CN116554629A - Low-temperature-resistant antistatic thermoplastic elastomer material and preparation method thereof - Google Patents
Low-temperature-resistant antistatic thermoplastic elastomer material and preparation method thereof Download PDFInfo
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- 229920002725 thermoplastic elastomer Polymers 0.000 title claims abstract description 117
- 239000000463 material Substances 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title abstract description 22
- 239000004743 Polypropylene Substances 0.000 claims abstract description 52
- 229920001155 polypropylene Polymers 0.000 claims abstract description 50
- 229920001577 copolymer Polymers 0.000 claims abstract description 45
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 30
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 30
- 239000000314 lubricant Substances 0.000 claims abstract description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 23
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 21
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 21
- -1 polypropylene Polymers 0.000 claims abstract description 16
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 claims abstract description 11
- 239000002048 multi walled nanotube Substances 0.000 claims description 34
- 238000002156 mixing Methods 0.000 claims description 33
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 32
- 238000001816 cooling Methods 0.000 claims description 32
- 238000001125 extrusion Methods 0.000 claims description 16
- 238000005469 granulation Methods 0.000 claims description 16
- 230000003179 granulation Effects 0.000 claims description 16
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 6
- 238000012360 testing method Methods 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 claims description 3
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical group CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 3
- 239000007983 Tris buffer Substances 0.000 claims description 2
- QAYPAJMIHQWDNR-UHFFFAOYSA-N [hydroxy-[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]phosphoryl] dioctadecyl phosphate Chemical compound O(P(OCCCCCCCCCCCCCCCCCC)(=O)OP(=O)(O)OCC(CO)(CO)CO)CCCCCCCCCCCCCCCCCC QAYPAJMIHQWDNR-UHFFFAOYSA-N 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 2
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- 239000003921 oil Substances 0.000 description 37
- 230000000052 comparative effect Effects 0.000 description 34
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011159 matrix material Substances 0.000 description 7
- 239000000956 alloy Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 241000218691 Cupressaceae Species 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000002109 single walled nanotube Substances 0.000 description 2
- WCVOGSZTONGSQY-UHFFFAOYSA-N 2,4,6-trichloroanisole Chemical compound COC1=C(Cl)C=C(Cl)C=C1Cl WCVOGSZTONGSQY-UHFFFAOYSA-N 0.000 description 1
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical group C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- BXOUVIIITJXIKB-UHFFFAOYSA-N ethene;styrene Chemical group C=C.C=CC1=CC=CC=C1 BXOUVIIITJXIKB-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- 229920000428 triblock copolymer Polymers 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
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
- C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention relates to a low-temperature-resistant antistatic thermoplastic elastomer material and a preparation method thereof. The low-temperature-resistant antistatic thermoplastic elastomer material is prepared from the following raw materials in parts by weight: 100 parts of thermoplastic elastomer, 7-14 parts of SEBS-g-MAH, 2-8 parts of E-MAH copolymer, 3-15 parts of carbon nano tube, 0-0.8 part of antioxidant and 0-0.8 part of lubricant, wherein the thermoplastic elastomer consists of hydrogenated (styrene-butadiene-styrene) block copolymer, polypropylene and white oil. The low-temperature-resistant antistatic thermoplastic elastomer material has excellent low-temperature resistance and excellent antistatic performance.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a low-temperature-resistant antistatic thermoplastic elastomer material and a preparation method thereof.
Background
Besides the high elasticity of rubber, the thermoplastic elastomer (Thermoplastic Elastomer, TPE for short) also has the workability of thermoplastic plastics, and in addition, the TPE has the advantages of wide adjustable range of hardness, good toughness, environmental protection and no toxicity, and very wide application field, and is mainly applied to the fields of daily consumer goods, kitchen supplies, automobiles, wires and cables, waterproof coiled materials, plastic floors/runways, electronic appliances and the like. TPE generally has a volume resistivity of 1012-1014 Ω·cm and good electrical insulation, but is prone to static electricity during use due to friction, and causes a series of disasters due to static discharge and electromagnetic interference. Static electricity accumulated on the surface of the product may cause difficulty in molding operation and affect the quality of the product. In the electronic and electrical industry, electrostatic discharge may cause breakdown of precision instruments and electronic components and may be scrapped. For the above reasons, research on the antistatic problem of TPE has been carried out domestically. The Chinese patent No. 106751080A discloses an antistatic thermoplastic elastomer alloy material, but the main resin is general plastic GPPS, the thermoplastic elastomer SEBS is only used as a toughening agent, the hardness of the obtained alloy material is higher, and the polyether type high-molecular antistatic agent is used, so that the alloy material is high in price, and the compatibility of polyether and the thermoplastic elastomer belonging to olefins is poor.
Therefore, a low-temperature-resistant antistatic thermoplastic elastomer material is developed, and the material has excellent low-temperature resistance and antistatic effect, and has wide market prospect and great economic value.
Disclosure of Invention
Based on the above, the invention aims to provide a low-temperature-resistant antistatic thermoplastic elastomer material which has excellent low-temperature resistance and excellent antistatic effect.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the low-temperature-resistant antistatic thermoplastic elastomer material is prepared from the following raw materials in parts by weight:
the thermoplastic elastomer consists of a hydrogenated (styrene-butadiene-styrene) block copolymer, polypropylene and white oil.
In some embodiments, the low temperature resistant antistatic thermoplastic elastomer material is prepared from the following raw materials in parts by weight:
in some of these embodiments, the thermoplastic elastomer is comprised of the following components in parts by weight: 37-48 parts of hydrogenated (styrene-butadiene-styrene) block copolymer, 7-18 parts of polypropylene and 43-53 parts of white oil. Experiments show that the thermoplastic elastomer with the composition in parts by weight has better technical effect.
In some of these embodiments, the thermoplastic elastomer is comprised of the following components in parts by weight: 40 parts of hydrogenated (styrene-butadiene-styrene) block copolymer, 15 parts of polypropylene and 45 parts of white oil.
In some of these embodiments, the SEBS-g-MAH and E-MAH copolymers have a mass ratio of 3:1.
in some of these embodiments, the mass ratio of the total amount of SEBS-g-MAH and E-MAH copolymer to the carbon nanotubes is 5:2.
In some of these embodiments, the SEBS-g-MAH has a maleic anhydride grafting of 1wt% to 2wt%.
In some of these embodiments, the E-MAH copolymer (ethylene-maleic anhydride copolymer) has a maleic anhydride content of 78wt%.
In some of these embodiments, a 10wt% toluene solution of the hydrogenated (styrene-butadiene-styrene) block copolymer has a viscosity ∈1000mpa.s at 25 ℃.
In some of these embodiments, the polypropylene is a random polypropylene having a melt index of 11 to 20g/10min at 230 ℃/2.16kg test conditions.
In some of these embodiments, the white oil is a paraffinic white oil having a kinematic viscosity at 40 ℃ of 25-90cSt.
In some of these embodiments, the carbon nanotubes are multiwall carbon nanotubes. The multi-wall carbon nano tube has smaller specific surface energy than the single-wall carbon nano tube, relatively smaller aggregation and easier dispersion because the pipe diameter of the multi-wall carbon nano tube is usually larger than that of the single-wall carbon nano tube, so that the carbon nano tube is preferably the multi-wall carbon nano tube, and the antistatic performance of the obtained low-temperature-resistant antistatic thermoplastic elastomer material can be better improved.
In some of these embodiments, the antioxidant is selected from at least one of pentaerythritol distearyl diphosphate, tris- (nonylphenyl) phosphite, and phenyl tris (2, 4-di-t-butyl) phosphite; the lubricant is selected from erucamide and/or oleamide.
The invention also provides a preparation method of the low-temperature-resistant antistatic thermoplastic elastomer material.
The specific technical scheme is as follows:
a preparation method of a low-temperature-resistant antistatic thermoplastic elastomer material comprises the following steps:
(1) Uniformly mixing the SEBS-g-MAH, E-MAH copolymer and the carbon nano tube, adding the mixture into a double-screw extruder, extruding, cooling and granulating to obtain master batch;
(2) And (3) uniformly mixing the master batch, the thermoplastic elastomer, the antioxidant and the lubricant, adding the mixture into a double-screw extruder, and obtaining the low-temperature-resistant antistatic thermoplastic elastomer material through melting, extrusion, cooling and granulation.
The low-temperature-resistant antistatic thermoplastic elastomer material is prepared from raw materials comprising components TPE (comprising SEBS, PP and white mineral oil), SEBS-g-MAH, an E-MAH copolymer and carbon nanotubes, the prepared thermoplastic elastomer material has lower hardness and low temperature resistance by adopting the SEBS, PP and the white mineral oil in a specific proportion, and the carbon nanotubes can be well dispersed in the TPE component by adding the maleic anhydride graft SEBS-g-MAH and the maleic anhydride copolymer E-MAH in a matching manner. Maleic anhydride is easy to react with active groups such as hydroxyl, carboxyl and the like on the surface of the carbon nano tube, so that the compatibility of the carbon nano tube with SEBS-g-MAH and E-MAH is improved; because the SEBS-g-MAH and the SEBS base material have excellent compatibility, and the E-MAH and the PP have excellent compatibility, the carbon nanotubes are well dispersed in the TPE and the TPE, and the agglomeration of the carbon nanotubes is prevented, so that the prepared low-temperature-resistant antistatic thermoplastic elastomer material has excellent low-temperature resistance and excellent antistatic performance.
The preparation method of the low-temperature-resistant antistatic thermoplastic elastomer material provided by the invention has the advantages of simple process, easiness in control, low requirement on equipment and contribution to industrial production.
Detailed Description
The technical scheme of the invention is further described by the following specific examples. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The terms "comprising" and "having" and any variations thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, apparatus, article, or device that comprises a list of steps is not limited to the elements or modules listed but may alternatively include additional steps not listed or inherent to such process, method, article, or device.
In the present invention, the term "plurality" means two or more. "and/or", describes an association relationship of an association object, and indicates that there may be three relationships, for example, a and/or B, and may indicate: a exists alone, A and B exist together, and B exists alone. The character "/" generally indicates that the context-dependent object is an "or" relationship.
The raw materials used in the examples and comparative examples of the present invention are as follows:
hydrogenated (styrene-butadiene-styrene) block copolymer is a linear triblock copolymer taking polystyrene as a terminal block and taking ethylene-butene copolymer obtained by hydrogenation of polybutadiene as an intermediate elastic block, and is called Styreethylenebutyl tyrene for short SEBS (styrene ethylene/butylene/styrene) for short, wherein 10% toluene solution viscosity at 25 ℃ is larger than or equal to 1000mPa.s; the SEBS used in the examples below was purchased from Tokyo Baling petrochemicals Co., ltd, and had a 10% toluene solution viscosity at 25℃of 1500 Pa.s;
the polypropylene (PP) is random polypropylene, and the melt index of the polypropylene under the test condition of 230 ℃/2.16kg is 11-20 g/10min; the PP used in the examples below was purchased from Ningbo Co., ltd, in the Table plastic industry, and had a melt index of 15g/10min at 230℃under 2.16kg test conditions;
the white oil is paraffin-based white oil with a kinematic viscosity of 25-90cSt at 40deg.C; the white oil used in the following examples was purchased from Jiangsu Oriental energy Co., ltd, and had a kinematic viscosity of 46cSt at 40 ℃;
hydrogenated (styrene-butadiene-styrene) block copolymer grafted maleic anhydride (SEBS-g-MAH), available from Koteng, USA, with a grafting ratio of 2% by weight of maleic anhydride;
ethylene-maleic anhydride copolymer (E-MAH copolymer) which is the product of free radical polymerization of ethylene and maleic anhydride, maleic anhydride being on the main chain of E-MAH polymer, available from Shanghai Nanjin Co., ltd, having a molecular weight of 60000 and a maleic anhydride content of 78wt%;
polypropylene grafted maleic anhydride (PP-g-MAH) available from Nanhai cypress morning polymer materials Co., fleenship, with a maleic anhydride grafting ratio of 1.35wt%;
POE grafted maleic anhydride (POE-g-MAH) purchased from Nanhai cypress morning polymer materials limited in Buddha, wherein the grafting rate of the maleic anhydride is 1.0wt%;
carbon nanotubes(CNT) is a multiwall carbon nanotubePurchased from Shanghai Jiupi New Material technologies Co., ltd;
the antioxidant is distearyl pentaerythritol diphosphite with the mark 619F, which is purchased from Shanghai Kaiyin chemical industry Co., ltd;
the lubricant was erucamide, available from Shanghai Kailn chemical Co.
Example 1
The low-temperature-resistant antistatic thermoplastic elastomer material provided by the embodiment is prepared from the following raw materials in parts by weight:
component (A) | Parts by weight of |
SEBS | 40 |
PP | 15 |
White oil | 45 |
SEBS-g-MAH | 7 |
E-MAH copolymer | 5 |
Multiwall carbon nanotubes | 3 |
Antioxidant | 0.2 |
Lubricant | 0.6 |
The preparation method of the low-temperature-resistant antistatic thermoplastic elastomer material provided by the embodiment comprises the following steps:
(1) And uniformly mixing the SEBS-g-MAH, the E-MAH copolymer and the multiwall carbon nanotubes, adding the mixture into a double-screw extruder, extruding, cooling and granulating to obtain master batch. Extruder aspect ratio L/d=40: 1, the screw speed of the extruder is 350rpm, screw sections and head temperatures of 70, 150, 170, 180 180, 180/175 ℃;
(2) The master batch, the TPE components (SEBS, PP and white oil), the antioxidant and the lubricant are uniformly mixed, and are added into a double-screw extruder to be melted, extruded, cooled and granulated at 180-210 ℃ to obtain the low-temperature-resistant antistatic thermoplastic elastomer material. Extruder aspect ratio L/d=44: 1, the screw speed of the extruder is 350rpm, screw sections and head temperatures of 180, 190, 200 200, 210, 200, 190/190 ℃.
Example 2
The low-temperature-resistant antistatic thermoplastic elastomer material provided by the embodiment is prepared from the following raw materials in parts by weight:
component (A) | Parts by weight of |
SEBS | 40 |
PP | 15 |
White oil | 45 |
SEBS-g-MAH | 7 |
E-MAH copolymer | 8 |
Multiwall carbon nanotubes | 3 |
Antioxidant | 0.2 |
Lubricant | 0.6 |
The preparation method of the low-temperature-resistant antistatic thermoplastic elastomer material provided by the embodiment comprises the following steps:
(1) Uniformly mixing SEBS-g-MAH, E-MAH copolymer and multi-wall carbon nano tubes, adding into a double-screw extruder, extruding, cooling and granulating to obtain master batch; extruder aspect ratio L/d=40: 1, the screw speed of the extruder is 350rpm, screw sections and head temperatures of 70, 150, 170, 180 180, 180/175 ℃;
(2) The master batch, the TPE components (SEBS, PP and white oil), the antioxidant and the lubricant are uniformly mixed, and are added into a double-screw extruder, and the low-temperature-resistant antistatic thermoplastic elastomer material is obtained through melt mixing extrusion, cooling and granulation at 180-210 ℃. Extruder aspect ratio L/d=44: 1, the screw speed of the extruder is 350rpm, screw sections and head temperatures of 180, 190, 200 200, 210, 200, 190/190 ℃.
Example 3
The low-temperature-resistant antistatic thermoplastic elastomer material provided by the embodiment is prepared from the following raw materials in parts by weight:
component (A) | Parts by weight of |
SEBS | 40 |
PP | 15 |
White oil | 45 |
SEBS-g-MAH | 7 |
E-MAH copolymer | 2 |
Multiwall carbon nanotubes | 3 |
Antioxidant | 0.2 |
Lubricant | 0.6 |
The preparation method of the low-temperature-resistant antistatic thermoplastic elastomer material provided by the embodiment comprises the following steps:
(1) Uniformly mixing SEBS-g-MAH, E-MAH copolymer and multi-wall carbon nano tubes, adding into a double-screw extruder, extruding, cooling and granulating to obtain master batch; extruder aspect ratio L/d=40: 1, the screw speed of the extruder is 350rpm, screw sections and head temperatures of 70, 150, 170, 180 180, 180/175 ℃;
(2) The master batch, the TPE components (SEBS, PP and white oil), the antioxidant and the lubricant are uniformly mixed, and are added into a double-screw extruder, and the low-temperature-resistant antistatic thermoplastic elastomer material is obtained through melt mixing extrusion, cooling and granulation at 180-210 ℃. Extruder aspect ratio L/d=44: 1, the screw speed of the extruder is 350rpm, screw sections and head temperatures of 180, 190, 200 200, 210, 200, 190/190 ℃.
Example 4
The low-temperature-resistant antistatic thermoplastic elastomer material provided by the embodiment is prepared from the following raw materials in parts by weight:
component (A) | Parts by weight of |
SEBS | 40 |
PP | 15 |
White oil | 45 |
SEBS-g-MAH | 10 |
E-MAH copolymer | 5 |
Multiwall carbon nanotubes | 3 |
Antioxidant | 0.2 |
Lubricant | 0.6 |
The preparation method of the low-temperature-resistant antistatic thermoplastic elastomer material provided by the embodiment comprises the following steps:
(1) Uniformly mixing SEBS-g-MAH, E-MAH copolymer and multi-wall carbon nano tubes, adding into a double-screw extruder, extruding, cooling and granulating to obtain master batch; extruder aspect ratio L/d=40: 1, the screw speed of the extruder is 350rpm, screw sections and head temperatures of 70, 150, 170, 180 180, 180/175 ℃;
(2) The master batch, the TPE components (SEBS, PP and white oil), the antioxidant and the lubricant are uniformly mixed, and are added into a double-screw extruder, and the low-temperature-resistant antistatic thermoplastic elastomer material is obtained through melt mixing extrusion, cooling and granulation at 180-210 ℃. Extruder aspect ratio L/d=44: 1, the screw speed of the extruder is 350rpm, screw sections and head temperatures of 180, 190, 200 200, 210, 200, 190/190 ℃.
Example 5
The low-temperature-resistant antistatic thermoplastic elastomer material provided by the embodiment is prepared from the following raw materials in parts by weight:
component (A) | Parts by weight of |
SEBS | 40 |
PP | 15 |
White oil | 45 |
SEBS-g-MAH | 14 |
E-MAH copolymer | 5 |
Multiwall carbon nanotubes | 3 |
Antioxidant | 0.2 |
Lubricant | 0.6 |
The preparation method of the low-temperature-resistant antistatic thermoplastic elastomer material provided by the embodiment comprises the following steps:
(1) Uniformly mixing SEBS-g-MAH, E-MAH copolymer and multi-wall carbon nano tubes, adding into a double-screw extruder, extruding, cooling and granulating to obtain master batch; extruder aspect ratio L/d=40: 1, the screw speed of the extruder is 350rpm, screw sections and head temperatures of 70, 150, 170, 180 180, 180/175 ℃;
(2) The master batch, the TPE components (SEBS, PP and white oil), the antioxidant and the lubricant are uniformly mixed, and are added into a double-screw extruder, and the low-temperature-resistant antistatic thermoplastic elastomer material is obtained through melt mixing extrusion, cooling and granulation at 180-210 ℃. Extruder aspect ratio L/d=44: 1, the screw speed of the extruder is 350rpm, screw sections and head temperatures of 180, 190, 200 200, 210, 200, 190/190 ℃.
Example 6
The low-temperature-resistant antistatic thermoplastic elastomer material provided by the embodiment is prepared from the following raw materials in parts by weight:
component (A) | Parts by weight of |
SEBS | 40 |
PP | 15 |
White oil | 45 |
SEBS-g-MAH | 10 |
E-MAH copolymer | 5 |
Multiwall carbon nanotubes | 8 |
Antioxidant | 0.2 |
Lubricant | 0.6 |
The preparation method of the low-temperature-resistant antistatic thermoplastic elastomer material provided by the embodiment comprises the following steps:
(1) Uniformly mixing SEBS-g-MAH, E-MAH copolymer and multi-wall carbon nano tubes, adding into a double-screw extruder, extruding, cooling and granulating to obtain master batch; extruder aspect ratio L/d=40: 1, the screw speed of the extruder is 350rpm, screw sections and head temperatures of 70, 150, 170, 180 180, 180/175 ℃;
(2) The master batch, the TPE components (SEBS, PP and white oil), the antioxidant and the lubricant are uniformly mixed, and are added into a double-screw extruder, and the low-temperature-resistant antistatic thermoplastic elastomer material is obtained through melt mixing extrusion, cooling and granulation at 180-210 ℃. Extruder aspect ratio L/d=44: 1, the screw speed of the extruder is 350rpm, screw sections and head temperatures of 180, 190, 200 200, 210, 200, 190/190 ℃.
Example 7
The low-temperature-resistant antistatic thermoplastic elastomer material provided by the embodiment is prepared from the following raw materials in parts by weight:
component (A) | Parts by weight of |
SEBS | 40 |
PP | 15 |
White oil | 45 |
SEBS-g-MAH | 10 |
E-MAH copolymer | 5 |
Multiwall carbon nanotubes | 15 |
Antioxidant | 0.2 |
Lubricant | 0.6 |
The preparation method of the low-temperature-resistant antistatic thermoplastic elastomer material provided by the embodiment comprises the following steps:
(1) Uniformly mixing SEBS-g-MAH, E-MAH copolymer and multi-wall carbon nano tubes, adding into a double-screw extruder, extruding, cooling and granulating to obtain master batch; extruder aspect ratio L/d=40: 1, the screw speed of the extruder is 350rpm, screw sections and head temperatures of 70, 150, 170, 180 180, 180/175 ℃;
(2) The master batch, the TPE components (SEBS, PP and white oil), the antioxidant and the lubricant are uniformly mixed, and are added into a double-screw extruder, and the low-temperature-resistant antistatic thermoplastic elastomer material is obtained through melt mixing extrusion, cooling and granulation at 180-210 ℃. Extruder aspect ratio L/d=44: 1, the screw speed of the extruder is 350rpm, screw sections and head temperatures of 180, 190, 200 200, 210, 200, 190/190 ℃.
Example 8
The low-temperature-resistant antistatic thermoplastic elastomer material provided by the embodiment is prepared from the following raw materials in parts by weight:
component (A) | Parts by weight of |
SEBS | 40 |
PP | 15 |
White oil | 45 |
SEBS-g-MAH | 14 |
E-MAH copolymer | 2 |
Multiwall carbon nanotubes | 3 |
The preparation method of the low-temperature-resistant antistatic thermoplastic elastomer material provided by the embodiment comprises the following steps:
(1) Uniformly mixing SEBS-g-MAH, E-MAH copolymer and multi-wall carbon nano tubes, adding into a double-screw extruder, extruding, cooling and granulating to obtain master batch; extruder aspect ratio L/d=40: 1, the screw speed of the extruder is 350rpm, screw sections and head temperatures of 70, 150, 170, 180 180, 180/175 ℃;
(2) The master batch and the TPE components (SEBS, PP and white oil) are uniformly mixed, added into a double-screw extruder, and subjected to melt mixing extrusion, cooling and granulation at 180-210 ℃ to obtain the low-temperature-resistant antistatic thermoplastic elastomer material. Extruder aspect ratio L/d=44: 1, the screw speed of the extruder is 350rpm, screw sections and head temperatures of 180, 190, 200 200, 210, 200, 190/190 ℃.
Example 9
The low-temperature-resistant antistatic thermoplastic elastomer material provided by the embodiment is prepared from the following raw materials in parts by weight:
component (A) | Parts by weight of |
SEBS | 40 |
PP | 15 |
White oil | 45 |
SEBS-g-MAH | 14 |
E-MAH copolymer | 8 |
Multiwall carbon nanotubes | 3 |
The preparation method of the low-temperature-resistant antistatic thermoplastic elastomer material provided by the embodiment comprises the following steps:
(1) Uniformly mixing SEBS-g-MAH, E-MAH copolymer and multi-wall carbon nano tubes, adding into a double-screw extruder, extruding, cooling and granulating to obtain master batch; extruder aspect ratio L/d=40: 1, the screw speed of the extruder is 350rpm, screw sections and head temperatures of 70, 150, 170, 180 180, 180/175 ℃;
(2) The master batch and the TPE components (SEBS, PP and white oil) are uniformly mixed, added into a double-screw extruder, and subjected to melt mixing extrusion, cooling and granulation at 180-210 ℃ to obtain the low-temperature-resistant antistatic thermoplastic elastomer material. Extruder aspect ratio L/d=44: 1, the screw speed of the extruder is 350rpm, screw sections and head temperatures of 180, 190, 200 200, 210, 200, 190/190 ℃.
Comparative example 1
The low-temperature-resistant antistatic thermoplastic elastomer material provided by the comparative example is prepared from the following raw materials in parts by weight:
component (A) | Parts by weight of |
SEBS | 40 |
PP | 15 |
White oil | 45 |
SEBS-g-MAH | 15 |
Multiwall carbon nanotubes | 8 |
Antioxidant | 0.2 |
Lubricant | 0.6 |
The preparation method of the low-temperature-resistant antistatic thermoplastic elastomer material provided by the comparative example comprises the following steps:
(1) Uniformly mixing SEBS-g-MAH and multi-wall carbon nanotubes, adding into a double-screw extruder, extruding, cooling and granulating to obtain master batch; extruder aspect ratio L/d=40: 1, the screw speed of the extruder is 350rpm, screw sections and head temperatures of 70, 150, 170, 180 180, 180/175 ℃;
(2) The master batch, the TPE components (SEBS, PP and white oil), the antioxidant and the lubricant are uniformly mixed, and are added into a double-screw extruder, and the low-temperature-resistant antistatic thermoplastic elastomer material is obtained through melt mixing extrusion, cooling and granulation at 180-210 ℃. Extruder aspect ratio L/d=44: 1, the screw speed of the extruder is 350rpm, screw sections and head temperatures of 180, 190, 200 200, 210, 200, 190/190 ℃.
Comparative example 2
The low-temperature-resistant antistatic thermoplastic elastomer material provided by the comparative example is prepared from the following raw materials in parts by weight:
the preparation method of the low-temperature-resistant antistatic thermoplastic elastomer material provided by the comparative example comprises the following steps:
(1) Uniformly mixing the E-MAH copolymer and the multi-wall carbon nano tube, adding the mixture into a double-screw extruder, extruding, cooling and granulating to obtain master batch; extruder aspect ratio L/d=40: 1, the screw speed of the extruder is 350rpm, screw sections and head temperatures of 70, 150, 170, 180 180, 180/175 ℃;
(2) The master batch, the TPE components (SEBS, PP and white oil), the antioxidant and the lubricant are uniformly mixed, and are added into a double-screw extruder, and the low-temperature-resistant antistatic thermoplastic elastomer material is obtained through melt mixing extrusion, cooling and granulation at 180-210 ℃. Extruder aspect ratio L/d=44: 1, the screw speed of the extruder is 350rpm, screw sections and head temperatures of 180, 190, 200 200, 210, 200, 190/190 ℃.
Comparative example 3
The low-temperature-resistant antistatic thermoplastic elastomer material provided by the comparative example is prepared from the following raw materials in parts by weight:
component (A) | Parts by weight of |
SEBS | 40 |
PP | 15 |
White oil | 45 |
Multiwall carbon nanotubes | 8 |
Antioxidant | 0.2 |
Lubricant | 0.6 |
The preparation method of the low-temperature-resistant antistatic thermoplastic elastomer material provided by the comparative example comprises the following steps:
uniformly mixing the multi-wall carbon nano tube with TPE components (SEBS, PP and white oil), an antioxidant and a lubricant, adding into a double-screw extruder, and carrying out melt mixing extrusion, cooling and granulation at 180-210 ℃ to obtain the low-temperature-resistant antistatic thermoplastic elastomer material. Extruder aspect ratio L/d=44: 1, the screw speed of the extruder is 350rpm, screw sections and head temperatures of 180, 190, 200 200, 210, 200, 190/190 ℃.
Comparative example 4
The low-temperature-resistant antistatic thermoplastic elastomer material provided by the comparative example is prepared from the following raw materials in parts by weight:
the preparation method of the low-temperature-resistant antistatic thermoplastic elastomer material provided by the comparative example comprises the following steps:
(1) Uniformly mixing SEBS-g-MAH, MAH-g-PP and multi-wall carbon nanotubes, adding into a double-screw extruder, extruding, cooling and granulating to obtain master batch; extruder aspect ratio L/d=40: 1, the screw speed of the extruder is 350rpm, screw sections and head temperatures of 70, 150, 170, 180 180, 180/175 ℃;
(2) The master batch, the TPE components (SEBS, PP and white oil), the antioxidant and the lubricant are uniformly mixed, and are added into a double-screw extruder, and the low-temperature-resistant antistatic thermoplastic elastomer material is obtained through melt mixing extrusion, cooling and granulation at 180-210 ℃. Extruder aspect ratio L/d=44: 1, the screw speed of the extruder is 350rpm, screw sections and head temperatures of 180, 190, 200 200, 210, 200, 190/190 ℃.
Comparative example 5
The low-temperature-resistant antistatic thermoplastic elastomer material provided by the comparative example is prepared from the following raw materials in parts by weight:
component (A) | Parts by weight of |
SEBS | 40 |
PP | 15 |
White oil | 45 |
POE-g-MAH | 10 |
E-MAH copolymer | 5 |
Multiwall carbon nanotubes | 3 |
Antioxidant | 0.2 |
Lubricant | 0.6 |
The preparation method of the low-temperature-resistant antistatic thermoplastic elastomer material provided by the comparative example comprises the following steps:
(1) Uniformly mixing POE-g-MAH, E-MAH copolymer and multi-wall carbon nano tubes, adding into a double-screw extruder, extruding, cooling and granulating to obtain master batch; extruder aspect ratio L/d=40: 1, the screw speed of the extruder is 350rpm, screw sections and head temperatures of 70, 150, 170, 180 180, 180/175 ℃;
(2) The master batch, the TPE components (SEBS, PP and white oil), the antioxidant and the lubricant are uniformly mixed, and are added into a double-screw extruder, and the low-temperature-resistant antistatic thermoplastic elastomer material is obtained through melt mixing extrusion, cooling and granulation at 180-210 ℃. Extruder aspect ratio L/d=44: 1, the screw speed of the extruder is 350rpm, screw sections and head temperatures of 180, 190, 200 200, 210, 200, 190/190 ℃.
Comparative example 6
The low-temperature-resistant antistatic thermoplastic elastomer material provided by the comparative example is prepared from the following raw materials in parts by weight:
component (A) | Parts by weight of |
SEBS | 30 |
PP | 50 |
White oil | 20 |
SEBS-g-MAH | 10 |
E-MAH copolymer | 5 |
Multiwall carbon nanotubes | 8 |
Antioxidant | 0.2 |
Lubricant | 0.6 |
The preparation method of the low-temperature-resistant antistatic thermoplastic elastomer material provided by the comparative example comprises the following steps:
(1) Uniformly mixing SEBS-g-MAH, E-MAH copolymer and multi-wall carbon nano tubes, adding into a double-screw extruder, extruding, cooling and granulating to obtain master batch; extruder aspect ratio L/d=40: 1, the screw speed of the extruder is 350rpm, screw sections and head temperatures of 70, 150, 170, 180 180, 180/175 ℃;
(2) The master batch, the TPE components (SEBS, PP and white oil), the antioxidant and the lubricant are uniformly mixed, and are added into a double-screw extruder, and the low-temperature-resistant antistatic thermoplastic elastomer material is obtained through melt mixing extrusion, cooling and granulation at 180-210 ℃. Extruder aspect ratio L/d=44: 1, the screw speed of the extruder is 350rpm, screw sections and head temperatures of 180, 190, 200 200, 210, 200, 190/190 ℃.
The raw material compositions (parts by weight) of the low temperature resistant antistatic thermoplastic elastomer materials of examples 1 to 9 and comparative examples 1 to 5 are shown in the following table.
Note that: a, replacing the E-MAH copolymer with 5 parts of MAH-g-PP in comparative example 4; b: in comparative example 5, 10 parts of POE-g-MAH were used instead of SEBS-g-MAH.
The results of the performance test of the low temperature resistant antistatic thermoplastic elastomer materials of examples 1 to 9 and comparative examples 1 to 5 are shown in the following table.
Shore hardness/Shore A | Surface resistivity/Ω | Low temperature brittleness/-60 DEG C | |
Test standard | GB/T 531-2008 | GB/T 1410-2006 | GB/T 15256-2014 |
Example 1 | 58 | 10 8 | No crack |
Example 2 | 59 | 10 8 | No crack |
Example 3 | 57 | 10 8 | No crack |
Example 4 | 58 | 10 8 | No crack |
Example 5 | 57 | 10 9 | No crack |
Example 6 | 59 | 10 8 | No crack |
Example 7 | 61 | 10 7 | No crack |
Example 8 | 57 | 10 8 | No crack |
Example 9 | 59 | 10 9 | No crack |
Comparative example 1 | 53 | 10 9 | No crack |
Comparative example 2 | 63 | 10 9 | No crack |
Comparative example 3 | 50 | 10 10 | No crack |
Comparative example 4 | 58 | 10 9 | No crack |
Comparative example 5 | 59 | 10 9 | No crack |
Comparative example 6 | 85 | 10 8 | With cracks |
As can be seen from the performance test results of the above examples and comparative examples, the carbon nanotubes can be well dispersed in the TPE matrix resin by adding the SEBS-g-MAH and the ethylene-maleic anhydride copolymer E-MAH with specific grafting rates, so that the prepared thermoplastic elastomer material has excellent antistatic performance while having low temperature resistance.
In comparison with example 3 and example 6, the carbon nanotubes are poorly dispersed in the matrix resin without the addition of SEBS-g-MAH and E-MAH copolymers, and may agglomerate and fail to form continuous conductive paths, thereby resulting in a thermoplastic elastomer material having a higher surface resistivity. Comparative examples 2 and 3 were compared with example 6, in which only a single SEBS-g-MAH or E-MAH copolymer was added, the dispersibility of the carbon nanotubes in the matrix resin was inferior to that of example 6, and the surface resistivity of the material was higher than that of example 6. Therefore, the cooperation of the SEBS-g-MAH and the E-MAH copolymer can play a synergistic role, and the dispersibility of the carbon nano tube in the matrix resin can be more effectively improved compared with the single SEBS-g-MAH or E-MAH copolymer, so that the antistatic performance of the obtained thermoplastic elastomer material is more effectively improved.
Comparative example 4 compared with example 6, the substitution of PP-g-MAH for the E-MAH copolymer of example 6 resulted in poor dispersion of the carbon nanotubes in the matrix resin compared with example 6, and higher surface resistivity of the material compared with example 6. Comparative example 5 compared with example 6, replacing SEBS-g-MAH in example 6 with POE-g-MAH, the dispersion of carbon nanotubes in the matrix resin was inferior to that of example 6, and the surface resistivity of the material was higher than that of example 6. Therefore, the compatibility of the SEBS-g-MAH and the E-MAH copolymer can more effectively improve the dispersibility of the carbon nano tube in the matrix resin compared with other compatilizers, thereby more effectively improving the antistatic performance of the obtained thermoplastic elastomer material.
Comparative example 6 compared with example 6, the proportions of SEBS, PP and white oil are different, so that the hardness of the composite material is higher, the low temperature resistance of the composite material is affected, cracks appear on the surface when a low temperature brittleness test at-60 ℃ is carried out, and the low temperature performance of the composite material is poor under the condition of the proportion.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (7)
1. The low-temperature-resistant antistatic thermoplastic elastomer material is characterized by being prepared from the following raw materials in parts by weight:
the thermoplastic elastomer consists of a hydrogenated (styrene-butadiene-styrene) block copolymer, polypropylene and white oil.
2. The low temperature resistant antistatic thermoplastic elastomer material according to claim 1, which is characterized by being prepared from the following raw materials in parts by weight:
3. the low temperature resistant antistatic thermoplastic elastomer material according to claim 1, wherein the thermoplastic elastomer is composed of the following components in parts by weight: 37-48 parts of hydrogenated (styrene-butadiene-styrene) block copolymer, 7-18 parts of polypropylene and 43-53 parts of white oil.
4. A low temperature resistant antistatic thermoplastic elastomer material according to claim 3, wherein the thermoplastic elastomer consists of the following components in parts by weight: 40 parts of hydrogenated (styrene-butadiene-styrene) block copolymer, 15 parts of polypropylene and 45 parts of white oil.
5. The low temperature resistant antistatic thermoplastic elastomer material according to any one of claims 1 to 4, wherein the grafting ratio of maleic anhydride of SEBS-g-MAH is 1wt% to 2wt%; and/or the E-MAH copolymer is a copolymer of ethylene-maleic anhydride, wherein the content of the maleic anhydride is 78wt%.
6. The low temperature resistant antistatic thermoplastic elastomer material according to claim 1, wherein a 10wt% toluene solution of the hydrogenated (styrene-butadiene-styrene) block copolymer has a viscosity ∈ of 1000mpa.s at 25 ℃; and/or the number of the groups of groups,
the polypropylene is random polypropylene, and the melt index of the polypropylene under the test condition of 230 ℃/2.16kg is 11-20 g/10min; and/or the number of the groups of groups,
the white oil is paraffin-based white oil, and the kinematic viscosity of the white oil at 40 ℃ is 25-90cSt; and/or the number of the groups of groups,
the carbon nanotubes are multi-wall carbon nanotubes; and/or the number of the groups of groups,
the antioxidant is at least one selected from pentaerythritol distearyl diphosphate, tris- (nonylphenyl) phosphite and phenyl tris (2, 4-di-tert-butyl) phosphite;
the lubricant is selected from erucamide and/or oleamide.
7. A method for preparing a low temperature resistant antistatic thermoplastic elastomer material according to any one of claims 1 to 6, comprising the steps of:
(1) Uniformly mixing the SEBS-g-MAH, E-MAH copolymer and the carbon nano tube, adding the mixture into a double-screw extruder, extruding, cooling and granulating to obtain master batch;
(2) And (3) uniformly mixing the master batch, the thermoplastic elastomer, the antioxidant and the lubricant, adding the mixture into a double-screw extruder, and obtaining the low-temperature-resistant antistatic thermoplastic elastomer material through melting, extrusion, cooling and granulation.
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