CN106632950A - Preparation method of ionic polyurethane based metallic composite - Google Patents
Preparation method of ionic polyurethane based metallic composite Download PDFInfo
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- CN106632950A CN106632950A CN201610875046.7A CN201610875046A CN106632950A CN 106632950 A CN106632950 A CN 106632950A CN 201610875046 A CN201610875046 A CN 201610875046A CN 106632950 A CN106632950 A CN 106632950A
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- Prior art keywords
- polyurethane
- electrode
- preparation
- metal composite
- base metal
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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
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Organic Insulating Materials (AREA)
Abstract
The invention discloses a preparation method of an ionic polyurethane based metallic composite. The preparation method comprises following steps: (1), preparation of polyurethane prepolymer: polyol is heated under the vacuum condition and subjected to vacuum drying, diisocyanate is added to polyol obtained after vacuum drying, and the polyurethane prepolymer is prepared through stirring and heating reactions under the shielding of inert gas; (2), preparation of polyurethane: a chain extender is added to the polyurethane prepolymer obtained in the step (1), and ionic polyurethane is prepared through stirring and heating reactions; (3), preparation of a polyurethane film: after a solvent is added to the ionic polyurethane obtained through the reaction in the step (2) and the ionic polyurethane is dissolved, the components are added to a die and dried, and the ionic polyurethane film is prepared; (4), electrode plating with the polyurethane film: an electrode is plated with the polyurethane film obtained in the step (3), and the ionic polyurethane based metallic composite is prepared. The method is simple in process, and actuating performance and anti-fatigue performance of the prepared metallic composite are good.
Description
Technical field
The present invention relates to field of material preparation, more particularly to a kind of polyurethane-base ion polymer-metal composite material
(IPMC) preparation method.
Background technology
Ionomer-metallic composite (IPMC) is a class electroactive material, low big with deformation with driving voltage
The characteristics of point, can be used for bionical and aerospace field.The braking mechanism of IPMC is that ion is determined in system in the presence of electric field
Cause material deformation to migration and activate.
There is its unique superiority as the joint transmission means of robot with IPMC：Simple structure, drive displacement are not received
Bearing is limited, light weight, easily cut into flexible, material softness required for shape, noiselessness etc..And polyurethane has
Excellent wearability, elasticity, weatherability, the nontoxic ideal material for being to prepare IPMC class artificial-muscles.Therefore how one kind is provided
The IPMC materials for activating function admirable are the problems for needing to solve.
The content of the invention
The present invention provides a kind of preparation method of ionic polyurethanes Base Metal composite, and its method is easy, and makes
Good for the IPMC materials braking for going out, fatigue resistance is good.
To solve above-mentioned technical problem, the present invention provides a kind of preparation side of ionic polyurethanes Base Metal composite
Method, comprises the following steps：
(1) base polyurethane prepolymer for use as is prepared：Polyalcohol is heated under vacuum and is vacuum dried, to after vacuum drying
Diisocyanate, inert gas shielding, agitating heating reaction is added to make base polyurethane prepolymer for use as in the polyalcohol for obtaining；
(2) polyurethane is prepared：Chain extender is added in the base polyurethane prepolymer for use as obtained to the step (1), agitating heating is anti-
Ionic polyurethanes should be obtained；
(3) polyurethane film is prepared：After solvent dissolving is added in the ionic polyurethanes that the step (2) reaction is obtained,
It is added in mould and is dried, makes polyurethane film；
(4) polyurethane film plated electrode：The polyurethane film plated electrode obtained to the step (3), that is, be obtained ionic and gather
Urethano metallic composite.
As seen from the above technical solution provided by the invention, the method process is simple, prepared IPMC materials
Having activate well performance, and with lasting fatigue resistance.
Description of the drawings
Fig. 1 is the actuating performance map of polyurethane-base IPMC materials prepared by the embodiment of the present invention.
Specific embodiment
The technical scheme in the embodiment of the present invention is clearly and completely described below, it is clear that described embodiment
Only a part of embodiment of the invention, rather than the embodiment of whole.Based on embodiments of the invention, ordinary skill
The every other embodiment that personnel are obtained under the premise of creative work is not made, belongs to protection scope of the present invention.
The embodiment of the present invention provides a kind of preparation method of ionic polyurethanes Base Metal composite, including following step
Suddenly：
(1) base polyurethane prepolymer for use as is prepared：
Polyalcohol is heated under vacuum and is vacuum dried, diisocyanate is added to many after vacuum drying
In first alcohol, inert gas shielding is sufficiently stirred for, and heating response makes base polyurethane prepolymer for use as；
In the step, polyalcohol used is one or more in PPG, PEPA；Two for adding are different
Cyanate is：Toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, naphthalene diisocyanate, IPDI
In one or more.
It it is 60～110 DEG C to the vacuum drying heating-up temperature of polyalcohol, vacuum drying time is 1～3h；
Using nitrogen or argon gas, mixing time is 0.5～2h to the inert gas, and reaction temperature is 60～80 DEG C, reaction
Time is 2～8h.
(2) polyurethane is prepared：
Add chain extender, agitating heating reaction that ion is obtained in the polyurethane prepolymer solution obtained to above-mentioned steps (1)
Type polyurethane；
In the step, the chain extender for being added is：One kind in 2,2- dihydromethyl propionic acids, 2,3- dihydroxy propanesulfonates
Or two kinds；The temperature of agitating heating is 60～80 DEG C, and the reaction time is 0.5～12h.
(3) polyurethane film is prepared：
Solvent dissolving is added in the polyurethane that above-mentioned steps (2) reaction is obtained, is added to afterwards in mould and is dried, made
Polyurethane film；
In the step, solvent used is：Tetrahydrofuran, dimethylformamide, dimethyl acetamide, in dimethyl sulfoxide (DMSO)
One or more；Baking temperature in a mold is 80～110 DEG C, and drying time is 2～12h.
(4) polyurethane film plated electrode：
The polyurethane film plated electrode that above-mentioned steps (3) are obtained.
When the electrode adopts Graphene electrodes, it is to the polyurethane film plated electrode that the step (3) is obtained：
Graphene oxide is distributed in the solvent added with obtained polyurethane and makes electrode solution, polyurethane is dense in solvent
Spend for 1～30wt%, it is preferred that graphene oxide consumption is 1 mass parts, and the solvent containing polyurethane is 20 parts by volume, if 1 matter
Amount part is 1g, then parts by volume is 1ml, the polyurethane film that the step (3) is obtained is placed in the electrode solution, 1～10min
After take out, be dried, be placed in 1～10min in hydroiodic acid, that is, complete to polyurethane film plated electrode；
When the electrode adopts other electrodes, the polyurethane film obtained to the step (3) is plated using electroless plating method
Electrode.
In said method, in parts by mass, consumption is each raw material：
The consumption of the polyalcohol is：1～70 part；
The consumption of the diisocyanate is：20～60 parts；
The consumption of the chain extender is：14～27 parts；
The consumption of the solvent is：30～80 parts.
The preparation method process is simple of the polyurethane-base IPMC that the present invention is provided, prepared IPMC materials have cause well
Dynamic performance, and with lasting fatigue resistance.
Below preparation method of the present invention is described further with specific embodiment：
For a further understanding of the present invention, the preparation method of polyurethane-base IPMC of the present invention is carried out with reference to embodiment
Describe in detail, protection scope of the present invention is not limited by the following examples.
Embodiment
By PolyTHF 20g, heated under vacuum is vacuum dried 0.5～2h to 80～110 DEG C；To vacuum drying
Methyl diphenylene diisocyanate 6.5g, condition of nitrogen gas protection is added to be sufficiently stirred for 0.5～2h in PolyTHF afterwards, plus
Heat is obtained base polyurethane prepolymer for use as to 60～80 DEG C of 2～8h of reaction；
2,2- dihydromethyl propionic acid 2.1g are added in obtained polyurethane prepolymer, 2～50min is sufficiently stirred for, plus
30mL dimethylformamides, in being poured into mould, in 80～110 DEG C of dryings, the time is 2～12h, and polyurethane film is obtained；
Graphene oxide 1g is distributed in the dimethyl formamide solution that the concentration of 20mL polyurethane is 1～30wt%,
Electrode solution is prepared into, polyurethane film obtained above is placed in into 1～10min in electrode solution and is taken out, be dried, be placed in 1 in hydroiodic acid
～10min, that is, be obtained polyurethane-base IPMC.
Jing is tested, and polyurethane-base IPMC obtained in the present embodiment has good actuating property.
The above, the only present invention preferably specific embodiment, but protection scope of the present invention is not limited thereto,
Any those familiar with the art in the technical scope of present disclosure, the change or replacement that can be readily occurred in,
All should be included within the scope of the present invention.Therefore, protection scope of the present invention should be with the protection model of claims
Enclose and be defined.
Claims (10)
1. a kind of preparation method of ionic polyurethanes Base Metal composite, it is characterised in that methods described includes following step
Suddenly：
(1) base polyurethane prepolymer for use as is prepared：Polyalcohol is heated under vacuum and is vacuum dried, obtained to after vacuum drying
Polyalcohol in add diisocyanate, base polyurethane prepolymer for use as is made in inert gas shielding, agitating heating reaction；
(2) polyurethane is prepared：Chain extender, agitating heating reaction system are added in the base polyurethane prepolymer for use as obtained to the step (1)
Obtain ionic polyurethanes；
(3) polyurethane film is prepared：After solvent dissolving is added in the ionic polyurethanes that the step (2) reaction is obtained, add
It is dried in mould, makes polyurethane film；
(4) polyurethane film plated electrode：The polyurethane film plated electrode obtained to the step (3), that is, be obtained ionic polyurethanes
Base Metal composite.
2. the preparation method of ionic polyurethanes Base Metal composite according to claim 1, it is characterised in that the side
In method, in parts by mass：
3. the preparation method of ionic polyurethanes Base Metal composite according to claim 1, it is characterised in that
In the step of methods described (1), polyalcohol used is one or more in PPG, PEPA；
Diisocyanate used is toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, naphthalene diisocyanate, different Fo Er
Any one or several in ketone diisocyanate.
4. according to claim 1 or 3 ionic polyurethanes Base Metal composite preparation method, it is characterised in that institute
In the step of stating method (1), the vacuum drying heating-up temperature is 60～110 DEG C, and vacuum drying time is 1～3h；
Inert gas used by the inert gas shielding is nitrogen or argon gas, and mixing time is 0.5～2h, agitating heating temperature
For 60～80 DEG C, the reaction time is 2～8h.
5. the preparation method of ionic polyurethanes Base Metal composite according to claim 1, it is characterised in that
In the step of methods described (2), the chain extender of addition is：In 2,2- dihydromethyl propionic acids, 2,3- dihydroxy propanesulfonates
Any one or several；
Hydroxyl and polyol hydroxyls molal quantity ratio in the chain extender is 1：0.1～1：0.9.
6. according to claim 1 or 5 ionic polyurethanes Base Metal composite preparation method, it is characterised in that
In the step of methods described (2), agitating heating temperature is 60～80 DEG C, and the reaction time is 0.5～12h.
7. the preparation method of ionic polyurethanes Base Metal composite according to claim 1, it is characterised in that
In methods described step (3), solvent used is tetrahydrofuran, dimethylformamide, dimethyl acetamide, dimethyl Asia
Any one or several in sulfone.
8. according to claim 1 or 7 ionic polyurethanes Base Metal composite preparation method, it is characterised in that institute
In stating method and step (3), the baking temperature being added in mould is 80～110 DEG C, and drying time is 2～12h.
9. the preparation method of ionic polyurethanes Base Metal composite according to claim 1, it is characterised in that the side
In method step (4), the electrode for being adopted is gold electrode, silver electrode, platinum electrode, Graphene electrodes, carbon nanotube electrode, polyaniline
Any one or several in electrode, polythiophene electrode, Platinum；
Solvent used is any one in tetrahydrofuran, dimethylformamide, dimethyl acetamide, dimethyl sulfoxide (DMSO) or several
Kind.
10. according to claim 1 or 9 ionic polyurethanes Base Metal composite preparation method, it is characterised in that institute
In stating method and step (4),
When the electrode adopts Graphene electrodes, it is to the polyurethane film plated electrode that the step (3) is obtained：
Graphene oxide is distributed in the solvent added with obtained polyurethane and makes electrode solution, the concentration of polyurethane is in solvent
1～30wt%, the polyurethane film that the step (3) is obtained is placed in the electrode solution, is taken out after 1～10min, is dried,
1～10min in hydroiodic acid is placed in, that is, is completed to polyurethane film plated electrode；
When the electrode adopts other electrodes, the polyurethane film obtained to the step (3) adopts electroless plating method plated electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610875046.7A CN106632950A (en) | 2016-09-30 | 2016-09-30 | Preparation method of ionic polyurethane based metallic composite |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610875046.7A CN106632950A (en) | 2016-09-30 | 2016-09-30 | Preparation method of ionic polyurethane based metallic composite |
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| CN201610875046.7A Pending CN106632950A (en) | 2016-09-30 | 2016-09-30 | Preparation method of ionic polyurethane based metallic composite |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102197503A (en) * | 2008-10-30 | 2011-09-21 | 拜尔材料科学股份公司 | Energy converter based on polyurethane solution |
| CN102942704A (en) * | 2012-11-20 | 2013-02-27 | 天津工业大学 | Polyurethane/cellulose composite membrane electro-active material and preparation method thereof |
-
2016
- 2016-09-30 CN CN201610875046.7A patent/CN106632950A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102197503A (en) * | 2008-10-30 | 2011-09-21 | 拜尔材料科学股份公司 | Energy converter based on polyurethane solution |
| CN102942704A (en) * | 2012-11-20 | 2013-02-27 | 天津工业大学 | Polyurethane/cellulose composite membrane electro-active material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| HU,YANOU ET AL: ""Exploration of the Possibility of Ionic Polyurethane used as IPMC Substrate"", 《PROCEEDINGS OF THE 2015 INTERNATIONAL SYMPOSIUM ON MATERIAL，ENERGY AND ENVIRONMENT ENGINEERING (ISM3E 2015)，ADVANCES IN ENGINEERING RESEARCH》 * |
| 姜涛等: ""离子聚合物-金属复合材料的研究进展"", 《材料导报A：综述篇》 * |
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Application publication date: 20170510 |