CN110105538A - A kind of sole polyurethane elastomer material - Google Patents
A kind of sole polyurethane elastomer material Download PDFInfo
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- CN110105538A CN110105538A CN201910373478.1A CN201910373478A CN110105538A CN 110105538 A CN110105538 A CN 110105538A CN 201910373478 A CN201910373478 A CN 201910373478A CN 110105538 A CN110105538 A CN 110105538A
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- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B13/00—Soles; Sole-and-heel integral units
- A43B13/02—Soles; Sole-and-heel integral units characterised by the material
- A43B13/04—Plastics, rubber or vulcanised fibre
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4202—Two or more polyesters of different physical or chemical nature
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6644—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
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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
- C08K9/00—Use of pretreated ingredients
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- 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
Abstract
The invention discloses a kind of sole polyurethane elastomer materials, and the substance by corresponding to parts by weight as follows is made: 75 ~ 80 parts of polyester polyol, 7 ~ 9 parts of chain extenders, 0.8 ~ 1.3 part of antioxidant, 0.3 ~ 0.5 part of catalyst, 35 ~ 40 parts of MDI, 4 ~ 6 parts of modified multiwalled carbon nanotubes, 0.1 ~ 0.3 part of organosilicon, 0.2 ~ 0.4 part of epoxidized soybean oil, 0.2 ~ 0.5 part of odium stearate.The raw material composition of polyurethane elastomer material of the present invention is simple, convenient for preparation and promotes and applies, the excellents such as whole mechanical quality, the production as sole can guarantee the use quality and service life of shoes, the great market competitiveness well.
Description
Technical field
The invention belongs to polyurethane material technical fields, and in particular to a kind of sole polyurethane elastomer material.
Background technique
Polyurethane elastomer is that a kind of elasticity in molecular backbone containing more carbamate groups (- NHCOO-) is poly-
Object is closed, is typical segmented copolymer material.Polyurethane elastomer usually with polymer polyatomic alcohol, isocyanates, chain extender,
Crosslinking agent and a small amount of auxiliary agent are that raw material carries out sudden reaction and is made.
Polyurethane elastomer is a kind of macromolecule polymeric material between rubber and plastics, have very high intensity and
Elongation, while its hardness range is wide, has good mechanical performance, wear-resisting property and resilience performance.
Common footwear material accessory article is mostly PVC (polyvinyl chloride) before, soft required for footwear material product in order to obtain
Soft hardness will add a large amount of plasticizer such as after processing: dioctyl phthalate, butyl phthalate phthalic acid
Plasticizer, and these plasticizer are harmful substances to human body, all limit its application in European Union and the U.S., it is therefore necessary to it to open
The new high molecular material of one kind is sent out to replace the application of PVC.Polyurethane shoe is with its good environmental-protecting performance, mechanical strength, wear-resisting
And good operating characteristics has obtained the favor of shoe industry.
Currently, more and more footwear material accessory articles are made of polyurethane elastomer in the market, such as application No. is:
CN201010277819.4 discloses a kind of footwear material polyurethane elastomeric compositions, wherein being prepared for component A and B component, mixes
Close the production for being prepared into polyurethane elastomer for shoes.Although it has good promotion compared to PVC material quality, its
It is still not very good in the qualities such as intensity, for a long time by external force friction the effects of it is easy to crack or fracture, finally affect service life.
Summary of the invention
The purpose of the present invention is being directed to existing problem, a kind of sole polyurethane elastomer material is provided.
The present invention is achieved by the following technical solutions:
A kind of sole polyurethane elastomer material, the substance by corresponding to parts by weight as follows are made:
75 ~ 80 parts of polyester polyol, 7 ~ 9 parts of chain extenders, 0.8 ~ 1.3 part of antioxidant, 0.3 ~ 0.5 part of catalyst, 35 ~ 40 parts of MDI,
4 ~ 6 parts of modified multiwalled carbon nanotubes, 0.1 ~ 0.3 part of organosilicon, 0.2 ~ 0.4 part of epoxidized soybean oil, 0.2 ~ 0.5 part of odium stearate.
Preferably, it is made of the substance for corresponding to parts by weight as follows:
78 parts of polyester polyol, 8 parts of chain extenders, 1 part of antioxidant, 0.4 part of catalyst, 37 parts of MDI, 5 parts of modified multi-wall carbon nano-tubes
Pipe, 0.2 part of organosilicon, 0.3 part of epoxidized soybean oil, 0.4 part of odium stearate.
Further, the polyester polyol is the mixture of polycaprolactone polyol and polycarbonate glycol, described
Polycaprolactone polyol and the corresponding weight ratio of polycarbonate glycol be 1.8 ~ 2:1.
Further, the chain extender is any one in ethylene glycol or trimethylolpropane.
Further, the antioxidant is antioxidant 1010, antioxidant 1076, any one in irgasfos 168.
Further, the catalyst is dibutyl tin dilaurate.
Further, the preparation method of the modified multiwalled carbon nanotube includes the following steps:
(1) first multi-walled carbon nanotube is put into ultraviolet irradiation case and carries out radiation treatment, taken out after 30 ~ 35min spare；
(2) it by step (1) treated multi-walled carbon nanotube is immersed in concentrated nitric acid immersion 1 ~ 1.5h of reflow treatment, then takes out
With deionized water rinse one time, be finally putting into drying box be dried 50 ~ 60min after take out it is spare；
(3) by step (2), treated, and multi-walled carbon nanotube is put into vapor tight tank, and ammonia is then passed through into vapor tight tank, and
Vapor tight tank is carried out to heat pressurized treatment, is taken out multi-walled carbon nanotube after 3 ~ 4h spare；
(4) by step (3), treated, and multi-walled carbon nanotube is put into ball mill, and then controlling the atmosphere in ball mill is chlorine
Gas, continuous 2 ~ 3h of ball-milling treatment finally take out up to modified multiwalled carbon nanotube.
Further, when radiation treatment as described in step (1) control ultraviolet irradiation case in irradiation power be 1000 ~
1200W, the wavelength control of ultraviolet light are 260 ~ 280nm.
Further, the mass fraction of nitric acid is 70% in concentrated nitric acid described in step (2)；When the described drying process
Controlling the temperature in drying box is 85 ~ 90 DEG C.
Further, heated described in step (3) pressurized treatment be control vapor tight tank in pressure be 0.2 ~
0.25MPa, temperature are 620 ~ 650 DEG C.
Production of the polyurethane elastomer material for footwear material is also relatively broad, and what is pursued in the art is constantly to be promoted
The qualities such as the mechanics of material, or its special function is assigned, constantly enhance in the qualities such as service life, function, intensity in the hope of shoes.
Polyurethane elastomer material can be used for sole production, and the qualities such as intensity have significantly affected the service life worn, existing material
Can be comparatively mediocre, the market competitiveness is not strong, it is therefore desirable to constantly improve.The present invention mainly prepares and is added to one
Kind modified multiwalled carbon nanotube ingredient is to be added as a kind of special functional stuffing, to promote material entirety
The qualities such as intensity, although the fillers such as carbon nanotube are used as filler additive for relatively conventional in the preparation of materials such as polyurethane,
But its existing main problem is that filler can not effectively disperse, and be easy to cause reunion, stress concentration phenomenon, is used this people
Coupling agent, such as silane coupling agent, titanate coupling agent carry out immersion modification, to promote the surface compatability of filler, promote
Its dispersion in high molecular material plays good effect, but this can not promote filler further and high molecular material
Matrix crosslinking, needs to be attached combination by coupling agent each other, there are certain interfacial effect, affect performance into one
Step enhancing.In this regard, the present invention has carried out special improvement, ultraviolet irradiation processing, benefit first are carried out to multi-walled carbon nanotube first
Pre-activate has been carried out to the surface of multi-walled carbon nanotube with the mutagenesis of ultraviolet light and energy field-effect, has been convenient for subsequent processing, so
After put it into and carry out immersion treatment in concentrated nitric acid, placed into ammonia atmosphere after taking-up, effectively promote to live after processing
Property nitrogen-atoms is incorporated into the tissue of multi-walled carbon nanotube, improve surface reactivity and its with it is high molecular compatible
Property, then again using chlorine as ambiance ball milling, and active chlorine atom is promoted to be incorporated into the tissue of multi-walled carbon nanotube, assisted
Whole surface property is improved with nitrogen-atoms, ensure that the using effect of multi-walled carbon nanotube, the modification after final process is more
Not only good dispersion after wall carbon nano tube filling, moreover it is possible to directly be grafted fixation with polyurethane high molecule chain, and as crystallite area crystalline substance
Point provides tie point for the macromolecular network structure of polyurethane, enhances mechanical quality and the service life of material well.
The present invention has the advantage that compared with prior art
The raw material composition of polyurethane elastomer material of the present invention is simple, convenient for preparation and promotes and applies, whole mechanical quality etc.
Excellent, the production as sole can guarantee the use quality and service life of shoes, the great market competitiveness well.
Specific embodiment
It is corresponding that following examples and experiment are provided in order to show the corresponding effect of the present invention well.
Embodiment 1
A kind of sole polyurethane elastomer material, the substance by corresponding to parts by weight as follows are made:
75 parts of polyester polyol, 7 parts of chain extenders, 0.8 part of antioxidant, 0.3 part of catalyst, 35 parts of MDI, 4 parts of modified multi wall carbon are received
Mitron, 0.1 part of organosilicon, 0.2 part of epoxidized soybean oil, 0.2 part of odium stearate.
Further, the polyester polyol is the mixture of polycaprolactone polyol and polycarbonate glycol, described
Polycaprolactone polyol and the corresponding weight ratio of polycarbonate glycol be 1.8:1.
Further, the chain extender is ethylene glycol.
Further, the antioxidant is antioxidant 1010.
Further, the catalyst is dibutyl tin dilaurate.
Further, the preparation method of the modified multiwalled carbon nanotube includes the following steps:
(1) first multi-walled carbon nanotube is put into ultraviolet irradiation case and carries out radiation treatment, taken out after 30min spare；
(2) it by step (1) treated multi-walled carbon nanotube is immersed in concentrated nitric acid immersion reflow treatment 1h, then takes out and spends
Ionized water rinse one time, be finally putting into drying box be dried 50min after take out it is spare；
(3) by step (2), treated, and multi-walled carbon nanotube is put into vapor tight tank, and ammonia is then passed through into vapor tight tank, and
Vapor tight tank is carried out to heat pressurized treatment, is taken out multi-walled carbon nanotube after 3h spare；
(4) by step (3), treated, and multi-walled carbon nanotube is put into ball mill, and then controlling the atmosphere in ball mill is chlorine
Gas, continuous ball-milling treatment 2h finally take out up to modified multiwalled carbon nanotube.
Further, irradiation power when radiation treatment as described in step (1) in control ultraviolet irradiation case is
1000W, the wavelength control of ultraviolet light are 260 ~ 265nm.
Further, the mass fraction of nitric acid is 70% in concentrated nitric acid described in step (2)；When the described drying process
Controlling the temperature in drying box is 85 DEG C.
Further, heated described in step (3) pressurized treatment be control vapor tight tank in pressure be 0.2MPa, temperature
It is 620 DEG C.
Embodiment 2
A kind of sole polyurethane elastomer material, the substance by corresponding to parts by weight as follows are made:
78 parts of polyester polyol, 8 parts of chain extenders, 1 part of antioxidant, 0.4 part of catalyst, 37 parts of MDI, 5 parts of modified multi-wall carbon nano-tubes
Pipe, 0.2 part of organosilicon, 0.3 part of epoxidized soybean oil, 0.4 part of odium stearate.
Further, the polyester polyol is the mixture of polycaprolactone polyol and polycarbonate glycol, described
Polycaprolactone polyol and the corresponding weight ratio of polycarbonate glycol be 1.9:1.
Further, the chain extender is ethylene glycol.
Further, the antioxidant is antioxidant 1076.
Further, the catalyst is dibutyl tin dilaurate.
Further, the preparation method of the modified multiwalled carbon nanotube includes the following steps:
(1) first multi-walled carbon nanotube is put into ultraviolet irradiation case and carries out radiation treatment, taken out after 33min spare；
(2) by step (1) treated multi-walled carbon nanotube is immersed in concentrated nitric acid immersion reflow treatment 1.2h, use is then taken out
Deionized water rinse one time, be finally putting into drying box be dried 55min after take out it is spare；
(3) by step (2), treated, and multi-walled carbon nanotube is put into vapor tight tank, and ammonia is then passed through into vapor tight tank, and
Vapor tight tank is carried out to heat pressurized treatment, is taken out multi-walled carbon nanotube after 3.5h spare；
(4) by step (3), treated, and multi-walled carbon nanotube is put into ball mill, and then controlling the atmosphere in ball mill is chlorine
Gas, continuous ball-milling treatment 2.5h finally take out up to modified multiwalled carbon nanotube.
Further, irradiation power when radiation treatment as described in step (1) in control ultraviolet irradiation case is
1100W, the wavelength control of ultraviolet light are 270 ~ 275nm.
Further, the mass fraction of nitric acid is 70% in concentrated nitric acid described in step (2)；When the described drying process
Controlling the temperature in drying box is 88 DEG C.
Further, heated described in step (3) pressurized treatment be control vapor tight tank in pressure be 0.23MPa, temperature
Degree is 635 DEG C.
Embodiment 3
A kind of sole polyurethane elastomer material, the substance by corresponding to parts by weight as follows are made:
80 parts of polyester polyol, 9 parts of chain extenders, 1.3 parts of antioxidant, 0.5 part of catalyst, 40 parts of MDI, 6 parts of modified multi wall carbon are received
Mitron, 0.3 part of organosilicon, 0.4 part of epoxidized soybean oil, 0.5 part of odium stearate.
Further, the polyester polyol is the mixture of polycaprolactone polyol and polycarbonate glycol, described
Polycaprolactone polyol and the corresponding weight ratio of polycarbonate glycol be 2:1.
Further, the chain extender is trimethylolpropane.
Further, the antioxidant is irgasfos 168.
Further, the catalyst is dibutyl tin dilaurate.
Further, the preparation method of the modified multiwalled carbon nanotube includes the following steps:
(1) first multi-walled carbon nanotube is put into ultraviolet irradiation case and carries out radiation treatment, taken out after 35min spare；
(2) by step (1) treated multi-walled carbon nanotube is immersed in concentrated nitric acid immersion reflow treatment 1.5h, use is then taken out
Deionized water rinse one time, be finally putting into drying box be dried 60min after take out it is spare；
(3) by step (2), treated, and multi-walled carbon nanotube is put into vapor tight tank, and ammonia is then passed through into vapor tight tank, and
Vapor tight tank is carried out to heat pressurized treatment, is taken out multi-walled carbon nanotube after 4h spare；
(4) by step (3), treated, and multi-walled carbon nanotube is put into ball mill, and then controlling the atmosphere in ball mill is chlorine
Gas, continuous ball-milling treatment 3h finally take out up to modified multiwalled carbon nanotube.
Further, irradiation power when radiation treatment as described in step (1) in control ultraviolet irradiation case is
1200W, the wavelength control of ultraviolet light are 275 ~ 280nm.
Further, the mass fraction of nitric acid is 70% in concentrated nitric acid described in step (2)；When the described drying process
Controlling the temperature in drying box is 90 DEG C.
Further, heated described in step (3) pressurized treatment be control vapor tight tank in pressure be 0.25MPa, temperature
Degree is 650 DEG C.
Comparative experiments example 1
A kind of sole polyurethane elastomer material, the substance by corresponding to parts by weight as follows are made:
78 parts of polyester polyol, 8 parts of chain extenders, 1 part of antioxidant, 0.4 part of catalyst, 37 parts of MDI, 5 parts of modified multi-wall carbon nano-tubes
Pipe, 0.2 part of organosilicon, 0.3 part of epoxidized soybean oil, 0.4 part of odium stearate.
Further, the preparation method of the modified multiwalled carbon nanotube includes the following steps:
(1) first multi-walled carbon nanotube is put into ultraviolet irradiation case and carries out radiation treatment, taken out after 33min spare；
(2) by step (1) treated multi-walled carbon nanotube is immersed in concentrated nitric acid immersion reflow treatment 1.2h, use is then taken out
Deionized water rinse one time, be finally putting into drying box be dried 55min after take out it is spare；
(3) by step (2), treated, and multi-walled carbon nanotube is put into vapor tight tank, and ammonia is then passed through into vapor tight tank, and
Vapor tight tank is carried out to heat pressurized treatment, takes out multi-walled carbon nanotube up to modified multiwalled carbon nanotube after 3.5h.
This comparative experiments example 1 eliminates in modified multiwalled carbon nanotube preparation method actually compared with above-described embodiment 2
Former step (4), method and step in addition to this is same, to characterize the treatment effect of step (4).
Comparative experiments example 2
A kind of sole polyurethane elastomer material, the substance by corresponding to parts by weight as follows are made:
78 parts of polyester polyol, 8 parts of chain extenders, 1 part of antioxidant, 0.4 part of catalyst, 37 parts of MDI, 5 parts of modified multi-wall carbon nano-tubes
Pipe, 0.2 part of organosilicon, 0.3 part of epoxidized soybean oil, 0.4 part of odium stearate.
Further, the preparation method of the modified multiwalled carbon nanotube includes the following steps:
(1) first multi-walled carbon nanotube is put into ultraviolet irradiation case and carries out radiation treatment, taken out after 33min spare；
(2) by step (1) treated multi-walled carbon nanotube is immersed in concentrated nitric acid immersion reflow treatment 1.2h, use is then taken out
Deionized water rinse one time, be finally putting into drying box be dried 55min after take out it is spare；
(3) by step (2), treated, and multi-walled carbon nanotube is put into ball mill, and then controlling the atmosphere in ball mill is chlorine
Gas, continuous ball-milling treatment 2.5h finally take out up to modified multiwalled carbon nanotube.
This comparative experiments example 2 eliminates in modified multiwalled carbon nanotube preparation method actually compared with above-described embodiment 2
Former step (3), method and step in addition to this is same, to characterize the treatment effect of step (3).
Comparative experiments example 3
A kind of sole polyurethane elastomer material, the substance by corresponding to parts by weight as follows are made:
78 parts of polyester polyol, 8 parts of chain extenders, 1 part of antioxidant, 0.4 part of catalyst, 37 parts of MDI, 5 parts it is silane coupler modified
Multi-walled carbon nanotube, 0.2 part of organosilicon, 0.3 part of epoxidized soybean oil, 0.4 part of odium stearate.
Further, after the silane coupler modified multi-walled carbon nanotube is conventional silane coupler modified processing
Multi-walled carbon nanotube, specific preparation method be multi-walled carbon nanotube is put into mass fraction be 20% silane coupling agent water
Immersion treatment 2h in solution is put into drying process 2h in drying box at a temperature of 90 °C and forms after taking-up.
This comparative experiments example 3 eliminates modified multiwalled carbon nanotube ingredient actually compared with above-described embodiment 2, with routine
Silane coupler modified multi-walled carbon nanotube is replaced, and method and step in addition to this is same, more with the former modification of characterization
The using effect of wall carbon nano tube.
Comparative experiments example 4
Application No. is: a kind of footwear material polyurethane elastomeric compositions disclosed in CN201010277819.4, specific choice is wherein
The processing method of embodiment 3.
It is corresponding obtained to above-described embodiment 2, comparative experiments example 1, comparative experiments example 2, comparative experiments example 3, comparative experiments example 4
The performance of polyurethane elastomeric compositions material detected, specific correlation data is as shown in table 1 below:
Table 1
Note: hardness described in upper table 1 is measured using Shore durometer；The tensile strength is carried out referring to GB/T529
Measurement；The elongation is measured using GB/T13022-1991；The tearing strength is surveyed referring to GB/T528
It is fixed.
Hardness, intensity and the elongation of polyurethane elastomer material produced by the present invention it can be seen from above-mentioned test experiments
Rate is obviously improved, and usual intensity and elongation can not improve simultaneously, but the application filler changes polymer molecular chain
Institutional framework extend its service life, the great market competitiveness so that comprehensive performance significantly increases.
Claims (10)
1. a kind of sole polyurethane elastomer material, which is characterized in that the substance by corresponding to parts by weight as follows is made:
75 ~ 80 parts of polyester polyol, 7 ~ 9 parts of chain extenders, 0.8 ~ 1.3 part of antioxidant, 0.3 ~ 0.5 part of catalyst, 35 ~ 40 parts of MDI,
4 ~ 6 parts of modified multiwalled carbon nanotubes, 0.1 ~ 0.3 part of organosilicon, 0.2 ~ 0.4 part of epoxidized soybean oil, 0.2 ~ 0.5 part of odium stearate.
2. a kind of sole polyurethane elastomer material according to claim 1, which is characterized in that by corresponding to weight as follows
The substance of part is made:
78 parts of polyester polyol, 8 parts of chain extenders, 1 part of antioxidant, 0.4 part of catalyst, 37 parts of MDI, 5 parts of modified multi-wall carbon nano-tubes
Pipe, 0.2 part of organosilicon, 0.3 part of epoxidized soybean oil, 0.4 part of odium stearate.
3. a kind of sole polyurethane elastomer material according to claim 1 or 2, which is characterized in that the polyester
Polyalcohol is the mixture of polycaprolactone polyol and polycarbonate glycol, the polycaprolactone polyol and polycarbonate two
The corresponding weight ratio of alcohol is 1.8 ~ 2:1.
4. a kind of sole polyurethane elastomer material according to claim 1 or 2, which is characterized in that the chain extension
Agent is any one in ethylene glycol or trimethylolpropane.
5. a kind of sole polyurethane elastomer material according to claim 1 or 2, which is characterized in that the antioxygen
Agent is antioxidant 1010, antioxidant 1076, any one in irgasfos 168.
6. a kind of sole polyurethane elastomer material according to claim 1 or 2, which is characterized in that the catalysis
Agent is dibutyl tin dilaurate.
7. a kind of sole polyurethane elastomer material according to claim 1 or 2, which is characterized in that the modification
The preparation method of multi-walled carbon nanotube includes the following steps:
(1) first multi-walled carbon nanotube is put into ultraviolet irradiation case and carries out radiation treatment, taken out after 30 ~ 35min spare；
(2) it by step (1) treated multi-walled carbon nanotube is immersed in concentrated nitric acid immersion 1 ~ 1.5h of reflow treatment, then takes out
With deionized water rinse one time, be finally putting into drying box be dried 50 ~ 60min after take out it is spare；
(3) by step (2), treated, and multi-walled carbon nanotube is put into vapor tight tank, and ammonia is then passed through into vapor tight tank, and
Vapor tight tank is carried out to heat pressurized treatment, is taken out multi-walled carbon nanotube after 3 ~ 4h spare；
(4) by step (3), treated, and multi-walled carbon nanotube is put into ball mill, and then controlling the atmosphere in ball mill is chlorine
Gas, continuous 2 ~ 3h of ball-milling treatment finally take out up to modified multiwalled carbon nanotube.
8. a kind of sole polyurethane elastomer material according to claim 7, which is characterized in that described in step (1)
Radiation treatment when control ultraviolet irradiation case in irradiation power be 1000 ~ 1200W, the wavelength control of ultraviolet light is 260 ~
280nm。
9. a kind of sole polyurethane elastomer material according to claim 7, which is characterized in that described in step (2)
Concentrated nitric acid in nitric acid mass fraction be 70%；Temperature when the described drying process in control drying box is 85 ~ 90 DEG C.
10. a kind of sole polyurethane elastomer material according to claim 7, which is characterized in that described in step (3)
Heat pressurized treatment be control vapor tight tank in pressure be 0.2 ~ 0.25MPa, temperature is 620 ~ 650 DEG C.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116554673A (en) * | 2023-05-16 | 2023-08-08 | 广东技塑新材料股份有限公司 | Degradable TPU (thermoplastic polyurethane) for shoe material and preparation method thereof |
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