CN115651378B - Antistatic PET composition and preparation method and application thereof - Google Patents
Antistatic PET composition and preparation method and application thereof Download PDFInfo
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- CN115651378B CN115651378B CN202211383894.8A CN202211383894A CN115651378B CN 115651378 B CN115651378 B CN 115651378B CN 202211383894 A CN202211383894 A CN 202211383894A CN 115651378 B CN115651378 B CN 115651378B
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- 239000000203 mixture Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 39
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 39
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 36
- -1 alkyl glycidyl ether Chemical compound 0.000 claims abstract description 29
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229920005989 resin Polymers 0.000 claims abstract description 19
- 239000011347 resin Substances 0.000 claims abstract description 19
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 48
- 229910052799 carbon Inorganic materials 0.000 claims description 19
- 239000003963 antioxidant agent Substances 0.000 claims description 15
- 239000012752 auxiliary agent Substances 0.000 claims description 8
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 7
- 229910052740 iodine Inorganic materials 0.000 claims description 7
- 239000011630 iodine Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 238000001179 sorption measurement Methods 0.000 claims description 7
- NVKSMKFBUGBIGE-UHFFFAOYSA-N 2-(tetradecoxymethyl)oxirane Chemical compound CCCCCCCCCCCCCCOCC1CO1 NVKSMKFBUGBIGE-UHFFFAOYSA-N 0.000 claims description 6
- 239000005022 packaging material Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 239000012745 toughening agent Substances 0.000 claims description 5
- 230000003078 antioxidant effect Effects 0.000 claims description 4
- 239000003063 flame retardant Substances 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 239000000945 filler Substances 0.000 claims description 3
- 239000002667 nucleating agent Substances 0.000 claims description 3
- 125000005375 organosiloxane group Chemical group 0.000 claims description 3
- 229940124543 ultraviolet light absorber Drugs 0.000 claims description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 2
- NPKKFQUHBHQTSH-UHFFFAOYSA-N 2-(decoxymethyl)oxirane Chemical compound CCCCCCCCCCOCC1CO1 NPKKFQUHBHQTSH-UHFFFAOYSA-N 0.000 claims description 2
- VMSIYTPWZLSMOH-UHFFFAOYSA-N 2-(dodecoxymethyl)oxirane Chemical compound CCCCCCCCCCCCOCC1CO1 VMSIYTPWZLSMOH-UHFFFAOYSA-N 0.000 claims description 2
- KEKXMAURKVLACV-UHFFFAOYSA-N 2-(nonoxymethyl)oxirane Chemical compound CCCCCCCCCOCC1CO1 KEKXMAURKVLACV-UHFFFAOYSA-N 0.000 claims description 2
- HRWYHCYGVIJOEC-UHFFFAOYSA-N 2-(octoxymethyl)oxirane Chemical compound CCCCCCCCOCC1CO1 HRWYHCYGVIJOEC-UHFFFAOYSA-N 0.000 claims description 2
- ZCZCZLVSKGCRTD-UHFFFAOYSA-N 2-(tridecoxymethyl)oxirane Chemical compound CCCCCCCCCCCCCOCC1CO1 ZCZCZLVSKGCRTD-UHFFFAOYSA-N 0.000 claims description 2
- HNJSJLKMMRCGKX-UHFFFAOYSA-N 2-(undecoxymethyl)oxirane Chemical compound CCCCCCCCCCCOCC1CO1 HNJSJLKMMRCGKX-UHFFFAOYSA-N 0.000 claims description 2
- 229920002799 BoPET Polymers 0.000 claims description 2
- 239000004065 semiconductor Substances 0.000 claims description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims 1
- 238000004100 electronic packaging Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 27
- 239000006229 carbon black Substances 0.000 abstract description 17
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 33
- 239000004594 Masterbatch (MB) Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 13
- 230000008859 change Effects 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000002048 multi walled nanotube Substances 0.000 description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 4
- 239000011241 protective layer Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 240000007839 Kleinhovia hospita Species 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical class OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
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- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical class OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 1
- BZQKBFHEWDPQHD-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-[2-(2,3,4,5,6-pentabromophenyl)ethyl]benzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1CCC1=C(Br)C(Br)=C(Br)C(Br)=C1Br BZQKBFHEWDPQHD-UHFFFAOYSA-N 0.000 description 1
- DGZQEAKNZXNTNL-UHFFFAOYSA-N 1-bromo-4-butan-2-ylbenzene Chemical class CCC(C)C1=CC=C(Br)C=C1 DGZQEAKNZXNTNL-UHFFFAOYSA-N 0.000 description 1
- DMSSTTLDFWKBSX-UHFFFAOYSA-N 1h-1,2,3-benzotriazin-4-one Chemical class C1=CC=C2C(=O)N=NNC2=C1 DMSSTTLDFWKBSX-UHFFFAOYSA-N 0.000 description 1
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 1
- YZUMRMCHAJVDRT-UHFFFAOYSA-N 2-(hexadecoxymethyl)oxirane Chemical compound CCCCCCCCCCCCCCCCOCC1CO1 YZUMRMCHAJVDRT-UHFFFAOYSA-N 0.000 description 1
- JMTMSDXUXJISAY-UHFFFAOYSA-N 2H-benzotriazol-4-ol Chemical class OC1=CC=CC2=C1N=NN2 JMTMSDXUXJISAY-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241000408939 Atalopedes campestris Species 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920001651 Cyanoacrylate Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229930193140 Neomycin Natural products 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- QYMGIIIPAFAFRX-UHFFFAOYSA-N butyl prop-2-enoate;ethene Chemical compound C=C.CCCCOC(=O)C=C QYMGIIIPAFAFRX-UHFFFAOYSA-N 0.000 description 1
- QXJJQWWVWRCVQT-UHFFFAOYSA-K calcium;sodium;phosphate Chemical compound [Na+].[Ca+2].[O-]P([O-])([O-])=O QXJJQWWVWRCVQT-UHFFFAOYSA-K 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- NLCKLZIHJQEMCU-UHFFFAOYSA-N cyano prop-2-enoate Chemical class C=CC(=O)OC#N NLCKLZIHJQEMCU-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229920006245 ethylene-butyl acrylate Polymers 0.000 description 1
- 229920006225 ethylene-methyl acrylate Polymers 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229960004927 neomycin Drugs 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses an antistatic PET composition, which comprises the following components in parts by weight: 70-85 parts of PET resin; 8-32 parts of conductive carbon black; 0.1-3 parts of carbon nano tube; 0.5-5 parts of alkyl glycidyl ether; 0.5-2.5 parts of silicone. According to the invention, a certain amount of carbon nano tube, alkyl glycidyl ether and silicone are added into a conductive carbon black filled PET material system, and the carbon nano tube, the alkyl glycidyl ether and the silicone are matched in a synergistic way, so that the conductivity and resistance stability of the material are obviously improved, good antistatic performance can be kept after the material is stretched, and meanwhile, the carbon black falling off of the surface of the material is effectively reduced, and the problems that the resistance of the conductive carbon black filled PET material is greatly increased and carbon black is easy to fall off due to stretching in the prior art are well solved.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to an antistatic PET composition, a preparation method and application thereof.
Background
Polyethylene terephthalate (PET) is crystalline polyester, has the advantages of high heat resistance, high toughness, high fatigue resistance, self lubrication, low friction coefficient and the like, and has wide application in the fields of fibers and non-fibers. An important application of PET in the non-fibrous field is the production of films for use as packaging materials in the electronics, electrical and other industries. Because of the insulating property of PET, static charge is easy to generate and accumulate in the contact and friction processes, and when the static charge capacity reaches a certain value, the static charge capacity can damage electronic and electric products (such as electronic elements, instruments and meters and the like) due to high-voltage discharge. Therefore, antistatic modification of PET materials is required.
At present, various methods for preparing antistatic polyester exist, such as blending with conductive carbon black to reduce resistance and improve conductivity of the material. However, in the process of stretching (particularly high stretching ratio) the interface between the conductive carbon black and the resin is seriously damaged under the stretching load, so that the resistance is greatly increased due to the interface debonding between the conductive carbon black and the resin before stretching, and the pollution problem is caused by easy falling of the carbon black, so that the use requirement of the electronic and electric appliance industry on the packaging material is difficult to meet.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide an antistatic PET composition which can still keep good antistatic performance after being stretched and processed and effectively reduce the falling-off of surface carbon black.
Another object of the present invention is to provide a process for preparing the above antistatic PET composition.
The invention is realized by the following technical scheme:
an antistatic PET composition comprises the following components in parts by weight:
70-85 parts of PET resin;
8-32 parts of conductive carbon black;
0.1-3 parts of carbon nano tube;
0.5-5 parts of alkyl glycidyl ether;
0.5 to 2.5 portions of silicone.
Preferably, the PET resin has an intrinsic viscosity of 0.52 to 0.85dL/g. The intrinsic viscosity is tested with reference to standard ASTM D4603-2003 (2011).
Preferably, the length-diameter ratio of the carbon nano tube is 350-1450, and the weight fraction of carbon is more than or equal to 95%. The carbon nanotube diameter was measured with a Transmission Electron Microscope (TEM), the length was measured with a field emission scanning electron microscope (FE-SEM), and the carbon weight fraction was measured with a thermogravimetric analyzer (TGA). The length-diameter ratio and the carbon weight fraction defined by the carbon nano tube refer to the length-diameter ratio and the carbon weight fraction of the raw material carbon nano tube, the raw material carbon nano tube is made of flexible materials, and is fed by adopting a mode of feeding from a side feeding port of a double-screw extruder, and the change of the length-diameter ratio is small and negligible after extrusion processing.
According to the invention, a certain amount of carbon nanotubes are added, a plurality of connection points can be formed with carbon black, the effect of connecting conductive carbon black is achieved, the conductivity of the material is improved, and the carbon nanotubes in the range of the required length-diameter ratio are not easy to fall off in the stretching process, so that the effect of stabilizing the resistance is achieved. Excessive addition of carbon nanotubes can result in excessive viscosity of the composition melt, poor dispersion of conductive carbon black and carbon nanotubes, reduced conductivity, and poor antistatic properties of the material. Preferably, the carbon nanotubes are 0.5-2 parts.
Preferably, the iodine adsorption number of the conductive carbon black is 70-100mg/g. The iodine adsorption number is measured with reference to standard ASTM D1510-2016. The carbon black with higher iodine adsorption number and the carbon nano tube can well form more connection points, but the too high iodine adsorption number of the conductive carbon black can lead to difficult dispersion to form an aggregate in the processing process, and the connection points with the carbon nano tube are less, so that the conductivity and the resistance stability after stretching processing are affected.
The addition of the alkyl glycidyl ether can effectively improve the binding force between the conductive carbon black and the resin, and the bonding force is in synergistic effect with the carbon nano tube, so that the interface between the conductive carbon black and the resin can not be debonded in the stretching process of the material, a good conductive path can still be formed, the resistance is kept stable, and the falling of the carbon black on the surface of the material is effectively prevented. Preferably, the alkyl glycidyl ether is 1 to 4 parts.
The alkyl glycidyl ether is preferably any one or more of C eight-C tetradecyl glycidyl ether; more preferably, it is a carbon dodecyl-carbon tetradecyl glycidyl ether.
Specifically, the carbon eight-carbon tetradecyl glycidyl ether comprises any one or more of octyl glycidyl ether, decyl glycidyl ether, nonyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether and tetradecyl glycidyl ether.
According to the invention, a certain amount of silicone is added, and after stretching processing, a stable protective layer can be formed on the surface of the material, and the stable protective layer and alkyl glycidyl ether are in synergistic effect, so that the shedding of carbon black on the surface of the material is further reduced. Preferably, the silicone is 0.9-2 parts.
Preferably, the silicone according to the invention is selected from high molecular weight organosiloxane polymers, the silicone having a weight average molecular weight of 400000-2500000, more preferably 1000000-1800000. The silicone has too small weight average molecular weight, which can affect the molding of materials and has poor stability of forming a protective layer on the surface of the product; the silicone has excessively large weight average molecular weight and poor dispersibility, and is unfavorable for migration out of the surface of the product to form a protective layer.
Preferably, the silicone is added in the form of master batch, has better smoothness and is beneficial to blanking during preparation. The silicone masterbatch is obtained by dispersing silicone in polyolefin, such as 50% -70% silicone in a density of 0.92g/cm 3 Is a low density polyethylene of (b).
According to the material performance requirement, the antistatic PET composition further comprises 0.2-10 parts of auxiliary agent according to parts by weight.
Preferably, the auxiliary agent is selected from any one or more of antioxidant, flame retardant, filler, toughening agent, nucleating agent or ultraviolet light absorber.
Suitable antioxidants include any one or more of hindered phenol antioxidants, phosphite antioxidants, thioether antioxidants, polyaromatic amine antioxidants and hindered amine antioxidants; the mixture of hindered phenol antioxidants and phosphite antioxidants is preferable, and the weight ratio of the hindered phenol antioxidants to the phosphite antioxidants is preferably 1:10-10:1.
Suitable flame retardants include any one or more of brominated epoxy, brominated polystyrene, brominated polycarbonate, decabromodiphenylethane, pentabromobenzyl polyacrylate, antimony-containing flame retardants, aluminum organic hypophosphite or melamine polyphosphate.
Suitable fillers include any one or more of silica, calcium carbonate, talc, wollastonite, glass spheres, kaolin, single crystal fibers, carbon fibers, glass fibers or barium sulfate.
Suitable toughening agents include any one or more of ethylene-acrylate-glycidyl methacrylate terpolymers, ethylene-methyl acrylate copolymers, ethylene-butyl acrylate copolymers, silicone based toughening agents or EVA type toughening agents.
Suitable nucleating agents include any one or more of talc, calcium carbonate, sodium bicarbonate, metal salts of monocarboxylic acids, metal salts of benzoic acid, metal salts of aromatic hydroxy sulfonates, metal salts of organic phosphorus compounds, polymer particles or alkali metal salts of polyester oligomers.
Suitable ultraviolet light absorbers include any one or more of hydroxybenzophenones, hydroxybenzotriazoles, hydroxybenzotriazines, cyanoacrylates, or nano-sized inorganic materials (e.g., titanium oxide, cerium oxide, or zinc oxide).
The invention also provides a preparation method of the antistatic PET composition, which comprises the following steps: mixing all components except the carbon nano tube according to the proportion, adding the mixture into a double-screw extruder, adding the carbon nano tube into the double-screw extruder through a side feeding port, extruding, cooling and granulating to prepare an antistatic PET composition; wherein the temperature of the twin-screw extruder is set to 240-280 ℃.
Preferably, the twin-screw extruder has 10 screw barrels in total, and the 7 th screw barrel sequentially fed from the main part to the machine head is provided with a side feeding port.
The invention also provides application of the antistatic PET composition in preparing PET films in semiconductor packaging materials and electronic and electric appliance packaging materials.
The invention has the following beneficial effects:
according to the invention, a certain amount of carbon nano tube, alkyl glycidyl ether and silicone are added into a conductive carbon black filled PET material system, and the carbon nano tube, the alkyl glycidyl ether and the silicone are matched in a synergistic way, so that the conductivity and resistance stability of the material are obviously improved, good antistatic performance can be kept after the material is stretched, and meanwhile, the carbon black falling off of the surface of the material is effectively reduced, and the problems that the resistance of the conductive carbon black filled PET material is greatly increased and carbon black is easy to fall off due to stretching in the prior art are well solved.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications could be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present invention.
The raw materials used in the examples and comparative examples of the present invention are described below, but are not limited to these materials:
PET resin 1: intrinsic viscosity was 0.68dL/g, PET FG600, ceremony;
PET resin 2: intrinsic viscosity is 0.8dL/g, PET BG80, and chemical fiber is measured;
PET resin 3: intrinsic viscosity is 0.9dL/g, EP901, ceremony chemical fiber;
PET resin 4: the intrinsic viscosity is 0.58dL/g, CR-7702, huarun chemical materials science and technology Co., ltd;
conductive carbon black 1: iodine adsorption number of 75 mg/g,7067, bola, according to ASTM D1510-2016;
conductive carbon black 2: iodine adsorption number of 95 mg/g according to ASTM D1510-2016; 7097, bola corporation;
carbon nanotube 1: multi-wall carbon nano tube with length-diameter ratio of 364, carbon weight fraction of 99%, TNGM5, middle-aged nanometer;
carbon nanotube 2: multi-wall carbon nano tube with length-diameter ratio of 1400 and carbon weight fraction of 95.5%, TNIM190F, middle age nano;
carbon nanotube 3: multi-wall carbon nano tube with length-diameter ratio of 333, carbon weight fraction of 98%, GT-301;
carbon nanotubes 4: multi-wall carbon nano tube with length-diameter ratio of 1533, carbon weight fraction of 93%, GT-210;
alkyl glycidyl ether 1: C12-C14 alkyl glycidyl ether, HELOXY 8, HELOXY;
alkyl glycidyl ether 2: new materials of C8-C10 alkyl glycidyl ether and neomycin;
alkyl glycidyl ether 3: butyl glycidyl ether, 501P, new technology;
alkyl glycidyl ether 4: cetyl glycidyl ether, HAGE16, SACHEM company, usa;
silicone masterbatch 1: silicone master batch with silicone weight average molecular weight of 1650000 content of 55%, GT-300, zhejiang Jiahua refinement Co., ltd;
silicone masterbatch 2: silicone master batch with silicone weight average molecular weight of 800000 and content of 50%, AS-025, culvert point technology;
silicone masterbatch 3: silicone master batch with silicone weight average molecular weight of 2050000 content of 70%, GW-6200P, zhejiang Jiahua refinement Co., ltd;
auxiliary agent: the weight ratio of the hindered phenol antioxidant (commercially available) to the phosphite antioxidant (commercially available) is 1:1; the auxiliaries (antioxidants) used in the examples and comparative examples are the same commercial products.
Preparation methods of examples and comparative examples:
according to the proportions shown in Table 1, table 2 and Table 3, the components except the carbon nanotubes were mixed and fed into a twin-screw extruder, the twin-screw extruder had 10 screw barrels in total, and the 7 th screw barrel in the order from the main feed to the head had a side feed port, and the carbon nanotubes were fed into the twin-screw extruder through the side feed port, and subjected to extrusion, cooling and pelleting to obtain a PET composition, wherein the extrusion temperature was 260℃and the mixing speed was 350 rpm, and the mixing time was 4 minutes.
Correlation performance test:
the PET composition was fed into a single screw extruder at 240℃to plasticize and extrude a sheet, the sheet was quenched in cold water, and then the sheet was subjected to a first stretching by heating at 180℃and immediately after the completion of the first stretching, the heating at 180℃was continued and a second stretching was simultaneously performed to obtain a molded article. The draw ratio of the secondarily stretched molded article was 3.5.
(1) Conductivity: the surface resistance of the extruded sheet and the molded article after the sheet was subjected to stretching processing was measured by using ASTM standard D257-2014, and the change rate of the resistance before and after stretching of the composition was (resistance of the molded article after stretching-resistance of the sheet before stretching)/resistance of the sheet before stretching was x 100%, and the larger the change rate was, the larger the increase of the resistance after stretching of the composition was.
(2) Carbon black drop: the molded article was pressed against white paper, and was slid 50 times in the same direction by applying a load of 0.5kg, and the sliding area was tested for L value by a color measuring apparatus X-riteColorEye 7000A using a 65D light source, and the smaller the L value, the darker the color, and the larger the amount of carbon black drop.
Table 1: examples 1-8 component ratios (in parts by weight) and related performance test results
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | Example 8 | |
| PET resin 1 | 80 | 80 | 80 | 80 | 80 | |||
| PET resin 2 | 80 | |||||||
| PET resin 3 | 80 | |||||||
| PET resin 4 | 80 | |||||||
| Conductive carbon black 1 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | |
| Conductive carbon black 2 | 20 | |||||||
| Carbon nanotube 1 | 1 | 1 | 1 | 1 | 1 | |||
| Carbon nanotubes 2 | 1 | |||||||
| Carbon nanotubes 3 | 1 | |||||||
| Carbon nanotubes 4 | 1 | |||||||
| Alkyl glycidyl ether 1 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 |
| Silicone masterbatch 1 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 |
| Auxiliary agent | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| Sheet resistance/ohm before stretching | 5.42E+03 | 5.33E+03 | 1.82E+04 | 1.56E+04 | 3.31E+03 | 2.86E+03 | 3.31E+03 | 3.22E+03 |
| Resistance/ohm of stretched molded article | 6.43E+04 | 7.21E+04 | 7.26E+05 | 5.24E+05 | 2.40E+05 | 2.57E+05 | 4.22E+05 | 4.31E+05 |
| Carbon black drop (L value) | 87 | 84 | 83 | 82 | 82 | 85 | 84 | 84 |
Table 2: examples 9-16 component ratios (in parts by weight) and related performance test results
| Example 9 | Example 10 | Example 11 | Example 12 | Example 13 | Example 14 | Example 15 | Example 16 | |
| PET resin 1 | 80 | 80 | 80 | 80 | 80 | 70 | 85 | 80 |
| Conductive carbon black 1 | 20 | 20 | 20 | 20 | 20 | 32 | 8 | 20 |
| Carbon nanotube 1 | 1 | 1 | 1 | 1 | 1 | 3 | 0.1 | 1 |
| Alkyl glycidyl ether 1 | 3 | 3 | 5 | 0.5 | 3 | |||
| Alkyl glycidyl ether 2 | 3 | |||||||
| Alkyl glycidyl ether 3 | 3 | |||||||
| Alkyl glycidyl ether 4 | 3 | |||||||
| Silicone masterbatch 1 | 2 | 2 | 2 | 4.5 | 1 | 2 | ||
| Silicone masterbatch 2 | 2 | |||||||
| Silicone masterbatch 3 | 1.5 | |||||||
| Auxiliary agent | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | / |
| Sheet resistance/ohm before stretching | 6.70E+03 | 1.47E+04 | 2.55E+04 | 3.71E+03 | 2.61E+04 | 4.31E+02 | 2.23E+05 | 5.45E+03 |
| Resistance/ohm of stretched molded article | 1.43E+05 | 5.44E+05 | 1.43E+06 | 7.43E+04 | 1.43E+06 | 5.62E+04 | 2.91E+07 | 7.82E+04 |
| Carbon black drop (L value) | 85 | 83 | 82 | 81 | 80 | 80 | 81 | 86 |
Table 3: comparative examples 1 to 8 the proportions of the respective components (in parts by weight) and the results of the related property tests
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | Comparative example 7 | Comparative example 8 | |
| PET resin 1 | 80 | 80 | 80 | 80 | 80 | 80 | 80 | 80 |
| Conductive carbon black 1 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 |
| Carbon nanotube 1 | 5 | / | 1 | 1 | 1 | 1 | 1 | 1 |
| Alkyl glycidyl ether 1 | 3 | 3 | 10 | 0.1 | / | 3 | 3 | 3 |
| Silicone masterbatch 1 | 2 | 2 | 2 | 2 | 2 | 9.1 | 0.2 | / |
| Auxiliary agent | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| Sheet resistance/ohm before stretching | 5.51E+02 | 6.63E+04 | 7.45E+05 | 5.56E+03 | 6.91E+03 | 5.15E+05 | 5.52E+03 | 4.32E+03 |
| Resistance/ohm of stretched molded article | 2.63E+05 | 2.58E+08 | 1.46E+09 | 7.46E+06 | 1.83E+07 | 1.62E+09 | 9.50E+04 | 8.70E+04 |
| Carbon black drop (L value) | 77 | 79 | 75 | 79 | 76 | 78 | 76 | 72 |
According to the embodiment and the comparative example, a certain amount of carbon nano tube, alkyl glycidyl ether and silicone are added into a conductive carbon black filled PET material system, and the carbon nano tube, the alkyl glycidyl ether and the silicone are matched, so that the resistance stability of the material can be remarkably improved, the resistance change is small after the material is stretched, and meanwhile, the carbon black falling off (the resistance change rate before and after stretching is less than 1.3E+04 percent, and the carbon black falling off (L value) is more than or equal to 80) on the surface of a formed product is effectively reduced.
Claims (12)
1. The antistatic PET composition is characterized by comprising the following components in parts by weight:
70-85 parts of PET resin;
8-32 parts of conductive carbon black;
0.1-3 parts of carbon nano tube;
0.5-5 parts of alkyl glycidyl ether;
0.5-2.5 parts of silicone.
2. The antistatic PET composition according to claim 1, wherein the alkyl glycidyl ether is selected from any one or more of carbon eight-carbon tetradecyl glycidyl ethers.
3. The antistatic PET composition of claim 2 wherein the glycidyl ether is selected from the group consisting of carbon dodecyl-carbon tetradecyl glycidyl ethers.
4. The antistatic PET composition according to claim 2, wherein the carbon eight-carbon tetradecyl glycidyl ether is selected from any one or more of octyl glycidyl ether, decyl glycidyl ether, nonyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, or tetradecyl glycidyl ether.
5. The antistatic PET composition according to claim 1, wherein the silicone is an organosiloxane polymer having a weight average molecular weight of 400000-2500000.
6. The antistatic PET composition of claim 5 wherein the silicone is an organosiloxane polymer having a weight average molecular weight of 1000000-1800000.
7. The antistatic PET composition of claim 1 wherein the PET resin has an intrinsic viscosity of 0.52 to 0.85dL/g.
8. The antistatic PET composition according to claim 1, wherein the conductive carbon black has an iodine adsorption number of 70-100mg/g.
9. The antistatic PET composition of claim 1 wherein the carbon nanotubes have an aspect ratio of 350-1450 and a carbon weight fraction of greater than or equal to 95%.
10. The antistatic PET composition of claim 1, further comprising 0.2-10 parts by weight of an auxiliary agent; the auxiliary agent is selected from any one or more of antioxidant, flame retardant, filler, toughening agent, nucleating agent or ultraviolet light absorber.
11. Process for the preparation of an antistatic PET composition according to any one of claims 1 to 10, characterized in that it comprises the following steps: mixing all components except the carbon nano tube according to the proportion, adding the mixture into a double-screw extruder, adding the carbon nano tube into the double-screw extruder through a side feeding port, extruding, cooling and granulating to prepare an antistatic PET composition; wherein the temperature of the twin-screw extruder is set to 240-280 ℃.
12. Use of an antistatic PET composition according to any of claims 1-10 for the preparation of PET films for use in semiconductor packaging materials, electronic packaging materials.
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