CN107501500B - Polyamide-amine functionalized graphene/hyperbranched waterborne polyurethane and preparation method thereof - Google Patents
Polyamide-amine functionalized graphene/hyperbranched waterborne polyurethane and preparation method thereof Download PDFInfo
- Publication number
- CN107501500B CN107501500B CN201710702482.9A CN201710702482A CN107501500B CN 107501500 B CN107501500 B CN 107501500B CN 201710702482 A CN201710702482 A CN 201710702482A CN 107501500 B CN107501500 B CN 107501500B
- Authority
- CN
- China
- Prior art keywords
- functionalized graphene
- polyamide
- amine
- amino
- amine functionalized
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
- C08G18/3893—Low-molecular-weight compounds having heteroatoms other than oxygen containing silicon
- C08G18/3895—Inorganic compounds, e.g. aqueous alkalimetalsilicate solutions; Organic derivatives thereof containing no direct silicon-carbon bonds
-
- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- 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
- C08G18/44—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
- C08G18/40—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
- C08G18/28—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
- C08G18/60—Polyamides or polyester-amides
- C08G18/603—Polyamides
-
- 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
- C08G18/6625—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/34
-
- 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
- C08G18/6629—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
-
- 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
- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
-
- 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
- C08G18/6662—Compounds of group C08G18/42 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
-
- 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
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
-
- 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
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6696—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
-
- 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
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
Abstract
The invention relates to polyamide-amine functionalized graphene/hyperbranched waterborne polyurethane and a preparation method thereof, which comprises the steps of firstly, selecting amino-terminated polyamide-amine to perform functional modification and reduction on graphite oxide to obtain functionalized graphene with rich primary amino groups on the surface; and then ultrasonically dispersing the functionalized graphene in acetone or N-methyl pyrrolidone, and adding the functionalized graphene into polyurethane by an in-situ polymerization method in the preparation process of the polyurethane to prepare the hyperbranched waterborne polyurethane taking the functionalized graphene as a core. The waterborne polyurethane prepared by the method takes functionalized graphene as a core, is highly branched, has a specific three-dimensional structure, has good mechanical properties and good antistatic properties when formed into a film, and can be applied to synthetic leather and fabric coatings to produce antistatic products.
Description
Technical Field
The invention relates to the technical field of polyurethane manufacturing, and particularly relates to polyamide-amine functionalized graphene/hyperbranched waterborne polyurethane and a preparation method thereof.
Background
The aqueous polyurethane resin is used as a substitute of solvent type polyurethane, has the advantages of non-inflammability, no toxicity, no pollution and the like, is acid-resistant, alkali-resistant, cold-resistant, good in air permeability and resistant to flex, and the finished synthetic leather product manufactured by the aqueous polyurethane resin is plump in hand feeling, soft in texture, comfortable and deeply favored by people. However, the aqueous polyurethane is also easy to generate static electricity in the production and use processes due to poor mechanical properties and electrical insulation, so that the application of the aqueous polyurethane in the aspects of electronic decorative leather and the like is limited. The polyamide-amine (PAMAM) dendrimer is a dendrimer which is highly branched, has a specific three-dimensional structure and highly controllable molecular size and configuration, has a wide application prospect in a plurality of fields due to the unique molecular structure and physicochemical properties, and is rapidly developed as one of research hotspots. Graphene is a novel material discovered following fullerenes, carbon nanotubes, with many excellent properties, such as: high specific surface area, good thermal conductivity, electrical conductivity, and the like. Has been paid attention by researchers and has been widely used for the preparation of composite materials. And the graphene is very easy to aggregate, has low reactivity and is difficult to be compatible with organic polymers, so that the graphene is difficult to be directly used for preparing the polymer/graphene composite material.
Disclosure of Invention
The invention aims to provide polyamide-amine functionalized graphene/hyperbranched waterborne polyurethane and a preparation method thereof.
The technical scheme adopted by the invention is as follows:
the preparation method of the polyamide-amine functionalized graphene/hyperbranched waterborne polyurethane is characterized by comprising the following steps:
firstly, selecting amino-terminated polyamide-amine to perform functional modification and reduction on graphite oxide to obtain functional graphene with rich primary amino groups on the surface;
and then ultrasonically dispersing the functionalized graphene in acetone or N-methyl pyrrolidone, and adding the functionalized graphene into polyurethane by an in-situ polymerization method in the preparation process of the polyurethane to prepare the hyperbranched waterborne polyurethane taking the functionalized graphene as a core.
The preparation method specifically comprises the following steps:
the method comprises the following steps: preparing graphite oxide by adopting a modified Hummers method:
uniformly mixing expanded graphite, concentrated sulfuric acid and phosphoric acid, slowly adding potassium permanganate, and reacting at 10-50 ℃ for 12-36 h; the mass ratio of the expanded graphite to the potassium permanganate is 1: (3-10), wherein the volume ratio of phosphoric acid to concentrated sulfuric acid is 1: (4-8), wherein the volume ratio of the mass of the expanded graphite to concentrated sulfuric acid is 20-100 mg/ml;
cooling to ice water bath after reaction, and dropwise adding hydrogen peroxide to reduce redundant potassium permanganate until no bubbles are generated;
standing for 12h, and pouring out supernatant after obvious layering;
repeatedly washing the precipitate with anhydrous ethanol and dilute hydrochloric acid, transferring to a dialysis bag after the supernatant is bright yellow, dialyzing until the pH reaches 7, and freeze-drying to obtain tawny graphite oxide;
step two: preparation of polyamide-amine functionalized graphene:
taking 0.5-2 g of graphite oxide prepared in the first step, adding the graphite oxide into 200-500 ml of solvent, ultrasonically dispersing for 0.5-2 h, adding the graphite oxide into a three-neck flask provided with a reflux condenser tube, a stirrer and a thermometer, adding 5-30 g of polyamide-amine and 4-10 g of dicyclohexylcarbodiimide, and reacting for 12-48 h at 80-110 ℃;
cooling to room temperature, centrifuging for 5-10min under the condition of 5000-10000 r/min, washing the mixture for 3-5 times by using methanol, and drying to obtain amino-terminated polyamide-amine functionalized graphene;
step three: preparing an amino-terminated polyamide-amine functionalized graphene dispersion liquid:
ultrasonically dispersing amino-terminated polyamide-amine functionalized graphene in acetone or N-methylpyrrolidone, and ultrasonically stripping for 0.5-2 hours under the condition that the power is 300-600 w to prepare an amino-terminated polyamide-amine functionalized graphene allyl ketone dispersion liquid or an amino-terminated polyamide-amine functionalized graphene pyrrolidone dispersion liquid, wherein the concentration of the amino-terminated polyamide-amine functionalized graphene is 0.5-8 mg/ml;
step four: preparing amino-terminated polyamide-amine functionalized graphite/hyperbranched waterborne polyurethane by an in-situ polymerization method:
adding 15-20 g of oligomer diol and 5-11 g of isophorone diisocyanate into a reaction kettle, wherein n (-NCO) in the isophorone diisocyanate and the oligomer diol is (3-5): 1;
adding an organic tin catalyst, and reacting at 85 ℃ for 1-2 h to obtain a prepolymer;
adding hydrophilic monomer dimethylolpropionic acid with the mass of 2-5% of that of the prepolymer for reaction for 1-2 h, cooling to 75 ℃, adding 30-100 ml of terminal amino polyamide-amine functionalized graphene allyl ketone dispersion or terminal amino polyamide-amine functionalized graphene pyrrolidone dispersion, wherein the concentration of the terminal amino polyamide-amine functionalized graphene is 0.5-5 mg/ml, and continuing the reaction for 2-3 h;
cooling to 60 ℃, adding micromolecular amine with the same molar weight as that of hydrophilic monomer dimethylolpropionic acid for neutralization for 30min, adding 30-60 ml of deionized water, emulsifying for 30min under high-speed shearing force, and removing acetone or N-methylpyrrolidone through reduced pressure distillation to obtain the amino-terminated polyamide-amine functionalized graphite/hyperbranched waterborne polyurethane with the solid content of 20-30%.
In the second step:
the polyamide-amine is selected from 1.0 generation polyamide-amine, 2.0 generation polyamide-amine;
the solvent is selected from N, N-dimethylformamide, N-methylpyrrolidone and methanol.
In the fourth step:
the oligomer dihydric alcohol is selected from polytetrahydrofuran dihydric alcohol, polycarbonate dihydric alcohol and polyester dihydric alcohol;
the organic tin catalyst is selected from dibutyltin dilaurate and dibutyltin didodecyl sulfide;
the small molecular amine is selected from triethylamine and diethylamine.
The polyamide-amine functionalized graphene/hyperbranched waterborne polyurethane prepared by the preparation method.
The invention has the following advantages:
the preparation method comprises the steps of firstly, selecting amino-terminated polyamide-amine (PAMAM) to functionally modify and reduce graphite oxide, so as to obtain functionalized graphene (N-FGs) with rich primary amino groups on the surface, ultrasonically dispersing the N-FGs in acetone or N-methylpyrrolidone, adding the N-FGs into polyurethane by an in-situ polymerization method in the preparation process of the polyurethane, and preparing hyperbranched waterborne polyurethane with N-FGs as a core.
Drawings
Fig. 1 is a schematic diagram of PAMAM-modified graphene oxide of generation 1.0 in example 1.
Fig. 2 is an XPS chart of PAMAM-modified graphene oxide of generation 1.0 in examples 1 and 2. (a) Middle 284.60,398.60,531.60eV is element C, N, O energy spectrum respectively; (b) the binding energy at 283.46eV, 285.03eV and 287.02eV is-C-O-, C-C in graphite,
(c) the binding energies of the intermediate 529.87eV and 531.87eV are respectively-O-and
(d) the binding energy of 397.45eV and 400.24eV is-CO-NH-, -CH2-NH2
Detailed Description
The present invention will be described in detail with reference to specific embodiments.
The invention relates to a preparation method of polyamide-amine functionalized graphene/hyperbranched waterborne polyurethane, which comprises the steps of firstly, selecting amino-terminated polyamide-amine to perform functional modification and reduction on graphite oxide to obtain functionalized graphene with rich primary amino groups on the surface; and then ultrasonically dispersing the functionalized graphene in acetone or N-methyl pyrrolidone, and adding the functionalized graphene into polyurethane by an in-situ polymerization method in the preparation process of the polyurethane to prepare the hyperbranched waterborne polyurethane taking the functionalized graphene as a core.
The preparation method specifically comprises the following steps:
the method comprises the following steps: preparing graphite oxide by adopting a modified Hummers method:
uniformly mixing expanded graphite, concentrated sulfuric acid and phosphoric acid, slowly adding potassium permanganate, and reacting at 10-50 ℃ for 12-36 h; the mass ratio of the expanded graphite to the potassium permanganate is 1: (3-10), wherein the volume ratio of phosphoric acid to concentrated sulfuric acid (mass fraction is 98%) is 1: (4-8), wherein the volume ratio of the mass of the expanded graphite to concentrated sulfuric acid is 20-100 mg/ml;
cooling to ice water bath after reaction, and dropwise adding hydrogen peroxide to reduce redundant potassium permanganate until no bubbles are generated;
standing for 12h, and pouring out supernatant after obvious layering;
repeatedly washing the precipitate with anhydrous ethanol and dilute hydrochloric acid, transferring to a dialysis bag after the supernatant is bright yellow, dialyzing until the pH reaches 7, and freeze-drying to obtain tawny graphite oxide;
step two: preparation of polyamide-amine functionalized graphene:
taking 0.5-2 g of graphite oxide prepared in the first step, adding the graphite oxide into 200-500 ml of solvent, adding the graphite oxide into a three-neck flask provided with a reflux condenser tube, a stirrer and a thermometer after ultrasonic dispersion for 0.5-2 h, adding 5-30 g of polyamide-amine (PAMAM) and 4-10 g of Dicyclohexylcarbodiimide (DCC), and reacting at 80-110 ℃ for 12-48 h;
cooling to room temperature, centrifuging for 5-10min under the condition of 5000-10000 r/min, washing the mixture for 3-5 times by using methanol, and drying to obtain amino-terminated polyamide-amine functionalized graphene (N-FGs);
step three: preparing an amino-terminated polyamide-amine functionalized graphene (N-FGs) dispersion liquid:
ultrasonically dispersing amino-terminated polyamide-amine functionalized graphene in acetone or N-methylpyrrolidone, and ultrasonically stripping for 0.5-2 hours under the condition that the power is 300-600 w to prepare an amino-terminated polyamide-amine functionalized graphene allyl ketone dispersion liquid or an amino-terminated polyamide-amine functionalized graphene pyrrolidone dispersion liquid, wherein the concentration of the amino-terminated polyamide-amine functionalized graphene is 0.5-8 mg/ml;
step four: preparing amino-terminated polyamide-amine functionalized graphite/hyperbranched waterborne polyurethane (N-FGs/HWPU) by an in-situ polymerization method:
adding 15-20 g of oligomer dihydric alcohol and 5-11 g of isophorone diisocyanate (IPDI) into a reaction kettle, wherein n (-NCO) in the isophorone diisocyanate and the oligomer dihydric alcohol is (3-5): 1;
adding an organic tin catalyst, and reacting at 85 ℃ for 1-2 h to obtain a prepolymer;
adding hydrophilic monomer dimethylolpropionic acid (DMPA) with the mass of 2-5% of that of the prepolymer for reaction for 1-2 h, cooling to 75 ℃, adding 30-100 ml of terminal amino polyamide-amine functionalized graphene allyl ketone dispersion liquid or terminal amino polyamide-amine functionalized graphene pyrrolidone dispersion liquid, wherein the concentration of the terminal amino polyamide-amine functionalized graphene is 0.5-5 mg/ml, and continuing the reaction for 2-3 h;
cooling to 60 ℃, adding micromolecular amine with the same molar weight as that of hydrophilic monomer dimethylolpropionic acid for neutralization for 30min, adding 30-60 ml of deionized water, emulsifying for 30min under high-speed shearing force, and removing acetone or N-methylpyrrolidone through reduced pressure distillation to obtain the amino-terminated polyamide-amine functionalized graphite/hyperbranched waterborne polyurethane with the solid content of 20-30%.
In the second step:
the polyamide-amine is selected from 1.0 generation polyamide-amine, 2.0 generation polyamide-amine;
the solvent is selected from N, N-dimethylformamide, N-methylpyrrolidone and methanol.
In the fourth step:
the oligomer dihydric alcohol is selected from polytetrahydrofuran dihydric alcohol, polycarbonate dihydric alcohol and polyester dihydric alcohol;
the organic tin catalyst is selected from dibutyltin dilaurate and dibutyltin didodecyl sulfide;
the small molecular amine is selected from triethylamine and diethylamine.
Example 1:
a preparation method of polyamide-amine functionalized graphene/hyperbranched waterborne polyurethane comprises the following steps:
1. preparing graphite oxide: 3g of expanded graphite, 350ml of concentrated sulfuric acid and 40ml of phosphoric acid are mixed, stirred for 20min at room temperature to ensure uniform mixing, 18g of potassium permanganate is slowly added, the temperature is controlled at 30 ℃, and the mixture is stirred for 24 h. And cooling to room temperature in the later period, slowly adding 200ml of deionized water for dilution, adding 30% hydrogen peroxide for reducing the redundant potassium permanganate until no bubbles are generated, standing for 12 hours, and pouring out the supernatant after layering is obvious. The reaction precipitate was washed repeatedly with absolute ethanol and dilute hydrochloric acid. When the supernatant is light yellow, centrifuging at 5000r/min for 5 min; dialyzing the separated substance in dialysis bag (8000-14000D) until pH reaches about 7, detecting with barium chloride to remove precipitate, and lyophilizing to obtain graphite oxide;
2. preparation of polyamide-amine functionalized graphene: adding 2g of graphite oxide into 500ml of N, N-dimethylformamide, ultrasonically dispersing for 1h, adding into a three-neck flask provided with a reflux condenser tube, a stirrer and a thermometer, adding 10g of Dicyclohexylcarbodiimide (DCC) and 30g of 1.0 generation polyamide-amine (1.0PAMAM), and mixing and stirring for 18h at 110 ℃; then cooling to room temperature, centrifuging for 5-10min under the condition of 5000-10000 r/min, washing the mixture for 3 times by using methanol, and drying to obtain amino-terminated polyamide-amine functionalized graphene (N-FGs);
3. adding 0.5000g N-FGs into 100ml of acetone, and ultrasonically dispersing for 1h at 30 ℃ to obtain 5mg/ml SGO acetone dispersion liquid;
4. preparing N-FGs/HWPU by an in-situ polymerization method: adding 15g of polytetrahydrofuran diol (2000) and 5g of isophorone diisocyanate into a reaction kettle, adding 4 drops of dibutyltin dilaurate catalyst, and reacting at 85 ℃ for 2h to obtain a prepolymer; adding 0.8g of hydrophilic monomer DMPA, reacting for 1h at 85 ℃, cooling to 75 ℃, adding 100ml of N-FGs acetone dispersion liquid of 5mg/ml, and continuing to react for 2 h; cooling to 60 ℃, adding triethylamine 0.67 for neutralization reaction for 30min, adding 51ml of deionized water, emulsifying for 30min under high-speed shearing force, and removing acetone by reduced pressure distillation to prepare the hyperbranched waterborne polyurethane emulsion with the solid content of about 30%.
Example 2:
a preparation method of polyamide-amine functionalized graphene/hyperbranched waterborne polyurethane comprises the following steps:
1. preparing graphite oxide: 3g of expanded graphite, 350ml of concentrated sulfuric acid and 40ml of phosphoric acid are mixed, stirred for 20min at room temperature to ensure uniform mixing, 18g of potassium permanganate is slowly added, the temperature is controlled at 30 ℃, and the mixture is stirred for 24 h. And cooling to room temperature in the later period, slowly adding 200ml of deionized water for dilution, adding 30% hydrogen peroxide for reducing the redundant potassium permanganate until no bubbles are generated, standing for 12 hours, and pouring out the supernatant after layering is obvious. The reaction precipitate was washed repeatedly with absolute ethanol and dilute hydrochloric acid. When the supernatant is light yellow, centrifuging at 5000r/min for 5 min; dialyzing the separated substance in dialysis bag (8000-14000D) until pH reaches about 7, detecting with barium chloride to remove precipitate, and lyophilizing to obtain graphite oxide;
2. preparation of polyamide-amine functionalized graphene: adding 1g of graphite oxide into 250ml of N, N-dimethylformamide, ultrasonically dispersing for 1h, adding into a three-neck flask, adding 5g of Dicyclohexylcarbodiimide (DCC) and 15g of 1.0-generation polyamide-amine (1.0GPAMAM), and mixing and stirring at 80 ℃ for 48 h; centrifuging for 5-10min under the condition of 5000-10000 r/min, washing the mixture for 3 times by using methanol, and drying to obtain amino-terminated polyamide-amine functionalized graphene (N-FGs);
3. adding 0.4500g N-FGs into 100ml of acetone, and ultrasonically dispersing for 1h at 30 ℃ to obtain 4.5mg/ml of N-FGs acetone dispersion liquid;
4. preparing N-FGs/HWPU by an in-situ polymerization method: adding 15g of polyester diol (2000) and 5g of isophorone diisocyanate into a reaction kettle, adding 4 drops of dibutyltin dilaurate catalyst, and reacting at 85 ℃ for 2h to obtain a prepolymer; adding 0.8g of hydrophilic monomer DMPA, reacting for 1h at 85 ℃, cooling to 75 ℃, adding 100ml of N-FGs acetone dispersion liquid with the concentration of 4.5mg/ml, and continuing to react for 2 h; cooling to 60 ℃, adding triethylamine 0.67 for neutralization reaction for 30min, adding 51ml of deionized water, emulsifying for 30min under high-speed shearing force, and removing acetone by reduced pressure distillation to prepare the hyperbranched waterborne polyurethane emulsion with the solid content of about 30%.
Example 3:
a preparation method of polyamide-amine functionalized graphene/hyperbranched waterborne polyurethane comprises the following steps:
1. preparing graphite oxide: 3g of expanded graphite, 350ml of concentrated sulfuric acid and 40ml of phosphoric acid are mixed, stirred for 20min at room temperature to ensure uniform mixing, 18g of potassium permanganate is slowly added, the temperature is controlled at 30 ℃, and the mixture is stirred for 24 h. And cooling to room temperature in the later period, slowly adding 200ml of deionized water for dilution, adding 30% hydrogen peroxide for reducing the redundant potassium permanganate until no bubbles are generated, standing for 12 hours, and pouring out the supernatant after layering is obvious. The reaction precipitate was washed repeatedly with absolute ethanol and dilute hydrochloric acid. When the supernatant is light yellow, centrifuging at 5000r/min for 5 min; dialyzing the separated substance in dialysis bag (8000-14000D) until pH reaches about 7, detecting with barium chloride to remove precipitate, and lyophilizing to obtain graphite oxide;
2. preparation of polyamide-amine functionalized graphene: adding 1.5g of graphite oxide into 300ml of N, N-dimethylformamide, ultrasonically dispersing for 1h, adding into a three-neck flask, adding 6g of Dicyclohexylcarbodiimide (DCC) and 30g of 1.0 generation polyamide-amine (1.0GPAMAM), and mixing and stirring at 90 ℃ for 36 h; centrifuging for 5-10min under the condition of 5000-10000 r/min, washing the mixture for 3 times by using methanol, and drying to obtain amino-terminated polyamide-amine functionalized graphene (N-FGs);
3. adding 0.3100g N-FGs into 100ml of acetone, and ultrasonically dispersing for 1h at 30 ℃ to obtain 3.1mg/ml of N-FGs acetone dispersion liquid;
4. preparing N-FGs/HWPU by an in-situ polymerization method: adding 15g of polyester diol (2000), 5g of polyether diol (2000) and 8.5g of isophorone diisocyanate into a reaction kettle, adding 5 drops of dibutyltin dilaurate catalyst, and reacting at 85 ℃ for 2 hours to obtain a prepolymer; adding 1.2g of hydrophilic monomer DMPA, reacting for 2h at 85 ℃, cooling to 75 ℃, adding, and continuing to react for 3h with 3.1mg/ml of N-FGs acetone dispersion liquid 100 ml; cooling to 60 ℃, adding 1.0g of triethylamine for neutralization reaction for 30min, adding 70ml of deionized water, emulsifying for 30min under high-speed shearing force, and removing acetone by reduced pressure distillation to prepare the hyperbranched waterborne polyurethane emulsion with the solid content of about 30%.
Example 4:
a preparation method of polyamide-amine functionalized graphene/hyperbranched waterborne polyurethane comprises the following steps:
1. preparing graphite oxide: 3g of expanded graphite, 350ml of concentrated sulfuric acid and 40ml of phosphoric acid are mixed, stirred for 20min at room temperature to ensure uniform mixing, 18g of potassium permanganate is slowly added, the temperature is controlled at 30 ℃, and the mixture is stirred for 24 h. And cooling to room temperature in the later period, slowly adding 200ml of deionized water for dilution, adding 30% hydrogen peroxide for reducing the redundant potassium permanganate until no bubbles are generated, standing for 12 hours, and pouring out the supernatant after layering is obvious. The reaction precipitate was washed repeatedly with absolute ethanol and dilute hydrochloric acid. When the supernatant is light yellow, centrifuging at 5000r/min for 5 min; dialyzing the separated substance in dialysis bag (8000-14000D) until pH reaches about 7, detecting with barium chloride to remove precipitate, and lyophilizing to obtain graphite oxide;
2. preparation of polyamide-amine functionalized graphene: adding 1G of graphite oxide into 300ml of N, N-dimethylformamide, ultrasonically dispersing for 1h, adding into a three-neck flask provided with a reflux condenser tube, a stirrer and a thermometer, adding 5G of Dicyclohexylcarbodiimide (DCC) and 15G of 2.0 generation polyamide-amine (2.0G PAMAM), and mixing and stirring for 24h at 100 ℃; then cooling to room temperature, centrifuging for 5-10min under the condition of 5000-10000 r/min, washing the mixture for 3 times by using methanol, and drying to obtain amino-terminated polyamide-amine functionalized graphene (N-FGs);
3. adding 0.4000g N-FGs into 100ml of acetone, and ultrasonically dispersing for 0.5h at 30 ℃ to obtain 4mg/ml N-FGs acetone dispersion liquid;
4. preparing N-FGs/HWPU by an in-situ polymerization method: adding 15g of polytetrahydrofuran diol (2000) and 8.5g of isophorone diisocyanate into a reaction kettle, adding 4 drops of dibutyltin dilaurate catalyst, and reacting at 85 ℃ for 2h to obtain a prepolymer; adding 0.6g of hydrophilic monomer DMPA, reacting for 1h at 85 ℃, cooling to 75 ℃, adding 100ml of 4mg/ml N-FGs acetone dispersion liquid, and continuing to react for 2h with 0.2g of DMPA; cooling to 60 ℃, adding triethylamine 0.67 for neutralization reaction for 30min, adding 60ml of deionized water, emulsifying for 30min under high-speed shearing force, and removing acetone by reduced pressure distillation to prepare the hyperbranched waterborne polyurethane emulsion with the solid content of about 30%.
Example 5:
a preparation method of polyamide-amine functionalized graphene/hyperbranched waterborne polyurethane comprises the following steps:
1. preparing graphite oxide: 2g of expanded graphite, 250ml of concentrated sulfuric acid and 30ml of phosphoric acid are mixed, stirred for 20min at room temperature to ensure uniform mixing, and slowly added with 12g of potassium permanganate, the temperature is controlled at 20 ℃, and the mixture is stirred for 24 h. And cooling to room temperature in the later period, slowly adding 200ml of deionized water for dilution, adding 30% hydrogen peroxide for reducing the redundant potassium permanganate until no bubbles are generated, standing for 12 hours, and pouring out the supernatant after layering is obvious. The reaction precipitate was washed repeatedly with absolute ethanol and dilute hydrochloric acid. When the supernatant is light yellow, centrifuging at 5000r/min for 5 min; dialyzing the separated substance in dialysis bag (8000-14000D) until pH reaches about 7, detecting with barium chloride to remove precipitate, and lyophilizing to obtain graphite oxide;
2. preparation of polyamide-amine functionalized graphene: adding 1G of graphite oxide into 300ml of N-methylpyrrolidone, adding the graphite oxide into a three-neck flask provided with a reflux condenser tube, a stirrer and a thermometer after ultrasonic dispersion for 1h, adding 5G of Dicyclohexylcarbodiimide (DCC) and 20G of 1.0 generation polyamide-amine (1.0G PAMAM), and mixing and stirring the materials at 110 ℃ for 12 h; then cooling to room temperature, centrifuging for 5-10min under the condition of 5000-10000 r/min, washing the mixture for 3 times by using methanol, and drying to obtain amino-terminated polyamide-amine functionalized graphene (N-FGs);
3. adding 0.4000g N-FGs into 50ml of N-methylpyrrolidone, and ultrasonically dispersing for 1.0h at 30 ℃ to obtain 8mg/ml of N-FGs N-methylpyrrolidone dispersion liquid;
4. preparing N-FGs/HWPU by an in-situ polymerization method: adding 10g of polytetrahydrofuran diol (2000), 10g of polycarbonate diol (2000) and 11.0g of isophorone diisocyanate into a reaction kettle, adding 5 drops of dibutyltin dilaurate catalyst, and reacting at 85 ℃ for 2h to obtain a prepolymer; adding 1.2g of hydrophilic monomer DMPA, reacting at 85 ℃ for 1h, cooling to 75 ℃, adding 50ml of 8mg/ml N-FGs N-methylpyrrolidone dispersion, and continuing to react for 2 h; cooling to 60 ℃, adding 0.9g of triethylamine for neutralization reaction for 30min, adding 30ml of deionized water, and emulsifying under high-speed shearing force for 30min to obtain the hyperbranched waterborne polyurethane emulsion with the solid content of about 30%.
Fig. 1 is a schematic diagram of 1.0G PAMAM modified graphene oxide in example 1; fig. 2 is XPS energy spectra of modified graphene oxides of examples 1 and 2.
In FIG. 2, (a) 284.60,398.60,531.60eV is an element C, N, O spectrum, (b)283.46eV, 285.03eV and 287.02eV are bond energies-C-O-, respectively, in graphite C-C,
(c)529.87eV and 531.87eV are respectively-O-and
(d)397.45eV and 400.24eV are-CO-NH-, -CH2-NH2(ii) a XPS energy spectrum analysis shows that-NH is successfully generated2And (4) adding the graphene oxide to successfully prepare the N-FGs.
TABLE 1 polyurethane film-Forming Properties obtained in the examples
| Blank space | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| Addition amount of N-FGs/%) | 0 | 2.2 | 2.0 | 1.0 | 1.5 | 1.2 |
| Tensile strength/MPa | 4.84 | 7.16 | 6.82 | 7.81 | 10.67 | 9.97 |
| Volume resistivity/Ω cm | 3.41×1012 | 2.52×107 | 2.67×107 | 2.97×108 | 3.71×107 | 1.04×108 |
The invention is not limited to the examples, and any equivalent changes to the technical solution of the invention by a person skilled in the art after reading the description of the invention are covered by the claims of the invention.
Claims (4)
1. The preparation method of the polyamide-amine functionalized graphene/hyperbranched waterborne polyurethane is characterized by comprising the following steps:
firstly, selecting amino-terminated polyamide-amine to perform functional modification and reduction on graphite oxide to obtain functional graphene with rich primary amino groups on the surface;
then ultrasonically dispersing the functionalized graphene in acetone or N-methyl pyrrolidone, and adding the functionalized graphene into polyurethane by an in-situ polymerization method in the preparation process of the polyurethane to prepare hyperbranched waterborne polyurethane taking the functionalized graphene as a core;
the preparation method specifically comprises the following steps:
the method comprises the following steps: preparing graphite oxide by adopting a modified Hummers method:
uniformly mixing expanded graphite, concentrated sulfuric acid and phosphoric acid, slowly adding potassium permanganate, and reacting at 10-50 ℃ for 12-36 h; the mass ratio of the expanded graphite to the potassium permanganate is 1: (3-10), wherein the volume ratio of phosphoric acid to concentrated sulfuric acid is 1: (4-8), wherein the volume ratio of the mass of the expanded graphite to concentrated sulfuric acid is 20-100 mg/ml;
cooling to ice water bath after reaction, and dropwise adding hydrogen peroxide to reduce redundant potassium permanganate until no bubbles are generated;
standing for 12h, and pouring out supernatant after obvious layering;
repeatedly washing the precipitate with anhydrous ethanol and dilute hydrochloric acid, transferring to a dialysis bag after the supernatant is bright yellow, dialyzing until the pH reaches 7, and freeze-drying to obtain tawny graphite oxide;
step two: preparation of polyamide-amine functionalized graphene:
taking 0.5-2 g of graphite oxide prepared in the first step, adding the graphite oxide into 200-500 ml of solvent, ultrasonically dispersing for 0.5-2 h, adding the graphite oxide into a three-neck flask provided with a reflux condenser tube, a stirrer and a thermometer, adding 5-30 g of polyamide-amine and 4-10 g of dicyclohexylcarbodiimide, and reacting for 12-48 h at 80-110 ℃;
cooling to room temperature, centrifuging for 5-10min under the condition of 5000-10000 r/min, washing the mixture for 3-5 times by using methanol, and drying to obtain amino-terminated polyamide-amine functionalized graphene;
step three: preparing an amino-terminated polyamide-amine functionalized graphene dispersion liquid:
ultrasonically dispersing amino-terminated polyamide-amine functionalized graphene in acetone or N-methylpyrrolidone, and ultrasonically stripping for 0.5-2 hours under the condition that the power is 300-600 w to prepare an amino-terminated polyamide-amine functionalized graphene allyl ketone dispersion liquid or an amino-terminated polyamide-amine functionalized graphene pyrrolidone dispersion liquid, wherein the concentration of the amino-terminated polyamide-amine functionalized graphene is 0.5-8 mg/ml;
step four: preparing amino-terminated polyamide-amine functionalized graphite/hyperbranched waterborne polyurethane by an in-situ polymerization method:
adding 15-20 g of oligomer diol and 5-11 g of isophorone diisocyanate into a reaction kettle, wherein n (-NCO) in the isophorone diisocyanate and the oligomer diol is (3-5): 1;
adding an organic tin catalyst, and reacting at 85 ℃ for 1-2 h to obtain a prepolymer;
adding hydrophilic monomer dimethylolpropionic acid with the mass of 2-5% of that of the prepolymer for reaction for 1-2 h, cooling to 75 ℃, adding 30-100 ml of amino-terminated polyamide-amine functionalized graphene allyl ketone dispersion or amino-terminated polyamide-amine functionalized graphene pyrrolidone dispersion, wherein the concentration of the amino-terminated polyamide-amine functionalized graphene is 0.5-5 mg/ml, and continuing the reaction for 2-3 h;
cooling to 60 ℃, adding micromolecular amine with the same molar weight as that of hydrophilic monomer dimethylolpropionic acid for neutralization for 30min, adding 30-60 ml of deionized water, emulsifying for 30min under high-speed shearing force, and removing acetone or N-methylpyrrolidone through reduced pressure distillation to obtain the amino-terminated polyamide-amine functionalized graphite/hyperbranched waterborne polyurethane with the solid content of 20-30%.
2. The method for preparing polyamide-amine functionalized graphene/hyperbranched aqueous polyurethane according to claim 1, wherein the method comprises the following steps:
in the second step:
the polyamide-amine is selected from 1.0 generation polyamide-amine, 2.0 generation polyamide-amine;
the solvent is selected from N, N-dimethylformamide, N-methylpyrrolidone and methanol.
3. The method for preparing polyamide-amine functionalized graphene/hyperbranched aqueous polyurethane according to claim 2, wherein the method comprises the following steps:
in the fourth step:
the oligomer dihydric alcohol is selected from polytetrahydrofuran dihydric alcohol, polycarbonate dihydric alcohol and polyester dihydric alcohol;
the organic tin catalyst is selected from dibutyltin dilaurate and dibutyltin didodecyl sulfide;
the small molecular amine is selected from triethylamine and diethylamine.
4. The polyamide-amine functionalized graphene/hyperbranched aqueous polyurethane prepared by the preparation method of claim 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710702482.9A CN107501500B (en) | 2017-08-16 | 2017-08-16 | Polyamide-amine functionalized graphene/hyperbranched waterborne polyurethane and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710702482.9A CN107501500B (en) | 2017-08-16 | 2017-08-16 | Polyamide-amine functionalized graphene/hyperbranched waterborne polyurethane and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107501500A CN107501500A (en) | 2017-12-22 |
| CN107501500B true CN107501500B (en) | 2020-05-19 |
Family
ID=60691186
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710702482.9A Active CN107501500B (en) | 2017-08-16 | 2017-08-16 | Polyamide-amine functionalized graphene/hyperbranched waterborne polyurethane and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107501500B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019143299A1 (en) * | 2018-01-18 | 2019-07-25 | Antony Prince James Selvaraj | Hyper-branched compounds, synthesis and uses thereof |
| CN108505049B (en) * | 2018-05-28 | 2019-12-10 | 中国科学院理化技术研究所 | Graphite oxide corrosion inhibitor and preparation and application thereof |
| CN108727962A (en) * | 2018-06-27 | 2018-11-02 | 南京林业大学 | A kind of aqueous polyurethane coating and graphene oxide composite coating interface ultrabranching polyamide adhering method |
| CN110156954B (en) * | 2019-05-30 | 2022-01-21 | 陕西科技大学 | Waterborne polyurethane capable of absorbing ultraviolet rays and preparation method thereof |
| CN110606934A (en) * | 2019-08-14 | 2019-12-24 | 惠东县鞋业科技创新中心 | Environment-friendly water-based anionic polyurethane adhesive and preparation method thereof |
| CN111234157B (en) * | 2020-03-09 | 2021-10-19 | 江苏科技大学 | Reactive extrusion preparation method of flame-retardant hyperbranched polyamide 6 elastomer |
| CN113980452A (en) * | 2021-12-13 | 2022-01-28 | 深圳市华美龙电子应用材料有限公司 | Antibacterial anti-static film |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101831046A (en) * | 2010-03-30 | 2010-09-15 | 上海交通大学 | Cross-linking agent, rigid polyurethane foam material and preparation method thereof |
| CN103805046A (en) * | 2014-01-26 | 2014-05-21 | 陕西科技大学 | Graphene-containing waterborne polyurethane composite conductive coating prepared in situ and preparation method thereof |
| CN105148995A (en) * | 2015-09-23 | 2015-12-16 | 吉首大学 | Application of PAMAM carboxylated graphene Co nano-composite material in 4-nitroaniline degradation and catalysis |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8927658B2 (en) * | 2012-09-19 | 2015-01-06 | National Taiwan University Of Science And Technology | Fluorescent hybrid of dendrimer and graphene oxide |
-
2017
- 2017-08-16 CN CN201710702482.9A patent/CN107501500B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101831046A (en) * | 2010-03-30 | 2010-09-15 | 上海交通大学 | Cross-linking agent, rigid polyurethane foam material and preparation method thereof |
| CN103805046A (en) * | 2014-01-26 | 2014-05-21 | 陕西科技大学 | Graphene-containing waterborne polyurethane composite conductive coating prepared in situ and preparation method thereof |
| CN105148995A (en) * | 2015-09-23 | 2015-12-16 | 吉首大学 | Application of PAMAM carboxylated graphene Co nano-composite material in 4-nitroaniline degradation and catalysis |
Non-Patent Citations (1)
| Title |
|---|
| Poly(amidoamine) modified grapheme oxide as an efficient adsorbent for heavy metal ions;Yang Yuan等;《Polymer Chemistry》;20131231(第201306期);第2164-2167页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107501500A (en) | 2017-12-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107501500B (en) | Polyamide-amine functionalized graphene/hyperbranched waterborne polyurethane and preparation method thereof | |
| CN107383302B (en) | Preparation method of sulfonated modified graphene oxide/high-solid-content aqueous polyurethane | |
| CN104861643A (en) | Preparing method of graphene/waterborne polyurethane composite material | |
| CN104628982B (en) | A kind of preparation method of alkali lignin base water polyurethane | |
| CN102408537B (en) | Preparation method of acrylate modified water-borne polyurethane emulsion for synthetic leather | |
| CN102093517B (en) | Aqueous polyurethane-acrylate resin for synthetic leather fabrics and preparation method thereof | |
| CN105385148A (en) | Sulfonated graphene-modified waterborne polyurethane resin and preparation method thereof | |
| CN106046287A (en) | Preparation method of graphene modified waterborne polyurethane | |
| CN103981716A (en) | Preparation method of organosilicon modified aqueous polyurethane for leather, and product prepared by using it | |
| KR101327871B1 (en) | Manufacturing method for floor material for energy saving and electromagnetic shielding and floor material prepared by using the same | |
| Jin et al. | Assembly of graphene oxide into the hyperbranched frameworks for the fabrication of flexible protein-based films with enhanced conductivities | |
| CN112724358B (en) | Preparation method of waterborne flame-retardant self-repairing polyurethane based on modified graphene | |
| CN115216219B (en) | Bionic environment-adaptive self-repairing coating and preparation method and application thereof | |
| CN111217974A (en) | Self-repairable polyurethane material and preparation method and application thereof | |
| CN114539763B (en) | Polyurethane elastomer composite material, preparation method and application | |
| CN113088064B (en) | Bionic nano composite material for realizing enhancement of electrical conductivity and mechanical property through supermolecule effect and preparation method thereof | |
| CN113370548A (en) | Polyurethane condom forming method based on wet process | |
| CN113667091B (en) | Graphene/waterborne polyurethane composite material and preparation method and application thereof | |
| CN110685159A (en) | Production method of water-based microfiber synthetic leather | |
| CN112795361B (en) | Preparation method of high-heat-resistance redwood binder capable of being bent by thermal change | |
| TWI384002B (en) | Method for fabricating aqueous polyurethanes | |
| CN112608440A (en) | Self-extinction waterborne polyurethane and preparation method thereof | |
| CN111155325B (en) | Three-dimensional composite nano carbon material, environment-friendly polyurethane synthetic leather with high folding fastness prepared from three-dimensional composite nano carbon material and preparation method of environment-friendly polyurethane synthetic leather | |
| CN110951028A (en) | Polyurethane resin and preparation method and application thereof | |
| CN112745657B (en) | Anti-slip thermoplastic polyurethane composite material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |