CN111040111A - Antistatic thermoplastic polyurethane and preparation method thereof - Google Patents
Antistatic thermoplastic polyurethane and preparation method thereof Download PDFInfo
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- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
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Abstract
The invention discloses antistatic thermoplastic polyurethane and a preparation method thereof, and belongs to the technical field of polyurethane preparation. The method comprises the following steps: heating the polymer diol, preserving heat, and respectively heating the isocyanate and the chain extender to 40-90 ℃ for heat preservation; according to parts by weight, 20-80 parts of heat-preserved polymer dihydric alcohol, 1.5-8.5 parts of chain extender, 0.01-5 parts of modified carbon nano tube under the condition of room temperature, 0.001-0.5 part of catalyst, 0.1-8 parts of antioxidant, 0.1-8 parts of heat stabilizer and 0.1-5 parts of hydrolysis stabilizer are mixed and stirred uniformly, then heat-preserved isocyanate is poured into the mixture, and the mixture is stirred uniformly and then placed in a constant-temperature environment for curing to obtain the antistatic thermoplastic polyurethane. The invention uses the modified carbon nano tube containing active functional groups to generate in-situ polymerization reaction with polymer dihydric alcohol, isocyanate and the like to obtain the thermoplastic polyurethane with good antistatic property, and the preparation process is simpler and easier to apply.
Description
Technical Field
The invention relates to the technical field of polyurethane preparation, in particular to antistatic thermoplastic polyurethane and a preparation method thereof.
Background
Polyurethane is a high molecular synthetic material containing a large number of carbamate groups in molecules, is generally prepared by using polymer polyol as a soft segment, isocyanate and a micromolecular chain extender as a hard segment through a gradual addition polymerization reaction, and has excellent mechanical properties. However, the polyurethane has electrical insulation property, so that the application of the polyurethane in the fields of electronic communication, intelligent sensors and the like is limited.
At present, the common preparation method of antistatic thermoplastic polyurethane is to add an antistatic agent into polyurethane, and the antistatic agent comprises an ionic compound and a composite additive type antistatic agent, wherein the ionic compound is usually coated on the surface or blended into the polyurethane. Therefore, the introduction of a composite additive type antistatic agent into polyurethane in the prior art is one of the alternative ways to prepare polyurethane with a long-term antistatic effect. Among them, carbon nanotubes are also used for the preparation of antistatic polymers because of their good thermodynamic properties and high electrical conductivity. For example, the invention patent of china with the application number of 201510953026.2 provides an antistatic polyurethane resin and application thereof, wherein the antistatic polyurethane resin comprises a polyurethane resin component a and a polyurethane resin component B, and the raw materials of the component a comprise polyester polyol P1 and conductive color paste; the conductive color paste is prepared by taking conductive carbon black and carbon nano tubes as raw materials. That is, the patent achieves the antistatic effect by adding the conductive color paste into the polyurethane, overcomes the defect of continuous migration of the organic antistatic agent, but the preparation process is more complex, and if the antistatic polyurethane is prepared, the conductive color paste needs to be prepared firstly:
(1) mixing 1-3 parts of carbon nanotubes, 0.05-0.1 part of dispersing agent and 50-100 parts of plasticizer, dispersing for 90-120 min under the combined action of ultrasonic oscillation and mechanical stirring (bubbles appear in the ultrasonic oscillation process, the temperature rises, the ultrasonic oscillation is continued after static cooling every half hour), and then putting into a ball mill for grinding for 120-150 min to obtain a nanotube dispersion liquid; (2) mixing 5-12 parts of conductive carbon black with the nanotube dispersion liquid obtained in the step (1), and putting the mixture into a ball mill for grinding for 240-300 min to obtain conductive color paste;
then, it is necessary to further prepare a polyurethane resin a component: adding polyester polyol P1, a chain extender and a foam stabilizer into a reaction kettle with a temperature control and stirring device, mixing for 2.5-3.5 h at the temperature of 45-55 ℃, cooling to 25-35 ℃, adding water, a catalyst and conductive color paste, fully stirring for 2-3 h, and uniformly mixing to obtain a polyurethane resin A component;
then, it is also necessary to prepare a polyurethane resin B component: adding polyester polyol P2, MDI and modified MDI into a reaction kettle with a temperature control and stirring device for mixing reaction at the temperature of 55-65 ℃ for 2-3 h to obtain a polyurethane resin component B;
then, mixing a polyurethane resin A component with the temperature of 48-52 ℃ and a polyurethane resin B component with the temperature of 43-47 ℃ in a two-component casting machine, injecting the mixture into a 45-50 ℃ mold for reaction for 5-7 min for molding, demolding, and curing in a 60-70 ℃ oven for 22-24 hours to obtain the antistatic polyurethane microporous elastomer;
therefore, the antistatic polyurethane microporous elastomer prepared by the method needs to undergo several necessary steps of preparation of conductive color paste, preparation of a polyurethane resin component A, preparation of a polyurethane resin component B, preparation of polyurethane by mixing of the components A and B, and the like, the preparation process is relatively complex, the preparation period is long, equipment such as an ultrasonic oscillation device, a ball mill, a two-component casting machine and the like is needed, and the equipment cost for realizing the preparation process is high.
Disclosure of Invention
Problem (A)
In view of the above, it is a technical problem to be solved by those skilled in the art to provide a preparation method for preparing polyurethane with excellent antistatic performance by introducing a composite additive type antistatic agent, wherein the preparation process is relatively simple and easy to implement.
(II) technical scheme
The invention aims to provide antistatic thermoplastic polyurethane and a preparation method thereof, so as to solve the technical problems.
In a first aspect of embodiments of the present invention, there is provided a method for preparing an antistatic thermoplastic polyurethane, comprising the steps of:
heating 800-7000 g/mol of polymer diol to 60-100 ℃, preserving heat, and respectively heating isocyanate and a chain extender to 40-90 ℃, preserving heat;
according to parts by weight, 20-80 parts of heat-insulated polymer dihydric alcohol, 1.5-8.5 parts of chain extender, 0.01-5 parts of modified carbon nano tube at room temperature, 0.001-0.5 part of catalyst, 0.1-8 parts of antioxidant, 0.1-8 parts of heat stabilizer and 0.1-5 parts of hydrolysis stabilizer are mixed and stirred uniformly, 10-70 parts of heat-insulated isocyanate is poured, the mixture is stirred uniformly and rapidly and is placed in a constant temperature environment at 60-120 ℃ for curing for 0.5-24 h (h), and the antistatic thermoplastic polyurethane is obtained.
Optionally, the polymeric glycol comprises: polyethylene adipate glycol, polybutylene adipate glycol, polyhexamethylene adipate glycol, polyethylene adipate-butylene glycol, polybutylene adipate glycol, polyethylene terephthalate glycol, polybutylene terephthalate-hexanediol glycol, polyethylene sebacate glycol, polybutylene sebacate glycol, polyethylene sebacate-hexanediol glycol, polytetrahydrofuran propylene oxide copolymer glycol, polytetrahydrofuran diol, polyricinoleate, polyoxypropylene glycol, polybutadiene glycol, poly (butylene adipate) glycol, poly (butylene glycol-butylene glycol), poly (butylene terephthalate) glycol, poly (butylene terephthalate-hexanediol), poly (tetramethylene oxide) glycol, poly (, One or more of polyethylene glycol, polypropylene glycol and polybutylene glycol.
Optionally, the isocyanate comprises: 4,4 '-diphenylmethane diisocyanate (MDI), 2, 4-diphenylmethane diisocyanate, 2' -diphenylmethane diisocyanate, naphthalene-1, 5-diisocyanate (NDI), naphthylene-1, 5-diisocyanate, isophorone diisocyanate (IPDI), trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, Hexamethylene Diisocyanate (HDI), heptamethylene diisocyanate, octamethylene diisocyanate, 2-methylpentamethylene-1, 5-diisocyanate, diphenylmethane-3, 3 '-dimethoxy-4, 4' -diisocyanate, Toluene Diisocyanate (TDI), 4 '-diisocyanato-1, 2-diphenylethane, Toluene Diisocyanate (TDI), 4' -diisocyanato-1, 2-diphenylethane, toluene diisocyanate (HDI), toluene, One or more of dicyclohexyl 1, 4-diisocyanate, decane 1, 10-diisocyanate, 3 ' -dimethyl-4, 4 ' -biphenyl diisocyanate (TODI), 1, 3-bis (isocyanatomethyl) cyclohexane, 1, 4-bis (isocyanatomethyl) cyclohexane, 1-methylcyclohexane-2, 4-diisocyanate, 1-methylcyclohexane-2, 6-diisocyanate, urethane-modified liquid 4,4 ' -diphenylmethane diisocyanate.
Optionally, the chain extender comprises: one or more of ethylene glycol, 1, 3-propylene glycol, 2-methyl-1, 3-propylene glycol, diethylene glycol, dipropylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, and neopentyl glycol.
Optionally, the modified carbon nanotube includes: one or more of oxidized carbon nanotubes, hydroxylated modified carbon nanotubes, carboxylated modified carbon nanotubes, aminated modified carbon nanotubes, alkylamine modified carbon nanotubes and silane coupling agent modified carbon nanotubes.
Optionally, the catalyst comprises: one or more of dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, dibutyltin maleate, stannous acetate, stannous isooctanoate and tin dilaurate.
Optionally, the antioxidant comprises: one or more of dilauryl thiodipropionate, 2,4, 6-tri-tert-butyl pentaerythritol diphosphite, spiroglycol bis [2, 2' -methylenebis (4, 6-di-tert-butylphenyl) ] phosphite, and di (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite.
Optionally, the heat stabilizer comprises: one or more of calcium stearate, zinc stearate, magnesium stearate and methyl tin mercaptide.
Optionally, the hydrolysis stabilizer comprises: dicyclohexylcarbodiimide, N '-diisopropylcarbodiimide, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide, 1- (3-dimethylaminopropyl) -3-ethyl-carbodiimide hydrochloride, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, N' -diisopropylcarbodiimide, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 1- (3-dimethylaminopropyl) carbodiimide hydrochloride, N '-dimethylcarbodiimide hydrochloride, N' -diisopropylcarbodiimide, N, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N- (3-dimethylaminopropyl) -N' -ethyl-carbodiimide hydrochloride, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride.
Optionally, the number average molecular weight of the polymer diol is 800-7000 g/mol.
In a second aspect of the embodiments of the present invention, there is also provided an antistatic thermoplastic polyurethane, which is prepared by the above preparation method of the antistatic thermoplastic polyurethane.
(III) technical effects
Compared with the prior art, the technical scheme provided by the invention has the following beneficial effects:
the antistatic thermoplastic polyurethane is prepared by in-situ polymerization reaction of the modified carbon nanotube containing active functional groups (hydroxyl, carboxyl or amino groups and the like) and polymer dihydric alcohol, isocyanate, a chain extender and the like, and has the advantages of simple preparation process, short preparation period, only temperature control and stirring equipment and low equipment requirement;
the volume resistivity of the permanent antistatic thermoplastic polyurethane prepared by the embodiment of the invention is tested according to the GB/T1410-2006 test method for the volume resistivity and the surface resistivity of solid insulating materials. Tests prove that the antistatic thermoplastic polyurethane prepared by the preparation method disclosed by the embodiment of the invention has lower volume resistivity of 9.8 multiplied by 102Ω·cm～8.5×109Omega cm, excellent antistatic performance;
the preparation process of the antistatic thermoplastic polyurethane provided by the embodiment of the invention does not need any organic solvent, and is environment-friendly.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The present invention will be described in more detail with reference to the following embodiments in order to make the technical aspects of the present invention more apparent and understandable.
The embodiment of the invention provides a preparation method of antistatic thermoplastic polyurethane, which is an implementation mode and comprises the following steps:
(1) heating polymer dihydric alcohol with the number average molecular weight of 800-7000 g/mol to 60-100 ℃, and preserving heat, and respectively heating isocyanate and a chain extender to 40-90 ℃ for heat preservation;
(2) mixing and stirring 20-80 parts by weight of heat-insulated polymer dihydric alcohol, 1.5-8.5 parts by weight of chain extender, 0.01-5 parts by weight of modified carbon nano tube at room temperature, 0.001-0.5 part by weight of catalyst, 0.1-8 parts by weight of antioxidant, 0.1-8 parts by weight of heat stabilizer and 0.1-5 parts by weight of hydrolysis stabilizerAfter uniformly mixing, pouring 10-70 parts of insulated isocyanate, quickly and uniformly mixing, and curing for 0.5-24 h in a constant temperature environment at 60-120 ℃ to obtain the antistatic thermoplastic polyurethane, wherein the volume resistivity of the polyurethane is 9.8 multiplied by 102Ω·cm～8.5×109Ω·cm。
In the embodiment of the invention, the antistatic performance of polyurethane is enhanced by using the modified carbon nano tube, and compared with the unmodified carbon nano tube, the modified carbon nano tube has better compatibility with polyurethane, so that the antistatic performance of the prepared polyurethane is further improved.
In the examples of the present invention, the polymer diol in step (1) or (2) is polyethylene adipate diol, polybutylene adipate diol, polyhexamethylene adipate diol, polyethylene adipate-butanediol-hexanediol, polyethylene terephthalate diol, polybutylene terephthalate diol, polyethylene terephthalate-butanediol diol, polyhexamethylene terephthalate diol, polybutylene terephthalate-hexanediol, polybutylene terephthalate-diol, polyethylene sebacate-hexanediol, polyethylene sebacate-butanediol-hexanediol, polytetrahydrofuran propylene oxide copolymer diol, polytetrahydrofuran diol, polytetramethylene oxide glycol, polyethylene glycol terephthalate, polybutylene terephthalate glycol terephthalate, polybutylene glycol, One or a mixture of any several of poly castor oil adipate glycol, polyoxypropylene glycol, polybutadiene glycol, polyethylene glycol, polypropylene glycol and polybutylene glycol in any ratio, wherein any several of the poly castor oil adipate glycol, the polyoxypropylene glycol, the polybutadiene glycol, the polyethylene glycol, the polypropylene glycol and the polybutylene glycol are more than two in the embodiment of the invention, and the mixture comprises two.
In the examples of the present invention, the isocyanate in step (1) or (2) is 4,4 '-diphenylmethane diisocyanate (MDI), 2, 4-diphenylmethane diisocyanate, 2' -diphenylmethane diisocyanate, naphthalene-1, 5-diisocyanate (NDI), naphthylene-1, 5-diisocyanate, isophorone diisocyanate (IPDI), trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, Hexamethylene Diisocyanate (HDI), heptamethylene diisocyanate, octamethylene diisocyanate, 2-methylpentamethylene-1, 5-diisocyanate, diphenylmethane-3, 3 '-dimethoxy-4, 4' diisocyanate, Toluene Diisocyanate (TDI), or mixtures thereof, 4,4 '-diisocyanato-1, 2-diphenylethane, dicyclohexyl 1, 4-diisocyanate, decane 1, 10-diisocyanate, 3' -dimethyl-4, 4 '-biphenyl diisocyanate (TODI), 1, 3-bis (isocyanatomethyl) cyclohexane, 1, 4-bis (isocyanatomethyl) cyclohexane, 1-methylcyclohexane-2, 4-diisocyanate, 1-methylcyclohexane-2, 6-diisocyanate, urethane-modified liquid 4, 4' -diphenylmethane diisocyanate or a mixture of any several of them in any ratio.
In the embodiment of the invention, in the step (1) or (2), the chain extender is one of ethylene glycol, 1, 3-propylene glycol, 2-methyl-1, 3-propylene glycol, diethylene glycol, dipropylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol and neopentyl glycol or a mixture of any of ethylene glycol, 1, 3-propanediol, dipropylene glycol and 1, 4-butanediol.
In the embodiment of the present invention, the modified carbon nanotube in step (2) is one or a mixture of any several of oxidized carbon nanotube, hydroxylated modified carbon nanotube, carboxylated modified carbon nanotube, aminated modified carbon nanotube, alkylamine modified carbon nanotube, and silane coupling agent modified carbon nanotube in any ratio.
In the embodiment of the invention, the catalyst in the step (2) is one or a mixture of any several of dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, dibutyltin maleate, stannous acetate, stannous isooctanoate and tin dilaurate in any ratio.
In the embodiment of the present invention, the antioxidant in step (2) is one or a mixture of any several of dilauryl thiodipropionate, 2,4, 6-tri-tert-butyl pentaerythritol diphosphite, spiroglycol bis [2, 2' -methylenebis (4, 6-di-tert-butylphenyl) ] phosphite, and pentaerythritol bis (2, 4-di-tert-butylphenyl) diphosphite in any ratio.
In the embodiment of the invention, in the step (2), one or a mixture of any several of calcium stearate, zinc stearate, magnesium stearate and tin methyl mercaptide in any ratio is used as a heat stabilizer;
in the examples of the present invention, the hydrolysis stabilizer in the step (2) is dicyclohexylcarbodiimide, N '-diisopropylcarbodiimide, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide, 1- (3-dimethylaminopropyl) -3-ethyl-carbodiimide hydrochloride, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, N' -diisopropylcarbodiimide hydrochloride, N '-dimethylaminopropyl-3-dimethylcarbodiimide hydrochloride, N' -diisopropylcarbodiimide hydrochloride, N, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N- (3-dimethylaminopropyl) -N' -ethyl-carbodiimide hydrochloride and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride or a mixture of any more of the above in any ratio.
To further illustrate the present invention, the following examples are given to illustrate the preparation of the present invention:
example 1
(1) Heating polybutylene adipate diol with the number average molecular weight of 2000g/mol and polyethylene glycol with the number average molecular weight of 2000g/mol to 90 ℃, preserving heat, heating 4, 4' -diphenylmethane diisocyanate and 1, 4-butanediol to 75 ℃, preserving heat;
(2) according to the weight portion, 62.5 portions of thermal-insulation polybutylene adipate glycol, 10 portions of polyethylene glycol, 4.1 portions of 1, 4-butanediol, 0.5 portion of hydroxylation modified carbon nano tube at room temperature, 0.01 portion of dibutyltin dilaurate, 0.89 portion of dilauryl thiodipropionate, 1 portion of calcium stearate and 1 portion of 1- (3-dimethylaminopropyl) -3-ethyl carbodiimide hydrochloride are mixed and stirred uniformly, 20 portions of thermal-insulation 4, 4' -diphenylmethane diisocyanate are poured, stirred uniformly and cured in a constant temperature environment of 90 ℃ for 6 hours to obtain the antistatic thermoplastic polyurethane.
The volume resistivity of the polyurethane was tested to be 8.5X 109Ω·cm。
Example 2
(1) Heating polybutylene adipate diol with the number average molecular weight of 2000g/mol to 80 ℃, preserving heat, heating 4, 4' -diphenylmethane diisocyanate and 1, 4-butanediol to 75 ℃, preserving heat;
(2) according to the weight portion, 72 portions of heat-preserved polybutylene adipate glycol, 4.1 portions of 1, 4-butanediol, 1 portion of alkylamine modified carbon nano tube at room temperature, 0.01 portion of dibutyltin dilaurate, 0.89 portion of dilauryl thiodipropionate, 1 portion of calcium stearate and 1 portion of 1- (3-dimethylaminopropyl) -3-ethyl carbodiimide hydrochloride are mixed and stirred uniformly, then 20 portions of heat-preserved 4, 4' -diphenylmethane diisocyanate are poured, stirred uniformly and rapidly, and then placed in a constant temperature environment of 90 ℃ for curing for 6 hours, so that the antistatic thermoplastic polyurethane is obtained.
The volume resistivity of the polyurethane was tested to be 5.2X 105Ω·cm。
Example 3
(1) Heating polybutylene adipate diol with the number average molecular weight of 2000g/mol and polyethylene glycol with the number average molecular weight of 2000g/mol to 90 ℃, preserving heat, heating 4, 4' -diphenylmethane diisocyanate and 1, 4-butanediol to 75 ℃, preserving heat;
(2) according to the weight portion, 40 portions of heat-preserved polybutylene adipate glycol, 27.8 portions of polyethylene glycol, 4.19 portions of 1, 4-butanediol, 1.5 portions of silane coupling agent modified carbon nano tube at room temperature, 0.01 portion of dibutyltin dilaurate, 1 portion of dilauryl thiodipropionate, 1 portion of zinc stearate and 1 portion of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride are mixed and stirred uniformly, 20 portions of heat-preserved 4, 4' -diphenylmethane diisocyanate are poured, stirred uniformly rapidly and then placed in a constant temperature environment of 90 ℃ for curing for 6 hours, and the antistatic thermoplastic polyurethane is obtained.
The volume resistivity of the polyurethane was tested to be 9.8X 104Ω·cm。
Example 4
(1) Heating polybutylene adipate diol with the number average molecular weight of 2000g/mol and polyethylene glycol with the number average molecular weight of 2000g/mol to 90 ℃, preserving heat, heating 4, 4' -diphenylmethane diisocyanate and 1, 4-butanediol to 75 ℃, preserving heat;
(2) according to the weight portion, 60.8 portions of thermal-insulation polybutylene adipate glycol, 10 portions of polyethylene glycol, 4.19 portions of 1, 4-butanediol, 2 portions of amination modified carbon nano tubes at room temperature, 0.01 portion of dibutyltin dilaurate, 1 portion of dilauryl thiodipropionate, 1 portion of zinc stearate and 1 portion of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride are mixed and stirred uniformly, 20 portions of thermal-insulation 4, 4' -diphenylmethane diisocyanate are poured, stirred uniformly rapidly and then placed in a constant temperature environment of 90 ℃ for curing for 6 hours, and the antistatic thermoplastic polyurethane is obtained.
The volume resistivity of the polyurethane was tested to be 6.1X 104Ω·cm。
Example 5
(1) Heating polybutylene adipate glycol with the number average molecular weight of 3000g/mol and polypropylene glycol with the number average molecular weight of 2000g/mol to 90 ℃, and keeping the temperature, and heating toluene diisocyanate and 1, 3-propylene glycol to 75 ℃ for keeping the temperature;
(2) according to the weight portion, 50 portions of heat-preserved polybutylene adipate glycol, 20 portions of polypropylene glycol, 3.58 portions of 1, 3-propylene glycol, 2.5 portions of hydroxylation modified carbon nano tube at room temperature, 0.02 portion of stannous dioctoate, 1 portion of pentaerythritol bis (2, 4-di-tert-butylphenyl) diphosphite, 1 portion of calcium stearate and 1 portion of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride are mixed and stirred uniformly, then 19.4 portions of heat-preserved toluene diisocyanate are poured in, stirred rapidly and uniformly and then placed in a constant temperature environment of 90 ℃ for curing for 6 hours, and the antistatic thermoplastic polyurethane is obtained.
The volume resistivity of the polyurethane was tested to be 1.3X 104Ω·cm。
Example 6
(1) Heating polyhexamethylene adipate glycol with the number average molecular weight of 4000g/mol and polyethylene glycol with the number average molecular weight of 2000g/mol to 90 ℃, preserving heat, heating toluene diisocyanate and 1, 3-propylene glycol to 75 ℃, preserving heat;
(2) according to the weight portion, 46 portions of heat-insulated polyhexamethylene adipate glycol, 20 portions of polyethylene glycol, 6.09 portions of 1, 3-propylene glycol, 3 portions of carboxylated modified carbon nano tubes at room temperature, 0.01 portion of dibutyltin dilaurate, 0.9 portion of dilauryl thiodipropionate, 1 portion of zinc stearate and 1 portion of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride are mixed and stirred uniformly, 22 portions of heat-insulated toluene diisocyanate are poured, stirred uniformly and quickly, and then placed in a constant temperature environment of 90 ℃ for curing for 6 hours to obtain the antistatic thermoplastic polyurethane.
The volume resistivity of the polyurethane was tested to be 9.6X 103Ω·cm。
Example 7
(1) Heating polybutylene adipate diol with the number average molecular weight of 2000g/mol and polyethylene glycol with the number average molecular weight of 2000g/mol to 90 ℃, preserving heat, and heating 4, 4' -diphenylmethane diisocyanate, isophorone diisocyanate and 1, 4-butanediol to 70 ℃, preserving heat;
(2) according to parts by weight, 40 parts of heat-insulated polybutylene adipate glycol, 29.3 parts of polyethylene glycol, 4.19 parts of 1, 4-butanediol, 1.5 parts of alkylamine modified carbon nano tube at room temperature, 2 parts of silane coupling agent modified carbon nano tube, 0.01 part of dibutyltin dilaurate, 1 part of dilauryl thiodipropionate, 1 part of zinc stearate and 1 part of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride are mixed and stirred uniformly, 10 parts of heat-insulated 4, 4' -diphenylmethane diisocyanate and 10 parts of isophorone diisocyanate are poured, stirred uniformly and quickly, and then the mixture is placed in a constant temperature environment of 90 ℃ to be aged for 6 hours, so that the antistatic thermoplastic polyurethane is obtained.
The volume resistivity of the polyurethane was tested to be 5.5X 103Ω·cm。
Example 8
(1) Heating polyhexamethylene adipate glycol with the number average molecular weight of 4000g/mol and polyethylene glycol with the number average molecular weight of 2000g/mol to 90 ℃, preserving heat, heating toluene diisocyanate and 1, 4-butanediol to 75 ℃, preserving heat;
(2) mixing 45 parts of heat-preserved polyhexamethylene glycol adipate diol, 20 parts of polyethylene glycol, 6.08 parts of 1, 4-butanediol, 4 parts of carboxylated modified carbon nano tube at room temperature, 0.02 part of stannous dioctoate, 0.9 part of pentaerythritol diphosphite bis (2, 4-di-tert-butylphenyl) ester, 1 part of zinc stearate and 1 part of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride according to parts by weightAfter being stirred uniformly, 22 parts of toluene diisocyanate after heat preservation is poured in, after being stirred uniformly rapidly, the mixture is put in a constant temperature environment of 90 ℃ for curing for 6 hours, and the antistatic thermoplastic polyurethane is obtained. The volume resistivity of the polyurethane was tested to be 9.8X 102Ω·cm。
In the embodiment of the invention, an antistatic thermoplastic polyurethane is obtained by in-situ polymerization reaction of a modified carbon nanotube containing an active functional group (hydroxyl, carboxyl or amino group and the like) and polymer diol, isocyanate, a chain extender and the like, wherein the volume resistivity of the polyurethane is 9.8 multiplied by 102Ω·cm～8.5×109Omega cm, excellent antistatic performance.
Compared with the prior art, the preparation method provided by the embodiment of the invention does not need any organic solvent, has low requirements on equipment, and is a more environment-friendly, low-cost, simple and easy-to-apply preparation process for the antistatic thermoplastic polyurethane.
The principles and embodiments of the present invention have been described herein using specific examples, which are provided only to help understand the method and the core concept of the present invention; meanwhile, for a person skilled in the art, according to the idea of the present invention, the specific embodiments and the application range may be changed. In view of the above, the present disclosure should not be construed as limiting the invention.
Claims (10)
1. The preparation method of the antistatic thermoplastic polyurethane is characterized by comprising the following steps:
heating polymer diol to 60-100 ℃, preserving heat, and respectively heating isocyanate and a chain extender to 40-90 ℃, preserving heat;
according to parts by weight, mixing and stirring uniformly 20-80 parts of the polymer dihydric alcohol, 1.5-8.5 parts of the chain extender, 0.01-5 parts of the modified carbon nano tube under the room temperature condition, 0.001-0.5 part of the catalyst, 0.1-8 parts of the antioxidant, 0.1-8 parts of the heat stabilizer and 0.1-5 parts of the hydrolysis stabilizer, pouring 10-70 parts of the isocyanate after heat preservation, stirring uniformly, and curing in a constant temperature environment at 60-120 ℃ for 0.5-24 hours to obtain the antistatic thermoplastic polyurethane.
2. The process for preparing antistatic thermoplastic polyurethane as claimed in claim 1, wherein the polymer diol comprises:
polyethylene adipate glycol, polybutylene adipate glycol, polyhexamethylene adipate glycol, polyethylene adipate-butylene glycol, polybutylene adipate glycol, polyethylene terephthalate glycol, polybutylene terephthalate-hexanediol glycol, polyethylene sebacate glycol, polybutylene sebacate glycol, polyethylene sebacate-hexanediol glycol, polytetrahydrofuran propylene oxide copolymer glycol, polytetrahydrofuran diol, polyricinoleate, polyoxypropylene glycol, polybutadiene glycol, poly (butylene adipate) glycol, poly (butylene glycol-butylene glycol), poly (butylene terephthalate) glycol, poly (butylene terephthalate-hexanediol), poly (tetramethylene oxide) glycol, poly (, One or more of polyethylene glycol, polypropylene glycol and polybutylene glycol.
3. The process for preparing an antistatic thermoplastic polyurethane as claimed in claim 1, wherein the isocyanate comprises:
4,4 '-diphenylmethane diisocyanate (MDI), 2, 4-diphenylmethane diisocyanate, 2' -diphenylmethane diisocyanate, naphthalene-1, 5-diisocyanate (NDI), naphthylene-1, 5-diisocyanate, isophorone diisocyanate (IPDI), trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, Hexamethylene Diisocyanate (HDI), heptamethylene diisocyanate, octamethylene diisocyanate, 2-methylpentamethylene-1, 5-diisocyanate, diphenylmethane-3, 3 '-dimethoxy-4, 4' -diisocyanate, Toluene Diisocyanate (TDI), 4 '-diisocyanato-1, 2-diphenylethane, Toluene Diisocyanate (TDI), 4' -diisocyanato-1, 2-diphenylethane, toluene diisocyanate (HDI), toluene, One or more of dicyclohexyl 1, 4-diisocyanate, decane 1, 10-diisocyanate, 3 ' -dimethyl-4, 4 ' -biphenyl diisocyanate (TODI), 1, 3-bis (isocyanatomethyl) cyclohexane, 1, 4-bis (isocyanatomethyl) cyclohexane, 1-methylcyclohexane-2, 4-diisocyanate, 1-methylcyclohexane-2, 6-diisocyanate, urethane-modified liquid 4,4 ' -diphenylmethane diisocyanate.
4. The process for preparing an antistatic thermoplastic polyurethane as claimed in claim 1, wherein the chain extender comprises:
one or more of ethylene glycol, 1, 3-propylene glycol, 2-methyl-1, 3-propylene glycol, diethylene glycol, dipropylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, and neopentyl glycol.
5. The method of claim 1, wherein the modified carbon nanotubes comprise:
one or more of oxidized carbon nanotubes, hydroxylated modified carbon nanotubes, carboxylated modified carbon nanotubes, aminated modified carbon nanotubes, alkylamine modified carbon nanotubes and silane coupling agent modified carbon nanotubes.
6. The process for the preparation of antistatic thermoplastic polyurethane according to claim 1, wherein the catalyst comprises:
one or more of dibutyltin dilaurate, dibutyltin diacetate, dibutyltin maleate, stannous diacetate, stannous dioctoate and stannous dilaurate.
7. The process for the preparation of antistatic thermoplastic polyurethane according to claim 1, characterized in that:
the antioxidant is one or more of dilauryl thiodipropionate, 2,4, 6-tri-tert-butyl pentaerythritol diphosphite, spiroglycol bis [2, 2' -methylenebis (4, 6-di-tert-butylphenyl) ] phosphite and pentaerythritol bis (2, 4-di-tert-butylphenyl) diphosphite;
and/or the heat stabilizer is one or more of calcium stearate, zinc stearate, magnesium stearate and methyl tin mercaptide.
8. The process for preparing antistatic thermoplastic polyurethane as claimed in claim 1, wherein the hydrolysis stabilizer is:
dicyclohexylcarbodiimide, N '-diisopropylcarbodiimide, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide, 1- (3-dimethylaminopropyl) -3-ethyl-carbodiimide hydrochloride, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, N' -diisopropylcarbodiimide, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 1- (3-dimethylaminopropyl) carbodiimide hydrochloride, N '-dimethylcarbodiimide hydrochloride, N' -diisopropylcarbodiimide, N, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N- (3-dimethylaminopropyl) -N' -ethyl-carbodiimide hydrochloride, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride.
9. The method of claim 1, wherein the number average molecular weight of the polymeric diol is 800 to 7000 g/mol.
10. An antistatic thermoplastic polyurethane, characterized in that it is obtained by a process for the preparation of an antistatic thermoplastic polyurethane according to any one of claims 1 to 9.
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