CN111019189A - Sponge modification method based on graphene waterborne polyurethane - Google Patents
Sponge modification method based on graphene waterborne polyurethane Download PDFInfo
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- CN111019189A CN111019189A CN201911363055.8A CN201911363055A CN111019189A CN 111019189 A CN111019189 A CN 111019189A CN 201911363055 A CN201911363055 A CN 201911363055A CN 111019189 A CN111019189 A CN 111019189A
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- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
- C08J9/40—Impregnation
- C08J9/42—Impregnation with macromolecular compounds
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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
- C08G18/08—Processes
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- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
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- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
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- 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
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Abstract
The invention belongs to the technical field of preparation of polyurethane sponge materials, and particularly relates to a graphene-based waterborne polyurethane sponge modification method.
Description
Technical Field
The invention belongs to the technical field of preparation of polyurethane sponge materials, and particularly relates to a sponge modification method based on graphene waterborne polyurethane.
Background
In recent years, the research of converting mechanical energy in the environment into electrical energy by using piezoelectric materials is more and more focused, and piezoresistive sensing materials with high sensitivity and large deformation range are the key points of the research in recent years, most of the current sensing materials cannot simultaneously maintain two important characteristics of high sensitivity and wide measurement range, for example, conductive polymer materials have good variability but are insensitive under small deformation and low pressure. The research in this field is therefore increasingly directed towards the organic integration of electrically variable materials with elastomeric materials.
Disclosure of Invention
The invention provides a sponge modification method based on graphene waterborne polyurethane, which comprises the following steps:
(1) modifying graphene oxide by using an amine modifier,
specifically, amine modifier is added into the ultrasonic dispersion liquid of the graphene oxide, after the temperature rise reaction, the unreacted amine modifier is removed, the modified graphene oxide is dispersed in deionized water to obtain the dispersion liquid of the modified graphene oxide,
in the ultrasonic dispersion liquid of the graphene oxide, the mass ratio of the graphene oxide to water is 1: 80 to 150 parts of a first resin composition,
the amine modifier is an amine compound with two or more amino groups, such as polyether amine, and the mass ratio of the amine modifier to the graphene oxide is (2-6): 1,
the reaction temperature of the temperature rise reaction is 40-60 ℃, the reaction time is 16-48 hours,
removing unreacted amine modifier by dialysis, centrifugation or filtration washing;
(2) firstly, mixing and reacting a diisocyanate compound, polyol and a hydrophilic monomer to a certain degree, adding the obtained reaction system into the dispersion liquid of the modified graphene oxide obtained in the step (1), fully mixing to obtain the aqueous polyurethane emulsion grafted with graphene,
specifically, adding a catalyst into a diisocyanate compound, dropwise adding a polyol, heating to react to a certain degree after dropwise adding, adding a hydrophilic monomer, continuously reacting for a period of time, dropwise adding the obtained reaction system into the modified graphene oxide dispersion liquid obtained in the step (1), and fully stirring,
wherein the diisocyanate compound is one or a combination of hexamethylene diisocyanate HDI, diphenylmethane diisocyanate MDI, toluene diisocyanate TDI, isophorone diisocyanate IPDI and methyl cyclohexyl diisocyanate,
the polyol is polyether polyol or polyester polyol, preferably polyethylene glycol, polypropylene glycol and the like, and is oligomer,
the hydrophilic monomer is dimethylolpropionic acid, dimethylolbutyric acid, 1, 2-dihydroxy-3-propanesulfonic acid sodium salt, etc.,
the mass ratio of the total mass of the diisocyanate compound, the polyol and the hydrophilic monomer to the amount of the modified graphene oxide in the dispersion liquid obtained in the step (1) is 4-12: 1,
the hydrophilic monomer accounts for 1 to 10 percent of the total mass of the diisocyanate compound, the polyalcohol and the hydrophilic monomer,
the temperature of the heating reaction is 45-60 ℃, the reaction time is 1-2 hours,
adding a hydrophilic monomer, continuing to react for 4-6 hours,
in the step, firstly, reacting a diisocyanate compound with polyol and a hydrophilic monomer with hydroxyl, reserving a certain amount of isocyanate groups, adding the isocyanate groups into the modified graphene dispersion liquid, and utilizing amino groups left on polyether amine molecules grafted to graphene to fully react and combine with the reserved isocyanate groups (exothermic reaction) to realize chemical connection between a polyurethane chain segment and the graphene; the hydrophilic monomer combined on the polyurethane chain segment endows the polyurethane chain segment with hydrophilicity due to the hydrophilic group, thereby realizing the emulsification of the polyurethane grafted graphene composite material in water,
preferably, the method comprises the following steps: after stirring and emulsifying, a reducing agent can be added into the emulsion to reduce the graphene oxide in the emulsion into graphene,
(3) placing polyurethane sponge in the aqueous polyurethane emulsion grafted with graphene obtained in the step (2), soaking and diffusing the polyurethane sponge by the emulsion, taking out the polyurethane sponge, drying (drying at 50-70 ℃) to obtain graphene aqueous polyurethane modified sponge,
a large amount of water exists in the emulsion, when the emulsion is in contact with the sponge, the water is easy to permeate and diffuse into the holes of the sponge body, and meanwhile, polyurethane macromolecules grafted with graphene are brought into the holes, polyurethane molecular chains are attached to the hole walls of the sponge body through the mutual attraction of hydrogen bonds, after the water is dried, the polyurethane molecular chains and the sponge molecular chains on the surfaces of the hole walls of the sponge body are wound to form coating solidification, and the graphene is naturally and stably fixed on the surfaces of the hole walls of the sponge body and is not easy to fall off. Because the graphite substance has good conductive capability, after the graphite substance is fixed on the sponge body, when the sponge body is compressed and deformed, contact points in the sponge body are greatly increased to form a large number of new conductive paths, and the integral resistance value of the sponge block is changed, so that the conversion between a mechanical signal and an electrical signal is realized, and the modified sponge can be used as a core material of a piezoresistive sensor;
meanwhile, the applicant finds that after the graphene materials are grafted on the macromolecules of the emulsion, the resistance of the emulsion in the pore passage of the sponge body can be reduced based on the high lubricity of the graphene, so that the diffusion rate of the emulsion in the sponge body is greatly improved, the time required for the emulsion to fully permeate the whole sponge body under the same condition is correspondingly reduced, and the production efficiency of the process is improved.
Drawings
FIG. 1 is a graph showing the effect of the emulsion in example 1 and comparative example 1 on the diffusion into a polyurethane sponge mass standing therein for the same period of time,
FIG. 2 is a graph showing the effect of the emulsion in example 2 of the present application and comparative example 2 after the emulsion has diffused into the polyurethane sponge mass standing therein for the same period of time,
FIG. 3 is an internal electron microscope image of the graphene waterborne polyurethane modified sponge obtained in step (3) of example 2 of the present application,
fig. 4 is an internal electron microscope image of the graphene aqueous polyurethane modified sponge obtained in step (3) of example 2 in the present application, and the wavy surface in fig. 4 is graphene, which illustrates that there is graphene coverage on the sponge matrix, and if there is no graphene, the morphology here should be relatively flat.
Detailed Description
Example 1
(1) Firstly, mixing 15g of graphene oxide prepared by a Hummers method with 1500g of deionized water, fully dispersing by ultrasonic to obtain graphene oxide dispersion liquid,
70g of polyetheramine D-230 was added to the graphene oxide dispersion, the mixture was sufficiently dispersed with stirring (stirring rate: 100 rpm), and the mixture was heated to 60 ℃ with stirring (oil bath heating) to react for 20 hours,
filtering and washing until the filtered cleaning solution is neutral (pH is 7), and re-dispersing the filter cake obtained by filtering into 1800g of deionized water to obtain a dispersion liquid of the modified graphene oxide;
(2) adding 2.2g of dibutyltin dilaurate into 457g of isophorone diisocyanate IPDI, dropwise adding 616g of polyethylene glycol 400 into the IPDI, dropwise adding the mixture after 4 hours, heating the mixture to 50 ℃ (heating in an oil bath) under a stirring state of 280 revolutions per minute, reacting for 1 hour, adding 36g of 1, 2-dihydroxy-3-propanesulfonic acid sodium into the mixture, keeping the stirring state and the 50 ℃ (heating in the oil bath), continuously reacting for 5 hours, averagely dividing the obtained reaction system mixture into two parts, wherein each part is 553.2g, completely dropwise adding one part into the modified graphene oxide dispersion liquid obtained in the step (1), dropwise adding the mixture after 2 hours, and stirring and mixing for 2 hours at 650 revolutions per minute to obtain the aqueous polyurethane emulsion grafted with graphene;
(3) standing a cuboid polyurethane sponge block with the length of 6cm at the left and right, the width of 1cm at the front and the back, the height of 5cm at the top and the bottom (the directions in the attached drawing 1 and the same below) in the step (2) of which the liquid level is 0.5cm and the volume is 12mL in total, in the graphene-grafted aqueous polyurethane emulsion obtained in the step (2), wherein the polyurethane sponge block falls to the bottom of the emulsion so that the height of the polyurethane sponge block above the liquid level of the emulsion is 4.5cm, and allowing the emulsion to freely diffuse into the polyurethane sponge block (the diffusion is carried out at the normal temperature (25 ℃, the same below)). After holding for 20 minutes in this resting state, the emulsion in the container diffused up to approximately half the height of the polyurethane sponge block, as in the sample on the right side of FIG. 1.
Comparative example 1
The graphene material was not grafted onto the macromolecules of the aqueous emulsion, and the rest of the procedure was the same as in example 1:
(1) dropwise adding the other part of the reaction system mixture remained in the step (2) in the example 1 into 1900g of deionized water, dropwise adding the mixture for 2 hours, stirring at 650 rpm for 2 hours to obtain an aqueous polyurethane emulsion, adding sodium hydroxide into the obtained polyurethane emulsion to adjust the pH value to be 11, dropwise adding a phenolphthalein reagent, and enabling the polyurethane emulsion to be pink after dispersion is stable (so as to ensure the visibility of the diffusion degree of the emulsion on the sponge block in the step 2 detection test);
(2) a cuboid polyurethane sponge block which is 6cm long at the left and right, 1cm wide at the front and back, 5cm high at the top and bottom and is made of the same material as that in the embodiment 1 is statically placed in the aqueous polyurethane emulsion obtained in the step (1) with the liquid level height of 0.5cm and the volume of 12mL, the polyurethane sponge block falls to the bottom of the emulsion, so that the height of the polyurethane sponge block above the liquid level of the emulsion is 4.5cm, and the emulsion is allowed to freely diffuse into the polyurethane sponge block (diffusion is carried out at normal temperature). After 20 minutes of holding in this resting state, the emulsion in the container can only diffuse up to a height above the liquid level on the polyurethane sponge block, as in the left-hand sample of fig. 1.
Example 2
(1) Same as in step (1) of example 1;
(2) adding 2.4g of dibutyltin dilaurate into 346g of hexamethylene diisocyanate HDI, dropwise adding 965g of polyethylene glycol 600, dropwise adding the polyethylene glycol 600 for 4.5 hours, heating to 50 ℃ (heating by an oil bath) under the stirring state of 300 revolutions per minute, reacting for 1.5 hours, adding 40g of 1, 2-dihydroxy-3-sodium propanesulfonate, keeping the stirring state and 50 ℃ (heating by the oil bath), continuously reacting for 5 hours, averagely dividing the obtained reaction system mixture into two parts, wherein each part is 673.4g, completely dropwise adding one part into the modified graphene oxide dispersion liquid obtained in the step (1), dropwise adding the mixture for 2 hours, and stirring and mixing for 2 hours at 700 revolutions per minute to obtain the aqueous polyurethane emulsion grafted with graphene;
(3) a rectangular polyurethane sponge block which is 6cm long left and right, 1cm wide front and back, 5cm high up and down and is made of the same material as that in the example 1 is statically placed in the aqueous polyurethane emulsion grafted with graphene obtained in the step (2) in which the liquid level height is 0.65cm and the volume is 15.6mL, and the polyurethane sponge block falls to the bottom of the emulsion so that the height of the polyurethane sponge block above the liquid level of the emulsion is 4.35cm, and the emulsion is allowed to freely diffuse into the polyurethane sponge block (diffusion is carried out at normal temperature). After holding for 60 minutes in this resting state, the emulsion in the container diffused up to the height of the sample on the sponge block as shown on the right in FIG. 2. At this time, the polyurethane sponge block is taken out of the emulsion and fully dried at 60 ℃ to obtain the graphene waterborne polyurethane modified sponge, and the microstructure of the area on the sponge block which is fully infiltrated by the emulsion is shown in the attached figures 3 and 4.
Comparative example 2
The graphene material was not grafted onto the macromolecules of the aqueous emulsion, and the rest of the procedure was the same as example 2:
(1) dropwise adding the other part of the reaction system mixture remained in the step (2) in the example 2 into 1900g of deionized water, dropwise adding the mixture for 2 hours, stirring at 700 rpm for 2 hours to obtain an aqueous polyurethane emulsion, adding sodium hydroxide into the obtained polyurethane emulsion to adjust the pH value to be 11, dropwise adding a phenolphthalein reagent, and stably dispersing to ensure that the polyurethane emulsion is pink (so as to ensure the visibility of the diffusion degree of the emulsion on the sponge block in the step 2 detection test);
(2) a cuboid polyurethane sponge block which is 6cm long at the left and right, 1cm wide at the front and back, 5cm high at the top and bottom and is made of the same material as that in the embodiment 1 is statically placed in the aqueous polyurethane emulsion obtained in the step (1) with the liquid level height of 0.65cm and the volume of 15.6mL, the polyurethane sponge block falls to the bottom of the emulsion, so that the height of the polyurethane sponge block above the liquid level of the emulsion is 4.35cm, and the emulsion is allowed to freely diffuse into the polyurethane sponge block (diffusion is carried out at normal temperature). After 60 minutes of holding in this resting state, the emulsion in the container can only diffuse up to a third of the height of the polyurethane sponge block, as in the left-hand sample of fig. 2.
Claims (9)
1. A sponge modification method based on graphene waterborne polyurethane is characterized by comprising the following steps: the method comprises the following steps of,
(1) modifying graphene oxide by using an amine modifier;
(2) firstly, mixing and reacting a diisocyanate compound, polyol and a hydrophilic monomer to a certain degree, adding the obtained reaction system into the dispersion liquid of the modified graphene oxide obtained in the step (1), and fully mixing and reacting to obtain the aqueous polyurethane emulsion grafted with graphene;
(3) and (3) placing the polyurethane sponge into the aqueous polyurethane emulsion grafted with the graphene obtained in the step (2), and after the emulsion soaks and diffuses the polyurethane sponge, taking out the polyurethane sponge and drying to obtain the graphene aqueous polyurethane modified sponge.
2. The method for modifying a sponge based on graphene waterborne polyurethane according to claim 1, wherein: specifically, in the step (1), an amine modifier is added into the ultrasonic dispersion liquid of the graphene oxide, the temperature is raised for reaction, unreacted amine modifier is removed, and the modified graphene oxide is dispersed in deionized water to obtain the dispersion liquid of the modified graphene oxide.
3. The method for modifying a sponge based on graphene waterborne polyurethane according to claim 2, wherein: in the ultrasonic dispersion liquid of the graphene oxide, the mass ratio of the graphene oxide to water is 1: 80-150 parts by weight.
4. The method for modifying a sponge based on graphene waterborne polyurethane according to claim 1, wherein: the amine modifier in the step (1) is polyether amine, and the mass ratio of the amine modifier to the graphene oxide is (2-6): 1.
5. the method for modifying a sponge based on graphene waterborne polyurethane according to claim 1, wherein: the diisocyanate compound in the step (2) is one or a combination of hexamethylene diisocyanate HDI, diphenylmethane diisocyanate MDI, toluene diisocyanate TDI, isophorone diisocyanate IPDI and methyl cyclohexyl diisocyanate.
6. The method for modifying a sponge based on graphene waterborne polyurethane according to claim 1, wherein: the polyol in the step (2) is polyether polyol or polyester polyol.
7. The method for modifying a sponge based on graphene waterborne polyurethane according to claim 1, wherein: the hydrophilic monomer in the step (2) is dimethylolpropionic acid, dimethylolbutyric acid or 1, 2-dihydroxy-3-sodium propanesulfonate.
8. The method for modifying a sponge based on graphene waterborne polyurethane according to claim 1, wherein: in the step (2), the mass ratio of the total mass of the diisocyanate compound, the polyol and the hydrophilic monomer to the amount of the modified graphene oxide in the dispersion liquid obtained in the step (1) is 4-12: 1.
9. the method for modifying a sponge based on graphene waterborne polyurethane according to claim 1, wherein: in the step (2), the hydrophilic monomer accounts for 1-10% of the total mass of the diisocyanate compound, the polyol and the hydrophilic monomer.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107828046A (en) * | 2017-11-09 | 2018-03-23 | 江南大学 | A kind of preparation method of aqueous polyurethane/dopamine modified graphene nano-composite emulsion |
| WO2018113698A1 (en) * | 2016-12-23 | 2018-06-28 | 北京赛特石墨烯科技有限公司 | Graphene polyurethane sponge, preparation method therefor and applications thereof |
| CN110193358A (en) * | 2019-06-27 | 2019-09-03 | 中素新科技有限公司 | Composite sponge and its preparation method and application containing amino modified graphene |
| CN110193357A (en) * | 2019-06-27 | 2019-09-03 | 中素新科技有限公司 | Composite sponge and its preparation method and application containing modified graphene |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018113698A1 (en) * | 2016-12-23 | 2018-06-28 | 北京赛特石墨烯科技有限公司 | Graphene polyurethane sponge, preparation method therefor and applications thereof |
| CN107828046A (en) * | 2017-11-09 | 2018-03-23 | 江南大学 | A kind of preparation method of aqueous polyurethane/dopamine modified graphene nano-composite emulsion |
| CN110193358A (en) * | 2019-06-27 | 2019-09-03 | 中素新科技有限公司 | Composite sponge and its preparation method and application containing amino modified graphene |
| CN110193357A (en) * | 2019-06-27 | 2019-09-03 | 中素新科技有限公司 | Composite sponge and its preparation method and application containing modified graphene |
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