CN114891291B - Antistatic packaging plastic film - Google Patents
Antistatic packaging plastic film Download PDFInfo
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- CN114891291B CN114891291B CN202210725861.0A CN202210725861A CN114891291B CN 114891291 B CN114891291 B CN 114891291B CN 202210725861 A CN202210725861 A CN 202210725861A CN 114891291 B CN114891291 B CN 114891291B
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- 239000002985 plastic film Substances 0.000 title claims abstract description 28
- 229920006255 plastic film Polymers 0.000 title claims abstract description 28
- 238000004806 packaging method and process Methods 0.000 title claims abstract description 17
- 239000002216 antistatic agent Substances 0.000 claims abstract description 44
- -1 polyethylene Polymers 0.000 claims abstract description 36
- 239000000945 filler Substances 0.000 claims abstract description 23
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- 239000004743 Polypropylene Substances 0.000 claims abstract description 14
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229920001155 polypropylene Polymers 0.000 claims abstract description 14
- 229920001903 high density polyethylene Polymers 0.000 claims abstract description 13
- 239000004700 high-density polyethylene Substances 0.000 claims abstract description 13
- 239000004698 Polyethylene Substances 0.000 claims abstract description 12
- 229920000573 polyethylene Polymers 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 8
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 8
- 238000007664 blowing Methods 0.000 claims abstract description 6
- 238000001125 extrusion Methods 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000007493 shaping process Methods 0.000 claims abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 48
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 45
- 238000006243 chemical reaction Methods 0.000 claims description 37
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 30
- 239000005543 nano-size silicon particle Substances 0.000 claims description 23
- 235000012239 silicon dioxide Nutrition 0.000 claims description 23
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 22
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 20
- 239000012043 crude product Substances 0.000 claims description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000000178 monomer Substances 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 11
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 10
- 238000002390 rotary evaporation Methods 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 10
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 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 claims description 8
- CVNPKVXQUCOSOI-UHFFFAOYSA-N 3-ethylheptane-2,3-diol Chemical compound CCCCC(O)(CC)C(C)O CVNPKVXQUCOSOI-UHFFFAOYSA-N 0.000 claims description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- UVHLUYZMNUCVJN-UHFFFAOYSA-N 3-methyloctane-4,4-diol Chemical compound CCCCC(O)(O)C(C)CC UVHLUYZMNUCVJN-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000000502 dialysis Methods 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000005096 rolling process Methods 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000003828 vacuum filtration Methods 0.000 claims description 5
- 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 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims 2
- 239000011159 matrix material Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 230000007774 longterm Effects 0.000 abstract description 2
- 238000004804 winding Methods 0.000 abstract 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 4
- 238000007792 addition Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
-
- 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
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—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
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/06—Polyethene
-
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
-
- 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
- C08K2201/011—Nanostructured additives
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing 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
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
Abstract
The invention discloses an antistatic packaging plastic film which comprises the following raw materials in parts by weight: 100-150 parts of high-density polyethylene, 5-25 parts of antistatic agent, 10-20 parts of modified filler, 1-2.5 parts of polyethylene wax, 3-5 parts of polypropylene grafted maleic anhydride and 0.1-1 part of antioxidant; adding high-density polyethylene, modified filler, antioxidant and polyethylene wax into a mixer, adding antistatic agent and polypropylene grafted maleic anhydride to prepare a mixture, feeding the mixture into an extruder for melt extrusion, blowing and shaping, traction and cutting, and winding to prepare a plastic film; the prepared antistatic film has a long-term antistatic effect, the antistatic agent is a quaternary ammonium salt cationic antistatic agent, and the hyperbranched compound a with a three-dimensional network structure is introduced, so that the synthesized antistatic agent has better dispersibility in a matrix and better antistatic performance, and the antistatic agent is more stable due to a special three-dimensional space macromolecular structure.
Description
Technical Field
The invention belongs to the technical field of electronic packaging materials, and particularly relates to an antistatic packaging plastic film.
Background
When the electronic article is packaged, static electricity is most feared to be generated, and the static electricity can generate certain harm to electronic components. The existing antistatic films cannot achieve permanent antistatic, and some films are only externally coated with some antistatic liquid, so that the films are easy to disappear for a long time.
Cationic antistatic agents are a type of antistatic agent that is currently under investigation for warmth. The antistatic agent mainly refers to quaternary ammonium salt antistatic agents. The quaternary ammonium salt antistatic agent has higher antistatic performance, and the quaternary ammonium salt not only has good water absorbability, but also contains ions which can enhance the antistatic performance, but also has weaker stability, and has certain influence on popularization of application.
The quaternary ammonium salt antistatic agent not only can absorb water by quaternary ammonium salt groups to form a water layer on the surface of the matrix, but also contains cations, and is also favorable for the conductive layer to have better conductive performance.
Disclosure of Invention
In order to solve the technical problems, the invention provides an antistatic packaging plastic film.
The aim of the invention can be achieved by the following technical scheme:
the antistatic packaging plastic film comprises the following raw materials in parts by weight: 100-150 parts of high-density polyethylene, 5-25 parts of antistatic agent, 10-20 parts of modified filler, 1-2.5 parts of polyethylene wax, 3-5 parts of polypropylene grafted maleic anhydride and 0.1-1 part of antioxidant;
the antistatic agent is prepared by the following steps:
s1, adding dimethylolpropionic acid and ethylbutyl propylene glycol into a four-necked flask, sequentially adding p-toluenesulfonic acid and dimethylbenzene, introducing nitrogen, slowly heating to 140-150 ℃, preserving heat and carrying out reflux reaction until the acid value of the system is 25 mgKOH.g -1 Removing dimethylbenzene by rotary evaporation after the reaction is finished to obtain a crude product, adding the crude product into acetone, stirring at constant speed for 30min, precipitating in toluene, filtering to obtain a compound a, and controlling the dosage ratio of dimethylolpropionic acid, ethylbutylpropanediol, p-toluenesulfonic acid and dimethylbenzene to be 0.3 mol:0.15 mol:0.1-0.2 g:12.5 g;
in the step S1, ethylbutyl propylene glycol is used as a nuclear monomer, p-toluenesulfonic acid is used as a catalyst, dimethylol propionic acid and ethylbutyl propylene glycol react in dimethylbenzene to generate a compound a, and the compound a is a hydroxyl-terminated hyperbranched compound, and the reaction process is as follows:
s2, adding the compound a into N, N-dimethylformamide, stirring at a constant speed for 30min under nitrogen atmosphere, adding sodium hydroxide and epoxy chloropropane, heating to 50 ℃, stirring at a constant speed, reacting for 12h, and carrying out vacuum filtration to obtain an intermediate 1, wherein the dosage ratio of the compound a to the sodium hydroxide to the epoxy chloropropane to the dimethylacetamide is controlled to be 0.01-0.02 mol:0.16-0.32 mol:0.05-0.1 mol:50 mL;
in the step S2, epoxy chloropropane is used as a grafting agent, reacts with a compound a under the action of a base catalyst, and chlorine is introduced onto the compound a, wherein the reaction process is as follows:
step S3, adding the intermediate 1 into a four-neck flask, slowly dropwise adding hexadecyl dimethyl tertiary amine, heating to 50 ℃, preserving heat for reaction for 12 hours, removing solvent by rotary evaporation after the reaction is finished to obtain a crude product, placing the crude product into a dialysis bag, dialyzing for 12 hours, drying to obtain an antistatic agent, and controlling the weight ratio of the intermediate 1 to the hexadecyl dimethyl tertiary amine to be 52.8-60.2:5.2.
In the step S3, the intermediate 1 and hexadecyldimethyl tertiary amine react to form an antistatic agent, and the reaction process is as follows:
from the structural aspect, the antistatic agent is a quaternary ammonium salt cationic antistatic agent, but the stability of the quaternary ammonium salt antistatic agent is weak at present, so that the use of the quaternary ammonium salt antistatic agent as an additive type antistatic agent is limited.
Further: the modified filler comprises the following steps:
s21, adding nano silicon dioxide and KH-570 into toluene, performing ultrasonic dispersion for 5min, uniformly stirring and heating to 120 ℃, performing heat preservation reaction for 4h, cooling to room temperature after the reaction is finished, standing for 12h, filtering, washing with acetone for three times, and drying at 60 ℃ to obtain modified nano silicon dioxide, wherein the dosage ratio of KH-570, nano silicon dioxide and toluene is controlled to be 2.0-2.2 mL:4 g:150 mL;
s22, adding modified nano silicon dioxide, deionized water and isopropanol into a three-neck flask, performing ultrasonic dispersion for 30min to form a suspension, heating to 75 ℃, slowly dropwise adding a potassium persulfate aqueous solution with the mass fraction of 0.5% and a multi-component monomer, heating to 95 ℃ after the dropwise adding is finished, continuously stirring and reacting for 30min, performing centrifugal separation after the reaction is finished, washing with deionized water for three times to obtain a modified filler, and controlling the dosage ratio of the modified nano silicon dioxide to the deionized water to the isopropanol to be 1 g/100 mL/1 g, wherein the dosage ratio of the suspension to the potassium persulfate aqueous solution to the multi-component monomer to be 100 mL/5 mL/3 g.
Further: the multi-component monomer is formed by mixing butyl acrylate, styrene and acrylic acid according to the weight ratio of 25:25:2.
Further: the antioxidant is any one of antioxidant 168 and antioxidant 1010.
Further: the grafting rate of the polypropylene grafted maleic anhydride is 1-1.5%.
Further: the plastic film comprises the following steps:
adding high-density polyethylene, modified filler, antioxidant and polyethylene wax into a mixer, mixing for 15min, adding antistatic agent and polypropylene grafted maleic anhydride, continuously stirring for 10min to obtain a mixture, feeding the mixture into an extruder for melt extrusion, then blowing and shaping by a die head, gradually increasing the temperature of the die head to 165-205 ℃, and then traction cutting and rolling to obtain the plastic film.
Further: the rotating speed of the extruder is 80-120r/min, and the melting temperature is 180-195 ℃.
The invention has the beneficial effects that:
the antistatic packaging plastic film takes high-density polyethylene as a matrix, an antistatic agent is added by blending, an external coating mode is not adopted, the prepared antistatic film has a long-term antistatic effect, the antistatic agent is a quaternary ammonium salt cationic antistatic agent, but the stability of the quaternary ammonium salt antistatic agent is weak at present, so that the application of the quaternary ammonium salt antistatic agent as an additive antistatic agent is limited.
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.
Example 1
The modified filler comprises the following steps:
s21, adding nano silicon dioxide and KH-570 into toluene, performing ultrasonic dispersion for 5min, uniformly stirring, heating to 120 ℃, performing heat preservation reaction for 4h, cooling to room temperature after the reaction is finished, standing for 12h, filtering, washing with acetone for three times, and drying at 60 ℃ to obtain modified nano silicon dioxide, wherein the dosage ratio of KH-570, nano silicon dioxide and toluene is controlled to be 2.0 mL/4 g/150 mL;
s22, adding modified nano silicon dioxide, deionized water and isopropanol into a three-neck flask, performing ultrasonic dispersion for 30min to form a suspension, heating to 75 ℃, slowly dropwise adding a potassium persulfate aqueous solution with the mass fraction of 0.5% and a multi-component monomer, heating to 95 ℃ after the dropwise adding is finished, continuously stirring and reacting for 30min, performing centrifugal separation after the reaction is finished, washing with deionized water for three times to obtain a modified filler, and controlling the dosage ratio of the modified nano silicon dioxide to the deionized water to the isopropanol to be 1 g/100 mL/1 g, wherein the dosage ratio of the suspension to the potassium persulfate aqueous solution to the multi-component monomer to be 100 mL/5 mL/3 g.
The multi-component monomer is formed by mixing butyl acrylate, styrene and acrylic acid according to the weight ratio of 25:25:2.
Example 2
The modified filler comprises the following steps:
s21, adding nano silicon dioxide and KH-570 into toluene, performing ultrasonic dispersion for 5min, uniformly stirring, heating to 120 ℃, performing heat preservation reaction for 4h, cooling to room temperature after the reaction is finished, standing for 12h, filtering, washing with acetone for three times, and drying at 60 ℃ to obtain modified nano silicon dioxide, wherein the dosage ratio of KH-570, nano silicon dioxide and toluene is controlled to be 2.1 mL/4 g/150 mL;
s22, adding modified nano silicon dioxide, deionized water and isopropanol into a three-neck flask, performing ultrasonic dispersion for 30min to form a suspension, heating to 75 ℃, slowly dropwise adding a potassium persulfate aqueous solution with the mass fraction of 0.5% and a multi-component monomer, heating to 95 ℃ after the dropwise adding is finished, continuously stirring and reacting for 30min, performing centrifugal separation after the reaction is finished, washing with deionized water for three times to obtain a modified filler, and controlling the dosage ratio of the modified nano silicon dioxide to the deionized water to the isopropanol to be 1 g/100 mL/1 g, wherein the dosage ratio of the suspension to the potassium persulfate aqueous solution to the multi-component monomer to be 100 mL/5 mL/3 g.
The multi-component monomer is formed by mixing butyl acrylate, styrene and acrylic acid according to the weight ratio of 25:25:2.
Example 3
The modified filler comprises the following steps:
s21, adding nano silicon dioxide and KH-570 into toluene, performing ultrasonic dispersion for 5min, uniformly stirring, heating to 120 ℃, performing heat preservation reaction for 4h, cooling to room temperature after the reaction is finished, standing for 12h, filtering, washing with acetone for three times, and drying at 60 ℃ to obtain modified nano silicon dioxide, wherein the dosage ratio of KH-570, nano silicon dioxide and toluene is controlled to be 2.2 mL/4 g/150 mL;
s22, adding modified nano silicon dioxide, deionized water and isopropanol into a three-neck flask, performing ultrasonic dispersion for 30min to form a suspension, heating to 75 ℃, slowly dropwise adding a potassium persulfate aqueous solution with the mass fraction of 0.5% and a multi-component monomer, heating to 95 ℃ after the dropwise adding is finished, continuously stirring and reacting for 30min, performing centrifugal separation after the reaction is finished, washing with deionized water for three times to obtain a modified filler, and controlling the dosage ratio of the modified nano silicon dioxide to the deionized water to the isopropanol to be 1 g/100 mL/1 g, wherein the dosage ratio of the suspension to the potassium persulfate aqueous solution to the multi-component monomer to be 100 mL/5 mL/3 g.
The multi-component monomer is formed by mixing butyl acrylate, styrene and acrylic acid according to the weight ratio of 25:25:2.
Example 4
The antistatic agent is prepared by the following steps:
s1, adding dimethylolpropionic acid and ethylbutyl propylene glycol into a four-necked flask, sequentially adding p-toluenesulfonic acid and dimethylbenzene, introducing nitrogen, slowly heating to 140 ℃, preserving heat and carrying out reflux reaction until the acid value of the system is 25 mgKOH.g -1 Removing dimethylbenzene by rotary evaporation after the reaction is finished to obtain a crude product, adding the crude product into acetone, stirring at constant speed for 30min, precipitating in toluene, filtering to obtain a compound a, and controlling the dosage ratio of dimethylolpropionic acid, ethylbutylpropanediol, p-toluenesulfonic acid and dimethylbenzene to be 0.3 mol:0.15 mol:0.1 g:12.5 g;
s2, adding the compound a into N, N-dimethylformamide, stirring at a constant speed for 30min under nitrogen atmosphere, adding sodium hydroxide and epoxy chloropropane, heating to 50 ℃, stirring at a constant speed, reacting for 12h, and carrying out vacuum filtration to obtain an intermediate 1, wherein the dosage ratio of the compound a to the sodium hydroxide to the epoxy chloropropane to the dimethylacetamide is controlled to be 0.01 mol:0.16 mol:0.05 mol:50 mL;
step S3, adding the intermediate 1 into a four-neck flask, slowly dropwise adding hexadecyl dimethyl tertiary amine, heating to 50 ℃, preserving heat for reaction for 12 hours, removing solvent by rotary evaporation after the reaction is finished to obtain a crude product, placing the crude product into a dialysis bag, dialyzing for 12 hours, drying to obtain an antistatic agent, and controlling the weight ratio of the intermediate 1 to the hexadecyl dimethyl tertiary amine to be 52.8:5.2.
Example 5
The antistatic agent is prepared by the following steps:
step S1, adding dimethylolpropionic acid and ethyl butyl propylene glycol into the four-port combustorAdding p-toluenesulfonic acid and dimethylbenzene in sequence into a bottle, introducing nitrogen, slowly heating to 145 ℃, preserving heat and carrying out reflux reaction until the acid value of the system is 25 mgKOH.g -1 Removing dimethylbenzene by rotary evaporation after the reaction is finished to obtain a crude product, adding the crude product into acetone, stirring at constant speed for 30min, precipitating in toluene, filtering to obtain a compound a, and controlling the dosage ratio of dimethylolpropionic acid, ethylbutylpropanediol, p-toluenesulfonic acid and dimethylbenzene to be 0.3 mol:0.15 mol:0.2 g:12.5 g;
s2, adding the compound a into N, N-dimethylformamide, stirring at a constant speed for 30min under nitrogen atmosphere, adding sodium hydroxide and epoxy chloropropane, heating to 50 ℃, stirring at a constant speed, reacting for 12h, and carrying out vacuum filtration to obtain an intermediate 1, wherein the dosage ratio of the compound a to the sodium hydroxide to the epoxy chloropropane to the dimethylacetamide is controlled to be 0.02 mol:0.28 mol:0.08 mol:50 mL;
step S3, adding the intermediate 1 into a four-neck flask, slowly dropwise adding hexadecyl dimethyl tertiary amine, heating to 50 ℃, preserving heat for reaction for 12 hours, removing solvent by rotary evaporation after the reaction is finished to obtain a crude product, placing the crude product into a dialysis bag, dialyzing for 12 hours, drying to obtain an antistatic agent, and controlling the weight ratio of the intermediate 1 to the hexadecyl dimethyl tertiary amine to be 58.2:5.2.
Example 6
The antistatic agent is prepared by the following steps:
s1, adding dimethylolpropionic acid and ethylbutyl propylene glycol into a four-necked flask, sequentially adding p-toluenesulfonic acid and dimethylbenzene, introducing nitrogen, slowly heating to 150 ℃, preserving heat and carrying out reflux reaction until the acid value of the system is 25 mgKOH.g -1 Removing dimethylbenzene by rotary evaporation after the reaction is finished to obtain a crude product, adding the crude product into acetone, stirring at constant speed for 30min, precipitating in toluene, filtering to obtain a compound a, and controlling the dosage ratio of dimethylolpropionic acid, ethylbutylpropanediol, p-toluenesulfonic acid and dimethylbenzene to be 0.3 mol:0.15 mol:0.2 g:12.5 g;
s2, adding the compound a into N, N-dimethylformamide, stirring at a constant speed for 30min under nitrogen atmosphere, adding sodium hydroxide and epoxy chloropropane, heating to 50 ℃, stirring at a constant speed, reacting for 12h, and carrying out vacuum filtration to obtain an intermediate 1, wherein the dosage ratio of the compound a to the sodium hydroxide to the epoxy chloropropane to the dimethylacetamide is controlled to be 0.02 mol:0.32 mol:0.1 mol:50 mL;
step S3, adding the intermediate 1 into a four-neck flask, slowly dropwise adding hexadecyl dimethyl tertiary amine, heating to 50 ℃, preserving heat for reaction for 12 hours, removing solvent by rotary evaporation after the reaction is finished to obtain a crude product, placing the crude product into a dialysis bag, dialyzing for 12 hours, drying to obtain an antistatic agent, and controlling the weight ratio of the intermediate 1 to the hexadecyl dimethyl tertiary amine to be 60.2:5.2.
Example 7
The antistatic packaging plastic film comprises the following raw materials in parts by weight: 100 parts of high-density polyethylene, 5 parts of antistatic agent, 10 parts of modified filler, 1 part of polyethylene wax, 3 parts of polypropylene grafted maleic anhydride (grafting ratio is 1%), and 0.1 part of antioxidant 168;
the plastic film comprises the following steps:
adding high-density polyethylene, modified filler, antioxidant 168 and polyethylene wax into a mixer, mixing for 15min, adding antistatic agent and polypropylene grafted maleic anhydride, continuously stirring for 10min to obtain a mixture, feeding into an extruder melt for extrusion, then blowing and shaping by a die head, gradually increasing the temperature of the die head to 165 ℃, and then traction cutting and rolling to obtain the plastic film.
The rotation speed of the extruder was 80r/min and the melting temperature was 180 ℃.
Example 8
The antistatic packaging plastic film comprises the following raw materials in parts by weight: 120 parts of high-density polyethylene, 20 parts of antistatic agent, 15 parts of modified filler, 2 parts of polyethylene wax, 4 parts of polypropylene grafted maleic anhydride (the grafting rate is 1.2%), and 0.5 part of antioxidant 168;
the plastic film comprises the following steps:
adding high-density polyethylene, modified filler, antioxidant 168 and polyethylene wax into a mixer, mixing for 15min, adding antistatic agent and polypropylene grafted maleic anhydride, continuously stirring for 10min to obtain a mixture, feeding into an extruder melt for extrusion, then blowing and shaping by a die head, gradually increasing the temperature of the die head to 180 ℃, and then traction cutting and rolling to obtain the plastic film.
The rotation speed of the extruder was 100r/min and the melting temperature was 190 ℃.
Example 9
The antistatic packaging plastic film comprises the following raw materials in parts by weight: 150 parts of high-density polyethylene, 25 parts of antistatic agent, 20 parts of modified filler, 2.5 parts of polyethylene wax, 5 parts of polypropylene grafted maleic anhydride (the grafting rate is 1.5%), and 1 part of antioxidant 168;
the plastic film comprises the following steps:
adding high-density polyethylene, modified filler, antioxidant 168 and polyethylene wax into a mixer, mixing for 15min, adding antistatic agent and polypropylene grafted maleic anhydride, continuously stirring for 10min to obtain a mixture, feeding into an extruder melt for extrusion, then blowing and shaping by a die head, gradually increasing the temperature of the die head to 205 ℃, and then traction cutting and rolling to obtain the plastic film.
The rotational speed of the extruder was 120r/min and the melting temperature was 195 ℃.
Comparative example 1
The comparative example is an antistatic film prepared in invention patent CN 201910270032.6.
Comparative example 2
The comparative example is an antistatic film prepared in invention patent CN 201410336093.5.
The antistatic films prepared in examples 7 to 9 and comparative examples 1 to 2 were examined for surface resistance and mechanical properties, and the results are shown in the following table:
surface resistance: GB/T1410-2006;
from the above table, it can be seen that the antistatic films prepared in examples 7 to 8 have excellent antistatic properties, and the addition of the modified filler having higher compatibility can reduce the influence on the mechanical properties of the antistatic films.
The foregoing is merely illustrative and explanatory of the principles of the invention, as various modifications and additions may be made to the specific embodiments described, or similar thereto, by those skilled in the art, without departing from the principles of the invention or beyond the scope of the appended claims.
Claims (7)
1. An antistatic packaging plastic film, characterized in that: comprises the following raw materials in parts by weight: 100-150 parts of high-density polyethylene, 5-25 parts of antistatic agent, 10-20 parts of modified filler, 1-2.5 parts of polyethylene wax, 3-5 parts of polypropylene grafted maleic anhydride and 0.1-1 part of antioxidant;
the antistatic agent is prepared by the following steps:
s1, adding dimethylolpropionic acid and ethylbutyl propylene glycol into a four-necked flask, sequentially adding p-toluenesulfonic acid and dimethylbenzene, introducing nitrogen, slowly heating to 140-150 ℃, preserving heat and carrying out reflux reaction until the acid value of the system is 25 mgKOH.g -1 Removing dimethylbenzene by rotary evaporation after the reaction is finished to obtain a crude product, adding the crude product into acetone, stirring at constant speed for 30min, precipitating in toluene, filtering to obtain a compound a, and controlling the dosage ratio of dimethylolpropionic acid, ethylbutylpropanediol, p-toluenesulfonic acid and dimethylbenzene to be 0.3 mol:0.15 mol:0.1-0.2 g:12.5 g;
s2, adding the compound a into N, N-dimethylformamide, stirring at a constant speed for 30min under nitrogen atmosphere, adding sodium hydroxide and epoxy chloropropane, heating to 50 ℃, stirring at a constant speed, reacting for 12h, and carrying out vacuum filtration to obtain an intermediate 1, wherein the dosage ratio of the compound a to the sodium hydroxide to the epoxy chloropropane to the N, N-dimethylformamide is controlled to be 0.01-0.02 mol:0.16-0.32 mol:0.05-0.1 mol:50 mL;
step S3, adding the intermediate 1 into a four-neck flask, slowly dropwise adding hexadecyl dimethyl tertiary amine, heating to 50 ℃, preserving heat and reacting for 12 hours, removing solvent by rotary evaporation after the reaction is finished to obtain a crude product, then placing the crude product into a dialysis bag, dialyzing for 12 hours, drying to obtain an antistatic agent, and controlling the weight ratio of the intermediate 1 to the hexadecyl dimethyl tertiary amine to be 52.8-60.2:5.2;
the modified filler comprises the following steps:
s21, adding nano silicon dioxide and KH-570 into toluene, performing ultrasonic dispersion for 5min, uniformly stirring and heating to 120 ℃, performing heat preservation reaction for 4h, cooling to room temperature after the reaction is finished, standing for 12h, filtering, washing with acetone for three times, and drying at 60 ℃ to obtain modified nano silicon dioxide;
and S22, adding the modified nano silicon dioxide, deionized water and isopropanol into a three-neck flask, performing ultrasonic dispersion for 30min to form a suspension, heating to 75 ℃, slowly dropwise adding a potassium persulfate aqueous solution with the mass fraction of 0.5% and a multi-component monomer, heating to 95 ℃ after the dropwise adding is finished, continuously stirring and reacting for 30min, performing centrifugal separation after the reaction is finished, and washing with deionized water for three times to obtain the modified filler.
2. An antistatic packaging plastic film according to claim 1, characterized in that: in the step S21, the dosage ratio of KH-570, nano-silica and toluene is controlled to be 2.0-2.2 mL:4 g:150 mL, and in the step S22, the dosage ratio of modified nano-silica, deionized water and isopropanol is controlled to be 1 g:100 mL:1 g, and the dosage ratio of suspension, potassium persulfate aqueous solution and multi-monomer is controlled to be 100 mL:5 mL:3 g.
3. An antistatic packaging plastic film according to claim 1, characterized in that: the multi-component monomer is formed by mixing butyl acrylate, styrene and acrylic acid according to the weight ratio of 25:25:2.
4. An antistatic packaging plastic film according to claim 1, characterized in that: the antioxidant is any one of antioxidant 168 and antioxidant 1010.
5. An antistatic packaging plastic film according to claim 1, characterized in that: the grafting rate of the polypropylene grafted maleic anhydride is 1-1.5%.
6. An antistatic packaging plastic film according to claim 1, characterized in that: the plastic film comprises the following steps:
adding high-density polyethylene, modified filler, antioxidant and polyethylene wax into a mixer, mixing for 15min, adding antistatic agent and polypropylene grafted maleic anhydride, continuously stirring for 10min to obtain a mixture, feeding the mixture into an extruder for melt extrusion, then blowing and shaping by a die head, gradually increasing the temperature of the die head to 165-205 ℃, and then traction cutting and rolling to obtain the plastic film.
7. An antistatic packaging plastic film according to claim 6, wherein: the rotating speed of the extruder is 80-120r/min, and the melting temperature is 180-195 ℃.
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