CN113736053A - Functional waterborne polyurethane material and preparation method thereof - Google Patents
Functional waterborne polyurethane material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of waterborne polyurethane materials, and discloses a functionalized waterborne polyurethane material and a preparation method thereof. The method comprises the following steps: 1) processing diethylene glycol terephthalate and graphene oxide to obtain a graphene oxide loaded BHET chain extender; or carrying out reduction reaction on the graphene oxide supported BHET chain extender through a reducing agent to obtain a reduced graphene supported BHET chain extender; 2) mixing polyester polyol with diisocyanate and a hydrophilic chain extender, adding a catalyst, and reacting to obtain a polyurethane prepolymer; 3) reacting the chain extender, the polyurethane prepolymer and the internal cross-linking agent in the step 1), diluting, neutralizing, adding water for emulsification, and forming a film to obtain the functionalized waterborne polyurethane material. The method overcomes the defects of poor compatibility, easy agglomeration and the like of the graphene and the polyurethane, and the prepared polyurethane material has better electric conductivity, heat conductivity and mechanical properties.
Description
Technical Field
The invention belongs to the field of functional polymer materials, and particularly relates to a functional waterborne polyurethane material and a preparation method thereof.
Background
Polyethylene terephthalate (PET) materials are lightweight, easy to process, dimensionally stable, and are widely used for packaging beverage bottles. With the development of society and the improvement of social ways, the usage amount of PET beverage bottles is larger and larger, and if the PET after consumption is discarded at will, not only is the environmental pollution caused, but also the resource waste is serious. How to recycle and reuse the waste PET materials in a high-valued manner is a hot spot of people's attention at present.
The water-based polyurethane is a polyurethane resin containing hydrophilic groups in the molecular chain of the polyurethane, and has strong affinity with water. The waterborne polyurethane takes water as a dispersion medium, has the characteristics of no toxicity, no pollution, convenient construction and the like, and is widely applied to the aspects of leather finishing, textile printing and dyeing, paper making industry, building coatings, adhesives and the like. However, the mechanical properties, electrical conductivity, thermal conductivity and the like of the waterborne polyurethane are all to be improved.
Graphene is a two-dimensional conductive and heat-conductive functional filler and is widely applied to high polymer materials. If the graphene is directly compounded with the waterborne polyurethane for improving the performances of the waterborne polyurethane such as electric conduction and heat conduction, the graphene is easy to agglomerate, is not uniformly dispersed, has poor compatibility and causes poor performance of the composite material. In order to improve the dispersion behavior of graphene in waterborne polyurethane, promote dispersion, inhibit agglomeration, improve the electric and thermal conductivity, mechanical properties and the like of the composite material, some related researches are carried out.
Chinese patent application publication No. CN106566227A discloses a method for preparing a graphene-modified aqueous polyurethane composite material, which comprises oxidizing graphene, reducing with vitamin C, dispersing the reduced graphene solids in sodium diphenylamine sulfonate, adding the graphene dispersion into an aqueous polyurethane solution, mixing, stirring, drying, and curing to obtain a polyurethane film, thereby achieving the purpose of modifying polyurethane. Although the method can improve the mechanical property and the conductivity of polyurethane, the preparation method has complex steps and great environmental pollution, and the modification of the chain segment of the polyurethane cannot be achieved only by blending the graphene dispersion liquid and the aqueous polyurethane emulsion in the reaction mechanism, so that the graphene cannot be uniformly dispersed in the polyurethane matrix. Therefore, the polyurethane material prepared by the method has the difficult performance of stable and excellent electric conduction, heat conduction, mechanics and the like.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention aims to provide a functionalized waterborne polyurethane material and a preparation method thereof. According to the invention, waste PET is used for alcoholysis to obtain diethylene glycol terephthalate (BHET), the diethylene glycol terephthalate (BHET) is modified with graphene, and the modified graphene presents a cross network structure in a polyurethane adhesive film, so that the interlayer spacing of the graphene can be effectively increased, the dispersion of a load-type chain extender in a polymer matrix is promoted, and the electric conduction, heat conduction and mechanical properties of the functional waterborne polyurethane composite material (WPU/graphene composite material) are greatly improved. The invention realizes high-valued recycling of waste PET, has low raw material price and abundant resources, can adjust the proportion of the functional chain extender according to the requirements of users, meets the performance requirements of the users on the electric and heat conductive polyurethane material, and has good development prospect. The functionalized waterborne polyurethane composite material is applied to the fields of 5G communication materials and electronic packaging materials.
The object of the present invention is achieved by the following means.
A functional waterborne polyurethane material is mainly prepared from the following raw materials in parts by weight:
the raw material of the functional waterborne polyurethane material also comprises a reducing agent, wherein the weight part of the reducing agent is 0.5-1.5.
The catalyst is more than one of dibutyltin dilaurate, stannous octoate and dibutyltin diacetate; the organic solvent is more than one of N-methyl pyrrolidone, N-dimethylformamide and acetone; the diluent is more than one of acetone, N-methyl pyrrolidone, N-dimethylformamide and dimethyl sulfoxide; the neutralizing agent is more than one of triethylamine, sodium hydroxide and potassium hydroxide.
The reducing agent is more than one of hydrazine hydrate, sodium borohydride and sodium citrate.
The polyester polyol is more than one of poly adipic acid-1, 4-butanediol, poly adipic acid-1, 6-hexanediol, poly hexanediol ethylene glycol, poly adipic acid propylene glycol and poly carbonic acid 1, 6-hexanediol glycol.
The molecular weight of the polyester polyol is 1000-3000.
The diisocyanate is more than one of isophorone diisocyanate (IPDI), Hexamethylene Diisocyanate (HDI), dicyclohexylmethane diisocyanate (HMDI) and Toluene Diisocyanate (TDI).
The hydrophilic chain extender is more than one of 2, 2-dimethylolpropionic acid, amino acid, diaminobenzoic acid, ethylene diamine ethyl sodium sulfonate, 1, 4-butanediol-2-sodium sulfonate and N-methyldiethanolamine.
The internal crosslinking agent is more than one of trimethylolpropane, glycerol, pentaerythritol and propylene glycol.
The diethylene glycol terephthalate (BHET) is obtained by PET alcoholysis; the preparation method comprises the following steps: under the protective atmosphere, reacting PET and an alcoholysis agent for 1-5h at the temperature of 200 ℃ under the action of a catalyst, and performing subsequent treatment to obtain an alcoholysis product, namely the diethylene glycol terephthalate BHET.
The mass ratio of the waste PET to the alcoholysis agent is 1: 4-7; the dosage of the catalyst is 3-6% of the mass of the PET;
the PET is preferably waste PET. The alcoholysis agent is ethylene glycol.
The catalyst is more than one of zinc acetate, manganese acetate, nickel acetate and copper acetate.
The subsequent treatment refers to filtering, cooling and crystallizing after the reaction is finished, washing the crystal with water, and drying in vacuum to obtain the alcoholysis product, namely the diethylene glycol terephthalate (BHET).
The preparation method of the functionalized waterborne polyurethane material comprises the following steps:
1) carrying out ultrasonic treatment on diethylene glycol terephthalate (BHET) and graphene oxide in an organic solvent, and then carrying out heat treatment at 80-100 ℃ for 1-2h to obtain a graphene oxide supported BHET chain extender which is marked as BHET-GO; or carrying out reduction reaction on the graphene oxide supported BHET chain extender through a reducing agent to obtain a reduced graphene supported BHET chain extender which is marked as BHET-G;
2) mixing polyester polyol with diisocyanate and a hydrophilic chain extender, adding a catalyst, and reacting at 80-100 ℃ to obtain a polyurethane prepolymer; the mixing is to stir at 80-100 ℃ for 1-2h, and the reaction time is 20-40 min;
3) dispersing a graphene oxide supported BHET chain extender or a reduced graphene supported BHET chain extender in an organic solvent to obtain a chain extender dispersion liquid; mixing the chain extender dispersion liquid, the polyurethane prepolymer and the internal crosslinking agent, reacting for 2-4h at 50-70 ℃, and adding a diluent to dilute in the reaction process; then adding a neutralizing agent for neutralization, and adding water for emulsification to obtain a polyurethane emulsion;
4) and (3) forming a film on the polyurethane emulsion to obtain the functionalized waterborne polyurethane material.
In the step 1), the organic solvent is more than one of N-methyl pyrrolidone, N-dimethylformamide and acetone.
The reducing agent in the step 1) is one or more of hydrazine hydrate, sodium borohydride and sodium citrate;
the specific preparation step of the graphene oxide supported BHET chain extender in the step 1) is to perform ultrasonic treatment on diethylene glycol terephthalate (BHET) and graphene oxide in an organic solvent, then perform heat treatment at 80-100 ℃ for 1-2h, and perform subsequent treatment to obtain the graphene oxide supported BHET chain extender. The weight ratio of the organic solvent to the BHET is (3-8) to (1-3).
The specific preparation step of the reduced graphene supported BHET chain extender in the step 1) is to perform ultrasonic treatment on diethylene glycol terephthalate (BHET) and graphene oxide in an organic solvent, then perform heat treatment at 80-100 ℃ for 1-2h, add a reducing agent, perform reduction reaction, and perform subsequent treatment to obtain the reduced graphene supported BHET chain extender. The organic solvent is more than one of N-methyl pyrrolidone, N-dimethyl formamide and acetone. The weight ratio of the organic solvent to the BHET is (3-8) to (1-3).
The reduction reaction is carried out for 1-2h at the temperature of 80-100 ℃.
In the graphene oxide loaded BHET chain extender, the subsequent treatment is centrifugation, supernatant liquid is removed, and vacuum freeze drying is carried out.
In the reduced graphene-loaded BHET chain extender, the subsequent treatment is centrifugation, supernatant liquid is removed, and vacuum freeze drying is carried out.
Vacuum freeze drying at-10-0 deg.C for 12-36 hr. The centrifugal rotating speed is 5000-10000 rpm; the centrifugation time is 5-15 min.
In the step 3), the organic solvent is more than one of N-methyl pyrrolidone, N-dimethylformamide and acetone.
The weight ratio of the organic solvent to the BHET in the chain extender in the step 3) is (0-8) to (1-3).
The emulsification in the step 3) refers to high-speed stirring for 20-40min, wherein the stirring speed is 500-800 rpm.
The neutralization in the step 3) is to add a neutralizing agent and stir for 10-20 min.
The film forming condition in the step 4) is drying for 12-36h at 20-40 ℃.
In the WPU/BHET-f functional polyurethane composite material, graphene is a two-dimensional material with a lamellar structure, is similar to a honeycomb latticed hexagonal planar film in shape, has high elastic modulus and high conductivity, and exists as a carrier of diethylene glycol terephthalate (BHET); BHET is fixed on the graphene sheet layer and reacts with the polyurethane prepolymer to promote the dispersion of graphene in polyurethane, so that a cross-linked network structure is formed in a polyurethane matrix, and the function of a functional chain extender is achieved. The hydrophilic chain extender endows the polyurethane material with a certain molecular weight, and the cross-linking agent endows the polyurethane material with a certain toughness.
The conductivity of the polyurethane material is measured by a conductivity method or a volume resistivity method.
The invention measures the heat-conducting property of the polyurethane material by a flash method heat-conducting coefficient instrument.
The mechanical property of the polyurethane material is measured by a tensile test method.
Compared with the prior art, the invention has the following beneficial effects:
1. in the invention, the alcoholysis product of diethylene glycol terephthalate (BHET) is introduced into the synthesis design of polyurethane as a micromolecular chain extender, so that the bonding strength and the mechanical property of the polyurethane adhesive are improved, and the polyurethane adhesive can be used for producing high-performance products.
2. The BHET used in the invention can be used as an organic micromolecule to improve the dispersion behavior of a two-dimensional inorganic material, so that the inorganic material can be promoted to be dispersed in a polymer matrix, and the BHET can be widely applied.
3. The preparation of the functional polyurethane material (WPU/BHET-f) is completed on the basis of a 'one-step method', the functional filler and the polyurethane emulsion do not need to be blended, and the implementation is convenient and efficient.
4. The functional polyurethane material (WPU/BHET-f) with the electric and thermal conductivity has the advantages of good electric conductivity, high thermal conductivity and excellent mechanical property.
Drawings
FIG. 1 is a scanning electron microscope image of the functionalized polyurethane composite material prepared in examples 1-2; (a) the method comprises the following steps WPU/GO, (b): WPU/HH-G, (c): WPU/BHET-GO (example 1), (d) WPU/BHET-G (example 2);
fig. 2 is a schematic diagram of preparation of a graphene oxide-loaded BHET chain extender and a reduced graphene loaded BHET chain extender; BHET-GO corresponds to a graphene oxide supported BHET chain extender, and BHET-G corresponds to a reduced graphene supported BHET chain extender;
FIG. 3 is a flow chart of the process for preparing the functionalized polyurethane composite material in example 1;
FIG. 4 is a mechanical property diagram of the functionalized polyurethane composite material prepared in examples 1-2;
FIG. 5 is a graph of the electrical conductivity of polyurethane composites prepared at different filler contents;
FIG. 6 is a graph of the thermal conductivity of polyurethane composites prepared at different filler contents;
FIG. 7 is a diagram showing the mechanical properties of aqueous polyurethane prepared by different chain extenders in comparative examples.
Detailed Description
Specific embodiments of the present invention will be further described below with reference to examples, but the embodiments of the present invention are not limited thereto.
FIG. 1 is a scanning electron microscope image of the functionalized polyurethane composite material prepared in examples 1-2; WPU/BHET-GO corresponds to example 1, and WPU/BHET-G corresponds to example 2; the preparation method of WPU/GO in figure 1 is different from that of example 1 in that: 1 part by weight of BHET and 0.5 part by weight of graphene oxide were dispersed in 4 parts by weight of an organic solvent, and then the BHET dispersion liquid, the graphene oxide dispersion liquid and the polyurethane prepolymer were mixed and reacted at 70 ℃ for 3 hours, and the other conditions were the same as in example 1.
WPU/HH-G was prepared in a manner different from that of example 1: dispersing 0.5 part by weight of graphene oxide in 4 parts by weight of organic solvent, adding 1 part by weight of reducing agent into the dispersion liquid, reacting for 24 hours at 100 ℃, centrifuging and washing, and dispersing the precipitate in 4 parts by weight of organic solvent to obtain reduced graphene oxide HH-G dispersion liquid; dispersing 1 part by weight of BHET in 4 parts by weight of organic solvent to obtain a chain extender dispersion liquid; the chain extender dispersion, the HH-G dispersion, the polyurethane prepolymer and the internal crosslinking agent were mixed and reacted at 70 ℃ for 3 hours under the same conditions as in example 1.
Fig. 2 is a schematic diagram of preparation of a graphene oxide-loaded BHET chain extender and a reduced graphene loaded BHET chain extender; BHET-GO corresponds to a graphene oxide supported BHET chain extender, and BHET-G corresponds to a reduced graphene supported BHET chain extender.
The flow chart of the preparation process of the WPU/graphene composite material (of the functionalized polyurethane composite material) in the example 1 is shown in FIG. 3.
FIG. 4 is a mechanical property diagram of the functionalized polyurethane composite material prepared in examples 1-2; WPU: graphene oxide was not used, and other conditions were the same as in example 1; WPU/BHET-GO corresponds to example 1, and WPU/BHET-G corresponds to example 2.
FIG. 5 is a graph of the electrical conductivity of polyurethane composites prepared at different filler contents; WPU/GO: respectively dispersing 1 part by weight of BHET and graphene oxide in 4 parts by weight of organic solvent, mixing the BHET dispersion liquid, the graphene oxide dispersion liquid and the polyurethane prepolymer at 70 ℃ and reacting for 3 hours, wherein other conditions are the same as those in example 1; wherein the dosage of the graphene oxide is 0.25, 0.5, 0.75, 1 and 2 parts by weight respectively. WPU/BHET-GO: the graphene oxide is used in the amount of 0.25, 0.5, 0.75, 1, 2 parts by weight in example 1. WPU/BHET-G: the graphene oxide is used in the amount of 0.25, 0.5, 0.75, 1, 2 parts by weight in example 2.
FIG. 6 is a graph of the thermal conductivity of polyurethane composites prepared at different filler contents; WPU/GO: respectively dispersing 1 part by weight of BHET and graphene oxide in 4 parts by weight of organic solvent, mixing the BHET dispersion liquid, the graphene oxide dispersion liquid and the polyurethane prepolymer at 70 ℃ and reacting for 3 hours, wherein other conditions are the same as those in example 1; wherein the dosage of the graphene oxide is 0.25, 0.5, 0.75, 1 and 2 parts by weight respectively. WPU/BHET-GO: the graphene oxide is used in the amount of 0.25, 0.5, 0.75, 1, 2 parts by weight in example 1. WPU/BHET-G: the graphene oxide is used in the amount of 0.25, 0.5, 0.75, 1, 2 parts by weight in example 2.
Example 1
(1) Mixing PET and alcoholysis agent ethylene glycol according to the mass ratio of 1: 4 and 3 wt% of catalyst (3% of the mass of PET), adding into a reaction container, stirring and reacting for 1h at 170 ℃, filtering, rotary steaming, cooling, crystallizing, washing and drying the product to obtain the diethylene glycol terephthalate (BHET).
(2) Dissolving 1 part by weight of diethylene glycol terephthalate (BHET) in 4 parts by weight of N-methyl pyrrolidone, adding 0.5 part by weight of graphene oxide, carrying out ultrasonic treatment (the ultrasonic power is 400W) for 2h, stirring at 90 ℃ for 1.5h at the rotating speed of 200rpm, carrying out centrifugal separation (6000rpm) to remove a supernatant, and carrying out vacuum freeze drying on a product at-5 ℃ for 24h to obtain the BHET-loaded graphene oxide-loaded chain extender BHET-GO for later use.
(3) 15 parts by weight of poly (1, 4-butylene glycol) with the molecular weight of 1000, 10 parts by weight of isophorone diisocyanate and 1.5 parts by weight of hydrophilic chain extender 2, 2-dimethylolpropionic acid are added into a reactor, stirred at the rotating speed of 200rpm at the temperature of 90 ℃ for 1 hour, then 0.3 part by weight of catalyst dibutyltin dilaurate is added, and stirred for 0.5 hour, so that a polyurethane prepolymer is prepared for later use.
(4) Dissolving the graphene-loaded micromolecule chain extender BHET-GO in the step (2) in 4 parts by weight of N-methyl pyrrolidone, adding the solution into the polyurethane prepolymer in the step (3), adding 0.5 part by weight of internal cross-linking agent trimethylolpropane, stirring at the rotating speed of 250rpm at 70 ℃ for 3 hours, and adding 5 parts by weight of acetone for dilution in the reaction process; and cooling the reaction system to 50 ℃, adding 1 part by weight of triethylamine, neutralizing, stirring for 15min, cooling to room temperature, adding 70 parts by weight of deionized water, mixing and stirring at the rotating speed of 650rpm for 30min, and obtaining the polyurethane emulsion.
(5) Uniformly spreading the prepared emulsion on a dry and clean die to form a liquid layer with uniform thickness and smooth and flat surface, drying in a 30 ℃ oven for 24 hours, and uncovering the film to obtain the WPU/BHET-GO polyurethane film with electric and thermal conductivity.
The scanning electron microscope image of the WPU/BHET-GO polyurethane composite material prepared in the embodiment is shown in FIG. 1 (c). As can be seen from fig. 1, the graphene oxide GO supports BHET, which promotes the GO dispersion in polyurethane. The mechanical property diagram of the WPU/BHET-GO polyurethane composite material prepared by the embodiment is shown in figure 4. As can be seen from FIG. 4, the tensile strength of the WPU/BHET-GO composite material reaches 17.3MPa, which is increased by 1.4 times compared with the tensile strength of 7.1MPa of WPU polyurethane (graphene oxide is not selected, and other conditions are the same as those of example 1); fracture of WPU/BHET-GO compositesThe elongation reaches 455.5%, and compared with the elongation at break of 368.7% of WPU polyurethane, the elongation at break is increased by 23.5%, and the toughness is improved. FIG. 5 is a graph of conductivity of the functionalized polyurethane composite materials prepared under different filler contents, and it can be seen from FIG. 5 that, under the condition of the same filler parts, the conductivity of the WPU/BHET-GO composite material is higher than that of the WPU/GO polyurethane material prepared from unmodified graphene oxide GO, and when the used amount is 2 parts, the conductivity of the prepared WPU/BHET-GO polyurethane composite material reaches 4.6 × 10-6S/m, 1.2X 10 conductivity compared to WPU/GO polyurethane-6S/m, increased by 2.8 times. FIG. 6 is a heat-conducting property diagram of polyurethane composite materials prepared under different filler contents, and research results show that under the condition of the same filler parts, the heat-conducting coefficients of the WPU/BHET-GO composite materials are higher than those of the WPU/GO polyurethane materials prepared from unmodified graphene oxide GO, and when the using amounts are 2 parts, the heat-conducting coefficients of the prepared WPU/BHET-GO polyurethane composite materials reach 0.495 W.m-1·K-1Compared with the WPU/GO polyurethane, the thermal conductivity coefficient is 0.41 W.m-1·K-1The improvement is 20.7%.
Example 2
(1) Mixing PET and alcoholysis agent according to the mass ratio of 1: 5 and 4 wt% of catalyst, adding into a reaction container, stirring and reacting for 2h at 180 ℃, filtering, rotary steaming, cooling and crystallizing, washing and drying the product to obtain the diethylene glycol terephthalate (BHET).
(2) Dissolving 1 part by weight of diethylene glycol terephthalate (BHET) in 4 parts by weight of N-methyl pyrrolidone, adding 0.5 part by weight of graphene oxide, carrying out ultrasonic treatment for 1-2h, stirring for 1h at 100 ℃, then dropwise adding 1 part by weight of reducing agent hydrazine hydrate (hydrazine hydrate) and stirring for 1.5h at 100 ℃, carrying out centrifugal separation to remove supernatant, and carrying out vacuum freeze drying on a product at-5 ℃ for 24h to obtain the reduced graphene oxide supported chain extender BHET-G for later use.
(3) 15 parts by weight of poly (1, 4-butylene glycol) with the molecular weight of 1000, 10 parts by weight of isophorone diisocyanate and 1.5 parts by weight of hydrophilic chain extender 2, 2-dimethylolpropionic acid are added into a reactor, stirred for 1 hour at 90 ℃, then 0.3 part by weight of catalyst dibutyltin dilaurate is added, and stirred for 0.5 hour, so that the polyurethane prepolymer is prepared for later use.
(4) Dissolving the chain extender BHET-G obtained in the step (2) in 4 parts by weight of N-methyl pyrrolidone, adding the chain extender BHET-G into the polyurethane prepolymer obtained in the step (3), adding 0.5 part by weight of internal cross-linking agent trimethylolpropane, stirring for 3 hours at 70 ℃, and adding 5 parts by weight of acetone for dilution in the reaction process; and cooling the reaction system to 50 ℃, adding 1 part by weight of triethylamine, neutralizing, stirring for 15min, cooling to room temperature, adding 70 parts by weight of deionized water, mixing and stirring at the rotating speed of 650rpm for 30min, and obtaining the polyurethane emulsion.
(5) And uniformly spreading the prepared emulsion on a dry and clean die to form a liquid layer with uniform thickness and smooth and flat surface, drying in a 30 ℃ oven for 24 hours, and uncovering the film to obtain the WPU/BHET-G polyurethane film with electric and thermal conductivity.
The scanning electron microscope image of the functionalized polyurethane composite material prepared in this example is shown in fig. 1(d), and as can be seen from fig. 1, the prepared BHET-G promotes the dispersion of graphene in polyurethane. The mechanical property diagram of the multifunctional polyurethane composite material prepared by the embodiment is shown in fig. 4, and as can be seen from fig. 4, the tensile strength of the WPU/BHET-G composite material reaches 25.8Mpa, which is increased by 49.1% compared with the tensile strength of 17.3Mpa of the WPU/BHET-GO polyurethane composite material; the elongation at break of the WPU/BHET-G composite material reaches 465.5%, and is improved by 2.4% compared with the elongation at break of 455.5% of WPU/BHET-GO polyurethane, and the toughness is improved. FIG. 5 is a graph of conductivity of the functionalized polyurethane composite materials prepared under different filler contents, and it can be seen from FIG. 5 that the conductivity of the WPU/BHET-G composite material is higher than that of the WPU/BHET-GO polyurethane composite material under the condition of the same filler parts, and when the used amount is 2 parts, the conductivity of the prepared WPU/BHET-G polyurethane composite material reaches 7.2 × 10-5S/m, 4.6X 10 conductivity compared to WPU/BHET-GO polyurethane composite-6S/m, increased by 14.7 times. FIG. 6 is a heat-conducting property diagram of the functionalized polyurethane composite materials prepared under different filler contents, and research results show that the WPU/BHET-G composite materials have the same filler contentThe thermal conductivity coefficient of the composite material is higher than that of the WPU/BHET-GO polyurethane composite material, and when the using amount is 2 parts, the thermal conductivity coefficient of the prepared WPU/BHET-G polyurethane composite material reaches 0.52 W.m-1·K-1Thermal conductivity coefficient of 0.495 W.m compared to WPU/GO polyurethane-1·K-1And the improvement is 5 percent.
Example 3
(1) Mixing PET and alcoholysis agent according to the mass ratio of 1: 6 and 5 wt% of catalyst, adding into a reaction container, stirring and reacting for 3h at 190 ℃, filtering, rotary steaming, cooling and crystallizing, washing and drying the product to obtain the diethylene glycol terephthalate (BHET).
(2) Dissolving 2 parts by weight of diethylene glycol terephthalate (BHET) in 3 parts by weight of N, N-dimethylformamide, adding 1 part by weight of graphene oxide, carrying out ultrasonic treatment for 2 hours, then stirring for 2 hours at 100 ℃, carrying out centrifugal separation to remove supernatant, and carrying out vacuum freeze drying on the product for 24 hours at-5 ℃ to obtain the graphene oxide supported small-molecular chain extender BHET-GO for later use.
(3) 15 parts by weight of poly adipic acid-1, 6-hexanediol with the molecular weight of 1000, 10 parts by weight of hexamethylene diisocyanate and 1.5 parts by weight of hydrophilic chain extender N-methyldiethanolamine are added into a reactor, stirred for 1 hour at 90 ℃, then 0.3 part by weight of catalyst dibutyltin dilaurate is added, and stirred for 0.5 hour, so as to prepare a polyurethane prepolymer for later use.
(4) Dissolving the chain extender BHET-GO obtained in the step (2) in 3 parts by weight of N, N-dimethylformamide, adding the solution into the polyurethane prepolymer obtained in the step (3), adding 0.5 part by weight of glycerol as an internal crosslinking agent, stirring the mixture for 3 hours at 70 ℃, and adding 5 parts by weight of acetone to dilute the mixture in the reaction process; and cooling the reaction system to 50 ℃, adding 0.8 part by weight of triethylamine, neutralizing, stirring for 15min, cooling to room temperature, adding 80 parts by weight of deionized water, mixing and stirring at the rotating speed of 650rpm for 30min, and obtaining the polyurethane emulsion.
(5) Uniformly spreading the prepared emulsion on a dry and clean die to form a liquid layer with uniform thickness and smooth and flat surface, drying in a 30 ℃ oven for 24 hours, and uncovering the film to obtain the WPU/BHET-GO polyurethane film with electric and thermal conductivity. Experimental results show that compared with WPU/GO and WPU polyurethane materials, the WPU/BHET-GO polyurethane has improved mechanical, electric and heat conducting properties.
Example 4
(1) Mixing PET and alcoholysis agent according to the mass ratio of 1: 7 and 6 wt% of catalyst, adding into a reaction container, stirring and reacting for 4h at 200 ℃, filtering, rotary steaming, cooling and crystallizing, washing and drying the product to obtain the diethylene glycol terephthalate (BHET).
(2) Dissolving 2 parts by weight of diethylene glycol terephthalate (BHET) in 4 parts by weight of N, N-dimethylformamide, adding 1 part by weight of single-layer graphene oxide, carrying out ultrasonic treatment for 2 hours, stirring for 1.5 hours at 100 ℃, then dropwise adding 1 part by weight of reducing agent hydrazine hydrate, stirring for 1.5 hours at 100 ℃, carrying out centrifugal separation to remove supernatant, and carrying out vacuum freeze drying on a product at-5 ℃ for 24 hours to obtain the BHET-loaded reduced graphene oxide supported chain extender BHET-G for later use.
(3) In a reactor, 15 parts by weight of poly adipic acid-1, 6-hexanediol with the molecular weight of 1000, 10 parts by weight of hexamethylene diisocyanate and 1.5 parts by weight of hydrophilic chain extender N-methyldiethanolamine are stirred for 1 hour at 90 ℃, then 0.3 part by weight of catalyst dibutyltin dilaurate is added, and the mixture is stirred for 0.5 hour to prepare a polyurethane prepolymer for later use.
(4) Dissolving the graphene-loaded micromolecule chain extender BHET-G prepared in the step (2) in 4 parts by weight of N, N-dimethylformamide, adding the solution into the polyurethane prepolymer obtained in the step (3), adding 0.5 part by weight of internal cross-linking agent glycerol, stirring for 3 hours at 70 ℃, and adding 6 parts by weight of acetone for dilution in the reaction process; and cooling the reaction system to 50 ℃, adding 1 part by weight of triethylamine, neutralizing, stirring for 15min, cooling to room temperature, adding 80 parts by weight of deionized water, mixing and stirring at the rotating speed of 650rpm for 30min, and obtaining the polyurethane emulsion.
(5) And uniformly spreading the prepared emulsion on a dry and clean die to form a liquid layer with uniform thickness and smooth and flat surface, drying in a 30 ℃ oven for 24 hours, and uncovering the film to obtain the WPU/BHET-G polyurethane film with good electric and thermal conductivity.
Example 5
(1) Mixing PET and alcoholysis agent according to the mass ratio of 1: 4 and 5 wt% of catalyst, adding into a reaction container, stirring and reacting for 5h at 190 ℃, filtering, rotary steaming, cooling and crystallizing, washing and drying the product to obtain the diethylene glycol terephthalate (BHET).
(2) Dissolving 3 parts by weight of diethylene glycol terephthalate (BHET) in 3 parts by weight of N-methyl pyrrolidone, adding 1.5 parts by weight of graphene oxide, carrying out ultrasonic treatment for 2 hours, stirring for 1.5 hours at 100 ℃, then dropwise adding 1 part by weight of reducing agent hydrazine hydrate, stirring for 1.5 hours at 100 ℃, carrying out centrifugal separation to remove supernatant, and carrying out vacuum freeze drying on a product at-5 ℃ for 24 hours to obtain a BHET-loaded reduced graphene oxide supported chain extender BHET-G for later use.
(3) In a reactor, 15 parts by weight of poly propylene glycol adipate with molecular weight of 1000, 10 parts by weight of dicyclohexylmethane diisocyanate and 1.5 parts by weight of hydrophilic chain extender 1, 4-butanediol-2-sodium sulfonate are stirred for 1 hour at 90 ℃, then 0.3 part by weight of catalyst dibutyltin dilaurate is added, and the mixture is stirred for 0.5 hour to prepare a polyurethane prepolymer for later use.
(4) Adding a functional micromolecule chain extender BHET-G and 0.5 part by weight of internal cross-linking agent pentaerythritol into the prepolymer, stirring for 3 hours at 70 ℃, and dropwise adding 4 parts by weight of acetone in the reaction process to adjust the viscosity; and cooling the reaction system to 50 ℃, adding 0.6 part by weight of triethylamine, neutralizing, stirring for 15min, cooling to room temperature, adding 90 parts by weight of deionized water, mixing and stirring at the rotating speed of 650rpm for 30min, and obtaining the polyurethane emulsion.
(5) And uniformly spreading the prepared emulsion on a dry and clean die to form a liquid layer with uniform thickness and smooth and flat surface, drying in a 30 ℃ oven for 24 hours, and uncovering the film to obtain the WPU/BHET-G polyurethane film with good electric and thermal conductivity.
Comparative example
(1) Mixing PET and alcoholysis agent ethylene glycol according to the mass ratio of 1: 4 and 3 wt% of catalyst (3% of the mass of PET), adding into a reaction container, stirring and reacting for 1h at 170 ℃, filtering, rotary steaming, cooling, crystallizing, washing and drying the product to obtain the diethylene glycol terephthalate (BHET).
(2) 15 parts by weight of poly (1, 4-butylene glycol) with the molecular weight of 1000, 10 parts by weight of isophorone diisocyanate and 1.5 parts by weight of hydrophilic chain extender 2, 2-dimethylolpropionic acid are added into a reactor, stirred at the rotating speed of 200rpm at the temperature of 90 ℃ for 1 hour, then 0.3 part by weight of catalyst dibutyltin dilaurate is added, and stirred for 0.5 hour, so that a polyurethane prepolymer is prepared for later use.
(3) Dissolving 1 part by weight of chain extender BHET or 1, 4-butanediol BDO in 4 parts by weight of N-methyl pyrrolidone, adding the chain extender BHET or 1, 4-butanediol BDO into the polyurethane prepolymer in the step (2), adding 0.5 part by weight of internal cross-linking agent trimethylolpropane, stirring at the rotating speed of 250rpm at 70 ℃ for 3 hours, and adding 5 parts by weight of acetone for dilution in the reaction process; and cooling the reaction system to 50 ℃, adding 1 part by weight of triethylamine, neutralizing, stirring for 15min, cooling to room temperature, adding 70 parts by weight of deionized water, mixing and stirring at the rotating speed of 650rpm for 30min, and obtaining the polyurethane emulsion.
The obtained waterborne polyurethane is subjected to mechanical property test, the test result is shown in figure 7, and the waterborne polyurethane prepared when the chain extender corresponding to WPU/BDO is BDO in the figure; when the chain extender corresponding to the WPU/BHET is BHET, the waterborne polyurethane is prepared.
The mechanical property and the adhesive property of the waterborne polyurethane synthesized by using BHET as a chain extender are better than those of BDO.
Claims (10)
1. A functional waterborne polyurethane material is characterized in that: the paint is mainly prepared from the following raw materials in parts by weight:
2. the functionalized aqueous polyurethane material of claim 1, wherein:
the polyester polyol is more than one of poly adipic acid-1, 4-butanediol, poly adipic acid-1, 6-hexanediol, poly hexanediol ethylene glycol, poly adipic acid propylene glycol and poly carbonic acid 1, 6-hexanediol glycol;
the molecular weight of the polyester polyol is 1000-3000;
the diisocyanate is more than one of isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate and toluene diisocyanate;
the hydrophilic chain extender is more than one of 2, 2-dimethylolpropionic acid, amino acid, diaminobenzoic acid, ethylene diamine ethyl sodium sulfonate, 1, 4-butanediol-2-sodium sulfonate and N-methyldiethanolamine;
the internal crosslinking agent is more than one of trimethylolpropane, glycerol, pentaerythritol and propylene glycol.
3. The functionalized aqueous polyurethane material of claim 1, wherein: the catalyst is more than one of dibutyltin dilaurate, stannous octoate and dibutyltin diacetate; the organic solvent is more than one of N-methyl pyrrolidone, N-dimethylformamide and acetone; the diluent is more than one of acetone, N-methyl pyrrolidone, N-dimethylformamide and dimethyl sulfoxide; the neutralizing agent is more than one of triethylamine, sodium hydroxide and potassium hydroxide;
the diethylene glycol terephthalate is obtained by PET alcoholysis; the preparation method comprises the following steps: under the protective atmosphere, reacting PET and an alcoholysis agent for 1-5h at the temperature of 200 ℃ under the action of a catalyst, and performing subsequent treatment to obtain an alcoholysis product, namely, diethylene glycol terephthalate (BHET); the alcoholysis agent is ethylene glycol.
4. The functionalized aqueous polyurethane material of claim 3, wherein: the mass ratio of the waste PET to the alcoholysis agent is 1: 4-7; the dosage of the catalyst is 3-6% of the mass of the PET;
the PET is waste PET;
the catalyst is more than one of zinc acetate, manganese acetate, nickel acetate and copper acetate;
and the subsequent treatment comprises filtering after the reaction is finished, cooling and crystallizing, washing the crystal with water, and drying in vacuum to obtain the alcoholysis product of the diethylene glycol terephthalate.
5. The functionalized aqueous polyurethane material of claim 1, wherein: the raw material of the functional waterborne polyurethane material also comprises a reducing agent, wherein the weight part of the reducing agent is 0.5-1.5.
6. The functionalized aqueous polyurethane material of claim 5, wherein: the reducing agent is more than one of hydrazine hydrate, sodium borohydride and sodium citrate.
7. The preparation method of the functionalized aqueous polyurethane material according to any one of claims 1 to 6, wherein the method comprises the following steps: the method comprises the following steps:
1) carrying out ultrasonic treatment on diethylene glycol terephthalate and graphene oxide in an organic solvent, and then carrying out heat treatment at 80-100 ℃ for 1-2h to obtain a graphene oxide supported BHET chain extender which is marked as BHET-GO; or carrying out reduction reaction on the graphene oxide supported BHET chain extender through a reducing agent to obtain a reduced graphene supported BHET chain extender which is marked as BHET-G;
2) mixing polyester polyol with diisocyanate and a hydrophilic chain extender, adding a catalyst, and reacting at 80-100 ℃ to obtain a polyurethane prepolymer; the mixing is to stir at 80-100 ℃ for 1-2h, and the reaction time is 20-40 min;
3) dispersing a graphene oxide supported BHET chain extender or a reduced graphene supported BHET chain extender in an organic solvent to obtain a chain extender dispersion liquid; mixing the chain extender dispersion liquid, the polyurethane prepolymer and the internal crosslinking agent, reacting for 2-4h at 50-70 ℃, and adding a diluent to dilute in the reaction process; then adding a neutralizing agent for neutralization, and adding water for emulsification to obtain a polyurethane emulsion;
4) and (3) forming a film on the polyurethane emulsion to obtain the functionalized waterborne polyurethane material.
8. The method for preparing the functionalized aqueous polyurethane material according to claim 7, wherein the method comprises the following steps:
the specific preparation step of the graphene oxide supported BHET chain extender in the step 1) is to perform ultrasonic treatment on diethylene glycol terephthalate and graphene oxide in an organic solvent, then perform heat treatment at 80-100 ℃ for 1-2h, and perform subsequent treatment to obtain the graphene oxide supported BHET chain extender;
the specific preparation step of the reduced graphene supported BHET chain extender in the step 1) is to perform ultrasonic treatment on diethylene glycol terephthalate and graphene oxide in an organic solvent, then perform heat treatment at 80-100 ℃ for 1-2h, add a reducing agent, perform reduction reaction, and perform subsequent treatment to obtain the reduced graphene supported BHET chain extender;
in the step 3), the organic solvent is more than one of N-methyl pyrrolidone, N-dimethylformamide and acetone;
the weight ratio of the organic solvent to BHET in the chain extender in the step 3) is (0-8) to (1-3);
the emulsification in the step 3) refers to high-speed stirring for 20-40min, wherein the stirring speed is 500-800 rpm.
9. The method for preparing the functionalized aqueous polyurethane material according to claim 8, wherein the method comprises the following steps: in the preparation of the graphene oxide supported BHET chain extender, the weight ratio of the organic solvent to the BHET is (3-8) to (1-3); the organic solvent is more than one of N-methyl pyrrolidone, N-dimethylformamide and acetone;
in the preparation of the reduced graphene loaded BHET chain extender, the organic solvent is more than one of N-methyl pyrrolidone, N-dimethylformamide and acetone; the weight ratio of the organic solvent to the BHET is (3-8) to (1-3); the reduction reaction is carried out for 1-2h at the temperature of 80-100 ℃;
in the graphene oxide loaded BHET chain extender, the subsequent treatment is centrifugation, supernatant liquid is removed, and vacuum freeze drying is carried out;
in the reduced graphene-loaded BHET chain extender, the subsequent treatment is centrifugation, supernatant liquid is removed, and vacuum freeze drying is carried out.
10. The application of the functionalized aqueous polyurethane material according to any one of claims 1 to 6, wherein: the functionalized waterborne polyurethane material is used in the fields of 5G communication materials and electronic packaging materials.
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