CN112322025A - Nano hybrid multifunctional polyurethane flame-retardant material and preparation method thereof - Google Patents

Nano hybrid multifunctional polyurethane flame-retardant material and preparation method thereof Download PDF

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CN112322025A
CN112322025A CN202011290356.5A CN202011290356A CN112322025A CN 112322025 A CN112322025 A CN 112322025A CN 202011290356 A CN202011290356 A CN 202011290356A CN 112322025 A CN112322025 A CN 112322025A
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申腾飞
靳洁琳
朱海鑫
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North China Institute of Science and Technology
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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
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Abstract

The invention provides a nanometer hybrid multifunctional polyurethane flame-retardant material and a preparation method thereof, wherein the preparation method comprises the following steps: (1) converting carboxyl on graphene oxide into acyl chloride groups to obtain Cl-GO, reacting the Cl-GO with a primary amine reagent, and converting the acyl chloride groups into amide groups to obtain A-GO; (2) v2O5Carrying out in-situ chemical oxidation polymerization reaction with DPA to obtain P-V2O5(ii) a (3) A-GO and P-V are mixed2O5Adding the mixture into polyurethane, heating, stirring, reacting, cooling and drying to obtain the double-nano hybrid multifunctional polyurethane composite material (mf-PUC). The invention relates to nitrogen-modified functionalized graphene oxide and pentoxideThe vanadium and the degradable shape memory polyurethane are obtained by compounding and hybridizing double nano particles, have the functional characteristics of degradability, shape memory, corrosion resistance, flame retardance and the like, and have great potential in the fields of flame retardance, corrosion resistance, intelligence, biological materials and the like.

Description

Nano hybrid multifunctional polyurethane flame-retardant material and preparation method thereof
Technical Field
The invention relates to the field of polymer-based nano composite materials, in particular to a nano hybrid multifunctional polyurethane flame-retardant material and a preparation method thereof.
Background
The polyurethane material can be conveniently designed by selecting synthetic raw materials, adjusting the proportion of soft and hard segments in molecules, adjusting the isocyanate value index and the like, so that the polyurethane material has wide application in the fields of foam materials, elastomer materials, coatings, adhesives, biological materials and the like. At present, with the rapid development of society, polyurethane materials with single performance, such as excellent mechanical property, solvent resistance and wear resistance, are difficult to meet the market requirement of refined materials, so that the development of multifunctional polyurethane materials is imperative. The design and synthesis of the multifunctional polymer-based nanocomposite through nano-hybridization is an effective method, but the practical use value of the unmodified single nanophase is limited due to the defects of easy agglomeration, relatively single functionality and the like in the use process. In view of the current market and the current technical situation, the development of a preparation method and technology of a multi-nanophase cooperative hybrid polyurethane composite material which is convenient to design and controllable in synthesis has very important significance.
Based on the problems existing in the existing polyurethane material body and the nanometer modification process, the invention designs a preparation method of a functionalized graphene and vanadium pentoxide double-nanometer hybrid polyurethane composite material, and the multifunctional polyurethane nanometer composite material is not reported yet.
Disclosure of Invention
The invention provides a nanometer hybrid multifunctional polyurethane flame retardant material and a preparation method thereof, the nanometer hybrid multifunctional polyurethane flame retardant material is prepared by compounding and hybridizing nitrogen-modified functionalized graphene oxide, vanadium pentoxide and degradable shape memory polyurethane through double nanoparticles, and has the functional characteristics of degradability, shape memory, corrosion resistance, flame retardance and the like, so that the nanometer hybrid multifunctional polyurethane flame retardant material has great potential application in the fields of flame retardance, corrosion resistance, intelligence, biological materials and the like.
The technical scheme of the invention is realized as follows: a preparation method of a nanometer hybrid multifunctional polyurethane flame-retardant material comprises the following steps:
(1) converting carboxyl on Graphene Oxide (GO) into an acyl chloride group to obtain chlorinated graphene oxide (Cl-GO), reacting the Cl-GO with a primary amine reagent, and converting the acyl chloride group into an amide group to obtain nitrogen-modified graphene oxide (A-GO);
(2) vanadium pentoxide (V)2O5) Carrying out in-situ chemical oxidation polymerization reaction with Diphenylamine (DPA) to obtain polydianiline coated vanadium pentoxide (P-V)2O5)；
(3) A-GO and P-V are mixed2O5Adding the mixture into Polyurethane (PU), heating, stirring, reacting, cooling and drying to obtain the double-nano hybrid multifunctional polyurethane composite material (mf-PUC).
Further, in the step (1), the preparation method of Cl-GO is as follows: mixing 100-300mgGO with 40-120ml of thionyl chloride (SOCl)2) And under the protection of nitrogen, reacting in 3-8ml of first solvent at 70-90 ℃ to obtain Cl-GO.
Further, the first solvent is Dimethylformamide (DMF) or Dimethylsulfoxide (DMSO).
Further, in the step (1), the preparation method of the A-GO is as follows: reacting 50-100mg of Cl-GO with 500-1500mg of micromolecular primary amine reagent in 20-50 ml of second solvent, purifying and drying to obtain A-GO, wherein the reaction temperature is 50-80 ℃.
Further, the second solvent is Dimethylformamide (DMF) or Dimethylsulfoxide (DMSO).
Further, the primary amine reagent is any one of aromatic amine, aliphatic amine, and alicyclic amine.
Further, the primary amine reagent is 2-naphthylamine, cyclohexylamine and dodecylamine.
Further, in the step (2), P-V2O5The preparation method comprises the following steps: at the temperature of 5-30 ℃, V with the molar ratio of 1:1-3 is mixed2O5Reacting with DPA in a deionized water system of persulfate, and purifying and drying to obtain P-V2O5。
Further, the persulfate is Ammonium Persulfate (APS) and potassium persulfate (KPS).
Further, in the step (3), the preparation method of PU is as follows: adding diisocyanate and polyester diol into a reactor, vacuumizing and drying at 120 ℃, and dropwise adding a catalyst to react for 2-4h at 60-90 ℃; cooling, adding a micromolecular chain extender, heating to 70-90 ℃, and reacting for 1-3h to obtain PU.
Further, the isocyanate index of PU is 1.0 to 1.2.
Further, the mole ratio of diisocyanate, polyester diol and small molecular chain extender is 1: 0.4-0.8: 0.1-0.6.
Further, 0.5-2 wt% of A-GO and P-V2O5Adding the mixture into 98-99.5 wt% of PU, stirring and reacting for 1-3h at 50-80 ℃, cooling and casting the mixture into a polytetrafluoroethylene mold, and drying the mixture to obtain mf-PUC.
Further, the diisocyanate is any one of toluene-2, 4-diisocyanate (TDI), 4' -diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), and Hexamethylene Diisocyanate (HDI).
Further, the polyester dibasic is polylactide glycol (PLA) with molecular weight of 600-2000 or polycaprolactone glycol (PCL) with molecular weight of 800-2000.
Further, the polylactide glycol is any one of PLA-600, PLA-1000 and PLA-2000.
Further, the polycaprolactone diol is any one of PCL-800, PCL-1000 and PCL-2000.
Further, the catalyst is organotin or tertiary amine.
Further, the organotin is stannous octoate or dibutyltin dilaurate.
Further, the tertiary amine is diethylenetriamine or triethylamine.
Further, the small-molecule chain extender is any one of propylene glycol, butanediol, glycerol and pentaerythritol.
A nanometer hybrid multifunctional polyurethane flame-retardant material is prepared from the following raw materials: A-GO, P-V2O5And PU, wherein A-GO and P-V2O5The total mass fraction of the components is 0.5-2 wt%, and the mass fraction of PU is 98-99.5 wt%.
The invention has the beneficial effects that:
carboxyl on GO is converted into acyl chloride groups with higher activity, Cl-GO containing the acyl chloride groups with high activity reacts with primary amine reagents of small molecules, so that amide groups are introduced into graphene more conveniently, and nitrogen modified graphene A-GO is obtained.
The invention relates to a2O5And DPA is easily wrapped in V in a persulfate water system through in-situ chemical oxidation polymerization reaction2O5To obtain P-V2O5Synthetic P-V2O5Avoid unmodified V2O5Because of the disadvantage that it is easy to agglomerate due to its higher surface energy. V2O5the-NH group on the coated poly diphenylamine can react with an isocyanate group in a polyurethane system to generate strong bonding effect with polyurethane, so that V is ensured2O5The nitrogen element introduced while the nano particles have the anti-corrosion effect can also have a good flame retardant effect.
The nitrogen-modified functional graphene oxide is obtained by compounding and hybridizing nitrogen-modified functional graphene oxide, vanadium pentoxide and degradable shape memory polyurethane through double nanoparticles, wherein the functional graphene is obtained by chloridizing the graphene oxide and then reacting the graphene oxide with an amine reagent; the functionalized vanadium pentoxide nano-particles are obtained by coating poly-diphenylamine on the surface of vanadium pentoxide through oxidative polymerization of diphenylamine. The composite material disclosed by the invention can synergistically play the functions of functionalized graphene, a vanadium pentoxide body and nitrogen modification of the vanadium pentoxide body, and endows the polyurethane material with good flame retardance and corrosion resistance. The main chain of the polyurethane contains degradable ester groups, and the controllable degradation can be realized under certain external conditions. Meanwhile, the introduced nano phase can further assist the micro-phase separation of the soft and hard segment structures of the polyurethane, thereby improving the shape memory performance of the polyurethane. The composite material synthesized by the preparation method provided by the invention can improve the mechanical property, wear resistance and solvent resistance of the traditional polyurethane material, and more importantly, introduces the functional characteristics of degradability, shape memory, corrosion resistance, flame retardance and the like, so that the composite material has great potential application in the fields of flame retardance, corrosion resistance, intelligence, biological materials and the like.
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In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is an SEM image of A-GO prepared in example 1;
FIG. 2 is a P-V prepared in example 12O5A TEM image of (B);
FIG. 3 is an SEM photograph of mf-PUC prepared in example 1.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
A preparation method of a novel nano-hybrid multifunctional polyurethane flame-retardant material comprises the following steps:
(1) preparing functionalized graphene and vanadium pentoxide: dry 200mg GO was mixed with 80mL SOCl2Reacting for 16h in 5mL of DMF at 80 ℃ under the protection of nitrogen, and purifying and drying to obtain Cl-GO. Taking 50mg Cl-GO to react with 500mg 2-naphthylamine in 20mL DMF at 50 ℃ for 12h, purifying and drying to obtain A-GO, wherein FIG. 1 is an SEM image of the prepared A-GO;
(2) will be provided with0.01mol V2O50.01mol DPA is dispersed in 50mL deionized water, APS aqueous solution is dripped at the temperature of 5 ℃ to react for 24 hours, and P-V is obtained after purification and drying2O5FIG. 2 is a diagram of P-V prepared2O5A TEM image of (B);
(3) preparing a double-nano hybrid multifunctional polyurethane composite material: 0.1mol IPDI, 0.06mol PLA-1000 was added to a 250mL four-necked flask in N2Vacuumizing and drying for 2h at 120 ℃ under protection, dropwise adding dibutyltin dilaurate, and reacting for 3h at 80 ℃; cooling to 50 ℃, adding 0.02mol of butanediol, heating to 85 ℃, and reacting for 1.5h to obtain PU; 1 wt% (0.5 wt% A-GO/0.5 wt% P-V)2O5) Adding the mixture into 99 wt% of PU to react for 3h at 50 ℃, cooling and casting the mixture into a polytetrafluoroethylene mold to dry the mixture to obtain mf-PUC, and FIG. 3 is an SEM picture of the prepared mf-PUC.
Mechanics experiments show that the tensile strength of the composite material is 15.5MPa, and the elongation is 620%; the oxygen index experiment shows that the limit oxygen index of the composite material is 23.9; electrochemical tests and salt spray tests show that the composite material has excellent corrosion resistance as a carbon steel plate coating, the corrosion voltage is-0.06V, and the corrosion current is 4.88 multiplied by 10-11A cm-2(ii) a The shape memory test shows that the shape fixing rate of the composite material is 94 percent, and the shape recovery rate is 93 percent.
Example 2
A preparation method of a novel nano-hybrid multifunctional polyurethane flame-retardant material comprises the following steps:
(1) preparing functionalized graphene and vanadium pentoxide: dry 100mg GO was mixed with 40mL SOCl2Reacting for 24h at 70 ℃ in 3mL of DMF under the protection of nitrogen, and purifying and drying to obtain Cl-GO. Taking 50mg of Cl-GO to react with 500mg of cyclohexylamine in 20mL of DMF at 80 ℃ for 6h, and obtaining A-GO after purification and drying;
(2) 0.01mol of V2O50.015mol of DPA is dispersed in 50mL of deionized water, APS aqueous solution is dripped at the temperature of 30 ℃ to react for 4 hours, and P-V is obtained after purification and drying2O5；
(3) Preparing a double-nano hybrid multifunctional polyurethane composite material: 0.1mol of HDI and 0.08mol of PCL-1000 portion was added to a 250mL four-necked flask in N2Vacuumizing and drying for 2h at 120 ℃ under protection, and dropwise adding diethylenetriamine to react for 4h at 60 ℃; cooling to 50 ℃, adding 0.01mol of propylene glycol, heating to 90 ℃, and reacting for 1h to obtain PU; 0.5 wt% (0.25 wt% A-GO/0.25 wt% P-V)2O5) Adding the mixture into PU to react for 3h at 50 ℃, cooling and casting the mixture into a polytetrafluoroethylene mould to obtain mf-PUC.
The mechanical experiment shows that the tensile strength of the composite material is 13.0MPa, and the elongation is 630%; the oxygen index experiment shows that the limit oxygen index of the composite material is 23.0; electrochemical tests and salt spray tests show that the composite material has excellent corrosion resistance as a carbon steel plate coating, the corrosion voltage is-0.10V, and the corrosion current is 3.28 multiplied by 10-10A cm-2(ii) a Shape memory tests show that the shape fixing rate of the composite material is 90%, and the shape recovery rate is 92%.
Example 3
(1) Preparing functionalized graphene and vanadium pentoxide: dry 150mg GO was mixed with 60mL SOCl2Reacting for 12h at 90 ℃ in 4mL of DMF under the protection of nitrogen, and purifying and drying to obtain Cl-GO. Taking 80mg of Cl-GO to react with 1000mg of dodecylamine in 30mL of DMF at 70 ℃ for 10h, and obtaining A-GO after purification and drying;
(2) 0.01mol of V2O50.02mol of DPA is dispersed in 50mL of deionized water, APS aqueous solution is dripped at 10 ℃ to react for 16h, and P-V is obtained after purification and drying2O5；
(3) Preparing a double-nano hybrid multifunctional polyurethane composite material: 0.1mol of MDI and 0.05mol of PLA-2000 were added to a 250mL four-necked flask in N2Vacuumizing and drying for 2h at 120 ℃ under protection, and dropwise adding stannous octoate to react for 2h at 90 ℃; cooling to 50 ℃, adding 0.015mol of glycerol, heating to 70 ℃, and reacting for 3h to obtain PU; 2 wt% (1 wt% A-GO/1 wt% P-V)2O5) Adding the mixture into 98 wt% of PU to react for 1h at the temperature of 80 ℃, cooling and casting the mixture into a polytetrafluoroethylene mold, and drying the mixture to obtain mf-PUC.
Mechanics experiments show that the tensile strength of the composite material is 18.2MPa, and the elongation is 605%; the oxygen index experiment shows that the composite materialA limiting oxygen index of 25.2; electrochemical tests and salt spray tests show that the composite material has excellent corrosion resistance as a carbon steel plate coating, the corrosion voltage is-0.03V, and the corrosion current is 6.25 multiplied by 10-12A cm-2(ii) a Shape memory tests show that the shape fixing rate of the composite material is 95% and the shape recovery rate is 95%.
Example 4
(1) Preparing functionalized graphene and vanadium pentoxide: mix dry 300mg GO with 120mL SOCl2Reacting for 14h in 8mL of DMF at 85 ℃ under the protection of nitrogen, and purifying and drying to obtain Cl-GO. Taking 100mg Cl-GO to react with 1500mg dodecylamine in 50mL DMF at 65 ℃ for 11h, and obtaining A-GO after purification and drying;
(2) 0.01mol of V2O50.03mol of DPA is dispersed in 50mL of deionized water, APS aqueous solution is dripped at the temperature of 5 ℃ for reaction for 36 hours, and P-V is obtained after purification and drying2O5；
(3) Preparing a double-nano hybrid multifunctional polyurethane composite material: 0.1mol MDI and 0.04mol PCL-2000 were added to a 250mL four-necked flask in N2Vacuumizing and drying for 2h at 120 ℃ under protection, and dropwise adding dibutyltin dilaurate to react for 2h at 90 ℃; cooling to 50 ℃, adding 0.012mol of pentaerythritol, heating to 75 ℃, and reacting for 2.5h to obtain PU; 2 wt% (1.5 wt% A-GO/0.5 wt% P-V)2O5) Adding the mixture into 98 wt% of PU to react for 2h at the temperature of 80 ℃, cooling and casting the mixture into a polytetrafluoroethylene mold, and drying the mixture to obtain mf-PUC.
Mechanics experiments show that the tensile strength of the composite material is 19.4MPa, and the elongation is 625%; the oxygen index experiment shows that the limit oxygen index of the composite material is 25.9; electrochemical tests and salt spray tests show that the composite material has excellent corrosion resistance as a carbon steel plate coating, the corrosion voltage is-0.05V, and the corrosion current is 2.24 multiplied by 10-11A cm-2(ii) a The shape memory test shows that the shape fixing rate of the composite material is 96 percent, and the shape recovery rate is 93 percent.
Example 5
A preparation method of a novel nano-hybrid multifunctional polyurethane flame-retardant material comprises the following steps:
(1) preparing functionalized graphene and vanadium pentoxide: dry 250mg GO was mixed with 100mL SOCl2Reacting for 18h at 75 ℃ in 6mL of DMF under the protection of nitrogen, and purifying and drying to obtain Cl-GO. Taking 90mg of Cl-GO to react with 1200mg of 2-naphthylamine in 40mL of DMF at 50 ℃ for 12h, and purifying and drying to obtain A-GO;
(2) 0.01mol of V2O50.02mol of DPA is dispersed in 50mL of deionized water, APS aqueous solution is dripped at 10 ℃ to react for 16h, and P-V is obtained after purification and drying2O5；
(3) Preparing a double-nano hybrid multifunctional polyurethane composite material: 0.1mol IPDI, 0.04mol PLA-1000 was added to a 250mL four-necked flask in N2Vacuumizing and drying for 2h at 120 ℃ under protection, dropwise adding dibutyltin dilaurate, and reacting for 2.5h at 90 ℃; cooling to 50 ℃, adding 0.06mol of propylene glycol, heating to 80 ℃, and reacting for 2h to obtain PU; 1 wt% (0.5 wt% A-GO/0.5 wt% P-V)2O5) Adding the mixture into 99 wt% of PU to react for 2.5h at 70 ℃, cooling and casting the mixture into a polytetrafluoroethylene mold to obtain mf-PUC.
The mechanical experiment shows that the tensile strength of the composite material is 16.1MPa, and the elongation is 560%; the oxygen index experiment shows that the limit oxygen index of the composite material is 23.4; electrochemical tests and salt spray tests show that the composite material has excellent corrosion resistance as a carbon steel plate coating, the corrosion voltage is-0.08V, and the corrosion current is 1.14 multiplied by 10-11A cm-2(ii) a Shape memory tests show that the shape fixing rate of the composite material is 90%, and the shape recovery rate is 89%.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (10)

1. A preparation method of a nanometer hybrid multifunctional polyurethane flame-retardant material is characterized by comprising the following steps:
(1) converting carboxyl on graphene oxide into acyl chloride groups to obtain chlorinated graphene oxide Cl-GO, reacting Cl-GO with a primary amine reagent, and converting the acyl chloride groups into amide groups to obtain nitrogen-modified graphene oxide A-GO;
(2) the vanadium pentoxide and the diphenylamine undergo an in-situ chemical oxidation polymerization reaction to obtain polydianiline-coated vanadium pentoxide P-V2O5；
(3) A-GO and P-V2O5Adding the mixture into polyurethane PU, heating, stirring, reacting, cooling and drying to obtain the double-nano hybrid multifunctional polyurethane composite material mf-PUC.
2. The preparation method of the nano hybrid multifunctional polyurethane flame retardant material according to claim 1, wherein in the step (1), the preparation method of Cl-GO is as follows: under the protection of nitrogen, reacting graphene oxide and thionyl chloride in a first solvent at 70-90 ℃ to obtain Cl-GO, wherein the first solvent is dimethylformamide or dimethyl sulfoxide.
3. The preparation method of the nano-hybrid multifunctional polyurethane flame retardant material according to claim 1 or 2, wherein in the step (1), the preparation method of A-GO is as follows: and (2) reacting Cl-GO with a primary amine reagent in a second solvent, purifying and drying to obtain A-GO, wherein the reaction temperature is 50-80 ℃, the second solvent is dimethylformamide or dimethyl sulfoxide, and the primary amine reagent is any one of aromatic amine, aliphatic amine and alicyclic amine.
4. The method for preparing nanometer hybrid multifunctional polyurethane flame retardant material according to claim 1, wherein in the step (2), P-V2O5The preparation method comprises the following steps: reacting vanadium pentoxide and diphenylamine in a deionized water system of persulfate at the temperature of 5-30 ℃, and then purifying and drying to obtain P-V2O5。
5. The preparation method of the nano-hybrid multifunctional polyurethane flame retardant material according to claim 1, wherein in the step (3), the preparation method of PU comprises the following steps: adding diisocyanate and polyester diol into a reactor, vacuumizing and drying at 120 ℃, and dropwise adding a catalyst to react for 2-4h at 60-90 ℃; cooling, adding a micromolecular chain extender, heating to 70-90 ℃, and reacting for 1-3h to obtain PU, wherein the isocyanate index of the PU is 1.0-1.2.
6. The method for preparing a nano-hybrid multifunctional polyurethane flame retardant material according to claim 1 or 5, wherein in the step (3), the mf-PUC is prepared by the following steps: 0.5-2 wt% of A-GO and P-V2O5Adding the mixture into 98-99.5 wt% of PU, stirring and reacting for 1-3h at 50-80 ℃, cooling and casting to obtain mf-PUC.
7. The method for preparing the nano-hybrid multifunctional polyurethane flame retardant material according to claim 5, wherein the diisocyanate is any one of toluene-2, 4-diisocyanate, 4' -diphenylmethane diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate; the polyester binary is polylactide glycol with molecular weight of 600-2000 or polycaprolactone glycol with molecular weight of 800-2000.
8. The preparation method of the nano hybrid multifunctional polyurethane flame retardant material as claimed in claim 5, wherein the catalyst is organic tin or tertiary amine.
9. The preparation method of the nano-hybrid multifunctional polyurethane flame retardant material according to claim 5, wherein the small molecular chain extender is any one of propylene glycol, butylene glycol, glycerol and pentaerythritol.
10. A nanometer hybrid multifunctional polyurethane flame-retardant material is prepared from the following raw materials: A-GO, P-V2O5And PU, wherein A-GO and P-V2O5The total mass fraction of the PU is 0.5-2%, and the mass fraction of the PU is 98-99.5%.
CN202011290356.5A 2020-11-17 2020-11-17 Nano hybrid multifunctional polyurethane flame-retardant material and preparation method thereof Pending CN112322025A (en)

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