80 ℃, adding dibutyltin dilaurate, heating to the temperature of 140-150 ℃, continuing to react for 5-7h, filtering to remove filtrate, drying a filter cake, adding into a double-screw extruder, and extruding, cooling and pelletizing under the conditions that the rotation speed is 60-90r/min, the first zone temperature is 240-250 ℃, the second zone temperature is 250-260 ℃, the third zone temperature is 265-275 ℃, the fourth zone temperature is 250-260 ℃ and the head temperature is 250 ℃ to obtain the color master batch of the carbon black colored polyethylene glycol terephthalate.
Further, the modified carbon black is prepared by the following steps:
uniformly mixing carbon black and concentrated nitric acid, reacting for 10-15h at the rotation speed of 300-90 ℃ at 500r/min, filtering to remove filtrate, washing filter cakes to obtain neutral washing liquid to obtain oxidized carbon black, uniformly mixing the oxidized carbon black, gamma-aminopropyltriethoxysilane and deionized water, reacting for 5-7h at the rotation speed of 150-200r/min and the temperature of 40-50 ℃, filtering to remove filtrate, and drying the filter cakes to obtain the modified carbon black.
Further, the mass ratio of the carbon black to the concentrated nitric acid is 1:6, the mass fraction of the concentrated nitric acid is 69%, and the mass ratio of the oxidized carbon black to the gamma-aminopropyltriethoxysilane is 10: 0.5.
Further, the modified polyethylene terephthalate is prepared by the following steps:
step A1: uniformly mixing p-chloromethylbenzoic acid, 2-amino-1, 3-propanediol and deionized water, reacting for 3-5h at the rotation speed of 150-90 ℃ for 3-5h, cooling to room temperature, filtering to remove filtrate, uniformly mixing a filter cake, terephthalic acid, ethylene glycol and antimony trioxide, introducing nitrogen for protection, reacting for 8-10h at the rotation speed of 30-60r/min, the temperature of 230-235 ℃ and the pressure of 0.02-0.03MPa, adjusting the pressure to 80-90Pa, heating to the temperature of 270-275 ℃, continuing to react for 8-10h, and cooling to room temperature to obtain pre-modified polyethylene terephthalate;
step A2: dissolving pre-modified polyethylene glycol terephthalate in nitrobenzene, adding deionized water, potassium carbonate and tetraethylammonium bromide, reacting for 1-1.5h at the rotation speed of 150-130 ℃ for 1-1.5h, standing for layering, removing a water layer, uniformly mixing an organic layer, toluene-2, 4-diisocyanate, gamma-aminopropyltriethoxysilane and potassium carbonate, reacting for 3-5h at the rotation speed of 200-300r/min and the temperature of 50-60 ℃, adding deionized water, stirring for 10-15min, standing for layering, removing the water layer, and distilling to remove a solvent at the temperature of 215 ℃ to prepare the modified polyethylene glycol terephthalate.
Further, the molar ratio of the p-chloromethylbenzoic acid to the 2-amino-1, 3-propanediol in the step A1 is 1:1, the molar ratio of the filter cake to the terephthalic acid to the ethylene glycol is 1.1:2.5:1.2, and the amount of the antimony trioxide is 1 per mill of the total mass of the filter cake, the terephthalic acid and the ethylene glycol.
Further, the mass ratio of the pre-modified polyethylene terephthalate, the deionized water, the potassium carbonate and the tetraethylammonium bromide in the step A2 is 5:30:9:1.6, and the mass ratio of the organic layer, the toluene-2, 4-diisocyanate, the gamma-aminopropyltriethoxysilane and the potassium carbonate is 10:4.3:6.8: 5.2.
Further, the antistatic synergist is prepared by the following steps:
uniformly mixing gamma-aminopropyltriethoxysilane, p-chloromethylbenzoic acid and diethyl ether, reacting for 3-5h at the rotation speed of 150-200r/min and the temperature of 30-40 ℃, heating and distilling to remove the diethyl ether, filtering to remove filter residue, uniformly mixing a substrate, triethanolamine, triethylamine and the diethyl ether, reacting for 1-1.5h at the rotation speed of 300-500r/min and the temperature of 90-95 ℃, cooling to room temperature, adding deionized water, stirring for 15-20min, standing for layering, removing a water layer, distilling an organic layer at the temperature of 50-60 ℃ to remove the diethyl ether, and preparing the antistatic synergist.
Furthermore, the molar ratio of the gamma-aminopropyltriethoxysilane to the p-chloromethylbenzoic acid is 1:1, and the molar ratio of the substrate to the triethanolamine is 1: 1.
The preparation method of the color master batch for coloring polyethylene glycol terephthalate with carbon black comprises the following steps:
dispersing modified carbon black, modified polyethylene glycol terephthalate and an antistatic synergist in deionized water, adjusting the pH value of a reaction solution to 10-11, stirring for 3-5h at the rotation speed of 300-80 ℃ for 500r/min, drying a filter cake, adding the filter cake into a double-screw extruder, extruding, cooling and pelletizing under the conditions that the rotation speed is 60-90r/min, the temperature of a first zone is 240-250 ℃, the temperature of a second zone is 250-260 ℃, the temperature of a third zone is 265-275 ℃, the temperature of a fourth zone is 250-260 ℃ and the temperature of a head is 250 ℃ to prepare the color master batch of the carbon black colored polyethylene glycol terephthalate.
The invention has the following beneficial effects:
the color master batch of carbon black colored polyethylene glycol terephthalate is prepared by hydrolysis polycondensation of modified carbon black, modified polyethylene glycol terephthalate and an antistatic synergist and melt extrusion, wherein the modified carbon black is prepared by taking carbon black as a raw material and carrying out oxidation treatment by concentrated nitric acid to prepare oxidized carbon black, the oxidized carbon black is reacted with gamma-aminopropyltriethoxysilane to ensure that active hydroxyl on the oxidized carbon black and amino on the gamma-aminopropyltriethoxysilane undergo dehydration condensation to prepare modified carbon black, the modified polyethylene glycol terephthalate is reacted with p-chloromethylbenzoic acid and 2-amino-1, 3-propanediol to ensure that carboxyl on the p-chloromethylbenzoic acid and amino on the 2-amino-1, 3-propanediol undergo esterification copolymerization after dehydration condensation, preparing pre-modified polyethylene glycol terephthalate, hydrolyzing the polyethylene glycol terephthalate to convert chloromethyl on the pre-modified polyethylene glycol terephthalate into methyl alcohol, adding toluene-2, 4-diisocyanate and gamma-aminopropyl triethoxysilane to react one isocyanate on the toluene-2, 4-diisocyanate with alcoholic hydroxyl, and react the other isocyanate with amino on the gamma-aminopropyl triethoxysilane to prepare the modified polyethylene glycol terephthalate, wherein the antistatic synergist takes the gamma-aminopropyl triethoxysilane and p-chloromethylbenzoic acid as raw materials to perform dehydration condensation on the amino on the gamma-aminopropyl triethoxysilane and carboxyl on the p-chloromethylbenzoic acid, and then reacts with the triethanolamine to perform nucleophilic attack on the center of carbon in a benzyl chloride structure by the triethanolamine, the method comprises the following steps of performing substitution reaction to form quaternary ammonium salt, hydrolyzing modified carbon black, modified polyethylene terephthalate and an antistatic synergist under an alkaline condition to hydrolyze siloxane into silanol, condensing adjacent silanol to connect the modified carbon black and the antistatic synergist on a molecular chain of the modified polyethylene terephthalate, and performing melt extrusion to uniformly disperse the modified carbon black and the antistatic synergist in the modified polyethylene terephthalate, so that the agglomeration phenomenon of the modified carbon black is avoided, meanwhile, a side chain contains an organosilicon polymeric long chain, the mechanical property of the color master batch can be greatly improved by compounding the modified carbon black and the carbon black, meanwhile, a large number of quaternary ammonium salt structures are formed on the surface of the color master batch, a layer of antistatic film can be formed on the surface of the color master batch, the film is connected with a main chain of the color master batch molecules, and the problem of falling of the antistatic film cannot occur.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all 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.
Example 1
The color master batch for carbon black coloring polyethylene glycol terephthalate comprises the following raw materials in parts by weight: 6 parts of modified carbon black, 40 parts of modified polyethylene terephthalate and 3 parts of antistatic synergist;
the color master batch for coloring the polyethylene glycol terephthalate by the carbon black is prepared by the following steps:
dispersing modified carbon black, modified polyethylene glycol terephthalate and an antistatic synergist in deionized water, adjusting the pH value of a reaction solution to 10, stirring for 3 hours at the rotation speed of 300r/min and the temperature of 70 ℃, adding dibutyltin dilaurate, wherein the using amount of the dibutyltin dilaurate is 3% of the mass sum of the modified carbon black, the modified polyethylene glycol terephthalate and the antistatic synergist, heating to 140 ℃, continuing to react for 5 hours, filtering to remove filtrate, drying a filter cake, adding into a double-screw extruder, extruding, cooling and pelletizing under the conditions that the rotation speed is 60r/min, the first-zone temperature is 240 ℃, the second-zone temperature is 250 ℃, the third-zone temperature is 265 ℃, the fourth-zone temperature is 250 ℃ and the head temperature is 250 ℃, so as to obtain the color master batch of carbon black colored polyethylene glycol terephthalate.
The modified carbon black is prepared by the following steps:
uniformly mixing 1g of carbon black and 6g of concentrated nitric acid with the mass fraction of 69%, reacting for 10 hours at the rotation speed of 300r/min and the temperature of 80 ℃, cooling to the temperature of 20 ℃, filtering to remove filtrate, washing filter cakes to obtain neutral washing liquid to obtain oxidized carbon black, uniformly mixing 10g of oxidized carbon black, 0.5g of gamma-aminopropyltriethoxysilane and deionized water, reacting for 5 hours at the rotation speed of 150r/min and the temperature of 40 ℃, filtering to remove filtrate, and drying the filter cakes to obtain the modified carbon black.
The modified polyethylene terephthalate is prepared by the following steps:
step A1: uniformly mixing 0.1mol of p-chloromethyl benzoic acid, 0.1mol of 2-amino-1, 3-propanediol and 50mL of deionized water, reacting for 3 hours at the temperature of 80 ℃ at the rotation speed of 150r/min, filtering to remove filtrate, mixing 0.11mol of filter cake, 0.25mol of terephthalic acid and 0.12mol of ethylene glycol, adding antimony trioxide, wherein the dosage of the antimony trioxide is 1 per mill of the total mass of the filter cake, the terephthalic acid and the ethylene glycol, uniformly mixing, introducing nitrogen for protection, reacting for 8 hours at the rotation speed of 30r/min at the temperature of 230 ℃ and the pressure of 0.02MPa, adjusting the pressure to 80Pa, heating to the temperature of 270 ℃, continuing to react for 8 hours, and cooling to room temperature to prepare pre-modified polyethylene terephthalate;
step A2: dissolving 5g of pre-modified polyethylene terephthalate in 50mL of nitrobenzene, adding 30g of deionized water, 9g of potassium carbonate and 1.6g of tetraethylammonium bromide, reacting for 1h at the rotation speed of 150r/min and the temperature of 120 ℃, standing for layering, removing a water layer, uniformly mixing 10g of an organic layer, 4.3g of toluene-2, 4-diisocyanate, 6.8g of gamma-aminopropyltriethoxysilane and 5.2g of potassium carbonate, reacting for 3h at the rotation speed of 200r/min and the temperature of 50 ℃, adding deionized water, stirring for 10min, standing for layering, removing the water layer, and distilling to remove the solvent at the temperature of 215 ℃ to obtain the modified polyethylene terephthalate.
The antistatic synergist is prepared by the following steps:
uniformly mixing 0.1mol of gamma-aminopropyltriethoxysilane, 0.1mol of p-chloromethylbenzoic acid and 80mL of diethyl ether, reacting for 3h at the temperature of 30 ℃ at the rotation speed of 150r/min, heating and distilling to remove the diethyl ether, filtering to remove filter residue, uniformly mixing 0.1mol of a substrate, 0.1mol of triethanolamine, 0.1mol of triethylamine and 50mL of diethyl ether, reacting for 1h at the rotation speed of 300r/min and the temperature of 90 ℃, cooling to room temperature, adding 50mL of deionized water, stirring for 15min, standing for layering, removing a water layer, distilling the organic layer at the temperature of 50 ℃ to remove the diethyl ether, and preparing the antistatic synergist.
Example 2
The color master batch for carbon black coloring polyethylene glycol terephthalate comprises the following raw materials in parts by weight: 7 parts of modified carbon black, 45 parts of modified polyethylene terephthalate and 4 parts of antistatic synergist;
the color master batch for coloring the polyethylene glycol terephthalate by the carbon black is prepared by the following steps:
dispersing modified carbon black, modified polyethylene glycol terephthalate and an antistatic synergist in deionized water, adjusting the pH value of a reaction solution to 10, stirring for 4 hours at the rotation speed of 500r/min and the temperature of 75 ℃, adding dibutyltin dilaurate, heating to 145 ℃, continuing to react for 6 hours, filtering to remove filtrate, drying a filter cake, adding into a double-screw extruder, extruding, cooling and pelletizing at the rotation speed of 60r/min, the temperature of 245 ℃ in a first area, the temperature of 255 ℃ in a second area, the temperature of 270 ℃ in a third area, the temperature of 255 ℃ in a fourth area and the temperature of 250 ℃ in a machine head to obtain the color master batch of the carbon black colored polyethylene glycol terephthalate.
The modified carbon black is prepared by the following steps:
uniformly mixing 1g of carbon black and 6g of concentrated nitric acid with the mass fraction of 69%, reacting for 13 hours at the rotation speed of 500r/min and the temperature of 85 ℃, cooling to the temperature of 23 ℃, filtering to remove filtrate, washing filter cakes to obtain neutral washing liquid to obtain oxidized carbon black, uniformly mixing 10g of oxidized carbon black, 0.5g of gamma-aminopropyltriethoxysilane and deionized water, reacting for 6 hours at the rotation speed of 180r/min and the temperature of 45 ℃, filtering to remove filtrate, and drying the filter cakes to obtain the modified carbon black.
The modified polyethylene terephthalate is prepared by the following steps:
step A1: uniformly mixing 0.1mol of p-chloromethylbenzoic acid, 0.1mol of 2-amino-1, 3-propanediol and 50mL of deionized water, reacting for 4h at 85 ℃ at a rotation speed of 180r/min, cooling to room temperature, filtering to remove filtrate, mixing 0.11mol of filter cake, 0.25mol of terephthalic acid and 0.12mol of ethylene glycol, adding antimony trioxide, wherein the dosage of the antimony trioxide is 1 per mill of the total mass of the filter cake, the terephthalic acid and the ethylene glycol, uniformly mixing, introducing nitrogen for protection, reacting for 9h at a rotation speed of 30r/min and a temperature of 235 ℃ and a pressure of 0.03MPa, adjusting the pressure to 85Pa, heating to 273 ℃, continuing to react for 9h, and cooling to room temperature to prepare the pre-modified polyethylene terephthalate;
step A2: dissolving 5g of pre-modified polyethylene glycol terephthalate in 50mL of nitrobenzene, adding 30g of deionized water, 9g of potassium carbonate and 1.6g of tetraethylammonium bromide, reacting for 1.3h at the rotation speed of 180r/min and the temperature of 125 ℃, standing for layering, removing a water layer, uniformly mixing 10g of an organic layer, 4.3g of toluene-2, 4-diisocyanate, 6.8g of gamma-aminopropyltriethoxysilane and 5.2g of potassium carbonate, reacting for 4h at the rotation speed of 300r/min and the temperature of 55 ℃, adding deionized water, stirring for 13min, standing for layering, removing the water layer, and distilling to remove the solvent at the temperature of 215 ℃ to obtain the modified polyethylene glycol terephthalate.
The antistatic synergist is prepared by the following steps:
uniformly mixing 0.1mol of gamma-aminopropyltriethoxysilane, 0.1mol of p-chloromethylbenzoic acid and 80mL of diethyl ether, reacting for 4 hours at the temperature of 35 ℃ at the rotation speed of 180r/min, heating and distilling to remove the diethyl ether, filtering to remove filter residue, uniformly mixing 0.1mol of a substrate, 0.1mol of triethanolamine, 0.1mol of triethylamine and 50mL of diethyl ether, reacting for 1.3 hours at the rotation speed of 500r/min and the temperature of 93 ℃, cooling to room temperature, adding 50mL of deionized water, stirring for 18 minutes, standing for layering, removing a water layer, distilling an organic layer at the temperature of 55 ℃ to remove the diethyl ether, and preparing the antistatic synergist.
Example 3
The color master batch for carbon black coloring polyethylene glycol terephthalate comprises the following raw materials in parts by weight: 8 parts of modified carbon black, 50 parts of modified polyethylene terephthalate and 5 parts of antistatic synergist;
the color master batch for coloring the polyethylene glycol terephthalate by the carbon black is prepared by the following steps:
dispersing modified carbon black, modified polyethylene glycol terephthalate and an antistatic synergist in deionized water, adjusting the pH value of a reaction solution to 11, stirring for 5 hours at the rotation speed of 500r/min and the temperature of 80 ℃, adding dibutyltin dilaurate, heating to the temperature of 150 ℃, continuing to react for 7 hours, filtering to remove filtrate, drying a filter cake, adding a double-screw extruder, extruding, cooling and pelletizing at the rotation speed of 90r/min, the temperature of 250 ℃ in a first area, the temperature of 260 ℃ in a second area, the temperature of 275 ℃ in a third area, the temperature of 260 ℃ in a fourth area and the temperature of 250 ℃ in a head to obtain the color master batch of the carbon black colored polyethylene glycol terephthalate.
The modified carbon black is prepared by the following steps:
uniformly mixing 1g of carbon black and 6g of concentrated nitric acid with the mass fraction of 69%, reacting for 15 hours at the rotation speed of 500r/min and the temperature of 90 ℃, cooling to the temperature of 25 ℃, filtering to remove filtrate, washing a filter cake to obtain neutral washing liquid to obtain oxidized carbon black, uniformly mixing 10g of oxidized carbon black, 0.5g of gamma-aminopropyltriethoxysilane and deionized water, reacting for 7 hours at the rotation speed of 200r/min and the temperature of 50 ℃, filtering to remove filtrate, and drying the filter cake to obtain the modified carbon black.
The modified polyethylene terephthalate is prepared by the following steps:
step A1: uniformly mixing 0.1mol of p-chloromethylbenzoic acid, 0.1mol of 2-amino-1, 3-propanediol and 50mL of deionized water, reacting at 90 ℃ for 5h at a rotation speed of 200r/min, cooling to room temperature, filtering to remove filtrate, mixing 0.11mol of filter cake, 0.25mol of terephthalic acid and 0.12mol of ethylene glycol, introducing nitrogen for protection, reacting at 235 ℃ and 0.03MPa at a rotation speed of 60r/min for 10h, adjusting the pressure to 90Pa, heating to 275 ℃, continuing to react for 10h, and cooling to room temperature to obtain pre-modified polyethylene terephthalate;
step A2: dissolving 5g of pre-modified polyethylene glycol terephthalate in 50mL of nitrobenzene, adding 30g of deionized water, 9g of potassium carbonate and 1.6g of tetraethylammonium bromide, reacting for 1.5h at the rotation speed of 200r/min and the temperature of 130 ℃, standing for layering, removing a water layer, uniformly mixing 10g of an organic layer, 4.3g of toluene-2, 4-diisocyanate, 6.8g of gamma-aminopropyltriethoxysilane and 5.2g of potassium carbonate, reacting for 5h at the rotation speed of 300r/min and the temperature of 60 ℃, adding deionized water, stirring for 15min, standing for layering, removing the water layer, and distilling to remove the solvent at the temperature of 215 ℃ to obtain the modified polyethylene glycol terephthalate.
The antistatic synergist is prepared by the following steps:
uniformly mixing 0.1mol of gamma-aminopropyltriethoxysilane, 0.1mol of p-chloromethylbenzoic acid and 80mL of diethyl ether, reacting for 5 hours at the temperature of 40 ℃ at the rotation speed of 200r/min, heating and distilling to remove the diethyl ether, filtering to remove filter residue, uniformly mixing 0.1mol of a substrate, 0.1mol of triethanolamine, 0.1mol of triethylamine and 50mL of diethyl ether, reacting for 1.5 hours at the rotation speed of 500r/min and the temperature of 95 ℃, cooling to room temperature, adding 50mL of deionized water, stirring for 20 minutes, standing for layering, removing a water layer, distilling an organic layer at the temperature of 60 ℃ to remove the diethyl ether, and preparing the antistatic synergist.
Comparative example 1
Compared with the example 1, the antistatic synergist is not added, and the antistatic synergist is prepared by directly melting and blending sodium dodecyl sulfate.
Comparative example 2
The comparative example is the plastic master batch disclosed in Chinese patent CN 108440919A.
Comparative example 3
The comparative example is the plastic master batch disclosed in Chinese patent CN 103183934A.
The plastic master batches prepared in the examples 1 to 3 and the comparative examples 1 to 3 are subjected to tensile strength detection according to the GB/T1040.1-2018 standard, the surface resistance of the plastic master batches is detected, and the surface resistance of the plastic master batches is continuously detected after the sample prepared from the plastic master batches is normally used for 6 months, so that the results are shown in the following table;
as can be seen from the above table, the color concentrates prepared in examples 1-3 have tensile strengths of 67-70MPa and surface resistances of 3.6X 10 6 -4.5×10 6 Omega, surface resistance after 6 months of use 3.6X 10 6 -4.5×10 6 Omega shows that the antistatic agent has good mechanical property and antistatic effect, and the antistatic effect cannot be reduced along with the increase of the service time and the agglomeration phenomenon of carbon black cannot occur.
The foregoing is illustrative and explanatory only of the present invention, and it is intended that the present invention cover modifications, additions, or substitutions by those skilled in the art, without departing from the spirit of the invention or exceeding the scope of the claims.
Claims (6)
1. The color master batch of carbon black coloring polyethylene glycol terephthalate is characterized in that: the feed comprises the following raw materials in parts by weight: 6-8 parts of modified carbon black, 40-50 parts of modified polyethylene glycol terephthalate and 3-5 parts of antistatic synergist;
the modified polyethylene glycol terephthalate is prepared by the following steps:
step A1: mixing p-chloromethylbenzoic acid, 2-amino-1, 3-propylene glycol and deionized water for reaction, cooling to room temperature, filtering to remove filtrate, mixing and reacting a filter cake, terephthalic acid, ethylene glycol and antimony trioxide, adjusting pressure and heating, continuing to react, and cooling to room temperature to obtain pre-modified polyethylene glycol terephthalate;
step A2: dissolving pre-modified polyethylene glycol terephthalate in nitrobenzene, adding deionized water, potassium carbonate and tetraethylammonium bromide, reacting, standing for layering, removing a water layer, mixing and reacting an organic layer, toluene-2, 4-diisocyanate, gamma-aminopropyltriethoxysilane and potassium carbonate, adding deionized water, stirring, standing for layering, removing the water layer, and distilling the organic layer to remove a solvent to obtain the modified polyethylene glycol terephthalate.
2. The carbon black-colored polyethylene terephthalate color masterbatch according to claim 1, characterized in that: the molar ratio of the p-chloromethylbenzoic acid to the 2-amino-1, 3-propanediol in the step A1 is 1:1, the molar ratio of the filter cake to the terephthalic acid to the ethylene glycol is 1.1:2.5:1.2, and the dosage of the antimony trioxide is 1 per mill of the total mass of the filter cake, the terephthalic acid and the ethylene glycol.
3. The color masterbatch of carbon black-colored polyethylene terephthalate according to claim 1, characterized in that: the mass ratio of the pre-modified polyethylene terephthalate, the deionized water, the potassium carbonate and the tetraethylammonium bromide in the step A2 is 5:30:9:1.6, and the mass ratio of the organic layer, the toluene-2, 4-diisocyanate, the gamma-aminopropyltriethoxysilane and the potassium carbonate is 10:4.3:6.8: 5.2.
4. The carbon black-colored polyethylene terephthalate color masterbatch according to claim 1, characterized in that: the antistatic synergist is prepared by the following steps:
mixing and reacting gamma-aminopropyltriethoxysilane, p-chloromethylbenzoic acid and diethyl ether, heating and distilling to remove the diethyl ether, filtering to remove filter residues, mixing and reacting a substrate, triethanolamine, triethylamine and the diethyl ether for h, cooling to room temperature, adding deionized water, stirring, standing for layering, removing a water layer, and distilling an organic layer to remove the diethyl ether to obtain the antistatic synergist.
5. The carbon black-colored polyethylene terephthalate color masterbatch according to claim 1, characterized in that: the molar ratio of the gamma-aminopropyltriethoxysilane to the p-chloromethylbenzoic acid is 1:1, and the molar ratio of the substrate to the triethanolamine is 1: 1.
6. The process for preparing a color masterbatch of carbon black-colored polyethylene terephthalate according to claim 1, wherein: the method specifically comprises the following steps:
dispersing modified carbon black, modified polyethylene glycol terephthalate and an antistatic synergist in deionized water, adjusting the pH value of a reaction solution to 10-11, stirring for 3-5h at the rotation speed of 300-80 ℃ for 500r/min, drying a filter cake, adding the filter cake into a double-screw extruder, extruding, cooling and pelletizing under the conditions that the rotation speed is 60-90r/min, the temperature of a first zone is 240-250 ℃, the temperature of a second zone is 250-260 ℃, the temperature of a third zone is 265-275 ℃, the temperature of a fourth zone is 250-260 ℃ and the temperature of a head is 250 ℃ to prepare the color master batch of the carbon black colored polyethylene glycol terephthalate.
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