CN111875887A - Antistatic polypropylene plastic and preparation method thereof - Google Patents
Antistatic polypropylene plastic and preparation method thereof Download PDFInfo
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- CN111875887A CN111875887A CN202010785762.2A CN202010785762A CN111875887A CN 111875887 A CN111875887 A CN 111875887A CN 202010785762 A CN202010785762 A CN 202010785762A CN 111875887 A CN111875887 A CN 111875887A
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- -1 polypropylene Polymers 0.000 title claims abstract description 67
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 62
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- 239000004033 plastic Substances 0.000 title claims abstract description 34
- 229920003023 plastic Polymers 0.000 title claims abstract description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims description 39
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 36
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 33
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 33
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 33
- 239000003607 modifier Substances 0.000 claims description 28
- 239000002041 carbon nanotube Substances 0.000 claims description 23
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 23
- 238000001125 extrusion Methods 0.000 claims description 18
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 239000003963 antioxidant agent Substances 0.000 claims description 8
- 230000003078 antioxidant effect Effects 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 239000000155 melt Substances 0.000 claims description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000012545 processing Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 3
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000011231 conductive filler Substances 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229920000576 tactic polymer Polymers 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000013585 weight reducing agent Substances 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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/12—Making granules characterised by structure or composition
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
-
- 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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
-
- 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
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/017—Additives being an antistatic agent
-
- 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)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention belongs to the technical field of high polymer materials, and particularly relates to an antistatic polypropylene plastic, wherein polypropylene master batches and maleic anhydride grafted polypropylene are mixed according to a specific ratio, and modified carbon nanotubes subjected to special treatment are added in the preparation process, so that the antistatic property of the prepared polypropylene plastic can be improved, and the excellent mechanical property of the polypropylene plastic can be ensured. The invention also relates to a preparation method of the polypropylene plastic.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to an antistatic polypropylene plastic and a preparation method thereof.
Background
Polypropylene is one of five general plastics, and is the first synthesized stereoregular polymer for realizing industrialization. The polypropylene has regular stereo structure, may be processed through extrusion, injection molding, extrusion molding, blow molding, hollow forming and other process, and has light weight, high wear resistance, high strength, high hydrophobicity and other excellent performance. The method is widely applied to industries such as textile, packaging, automobile and the like. However, conventional polypropylene tends to build up charge on its surface, which can cause discomfort when contacting such articles, limiting its application.
In the prior art, some fillers such as carbon black, graphene and the like are added to increase the antistatic property of polypropylene, but the antistatic effect still does not reach a more ideal level. Therefore, it is required to provide a polypropylene plastic with higher antistatic property and good mechanical property to solve the problems in the prior art.
Disclosure of Invention
The invention provides antistatic polypropylene plastic, which is characterized in that polypropylene master batches and maleic anhydride grafted polypropylene are mixed according to a specific ratio, and modified carbon nanotubes subjected to special treatment are added in the preparation process, so that the antistatic property of the prepared polypropylene plastic can be improved, and the excellent mechanical property of the polypropylene plastic can be ensured. The invention also provides a preparation method of the polypropylene plastic.
An antistatic polypropylene plastic is prepared from raw materials containing polypropylene and antistatic master batches;
the preparation method of the antistatic master batch comprises the following steps: step one, sequentially adding deionized water, a carboxylated carbon nanotube and a modifier into a reactor, controlling the temperature of the reactor to be 40-90 ℃, ultrasonically stirring the mixture, stirring for 6-10 hours, and then filtering, washing and drying to obtain a modified carbon nanotube; mixing and stirring maleic anhydride grafted polypropylene, an antioxidant and the modified carbon nano tube in a high-speed stirrer, and adding the mixture into an extruder for extrusion granulation to obtain the antistatic master batch;
the preparation method of the modifier comprises the following steps: adding 3-chloropropyltrimethoxysilane, triethylamine and benzyl alcohol into a reactor under the protection of inert gas, starting stirring, adding potassium iodide after uniformly stirring, controlling the temperature of the reactor at 80-95 ℃ for reaction, and removing the solvent by reduced pressure distillation after the reaction is finished to obtain the modifier.
In order to improve the antistatic performance of polypropylene, the prior art generally adopts a method of adding conductive fillers, for example, adding materials such as carbon black, graphene, carbon nanotubes and the like, but whether the conductive fillers can be uniformly dispersed in the polypropylene is a main factor influencing the antistatic performance. In particular, carbon nanotubes have excellent conductivity, but are extremely likely to agglomerate. The inventor of the invention discovers through a great deal of research that 3-chloropropyltrimethoxysilane and triethylamine are prepared to generate a special quaternary ammonium salt in the presence of a catalyst, and the quaternary ammonium salt can be compounded with a carboxylated carbon nanotube to form a modified carbon nanotube with a siloxane chain segment. On one hand, the modified carbon nano tube is not easy to agglomerate due to the specific molecular structure and the steric hindrance, and the other types of quaternary ammonium salt modified carbon nano tubes adopted in the field can not achieve the beneficial effects of the invention; on the other hand, the siloxane chain segment carried by the modified carbon nanotube enables the modified carbon nanotube to have better fluidity and compatibility in molten polypropylene, and further improves the dispersion effect.
In addition, in the preparation method, the modified carbon nano tube is firstly blended with the maleic anhydride grafted polypropylene, and the carbon nano tube is pre-dispersed to obtain the antistatic master batch; the maleic anhydride grafted polypropylene has good compatibility with polypropylene, the modified carbon nano tube has better dispersion effect in the maleic anhydride grafted polypropylene than the modified carbon nano tube directly blended with the polypropylene, and the pre-dispersion can improve the dispersion effect of the carbon nano tube in the final polypropylene so as to improve the antistatic property of the polypropylene plastic.
The carboxylated carbon nanotube can be prepared by the method commonly used in the field or obtained by commercial purchase.
The polypropylene and the maleic anhydride-grafted polypropylene may be those commonly used in the art, preferably those in pellet form which facilitate melt processing. Preferably, the melt index of the polypropylene is 10-56 g/min. Preferably, the maleic anhydride grafting rate of the maleic anhydride grafted polypropylene is 5-10%, and the weight average molecular weight is 30000-45000.
Taking the total mass of the 3-chloropropyltrimethoxysilane, triethylamine, potassium iodide and benzyl alcohol as a reference:
the mass fraction of the 3-chloropropyltrimethoxysilane is 15-28%;
the mass fraction of triethylamine is 3-8%;
the mass fraction of potassium iodide is 0.1-0.4%;
the mass fraction of the benzyl alcohol is 65-80%.
In the process of preparing the modifier, the dosage of each component is preferably controlled, the dosage of the 3-chloropropyltrimethoxysilane is slightly higher than that of triethylamine, on one hand, excessive impurities in the product are prevented, on the other hand, the preparation cost is reduced, the material waste is avoided, and the complexity of purification is reduced.
In the first step of the preparation method of the antistatic master batch, the total mass of the deionized water, the carboxylated carbon nanotubes and the modifier is taken as a reference: the mass fraction of the deionized water is 70-80%, the mass fraction of the carboxylated carbon nano tube is 3-5%, and the mass fraction of the modifier is 17-25%.
In the second step of the preparation method of the antistatic master batch, the total mass of the maleic anhydride grafted polypropylene, the antioxidant and the modified carbon nano tube is taken as a reference: 75-85% of maleic anhydride grafted polypropylene, 1-5% of antioxidant and 12-24% of modified carbon nano tube. The antioxidant may be any one commonly used in the art, such as antioxidant 1010, antioxidant 168, etc.
Taking the total mass of the polypropylene master batch and the antistatic master batch as a reference: the mass fraction of the polypropylene master batch is 80-90%, and the mass fraction of the antistatic master batch is 10-20%.
In the second step of the preparation method of the antistatic master batch, the extruder is a double-screw extruder, the temperature of a melting section in the extrusion process is 220-230 ℃, the temperature of a mixing section is 230-250 ℃, the temperature of an extrusion section is 210-220 ℃, and the extrusion speed is 230-250 r/min. The extrusion temperature in the preparation process of the antistatic master batch is controlled to be slightly higher than the conventional processing temperature in the field, because the higher temperature can promote the dispersion effect of the modified carbon nano tube, but the temperature exceeding the preferable temperature range of the invention can cause the molecular weight reduction of the prepared polypropylene, the mechanical property reduction and the product appearance slight yellow.
The preparation method of the antistatic polypropylene plastic comprises the following preparation steps: and adding the polypropylene master batch and the antistatic master batch into a high-speed stirrer, uniformly mixing and stirring, and then extruding through an extruder to obtain the antistatic polypropylene plastic. Preferably, the double-screw extruder is a double-screw extruder, the temperature of a melting section in the extrusion process is 190-210 ℃, the temperature of a mixing section is 220-240 ℃, the temperature of an extrusion section is 200-210 ℃, and the extrusion speed is 190-210 r/min.
The invention has the beneficial effects that: the carboxyl carbon nano tube is modified by a special quaternary ammonium salt modifier with siloxane, so that the compatibility and the dispersibility of the carboxyl carbon nano tube in polypropylene are improved; the modified carbon nano tube and the maleic anhydride grafted polypropylene are blended for pre-dispersion, so that the dispersibility of the carbon nano tube in a final product is improved, and the antistatic property of the product is further improved; the types and the use amounts of the raw materials of the components are controlled within the preferable range of the invention, so that the prepared polypropylene plastic has excellent mechanical properties.
It should be noted that, the processes, methods, steps, devices, parameters, material amounts and kinds, etc. which are not described in the present invention can be performed by using the technical solutions commonly used in the art, and do not affect the implementation of the present invention.
The melt index test standard described throughout the present invention is GB/T3682 (230 ℃, 2.16 kg).
Detailed Description
The present invention is further illustrated by the following specific examples, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
Examples and comparative examples used starting materials:
polypropylene master batch 1, brand B4808, melt index 10g/10min, China petrochemical production;
2 parts of polypropylene master batch, the mark K7760, the melt index of 56g/10min, and the petrochemical production in China;
3 parts of polypropylene master batch, the mark K7726, the melt index of 30g/10min, and the petrochemical production in China;
maleic anhydride-grafted Polypropylene 1, No. UMEX1010, maleic anhydride grafting Rate 10 wt%, weight average molecular weight 30000, produced by Sanyo chemical industries, Japan;
maleic anhydride-grafted Polypropylene 2, trade name UMEX1001, maleic anhydride grafting ratio of 5 wt%, weight average molecular weight of 45000, produced by Sanyo chemical industries, Japan;
antioxidant 1010, manufactured by basf corporation;
carboxylated carbon nanotubes, under the designation XFS27, produced by Nanjing Xiifeng Nanko.
The parts by mass in the invention refer to the relative mass ratio of the components in the specially specified preparation method.
The preparation method of the modifier 1 comprises the following steps: under the protection of nitrogen, 15 parts by mass of 3-chloropropyltrimethoxysilane, 8 parts by mass of triethylamine and 76.6 parts by mass of benzyl alcohol are added into a reactor, stirring is started, 0.4 part by mass of potassium iodide is added after uniform stirring, the temperature of the reactor is controlled at 80 ℃ for reaction after uniform stirring, and the solvent is removed by reduced pressure distillation after 48 hours, so that the modifier 1 is obtained.
The preparation method of the modifier 2 comprises the following steps: under the protection of nitrogen, 28 parts by mass of 3-chloropropyltrimethoxysilane, 3 parts by mass of triethylamine and 68.9 parts by mass of benzyl alcohol are added into a reactor, stirring is started, 0.1 part by mass of potassium iodide is added after uniform stirring, the temperature of the reactor is controlled to react at 95 ℃ after uniform stirring, and the solvent is removed by reduced pressure distillation after 48 hours, so that the modifier 2 is obtained.
The preparation method of the modifier 3 comprises the following steps: under the protection of nitrogen, 20 parts by mass of 3-chloropropyltrimethoxysilane, 5 parts by mass of triethylamine and 74.7 parts by mass of benzyl alcohol are added into a reactor, stirring is started, 0.3 part by mass of potassium iodide is added after uniform stirring, the temperature of the reactor is controlled at 90 ℃ for reaction after uniform stirring, and the solvent is removed by reduced pressure distillation after 48 hours, thus obtaining the modifier 3.
The preparation method of the modifier 4 comprises the following steps: under the protection of nitrogen, 20 parts by mass of (3-chloropropyl) triethoxysilane, 5 parts by mass of triethylamine and 74.7 parts by mass of benzyl alcohol are added into a reactor, stirring is started, 0.3 part by mass of potassium iodide is added after uniform stirring, the temperature of the reactor is controlled at 90 ℃ after uniform stirring for reaction, and the solvent is removed by reduced pressure distillation after 48 hours to obtain the modifier 4.
The preparation method of the modifier 5 comprises the following steps: under the protection of nitrogen, 20 parts by mass of 3-chloropropyltrimethoxysilane, 5 parts by mass of N, N-dimethyllaurylamine and 74.7 parts by mass of benzyl alcohol are added into a reactor, stirring is started, 0.3 part by mass of potassium iodide is added after uniform stirring, the temperature of the reactor is controlled at 90 ℃ after uniform stirring for reaction, and the solvent is removed by reduced pressure distillation after 48 hours, thus obtaining the modifier 5.
The preparation method of the modified carbon nanotube 1 comprises the following steps: and sequentially adding 78 parts by mass of deionized water, 5 parts by mass of carboxylated carbon nanotubes and 17 parts by mass of modifier 1 into a reactor, controlling the temperature of the reactor to be 90 ℃, ultrasonically stirring the mixture, stirring for 6 hours, and then filtering, washing and drying to obtain the modified carbon nanotube 1.
The preparation method of the modified carbon nanotube 2 comprises the following steps: and sequentially adding 72 parts by mass of deionized water, 3 parts by mass of carboxylated carbon nanotubes and 25 parts by mass of modifier 2 into a reactor, controlling the temperature of the reactor to be 40 ℃, ultrasonically stirring the mixture, stirring for 10 hours, and then filtering, washing and drying to obtain the modified carbon nanotubes 2.
The preparation method of the modified carbon nano tube 3 comprises the following steps: and sequentially adding 76 parts by mass of deionized water, 4 parts by mass of carboxylated carbon nanotubes and 20 parts by mass of modifier 3 into a reactor, controlling the temperature of the reactor to be 60 ℃, ultrasonically stirring the mixture, stirring for 8 hours, and then filtering, washing and drying to obtain the modified carbon nanotubes 3.
The preparation method of the modified carbon nanotube 4 comprises the following steps: and sequentially adding 76 parts by mass of deionized water, 4 parts by mass of carboxylated carbon nanotubes and 20 parts by mass of modifier 4 into a reactor, controlling the temperature of the reactor to be 60 ℃, ultrasonically stirring the mixture, stirring for 8 hours, and then filtering, washing and drying to obtain the modified carbon nanotubes 4.
The preparation method of the modified carbon nanotube 5 comprises the following steps: and sequentially adding 76 parts by mass of deionized water, 4 parts by mass of carboxylated carbon nanotubes and 20 parts by mass of modifier 5 into a reactor, controlling the temperature of the reactor to be 60 ℃, ultrasonically stirring the mixture, stirring for 8 hours, and then filtering, washing and drying to obtain the modified carbon nanotubes 5.
The preparation method of the modified carbon nanotube 6 comprises the following steps: and sequentially adding 76 parts by mass of deionized water, 4 parts by mass of carboxylated carbon nanotubes and 20 parts by mass of hexadecyl trimethyl ammonium bromide into a reactor, controlling the temperature of the reactor to be 60 ℃, ultrasonically stirring the mixture, stirring for 8 hours, and then filtering, washing and drying to obtain the modified carbon nanotube 6.
The preparation raw materials and the processing conditions of the antistatic master batch are listed in table 1, and the preparation method comprises the following steps: according to the raw materials and processing conditions shown in Table 1, maleic anhydride grafted polypropylene, the modified carbon nano tube and an antioxidant are mixed and stirred in a high-speed stirrer, and then added into an extruder for extrusion granulation, so that the antistatic master batch is obtained.
TABLE 1 preparation of antistatic masterbatch (parts by mass) and processing conditions
The preparation raw materials and processing conditions of the polypropylene plastics of the examples and the comparative examples are shown in Table 2, and the preparation method comprises the following steps: according to the raw materials and processing conditions shown in Table 2, the polypropylene master batch and the antistatic master batch are added into a high-speed stirrer to be uniformly mixed and stirred, and then extruded by a double-screw extruder to obtain the antistatic polypropylene plastic.
TABLE 2 raw materials (parts by mass) for the preparation of antistatic polypropylene plastics and processing conditions
The polypropylene plastic samples obtained in the examples and comparative examples were subjected to a performance test:
the test standard of the tensile yield stress is GB/T1040;
the test standard of the cantilever beam impact strength is GB/T1843, 23 ℃;
the test standard of the surface resistivity is IEC60093-1980, 3mm thickness template test.
The test results of the performance tests of the examples and comparative examples are shown in Table 3.
TABLE 3 results of Performance test of examples and comparative examples
The test results in table 3 show that the modifier modified carboxylated carbon nanotubes prepared by the invention can improve the conductivity of polypropylene plastics and avoid the formation of static electricity due to charge accumulation under the condition of ensuring higher mechanical properties.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. The antistatic polypropylene plastic is characterized in that the antistatic polypropylene plastic is prepared from raw materials containing polypropylene master batches and antistatic master batches;
the preparation method of the antistatic master batch comprises the following steps: step one, sequentially adding deionized water, a carboxylated carbon nanotube and a modifier into a reactor, controlling the temperature of the reactor to be 40-90 ℃, ultrasonically stirring the mixture, stirring for 6-10 hours, and then filtering, washing and drying to obtain a modified carbon nanotube; mixing and stirring maleic anhydride grafted polypropylene, an antioxidant and the modified carbon nano tube in a high-speed stirrer, and adding the mixture into an extruder for extrusion granulation to obtain the antistatic master batch;
the preparation method of the modifier comprises the following steps: adding 3-chloropropyltrimethoxysilane, triethylamine and benzyl alcohol into a reactor under the protection of inert gas, starting stirring, adding potassium iodide after uniformly stirring, controlling the temperature of the reactor at 80-95 ℃ for reaction, and removing the solvent by reduced pressure distillation after the reaction is finished to obtain the modifier.
2. The antistatic polypropylene plastic according to claim 1, wherein the melt index of the polypropylene master batch is 10-56 g/min.
3. The antistatic polypropylene plastic as claimed in claim 1, wherein the maleic anhydride grafted polypropylene has a maleic anhydride grafting rate of 5-10% and a weight average molecular weight of 30000-45000.
4. The antistatic polypropylene plastic according to claim 1, wherein the total mass of the 3-chloropropyltrimethoxysilane, triethylamine, potassium iodide and benzyl alcohol is taken as a reference:
the mass fraction of the 3-chloropropyltrimethoxysilane is 15-28%;
the mass fraction of triethylamine is 3-8%;
the mass fraction of potassium iodide is 0.1-0.4%;
the mass fraction of the benzyl alcohol is 65-80%.
5. The antistatic polypropylene plastic of claim 1, wherein in the first preparation method step of the antistatic master batch, based on the total mass of the deionized water, the carboxylated carbon nanotubes and the modifier: the mass fraction of the deionized water is 70-80%, the mass fraction of the carboxylated carbon nano tube is 3-5%, and the mass fraction of the modifier is 17-25%.
6. The antistatic polypropylene plastic of claim 1, wherein in the second step of the preparation method of the antistatic masterbatch, based on the total mass of the maleic anhydride grafted polypropylene, the antioxidant and the modified carbon nanotubes: 75-85% of maleic anhydride grafted polypropylene, 1-5% of antioxidant and 12-24% of modified carbon nano tube.
7. The antistatic polypropylene plastic of claim 1, wherein the total mass of the polypropylene master batch and the antistatic master batch is taken as a reference: the mass fraction of the polypropylene master batch is 80-90%, and the mass fraction of the antistatic master batch is 10-20%.
8. The antistatic polypropylene plastic of claim 1, wherein in the second preparation method of the antistatic master batch, the extruder is a twin-screw extruder, the temperature of the melting section in the extrusion process is 220-230 ℃, the temperature of the mixing section is 230-250 ℃, the temperature of the extrusion section is 210-220 ℃, and the extrusion speed is 230-250 r/min.
9. A preparation method of the antistatic polypropylene plastic as claimed in claims 1 to 8, which is characterized by comprising the following preparation steps: and adding the polypropylene master batch and the antistatic master batch into a high-speed stirrer, uniformly mixing and stirring, and then extruding through an extruder to obtain the antistatic polypropylene plastic.
10. The preparation method of claim 9, wherein the extruder is a twin-screw extruder, the temperature of the melting section of the extrusion process is 190-210 ℃, the temperature of the mixing section is 220-240 ℃, the temperature of the extrusion section is 200-210 ℃, and the extrusion speed is 190-210 r/min.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112442236A (en) * | 2020-11-23 | 2021-03-05 | 江苏金发科技新材料有限公司 | Low-temperature impact-resistant flame-retardant polypropylene composition and preparation method thereof |
| CN114775085A (en) * | 2022-04-21 | 2022-07-22 | 朱继武 | A kind of antistatic fabric and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112442236A (en) * | 2020-11-23 | 2021-03-05 | 江苏金发科技新材料有限公司 | Low-temperature impact-resistant flame-retardant polypropylene composition and preparation method thereof |
| CN112442236B (en) * | 2020-11-23 | 2023-03-14 | 江苏金发科技新材料有限公司 | Low-temperature impact-resistant flame-retardant polypropylene composition and preparation method thereof |
| CN114775085A (en) * | 2022-04-21 | 2022-07-22 | 朱继武 | A kind of antistatic fabric and preparation method thereof |
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