CN111499827B - Preparation method of super-toughness bio-based polyurethane composite material - Google Patents
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Abstract
The invention discloses a preparation method of a super-toughness bio-based polyurethane composite material. Modifying the purified waste oil with peroxyacetic acid and ethylene glycol in sequence to obtain alcoholized oil; b. fully dissolving a toughening agent in a volatile organic solvent to obtain a toughening agent solution; c. uniformly mixing the alcoholized oil and the organic silicon, placing the mixture in an oil bath, magnetically stirring, adding a toughening agent solution, adding a crosslinking agent after the organic solvent is completely volatilized, and continuing to react; and (4) solidifying the product after the reaction is finished, thus obtaining the product. The invention breaks through the limitation of the traditional single modification on the improvement of the performance of the polyurethane material, overcomes the problems of pollution of a solvent to a product, difficult degradation of the material and the like, realizes the improvement of the multiple performance of the polyurethane material, simultaneously prepares the green super-tough polyurethane composite material with excellent comprehensive performance by regulating and controlling the internal mosaic structure of the polyurethane composite material, and provides the preparation method of the composite material which is green, environment-friendly, multifunctional and easy for industrial production.
Description
Technical Field
The invention relates to the technical field of coating materials, thermoplastic elastomers and porous materials, in particular to a preparation method of a super-toughness bio-based polyurethane composite material.
Background
Polyurethane is used as a polymer material with the most extensive application at present, and can be applied to the fields of coatings, foams, adhesives, sealants, thermoplastic elastomers, fertilizer slow release and the like. At present, raw materials for producing polyurethane mainly come from petroleum resources, and along with the gradual depletion of the petroleum resources, the cost of the raw materials for producing the polyurethane is gradually increased, and the environmental protection cost of petroleum processing is further increased due to the increasingly severe environmental problems, so that the cost of final products is increased more and more. Due to the problems, the development of the polyurethane polymer material industry is greatly restricted. In summary, the research on the utilization of renewable biological resources as raw materials for synthesizing polyurethane is significant for the development of polyurethane polymer material industry.
Disclosure of Invention
The invention aims to provide a preparation method of an ultra-toughness bio-based polyurethane composite material. The invention breaks through the limitation of the traditional single modification on the improvement of the performance of the polyurethane material, overcomes the problems of pollution of a solvent to a product, difficult degradation of the material and the like, realizes the improvement of the multiple performance of the polyurethane material, simultaneously prepares the green super-tough polyurethane composite material with excellent comprehensive performance by regulating and controlling the internal mosaic structure of the polyurethane composite material, and provides the preparation method of the composite material which is green, environment-friendly, multifunctional and easy for industrial production.
The technical scheme of the invention is as follows: a preparation method of a super-toughness bio-based polyurethane composite material comprises the following steps:
a. preparing raw materials: modifying the purified waste oil with peroxyacetic acid and ethylene glycol in sequence to obtain alcoholized oil;
b. preparing a toughening agent solution: fully dissolving a toughening agent in a volatile organic solvent to obtain a toughening agent solution;
c. preparing a composite material: uniformly mixing the alcoholized oil and the organic silicon, placing the mixture in an oil bath for magnetic stirring, then adding a toughening agent solution, and adding a crosslinking agent for continuous reaction after the organic solvent is completely volatilized; and (4) solidifying the product after the reaction is finished, thus obtaining the product.
In the step a of the preparation method of the super-tough bio-based polyurethane composite material, the modification of the purified waste oil is as follows: modifying with excessive peroxyacetic acid and glycol in sequence under the condition of a catalyst; wherein, the catalyst is: aluminum chloride accounting for 1-10% of the weight of the purified waste oil; the modification conditions are as follows: and (3) modifying for 1-5 h in a nitrogen atmosphere at the temperature of 80-90 ℃.
In the step b of the preparation method of the super-toughness bio-based polyurethane composite material, the toughening agent solution is a viscous solution.
In step b of the preparation method of the super-tough bio-based polyurethane composite material, the toughening agent is: PCL accounting for 10-40% of the weight of the alcoholized oil.
In the step b of the preparation method of the super-toughness bio-based polyurethane composite material, the volatile organic solvent is CH2Cl2A solvent.
In the step c of the preparation method of the super-toughness bio-based polyurethane composite material, the structure of the organic silicon is short chain molecules, and the amount of the organic silicon accounts for 20% of the weight of the alcoholized oil.
According to the preparation method of the super-toughness bio-based polyurethane composite material, the organic silicon is a mixture of KH550 and HTPMS; the weight ratio of KH550 to HTPMS is 0.3: 0.7 based on 1 part of the total weight of the mixture.
In step c of the preparation method of the super-tough bio-based polyurethane composite material, the cross-linking agent is: MDI-50 with the weight accounting for 50-60% of the total mixture after the organic solvent is completely volatilized.
In the step c of the preparation method of the super-toughness bio-based polyurethane composite material, the oil bath temperature is 75-85 ℃; the magnetic stirring time is 1-3 h; and adding a cross-linking agent for continuous reaction for 5-15 min.
In step c of the preparation method of the super-tough bio-based polyurethane composite material, the curing operation is: and (3) curing the product in a vacuum oven at 40-50 ℃ for 1-2 days.
Compared with the prior art, the waste grease (illegal cooking oil) is used as the raw material for producing the polyurethane composite material, so that the limit of producing polyurethane by using petroleum as the raw material is broken through, and the raw material source is widened; and as the illegal cooking oil has large yield and low price, the pressure of the cost of raw materials is effectively relieved, and simultaneously compared with petroleum, the production by adopting the illegal cooking oil can reduce environmental pollution and reduce environmental protection cost.
According to the invention, the toughening agent is dissolved by using a volatile organic solvent, on one hand, by utilizing the principle that the organic solvent is volatile when being heated, bubbles generated when the organic solvent is heated form impact force, and the viscous toughening agent is continuously impacted, so that the toughening agent forms a porous structure, and the formation of a dual-damascene structure is further facilitated; on the other hand, organic solvent residue is avoided, the compatibility of two phases is improved, and the product does not need to be purified. In addition, the toughening agent solution prepared by the invention is a viscous solution, and the solution in the state is more beneficial to the formation of a porous structure. The toughening agent is dissolved in the volatile solvent and forms a sticky solution, so that a novel method is provided for preparing the porous material.
According to the invention, the organic silicon block modified polyurethane is adopted, and the toughening agent solution formed by dissolving the toughening agent by using the volatile organic solvent is used for toughening the polyurethane, so that the improvement of the multiple properties of the polyurethane material is realized by the cooperation of the organic silicon block modified polyurethane and the polyurethane, the limitation of single modification on the improvement of the performance of the polyurethane material is broken through, the problem that the existing single modified polyurethane has single function and cannot meet the increasingly growing functional requirements of the material is solved, and the improvement of the multiple properties of the composite material is realized. Polyurethane is modified by various materials, and the tough polyurethane composite material with a dual-mosaic structure is finally prepared by utilizing the synergistic effect of different materials, wherein the material with the structure has comprehensive excellent performances of excellent humidity and heat resistance, high toughness and hardness and the like, so that the application field of the polyurethane is widened.
The organic silicon is a short-chain molecule, namely a mixture of gamma-aminopropyltriethoxysilane (KH5509) and oligomeric hydroxyl-terminated polydimethylsiloxane (HTPMS), and can effectively increase the hard segment of a polyurethane molecular chain and improve the hardness of polyurethane.
The invention can also regulate and control the internal mosaic structure of the polyurethane composite material by regulating the consumption of PCL, thereby being beneficial to preparing the super-tough polyurethane composite material with excellent comprehensive performance according to actual requirements; the method has the advantages that the application performance of the material is well expanded, and the applicability is stronger.
The operation of curing in the invention is as follows: placing the product in a vacuum oven with the temperature of 40-50 ℃ (optimally 45 ℃) for curing for 1-2 days (optimally 24 hours); by the method, the PCL can be prevented from melting, and the solidification reaction can be better completed.
In conclusion, the invention breaks through the limitation of the traditional single modification on the improvement of the performance of the polyurethane material, overcomes the problems of pollution of a solvent to a product, difficult degradation of the material and the like, realizes the improvement of the multiple performance of the polyurethane material, simultaneously prepares the green super-tough polyurethane composite material with excellent comprehensive performance by regulating and controlling the internal mosaic structure of the polyurethane composite material, and provides the preparation method of the composite material which is green, environment-friendly, multifunctional and easy for industrial production.
Drawings
FIG. 1 shows FTIR spectra (a), XPS spectra (b) and O1s spectra (c, d) of K-H-PU and P/K-H-PU composites;
FIG. 2 is a cross-sectional SEM morphology of the P/K-H-PU composite material: before acetone treatment: (a) K-H-PU, (b) P/K-H-PU-1, (c) P/K-H-PU-2, (d) P/K-H-PU-3, (e) P/K-H-PU-4; after acetone treatment: (f) K-H-PU, (g) P/K-H-PU-1, (H) P/K-H-PU-2, (i) P/K-H-PU-3, and (j) P/K-H-PU-4;
FIG. 3 is an SEM morphology of the P/K-H-PU-3 composite material after acetone treatment;
FIG. 4 is a graph showing the permeability, component fixation rate and water contact angle analysis of P/K-H-PU composite material
FIG. 5 shows the toughness analysis of P/K-H-PU composite material, (a) K-H-PU, (b) P/K-H-PU-1, (c) P/K-H-PU-2, (d) P/K-H-PU-3, and (e) P/K-H-PU-4.
Detailed Description
The present invention is further illustrated by the following examples, which are not to be construed as limiting the invention.
Example 1. A preparation method of a super-toughness bio-based polyurethane composite material comprises the following steps:
a. preparing raw materials: modifying the purified waste oil with peroxyacetic acid and ethylene glycol in sequence to obtain alcoholized oil;
the purification of the waste oil is as follows: sequentially carrying out suction filtration, acid washing, water washing, alkali washing, salt washing and active carbon moisture removal on the recovered waste oil;
the modification of the purified waste oil is as follows: modifying with excessive peroxyacetic acid and glycol in sequence under the condition of a catalyst; wherein, the catalyst is: aluminum chloride accounting for 1-10% (optimally 5%) of the weight of the purified waste oil fat; the modification conditions are as follows: and (3) in a nitrogen atmosphere, wherein the temperature is 80-90 ℃ (optimally 85 ℃), and the modification time is 1-5 h (optimally 2 h). The modified oil needs to be purified after each modification.
b. Preparing a toughening agent solution: fully dissolving a toughening agent in a volatile organic solvent to obtain a toughening agent solution;
the toughening agent is: PCL (polycaprolactone) accounting for 10-40% of the weight of the alcoholized oil; when the content of PCL reaches 40%, only toughness is increased, and other properties are reduced;
the volatile organic solvent is CH2Cl2A solvent;
the toughening agent solution finally prepared is a viscous solution.
c. Preparing a composite material: uniformly mixing the alcoholized oil and the organic silicon, placing the mixture in an oil bath for magnetic stirring, then adding a toughening agent solution, and adding a crosslinking agent for continuous reaction after the organic solvent is completely volatilized; after the reaction is finished, curing the product to obtain the catalyst;
the structure of the organic silicon is short chain molecules, and the amount of the organic silicon accounts for 20 percent of the weight of the alcoholized oil; specifically, the organosilicon is a mixture of KH550 (gamma-aminopropyltriethoxysilane) and HTPMS (oligomeric hydroxyl-terminated polydimethylsiloxane); the weight ratio of the KH550 to the HTPMS is 0.3: 0.7 according to 1 part of the total weight of the mixture;
the crosslinking agent is: MDI-50 (isocyanate) with the weight accounting for 50-60% (optimally 55%) of the total weight of the mixture after the organic solvent is completely volatilized;
the oil bath temperature is 75-85 ℃ (optimally 80 ℃); the magnetic stirring time is 1-3 h (optimally 2 h); adding a cross-linking agent for continuous reaction for 5-15 min (optimally 10 min);
the curing operation comprises the following steps: and (3) curing the product in a vacuum oven at 40-50 ℃ (optimally at 45 ℃) for 1-2 days (optimally at 24 hours).
The finally prepared polyurethane composite material is a PCL and organic silicon modified polyurethane composite, and is recorded as: P/K-H-PU-x, wherein x is defined as 1, 2, 3 and 4, respectively representing the polyurethane composite material with PCL content of 10%, 20%, 30% and 40%. And then the dual-organic modified polyurethane (K-H-PU) with the PCL content of 0 percent is prepared by the method and used as a control experiment.
Experiments show that the prepared tough polyurethane composite material with the dual-damascene structure has different microstructures formed by polycaprolactone with different contents and the modified polyurethane under the action of bubble impact force, physical blending is carried out between the two phases through hydrogen bonds, and as shown in figure 1, hydrogen bonding action exists between C ═ O of the modified polyurethane and-OH of the polycaprolactone. Wherein, an imitated pomegranate wrapping structure and an inlaid network structure are formed between the polycaprolactone with the content of 30% and the polyurethane, as shown in fig. 2 and fig. 3. Compared with modified polyurethane, the water permeability of the composite is reduced by 61.9%, the hydrophobicity is increased by 15.6%, and the component fixing rate is as high as 80.8% due to the dual-damascene structure, which is shown in fig. 4. The introduction of polycaprolactone causes the polyurethane to be transformed from brittleness to toughness, and the toughness test is shown in figure 5, and as the content of PCL continues to increase, P/K-H-PU is gradually transformed from brittleness to toughness to show flexibility as can be seen from figure 5. When the content of PCL is increased to 40%, the flexibility of P/K-H-PU-4 is greatly increased, and the bending test result shows that the composite is not fractured along with the increase of the bending degree and is still not fractured after multiple bending, but the miscibility and the component fixation rate of the composite are slightly reduced. The preparation process of the tough bio-based polyurethane composite provides a new idea for the preparation of the porous material.
Claims (3)
1. The preparation method of the super-toughness bio-based polyurethane composite material is characterized by comprising the following steps of:
a. preparing raw materials: modifying the purified waste oil with peroxyacetic acid and ethylene glycol in sequence to obtain alcoholized oil; the modification of the purified waste oil is as follows: modifying with excessive peroxyacetic acid and glycol in sequence under the condition of a catalyst; wherein, the catalyst is: aluminum chloride accounting for 1-10% of the weight of the purified waste oil; the modification conditions are as follows: in a nitrogen atmosphere, the temperature is 80-90 ℃, and the modification time is 1-5 h;
b. preparing a toughening agent solution: fully dissolving a toughening agent in a volatile organic solvent to obtain a toughening agent solution; the toughening agent is: weight ofPCL which is 10-40% of the weight of the alcoholized oil; the volatile organic solvent is CH2Cl2A solvent;
c. preparing a composite material: uniformly mixing the alcoholized oil and the organic silicon, placing the mixture in an oil bath for magnetic stirring, then adding a toughening agent solution, and adding a crosslinking agent for continuous reaction after the organic solvent is completely volatilized; after the reaction is finished, curing the product to obtain the catalyst; the structure of the organic silicon is short chain molecules, and the amount of the organic silicon accounts for 20 percent of the weight of the alcoholized oil; the organic silicon is a mixture of KH550 and HTPMS; the weight ratio of the KH550 to the HTPMS is 0.3: 0.7 according to 1 part of the total weight of the mixture; the cross-linking agent is: MDI-50 with the weight accounting for 50-60% of the total mixture weight after the organic solvent is completely volatilized; the oil bath temperature is 75-85 ℃; the magnetic stirring time is 1-3 h; and adding a cross-linking agent for continuous reaction for 5-15 min.
2. The method of claim 1, wherein in the step b, the toughening agent solution is a viscous solution.
3. The method for preparing the ultra-tough bio-based polyurethane composite according to claim 1, wherein in the step c, the curing is performed by: and (3) curing the product in a vacuum oven at 40-50 ℃ for 1-2 days.
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| US4202957A (en) * | 1974-09-09 | 1980-05-13 | The Upjohn Company | Thermoplastic polyurethane elastomers from polyoxypropylene polyoxyethylene block copolymers |
| WO1996017880A1 (en) * | 1994-12-06 | 1996-06-13 | The Dexter Corporation | Novel polyurethane toughener, thermosetting resin compositions and adhesives |
| CN101230189B (en) * | 2008-01-29 | 2010-06-02 | 武汉理工大学 | Method for preparing polysaccharide nano-crystalline grafted polyester modified polyurethane material |
| US20150252187A1 (en) * | 2014-03-07 | 2015-09-10 | Sunko Ink Co., Ltd. | Multifunctional environmentally protective polyurethane composite material and method of making the same |
| CN104130365B (en) * | 2014-07-22 | 2016-11-02 | 南京林业大学 | A kind of linear polyurethane elastic body toughening agent of toughness reinforcing Biopolvester PHA and its preparation method and application |
| CN104448200A (en) * | 2014-12-19 | 2015-03-25 | 江南大学 | Preparation method of plant oil-based UV-curable waterborne organosilicone polyurethane resin |
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| CN108864393B (en) * | 2018-08-28 | 2021-04-30 | 贵州大学 | Preparation method of modified bio-based polyurethane and application of modified bio-based polyurethane in slow release fertilizer |
| CN109880047B (en) * | 2019-03-05 | 2021-08-31 | 贵州大学 | Preparation method and application of dual-organic-silicon block modified polyurethane |
| CN110105525B (en) * | 2019-05-21 | 2021-11-16 | 株洲时代新材料科技股份有限公司 | NDI-based polyurethane microporous elastomer resistant to damp-heat aging and preparation method thereof |
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