CN115141480A - Antistatic thermoplastic polyurethane and preparation method and application thereof - Google Patents
Antistatic thermoplastic polyurethane and preparation method and application thereof Download PDFInfo
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- CN115141480A CN115141480A CN202210785287.8A CN202210785287A CN115141480A CN 115141480 A CN115141480 A CN 115141480A CN 202210785287 A CN202210785287 A CN 202210785287A CN 115141480 A CN115141480 A CN 115141480A
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- thermoplastic polyurethane
- antistatic
- ionic liquid
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- 239000004433 Thermoplastic polyurethane Substances 0.000 title claims abstract description 131
- 229920002803 thermoplastic polyurethane Polymers 0.000 title claims abstract description 131
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 153
- 239000002608 ionic liquid Substances 0.000 claims abstract description 60
- 229920000728 polyester Polymers 0.000 claims abstract description 58
- 238000002156 mixing Methods 0.000 claims abstract description 8
- -1 dicyandiamide ion Chemical group 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 10
- 238000001125 extrusion Methods 0.000 claims description 9
- 238000005469 granulation Methods 0.000 claims description 9
- 230000003179 granulation Effects 0.000 claims description 9
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical group [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 claims description 7
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical group [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 4
- 229940006460 bromide ion Drugs 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- HDXFBBSZRMZTFF-UHFFFAOYSA-N 1-methyl-3-pentyl-2h-imidazole Chemical compound CCCCCN1CN(C)C=C1 HDXFBBSZRMZTFF-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- DBAYTBHFIAGLLO-UHFFFAOYSA-N 1-methyl-3-nonyl-2h-imidazole Chemical compound CCCCCCCCCN1CN(C)C=C1 DBAYTBHFIAGLLO-UHFFFAOYSA-N 0.000 claims description 2
- FIOYZGZRZWNKTB-UHFFFAOYSA-N 1-methyl-3-tetradecyl-2h-imidazole Chemical compound CCCCCCCCCCCCCCN1CN(C)C=C1 FIOYZGZRZWNKTB-UHFFFAOYSA-N 0.000 claims description 2
- HXZXMPPOBOILQK-UHFFFAOYSA-N CCCCCN1C=CN(C)C1.N#CS Chemical compound CCCCCN1C=CN(C)C1.N#CS HXZXMPPOBOILQK-UHFFFAOYSA-N 0.000 claims description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 21
- 239000002216 antistatic agent Substances 0.000 abstract description 12
- 239000002861 polymer material Substances 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 17
- 238000012360 testing method Methods 0.000 description 9
- 229920001971 elastomer Polymers 0.000 description 7
- 239000008188 pellet Substances 0.000 description 7
- 238000010998 test method Methods 0.000 description 7
- 239000000806 elastomer Substances 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000008187 granular material Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000011231 conductive filler Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- FRDMOHWOUFAYLD-UHFFFAOYSA-N 1-methyl-3-nonylimidazol-1-ium Chemical compound CCCCCCCCCN1C=C[N+](C)=C1 FRDMOHWOUFAYLD-UHFFFAOYSA-N 0.000 description 1
- LSFWFJFDPRFPBK-UHFFFAOYSA-N 1-methyl-3-pentylimidazol-1-ium Chemical compound CCCCCN1C=C[N+](C)=C1 LSFWFJFDPRFPBK-UHFFFAOYSA-N 0.000 description 1
- PXFKRXXEFJDOMO-UHFFFAOYSA-M 1-methyl-3-pentylimidazol-1-ium;bromide Chemical compound [Br-].CCCCC[N+]=1C=CN(C)C=1 PXFKRXXEFJDOMO-UHFFFAOYSA-M 0.000 description 1
- PBNUQTNCQMKXBF-UHFFFAOYSA-M 1-methyl-3-pentylimidazol-1-ium;thiocyanate Chemical compound [S-]C#N.CCCCCN1C=C[N+](C)=C1 PBNUQTNCQMKXBF-UHFFFAOYSA-M 0.000 description 1
- BMKLRPQTYXVGNK-UHFFFAOYSA-N 1-methyl-3-tetradecylimidazol-1-ium Chemical compound CCCCCCCCCCCCCCN1C=C[N+](C)=C1 BMKLRPQTYXVGNK-UHFFFAOYSA-N 0.000 description 1
- 101100481028 Arabidopsis thaliana TGA2 gene Proteins 0.000 description 1
- OKNYKSQQHXWKRK-UHFFFAOYSA-N C(#N)[N-]C#N.C[N+]1=CN(C=C1)CCCCC Chemical compound C(#N)[N-]C#N.C[N+]1=CN(C=C1)CCCCC OKNYKSQQHXWKRK-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000006069 physical mixture Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3445—Five-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-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
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/372—Sulfides, e.g. R-(S)x-R'
- C08K5/3725—Sulfides, e.g. R-(S)x-R' containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/43—Compounds containing sulfur bound to nitrogen
- C08K5/435—Sulfonamides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses antistatic thermoplastic polyurethane and a preparation method and application thereof. The preparation method of the antistatic thermoplastic polyurethane comprises the following steps: mixing the imidazole ionic liquid and the polyester thermoplastic polyurethane, extruding and granulating. The antistatic thermoplastic polyurethane disclosed by the invention has the advantages of good antistatic property, good antistatic durability, good washability and small influence on the mechanical property of a high polymer material after an antistatic agent is added, and further can realize the effects of small addition amount of the antistatic agent, low cost and small influence on the antistatic effect by the environmental humidity; meanwhile, the preparation method of the antistatic thermoplastic polyurethane is simple.
Description
Technical Field
The invention relates to antistatic thermoplastic polyurethane and a preparation method and application thereof.
Background
The polyester type Thermoplastic Polyurethane (TPU) is obtained by the stepwise addition polymerization reaction of polyester diol serving as polyol, diisocyanate and micromolecular diol serving as a chain extender,the rubber has the advantages of high mechanical strength, good thermal stability, good wear resistance, oxidation resistance and the like, and is widely applied to the aspects of soles, conveyor belts, mechanical sealing elements, automobile parts, medical devices and the like. However, polyester type Thermoplastic Polyurethane (TPU) has high electrical insulation property and volume resistivity as high as 10, like most high molecular materials 12 Omega m is liable to form static charge accumulation during use to generate discharge, and may even cause fire to cause serious loss of life and property. Therefore, the polyester TPU elastomer has important practical significance in the antistatic property.
Currently, to improve the antistatic properties of polyester type TPU elastomers, the addition of antistatic agents is the most used and most effective method. There are two kinds of common antistatic additives, one is conductive filler, such as carbon black, metal, graphite, etc., and the addition of the conductive filler to the polyester type TPU elastomer can improve the antistatic performance, but the addition amount needs to be as high as more than 30wt% of the polyester type TPU elastomer, and there are problems of high cost, large influence on the mechanical strength performance of the polyester type TPU elastomer, etc. The other is a high molecular permanent antistatic agent, for example, antistatic polyether glycol prepared from sodium perchlorate and polyethylene glycol, which is added into polyester TPU elastomer, has the advantages of good antistatic durability, good washing fastness, small influence of environmental humidity on antistatic effect and the like, but still has the defects of high cost and large influence on the mechanical property of high molecular materials.
Therefore, it is highly desirable to provide an antistatic thermoplastic polyurethane which can simultaneously realize small addition amount of an antistatic agent, low cost, small influence on the mechanical properties of a polymer material, difficult migration of the antistatic agent to the surface of the polymer material, good antistatic durability, good washing fastness and small influence of environmental humidity on the antistatic effect.
Disclosure of Invention
The invention aims to solve the problems that in the prior art, antistatic thermoplastic polyurethane has the defects of more antistatic agent addition amount, high cost, poor antistatic durability, washability and large influence of an antistatic effect on environmental humidity and mechanical properties of a high polymer material after the antistatic agent is added, and provides the antistatic thermoplastic polyurethane and the preparation method and application thereof. The antistatic thermoplastic polyurethane disclosed by the invention has the advantages of good antistatic property, good antistatic durability, good washability and small influence on the mechanical property of a high polymer material after an antistatic agent is added, and further can realize the effects of small addition amount of the antistatic agent, low cost and small influence on the antistatic effect by the environmental humidity; meanwhile, the preparation method of the antistatic thermoplastic polyurethane is simple.
In order to achieve the above object, the present invention provides the following technical solutions:
one of the technical schemes provided by the invention is as follows: a preparation method of antistatic thermoplastic polyurethane. The preparation method comprises the following steps: mixing the imidazole ionic liquid and the polyester thermoplastic polyurethane, extruding and granulating;
wherein the imidazole ionic liquid is shown as a formula (I):
in the formula (I), n is 1-14; x is bromide ion, thiocyanate ion, dicyandiamide ion or bis (trifluoromethyl) sulfimide ion.
In the invention, the dosage of the imidazole ionic liquid can be 0.5wt% -20 wt%, preferably 0.5wt% -10 wt%, more preferably 0.5wt% -2 wt%, and further preferably 1wt% -1.5 wt%; the percentage is the mass percentage of the imidazole ionic liquid in the polyester type thermoplastic polyurethane.
In the present invention, in the formula (I), n is preferably 3 to 10, more preferably 5 to 9, for example 7.
In the invention, in the formula (I), C n H 2n+1 Is in a straight chain structure.
In the present invention, in formula (I), the cation may be a 1-alkyl-3-methylimidazolium cation; preferably a 1-pentyl-3-methylimidazolium cation, or alternatively a 1-nonyl-3-methylimidazolium cation, or alternatively a 1-tetradecyl-3-methylimidazolium cation.
In the present invention, in formula (I), the anion may be X, and X is as defined above.
In the invention, the imidazole ionic liquid is preferably as follows
Among them, the ionic liquids represented by the formulae (II) to (V) are preferably 1-alkyl-3-methylimidazolium bromide, 1-alkyl-3-methylimidazolium thiocyanate, 1-alkyl-3-methylimidazolium dicyanamide salt, and 1-alkyl-3-methylimidazolium bistrifluoromethylsulfonyl imide salt, respectively. Among them, the alkyl group preferably has a linear structure.
In the invention, the imidazole ionic liquid is more preferably as
Among them, preferred ionic liquids represented by the formulae (VI) to (XI) are 1-pentyl-3-methylimidazolium bromide, 1-pentyl-3-methylimidazolium thiocyanate, 1-pentyl-3-methylimidazolium dicyanamide salt, 1-pentyl-3-methylimidazolium bistrifluoromethylsulfonyl imide salt, 1-nonyl-3-methylimidazolium bistrifluoromethylsulfonyl imide salt, and 1-tetradecyl-3-methylimidazolium bistrifluoromethylsulfonyl imide salt, respectively. Among them, pentyl group, nonyl group and tetradecyl group are each preferably a straight chain structure as is conventional in the art.
In the present invention, the polyester type thermoplastic polyurethane may be a polymer compound which is conventional in the art, and is generally obtained by the following method: the dibasic acid reacts with excessive polyol to prepare hydroxyl-containing polyester serving as a hydroxyl component, and then the hydroxyl-containing polyester reacts with diisocyanate or polyisocyanate to obtain the polyester.
In the present invention, the polyester-based thermoplastic polyurethane is preferably a dried polyester-based thermoplastic polyurethane; for example, polyester type thermoplastic polyurethane obtained after drying for 4 hours under vacuum condition at 100 ℃.
In the invention, the mixing can be conventional in the field, and the imidazole ionic liquid and the polyester thermoplastic polyurethane are preferably uniformly mixed.
In the invention, after the mixing, the ionic liquid/polyester type thermoplastic polyurethane granules, namely the physical mixture of the ionic liquid and the polyester type TPU, can be obtained.
In the present invention, the extrusion granulation method may be conventional in the art, for example, twin-screw extrusion granulation.
In the invention, the temperature of the extrusion granulation can be conventional in the field, and is preferably 160-220 ℃; more preferably 160 ℃ to 190 ℃; for example 170 deg.C, 180 deg.C or 185 deg.C. Generally, the temperature of the extrusion granulation refers to the temperature of 1-10 sections of a double-screw extruder and the temperature of a machine head; wherein, the sections 1-10 of the double-screw extruder can be a conveying section, a melting section, a mixing section, an exhaust section, a homogenizing section and the like of the double-screw extruder which is conventional in the field. Preferably, the temperatures of the 1-10 sections of the double-screw extruder are 160 ℃, 170 ℃, 180 ℃, 185 ℃, 190 ℃ and 190 ℃ respectively; the head temperature of the twin-screw extruder was 190 ℃.
In the present invention, the extrusion granulation equipment may be conventional in the art, and is preferably a twin-screw extruder.
Wherein the rotation speed of the main machine screw of the double-screw extruder can be conventional in the field, such as 200-400 rpm, and 300rpm is preferred.
The feeding speed of the twin-screw extruder may be conventional in the art, for example, 20 to 30rpm, preferably 25rpm.
The second technical scheme provided by the invention is as follows: an antistatic thermoplastic polyurethane. The antistatic thermoplastic polyurethane is prepared by the preparation method of the antistatic thermoplastic polyurethane.
The third technical scheme provided by the invention is as follows: an antistatic thermoplastic polyurethane. The antistatic thermoplastic polyurethane comprises imidazole ionic liquid and polyester thermoplastic polyurethane;
wherein the imidazole ionic liquid is shown as a formula (I):
in the formula (I), n is 1-14; x is bromide ion, thiocyanate ion, dicyandiamide ion or bis (trifluoromethyl) sulfimide ion.
In the invention, the mass ratio of the imidazole ionic liquid to the polyester thermoplastic polyurethane can be (0.5-20): 100, respectively; preferably (1 to 10): 100.
in the invention, the imidazole ionic liquid and the polyester thermoplastic polyurethane are as described above.
The fourth technical scheme provided by the invention is as follows: an antistatic thermoplastic polyurethane is used as raw material for mechanical sealing parts, automobile parts or medical devices.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
(1) The antistatic thermoplastic polyurethane of the present invention is excellent in antistatic properties and has an initial surface resistivity of 7.08X 10 9 Ω～4.12×10 11 Ω, initial volume resistivity of 2.65X 10 7 Ω·m～2.41×10 8 Ω·m；
(2) The antistatic thermoplastic polyurethane of the invention has good antistatic durability, and the surface resistivity after being placed for 40 days is 7.50 multiplied by 10 9 Ω～8.17×10 10 Omega, volume resistivity after standing for 40 days is 8.45X 10 6 Ω·m～1.55×10 8 Ω·m；
(3) The antistatic thermoplastic polyurethane of the invention has good antistatic washfastness, and the surface resistivity after being washed by methanol is 5.34 multiplied by 10 9 Ω～8.01×10 10 Ω, volume resistivity after methanol washing was 9.51X 10 6 Ω·m～6.97×10 8 Ω·m；
(4) The antistatic thermoplastic polyurethane has good thermal stability, and compared with thermoplastic polyurethane, the initial decomposition temperature is only within 28 ℃;
(5) Furthermore, after the antistatic agent (namely the ionic liquid) is added, the mechanical properties (tensile strength and elongation at break) of the high polymer material are slightly influenced, and the mechanical properties of the antistatic thermoplastic polyurethane are basically equivalent to those of the thermoplastic polyurethane; moreover, the antistatic effect of the antistatic thermoplastic polyurethane is less influenced by the environmental humidity, and the effects of less addition of the antistatic agent and low cost can be further realized; meanwhile, the preparation method of the antistatic thermoplastic polyurethane is simple.
Drawings
FIG. 1 is a flow chart of the process for preparing the antistatic thermoplastic polyurethane of examples 1 to 7.
FIG. 2 is a graph comparing the thermogravimetric curves of the antistatic thermoplastic polyurethanes of examples 1,3-7 and the thermoplastic polyurethane of comparative example 1.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
The flow chart of the preparation method of the antistatic thermoplastic polyurethane in the following examples 1-7 is shown in figure 1.
Example 1
The preparation method of the antistatic thermoplastic polyurethane comprises the following steps:
(1) Putting the polyester type thermoplastic polyurethane granules into a vacuum oven at the temperature of 100 ℃ for drying for 4h;
(2) Imidazole ionic liquid 1-amyl-3-methylimidazole bistrifluoromethylsulfonyl imide salt ([ C) 5 mim][Tf 2 N]) And (2) the polyester type thermoplastic polyurethane obtained in the step (1) are evenly mixed to obtain [ C ] 5 mim][Tf 2 N]Polyester type thermoplastic polyurethane pellets;
wherein, the imidazole ionic liquid is shown as a formula (IX):
in the formula (IX), C 5 H 11 Is a straight chain structure;
wherein the dosage of the imidazole ionic liquid is 1.0wt%, and the percentage is the mass percentage of the imidazole ionic liquid in the polyester type thermoplastic polyurethane;
(3) Will [ C ] 5 mim][Tf 2 N]The polyester type thermoplastic polyurethane granules are extruded, blended and granulated through a double-screw extruder to obtain antistatic thermoplastic polyurethane;
wherein, in the process of extruding and granulating, the rotating speed of a main machine screw of the double-screw extruder is 300rpm; the feeding speed is 25rpm; the temperatures of the first to the tenth sections of the double-screw extruder are respectively 160 ℃, 170 ℃, 180 ℃, 185 ℃, 190 ℃ and 190 ℃, and the head temperature is 190 ℃.
Example 2
The preparation method of the antistatic thermoplastic polyurethane comprises the following steps:
(1) The same as example 1;
(2) Imidazole ionic liquid 1-amyl-3-methylimidazole bistrifluoromethylsulfonyl imide salt [ C 5 mim][Tf 2 N]And (2) the polyester type thermoplastic polyurethane obtained in the step (1) are evenly mixed to obtain [ C ] 5 mim][Tf 2 N]Polyester type thermoplastic polyurethane pellets;
wherein, the imidazole ionic liquid is shown as a formula (IX):
in the formula (IX), C 5 H 11 Is a straight chain structure;
wherein the dosage of the imidazole ionic liquid is 1.5wt%, and the percentage is the mass percentage of the imidazole ionic liquid in the polyester thermoplastic polyurethane;
(3) The same as in example 1.
Example 3
The preparation method of the antistatic thermoplastic polyurethane comprises the following steps:
(1) The same as example 1;
(2) Imidazole ionic liquid 1-nonyl-3-methylimidazole bistrifluoromethylsulfonyl imide salt ([ C) 9 mim][Tf 2 N]) And the polyester type thermoplastic polyurethane obtained in the step (1) are evenly mixed to obtain [ C ] 9 mim][Tf 2 N]Polyester type thermoplastic polyurethane pellets;
wherein, the imidazole ionic liquid is shown as a formula (X):
in the formula (X), C 9 H 19 Is a straight chain structure;
wherein the dosage of the imidazole ionic liquid is 1.0wt%, and the percentage is the mass percentage of the imidazole ionic liquid in the polyester thermoplastic polyurethane;
(3) The same as in example 1.
Example 4
(1) The same as example 1;
(2) 1-tetradecyl-3-methylimidazole bistrifluoromethylsulfonyl imide salt ([ C ] of imidazole ionic liquid 14 mim][Tf 2 N]) And (2) the polyester type thermoplastic polyurethane obtained in the step (1) are evenly mixed to obtain [ C ] 14 mim][Tf 2 N]Polyester type thermoplastic polyurethane pellets;
wherein, the imidazole ionic liquid is shown as a formula (XI):
in the formula (XI), C 14 H 29 Is a straight chain structure;
wherein the dosage of the imidazole ionic liquid is 1.0wt%, and the percentage is the mass percentage of the imidazole ionic liquid in the polyester thermoplastic polyurethane;
(3) The same as in example 1.
Example 5
The preparation method of the antistatic thermoplastic polyurethane comprises the following steps:
(1) The same as example 1;
(2) Imidazole ionic liquid 1-amyl-3-methylimidazole bromine salt ([ C ] 5 mim]Br) and the polyester type thermoplastic polyurethane obtained in the step (1) are evenly mixed to obtain [ C ] 5 mim]Br/polyester type thermoplastic polyurethane pellets;
wherein, the imidazole ionic liquid is shown as a formula (VI):
in the formula (VI), C 5 H 11 Is a straight chain structure;
wherein the dosage of the imidazole ionic liquid is 1.0wt%, and the percentage is the mass percentage of the imidazole ionic liquid in the polyester type thermoplastic polyurethane;
(3) The same as in example 1.
Example 6
The preparation method of the antistatic thermoplastic polyurethane comprises the following steps:
(1) The same as example 1;
(2) Imidazole ionic liquid 1-amyl-3-methylimidazole thiocyanate ([ C ] 5 mim]SCN) and the polyester type thermoplastic polyurethane obtained in the step (1) are evenly mixed to obtain [ C ] 5 mim]SCN/polyester type thermoplastic polyurethane pellets;
wherein, the imidazole ionic liquid is shown as a formula (VII):
in the formula (VII), C 5 H 11 Is a straight chain structure;
wherein the dosage of the imidazole ionic liquid is 1.0wt%, and the percentage is the mass percentage of the imidazole ionic liquid in the polyester thermoplastic polyurethane;
(3) The same as in example 1.
Example 7
The preparation method of the antistatic thermoplastic polyurethane comprises the following steps:
(1) The same as example 1;
(2) Imidazole ionic liquid 1-amyl-3-methylimidazole dicyandiamide salt ([ C ] 5 mim][DCA]) And (2) the polyester type thermoplastic polyurethane obtained in the step (1) are evenly mixed to obtain [ C ] 5 mim][DCA]Polyester type thermoplastic polyurethane pellets;
wherein, the imidazole ionic liquid is shown as a formula (VIII):
in the formula (VIII), C 5 H 11 Is a straight chain structure;
wherein the dosage of the imidazole ionic liquid is 1.0wt%, and the percentage is the mass percentage of the imidazole ionic liquid in the polyester thermoplastic polyurethane;
(3) The same as in example 1.
Comparative example 1
The preparation method of the thermoplastic polyurethane comprises the following steps:
(1) The same as example 1;
(2) Extruding, blending and granulating the polyester type thermoplastic polyurethane obtained in the step (1) through a double-screw extruder to obtain thermoplastic polyurethane;
wherein, the parameter conditions in the process of extrusion granulation are the same as those of the examples 1 to 4; namely: the rotating speed of a main machine screw of the double-screw extruder is 300rpm; the feeding speed is 25rpm; the temperatures of the first to the tenth sections of the double-screw extruder are respectively 160 ℃, 170 ℃, 180 ℃, 185 ℃, 190 ℃ and 190 ℃, and the head temperature is 190 ℃.
Effect example 1 antistatic Effect and antistatic durability Effect
The antistatic thermoplastic polyurethanes of examples 1 to 7 and, in comparative example 1, the surface resistivity and the volume resistivity of the thermoplastic polyurethane were tested:
respectively preparing templates for testing antistatic performance by an injection molding machine for the antistatic thermoplastic polyurethane obtained in the embodiments 1-7 and the thermoplastic polyurethane obtained in the comparative example 1; wherein the temperatures of the sections 1-3 of the injection molding machine are 180 ℃, 190 ℃ and 180 ℃, and the temperature of an injection molding opening is 170 ℃.
(1) The initial surface resistivity and initial volume resistivity of the sample plates were measured by the test method in GB/T1410-2006 test method for volume resistivity and surface resistivity of solid insulating materials, using ZC36 type high resistance meter test equipment, and the results are shown in Table 1 below.
(2) The sample plate is placed for 40 days, and according to the test method in GB/T1410-2006 test method for volume resistivity and surface resistivity of solid insulating materials, ZC36 type high resistance meter test equipment is adopted to test the surface resistivity of the sample plate after the sample plate is placed for 40 days and the volume resistivity of the sample plate after the sample plate is placed for 40 days, and the results are shown in the following table 1.
TABLE 1 surface and volume resistivities initially and after 40 days of standing
| Initial surface resistivity | Surface resistivity after 40 days | Initial volume resistivity | Volume resistivity after 40 days | |
| Example 1 | 5.26×10 10 Ω | 5.66×10 10 Ω | 1.24×10 8 Ω·m | 1.58×10 7 Ω·m |
| Example 2 | 7.08×10 9 Ω | 7.50×10 9 Ω | 3.26×10 7 Ω·m | 9.24×10 6 Ω·m |
| Example 3 | 1.58×10 10 Ω | 2.01×10 10 Ω | 3.76×10 7 Ω·m | 9.56×10 6 Ω·m |
| Example 4 | 3.17×10 10 Ω | 3.58×10 10 Ω | 2.65×10 7 Ω·m | 8.45×10 6 Ω·m |
| Example 5 | 4.12×10 11 Ω | 8.17×10 10 Ω | 2.41×10 8 Ω·m | 1.55×10 8 Ω·m |
| Example 6 | 2.54×10 11 Ω | 5.70×10 10 Ω | 5.79×10 7 Ω·m | 8.44×10 7 Ω·m |
| Example 7 | 9.03×10 10 Ω | 7.71×10 10 Ω | 3.36×10 7 Ω·m | 7.26×10 7 Ω·m |
| Comparative example 1 | 1.29×10 14 Ω | 9.82×10 13 Ω | 5.64×10 11 Ω·m | 1.58×10 11 Ω·m |
As can be seen from table 1, the initial surface resistivity and initial volume resistivity of the antistatic thermoplastic polyurethanes in examples 1 to 7 were significantly lower than those of comparative example 1 in which the imidazole-based ionic liquid was not added to the polyester-based thermoplastic polyurethane, and it can be seen that the antistatic thermoplastic polyurethanes in examples 1 to 7 had excellent antistatic properties. Wherein, in the ionic liquids of examples 1 to 4, the anions are all [ Tf 2 N]However, examples 3 to 4 are more excellent in antistatic effect than example 1 due to the difference in the chain length of the alkyl group in the cation.
Meanwhile, after the antistatic thermoplastic polyurethane in examples 1 to 7 was left to stand for 40 days, the surface resistivity and the volume resistivity were still low; moreover, compared with the initial surface resistivity and the initial volume resistivity, there is no significant difference, and the variation range is small, which shows that the antistatic thermoplastic polyurethane of examples 1 to 7 has good antistatic durability.
Effect example 2 antistatic washfastness Effect
Effects examples 1 to 7 of example 1 after being left for 40 days and the sample of comparative example 1 were sonicated in methanol for 10s, then freeze-dried overnight, then air-dried at 25 ℃ for 4h, and finally the surface resistivity and volume resistivity of the sample plate were measured using a ZC36 type high resistivity meter, the results of which are shown in Table 2.
TABLE 2 surface resistivity and volume resistivity after 40 days of standing and after methanol washing
As can be seen from Table 2, the test values of the sample plates after being washed with methanol were not much different from those before being washed without methanol, and it can be seen that the antistatic thermoplastic polyurethanes in examples 1 to 7 had excellent antistatic washfastness.
Effect example 3 thermal stabilization Effect
According to the test method in GB/T27761-2011 Experimental method for weight loss and residual amount of a thermogravimetric analyzer, TGA2 type thermogravimetric analyzer test equipment is adopted, nitrogen is used in the atmosphere, the flow is 50mL/min, the test temperature range is 30-600 ℃, the thermal weight loss curves of the antistatic thermoplastic polyurethanes of examples 1,3 to 7 and the thermoplastic polyurethane of comparative example 1 were measured at a temperature rise rate of 20 ℃/min, and the comparative graph is shown in FIG. 2.
FIG. 2 is a graph comparing the thermogravimetric curves of the antistatic thermoplastic polyurethanes of examples 1, 3-7 and the thermoplastic polyurethane of comparative example 1, wherein TPU1 is the thermogravimetric curve of the thermoplastic polyurethane of comparative example 1.
The initial decomposition temperatures of the antistatic thermoplastic polyurethanes of examples 1 and 3 to 7 and the thermoplastic polyurethane of comparative example 1 are shown in Table 3.
TABLE 3
| Initial decomposition temperature | |
| Example 1 | 305℃ |
| Example 3 | 300℃ |
| Example 4 | 306℃ |
| Example 5 | 284℃ |
| Example 6 | 305℃ |
| Example 7 | 279℃ |
| Comparative example 1 | 307℃ |
As can be seen from FIG. 2 and Table 3, the antistatic thermoplastic polyurethanes of examples 1 and 3 to 7 are less different in initial decomposition temperature than the polyester type thermoplastic polyurethane of comparative example 1, and thus it is demonstrated that the antistatic thermoplastic polyurethanes of examples 1 and 3 to 7 are excellent in heat-stabilizing effect.
Effect example 4 mechanical property test
The antistatic thermoplastic polyurethanes of examples 1 to 4 and the thermoplastic polyurethane of comparative example 1 were tested for tensile strength and elongation at break according to the test methods in GB/T1040-1992, test method for tensile Property of plastics, using a CMT-4000 type electronic Universal tester test apparatus, and the results are shown in Table 4 below.
TABLE 4
| Tensile Strength (MPa) | Elongation at Break (%) | |
| Example 1 | 27.74 | >936 |
| Example 2 | 28.67 | >936 |
| Example 3 | 27.81 | >936 |
| Example 4 | 29.09 | >936 |
| Comparative example 1 | 30.05 | >936 |
As can be seen from the above table, the tensile strength and elongation at break of the antistatic thermoplastic polyurethanes in examples 1 to 4 are less different than those of the thermoplastic polyurethane in comparative example 1. It can be seen that, in examples 1 to 4, the mechanical properties of the polymer material are less affected after the ionic liquid is added.
Claims (10)
1. The preparation method of the antistatic thermoplastic polyurethane is characterized by comprising the following steps: mixing the imidazole ionic liquid and the polyester thermoplastic polyurethane, extruding and granulating;
wherein the imidazole ionic liquid is shown as a formula (I):
in the formula (I), n is 1-14; x is bromide ion, thiocyanate ion, dicyandiamide ion or bistrifluoromethylsulfonyl imide ion.
2. The process for the preparation of antistatic thermoplastic polyurethanes according to claim 1, characterized in that the imidazole-based ionic liquids are used in an amount of 0.5 to 20% by weight, preferably 0.5 to 10% by weight, more preferably 0.5 to 2% by weight, even more preferably 1 to 1.5% by weight; the percentage is that the imidazole ionic liquid accounts for the mass percentage of the polyester thermoplastic polyurethane;
and/or, in formula (I), n is from 3 to 10, preferably from 5 to 9, for example 7;
and/or, in the formula (I), C n H 2n+1 Is in a straight chain structure.
3. The process for preparing antistatic thermoplastic polyurethanes as claimed in claim 1, wherein in the formula (I), the cation is a 1-alkyl-3-methylimidazolium cation; preferably a 1-pentyl-3-methylimidazolium cation, or alternatively a 1-nonyl-3-methylimidazolium cation, or alternatively a 1-tetradecyl-3-methylimidazolium cation.
4. The process for preparing antistatic thermoplastic polyurethane as claimed in claim 1 wherein the imidazole based ionic liquid is selected from the group consisting of
wherein the ionic liquids shown in the formulas (II) to (V) are respectively 1-alkyl-3-methylimidazole bromine salt, 1-alkyl-3-methylimidazole thiocyanate, 1-alkyl-3-methylimidazole dicyandiamide salt and 1-alkyl-3-methylimidazole bistrifluoromethylsulfonyl imide salt; among them, the alkyl group is preferably of a linear structure;
preferably, the imidazole ionic liquids are as follows
wherein the ionic liquids shown in the formulas (VI) to (XI) are respectively 1-pentyl-3-methylimidazole bromine salt, 1-pentyl-3-methylimidazole thiocyanate, 1-pentyl-3-methylimidazole dicyandiamide salt, 1-pentyl-3-methylimidazole bistrifluoromethylsulfonyl imide salt, 1-nonyl-3-methylimidazole bistrifluoromethylsulfonyl imide salt and 1-tetradecyl-3-methylimidazole bistrifluoromethylsulfonyl imide salt; among them, pentyl group, nonyl group and tetradecyl group are each preferably of a straight chain structure.
5. The method for preparing an antistatic thermoplastic polyurethane as claimed in claim 1, wherein the polyester type thermoplastic polyurethane is a dried polyester type thermoplastic polyurethane; for example, a polyester-type thermoplastic polyurethane obtained after drying for 4 hours at 100 ℃ under vacuum.
6. The method for preparing antistatic thermoplastic polyurethane as claimed in claim 1, wherein the mixing is to mix the imidazole-based ionic liquid and the polyester-based thermoplastic polyurethane uniformly.
7. The process for preparing antistatic thermoplastic polyurethanes as claimed in claim 1, wherein the extrusion granulation process is twin-screw extrusion granulation;
and/or the temperature of the extrusion granulation is 160-220 ℃; preferably 160-190 ℃; e.g., 170 ℃, 180 ℃ or 185 ℃;
and/or the equipment for extruding and granulating is a double-screw extruder;
wherein the main machine screw rotating speed of the double-screw extruder is preferably 200-400 rpm, and more preferably 300rpm; the feeding speed of the twin-screw extruder is preferably 20 to 30rpm, more preferably 25rpm.
8. Antistatic thermoplastic polyurethane, characterized in that it is obtained by the process for the preparation of antistatic thermoplastic polyurethane according to any one of claims 1 to 7.
9. The antistatic thermoplastic polyurethane is characterized by comprising imidazole ionic liquid and polyester thermoplastic polyurethane;
wherein the imidazole ionic liquid is shown as a formula (I):
in the formula (I), n is 1-14; x is bromide ion, thiocyanate ion, dicyandiamide ion or bis (trifluoromethyl) sulfimide ion;
the mass ratio of the imidazole ionic liquid to the polyester thermoplastic polyurethane is preferably (0.5-20): 100; more preferably (1 to 10): 100.
10. use of an antistatic thermoplastic polyurethane as claimed in claim 8 or 9 as a starting material in mechanical seals, automotive parts or medical devices.
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