CN107501500A - Daiamid functionalization graphene/hyperbranched aqueous polyurethane and preparation method thereof - Google Patents
Daiamid functionalization graphene/hyperbranched aqueous polyurethane and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to daiamid functionalization graphene/hyperbranched aqueous polyurethane and preparation method thereof, carries out functional modification to graphite oxide from the daiamid of Amino End Group first and reduces, obtains the functionalization graphene that abundant primary amino radical is contained on surface；Functionalization graphene ultrasonic disperse is added in polyurethane in acetone or N methyl pyrrolidones in the preparation process of polyurethane by in-situ polymerization again, prepares the hyperbranched aqueous polyurethane using functionalization graphene as core.Aqueous polyurethane prepared by this method is highly branched, have specific three dimensional structure using functionalization graphene as core, and film forming has preferable mechanical property and good antistatic behaviour, can be applied to synthetic leather, fabric coating, production antistatic products.
Description
Technical field
The present invention relates to the manufacturing technology field of polyurethane, and in particular to a kind of polyamide-amide functionalization graphene/over-expense
Change aqueous polyurethane and preparation method thereof.
Background technology
Substitute of the waterborne polyurethane resin as solvent borne polyurethane, have the advantages that it is non-ignitable, nontoxic, pollution-free, its
Film forming is acidproof, alkaline-resisting, cold-resistant, good permeability, resistance to flexion, and made synthetic leather products good hand feeling, soft texture, comfortably,
It is deep to be favored by people.But aqueous polyurethane also because of its poor mechanical property, electric insulation, easily produces in the production and use process
Electrostatic, limit its application in electronics decoration leather etc..Polyamide-amide (PAMAM) class dendrimer is that a kind of height is propped up
Change, there is specific three dimensional structure, molecular dimension and the highly controllable dendritic macromole of configuration, its unique molecular structure and thing
Physicochemical property is allowed to have a wide range of applications in various fields, and develops rapidly as one of study hotspot.Graphene is
The new material found after fullerene, CNT, has many excellent properties, such as：High-specific surface area, good lead
Hot, electric conductivity etc..Paid close attention to all the time by researchers, have been widely used for the preparation of composite.Again because of graphite
Dilute itself to be very easy to aggregation, reactivity is not high and is difficult compatible between organic polymer, and it is difficult directly to use to cause it
The preparation of polymer/graphene composite material.
The content of the invention
It is an object of the invention to provide a kind of polyamide-amide functionalization graphene/hyperbranched aqueous polyurethane and its preparation
Method, the aqueous polyurethane of preparation is highly branched, have specific three dimensional structure using N-FGs as core, and film forming has preferable mechanics
Performance and good antistatic behaviour, solve traditional waterborne polyurethane poor mechanical property, electric insulation, not easy heat radiation the shortcomings of.
The technical solution adopted in the present invention is：
The preparation method of polyamide-amide functionalization graphene/hyperbranched aqueous polyurethane, it is characterised in that：
Functional modification is carried out to graphite oxide from the polyamide-amide of Amino End Group first and reduced, surface is obtained and contains
The functionalization graphene of abundant primary amino radical；
Again by functionalization graphene ultrasonic disperse in acetone or 1-METHYLPYRROLIDONE, in the preparation process of polyurethane
It is added to by in-situ polymerization in polyurethane, prepares the hyperbranched aqueous polyurethane using functionalization graphene as core.
The preparation method specifically includes following steps：
Step 1：Graphite oxide is prepared using improved Hummers methods：
Expanded graphite, the concentrated sulfuric acid, phosphoric acid are well mixed, are then slowly added into potassium permanganate, is reacted at 10-50 DEG C
12-36h；Expanded graphite, potassium permanganate mass ratio are 1：(3~10), phosphoric acid and concentrated sulfuric acid volume ratio 1：(4~8), expanded graphite
Quality is with concentrated sulfuric acid volume than 20~100mg/ml of scope；
Ice-water bath is cooled to after reaction, hydrogen peroxide is added dropwise and reduces unnecessary potassium permanganate, until bubble-free produces；
Static 12h, after treating that layering is obvious, outwell supernatant；
With absolute ethyl alcohol and watery hydrochloric acid washing precipitate repeatedly, after supernatant is in glassy yellow, bag filter dialysis is transferred to
Reach 7 to pH, be then freeze-dried and filemot graphite oxide is made；
Step 2：The preparation of polyamide-amide functionalization graphene：
0.5~the 2g of graphite oxide for taking step 1 to prepare, add in 200~500ml solvents, after 0.5~2h of ultrasonic disperse
Add in the three-necked flask of dress reflux condensing tube, agitator and thermometer, add 5~30g of polyamide-amide and dicyclohexyl carbon two
4~10g of imines, react 12~48h at 80 DEG C~110 DEG C；
It is cooled to room temperature and 5-10min is centrifuged under the conditions of 5000~10000r/min, mixture is washed 3-5 times with methanol,
Dry, Amino End Group polyamide-amide functionalization graphene is made；
Step 3：It is prepared by Amino End Group polyamide-amide functionalization graphene dispersion liquid：
By Amino End Group polyamide-amide functionalization graphene ultrasonic disperse in acetone or 1-METHYLPYRROLIDONE, power
Ultrasound peels off 0.5~2h under the conditions of 300w~600w, and Amino End Group polyamide-amide functionalization graphene acetone dispersion liquor or end is made
Amino polyamide-amide functionalization graphene pyrrolidones dispersion liquid, Amino End Group polyamide-amide functionalization graphene concentration are 0.5
~8mg/ml；
Step 4：Situ aggregation method prepares Amino End Group polyamide-amide function graphite/hyperbranchedization aqueous polyurethane：
15~20g of oligomer dihydric alcohol, 5~11g of IPDI are added in reactor, wherein different Fo Er
N (- NCO) in ketone diisocyanate and oligomer dihydric alcohol:N (- OH) is (3~5)：1；
Organic tin catalyst is added, performed polymer is made in 85 DEG C of reaction 1~2h reactions；
The hydrophilic monomer dihydromethyl propionic acid for adding performed polymer quality 2%~5% reacts 1~2h, is cooled to 75 DEG C of additions
Amino End Group polyamide-amide functionalization graphene acetone dispersion liquor or Amino End Group polyamide-amide functionalization graphene pyrrolidones point
30~100ml of dispersion liquid, Amino End Group polyamide-amide functionalization graphene concentration is 0.5~5mg/ml, continues 2~3h of reaction；
60 DEG C of cooling, add in the small molecule amine with hydrophilic monomer dihydromethyl propionic acid equimolar amounts and gone with 30min, addition
30~60ml of ionized water, in the emulsified 30min of high shear and removing acetone or 1-METHYLPYRROLIDONE are evaporated under reduced pressure, is made
Solid content is 20%-30% Amino End Group polyamide-amide function graphite/hyperbranchedization aqueous polyurethane.
In described step two：
Polyamide-amide is selected from 1.0 PAMAMs, 2.0 PAMAMs；
Solvent is selected from N,N-dimethylformamide, 1-METHYLPYRROLIDONE, methanol.
In described step four：
Oligomer dihydric alcohol is selected from PolyTHF dihydric alcohol, PCDL, polyester diol；
Organic tin catalyst is selected from dibutyltin dilaurate, two (dodecyl sulphur) dibutyl tins；
Small molecule amine is selected from triethylamine, diethylamine.
Polyamide-amide functionalization graphene/hyperbranched aqueous polyurethane made from preparation method as mentioned.
The present invention has advantages below：
The present invention carries out functional modification to graphite oxide from the polyamide-amide (PAMAM) of Amino End Group first and reduced,
The functionalization graphene (N-FGs) for containing abundant primary amino radical so as to obtain surface, then N-FGs ultrasonic disperses are in acetone or N- methyl
In pyrrolidones, it is added in the preparation process of polyurethane by in-situ polymerization in polyurethane, is prepared using N-FGs as core
Hyperbranched aqueous polyurethane, aqueous polyurethane prepared by this method is highly branched, have specific three dimensional knot using N-FGs as core
Structure, film forming have preferable mechanical property and good antistatic behaviour, can be applied to synthetic leather, fabric coating, and production is antistatic
Product.
Brief description of the drawings
Fig. 1 is the schematic diagram of 1.0 generation PAMAM modified graphene oxides in embodiment 1.
Fig. 2 is the XPS figures of 1.0 generation PAMAM modified graphene oxides in embodiment 1 and embodiment 2.(a) 284.60 in,
398.60,531.60eV respectively Elements C, N, O power spectrum；(b) 283.46eV in, 285.03eV, at 287.02eV combination can divide
Not Wei-C-O-, C-C in graphite,(c) 529.87eV in, 531.87eV combination can be respectively-O- and
(d) 397.45eV in, 400.24eV combination can be-CO-NH- ,-CH2-NH2
Embodiment
With reference to embodiment, the present invention will be described in detail.
The preparation method of polyamide-amide functionalization graphene/hyperbranched aqueous polyurethane of the present invention, is selected first
The polyamide-amide of Amino End Group carries out functional modification to graphite oxide and reduced, and obtains the function that abundant primary amino radical is contained on surface
Graphite alkene；Again by functionalization graphene ultrasonic disperse in acetone or 1-METHYLPYRROLIDONE, in the preparation process of polyurethane
In be added to by in-situ polymerization in polyurethane, prepare the hyperbranched aqueous polyurethane using functionalization graphene as core.
The preparation method specifically includes following steps：
Step 1：Graphite oxide is prepared using improved Hummers methods：
Expanded graphite, the concentrated sulfuric acid, phosphoric acid are well mixed, are then slowly added into potassium permanganate, is reacted at 10-50 DEG C
12-36h；Expanded graphite, potassium permanganate mass ratio are 1：(3~10), phosphoric acid and the concentrated sulfuric acid (mass fraction 98%) volume ratio 1：
(4~8), expanded graphite quality is with concentrated sulfuric acid volume than 20~100mg/ml of scope；
Ice-water bath is cooled to after reaction, hydrogen peroxide is added dropwise and reduces unnecessary potassium permanganate, until bubble-free produces；
Static 12h, after treating that layering is obvious, outwell supernatant；
With absolute ethyl alcohol and watery hydrochloric acid washing precipitate repeatedly, after supernatant is in glassy yellow, bag filter dialysis is transferred to
Reach 7 to pH, be then freeze-dried and filemot graphite oxide is made；
Step 2：The preparation of polyamide-amide functionalization graphene：
0.5~the 2g of graphite oxide for taking step 1 to prepare, add in 200~500ml solvents, after 0.5~2h of ultrasonic disperse
Add in the three-necked flask of dress reflux condensing tube, agitator and thermometer, add polyamide-amide (PAMAM) 5~30g and two rings
Hexyl carbodiimide (DCC) 4~10g, react 12~48h at 80 DEG C~110 DEG C；
It is cooled to room temperature and 5-10min is centrifuged under the conditions of 5000~10000r/min, mixture is washed 3-5 times with methanol,
Dry, Amino End Group polyamide-amide functionalization graphene (N-FGs) is made；
Step 3：It is prepared by Amino End Group polyamide-amide functionalization graphene (N-FGs) dispersion liquid：
By Amino End Group polyamide-amide functionalization graphene ultrasonic disperse in acetone or 1-METHYLPYRROLIDONE, power
Ultrasound peels off 0.5~2h under the conditions of 300w~600w, and Amino End Group polyamide-amide functionalization graphene acetone dispersion liquor or end is made
Amino polyamide-amide functionalization graphene pyrrolidones dispersion liquid, Amino End Group polyamide-amide functionalization graphene concentration are 0.5
~8mg/ml；
Step 4：Situ aggregation method prepares Amino End Group polyamide-amide function graphite/hyperbranchedization aqueous polyurethane (N-
FGs/HWPU)：
15~20g of oligomer dihydric alcohol, IPDI (IPDI) 5~11g are added in reactor, wherein
N (- NCO) in IPDI and oligomer dihydric alcohol:N (- OH) is (3~5)：1；
Organic tin catalyst is added, performed polymer is made in 85 DEG C of reaction 1~2h reactions；
The hydrophilic monomer dihydromethyl propionic acid (DMPA) for adding performed polymer quality 2%~5% reacts 1~2h, is cooled to 75
DEG C add Amino End Group polyamide-amide functionalization graphene acetone dispersion liquor or Amino End Group polyamide-amide functionalization graphene pyrroles
Alkanone 30~100ml of dispersion liquid, Amino End Group polyamide-amide functionalization graphene concentration is 0.5~5mg/ml, continue reaction 2~
3h；
60 DEG C of cooling, add in the small molecule amine with hydrophilic monomer dihydromethyl propionic acid equimolar amounts and gone with 30min, addition
30~60ml of ionized water, in the emulsified 30min of high shear and removing acetone or 1-METHYLPYRROLIDONE are evaporated under reduced pressure, is made
Solid content is 20%-30% Amino End Group polyamide-amide function graphite/hyperbranchedization aqueous polyurethane.
In described step two：
Polyamide-amide is selected from 1.0 PAMAMs, 2.0 PAMAMs；
Solvent is selected from N,N-dimethylformamide, 1-METHYLPYRROLIDONE, methanol.
In described step four：
Oligomer dihydric alcohol is selected from PolyTHF dihydric alcohol, PCDL, polyester diol；
Organic tin catalyst is selected from dibutyltin dilaurate, two (dodecyl sulphur) dibutyl tins；
Small molecule amine is selected from triethylamine, diethylamine.
Embodiment 1：
A kind of preparation method of polyamide-amide functionalization graphene/hyperbranched aqueous polyurethane, comprises the following steps：
1st, the preparation of graphite oxide：3g expanded graphites, the 350ml concentrated sulfuric acids, the mixing of 40ml phosphoric acid, 20min guarantors are stirred at room temperature
Card is well mixed, is slowly added to 18g potassium permanganate, and temperature control stirs 24h at 30 DEG C.Post drop is slowly added to room temperature
200ml deionized waters dilute, and add the unnecessary potassium permanganate of 30% hydrogen-peroxide reduction, until bubble-free produces, static 12h,
After treating that layering is obvious, supernatant is outwelled.Above-mentioned reaction precipitate is washed repeatedly with absolute ethyl alcohol and watery hydrochloric acid.Treat that supernatant is in
Faint yellow, 5000r/min centrifuges 5min；Isolate is placed in into bag filter (8000-14000D) to be dialysed, until pH it
Reach 7 or so, while produced with barium chloride detection without precipitation, be freeze-dried and graphite oxide is made；
2nd, the preparation of polyamide-amide functionalization graphene：Graphite oxide 2g, add in 500ml DMFs,
Added after ultrasonic disperse 1h in the three-necked flask of dress reflux condensing tube, agitator and thermometer, add dicyclohexylcarbodiimide
(DCC) 10g, 1.0 PAMAMs (1.0PAMAM) 30g, 18h is mixed at 110 DEG C；Room temperature is subsequently cooled to 5000
5-10min is centrifuged under the conditions of~10000r/min, mixture is washed 3 times with methanol, is dried, Amino End Group polyamide-amide work(is made
Can graphite alkene (N-FGs)；
3rd, 0.5000g N-FGs are added in 100ml acetone, in 30 DEG C of ultrasonic disperse 1h, obtain 5mg/ml SGO third
Ketone dispersion liquid；
4th, situ aggregation method prepares N-FGs/HWPU：By 15g polytetrahydrofuran diols (2000), the isocyanide of 5g isophorones two
Acid esters is added in reactor, adds 4 drop dibutyltin dilaurate catalyst, 85 DEG C of reaction 2h reactions and performed polymer is made；Add
Hydrophilic monomer DMPA 0.8g react 1h at 85 DEG C, are cooled to 75 DEG C and add 5mg/ml N-FGs acetone dispersion liquors 100ml continuation instead
Answer 2h；60 DEG C of addition neutralization reaction 30min of triethylamine 0.67 are cooled to, add 51ml deionized waters, it is newborn under high shear
Change 30min and be evaporated under reduced pressure removing acetone, the hyperbranched aqueous polyurethane emulsion that obtained solid content is about 30%.
Embodiment 2：
A kind of preparation method of polyamide-amide functionalization graphene/hyperbranched aqueous polyurethane, comprises the following steps：
1st, the preparation of graphite oxide：3g expanded graphites, the 350ml concentrated sulfuric acids, the mixing of 40ml phosphoric acid, 20min guarantors are stirred at room temperature
Card is well mixed, is slowly added to 18g potassium permanganate, and temperature control stirs 24h at 30 DEG C.Post drop is slowly added to room temperature
200ml deionized waters dilute, and add the unnecessary potassium permanganate of 30% hydrogen-peroxide reduction, until bubble-free produces, static 12h,
After treating that layering is obvious, supernatant is outwelled.Above-mentioned reaction precipitate is washed repeatedly with absolute ethyl alcohol and watery hydrochloric acid.Treat that supernatant is in
Faint yellow, 5000r/min centrifuges 5min；Isolate is placed in into bag filter (8000-14000D) to be dialysed, until pH it
Reach 7 or so, while produced with barium chloride detection without precipitation, be freeze-dried and graphite oxide is made；
2nd, the preparation of polyamide-amide functionalization graphene：Graphite oxide 1g, add in 250ml DMFs,
Added after ultrasonic disperse 1h in three-necked flask, add dicyclohexylcarbodiimide (DCC) 5g, 1.0 PAMAM (1.0G
PAMAM) 15g, 48h is mixed at 80 DEG C；Then 5-10min is centrifuged under the conditions of 5000~10000r/min, is washed with methanol
Mixture 3 times, dry, Amino End Group polyamide-amide functionalization graphene (N-FGs) is made；
3rd, 0.4500g N-FGs are added in 100ml acetone, in 30 DEG C of ultrasonic disperse 1h, obtain 4.5mg/ml N-
FGs acetone dispersion liquors；
4th, situ aggregation method prepares N-FGs/HWPU：By 15g polyester diols (2000), 5g IPDIs
Add in reactor, add 4 drop dibutyltin dilaurate catalyst, 85 DEG C of reaction 2h reactions and performed polymer is made；Add hydrophilic
Monomer DMPA 0.8g react 1h at 85 DEG C, are cooled to 75 DEG C of addition 4.5mg/ml N-FGs acetone dispersion liquors 100ml and continue to react
2h；60 DEG C of addition neutralization reaction 30min of triethylamine 0.67 are cooled to, add 51ml deionized waters, it is emulsified in high shear
30min is simultaneously evaporated under reduced pressure removing acetone, the hyperbranched aqueous polyurethane emulsion that obtained solid content is about 30%.
Embodiment 3：
A kind of preparation method of polyamide-amide functionalization graphene/hyperbranched aqueous polyurethane, comprises the following steps：
1st, the preparation of graphite oxide：3g expanded graphites, the 350ml concentrated sulfuric acids, the mixing of 40ml phosphoric acid, 20min guarantors are stirred at room temperature
Card is well mixed, is slowly added to 18g potassium permanganate, and temperature control stirs 24h at 30 DEG C.Post drop is slowly added to room temperature
200ml deionized waters dilute, and add the unnecessary potassium permanganate of 30% hydrogen-peroxide reduction, until bubble-free produces, static 12h,
After treating that layering is obvious, supernatant is outwelled.Above-mentioned reaction precipitate is washed repeatedly with absolute ethyl alcohol and watery hydrochloric acid.Treat that supernatant is in
Faint yellow, 5000r/min centrifuges 5min；Isolate is placed in into bag filter (8000-14000D) to be dialysed, until pH it
Reach 7 or so, while produced with barium chloride detection without precipitation, be freeze-dried and graphite oxide is made；
2nd, the preparation of polyamide-amide functionalization graphene：Graphite oxide 1.5g, add 300ml DMFs
In, added after ultrasonic disperse 1h in three-necked flask, add dicyclohexylcarbodiimide (DCC) 6g, 1.0 PAMAM (1.0G
PAMAM) 30g, 36h is mixed at 90 DEG C；Then 5-10min is centrifuged under the conditions of 5000~10000r/min, is washed with methanol
Mixture 3 times, dry, Amino End Group polyamide-amide functionalization graphene (N-FGs) is made；
3rd, 0.3100g N-FGs are added in 100ml acetone, in 30 DEG C of ultrasonic disperse 1h, obtain 3.1mg/ml N-
FGs acetone dispersion liquors；
4th, situ aggregation method prepares N-FGs/HWPU：By 15g polyester diols (2000), 5g polyether Glycols (2000),
8.5g IPDIs are added in reactor, add 5 drop dibutyltin dilaurate catalyst, 85 DEG C of reaction 2h
Performed polymer is made in reaction；Add hydrophilic monomer DMPA 1.2g and react 2h at 85 DEG C, be cooled to 75 DEG C of additions, 3.1mg/mlN-FGs
Acetone dispersion liquor 100ml continues to react 3h；Be cooled to 60 DEG C addition triethylamine 1.0g neutralization reaction 30min, add 70ml go from
Sub- water, in the emulsified 30min of high shear and be evaporated under reduced pressure removing acetone, obtained solid content be about 30% it is hyperbranched aqueous
Polyaminoester emulsion.
Embodiment 4：
A kind of preparation method of polyamide-amide functionalization graphene/hyperbranched aqueous polyurethane, comprises the following steps：
1st, the preparation of graphite oxide：3g expanded graphites, the 350ml concentrated sulfuric acids, the mixing of 40ml phosphoric acid, 20min guarantors are stirred at room temperature
Card is well mixed, is slowly added to 18g potassium permanganate, and temperature control stirs 24h at 30 DEG C.Post drop is slowly added to room temperature
200ml deionized waters dilute, and add the unnecessary potassium permanganate of 30% hydrogen-peroxide reduction, until bubble-free produces, static 12h,
After treating that layering is obvious, supernatant is outwelled.Above-mentioned reaction precipitate is washed repeatedly with absolute ethyl alcohol and watery hydrochloric acid.Treat that supernatant is in
Faint yellow, 5000r/min centrifuges 5min；Isolate is placed in into bag filter (8000-14000D) to be dialysed, until pH it
Reach 7 or so, while produced with barium chloride detection without precipitation, be freeze-dried and graphite oxide is made；
2nd, the preparation of polyamide-amide functionalization graphene：Graphite oxide 1g, add in 300ml DMFs,
Added after ultrasonic disperse 1h in the three-necked flask of dress reflux condensing tube, agitator and thermometer, add dicyclohexylcarbodiimide
(DCC) 5g, 2.0 PAMAMs (2.0G PAMAM) 15g, 24h is mixed at 100 DEG C；Room temperature is subsequently cooled to 5000
5-10min is centrifuged under the conditions of~10000r/min, mixture is washed 3 times with methanol, is dried, Amino End Group polyamide-amide work(is made
Can graphite alkene (N-FGs)；
3rd, 0.4000g N-FGs are added in 100ml acetone, in 30 DEG C of ultrasonic disperse 0.5h, obtain 4mg/ml N-
FGs acetone dispersion liquors；
4th, situ aggregation method prepares N-FGs/HWPU：15g polytetrahydrofuran diols (2000), 8.5g isophorones two is different
Cyanate is added in reactor, adds 4 drop dibutyltin dilaurate catalyst, 85 DEG C of reaction 2h reactions and performed polymer is made；Add
Enter hydrophilic monomer DMPA 0.6g and react 1h at 85 DEG C, be cooled to 75 DEG C of addition 4mg/ml N-FGs acetone dispersion liquor 100ml,
DMPA 0.2g continue to react 2h；60 DEG C of addition neutralization reaction 30min of triethylamine 0.67 are cooled to, add 60ml deionized waters,
The emulsified 30min of high shear is simultaneously evaporated under reduced pressure removing acetone, the hyperbranched aqueous polyurethane that obtained solid content is about 30%
Emulsion.
Embodiment 5：
A kind of preparation method of polyamide-amide functionalization graphene/hyperbranched aqueous polyurethane, comprises the following steps：
1st, the preparation of graphite oxide：2g expanded graphites, the 250ml concentrated sulfuric acids, the mixing of 30ml phosphoric acid, 20min guarantors are stirred at room temperature
Card is well mixed, is slowly added to 12g potassium permanganate, and temperature control stirs 24h at 20 DEG C.Post drop is slowly added to room temperature
200ml deionized waters dilute, and add the unnecessary potassium permanganate of 30% hydrogen-peroxide reduction, until bubble-free produces, static 12h,
After treating that layering is obvious, supernatant is outwelled.Above-mentioned reaction precipitate is washed repeatedly with absolute ethyl alcohol and watery hydrochloric acid.Treat that supernatant is in
Faint yellow, 5000r/min centrifuges 5min；Isolate is placed in into bag filter (8000-14000D) to be dialysed, until pH it
Reach 7 or so, while produced with barium chloride detection without precipitation, be freeze-dried and graphite oxide is made；
2nd, the preparation of polyamide-amide functionalization graphene：Graphite oxide 1g, add in 300ml 1-METHYLPYRROLIDONEs,
Added after ultrasonic disperse 1h in the three-necked flask of dress reflux condensing tube, agitator and thermometer, add dicyclohexylcarbodiimide
(DCC) 5g, 1.0 PAMAMs (1.0G PAMAM) 20g, 12h is mixed at 110 DEG C；Room temperature is subsequently cooled to 5000
5-10min is centrifuged under the conditions of~10000r/min, mixture is washed 3 times with methanol, is dried, Amino End Group polyamide-amide work(is made
Can graphite alkene (N-FGs)；
3rd, 0.4000g N-FGs are added in 50ml 1-METHYLPYRROLIDONEs, in 30 DEG C of ultrasonic disperse 1.0h, obtained
8mg/ml N-FGs 1-METHYLPYRROLIDONE dispersion liquids；
4th, situ aggregation method prepares N-FGs/HWPU：By 10g polytetrahydrofuran diols (2000), 10g PCDLs
(2000), 11.0g IPDIs are added in reactor, add 5 drop dibutyltin dilaurate catalyst 85
DEG C reaction 2h reaction be made performed polymer；Add hydrophilic monomer DMPA 1.2g and react 1h at 85 DEG C, be cooled to 75 DEG C of addition 8mg/ml
N-FGs 1-METHYLPYRROLIDONE dispersion liquid 50ml, continue to react 2h；It is cooled to 60 DEG C of addition triethylamine 0.9g neutralization reactions
30min, add 30ml deionized waters, in the emulsified 30min of high shear, obtained solid content be about 30% it is hyperbranched aqueous
Polyaminoester emulsion.
Fig. 1 is the schematic diagram of 1.0G PAMAM modified graphene oxides in embodiment 1；Fig. 2 is embodiment 1 and embodiment 2
The xps energy spectrum figure of modified graphene oxide.
In (a) 284.60,398.60,531.60eV it is respectively Elements C, N, O power spectrum in Fig. 2, (b) 283.46eV,
Combination can be respectively-C-O-, C-C in graphite at 285.03eV, 287.02eV,(c) 529.87eV, 531.87eV are combined
Can be respectively-O- and(d) 397.45eV, 400.24eV combination can be-CO-NH- ,-CH2-NH2；Pass through XPS energy
Analytic explanation is composed successfully by-NH2Enter onto graphene oxide, successfully prepare N-FGs.
Polyurethane film-forming performance obtained by the embodiment of table 1
| Blank | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| N-FGs additions/% | 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 |
| Specific insulation/Ω cm | 3.41×1012 | 2.52×107 | 2.67×107 | 2.97×108 | 3.71×107 | 1.04×108 |
Present disclosure is not limited to cited by embodiment, and those of ordinary skill in the art are by reading description of the invention
And any equivalent conversion taken technical solution of the present invention, it is that claim of the invention is covered.
Claims (5)
1. the preparation method of polyamide-amide functionalization graphene/hyperbranched aqueous polyurethane, it is characterised in that：
First graphite oxide functional modification and reduce from the polyamide-amide of Amino End Group, obtain surface contain it is abundant
The functionalization graphene of primary amino radical；
Again by functionalization graphene ultrasonic disperse in acetone or 1-METHYLPYRROLIDONE, pass through in the preparation process of polyurethane
In-situ polymerization is added in polyurethane, prepares the hyperbranched aqueous polyurethane using functionalization graphene as core.
2. the preparation method of polyamide-amide functionalization graphene/hyperbranched aqueous polyurethane according to claim 1, its
It is characterised by：
The preparation method specifically includes following steps：
Step 1：Graphite oxide is prepared using improved Hummers methods：
Expanded graphite, the concentrated sulfuric acid, phosphoric acid are well mixed, are then slowly added into potassium permanganate, reacts 12- at 10-50 DEG C
36h；Expanded graphite, potassium permanganate mass ratio are 1：（3~10）, phosphoric acid and concentrated sulfuric acid volume ratio 1：（4~8）, expanded graphite quality
With concentrated sulfuric acid volume than 20 ~ 100mg/ml of scope；
Ice-water bath is cooled to after reaction, hydrogen peroxide is added dropwise and reduces unnecessary potassium permanganate, until bubble-free produces；
Static 12h, after treating that layering is obvious, outwell supernatant；
With absolute ethyl alcohol and watery hydrochloric acid washing precipitate repeatedly, after supernatant is in glassy yellow, it is transferred to bag filter and dialyses to pH
Reach 7, be then freeze-dried and filemot graphite oxide is made；
Step 2：The preparation of polyamide-amide functionalization graphene：
0.5 ~ the 2g of graphite oxide for taking step 1 to prepare, add in 200 ~ 500ml solvents, dress is added after 0.5 ~ 2h of ultrasonic disperse
In the three-necked flask of reflux condensing tube, agitator and thermometer, add 5 ~ 30g of polyamide-amide and dicyclohexylcarbodiimide 4 ~
10g, react 12 ~ 48h at 80 DEG C ~ 110 DEG C；
It is cooled to room temperature and 5-10min is centrifuged under the conditions of 5000 ~ 10000r/min, mixture is washed 3-5 times with methanol, dries,
Amino End Group polyamide-amide functionalization graphene is made；
Step 3：It is prepared by Amino End Group polyamide-amide functionalization graphene dispersion liquid：
By Amino End Group polyamide-amide functionalization graphene ultrasonic disperse in acetone or 1-METHYLPYRROLIDONE, power 300w ~
Ultrasound peels off 0.5 ~ 2h under the conditions of 600w, and Amino End Group polyamide-amide functionalization graphene acetone dispersion liquor is made or Amino End Group gathers
Amide-amine functionalization graphene pyrrolidones dispersion liquid, Amino End Group polyamide-amide functionalization graphene concentration are 0.5 ~ 8mg/
ml；
Step 4：Situ aggregation method prepares Amino End Group polyamide-amide function graphite/hyperbranchedization aqueous polyurethane：
15 ~ 20g of oligomer dihydric alcohol, 5 ~ 11g of IPDI are added in reactor, wherein isophorone two is different
N in cyanate and oligomer dihydric alcohol（-NCO）:N (- OH) is（3~5）：1；
Organic tin catalyst is added, performed polymer is made in 85 DEG C of reaction 1 ~ 2h reactions；
The hydrophilic monomer dihydromethyl propionic acid for adding performed polymer quality 2% ~ 5% reacts 1 ~ 2h, is cooled to 75 DEG C of addition Amino End Groups and gathers
Amide-amine functionalization graphene acetone dispersion liquor or Amino End Group polyamide-amide functionalization graphene pyrrolidones dispersion liquid 30 ~
100ml, Amino End Group polyamide-amide functionalization graphene concentration is 0.5 ~ 5mg/ml, continues 2~3h of reaction；
60 DEG C of cooling, add with the small molecule amine of hydrophilic monomer dihydromethyl propionic acid equimolar amounts and 30min, adding deionization
30 ~ 60ml of water, in the emulsified 30min of high shear and removing acetone or 1-METHYLPYRROLIDONE are evaporated under reduced pressure, is made and contains admittedly
Measure Amino End Group polyamide-amide function graphite/hyperbranchedization aqueous polyurethane for 20%-30%.
3. the preparation method of polyamide-amide functionalization graphene/hyperbranched aqueous polyurethane according to claim 2, its
It is characterised by：
In described step two：
Polyamide-amide is selected from 1.0 PAMAMs, 2.0 PAMAMs；
Solvent is selected from N,N-dimethylformamide, 1-METHYLPYRROLIDONE, methanol.
4. the preparation method of polyamide-amide functionalization graphene/hyperbranched aqueous polyurethane according to claim 2, its
It is characterised by：
In described step four：
Oligomer dihydric alcohol is selected from PolyTHF dihydric alcohol, PCDL, polyester diol；
Organic tin catalyst is selected from dibutyltin dilaurate, two (dodecyl sulphur) dibutyl tins；
Small molecule amine is selected from triethylamine, diethylamine.
5. polyamide-amide functionalization graphene/hyperbranched aqueous polyurethane made from preparation method as claimed in claim 1.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108505049A (en) * | 2018-05-28 | 2018-09-07 | 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 |
| WO2019143299A1 (en) * | 2018-01-18 | 2019-07-25 | Antony Prince James Selvaraj | Hyper-branched compounds, synthesis and uses thereof |
| CN110156954A (en) * | 2019-05-30 | 2019-08-23 | 陕西科技大学 | A kind of aqueous polyurethane and preparation method thereof of absorbable ultraviolet light |
| 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 |
| CN111234157A (en) * | 2020-03-09 | 2020-06-05 | 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 (4)
| 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 |
| US20140080980A1 (en) * | 2012-09-19 | 2014-03-20 | Toyoko Imae | Fluorescent hybrid of dendrimer and graphene oxide |
| 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 |
-
2017
- 2017-08-16 CN CN201710702482.9A patent/CN107501500B/en active Active
Patent Citations (4)
| 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 |
| US20140080980A1 (en) * | 2012-09-19 | 2014-03-20 | Toyoko Imae | Fluorescent hybrid of dendrimer and graphene oxide |
| 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 |
|---|
| YANG YUAN等: "Poly(amidoamine) modified grapheme oxide as an efficient adsorbent for heavy metal ions", 《POLYMER CHEMISTRY》 * |
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| 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 |
| US11530178B2 (en) | 2018-01-18 | 2022-12-20 | Memsift Innovations Pte. Ltd. | Hyper-branched compounds, synthesis and uses thereof |
| CN108505049A (en) * | 2018-05-28 | 2018-09-07 | 中国科学院理化技术研究所 | Graphite oxide corrosion inhibitor and preparation and application 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 |
| CN110156954A (en) * | 2019-05-30 | 2019-08-23 | 陕西科技大学 | A kind of aqueous polyurethane and preparation method thereof of absorbable ultraviolet light |
| 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 |
| CN111234157A (en) * | 2020-03-09 | 2020-06-05 | 江苏科技大学 | Reactive extrusion preparation method of flame-retardant hyperbranched polyamide 6 elastomer |
| 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 |
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