WO2021078086A1 - Modified nanocrystalline cellulose and preparation method thereof - Google Patents

Modified nanocrystalline cellulose and preparation method thereof Download PDF

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WO2021078086A1
WO2021078086A1 PCT/CN2020/121793 CN2020121793W WO2021078086A1 WO 2021078086 A1 WO2021078086 A1 WO 2021078086A1 CN 2020121793 W CN2020121793 W CN 2020121793W WO 2021078086 A1 WO2021078086 A1 WO 2021078086A1
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crystals
diisocyanate
nanocellulose
modified
preparation
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PCT/CN2020/121793
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French (fr)
Chinese (zh)
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彭宝亮
罗健辉
雷群
王小聪
肖沛文
张欣向
王平美
丁彬
耿向飞
李莹莹
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中国石油天然气股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
    • C08B15/05—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur
    • C08B15/06—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur containing nitrogen, e.g. carbamates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes

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  • the invention specifically relates to a method for modifying the hydrophobic grafting of nano cellulose crystals, and belongs to the technical field of hydrophobic grafting modification on the surface of nano particles.
  • Nano-cellulose crystals are a new type of renewable, degradable, and low-toxic nano-materials. They come from a wide range of sources in nature. Because of their high aspect ratio, low density, and high mechanical strength, they are used in composite materials, new energy, The fields of medicine, chemical industry and food have great potential application value.
  • nano-cellulose crystals in the preparation of Pickering emulsion has attracted wide attention from scientific researchers.
  • the prepared emulsion has better stability, low foam and other characteristics, and compared with traditional spherical nanoparticles, it has unique characteristics.
  • the rod-like structure of nanocellulose crystals has an adjustable aspect ratio, which can realize the control of the size and morphology of the Pickering emulsion droplets.
  • As a nanoparticle emulsifier to prepare Pickering emulsion it has broad application prospects in tertiary oil recovery.
  • nano-cellulose crystals As emulsifiers, the application of nano-cellulose crystals as emulsifiers is relatively limited. This is mainly due to the large polarity and specific surface of nano-cellulose crystals.
  • the surface of nano-cellulose crystals contains a large number of hydroxyl groups, which causes nano-cellulose crystals. Crystals cannot be dispersed well in most non-aqueous solvents; on the other hand, nano-cellulose crystals are prone to agglomeration due to their large surface area and hydrogen bonding. Therefore, how to effectively improve the emulsification performance of nanocellulose and at the same time solve the problem of limited use of nanocellulose crystals due to excessive polarity has become the focus of research in this field.
  • the prior art mainly uses esterification, organosilanization, etc. to modify nanocellulose.
  • fatty acids when used for modification, a strong acid is required as a catalyst, and it also has the disadvantage of higher reaction temperature.
  • Organosiloxane is the most commonly used modifier for organosilanization.
  • the -Si-OH bond formed by the hydrolysis of organosiloxane is difficult to condense with -C-OH on the surface of nanocellulose crystals to form -CO-Si bond , Therefore, its modified durability is poor. Therefore, how to prepare modified nanofiber crystals with excellent emulsification performance under mild reaction conditions is another issue that those skilled in the art need to consider.
  • the purpose of the present invention is to provide a modified nano cellulose crystal with excellent emulsifying properties.
  • the present invention provides a modified nano cellulose crystal
  • the modified nano cellulose crystal is a diisocyanate modified nano cellulose crystal, the two -NCO groups of the diisocyanate and the nano cellulose respectively
  • the -OH on the surface reacts and is connected to the surface of the nanocellulose through the -NH-COO- bond; the mass ratio of the diisocyanate used in the modified nanocellulose crystal to the nanocellulose crystal is 0.01:1 to 6:1.
  • the diisocyanate includes hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethyl At least one of hexamethylene diisocyanate and 4,4-dicyclohexylmethane diisocyanate;
  • the mass ratio of the diisocyanate used for modifying the nanocellulose crystals to the nanocellulose crystals is 0.5:1 to 6:1.
  • the terminal groups of the modified nanocellulose crystal can be modified by the diisocyanate.
  • the mass ratio of the diisocyanate used for modifying the nanocellulose crystals to the nanocellulose crystals is 0.5:1 to 3:1.
  • the present invention also provides a preparation method of the above-mentioned modified nanocellulose crystals, wherein the preparation method includes:
  • the catalyst is dibutyltin dilaurate.
  • dibutyltin dilaurate as a catalyst can realize the modification of nanocellulose at room temperature, which is fundamentally different from the conventional cellulose modification that must be carried out under heating.
  • the reaction temperature is 15-60°C; more preferably 25-50°C.
  • the method for preparing the above-mentioned modified nanocellulose crystals includes: adding dilauric acid after mixing the nanocellulose crystals with a part of the organic solvent (to disperse the nanocellulose crystals in the organic solvent) Dibutyltin is added to a mixed solution of diisocyanate and remaining organic solvent under a protective gas atmosphere and reacted at room temperature to obtain the modified nano cellulose crystals.
  • the mass ratio of dibutyltin dilaurate to diisocyanate is 0.1:1 to 5:1; more preferably, the mass ratio of dibutyltin dilaurate to isocyanate is 0.5:1 to 2: 1.
  • the mass ratio of the organic solvent to the nanocellulose crystals is 100:1-200:1, wherein a part of the organic solvent is used for mixing with the nanocellulose, and the remaining part is mixed with the diisocyanate;
  • the usage amount of the two parts of organic solvent can be controlled as needed.
  • the organic solvent includes at least one of tetrahydrofuran and acetone; for example, tetrahydrofuran.
  • the reaction time is 1-24 h; more preferably, 12-24 h.
  • the protective gas is nitrogen.
  • the reaction is carried out by means of stirring; wherein, the stirring can be carried out by means of magnetic stirring, electric stirring, etc., but is not limited thereto.
  • the adding of the mixed liquid of the diisocyanate and the remaining organic solvent is carried out by dropwise addition; for example, the mixed liquid of the isocyanate and the remaining organic solvent can be added dropwise using a constant pressure funnel.
  • the above preparation method may further include: filtering, washing, and drying the product obtained by the reaction; wherein, the filtering is preferably carried out using a partial fluoride membrane; the washing preferably uses an organic solvent (the organic solvent is preferably tetrahydrofuran and acetone. At least one of, more preferably tetrahydrofuran) is used as a detergent; drying can be carried out by at least one of air drying, vacuum drying and spray drying, but is not limited thereto.
  • the filtering is preferably carried out using a partial fluoride membrane
  • the washing preferably uses an organic solvent (the organic solvent is preferably tetrahydrofuran and acetone. At least one of, more preferably tetrahydrofuran) is used as a detergent; drying can be carried out by at least one of air drying, vacuum drying and spray drying, but is not limited thereto.
  • the modified nano cellulose crystal provided by the present invention bonds the two -NCO groups of the diisocyanate with the -OH on the surface of the nano cellulose respectively, so that the diisocyanate is connected to the nanometer by a covalent bond -NH-COO connection.
  • the surface of cellulose, and its special structure makes the surface of modified nano cellulose have excellent emulsifying properties.
  • the problem of excessive polarity of the modified cellulose crystals can be improved, and the problem of limited application of nanocellulose due to excessive polarity is well alleviated.
  • the method for preparing modified nano cellulose crystals provided by the present invention is simple and beneficial to industrialization; and the preferred technical solution of using dibutyl tin dilaurate as a catalyst can realize the modification of nano cellulose at room temperature.
  • the method of cellulose modification is fundamentally different.
  • Figure 1 is a diagram showing the contact angle of the modified nanocellulose crystals provided in Examples 1, 2, 3, 4, 5 and 7 and the nanocellulose crystals provided in Comparative Example 1 to water.
  • FIG. 3A is a graph showing the effect of emulsification performance test in Example 1.
  • Figure 3B is a graph showing the emulsification performance test effect of Comparative Example 1.
  • This embodiment provides a modified nano cellulose crystal, wherein the modified cellulose crystal is prepared by any one of the following method 1 or method 2:
  • step 2) the reaction temperature is 35°C.
  • test the contact angle of the modified nano-cellulose crystals (testing instrument: Krüss DSA100 dynamic water contact angle measuring instrument): spread the modified nano-cellulose crystals evenly on a glass slide to test its dynamic contact angle to water, The volume of the test drop is 5 microliters.
  • the test results show that the contact angle of hexamethylene diisocyanate-modified nanocellulose crystals is 72° (as shown in (b) in Figure 1), which is compared with unmodified nanocellulose crystals (as shown in the comparative example). 1
  • the contact angle performance test conducted, the contact angle is 0°), which shows better non-polarity, alleviates the problem of too high polarity of nanocellulose crystals, and has better application prospects.
  • This embodiment provides a modified nano cellulose crystal, wherein the modified cellulose crystal is prepared by any one of the following method 1 or method 2:
  • step 2) the reaction temperature is 45°C.
  • the FTIR spectrum of 2,2,4-trimethylhexamethylene diisocyanate modified nanocellulose crystals was tested by Fourier infrared spectrometer (shown in Figure 2(b)). Compared with the unmodified nanocellulose, the 2,2,4-trimethylhexamethylene diisocyanate modified nanocellulose has a carbamate ester group absorption peak at 1710 cm -1, which shows that two The -NCO group of the isocyanate reacts with the -OH on the surface of the nanocellulose crystal to produce -NH-COO-.
  • test the contact angle of the modified nano-cellulose crystals (testing instrument: Krüss DSA100 dynamic water contact angle measuring instrument): spread the modified nano-cellulose crystals evenly on a glass slide to test its dynamic contact angle to water, The volume of the test drop is 5 microliters.
  • the test results show that the contact angle of nanocellulose crystals modified by 2,2,4-trimethylhexamethylene diisocyanate is 102° (as shown in (c) in Figure 1), which is compared with unmodified Nano cellulose crystals (such as the contact angle performance test conducted in Comparative Example 1, the contact angle is 0°), which exhibits better non-polarity, alleviates the problem of excessively high polarity of nano cellulose crystals, and has better Good application prospects.
  • the FTIR spectrum of 2,2,4-trimethylhexamethylene diisocyanate modified nanocellulose crystals was tested by Fourier infrared spectrometer (shown in Figure 2(b)).
  • the 2,2,4-trimethylhexamethylene diisocyanate modified nanocellulose has a carbamate ester group absorption peak at 1710 cm -1, which shows that two The -NCO group of the isocyanate reacts with the -OH on the surface of the nanocellulose crystal to produce -NH-COO-.
  • the absorption peak intensity of methylene groups at 2855 cm -1 and 1460 cm -1 increased, indicating that the alkyl chain was successfully introduced into the surface of nanocellulose.
  • This embodiment provides a modified nano cellulose crystal, wherein the modified cellulose crystal is prepared by any one of the following method 1 or method 2:
  • step 2) the reaction temperature is 50°C.
  • test the contact angle of the modified nano-cellulose crystals (testing instrument: Krüss DSA100 dynamic water contact angle measuring instrument): spread the modified nano-cellulose crystals evenly on a glass slide to test its dynamic contact angle to water, The volume of the test drop is 5 microliters.
  • the test results show that the contact angle of nanocellulose crystals modified by 2,4,4-trimethylhexamethylene diisocyanate is 110° (as shown in (d) in Figure 1), which is compared with unmodified Nano cellulose crystals (such as the contact angle performance test conducted in Comparative Example 1, the contact angle is 0°), which exhibits better non-polarity, alleviates the problem of excessively high polarity of nano cellulose crystals, and has better Good application prospects.
  • This embodiment provides a modified nano cellulose crystal, wherein the modified cellulose crystal is prepared by the following method:
  • a Fourier infrared spectrometer was used to test the FTIR spectrum of 4,4'-dicyclohexylmethane diisocyanate modified nanocellulose crystals (shown in (d) in Figure 2).
  • the diisocyanate modified nanocellulose has the ester group absorption peak of the carbamate at 1710cm -1 , which indicates that the -NCO group of the diisocyanate is related to the surface of the nanocellulose crystal.
  • -OH reacts to produce -NH-COO-.
  • test the contact angle of the modified nano-cellulose crystals (testing instrument: Krüss DSA100 dynamic water contact angle measuring instrument): spread the modified nano-cellulose crystals evenly on a glass slide to test its dynamic contact angle to water, The volume of the test drop is 5 microliters.
  • the test results show that the contact angle of nanocellulose crystals modified by 4,4'-dicyclohexylmethane diisocyanate is 132° (as shown in (e) in Figure 1), which is compared with unmodified nanocellulose Crystals (such as the contact angle performance test conducted in Comparative Example 1, the contact angle is 0°), which exhibits better non-polarity, alleviates the problem of excessively high polarity of nanocellulose crystals, and has better application prospects .
  • This embodiment provides a modified nano cellulose crystal, wherein the modified cellulose crystal is prepared by any one of the following method 1 or method 2:
  • step 2) Mix 1.0g of 4,4'-dicyclohexylmethane diisocyanate and 50g of tetrahydrofuran to obtain mixed solution A; under nitrogen protection, add dibutyltin dilaurate to step 1) through a constant pressure funnel.
  • the mixed solution A was added dropwise to the container, and the reaction was stirred at room temperature for 12 hours; the product obtained by the reaction was filtered with a PVDF membrane, washed with tetrahydrofuran, and then dried at 65° C. to obtain modified nano cellulose crystals.
  • step 2) the reaction temperature is 35°C.
  • test the contact angle of the modified nano-cellulose crystals (testing instrument: Krüss DSA100 dynamic water contact angle measuring instrument): spread the modified nano-cellulose crystals evenly on a glass slide to test its dynamic contact angle to water, The volume of the test drop is 5 microliters.
  • the test results show that the contact angle of nanocellulose crystals modified by 4,4'-dicyclohexylmethane diisocyanate is 130° (as shown in (f) in Figure 1), which is compared with unmodified nanocellulose Crystals (such as the contact angle performance test conducted in Comparative Example 1, the contact angle is 0°), which exhibits better non-polarity, alleviates the problem of excessively high polarity of nanocellulose crystals, and has better application prospects .
  • the modified nanocellulose crystals provided in Example 4 and Example 5 are all 4,4'-dicyclohexylmethane diisocyanate modified nanocellulose crystals; comparing the data of Example 4 and Example 5, it can be seen that 4 The contact angle of 4'-dicyclohexylmethane diisocyanate does not change when added in excess, so it can be judged that the end groups of the nanocellulose crystals are modified.
  • This comparative example provides an unmodified nano cellulose crystal, which is prepared by the following method:
  • test of unmodified nano cellulose crystals (testing instrument: Krüss DSA100 dynamic water contact angle measuring instrument).
  • the unmodified nano cellulose crystals were evenly spread on a glass slide, and the dynamic contact angle to water was tested.
  • the volume of the test water droplet was 5 microliters.
  • the test results show that when the water droplets touch the surface of the nanocellulose crystals, the water droplets are quickly absorbed, and the contact angle of the unmodified nanocellulose crystals is 0° (as shown in Figure 1 (a)), which has a very high affinity.

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Abstract

Provided in the present invention are a type of modified nanocrystalline cellulose and a preparation method thereof. The modified nanocrystalline cellulose is a diisocyanate-modified nanocrystalline cellulose, the two -NCO of the diisocyanate each reacting with an -OH of nanocellulose and being connected to a nanocellulose surface by means of a -NH-COO- bond; a mass ratio of diisocyanate to nanocrystalline cellulose is 0.01:1-6:1. The method comprises: mixing nanocrystalline cellulose with some of an organic solvent, then adding a catalyst, and adding a mixed liquid of diisocyanate and the remaining organic solvent under a protective atmosphere and reacting, obtaining the modified nanocrystalline cellulose. The present modified nanocrystalline cellulose has good emulsifying properties and combats the problem of limited application caused by nanocrystalline cellulose polarity being too high.

Description

一种改性纳米纤维素晶体及其制备方法Modified nano cellulose crystal and preparation method thereof 技术领域Technical field
本发明具体涉及一种纳米纤维素晶体疏水接枝的改性方法，属于纳米粒子表面的疏水接枝改性技术领域。The invention specifically relates to a method for modifying the hydrophobic grafting of nano cellulose crystals, and belongs to the technical field of hydrophobic grafting modification on the surface of nano particles.
背景技术Background technique
纳米纤维素晶体是一种可再生、可降解、低毒性的新型纳米材料，自然界中来源非常广泛，因其具有高长径比、低密度、高机械强度等特点，在复合材料、新能源、医药、化工和食品等领域有较大的潜在应用价值。Nano-cellulose crystals are a new type of renewable, degradable, and low-toxic nano-materials. They come from a wide range of sources in nature. Because of their high aspect ratio, low density, and high mechanical strength, they are used in composite materials, new energy, The fields of medicine, chemical industry and food have great potential application value.
近年来，将纳米纤维素晶体用于制备Pickering乳液受到科研工作者的广泛关注，所制备得到的乳液具有较好的稳定性、低泡等特征，而与传统的球形纳米颗粒相比，具有独特棒状结构的纳米纤维素晶体的长径比可调，由此能够实现对Pickering乳液液滴尺寸、形貌的调控，其作为纳米颗粒乳化剂制备Pickering乳液在三次采油中具有广阔的应用前景。In recent years, the use of nano-cellulose crystals in the preparation of Pickering emulsion has attracted wide attention from scientific researchers. The prepared emulsion has better stability, low foam and other characteristics, and compared with traditional spherical nanoparticles, it has unique characteristics. The rod-like structure of nanocellulose crystals has an adjustable aspect ratio, which can realize the control of the size and morphology of the Pickering emulsion droplets. As a nanoparticle emulsifier to prepare Pickering emulsion, it has broad application prospects in tertiary oil recovery.
首先，为了适应工业应用特别是在三次采油中的应用，纳米纤维素晶体的乳化性能有待提高。其次纳米纤维素素晶体作为乳化剂的应用较为受限，这主要是由于纳米纤维素晶体具有较大的极性和比表面，一方面，纳米纤维素晶体表面含有大量的羟基，致使纳米纤维素晶体在大部分的非水溶剂中不能很好的分散；另一方面，纳米纤维素晶体因比表面大以及氢键作用，很容易发生团聚。因此如何能够有效提高纳米纤维素的乳化性能，同时解决纳米纤维素晶体因极性过高导致使用受限的问题成为本领域研究的焦点。First of all, in order to adapt to industrial applications, especially applications in tertiary oil recovery, the emulsifying properties of nano cellulose crystals need to be improved. Secondly, the application of nano-cellulose crystals as emulsifiers is relatively limited. This is mainly due to the large polarity and specific surface of nano-cellulose crystals. On the one hand, the surface of nano-cellulose crystals contains a large number of hydroxyl groups, which causes nano-cellulose crystals. Crystals cannot be dispersed well in most non-aqueous solvents; on the other hand, nano-cellulose crystals are prone to agglomeration due to their large surface area and hydrogen bonding. Therefore, how to effectively improve the emulsification performance of nanocellulose and at the same time solve the problem of limited use of nanocellulose crystals due to excessive polarity has become the focus of research in this field.
另外，现有技术主要采用酯化、有机硅烷化等对纳米纤维素进行改性。但是，采用脂肪酸进行改性时，需要采用强酸作为催化剂，同时具有反应温度较高的缺点。有机硅氧烷是有机硅烷化最常用的改性剂，但是，有机硅氧烷水解形成的-Si-OH键很难与纳米纤维素晶体表面的-C-OH缩合，形成-C-O-Si键，因此，其改性的耐久性差。因此如何能够以温和的反应条件制备乳化性能优异的改性纳米纤维晶体是本领域技术人员需要考虑的另一问题。In addition, the prior art mainly uses esterification, organosilanization, etc. to modify nanocellulose. However, when fatty acids are used for modification, a strong acid is required as a catalyst, and it also has the disadvantage of higher reaction temperature. Organosiloxane is the most commonly used modifier for organosilanization. However, the -Si-OH bond formed by the hydrolysis of organosiloxane is difficult to condense with -C-OH on the surface of nanocellulose crystals to form -CO-Si bond , Therefore, its modified durability is poor. Therefore, how to prepare modified nanofiber crystals with excellent emulsification performance under mild reaction conditions is another issue that those skilled in the art need to consider.
发明内容Summary of the invention
本发明的目的在于提供一种具备优异乳化性能的改性纳米纤维素晶体。The purpose of the present invention is to provide a modified nano cellulose crystal with excellent emulsifying properties.
为了实现上述目的，本发明提供了一种改性纳米纤维素晶体，该改性纳米纤维素晶体为二异氰酸酯改性的纳米纤维素晶体，二异氰酸酯的两个-NCO基团分别与纳米纤维素表面的-OH发生反应通过-NH-COO-键连接至纳米纤维素表面；所述改性纳米纤维素 晶体使用的二异氰酸酯与纳米纤维素晶体的质量比为0.01:1-6:1。In order to achieve the above objective, the present invention provides a modified nano cellulose crystal, the modified nano cellulose crystal is a diisocyanate modified nano cellulose crystal, the two -NCO groups of the diisocyanate and the nano cellulose respectively The -OH on the surface reacts and is connected to the surface of the nanocellulose through the -NH-COO- bond; the mass ratio of the diisocyanate used in the modified nanocellulose crystal to the nanocellulose crystal is 0.01:1 to 6:1.
在上述改性纳米纤维素晶体中，优选地，所述二异氰酸酯包括六亚甲基二异氰酸酯、2,2,4-三甲基六亚甲基二异氰酸酯、2,4,4-三甲基六亚甲基二异氰酸酯、4,4-二环己基甲烷二异氰酸酯中的至少一种；In the above modified nanocellulose crystals, preferably, the diisocyanate includes hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethyl At least one of hexamethylene diisocyanate and 4,4-dicyclohexylmethane diisocyanate;
其中，六亚甲基二异氰酸酯的化学结构为：Among them, the chemical structure of hexamethylene diisocyanate is:
Figure PCTCN2020121793-appb-000001
Figure PCTCN2020121793-appb-000001
其中，2,2,4-三甲基六亚甲基二异氰酸酯的化学结构为：Among them, the chemical structure of 2,2,4-trimethylhexamethylene diisocyanate is:
Figure PCTCN2020121793-appb-000002
Figure PCTCN2020121793-appb-000002
其中，2,4,4-三甲基六亚甲基二异氰酸酯的化学结构为：Among them, the chemical structure of 2,4,4-trimethylhexamethylene diisocyanate is:
Figure PCTCN2020121793-appb-000003
Figure PCTCN2020121793-appb-000003
其中，4,4-二环己基甲烷二异氰酸酯的化学结构为：Among them, the chemical structure of 4,4-dicyclohexylmethane diisocyanate is:
Figure PCTCN2020121793-appb-000004
Figure PCTCN2020121793-appb-000004
根据本发明的具体实施方案，优选地，对纳米纤维素晶体进行改性使用的二异氰酸酯与纳米纤维素晶体的质量比为0.5:1-6:1。当二异氰酸酯与纳米纤维素晶体的质量比达到0.5:1以上时，改性纳米纤维素晶体的端基的基团可以实现被二异氰酸酯修饰。According to the specific embodiment of the present invention, preferably, the mass ratio of the diisocyanate used for modifying the nanocellulose crystals to the nanocellulose crystals is 0.5:1 to 6:1. When the mass ratio of the diisocyanate to the nanocellulose crystal reaches 0.5:1 or more, the terminal groups of the modified nanocellulose crystal can be modified by the diisocyanate.
根据本发明的具体实施方案，优选地，对纳米纤维素晶体进行改性使用的二异氰酸酯与纳米纤维素晶体的质量比为0.5:1-3:1。According to the specific embodiment of the present invention, preferably, the mass ratio of the diisocyanate used for modifying the nanocellulose crystals to the nanocellulose crystals is 0.5:1 to 3:1.
本发明还提供上述改性纳米纤维素晶体的制备方法，其中，该制备方法包括：The present invention also provides a preparation method of the above-mentioned modified nanocellulose crystals, wherein the preparation method includes:
将纳米纤维素晶体与部分有机溶剂混合后(使得纳米纤维素晶体分散至有机溶剂中)加入催化剂，在保护气体氛围下加入二异氰酸酯与剩余有机溶剂的混合液进行反应，得到所述改性纳米纤维素晶体。After mixing the nano cellulose crystals with part of the organic solvent (to disperse the nano cellulose crystals in the organic solvent), add a catalyst, and add a mixture of diisocyanate and the remaining organic solvent to react under a protective gas atmosphere to obtain the modified nano Cellulose crystals.
在上述制备方法中，优选地，所述催化剂为二月桂酸二丁基锡。使用二月桂酸二丁基锡作为催化剂能够实现常温下改性纳米纤维素，与常规必须在加热下进行纤维素改性具备根本性不同。In the above preparation method, preferably, the catalyst is dibutyltin dilaurate. The use of dibutyltin dilaurate as a catalyst can realize the modification of nanocellulose at room temperature, which is fundamentally different from the conventional cellulose modification that must be carried out under heating.
在上述制备方法中，优选地，所述反应的温度为15-60℃；更优选为25-50℃。In the above preparation method, preferably, the reaction temperature is 15-60°C; more preferably 25-50°C.
根据本发明的具体实施方案，优选地，上述改性纳米纤维素晶体的制备方法包括：将纳米纤维素晶体与部分有机溶剂混合后(使得纳米纤维素晶体分散至有机溶剂中)加入二月桂酸二丁基锡，在保护气体氛围下加入二异氰酸酯与剩余有机溶剂的混合液并于 常温下反应，得到所述改性纳米纤维素晶体。According to a specific embodiment of the present invention, preferably, the method for preparing the above-mentioned modified nanocellulose crystals includes: adding dilauric acid after mixing the nanocellulose crystals with a part of the organic solvent (to disperse the nanocellulose crystals in the organic solvent) Dibutyltin is added to a mixed solution of diisocyanate and remaining organic solvent under a protective gas atmosphere and reacted at room temperature to obtain the modified nano cellulose crystals.
在上述制备方法中，优选地，二月桂酸二丁基锡与二异氰酸酯的质量比为0.1:1-5:1；更优选地，二月桂酸二丁基锡与异氰酸酯的质量比为0.5:1-2:1。In the above preparation method, preferably, the mass ratio of dibutyltin dilaurate to diisocyanate is 0.1:1 to 5:1; more preferably, the mass ratio of dibutyltin dilaurate to isocyanate is 0.5:1 to 2: 1.
在上述制备方法中，优选地，有机溶剂与纳米纤维素晶体的质量比为100:1-200:1，其中有机溶剂中的一部分用来与纳米纤维素进行混合，剩余部分与二异氰酸酯混合；两部分有机溶剂的使用量可以根据需要进行控制。In the above preparation method, preferably, the mass ratio of the organic solvent to the nanocellulose crystals is 100:1-200:1, wherein a part of the organic solvent is used for mixing with the nanocellulose, and the remaining part is mixed with the diisocyanate; The usage amount of the two parts of organic solvent can be controlled as needed.
在上述制备方法中，优选地，所述有机溶剂包括四氢呋喃和丙酮中的至少一种；例如四氢呋喃。In the above preparation method, preferably, the organic solvent includes at least one of tetrahydrofuran and acetone; for example, tetrahydrofuran.
在上述制备方法中，优选地，所述反应的时间为1-24h；更优选为12-24h。In the above preparation method, preferably, the reaction time is 1-24 h; more preferably, 12-24 h.
在上述制备方法中，优选地，所述保护气体为氮气。In the above preparation method, preferably, the protective gas is nitrogen.
在上述制备方法中，优选地，所述反应通过搅拌的方式进行；其中，所述搅拌可以通过磁力搅拌、电动搅拌等形式进行，但不限于此。In the above preparation method, preferably, the reaction is carried out by means of stirring; wherein, the stirring can be carried out by means of magnetic stirring, electric stirring, etc., but is not limited thereto.
在上述制备方法中，优选地，所述加入二异氰酸酯与剩余有机溶剂的混合液通过滴加的方式进行；例如可以使用恒压漏斗逐滴加入异氰酸酯与剩余有机溶剂的混合液。In the above preparation method, preferably, the adding of the mixed liquid of the diisocyanate and the remaining organic solvent is carried out by dropwise addition; for example, the mixed liquid of the isocyanate and the remaining organic solvent can be added dropwise using a constant pressure funnel.
在上述制备方法中，还可以进一步包括：将反应得到的产物进行过滤、洗涤、干燥的步骤；其中，过滤优选使用偏氟膜进行；洗涤优选使用有机溶剂(该有机溶剂优选为四氢呋喃和丙酮中的至少一种，更优选为四氢呋喃)作为洗涤剂；干燥可以通过鼓风干燥、真空干燥和喷雾干燥等方式中的至少一种进行，但不限于此。In the above preparation method, it may further include: filtering, washing, and drying the product obtained by the reaction; wherein, the filtering is preferably carried out using a partial fluoride membrane; the washing preferably uses an organic solvent (the organic solvent is preferably tetrahydrofuran and acetone. At least one of, more preferably tetrahydrofuran) is used as a detergent; drying can be carried out by at least one of air drying, vacuum drying and spray drying, but is not limited thereto.
本发明提供的改性纳米纤维素晶体将二异氰酸酯的两个-NCO基团分别与纳米纤维素表面的-OH发生键和，使得二异氰酸酯以共价键-NH-COO连接的方式连接至纳米纤维素表面，其特殊的结构使得改性纳米纤维素表面具备优异的乳化性能。除此之外，该改性纤维素晶体的极性过大问题得以改善，很好的缓解了纳米纤维素由于极性过大导致的应用受限的问题。The modified nano cellulose crystal provided by the present invention bonds the two -NCO groups of the diisocyanate with the -OH on the surface of the nano cellulose respectively, so that the diisocyanate is connected to the nanometer by a covalent bond -NH-COO connection. The surface of cellulose, and its special structure makes the surface of modified nano cellulose have excellent emulsifying properties. In addition, the problem of excessive polarity of the modified cellulose crystals can be improved, and the problem of limited application of nanocellulose due to excessive polarity is well alleviated.
本发明提供的改性纳米纤维素晶体的制备方法简单有利于工业化；并且使用二月桂酸二丁基锡作为催化剂的优选技术方案能够实现常温下对纳米纤维素进行改性，与过去必须在加热条件下进行纤维素改性的方法具备根本性的不同。The method for preparing modified nano cellulose crystals provided by the present invention is simple and beneficial to industrialization; and the preferred technical solution of using dibutyl tin dilaurate as a catalyst can realize the modification of nano cellulose at room temperature. The method of cellulose modification is fundamentally different.
附图说明Description of the drawings
图1为实施例1、2、3、4、5和7提供的改性纳米纤维素晶体以及对比例1提供的纳米纤维素晶体对水的接触角图。Figure 1 is a diagram showing the contact angle of the modified nanocellulose crystals provided in Examples 1, 2, 3, 4, 5 and 7 and the nanocellulose crystals provided in Comparative Example 1 to water.
图2为实施例2、3、4、5提供的改性纳米纤维素晶体以及对比例1提供的纳米纤维素晶体的FTIR谱图。2 is the FTIR spectra of the modified nanocellulose crystals provided in Examples 2, 3, 4, and 5 and the nanocellulose crystals provided in Comparative Example 1.
图3A为实施例1乳化性能测试效果图。FIG. 3A is a graph showing the effect of emulsification performance test in Example 1. FIG.
图3B为对比例1乳化性能测试效果图。Figure 3B is a graph showing the emulsification performance test effect of Comparative Example 1.
具体实施方式Detailed ways
为了对本发明的技术特征、目的和有益效果有更加清楚的理解，现对本发明的技术方案进行以下详细说明，但不能理解为对本发明的可实施范围的限定。In order to have a clearer understanding of the technical features, objectives, and beneficial effects of the present invention, the technical solutions of the present invention are now described in detail below, but they should not be understood as limiting the scope of implementation of the present invention.
实施例1Example 1
本实施例提供了一种改性纳米纤维素晶体，其中，该改性纤维素晶体通过下述方法一或方法二中的任意一种制备得到：This embodiment provides a modified nano cellulose crystal, wherein the modified cellulose crystal is prepared by any one of the following method 1 or method 2:
方法一：method one:
1)向反应容器中加入100g四氢呋喃与1g纳米纤维素晶体，通过磁力搅拌将纳米纤维素晶体均匀分散；继续向反应容器中加入1.0g二月桂酸二丁基锡，然后向反应容器中通入氮气；1) Add 100g of tetrahydrofuran and 1g of nanocellulose crystals to the reaction vessel, and disperse the nanocellulose crystals uniformly by magnetic stirring; continue to add 1.0g of dibutyltin dilaurate to the reaction vessel, and then pass nitrogen into the reaction vessel;
2)将0.5g六亚甲基二异氰酸酯和50g四氢呋喃混合得到混合液A；在氮气保护的情况下，通过恒压漏斗向步骤1)加入二月桂酸二丁基锡后的反应容器中逐滴加入混合液A，于室温下搅拌反应12h；反应得到的产物采用偏氟膜过滤，并用四氢呋喃洗涤，然后于65℃烘干，得到改性纳米纤维素晶体；其中，六亚甲基二异氰酸酯改性纳米纤维素晶体的反应式为：2) Mix 0.5g of hexamethylene diisocyanate and 50g of tetrahydrofuran to obtain mixed solution A; under nitrogen protection, add dropwise to the reaction vessel after adding dibutyltin dilaurate to step 1) through a constant pressure funnel under nitrogen protection. Solution A, stirred and reacted at room temperature for 12h; the product obtained by the reaction was filtered with a PVDF membrane, washed with tetrahydrofuran, and then dried at 65°C to obtain modified nano-cellulose crystals; among them, the hexamethylene diisocyanate modified nano-cellulose The reaction formula of cellulose crystals is:
Figure PCTCN2020121793-appb-000005
Figure PCTCN2020121793-appb-000005
方法二：Method Two:
方法二与方法一的区别仅在于步骤2)反应温度为35℃。The difference between method two and method one is that step 2) the reaction temperature is 35°C.
对本实施例提供的改性的纳米纤维素晶体进行乳化性能测试：The emulsification performance test is performed on the modified nanocellulose crystals provided in this embodiment:
将本实施例提供的改性纳米纤维素晶体分散到水中作为水相，其中，以改性纳米纤维素晶体与水的总质量计，改性纳米纤维素晶体的浓度为0.5wt％；以十六烷作为有机相；以水相与有机相的体积比2:1制备Pickering乳液，具体为将水相与有机相混合均匀后超声处理1分钟，然后静置观察乳状液形成情况。通过观察发现上层乳状液形成，证明二异氰酸酯改性后的纳米纤维素晶体具备良好的乳化性能(如图3B所示)也间接说明改性成功。相较于未改性的纳米纤维素晶体(如对比例1进行的乳化测试，未发现乳 状液)，其乳化特性明显得到改善。Disperse the modified nanocellulose crystals provided in this embodiment into water as an aqueous phase, wherein, based on the total mass of the modified nanocellulose crystals and water, the concentration of the modified nanocellulose crystals is 0.5% by weight; Hexane was used as the organic phase; the Pickering emulsion was prepared with the volume ratio of the water phase and the organic phase 2:1, specifically, the water phase and the organic phase were mixed uniformly and ultrasonically treated for 1 minute, and then stood to observe the formation of the emulsion. The formation of the upper emulsion is found through observation, which proves that the nanocellulose crystals modified by diisocyanate have good emulsifying properties (as shown in Fig. 3B) and indirectly indicates the success of the modification. Compared with the unmodified nanocellulose crystals (for example, in the emulsification test conducted in Comparative Example 1, no emulsion was found), its emulsification characteristics were significantly improved.
对改性的纳米纤维素晶体进行接触角测试(测试仪器：Krüss DSA100动态水接触角测量仪)：将改性的纳米纤维素晶体均匀地铺在载玻片上，测试其对水的动态接触角，测试水滴体积为5微升。测试结果表明经六亚甲基二异氰酸酯改性的纳米纤维素晶体接触角为72°(如图1中的(b)所示)，相较于未改性的纳米纤维素晶体(如对比例1进行的接触角性能测试，其接触角为0°)，其体现出更好的非极性，缓解了纳米纤维素晶体极性过高的问题，具备较好的应用前景。Test the contact angle of the modified nano-cellulose crystals (testing instrument: Krüss DSA100 dynamic water contact angle measuring instrument): spread the modified nano-cellulose crystals evenly on a glass slide to test its dynamic contact angle to water, The volume of the test drop is 5 microliters. The test results show that the contact angle of hexamethylene diisocyanate-modified nanocellulose crystals is 72° (as shown in (b) in Figure 1), which is compared with unmodified nanocellulose crystals (as shown in the comparative example). 1 The contact angle performance test conducted, the contact angle is 0°), which shows better non-polarity, alleviates the problem of too high polarity of nanocellulose crystals, and has better application prospects.
实施例2Example 2
本实施例提供了一种改性纳米纤维素晶体，其中，该改性纤维素晶体通过下述方法一或方法二中的任意一种制备得到：This embodiment provides a modified nano cellulose crystal, wherein the modified cellulose crystal is prepared by any one of the following method 1 or method 2:
方法一：method one:
1)向反应容器中加入150g四氢呋喃与1g纳米纤维素晶体，通过磁力搅拌将纳米纤维素晶体均匀分散；继续向反应容器中加入1.0g二月桂酸二丁基锡，然后向反应容器中通入氮气；1) Add 150g of tetrahydrofuran and 1g of nanocellulose crystals to the reaction vessel, and uniformly disperse the nanocellulose crystals by magnetic stirring; continue to add 1.0g of dibutyltin dilaurate to the reaction vessel, and then pass nitrogen into the reaction vessel;
2)将1.0g的2,2,4-三甲基六亚甲基二异氰酸酯和50g四氢呋喃混合得到混合液A；在氮气保护的情况下，通过恒压漏斗向步骤1)加入二月桂酸二丁基锡后的反应容器中逐滴加入混合液A，于室温下搅拌反应18h；反应得到的产物采用偏氟膜过滤，并用四氢呋喃洗涤，然后于80℃烘干，得到改性纳米纤维素晶体；其中，2,2,4-三甲基六亚甲基二异氰酸酯改性纳米纤维素晶体的反应式为：2) Mix 1.0g of 2,2,4-trimethylhexamethylene diisocyanate and 50g of tetrahydrofuran to obtain mixed solution A; under nitrogen protection, add dilauric acid to step 1) through a constant pressure funnel. The mixed solution A was added dropwise to the reaction vessel after butyl tin, and the reaction was stirred at room temperature for 18 hours; the product obtained by the reaction was filtered with a PVDF membrane, washed with tetrahydrofuran, and then dried at 80°C to obtain modified nanocellulose crystals; , The reaction formula of 2,2,4-trimethylhexamethylene diisocyanate modified nano-cellulose crystals is:
Figure PCTCN2020121793-appb-000006
Figure PCTCN2020121793-appb-000006
方法二与方法一的区别仅在于步骤2)反应温度为45℃。The difference between method two and method one is that step 2) the reaction temperature is 45°C.
采用傅利叶红外光谱仪测试2,2,4-三甲基六亚甲基二异氰酸酯改性的纳米纤维素晶体的FTIR谱图(图2中的(b)所示)。与未改性纳米纤维素相比，2,2,4-三甲基六亚甲基二异氰酸酯改性纳米纤维素在1710cm -1处出现了氨基甲酸酯的酯基吸收峰，这说明二异氰酸酯的-NCO基团与纳米纤维素晶体表面的-OH发生反应产生了-NH-COO-。同时，在2855cm -1和1460cm -1处亚甲基的吸收峰强度增强，说明2,2,4-三甲基六亚甲基二异氰酸酯的烷基链被成功引入纳米纤维素表面。 The FTIR spectrum of 2,2,4-trimethylhexamethylene diisocyanate modified nanocellulose crystals was tested by Fourier infrared spectrometer (shown in Figure 2(b)). Compared with the unmodified nanocellulose, the 2,2,4-trimethylhexamethylene diisocyanate modified nanocellulose has a carbamate ester group absorption peak at 1710 cm -1, which shows that two The -NCO group of the isocyanate reacts with the -OH on the surface of the nanocellulose crystal to produce -NH-COO-. At the same time, the intensity of the methylene absorption peaks at 2855 cm -1 and 1460 cm -1 increased, indicating that the alkyl chains of 2,2,4-trimethylhexamethylene diisocyanate were successfully introduced onto the surface of nanocellulose.
对改性的纳米纤维素晶体进行接触角测试(测试仪器：Krüss DSA100动态水接触角测量仪)：将改性的纳米纤维素晶体均匀地铺在载玻片上，测试其对水的动态接触角，测试水滴体积为5微升。测试结果表明经2,2,4-三甲基六亚甲基二异氰酸酯改性的纳米纤维素晶体接触角为102°(如图1中的(c)所示)，相较于未改性的纳米纤维素晶体(如对比例1进行的接触角性能测试，其接触角为0°)，其体现出更好的非极性，缓解了纳米纤维素晶体极性过高的问题，具备较好的应用前景。Test the contact angle of the modified nano-cellulose crystals (testing instrument: Krüss DSA100 dynamic water contact angle measuring instrument): spread the modified nano-cellulose crystals evenly on a glass slide to test its dynamic contact angle to water, The volume of the test drop is 5 microliters. The test results show that the contact angle of nanocellulose crystals modified by 2,2,4-trimethylhexamethylene diisocyanate is 102° (as shown in (c) in Figure 1), which is compared with unmodified Nano cellulose crystals (such as the contact angle performance test conducted in Comparative Example 1, the contact angle is 0°), which exhibits better non-polarity, alleviates the problem of excessively high polarity of nano cellulose crystals, and has better Good application prospects.
采用傅利叶红外光谱仪测试2,2,4-三甲基六亚甲基二异氰酸酯改性的纳米纤维素晶体的FTIR谱图(图2中的(b)所示)。与未改性纳米纤维素相比，2,2,4-三甲基六亚甲基二异氰酸酯改性纳米纤维素在1710cm -1处出现了氨基甲酸酯的酯基吸收峰，这说明二异氰酸酯的-NCO基团与纳米纤维素晶体表面的-OH发生反应产生了-NH-COO-。同时，在2855cm -1和1460cm -1处亚甲基的吸收峰强度增强，说明烷基链被成功引入纳米纤维素表面。 The FTIR spectrum of 2,2,4-trimethylhexamethylene diisocyanate modified nanocellulose crystals was tested by Fourier infrared spectrometer (shown in Figure 2(b)). Compared with the unmodified nanocellulose, the 2,2,4-trimethylhexamethylene diisocyanate modified nanocellulose has a carbamate ester group absorption peak at 1710 cm -1, which shows that two The -NCO group of the isocyanate reacts with the -OH on the surface of the nanocellulose crystal to produce -NH-COO-. At the same time, the absorption peak intensity of methylene groups at 2855 cm -1 and 1460 cm -1 increased, indicating that the alkyl chain was successfully introduced into the surface of nanocellulose.
实施例3Example 3
本实施例提供了一种改性纳米纤维素晶体，其中，该改性纤维素晶体通过下述方法一或方法二中的任意一种制备得到：This embodiment provides a modified nano cellulose crystal, wherein the modified cellulose crystal is prepared by any one of the following method 1 or method 2:
方法一：method one:
1)向反应容器中加入50g四氢呋喃与1g纳米纤维素晶体，通过磁力搅拌将纳米纤维素晶体均匀分散；继续向反应容器中加入1.5g二月桂酸二丁基锡，然后向反应容器中通入氮气；1) Add 50g of tetrahydrofuran and 1g of nanocellulose crystals into the reaction vessel, and uniformly disperse the nanocellulose crystals by magnetic stirring; continue to add 1.5g of dibutyltin dilaurate to the reaction vessel, and then pour nitrogen into the reaction vessel;
2)将2.0g的2,4,4-三甲基六亚甲基二异氰酸酯和50g四氢呋喃混合得到混合液A；在氮气保护的情况下，通过恒压漏斗向步骤1)加入二月桂酸二丁基锡后的反应容器中逐滴加入混合液A，于室温下搅拌反应18h；反应得到的产物采用偏氟膜过滤，并用四氢呋喃洗涤，然后于90℃烘干，得到改性纳米纤维素晶体；其中，2,4,4-三甲基六亚甲基二异氰酸酯改性纳米纤维素晶体的反应式为：2) Mix 2.0g of 2,4,4-trimethylhexamethylene diisocyanate and 50g of tetrahydrofuran to obtain mixed solution A; under nitrogen protection, add dilauric acid to step 1) through a constant pressure funnel. The mixed solution A was added dropwise to the reaction container after butyl tin, and the reaction was stirred at room temperature for 18 hours; the product obtained by the reaction was filtered with a PVDF membrane, washed with tetrahydrofuran, and then dried at 90°C to obtain modified nano cellulose crystals; , The reaction formula of 2,4,4-trimethylhexamethylene diisocyanate modified nano-cellulose crystals is:
Figure PCTCN2020121793-appb-000007
Figure PCTCN2020121793-appb-000007
方法二与方法一的区别仅在于步骤2)反应温度为50℃。The difference between method two and method one is that step 2) the reaction temperature is 50°C.
采用傅利叶红外光谱仪测试2,4,4-三甲基六亚甲基二异氰酸酯改性的纳米纤维素晶 体的FTIR谱图(图2中的(c)所示)。与未改性纳米纤维素相比，2,4,4-三甲基六亚甲基二异氰酸酯改性纳米纤维素在1710cm -1处出现了氨基甲酸酯的酯基吸收峰，这说明二异氰酸酯的-NCO基团与纳米纤维素晶体表面的-OH发生反应产生了-NH-COO-。同时，在2855cm -1和1460cm -1处亚甲基的吸收峰强度增强，说明2,4,4-三甲基六亚甲基二异氰酸酯的烷基链被成功引入纳米纤维素表面。 The FTIR spectrum of 2,4,4-trimethylhexamethylene diisocyanate modified nanocellulose crystals was tested by Fourier infrared spectrometer (shown in (c) in Figure 2). Compared with unmodified nanocellulose, 2,4,4-trimethylhexamethylene diisocyanate modified nanocellulose has a carbamate ester group absorption peak at 1710cm -1, which shows that two The -NCO group of the isocyanate reacts with the -OH on the surface of the nanocellulose crystal to produce -NH-COO-. At the same time, the intensity of the methylene absorption peaks at 2855 cm -1 and 1460 cm -1 increased, indicating that the alkyl chains of 2,4,4-trimethylhexamethylene diisocyanate were successfully introduced onto the surface of nanocellulose.
对改性的纳米纤维素晶体进行接触角测试(测试仪器：Krüss DSA100动态水接触角测量仪)：将改性的纳米纤维素晶体均匀地铺在载玻片上，测试其对水的动态接触角，测试水滴体积为5微升。测试结果表明经2,4,4-三甲基六亚甲基二异氰酸酯改性的纳米纤维素晶体接触角为110°(如图1中的(d)所示)，相较于未改性的纳米纤维素晶体(如对比例1进行的接触角性能测试，其接触角为0°)，其体现出更好的非极性，缓解了纳米纤维素晶体极性过高的问题，具备较好的应用前景。Test the contact angle of the modified nano-cellulose crystals (testing instrument: Krüss DSA100 dynamic water contact angle measuring instrument): spread the modified nano-cellulose crystals evenly on a glass slide to test its dynamic contact angle to water, The volume of the test drop is 5 microliters. The test results show that the contact angle of nanocellulose crystals modified by 2,4,4-trimethylhexamethylene diisocyanate is 110° (as shown in (d) in Figure 1), which is compared with unmodified Nano cellulose crystals (such as the contact angle performance test conducted in Comparative Example 1, the contact angle is 0°), which exhibits better non-polarity, alleviates the problem of excessively high polarity of nano cellulose crystals, and has better Good application prospects.
实施例4Example 4
本实施例提供了一种改性纳米纤维素晶体，其中，该改性纤维素晶体通过下述方法制备得到：This embodiment provides a modified nano cellulose crystal, wherein the modified cellulose crystal is prepared by the following method:
1)向反应容器中加入50g四氢呋喃与1g纳米纤维素晶体，通过磁力搅拌将纳米纤维素晶体均匀分散；继续向反应容器中加入0.5g二月桂酸二丁基锡，然后向反应容器中通入氮气；1) Add 50g of tetrahydrofuran and 1g of nanocellulose crystals to the reaction vessel, and disperse the nanocellulose crystals uniformly by magnetic stirring; continue to add 0.5g of dibutyltin dilaurate to the reaction vessel, and then pour nitrogen into the reaction vessel;
2)将0.5g的4,4’-二环己基甲烷二异氰酸酯和50g四氢呋喃混合得到混合液A；在氮气保护的情况下，通过恒压漏斗向步骤1)加入二月桂酸二丁基锡后的反应容器中逐滴加入混合液A，于室温25℃下搅拌反应12h；反应得到的产物采用偏氟膜过滤，并用四氢呋喃洗涤，然后于50℃烘干，得到改性纳米纤维素晶体；其中，4,4’-二环己基甲烷二异氰酸酯改性纳米纤维素晶体的反应式为：2) Mix 0.5g of 4,4'-dicyclohexylmethane diisocyanate and 50g of tetrahydrofuran to obtain mixed solution A; under nitrogen protection, add dibutyltin dilaurate to step 1) through a constant pressure funnel. The mixed solution A was added dropwise to the container, and the reaction was stirred at room temperature 25°C for 12h; the product obtained by the reaction was filtered with a PVDF membrane, washed with tetrahydrofuran, and then dried at 50°C to obtain modified nanocellulose crystals; among them, 4 The reaction formula of 4'-dicyclohexylmethane diisocyanate modified nano cellulose crystals is:
Figure PCTCN2020121793-appb-000008
Figure PCTCN2020121793-appb-000008
采用傅利叶红外光谱仪测试4,4’-二环己基甲烷二异氰酸酯改性的纳米纤维素晶体的FTIR谱图(图2中的(d)所示)。与未改性纳米纤维素相比，二异氰酸酯改性纳米纤维素在1710cm -1处出现了氨基甲酸酯的酯基吸收峰，这说明二异氰酸酯的-NCO基团与纳米纤维素晶体表面的-OH发生反应产生了-NH-COO-。同时，在2855cm -1和1460cm -1 处亚甲基的吸收峰强度增强，说明4,4’-二环己基甲烷二异氰酸酯的环己基被成功引入纳米纤维素表面。 A Fourier infrared spectrometer was used to test the FTIR spectrum of 4,4'-dicyclohexylmethane diisocyanate modified nanocellulose crystals (shown in (d) in Figure 2). Compared with the unmodified nanocellulose, the diisocyanate modified nanocellulose has the ester group absorption peak of the carbamate at 1710cm -1 , which indicates that the -NCO group of the diisocyanate is related to the surface of the nanocellulose crystal. -OH reacts to produce -NH-COO-. At the same time, the intensity of the methylene absorption peaks at 2855 cm -1 and 1460 cm -1 increased, indicating that the cyclohexyl group of 4,4'-dicyclohexylmethane diisocyanate was successfully introduced onto the surface of nanocellulose.
对改性的纳米纤维素晶体进行接触角测试(测试仪器：Krüss DSA100动态水接触角测量仪)：将改性的纳米纤维素晶体均匀地铺在载玻片上，测试其对水的动态接触角，测试水滴体积为5微升。测试结果表明经4,4’-二环己基甲烷二异氰酸酯改性的纳米纤维素晶体接触角为132°(如图1中的(e)所示)，相较于未改性的纳米纤维素晶体(如对比例1进行的接触角性能测试，其接触角为0°)，其体现出更好的非极性，缓解了纳米纤维素晶体极性过高的问题，具备较好的应用前景。Test the contact angle of the modified nano-cellulose crystals (testing instrument: Krüss DSA100 dynamic water contact angle measuring instrument): spread the modified nano-cellulose crystals evenly on a glass slide to test its dynamic contact angle to water, The volume of the test drop is 5 microliters. The test results show that the contact angle of nanocellulose crystals modified by 4,4'-dicyclohexylmethane diisocyanate is 132° (as shown in (e) in Figure 1), which is compared with unmodified nanocellulose Crystals (such as the contact angle performance test conducted in Comparative Example 1, the contact angle is 0°), which exhibits better non-polarity, alleviates the problem of excessively high polarity of nanocellulose crystals, and has better application prospects .
实施例5Example 5
本实施例提供了一种改性纳米纤维素晶体，其中，该改性纤维素晶体通过下述方法一或方法二中的任意一种制备得到：This embodiment provides a modified nano cellulose crystal, wherein the modified cellulose crystal is prepared by any one of the following method 1 or method 2:
方法一：method one:
1)向反应容器中加入100g四氢呋喃与1g纳米纤维素晶体，通过磁力搅拌将纳米纤维素晶体均匀分散；继续向反应容器中加入1.0g二月桂酸二丁基锡，然后向反应容器中通入氮气；1) Add 100g of tetrahydrofuran and 1g of nanocellulose crystals to the reaction vessel, and disperse the nanocellulose crystals uniformly by magnetic stirring; continue to add 1.0g of dibutyltin dilaurate to the reaction vessel, and then pass nitrogen into the reaction vessel;
2)将1.0g的4,4’-二环己基甲烷二异氰酸酯和50g四氢呋喃混合得到混合液A；在氮气保护的情况下，通过恒压漏斗向步骤1)加入二月桂酸二丁基锡后的反应容器中逐滴加入混合液A，室温下搅拌反应12h；反应得到的产物采用偏氟膜过滤，并用四氢呋喃洗涤，然后于65℃烘干，得到改性纳米纤维素晶体。2) Mix 1.0g of 4,4'-dicyclohexylmethane diisocyanate and 50g of tetrahydrofuran to obtain mixed solution A; under nitrogen protection, add dibutyltin dilaurate to step 1) through a constant pressure funnel. The mixed solution A was added dropwise to the container, and the reaction was stirred at room temperature for 12 hours; the product obtained by the reaction was filtered with a PVDF membrane, washed with tetrahydrofuran, and then dried at 65° C. to obtain modified nano cellulose crystals.
方法二与方法一的区别仅在于步骤2)反应温度为35℃。The difference between method two and method one is that step 2) the reaction temperature is 35°C.
采用傅利叶红外光谱仪测试4,4’-二环己基甲烷二异氰酸酯改性的纳米纤维素晶体的FTIR谱图(图2中的(e)所示)。与未改性纳米纤维素相比，4,4’-二环己基甲烷二异氰酸酯改性纳米纤维素在1710cm -1处出现了氨基甲酸酯的酯基吸收峰，这说明4,4’-二环己基甲烷二异氰酸酯的-NCO基团与纳米纤维素晶体表面的-OH发生反应-NH-COO-。同时，在2855cm -1和1460cm -1处亚甲基的吸收峰强度增强，说明4,4’-二环己基甲烷二异氰酸酯的环己基被成功引入纳米纤维素表面。 Fourier infrared spectrometer was used to test the FTIR spectrum of 4,4'-dicyclohexylmethane diisocyanate modified nanocellulose crystals (shown in (e) in Figure 2). Compared with unmodified nanocellulose, 4,4'-dicyclohexylmethane diisocyanate modified nanocellulose has a carbamate ester group absorption peak at 1710cm -1, which shows that 4,4'- The -NCO group of dicyclohexylmethane diisocyanate reacts -NH-COO- with the -OH on the surface of the nano cellulose crystal. At the same time, the intensity of the methylene absorption peaks at 2855 cm -1 and 1460 cm -1 increased, indicating that the cyclohexyl group of 4,4'-dicyclohexylmethane diisocyanate was successfully introduced onto the surface of nanocellulose.
对改性的纳米纤维素晶体进行接触角测试(测试仪器：Krüss DSA100动态水接触角测量仪)：将改性的纳米纤维素晶体均匀地铺在载玻片上，测试其对水的动态接触角，测试水滴体积为5微升。测试结果表明经4,4’-二环己基甲烷二异氰酸酯改性的纳米纤维素晶体接触角为130°(如图1中的(f)所示)，相较于未改性的纳米纤维素晶体(如对比例1进行的接触角性能测试，其接触角为0°)，其体现出更好的非极性，缓解了纳米 纤维素晶体极性过高的问题，具备较好的应用前景。Test the contact angle of the modified nano-cellulose crystals (testing instrument: Krüss DSA100 dynamic water contact angle measuring instrument): spread the modified nano-cellulose crystals evenly on a glass slide to test its dynamic contact angle to water, The volume of the test drop is 5 microliters. The test results show that the contact angle of nanocellulose crystals modified by 4,4'-dicyclohexylmethane diisocyanate is 130° (as shown in (f) in Figure 1), which is compared with unmodified nanocellulose Crystals (such as the contact angle performance test conducted in Comparative Example 1, the contact angle is 0°), which exhibits better non-polarity, alleviates the problem of excessively high polarity of nanocellulose crystals, and has better application prospects .
实施例4、实施例5提供的改性的纳米纤维素晶体均为4,4’-二环己基甲烷二异氰酸酯改性的纳米纤维素晶体；对比实施例4、实施例5的数据可知，4,4’-二环己基甲烷二异氰酸酯过量加入接触角不发生变化，从而可以判断纳米纤维素晶体端基的基团被修饰。The modified nanocellulose crystals provided in Example 4 and Example 5 are all 4,4'-dicyclohexylmethane diisocyanate modified nanocellulose crystals; comparing the data of Example 4 and Example 5, it can be seen that 4 The contact angle of 4'-dicyclohexylmethane diisocyanate does not change when added in excess, so it can be judged that the end groups of the nanocellulose crystals are modified.
对比例1Comparative example 1
本对比例提供一种未改性的纳米纤维素晶体，该未改性的纤维素晶体通过下述方法制备得到：This comparative example provides an unmodified nano cellulose crystal, which is prepared by the following method:
1)向反应容器中加入100g四氢呋喃与1g纳米纤维素晶体，通过磁力搅拌将纳米纤维素晶体均匀分散；继续向反应容器中加入0.5g二月桂酸二丁基锡，然后向反应容器中通入氮气；1) Add 100g of tetrahydrofuran and 1g of nanocellulose crystals to the reaction vessel, and uniformly disperse the nanocellulose crystals by magnetic stirring; continue to add 0.5g of dibutyltin dilaurate to the reaction vessel, and then pour nitrogen into the reaction vessel;
2)在氮气保护的情况下于室温25℃下搅拌12h；搅拌后的产物采用偏氟膜过滤，并用四氢呋喃洗涤，然后于50℃烘干，得到未改性的纳米纤维素晶体。2) Stir at room temperature 25°C for 12h under the protection of nitrogen; the product after stirring is filtered with a PVDF membrane, washed with tetrahydrofuran, and then dried at 50°C to obtain unmodified nanocellulose crystals.
采用傅利叶红外光谱仪测试未改性的纳米纤维素晶体的FTIR谱图(图2中的(a)所示)。未改性纳米纤维素晶体在3370cm -1处出现了O-H的伸缩振动吸收峰，在2905cm -1上出现了-CH 2伸缩与反伸缩振动吸收峰，在1055cm -1和1640cm -1处分别出现了C-O和C＝O的伸缩振动峰，在1370cm -1出现的是C-H的弯曲振动峰以及890cm -1处是O-H纤维素糖苷键伸缩振动峰。3370cm -1和890cm -1出现较强的-OH吸收峰，说明纳米纤维素晶体含有大量的羟基，这与图1中的(a)所测的接触角结果相吻合。 A Fourier infrared spectrometer was used to test the FTIR spectrum of the unmodified nanocellulose crystals (shown in (a) in Figure 2). Unmodified cellulose nano crystals appeared OH stretching vibration absorption peak at 3370cm -1, appeared on 2905cm -1 -CH 2 and anti-telescoping stretching vibration absorption peak appears at 1055cm -1 and 1640cm -1, respectively, CO and C = O stretching vibration of 1370 cm -1 is occurring in CH bending vibration peak of the cellulose glycosidic bonds and OH stretching vibration peak at 890cm -1 yes. 3370cm -1 and 890cm -1 is relatively strong absorption peak -OH, described nanocellulose crystals containing a large amount of hydroxyl groups, which is consistent with the results of the contact angle (a) measured in FIG.
将本对比例提供的未改性的纳米纤维素晶体分散到水中作为水相，其中，以未改性的纳米纤维素晶体与水的总质量计，未改性的纳米纤维素晶体的浓度为0.5wt％；以十六烷作为有机相；以水相与有机相的体积比2:1制备Pickering乳液，具体为将水相与有机相混合均匀后超声处理1分钟，然后静置观察乳状液形成情况。发现没有乳液形成(如图3A所示)。Disperse the unmodified nanocellulose crystals provided in this comparative example into water as an aqueous phase, wherein, based on the total mass of unmodified nanocellulose crystals and water, the concentration of unmodified nanocellulose crystals is 0.5wt%; hexadecane is used as the organic phase; Pickering emulsion is prepared with the volume ratio of the water phase and the organic phase 2:1. Specifically, the water phase and the organic phase are mixed uniformly and ultrasonically treated for 1 minute, and then the emulsion is left to observe Form the situation. No emulsion was found to form (as shown in Figure 3A).
对未改性的纳米纤维素晶体进行接触角测试(测试仪器：Krüss DSA100动态水接触角测量仪)。将未改性的纳米纤维素晶体均匀地铺在载玻片上，测试其对水的动态接触角，测试水滴体积为5微升。测试结果表明：当水滴接触到纳米纤维素晶体表面，水滴被迅速吸收，未改性的纳米纤维素晶体接触角为0°(如图1中的(a)所示)，亲性极高。The contact angle test of unmodified nano cellulose crystals (testing instrument: Krüss DSA100 dynamic water contact angle measuring instrument). The unmodified nano cellulose crystals were evenly spread on a glass slide, and the dynamic contact angle to water was tested. The volume of the test water droplet was 5 microliters. The test results show that when the water droplets touch the surface of the nanocellulose crystals, the water droplets are quickly absorbed, and the contact angle of the unmodified nanocellulose crystals is 0° (as shown in Figure 1 (a)), which has a very high affinity.

Claims (15)

  1. 一种改性纳米纤维素晶体，该改性纳米纤维素晶体为二异氰酸酯改性的纳米纤维素晶体，二异氰酸酯的两个-NCO基团分别与纳米纤维素表面的-OH发生反应通过-NH-COO-键连接至纳米纤维素表面；对纳米纤维素晶体进行改性使用的二异氰酸酯与纳米纤维素晶体的质量比为0.01:1-6:1。A modified nano cellulose crystal. The modified nano cellulose crystal is a diisocyanate modified nano cellulose crystal. The two -NCO groups of the diisocyanate react with -OH on the surface of the nano cellulose and pass -NH The -COO- bond is connected to the surface of the nanocellulose; the mass ratio of diisocyanate to nanocellulose crystals used for modifying the nanocellulose crystals is 0.01:1-6:1.
  2. 根据权利要求1所述的改性纳米纤维素晶体，其中，所述二异氰酸酯包括六亚甲基二异氰酸酯、2,2,4-三甲基六亚甲基二异氰酸酯、2,4,4-三甲基六亚甲基二异氰酸酯、4,4-二环己基甲烷二异氰酸酯中的至少一种。The modified nanocellulose crystals according to claim 1, wherein the diisocyanate comprises hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4- At least one of trimethylhexamethylene diisocyanate and 4,4-dicyclohexylmethane diisocyanate.
  3. 根据权利要求1所述的改性纳米纤维素晶体，其中，对纳米纤维素晶体进行改性使用的二异氰酸酯与纳米纤维素晶体的质量比为0.5:1-6:1。The modified nanocellulose crystals according to claim 1, wherein the mass ratio of the diisocyanate used for modifying the nanocellulose crystals to the nanocellulose crystals is 0.5:1 to 6:1.
  4. 根据权利要求1所述的改性纳米纤维素晶体，其中，对纳米纤维素晶体进行改性使用的二异氰酸酯与纳米纤维素晶体的质量比为0.5:1-3:1。The modified nanocellulose crystals according to claim 1, wherein the mass ratio of the diisocyanate used for modifying the nanocellulose crystals to the nanocellulose crystals is 0.5:1 to 3:1.
  5. 权利要求1-4任一项所述的改性纳米纤维素晶体的制备方法，其中，该制备方法包括：The preparation method of modified nanocellulose crystals according to any one of claims 1 to 4, wherein the preparation method comprises:
    将纳米纤维素晶体与部分有机溶剂混合后加入催化剂，在保护气体氛围下加入二异氰酸酯与剩余有机溶剂的混合液进行反应，得到所述改性纳米纤维素晶体。After mixing the nano cellulose crystals with part of the organic solvent, a catalyst is added, and a mixed solution of diisocyanate and the remaining organic solvent is added under a protective gas atmosphere for reaction to obtain the modified nano cellulose crystals.
  6. 根据权利要求5所述的制备方法，其中，所述催化剂为二月桂酸二丁基锡。The preparation method according to claim 5, wherein the catalyst is dibutyl tin dilaurate.
  7. 根据权利要求6所述的制备方法，其中，所述反应的温度为15-60℃。The preparation method according to claim 6, wherein the temperature of the reaction is 15-60°C.
  8. 根据权利要求7所述的制备方法，其中，所述反应的温度为25-50℃。The preparation method according to claim 7, wherein the temperature of the reaction is 25-50°C.
  9. 根据权利要求5所述的制备方法，其中，该制备方法包括：The preparation method according to claim 5, wherein the preparation method comprises:
    将纳米纤维素晶体与部分有机溶剂混合后加入二月桂酸二丁基锡，在保护气体氛围下加入二异氰酸酯与剩余有机溶剂的混合液并于常温下反应，得到所述改性纳米纤维素晶体。After mixing the nano cellulose crystals with a part of the organic solvent, adding dibutyl tin dilaurate, adding a mixture of diisocyanate and the remaining organic solvent under a protective gas atmosphere and reacting at room temperature to obtain the modified nano cellulose crystals.
  10. 根据权利要求5或9所述的制备方法，其中，二月桂酸二丁基锡与二异氰酸酯的质量比为0.1:1-5:1。The preparation method according to claim 5 or 9, wherein the mass ratio of dibutyltin dilaurate to diisocyanate is 0.1:1 to 5:1.
  11. 根据权利要求10所述的制备方法，其中，二月桂酸二丁基锡与异氰酸酯的质量比为0.5:1-2:1。The preparation method according to claim 10, wherein the mass ratio of dibutyltin dilaurate to isocyanate is 0.5:1 to 2:1.
  12. 根据权利要求5或9所述的制备方法，其中，有机溶剂与纳米纤维素晶体的质量比为100:1-200:1。The preparation method according to claim 5 or 9, wherein the mass ratio of the organic solvent to the nanocellulose crystals is 100:1-200:1.
  13. 根据权利要求5或9所述的制备方法，其中，所述有机溶剂包括四氢呋喃和丙酮中的至少一种。The preparation method according to claim 5 or 9, wherein the organic solvent includes at least one of tetrahydrofuran and acetone.
  14. 根据权利要求5或9所述的制备方法，其中，所述反应的时间为1-24h。The preparation method according to claim 5 or 9, wherein the reaction time is 1-24 h.
  15. 根据权利要求5或9所述的制备方法，其中，所述保护气体为氮气。The preparation method according to claim 5 or 9, wherein the protective gas is nitrogen.
PCT/CN2020/121793 2019-10-24 2020-10-19 Modified nanocrystalline cellulose and preparation method thereof WO2021078086A1 (en)

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