CN114213666A - Hydrophobic and oleophobic fluoropolyether modified cellulose and preparation method thereof - Google Patents
Hydrophobic and oleophobic fluoropolyether modified cellulose and preparation method thereof Download PDFInfo
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Abstract
The invention provides hydrophobic and oleophobic fluoropolyether modified cellulose and a preparation method thereof, wherein the preparation method comprises the following steps: diluting oxidized nano-cellulose with water to form a suspension with the concentration of 2-3%, evaporating, and mixing with an aprotic organic solvent to obtain a nano-cellulose suspension; adding a silane coupling agent, a diisocyanate compound and modified silicone oil into the nano cellulose suspension, stirring at room temperature, stirring at 85-90 ℃, and cooling to obtain siloxane modified nano cellulose; adding fluorine-containing solution of fluorine-silicon polymer into a container with a stirrer, then adding siloxane modified nano-cellulose, mixing to obtain mixed reaction liquid, stirring and reacting at the temperature of 60-70 ℃, and after the reaction is finished, centrifuging and washing the product to obtain the fluorine-containing polyether modified cellulose. The preparation method is simple and efficient, the synthetic route is environment-friendly and pollution-free, and the modified product obtained by the method has good hydrophobic and oleophobic properties and is uniformly dispersed.
Description
Technical Field
The invention relates to the technical field of modified materials, in particular to hydrophobic and oleophobic fluoropolyether modified cellulose and a preparation method thereof.
Background
With the improvement of environmental protection consciousness and the promulgation of national plastic banning orders, plastic is no longer used as a packaging material in many areas, but recyclable, degradable and white pollution-free paper is used instead. However, the food wrapping paper has the disadvantages of poor oxygen resistance and water vapor resistance under the condition of high environmental humidity, so that the using effect and the safety of the packaged food are affected, and the adoption of waxing or film coating also has safety risks. Since cellulose has a similar composition to paper and a strong binding force, the properties of the paper surface can be improved by the modified cellulose. The nano-cellulose has the advantages of wide source, reproducibility, biocompatibility, environmental protection, no pollution and the like, and has a plurality of excellent performances such as high crystallinity, high strength, high hydrophilicity and the like. However, the surface of the nanocellulose has numerous hydroxyl groups and extremely strong hydrophilicity, and hydrogen bonds are easily formed among molecules, so that the nanocellulose is easy to agglomerate and disperse unevenly, and the interface compatibility in a hydrophobic organic system is poor, so that the application of the nanocellulose in various fields is greatly limited. Therefore, it is important to modify the surface hydroxyl groups of the nanocellulose to improve the dispersibility of the nanocellulose.
At present, the modification of the nano-cellulose is mainly hydrophobic modification, so that the dispersibility and the interfacial compatibility of the nano-cellulose in a hydrophobic organic system are improved. Graft polymerization modification is a modification means which is researched more at present, but the reaction condition is harsh, the product separation process is complex, and secondary pollution is easy to generate. Therefore, it is necessary to develop a simple and efficient nanocellulose modification method with an environmental-friendly and pollution-free technical route, and particularly, a modified nanocellulose which has good hydrophobicity and oleophobicity, uniform dispersion and good interfacial compatibility with hydrophobic organic systems can be prepared.
Disclosure of Invention
The technical problem to be solved is as follows: aiming at the defects in the prior art, the invention provides the hydrophobic and oleophobic fluoropolyether modified cellulose and the preparation method thereof, the preparation method is simple and efficient, the synthetic route is environment-friendly and pollution-free, and the modified product obtained by the method has good hydrophobic and oleophobic properties, uniform dispersion, good interface compatibility with an organic system, and potential popularization and application prospects.
The technical scheme is as follows: a preparation method of hydrophobic and oleophobic fluoropolyether modified cellulose comprises the following preparation steps:
(1) diluting oxidized nanocellulose with water into a suspension with the concentration of 2-3%, evaporating to obtain gel-like nanocellulose, uniformly mixing with an aprotic organic solvent, and continuously stirring at a constant temperature of 85-90 ℃ for 3-6 hours to obtain a nanocellulose suspension, wherein the mass ratio of the oxidized nanocellulose to the aprotic organic solvent is 1 (1-5);
(2) adding a silane coupling agent, a diisocyanate compound and modified silicone oil into the nano cellulose suspension obtained in the step (1), continuously stirring for 1-2 hours at room temperature, then continuously stirring for 3-6 hours at constant temperature of 85-90 ℃, and then cooling to obtain siloxane modified nano cellulose, wherein the adding amounts of the silane coupling agent, the diisocyanate compound and the modified silicone oil respectively account for 3-5 wt%, 2-3 wt% and 2-5 wt% of the mass of the nano cellulose suspension;
(3) adding a fluorine-containing solution of a fluorine-silicon polymer into a container with a stirrer, then adding the siloxane modified nano-cellulose obtained in the step (2), uniformly mixing to obtain a mixed reaction solution, stirring and reacting at a constant temperature of 60-70 ℃ for 2-6h, and after the reaction is finished, centrifuging and washing a product to obtain the fluorine-containing polyether modified cellulose, wherein the fluorine-containing solution of the fluorine-silicon polymer consists of siloxane modified perfluoropolyether and a fluorine solvent in a mass ratio of 1:4, and the mass ratio of the siloxane modified perfluoropolyether to the oxidized nano-cellulose in the step (1) is (0.03-0.08): 1.
The aprotic organic solvent in the step (1) is tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide or N-methylpyrrolidone.
The silane coupling agent in the step (2) is one or more of aminopropyltriethoxysilane, aminopropyltrimethoxysilane, bis [ trimethoxysilylpropyl ] amine, glycidyl ether modified silane coupling agent and triethoxysilylpropyl isocyanate.
The diisocyanate compound in the step (2) is decane-1, 10-diisocyanate, cyclohexane-1, 4-diisocyanate or p-phenylene diisocyanate.
The modified silicone oil in the step (2) is amino modified silicone oil, hydroxymethyl modified silicone oil or epoxypropyl modified silicone oil.
The number average molecular weight of the siloxane-modified perfluoropolyether in the step (3) is 1000-2000, and the fluorine solvent is m-ditrifluorotoluene, nonafluorobutyl ethyl ether or nonafluorobutyl methyl ether.
The chemical formula of the siloxane modified perfluoropolyether is Rf- [ Si (R')3-n(OR)n]mWherein n is an integer of 0 to 3, m is an integer of 1 to 2, R and R' are alkyl groups, Rf is CF3CF2(OC2F4)p(OCF2)qOC(Z)F(CF2)r-or CF3CF2CF2(OCF(CF3)CF2)sCF(CF3) -, wherein p, q, r and s are each independently an integer of 0 to 200 inclusive, the sum of p, q, r and s is at least 1, and the order and number of the occurrence of each repeating unit with p, q, r and s enclosed in parentheses are arbitrary in the formula; n is an integer of 0 to 30 inclusive, and Z is F or CF3。
The hydrophobic and oleophobic fluoropolyether modified cellulose prepared by the preparation method is provided.
Has the advantages that: the hydrophobic and oleophobic fluoropolyether modified cellulose and the preparation method thereof provided by the invention have the following beneficial effects: the preparation method is simple and efficient, the whole process is environment-friendly and pollution-free, and the nano-cellulose prepared by the method has good hydrophobic and oleophobic properties, uniform dispersion and good interface compatibility with organic systems, and has great application and popularization prospects in the fields of textile, papermaking, coating and the like.
Drawings
FIG. 1 shows a nuclear magnetic resonance hydrogen spectrum of a perfluoropolyether-based silane compound (Compound A) of example 3.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, specific embodiments thereof are described in detail below. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, and in order to provide a preferred embodiment of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete. This invention can be embodied in many different forms than those herein described and many modifications may be made by those skilled in the art without departing from the spirit of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The preparation method comprises the step of preparing the nano-cellulose suspension, wherein the mass ratio of the aprotic organic solvent to the nano-cellulose is (1-5): 1. In order to ensure the sufficient dispersion of the nano-cellulose, the mass ratio of the solvent to the nano-cellulose is at least 1: 1. The appropriate increase of the solvent dosage can lead the nano-cellulose to be better dispersed, which is beneficial to the reaction, but when the solvent dosage exceeds 5 times of the cellulose by mass, the dispersion effect can not be further improved, but the single-batch capacity is reduced due to the large solvent dosage, thereby further influencing the production efficiency. Therefore, the mass ratio of the aprotic organic solvent to the nanocellulose is preferably (1 to 5):1, and more preferably 2: 1.
Wherein the aprotic organic solvent is one selected from tetrahydrofuran, N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone, and is more preferably N, N-dimethylformamide.
The silane coupling agent in the preparation method of the invention is selected from one or more of aminopropyltriethoxysilane, aminopropyltrimethoxysilane, bis [ trimethoxysilylpropyl ] amine, glycidyl ether modified silane coupling agent and triethoxysilylpropyl isocyanate, and is more preferably aminopropyltrimethoxysilane.
The diisocyanate compound in the preparation method of the invention is one selected from decane-1, 10-diisocyanate, cyclohexane-1, 4-diisocyanate and p-phenylene diisocyanate, and more preferably decane-1, 10-diisocyanate and cyclohexane-1, 4-diisocyanate.
The modified silicone oil in the preparation method of the invention is selected from one of amino modified silicone oil, hydroxymethyl modified silicone oil and glycidyl modified silicone oil, and more preferably amino modified silicone oil.
When the mass ratio of the siloxane modified perfluoropolyether to the oxidized nanocellulose in the fluorine-containing solution of the fluorine-silicon polymer is lower than 0.03:1, the waterproof and oilproof effects of the oxidized nanocellulose are not obviously improved; when the mass ratio is more than or equal to 0.03:1, the water and oil proofing effects of the modified cellulose are gradually improved; when the mass ratio is further increased to 0.08:1 or more, the water-and oil-repellent effect of the modified cellulose is not further improved, so that the mass ratio of the fluorine-containing silane to the nanocellulose is preferably (0.03 to 0.08): 1.
The fluorine-containing solutions of fluorosilicone polymers used in examples 1 and 2 below were obtained from Kyoto chemical industries, Inc. and were designated as X-71-197.
Example 1
The embodiment provides a preparation method of hydrophobic and oleophobic fluoropolyether modified cellulose, which comprises the following preparation steps:
(1) diluting 50g of oxidized nano-cellulose with water to obtain a suspension with the concentration of 2%, evaporating to obtain gel-like nano-cellulose, adding 100g N-N-dimethylformamide and the gel-like nano-cellulose into another reactor, uniformly mixing, and continuously stirring at a constant temperature of 85 ℃ for 3 hours to obtain a nano-cellulose suspension;
(2) adding 5g of aminopropyltriethoxysilane, 10g of decane-1, 10-diisocyanate and 5g of amino modified silicone oil into the nano cellulose suspension obtained in the step (1), continuously stirring for 1h at room temperature, then continuously stirring for 6h at constant temperature of 85 ℃, and cooling to obtain siloxane modified nano cellulose;
(3) adding 10g of fluorine-containing solution of fluorine-silicon polymer into a container with a stirrer, then adding the siloxane modified nano-cellulose obtained in the step (2), uniformly mixing to obtain a mixed reaction solution, stirring and reacting at a constant temperature of 65 ℃ for 2 hours, centrifuging and washing with ethanol for three times after the reaction is finished, and finally freeze-drying to obtain 55g of fluoropolyether modified cellulose.
Example 2
Example 2 differs from example 1 in that "5 g of amino-modified silicone oil" in step (2) was replaced with "5 g of glycidyl-modified silicone oil" to give 54g of fluoropolyether-modified cellulose.
Example 3
Example 3 is different from example 1 in that a fluorine-containing solution of a fluorosilicone polymer was different, and 54g of fluorine-containing hydrophobic oil-repellent modified nanocellulose was obtained.
The preparation method of the fluorine-containing solution of the fluorine-silicon polymer comprises the following steps: a100 mL single neck round bottom flask equipped with a dropping funnel, a thermometer and a stirrer was charged with 10g of perfluoropolyether carboxylic acid compound (commercially available, COOH-5200, Chen fluorine chemical Co., Ltd., Hunan, color), 15mL of 1, 3-bis (trifluoromethyl) benzene was dissolved, 0.3mL of oxalyl chloride was added thereto, 0.2mL of DMF was dissolved in 5mL of 1, 3-bis (trifluoromethyl) benzene was slowly dropped from the dropping funnel, the mixture was stirred at 50 ℃ for 4 hours, and after the temperature was lowered to room temperature, the mixture was slowly dropped into a 100mL single neck round bottom flask containing 5mL of 1, 3-bis (trifluoromethyl) benzene, 4.2mL of diisopropylethylamine and 4mL of bis (3-trimethoxysilylpropyl) amine, and stirred at room temperature for 5 hours. 40mL of perfluorohexane was added, extraction was carried out three times with 18mL of methanol, and the fluorine phase was distilled under reduced pressure to remove volatile components, whereby a colorless to pale yellow product, i.e., a silane compound having the following perfluoropolyether group having trimethoxysilane at the end was obtained: CF (compact flash)3CF2CF2(OCF2CF2)r(OCF2)sOCF(CF3)CON[CH2CH2CH2Si(OCH3)3]2(Compound A). Preparing the compound A and nonafluorobutyl ethyl ether into a fluorosilicone polymer with the mass fraction of 20%The fluorine-containing solution of (1).
The hydrogen nuclear magnetic resonance spectrum of the perfluoropolyether-based silane compound (compound a) is shown in fig. 1.
The characteristics of the newly added structure are identified by a nuclear magnetic resonance spectrometer1The H NMR chemical shifts are shown in table 1 below.
TABLE 1
| Radical structure | δ，ppm |
| -CH2CH2Si(OMe)3 | 0.58-0.66(m) |
| -CH2CH2CH2Si(OMe)3 | 1.70-1.81(m) |
| ＝NCH2CH2CH2Si(OMe)3 | 3.29-3.36(m) |
| ＝NCH2CH2CH2Si(OMe)3 | 3.51-3.56(m) |
| -CH2CH2Si(OMe)3 | 3.59(s) |
The performance test was performed on commercially available unmodified nanocellulose and modified cellulose prepared according to the present invention.
The water and oil repellency effect was evaluated as follows: a2% aqueous suspension of unmodified nanocellulose (Wuhananea white pharmaceutical chemical Co., Ltd.) and a 2% modified cellulose suspension (ethanol: nonafluorobutylether ═ 8:2) obtained in example 1, example 2 and example 3 of the present invention were applied to the surface of base paper at a coating amount of 1 wt%, respectively, and then the water repellency grade was tested by the water dropping test method, and the oil repellency grade was tested by GB/T19977-.
Drip test method: the mixed liquid of water and isopropanol (detailed in the following table) with different proportions is dripped on the surface of paper by a dropper, and the water-proof grade is passed after the mixed liquid is not wetted within 5s, wherein the water-proof grade is 0 grade to 3 grade, and the higher the grade is, the better the water-proof effect is (shown in the following table 2).
TABLE 2
| Water resistance rating | 0 | 1 | 2 | 3 |
| Water: isopropanol (volume ratio) | 100∶0 | 98∶2 | 95∶5 | 90∶10 |
TABLE 3
| Sample (I) | Water resistance rating | Oil repellency rating |
| Base paper | 0 | 1 |
| Unmodified | 0 | 4 |
| Example 1 | 3 | 7 |
| Example 2 | 2 | 7 |
| Example 3 | 3 | 7 |
As can be seen from table 3, the water resistance grade of the surface of the base paper was 0 grade, and the oil resistance grade was 1 grade; the surface of the paper coated with unmodified nanocellulose had a water resistance rating of 0 and an oil resistance rating of 4; example 1 the coated paper surface had a water resistance rating of 3 and an oil resistance rating of 7; example 2 the coated paper surface had a water resistance rating of 2 and an oil resistance rating of 7; example 3 the coated paper surface had a water resistance rating of 3 and an oil resistance rating of 7.
The above results indicate that the nanocellulose modified by the fluoropolyether has hydrophobic and oleophobic effects.
While the embodiments of the present invention have been described in detail, those skilled in the art will recognize that the embodiments of the present invention can be practiced without departing from the spirit and scope of the claims.
Claims (8)
1. A preparation method of hydrophobic and oleophobic fluoropolyether modified cellulose is characterized by comprising the following preparation steps:
(1) diluting oxidized nanocellulose with water into a suspension with the concentration of 2-3%, evaporating to obtain gel-like nanocellulose, uniformly mixing with an aprotic organic solvent, and continuously stirring at a constant temperature of 85-90 ℃ for 3-6 hours to obtain a nanocellulose suspension, wherein the mass ratio of the oxidized nanocellulose to the aprotic organic solvent is 1 (1-5);
(2) adding a silane coupling agent, a diisocyanate compound and modified silicone oil into the nano cellulose suspension obtained in the step (1), continuously stirring for 1-2 hours at room temperature, then continuously stirring for 3-6 hours at constant temperature of 85-90 ℃, and then cooling to obtain siloxane modified nano cellulose, wherein the adding amounts of the silane coupling agent, the diisocyanate compound and the modified silicone oil respectively account for 3-5 wt%, 2-3 wt% and 2-5 wt% of the mass of the nano cellulose suspension;
(3) adding a fluorine-containing solution of a fluorine-silicon polymer into a container with a stirrer, then adding the siloxane modified nano-cellulose obtained in the step (2), uniformly mixing to obtain a mixed reaction solution, stirring and reacting at a constant temperature of 60-70 ℃ for 2-6h, and after the reaction is finished, centrifuging and washing a product to obtain the fluorine-containing polyether modified cellulose, wherein the fluorine-containing solution of the fluorine-silicon polymer consists of siloxane modified perfluoropolyether and a fluorine solvent in a mass ratio of 1:4, and the mass ratio of the siloxane modified perfluoropolyether to the oxidized nano-cellulose in the step (1) is (0.03-0.08): 1.
2. The preparation method of the hydrophobic and oleophobic fluoropolyether modified cellulose according to claim 1, characterized in that: the aprotic organic solvent in the step (1) is tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide or N-methylpyrrolidone.
3. The preparation method of the hydrophobic and oleophobic fluoropolyether modified cellulose according to claim 1, characterized in that: the silane coupling agent in the step (2) is one or more of aminopropyltriethoxysilane, aminopropyltrimethoxysilane, bis [ trimethoxysilylpropyl ] amine, glycidyl ether modified silane coupling agent and triethoxysilylpropyl isocyanate.
4. The preparation method of the hydrophobic and oleophobic fluoropolyether modified cellulose according to claim 1, characterized in that: the diisocyanate compound in the step (2) is decane-1, 10-diisocyanate, cyclohexane-1, 4-diisocyanate or p-phenylene diisocyanate.
5. The preparation method of the hydrophobic and oleophobic fluoropolyether modified cellulose according to claim 1, characterized in that: the modified silicone oil in the step (2) is amino modified silicone oil, hydroxymethyl modified silicone oil or epoxy propyl modified silicone oil.
6. The preparation method of the hydrophobic and oleophobic fluoropolyether modified cellulose according to claim 1, characterized in that: the number average molecular weight of the siloxane modified perfluoropolyether in the step (3) is 1000-2000, and the fluorine solvent is m-ditrifluorotoluene, nonafluorobutyl ethyl ether or nonafluorobutyl methyl ether.
7. The preparation method of the hydrophobic and oleophobic fluoropolyether modified cellulose according to claim 6, characterized in that: the chemical formula of the siloxane modified perfluoropolyether is Rf- [ Si (R')3-n(OR)n]mWherein n is0 to 3, m is an integer of 1 to 2, R and R' are alkyl groups, Rf is CF3CF2(OC2F4)p(OCF2)qOC(Z)F(CF2)r-or CF3CF2CF2(OCF(CF3)CF2)sCF(CF3) -, wherein p, q, r and s are each independently an integer of 0 to 200 inclusive, the sum of p, q, r and s is at least 1, and the order and number of the occurrence of each repeating unit with p, q, r and s enclosed in parentheses are arbitrary in the formula; n is an integer of 0 to 30 inclusive, and Z is F or CF3。
8. A hydrophobic and oleophobic fluoropolyether modified cellulose prepared by the preparation method of any one of claims 1-7.
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