CN118344934B - A bio-based fluorine-free water repellent for synthetic leather and preparation method thereof - Google Patents
A bio-based fluorine-free water repellent for synthetic leather and preparation method thereof Download PDFInfo
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- CN118344934B CN118344934B CN202410455517.3A CN202410455517A CN118344934B CN 118344934 B CN118344934 B CN 118344934B CN 202410455517 A CN202410455517 A CN 202410455517A CN 118344934 B CN118344934 B CN 118344934B
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
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- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
Abstract
本发明提供了本发明创造性地提出了一种合成革用生物基无氟泼水剂的制备方法，包括以下步骤：1)将生物基多元醇与特种异氰酸酯反应，得到多官能度封端的中间体；2)再将该多官能度封端的中间体通过酯交换的方式获得向外延伸的生物基长碳链端，得到生物基无氟泼水剂。本发明还创造性地提出了一种合成革用生物基无氟泼水剂，采用上述任一种方法制备得到。本发明选用生物基原料并在结构上有效调控反应过程中的官能度，设计外伸拒水链段，使泼水剂具有良好的性能。本发明制备的泼水剂不含氟的同时更加易于降解，低碳环保，符合绿色化工、可再生的理念。The present invention provides a method for preparing a bio-based fluorine-free water repellent for synthetic leather, which includes the following steps: 1) reacting a bio-based polyol with a special isocyanate to obtain a multi-functional end-capped intermediate; 2) subjecting the multi-functional end-capped intermediate to an ester exchange to obtain an outwardly extending bio-based long carbon chain end to obtain a bio-based fluorine-free water repellent. The present invention also creatively proposes a bio-based fluorine-free water repellent for synthetic leather, which is prepared by any of the above methods. The present invention selects bio-based raw materials and effectively regulates the functionality in the reaction process in the structure, designs the outwardly extending water-repellent chain segments, and makes the water repellent have good performance. The water repellent prepared by the present invention is fluorine-free and easier to degrade, low-carbon and environmentally friendly, and conforms to the concepts of green chemical industry and renewable.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a bio-based fluorine-free water repellent agent for synthetic leather and a preparation method thereof.
Background
The water repellent agent can give leather, vamp leather and the like excellent waterproof effect and durable waterproof, oil-proof and anti-staining properties. Meanwhile, the color, the hand feeling and the air permeability of the base material cannot be changed. The polyurethane resin has good film forming property, and the polyurethane resin containing the water repellent agent is coated on the surface of the synthetic leather to obtain excellent water impact resistance, water penetration resistance, water diversion and hydrostatic pressure resistance, so the water repellent agent is widely used in the field of synthetic leather.
Most of fluorine-containing water repellent agents used in the current market have excellent water repellent effect due to the characteristic of fluorine atoms. The high-performance fluorine-containing derivatives inevitably bring residual perfluorooctanoic acid (PFOA) or perfluorooctyl sulfonic acid (PFOS) in the production process, are one of the most difficult-to-degrade organic pollutants found in the world, have durability, bioaccumulation and biotoxicity, are difficult to degrade continuously in natural environments, and have great harm to human health and living environment. In the face of the global trend of disabling PFOA, the development of their alternatives is particularly urgent.
The Chinese patent application with publication number of CN112646118A provides a preparation method of fluorine-free water repellent agent for polyurethane. By using a polymeric silicone oil polyol with two functional groups as the main material, the technical scheme avoids using a fluoropolymer as the raw material for the reaction. However, the silicone polyol still has low degradation rate and is easy to produce harmful substances or residues.
Disclosure of Invention
The invention aims at providing a preparation method of a bio-based fluorine-free water repellent agent for synthetic leather.
Another object of the present invention is to provide a bio-based fluorine-free water repellent for synthetic leather, aiming at the above problems.
The invention creatively provides a preparation method of a bio-based fluorine-free water repellent agent for synthetic leather, which comprises the following steps:
1) Reacting a bio-based polyol with a special isocyanate to obtain a multi-functionality end-capped intermediate;
2) And then the intermediate with the end capped by the polyfunctional group is subjected to transesterification to obtain an outwards extending biological base long carbon chain end, so as to obtain the biological base fluorine-free water repellent agent.
In the above preparation method of the bio-based fluorine-free water repellent for synthetic leather, the specific method of the step 1) includes:
Firstly, heating the bio-based polyol to above 100 ℃ for vacuum dehydration, then cooling to 50-60 ℃, adding special isocyanate, adding an organic bismuth catalyst under the protection of inert gas atmosphere, and heating to 75-80 ℃ for reaction.
In the preparation method of the bio-based fluorine-free water repellent agent for synthetic leather, the dehydration time is 0.5-1.5 h, and the reaction time is 2-3 h.
In the preparation method of the bio-based fluorine-free water repellent agent for the synthetic leather, the molar ratio of the bio-based polyol to the special isocyanate is 0.95-1.0:3.05-3.15, and the addition amount of the organic bismuth catalyst is 0.05-0.4% of the mass of the bio-based polyol.
In the preparation method of the bio-based fluorine-free water repellent for synthetic leather, the bio-based polyol is characterized by comprising at least one of castor oil and hydrogenated castor oil.
In the preparation method of the bio-based fluorine-free water repellent agent for synthetic leather, the special isocyanate comprises methyl- (3-isocyanatopropyl) dimethyl silane.
In the above preparation method of the bio-based fluorine-free water repellent for synthetic leather, the specific method of the step 2) includes:
And (3) cooling the reaction system after the reaction in the step (1) to 50-60 ℃, adding N, N-dimethylformamide, bio-based micromolecule alcohol and a catalyst under the protection of inert gas atmosphere, and heating to 90-100 ℃ for reaction to obtain the bio-based fluorine-free water repellent.
In the preparation method of the bio-based fluorine-free water repellent agent for the synthetic leather, the reaction time is 4-5 hours.
In the preparation method of the bio-based fluorine-free water repellent agent for synthetic leather, the molar ratio of the bio-based polyol to the bio-based small molecular alcohol is 0.95-1.0:3.1-3.2.
In the preparation method of the bio-based fluorine-free water repellent agent for synthetic leather, the catalyst comprises sodium citrate, and the addition amount of the catalyst is 0.1-2% of the mass of N, N-dimethylformamide.
In the preparation method of the bio-based fluorine-free water repellent agent for synthetic leather, the bio-based small molecular alcohol comprises at least one of lauryl alcohol, palmityl alcohol and stearyl alcohol.
In the preparation method of the bio-based fluorine-free water repellent agent for synthetic leather, the inert gas comprises nitrogen or other protective gases.
The invention also creatively provides a bio-based fluorine-free water repellent agent for synthetic leather, which is prepared by adopting any one of the methods.
Compared with the prior art, the invention has the advantages that:
The invention selects the bio-based raw materials and effectively regulates and controls the functionality in the reaction process structurally, and designs the overhanging water repellent chain segment so that the water repellent agent has good performance. The water repellent agent prepared by the invention is easier to degrade while containing no fluorine, is low-carbon and environment-friendly, and accords with the concept of green chemical industry and reproducibility.
The invention is used for polyurethane resin, especially for polyurethane resin for synthetic leather, does not need to change the original process flow, and can meet the performances of water resistance and the like.
The invention uses castor oil and hydrogenated castor oil as raw materials of the bio-based polyol, has abundant hydroxyl groups compared with other bio-based alcohols, is favorable for chemical modification, has good degradability, and further improves the environmental protection performance of the fluorine-free water repellent.
Detailed Description
Further illustrated by the following specific examples;
The application will be further illustrated with reference to specific examples, which are to be understood as illustrative only and are not intended to limit the scope of the application. Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the teachings of the present application, and such equivalents are intended to fall within the scope of the application as defined in the appended claims.
Example 1
(1) 466.5G of castor oil is heated to 100 ℃ for vacuum dehydration for 1 hour, the temperature is reduced to 50-60 ℃, 98.4g of methyl- (3-isocyanatopropyl) dimethyl silane is added, 0.4g of organic bismuth catalyst is added under continuous stirring and nitrogen atmosphere protection, and the temperature is raised to 75-80 ℃ for reaction for 2-3 hours;
(2) And cooling to 50-60 ℃, adding 50g of N, N-dimethylformamide, 290.6g of lauryl alcohol and 0.5g of sodium citrate into a reaction container under the continuous stirring and the protection of nitrogen atmosphere, and heating to 90-100 ℃ for reacting for 4-5 hours to obtain the bio-based fluorine-free water repellent.
Example 2
(1) 466.5G of castor oil is heated to 100 ℃ for vacuum dehydration for 1 hour, the temperature is reduced to 50-60 ℃, 98.4g of methyl- (3-isocyanatopropyl) dimethyl silane is added, 0.4g of organic bismuth catalyst is added under continuous stirring and nitrogen atmosphere protection, and the temperature is raised to 75-80 ℃ for reaction for 2-3 hours;
(2) And cooling to 50-60 ℃, adding 50g of N, N-dimethylformamide, 378.1g of palmitol and 0.5g of sodium citrate into a reaction container under the continuous stirring and the protection of nitrogen atmosphere, and heating to 90-100 ℃ for reacting for 4-5 hours to obtain the bio-based fluorine-free water repellent.
Example 3
(1) 466.5G of castor oil is heated to 100 ℃ for vacuum dehydration for 1 hour, the temperature is reduced to 50-60 ℃, 98.4g of methyl- (3-isocyanatopropyl) dimethyl silane is added, 0.4g of organic bismuth catalyst is added under continuous stirring and nitrogen atmosphere protection, and the temperature is raised to 75-80 ℃ for reaction for 2-3 hours;
(2) And cooling to 50-60 ℃, adding 50g of N, N-dimethylformamide, 422g of stearyl alcohol and 0.5g of sodium citrate into a reaction container under the continuous stirring and the protection of nitrogen atmosphere, and heating to 90-100 ℃ for reacting for 4-5 hours to obtain the bio-based fluorine-free water repellent.
Application example
The bio-based fluorine-free water repellent agent prepared in examples 1 to 3 was added to polyurethane resin in an amount of 1wt% of the polyurethane resin, and the performance parameters of the obtained polyurethane resin were all required as shown in the following table (test method reference QB/T4197-2011).
| Index (I) | Specific requirements |
| Modulus of elasticity | The polyurethane resin of the bio-based fluorine-free water repellent agent obtained by the invention is added, the elastic modulus is reduced by 0-10% compared with that of the non-additive material |
| Surface waterproof grade | 4 Or more stages |
| Hydrolysis resistance | For more than two weeks |
| Solids content | 35~40% |
| Viscosity (cps/25 ℃ C.) | 5000~10000 |
| Color of | Colorless to pale yellow |
The result shows that the bio-based fluorine-free water repellent agent prepared by the method has no obvious influence on the process flow, the waterproof performance and the like of polyurethane resin, and compared with the fluorine-containing water repellent agent and the water repellent agent taking the polymerized silicone oil polyol as raw materials, the bio-based fluorine-free water repellent agent is more environment-friendly, accords with the concept of green chemical industry and reproducibility, and actively promotes the sustainable development of the synthetic leather processing technology.
The specific embodiments described herein are offered by way of example only to illustrate the spirit of the invention. Those skilled in the art may make various modifications or additions to the described embodiments or substitutions thereof without departing from the spirit of the invention or exceeding the scope of the invention as defined in the accompanying claims.
Although the terms biobased non-fluorinated water repellent, biobased polyol, specialty isocyanate, biobased non-fluorinated water repellent, and the like are used more herein. These terms are only used to more conveniently describe and explain the nature of the invention and should be construed in a manner consistent with their spirit and scope.
Claims (3)
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| CN202410455517.3A CN118344934B (en) | 2024-04-16 | 2024-04-16 | A bio-based fluorine-free water repellent for synthetic leather and preparation method thereof |
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| JP5597716B2 (en) * | 2010-09-22 | 2014-10-01 | 三井化学株式会社 | Polyurethane resin composition, polyurethane dispersion, anchor coat film for vapor deposition and anchor-coated vapor deposition film |
| TWI480299B (en) * | 2013-09-23 | 2015-04-11 | Univ Tamkang | Non-fluoro hydrophobic aqueous polyurethane resin dispersion, and production method and use thereof |
| WO2020186377A1 (en) * | 2019-03-15 | 2020-09-24 | Dow Global Technologies Llc | Waterborne polyurethane dispersion and method for preparing same |
| CN117227297A (en) * | 2023-09-12 | 2023-12-15 | 华懋（厦门）特种材料有限公司 | Manufacturing process of washable durable waterproof outdoor environment-friendly fabric |
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