Low-carbon environment-friendly bio-based polyurethane as well as preparation method and application thereof
By using the preparation method of bio-based polyurethane, the problems of non-renewable, toxic and degradable polyurethane raw materials are solved, low-carbon, environmentally friendly, biodegradable polyurethane fibers are realized, and their application scope is expanded.
Patent Information
- Application Number
- CN202311618402.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2023-11-30
- Publication Date
- 2025-05-30
AI Technical Summary
The raw materials for polyurethane preparation are non-renewable, highly toxic, and difficult to degrade. The content of bio-based components is low, cytotoxic, and the application range is narrow.
Low-carbon and environmentally friendly bio-based polyurethane is prepared from raw materials such as polylactic acid polyol, polycarbonate polyol, small molecule diol, antioxidants, isocyanates, catalysts, reaction terminators, etc., and the reaction is avoided by the protection of inert gases.
The prepared bio-based polyurethane has the advantages of green and environmental protection, reducing carbon carbon. The fiber has better affinity, skin feeling, toughness, rebound rate and strength, and is biodegradable and has a wider range of applications.
Smart Images
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Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of polyurethanes, and in particular to a low-carbon and environmentally friendly bio-based polyurethane and its preparation method and application. Background Art
[0002] Polyurethane is an important industrial polymer material, which has advantages such as wear resistance, tear resistance, and good flexural resistance, and is applied in many fields such as sofas, shoes, luggage, furniture, automobiles, and electronic products. Polyurethane fiber, namely spandex, is widely used in the clothing and textile industries. With the continuous improvement of consumers' requirements for the comfort and functions of clothing and the deepening of the environmental protection concept, high-quality bio-based spandex will become a new direction for the development of the spandex industry.
[0003] Due to the increasingly severe environmental and resource problems, it is urgent to use biodegradable materials to replace petroleum-based materials to solve the "white pollution" problem.
[0004] Polylactic acid (PLA) is a biodegradable and environmentally friendly material made from renewable resources such as straw and corn. However, pure polylactic acid has high hardness, low elasticity, poor toughness, is not resistant to high temperature, and has a poor skin feel, which limits its large-scale application.
[0005] The raw materials for traditional polyurethane preparation come from petroleum, which are non-renewable and highly toxic. At the same time, waste polyurethane is difficult to degrade. Bio-based polyurethane materials have good biodegradability, wide raw material sources, and low environmental load, and have become the top priority for sustainable development in the current materials industry.
[0006] CN 114085356A discloses a polylactic acid biodegradable polyurethane synthetic leather and its preparation method, and CN112482045A discloses a surface layer polyurethane resin for chemical-resistant and biodegradable synthetic leather and its preparation method. The polyurethanes reported in both only contain partial bio-based components, and highly organic bismuth catalysts are used. The cytotoxicity of residual metals limits their promotion in the fields of medicine, clothing fabrics, and biomaterials. Moreover, the above reports did not study the application of polyurethane in the fiber direction. Although polylactic acid polyol and polycarbonate polyol based on renewable resources have been successfully synthesized by researchers, there are few reports on the development and application of bio-based polyurethane fibers, especially fully bio-based polyurethane fibers. Summary of the Invention
[0007] The purpose of the present invention is to provide a low-carbon and environmentally friendly bio-based polyurethane and its preparation method and application to solve the problems of non-renewable, highly toxic, and difficult-to-degrade raw materials for polyurethane preparation, low bio-based component content, cytotoxicity in the improvement method, and narrow application range.
[0008] To achieve the above object, the present invention provides a low-carbon and environmentally friendly bio-based polyurethane and its preparation method and application. A low-carbon and environmentally friendly bio-based polyurethane is prepared from the following raw materials: an organic solvent, a polylactic acid polyol, a polycarbonate polyol, a small molecule diol, an antioxidant, an isocyanate, a catalyst, and a reaction terminator.
[0009] Preferably, the bio-based polyurethane is prepared from the following raw materials in parts by mass: 100-150 parts of an organic solvent, 15-25 parts of an isocyanate, 0-200 parts of a polycarbonate polyol, 0-200 parts of a polylactic acid polyol, 2-8 parts of a small molecule diol, 0.5-2.0 parts of an antioxidant, 0.5-2.0 parts of a catalyst, and 0.1-0.6 parts of a reaction terminator.
[0010] Preferably, the bio-based polyurethane is prepared from the following raw materials in parts by mass: 100 parts of an organic solvent, 25 parts of an isocyanate, 180 parts of a polycarbonate polyol, 6.2 parts of a small molecule diol, 1 part of an antioxidant, 1.5 parts of a catalyst, and 0.1 part of a reaction terminator.
[0011] Preferably, the bio-based polyurethane is prepared from the following raw materials in parts by mass: 100 parts of an organic solvent, 25 parts of an isocyanate, 180 parts of a polylactic acid polyol, 6.2 parts of a small molecule diol, 1 part of an antioxidant, 1.5 parts of a catalyst, and 0.1 part of a reaction terminator.
[0012] Preferably, the bio-based polyurethane is prepared from the following raw materials in parts by mass: 100 parts of an organic solvent, 15.5 parts of an isocyanate, 100 parts of a polycarbonate polyol, 80 parts of a polylactic acid polyol, 6.2 parts of a small molecule diol, 1 part of an antioxidant, 1.5 parts of a catalyst, and 0.1 part of a reaction terminator.
[0013] Preferably, the organic solvent is one of N,N-dimethylformamide and N,N-dimethylacetamide; the isocyanate is one or more of toluene diisocyanate, 4,4'-methylenebis(phenyl isocyanate), diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, bio-based 1,5-pentane diisocyanate, and bio-based L-lysine diisocyanate.
[0014] Preferably, the molecular weight of the polycarbonate polyol is 1000-3000 g / mol; the molecular weight of the polylactic acid polyol is 1000-3000 g / mol.
[0015] Preferably, the small molecule diol is one of ethylene glycol, propylene glycol, butanediol, and hexanediol; the antioxidant is antioxidant 1010; the catalyst is zinc 5,10,15,20-tetrakis(4-pyridyl)-21H,23H-porphyrin, and the terminator is methanol.
[0016] A preparation method of the low-carbon and environmentally friendly bio-based polyurethane as described above is as follows: Under the protection of an inert gas, an organic solvent, an isocyanate, a polycarbonate polyol, a polylactic acid polyol, a small molecule diol, an antioxidant, and a catalyst are successively added to a reaction kettle, heated to 60 - 90 °C and reacted for 1 - 4 h. After the reaction until the viscosity no longer increases, it is cooled to room temperature, and a terminator is added and stirred evenly.
[0017] An application of the low-carbon and environmentally friendly bio-based polyurethane as described above in the fields of artificial fibers, leather, membrane materials, and coatings.
[0018] Therefore, a low-carbon and environmentally friendly bio-based polyurethane provided by the present invention, its preparation method and application have the following beneficial effects:
[0019] 1. The starting materials of the polylactic acid polyol used in the present invention include industrial corn, straw, etc. The polycarbonate polyol is synthesized by the conversion of carbon dioxide, and the isocyanate is prepared from bio-based raw materials, with low cost. The polyurethane prepared therefrom belongs to a fully bio-based polyurethane material, having the advantages of environmental friendliness, carbon reduction and carbon emission reduction.
[0020] 2. The present invention uses a highly active organic compound as a catalyst, avoiding the use and residue of metal catalysts during the reaction process, and solving the problems of product contamination and limited application range caused by traditional metal residues.
[0021] 3. The polylactic acid-based polyurethane fiber used in the method provided by the present invention solves the problems of high hardness, poor toughness, and easy brittleness of pure polylactic acid fibers.
[0022] 4. The fiber prepared by using the bio-based polyurethane provided by the present invention has better affinity with human skin, better skin feel, high toughness, high resilience rate, high strength, and can be biodegradable after use.
[0023] 5. The preparation method of the low-carbon and environmentally friendly bio-based polyurethane provided by the present invention is simple and easy to operate, does not require high temperature and high pressure, has low requirements for instrument equipment, has no emission of toxic and harmful substances, and is environmentally friendly.
[0024] The technical solution of the present invention will be further described in detail below through examples. Specific Embodiments
[0025] The technical solution of the present invention will be further described below through examples.
[0026] In order to make the objectives, technical solutions and advantages of the present application clearer, more thorough and complete, the technical solutions in the embodiments of the present invention will be clearly and completely described below through examples. The following detailed descriptions are all descriptions of examples, aiming to provide further detailed descriptions of the present invention. Unless otherwise specified, all technical terms used in the present invention have the same meanings as commonly understood by those of ordinary skill in the art to which this application belongs.
[0027] The instruments, equipment and reagents used in the examples were all obtained through commercial channels.
[0028] Example 1
[0029] To prepare a low-carbon and environmentally friendly bio-based polyurethane resin, the method is as follows:
[0030] Under the condition of introducing nitrogen into the polymerization kettle, 100 g of N,N-dimethylformamide, 25 g of diphenylmethane diisocyanate (MDI), 180 g of polycarbonate polyol with a molecular weight of 2000 g / mol, 0.62 g of ethylene glycol, 1 g of antioxidant 1010, and 1.5 g of zinc 5,10,15,20-tetrakis(4-pyridyl)-21H,23H-porphyrin were successively added to the reaction kettle, heated to 70 °C and reacted for 1 h. Measured with a digital viscometer (model NDJ-8S), the apparent viscosity was 101000 mPa·s. After cooling to room temperature, 0.1 g of methanol was added to obtain the low-carbon and environmentally friendly bio-based polyurethane resin.
[0031] Example 2
[0032] To prepare a low-carbon and environmentally friendly bio-based polyurethane resin, the method is as follows:
[0033] Under the condition of introducing argon into the polymerization kettle, 100 g of N,N-dimethylformamide, 25 g of diphenylmethane diisocyanate (MDI), 180 g of polylactic acid polyol with a molecular weight of 2000 g / mol, 0.62 g of ethylene glycol, 1 g of antioxidant 1010, and 1.5 g of zinc 5,10,15,20-tetrakis(4-pyridyl)-21H,23H-porphyrin were successively added to the reaction kettle, heated to 80 °C and reacted for 3 h. Measured with a digital viscometer (model NDJ-8S), the apparent viscosity was 98000 mPa·s. After cooling to room temperature, 0.1 g of methanol was added to obtain the low-carbon and environmentally friendly bio-based polyurethane resin.
[0034] Example 3
[0035] To prepare a low-carbon and environmentally friendly bio-based polyurethane resin, the method is as follows:
[0036] Under the condition of introducing nitrogen into the polymerization kettle, 100 g of N,N-dimethylformamide, 15.5 g of bio-based 1,5-pentanediisocyanate, 100 g of polycarbonate polyol with a molecular weight of 2000 g / mol, 80 g of polylactic acid polyol with a molecular weight of 2000 g / mol, 0.62 g of ethylene glycol, 1 g of antioxidant 1010, and 1.5 g of zinc 5,10,15,20-tetrakis(4-pyridyl)-21H,23H-porphyrin were successively added to the reaction kettle. It was heated to 60 °C and reacted for 2 h. Measured with a digital viscometer (model NDJ-8S), when the apparent viscosity reached about 110000 mPa·s, the reaction was stopped and cooled to room temperature. 0.1 g of methanol was added to obtain a low-carbon and environmentally friendly bio-based polyurethane resin.
[0037] Example 4
[0038] To prepare a low-carbon and environmentally friendly bio-based polyurethane resin, the method is as follows:
[0039] Under the condition of introducing nitrogen into the polymerization kettle, 100 g of N,N-dimethylformamide, 22.6 g of L-lysine diisocyanate, 150 g of polycarbonate polyol with a molecular weight of 3000 g / mol, 120 g of polylactic acid polyol with a molecular weight of 3000 g / mol, 0.62 g of ethylene glycol, 1 g of antioxidant 1010, and 1.5 g of zinc 5,10,15,20-tetrakis(4-pyridyl)-21H,23H-porphyrin were successively added to the reaction kettle. It was heated to 90 °C and reacted for 3 h. Measured with a digital viscometer (model NDJ-8S), when the apparent viscosity reached about 125000 mPa·s, the reaction was stopped, cooled to room temperature, and 0.1 g of methanol was added to obtain a low-carbon and environmentally friendly bio-based polyurethane resin.
[0040] Comparative Example 1
[0041] To prepare a polyurethane resin, the method is as follows:
[0042] Under the condition of introducing nitrogen into the polymerization kettle, 100 g of N,N-dimethylacetamide formamide, 15.5 g of 1,5-pentanediisocyanate, 100 g of polycarbonate polyol with a molecular weight of 2000 g / mol, 80 g of polylactic acid polyol with a molecular weight of 2000 g / mol, 0.62 g of ethylene glycol, 1 g of antioxidant 1010 were successively added to the reaction kettle. It was heated to 80 - 90 °C and reacted for 3 h. The degree of polymerization was very low and the apparent viscosity was 1000 mPa·s.
[0043] That is, the polymerization effect is poor without adding a catalyst, indicating that the catalyst plays a key role in the reaction.
[0044] Comparative Example 2
[0045] To prepare a polyurethane resin, the method is as follows:
[0046] Under the condition of introducing nitrogen into the polymerization kettle, 100 g of N,N-dimethylformamide, 25 g of diphenylmethane diisocyanate (MDI), 180 g of petroleum-based poly(butylene adipate) diol with a molecular weight of 2000 g / mol, 0.62 g of ethylene glycol, 1 g of antioxidant 1010, and 1.5 g of zinc 5,10,15,20-tetrakis(4-pyridyl)-21H,23H-porphyrin were successively added to the reaction kettle. The mixture was heated to 80 - 90 °C and reacted for 3 h. Measured with a digital viscometer (model NDJ-8S), the apparent viscosity was 102600 mPa·s.
[0047] Effect Example 1
[0048] Examine the application performance of the polyurethane resins prepared in Example 1 to Example 4 and Comparative Example 2 in the fiber industry. Conduct a spinning processing experiment on the polyurethane resins prepared in Example 1 to Example 4 and Comparative Example 2 by wet spinning. The method is as follows:
[0049] The above polyurethane solution was metered by a metering pump and sprayed into the coagulating liquid through a spinneret to form fibrous substances. The fibers were then washed with water, guided by a godet roller for stretching, and wound by a winder to form functional polyurethane fibers.
[0050] Test the performance of the prepared functional polyurethane fibers according to GB / T 14344-2022. The results are shown in Table 1.
[0051] Table 1 Performance test data of examples and comparative examples
[0052]
[0053]
[0054] Examples 1, 2, 3, and 4 are bio-based polyurethanes, and petroleum-based raw materials are used in Comparative Example 2. It can be seen from Table 1 that the bio-based polyurethanes prepared in Examples 1, 2, 3, and 4 have higher elongation at break, better flexibility, and a smooth handfeel.
[0055] From the results of Example 1 and Example 2, the strength and modulus of the polyurethane fibers prepared by polymerizing polycarbonate polyol and MDI in Example 1 are relatively small, but the elongation at break is high. The elongation at break of the polyurethane polymerized from polylactic acid polyol and MDI in Example 2 is lower than that in Example 1 because the bond energy of the core functional groups of polylactic acid is high.
[0056] In Example 1, the polyurethane fiber prepared by polymerizing polycarbonate polyol and MDI has relatively high strength but relatively small elongation at break because the aromatic diphenylmethane diisocyanate has strong rigidity. In Examples 3 and 4, while adding mixed bio-based polyol for copolymerization, aliphatic isocyanate is used for copolymerization. The strength and toughness of the prepared polyurethane fiber are significantly higher than those in Examples 1 and 2. On the one hand, it is due to the influence of the properties of bio-based polyol, and on the other hand, because the aliphatic isocyanate has smaller steric hindrance, the polymerization efficiency of the product is higher, and at the same time, the flexible chain of the aliphatic group endows the polyurethane fiber with higher toughness.
[0057] Effect Example 2
[0058] To investigate the biodegradability of the polyurethane resins prepared in Examples 1 to 4 and Comparative Example 2, the method is as follows:
[0059] The polyurethane resins prepared in Examples 1 to 4 and Comparative Example 2 were respectively buried underground. Before treatment, the prepared materials were weighed respectively. After 3 months under composting conditions, each polyurethane resin was taken out and weighed, and the mass loss rate of the polyurethane resins prepared in Examples 1 to 4 and Comparative Example 2 in 3 months was calculated. The results are shown in Table 2.
[0060] Table 2 Test Results of Biodegradability
[0061]
[0062]
[0063] As can be seen from Table 2, the mass loss of Example 1 is 12.3%, the mass loss of Example 2 is 11.8%, the mass loss of Example 3 is 11.2%, the mass loss of Example 4 is 12.1%, while the mass loss of Comparative Example 2 is only 3.5%, indicating that the polyurethane resin prepared from polylactic acid polyol and polycarbonate polyol has obvious biodegradability.
[0064] Therefore, the low-carbon and environmentally friendly bio-based polyurethane provided by the present invention has the advantages of wide sources, low cost, biodegradability, environmental friendliness, no metal residue, and wider application range; the fiber prepared therefrom has better affinity, skin feel, higher toughness, resilience rate and strength, is safer and more friendly to users, the preparation method is simple and easy to operate, does not require high temperature and high pressure, has low requirements for equipment, and is environmentally friendly.
[0065] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit them. Although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that they can still modify or equivalently replace the technical solutions of the present invention, and these modifications or equivalent replacements cannot make the modified technical solutions deviate from the spirit and scope of the technical solutions of the present invention.
Claims
1. A low-carbon and environmentally friendly bio-based polyurethane, characterized in that, the bio-based polyurethane is prepared from the following raw materials: organic solvent, polylactic acid polyol, polycarbonate polyol, small molecule diol, antioxidant, isocyanate, catalyst, reaction terminator.
2. The low-carbon and environmentally friendly bio-based polyurethane according to claim 1, characterized in that, the bio-based polyurethane is prepared from the following raw materials in parts by mass: 100 - 150 parts of organic solvent, 15 - 25 parts of isocyanate, 0 - 200 parts of polycarbonate polyol, 0 - 200 parts of polylactic acid polyol, 2 - 8 parts of small molecule diol, 0.5 - 2.0 parts of antioxidant, 0.5 - 2.0 parts of catalyst, 0.1 - 0.6 parts of reaction terminator.
3. The low-carbon and environmentally friendly bio-based polyurethane according to claim 1, characterized in that, the bio-based polyurethane is prepared from the following raw materials in parts by mass: 100 parts of organic solvent, 25 parts of isocyanate, 180 parts of polycarbonate polyol, 6.2 parts of small molecule diol, 1 part of antioxidant, 1.5 parts of catalyst, 0.1 part of reaction terminator.
4. The low-carbon and environmentally friendly bio-based polyurethane according to claim 1, characterized in that, the bio-based polyurethane is prepared from the following raw materials in parts by mass: 100 parts of organic solvent, 25 parts of isocyanate, 180 parts of polylactic acid polyol, 6.2 parts of small molecule diol, 1 part of antioxidant, 1.5 parts of catalyst, 0.1 part of reaction terminator.
5. The low-carbon and environmentally friendly bio-based polyurethane according to claim 1, characterized in that, the bio-based polyurethane is prepared from the following raw materials in parts by mass: 100 parts of organic solvent, 15.5 parts of isocyanate, 100 parts of polycarbonate polyol, 80 parts of polylactic acid polyol, 6.2 parts of small molecule diol, 1 part of antioxidant, 1.5 parts of catalyst, 0.1 part of reaction terminator.
6. The low-carbon and environmentally friendly bio-based polyurethane according to claim 1, characterized in that: the organic solvent is one of N,N-dimethylformamide and N,N-dimethylacetamide; the isocyanate is one or more of toluene diisocyanate, 4,4'-methylenebis(phenyl isocyanate), diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, bio-based 1,5-pentane diisocyanate, and bio-based L-lysine diisocyanate.
7. The low-carbon and environmentally friendly bio-based polyurethane according to claim 1, characterized in that: the molecular weight of the polycarbonate polyol is 1000 - 3000 g / mol; the molecular weight of the polylactic acid polyol is 1000 - 3000 g / mol.
8. The low-carbon and environmentally friendly bio-based polyurethane according to claim 1, characterized in that: the small molecule diol is one of ethylene glycol, propylene glycol, butylene glycol, and hexylene glycol; the antioxidant is antioxidant 1010; the catalyst is zinc 5,10,15,20-tetrakis(4-pyridyl)-21H,23H-porphyrin, and the terminator is methanol.
9. A preparation method of the low-carbon and environmentally friendly bio-based polyurethane according to any one of claims 1-8, characterized in that, the steps are as follows: under the protection of inert gas, successively add organic solvent, isocyanate, polycarbonate polyol, polylactic acid polyol, small molecule diol, antioxidant, catalyst into the reaction kettle, heat to 60-90 °C and react for 1-4 h, after the reaction until the viscosity no longer increases, cool to room temperature, add a terminator and stir evenly.
10. An application of the low-carbon and environmentally friendly bio-based polyurethane according to any one of claims 1-8 in the fields of artificial fibers, leather, membrane materials, and coatings.