CN113861495A - In situ grafted PDMS highly elastic superhydrophobic hybrid aerogel and preparation method thereof - Google Patents
In situ grafted PDMS highly elastic superhydrophobic hybrid aerogel and preparation method thereof Download PDFInfo
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
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- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/048—Elimination of a frozen liquid phase
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Abstract
本发明公开了一种原位接枝PDMS高弹超疏水杂化气凝胶，以重量百分比计，包括如下组份：0.2～1.2wt％的纤维素分散液，1～2wt％的交联剂，0.2～1.0wt％的低表面能聚合物、以及0.02～0.1wt％的光固化剂。该发明基于化学键合原位接枝低表面能聚合物的原理及紫外光引发快速固化机制，制备了紫外固化原位接枝PDMS高弹超疏水杂化气凝胶，具有轻质、高弹、超疏水及结构稳定的特性，工艺简单、用时短、易于产业化大规模制备。
The invention discloses an in-situ grafted PDMS high-elasticity super-hydrophobic hybrid aerogel, which comprises the following components in weight percentage: 0.2-1.2 wt % of cellulose dispersion, 1-2 wt % of cross-linking agent , 0.2-1.0wt% of low surface energy polymer, and 0.02-0.1wt% of photocuring agent. Based on the principle of chemical bonding in-situ grafting of low surface energy polymers and the UV-induced rapid curing mechanism, the invention prepares UV-curing in-situ grafted PDMS high-elasticity superhydrophobic hybrid aerogels, which have the advantages of light weight, high elasticity, With the characteristics of superhydrophobicity and stable structure, the process is simple, the time is short, and it is easy to industrialize large-scale preparation.
Description
Technical Field
The invention relates to the technical field of aerogel, in particular to an in-situ grafted PDMS high-elastic super-hydrophobic hybrid aerogel and a preparation method thereof.
Background
The problems of fossil energy shortage and environmental pollution are becoming serious day by day, and renewable and sustainable materials become an effective solution. Cellulose is a natural renewable high polymer which is most abundant and widely distributed in nature, and has the characteristics of wide source, high strength, large length-diameter ratio and the like. The cellulose-based aerogel is prepared by taking cellulose as a raw material, is combined with the characteristics of light weight and adjustable three-dimensional network structure of the aerogel, and is widely applied to the fields of heat insulation, oil absorption and the like. However, cellulose has strong hydrophilicity, which causes the cellulose-based aerogel to absorb moisture easily, and the aerogel has disadvantages of large brittleness, poor mechanical properties, and the like, thereby limiting the application of the cellulose aerogel. Water molecules widely exist in nature, and no matter the water molecules are used in the fields of cold protection and warm keeping or oil absorption, the hydrophobic modification of the aerogel becomes a hotspot of current aerogel application research and a difficult problem to be solved urgently.
Chinese patent CN201610311152.2 discloses a super-hydrophobic silica aerogel micro powder, a preparation method and application thereof, wherein a low surface tension organic solvent, a hydrophobic modifier and a silicon source are mixed to prepare the super-hydrophobic aerogel micro powder, the super-hydrophobic characteristic is realized by coating the micro powder on the surface of the bacterial cellulose aerogel, although the hydrophobic property of the bacterial cellulose aerogel is improved, the process flow is complex, the binding force between the hydrophobic micro powder and the aerogel is hydrogen bond combination, and the uniform coating and the structural stability have certain limitations.
Chinese patent CN201710264349.X discloses a super-hydrophobic composite carbon aerogel oil absorption material and a preparation method thereof, wherein carbon aerogel is soaked in a dimethylformamide solution, trichloroacetyl chloride is added to obtain initiator composite carbon aerogel, the composite carbon aerogel is dissolved in dimethylformamide again, then a monomer and a catalytic system are added, after reaction, a graft polymer is prepared by suction filtration, washing and vacuum drying, and the method grafts a low surface tension polymer on a carbon aerogel substrate, but the process flow is long, 5 hours under a nitrogen atmosphere are needed, continuous washing and vacuum drying are needed, and a large amount of DMF and other organic solvents are used in the modification process.
Chinese patent CN201510066395.X discloses a super-hydrophobic MTMS/graphite oxide composite aerogel and a preparation method thereof, wherein an MTMS silane hydrophobic modifier is added into graphene dispersion liquid, and after the mixture is subjected to a closed reaction at 130-180 ℃ for 2-5h, the super-hydrophobic aerogel is obtained through vacuum drying.
Chinese patent CN202010085546.7 discloses an intrinsic super-hydrophobic nano-cellulose aerogel and a preparation method thereof, wherein nano-cellulose fiber dispersion liquid is used as a precursor, ice crystals are used as a template, the nucleation and growth speed and direction of the ice crystals are regulated and controlled by changing temperature gradient, the ice template is removed by freeze drying to prepare a three-dimensional ordered nano-cellulose aerogel material, and the super-hydrophobic aerogel with a low surface energy polymer/micro-nano coarse structure is constructed by adding polydimethylsiloxane and micron/nano titanium dioxide particles; the bonding force between the low surface energy polymer and the aerogel in the patent is a hydrogen bond, the bonding force between the coating and the substrate is weak, the resilience of the aerogel is 80.6% at most, the hydrophobic angle is 148% at most, and although the hydrophobicity and the physical properties are improved to a certain extent, the improvement on the properties is still limited.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the cellulose-based aerogel has poor structural stability and is easy to absorb moisture, the further application of the cellulose-based aerogel is limited, the existing aerogel hydrophobic modification process flow is complex, a large amount of organic solvents are used, the improvement on the mechanical property of a cellulose aerogel matrix is limited, and the like. The invention provides an in-situ grafted PDMS high-elastic super-hydrophobic hybrid aerogel and a preparation method thereof.
In order to achieve the purpose, the invention provides the following technical scheme: the in-situ grafted PDMS high-elastic super-hydrophobic hybrid aerogel comprises the following components in percentage by weight:
0.2 to 1.2 wt% of cellulose dispersion, 1 to 2 wt% of cross-linking agent, 0.2 to 1.0 wt% of low surface energy polymer, and 0.02 to 0.1 wt% of light curing agent.
Preferably, the cellulose in the cellulose dispersion liquid includes microcrystalline cellulose, nanocellulose, and chitosan.
Preferably, the crosslinking agent comprises one or both of 3-mercaptopropyltrimethoxysilane and KH 571.
Preferably, the low surface energy polymer comprises polydimethylsiloxane.
Preferably, the light curing agent comprises at least one of 1173, ITX, 184/907/369, TPO, XBPO dibenzoyl, benzil derivative I-651, benzoin dimethyl ether, benzoin isopropyl ether, OXB-1 and OXB-2.
The preparation method of the in-situ grafted PDMS high-elastic super-hydrophobic hybrid aerogel comprises the following steps:
step 1), preparation of a three-dimensional ordered cellulose-based aerogel matrix:
adding a cross-linking agent into the cellulose dispersion liquid to obtain a cellulose-based precursor solution, and then performing oriented freezing and drying on the cellulose-based precursor solution to obtain a three-dimensional ordered cellulose-based aerogel matrix;
step 2), preparation of low surface energy polymer modified solution:
dissolving a low surface energy polymer and a light curing agent in a polar solvent, and performing ultrasonic dispersion to form a low surface energy polymer modified solution;
step 3), ultraviolet light rapid curing:
soaking the three-dimensional ordered cellulose base aerogel matrix in the step 1) in the low surface energy polymer modification solution in the step 2), initiating in-situ grafting of the low surface energy polymer on the three-dimensional ordered cellulose base aerogel matrix through UV ultraviolet, and curing to prepare the high-elastic super-hydrophobic cellulose hybrid aerogel.
Preferably, in the step 1), liquid nitrogen is used as a cold source for the oriented freezing, and the oriented freezing is performed by an ice template method; the drying is freeze drying, and the drying time is 24-48 h.
Preferably, in step 2), the polar solvent includes at least one of n-hexane, cyclohexane and acetone.
Preferably, in step 2), the ultrasonic dispersion time is 10-30 min.
Preferably, in the step 3), the curing mode is ultraviolet curing, the curing time is 20-40 s, and the distance is 8-15 cm; chemical bonding is formed between the cellulose aerogel matrix and the PDMS.
The invention prepares the ultraviolet-cured in-situ grafted PDMS high-elastic super-hydrophobic hybrid aerogel based on the principle of chemically bonding in-situ grafted low-surface-energy polymers and an ultraviolet-initiated rapid curing mechanism, has the characteristics of light weight, high elasticity, super hydrophobicity and stable structure, and is simple in process, short in time consumption and easy for industrial large-scale preparation.
Compared with the prior art, the invention has the beneficial effects that:
the N-N-methylene bisacrylamide cross-linking agent in the Chinese patent CN202010085546.7 is only used for cross-linking between nano-celluloses and is used for connecting the nano-celluloses to form a network structure, so that the strength of the nano-cellulose aerogel matrix is improved. Subsequently, the nanocellulose aerogel is soaked in the low surface energy polymer, and after the PDMS is deposited on the nanocellulose substrate, the ultraviolet curing only acts on the low surface energy polymer to enable the low surface energy polymer to be cured to form a coating. Therefore, only hydrogen bond attraction exists at the interface between the substrate and the coating, and the interface bonding force is small.
According to the invention, 3-mercaptopropyl trimethoxy silane is added into nano dispersion liquid, and the cross-linking agent reacts with hydroxyl in nano cellulose to form S-H bonds to provide grafting sites; and then, soaking the nano-cellulose aerogel in a low-surface-energy polymer, depositing PDMS on a nano-cellulose substrate, wherein S-H on the nano-cellulose substrate and-C ═ C bond on the PDMS undergo a sulfydryl reaction through an ultraviolet light initiation mechanism, so that a chemical bonding is formed between the substrate and the coating, and an interlocking interface with strong interface bonding force is formed. Finally, the chemical bonding improves the structural stability of the hybrid aerogel, and the mechanical property of the hybrid aerogel is greatly improved.
According to the invention, an in-situ grafting chemical bonding mode is adopted, the low-surface-energy PDMS is in-situ grafted on the cellulose aerogel matrix through ultraviolet rapid curing, and chemical bonding is formed between the matrix and the polymer, so that the structural stability and the hydrophobic performance of the hybrid aerogel are greatly improved. Meanwhile, the time consumption of the ultraviolet curing process is short, the process is simple, and the large-scale production is easy to realize; the prepared aerogel material has the advantages of small density, high porosity, low thermal conductivity, compression recovery performance, good flexibility and excellent hydrophobic durability. Test analysis results show that under the compression rate of 80%, the recovery rate of the cellulose-based aerogel is 77.6%, and after PDMS deposition modification, the compression rebound rate of the high-elasticity super-hydrophobic aerogel reaches 95.9%. Compared with the existing super-hydrophobic coating technology, the integrated high-elasticity hydrophobic material prepared by using the low-surface-energy polymer and the ultraviolet curing process has the hydrophobic angle as high as 168 degrees, and belongs to a super-hydrophobic material. The process is less in time consumption, and the material is high in elasticity and hydrophobic and has better hydrophobic durability.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of hybrid aerogel materials prepared in comparative example 1 and examples 1-5;
FIG. 2 is a contact angle image of hybrid aerogel materials prepared according to examples 1-5;
FIG. 3 is a graph comparing the compression resiliency of hybrid aerogels prepared in comparative example 1 and examples 1-5.
Detailed Description
The invention is further described with reference to the accompanying drawings.
The embodiment discloses an in-situ grafted PDMS high-elastic super-hydrophobic hybrid aerogel, which comprises the following components in percentage by weight: 0.2 to 1.2 wt% of cellulose dispersion, 1 to 2 wt% of cross-linking agent, 0.2 to 1.0 wt% of low surface energy polymer, and 0.02 to 0.1 wt% of light curing agent. Wherein the cellulose in the cellulose dispersion liquid comprises microcrystalline cellulose, nano-cellulose and chitosan, and the solvent is distilled water; the cross-linking agent comprises one or two of 3-mercaptopropyltrimethoxysilane and KH 571; the low surface energy polymer includes polydimethylsiloxane; the light curing agent comprises at least one of 1173, ITX, 184/907/369, TPO, XBPO bibenzoyl, benzil derivatives I-651, benzoin dimethyl ether, benzoin isopropyl ether, OXB-1 and OXB-2.
The preparation method of the in-situ grafted PDMS high-elastic super-hydrophobic hybrid aerogel comprises the following steps:
step 1), preparation of a three-dimensional ordered cellulose-based aerogel matrix:
adding a cross-linking agent for providing in-situ grafting sites into the cellulose dispersion to obtain a cellulose-based precursor solution, and then performing oriented freezing and drying on the cellulose-based precursor solution to obtain a three-dimensional ordered cellulose-based aerogel matrix; wherein, the orientation freezing adopts liquid nitrogen as a cold source, and the orientation freezing is carried out by an ice template method; the drying is freeze drying, and the drying time is 24-48 h;
step 2), preparation of low surface energy polymer modified solution:
dissolving a low surface energy polymer and a light curing agent in a polar solvent, and performing ultrasonic dispersion to form a low surface energy polymer modified solution; wherein the polar solvent comprises at least one of n-hexane, cyclohexane and acetone, and the ultrasonic dispersion time is 10-30 min;
step 3), ultraviolet light rapid curing:
dipping the three-dimensional ordered cellulose base aerogel matrix in the step 1) into the low surface energy polymer modification solution in the step 2), initiating in-situ grafting of a low surface energy polymer on the three-dimensional ordered cellulose base aerogel matrix through UV ultraviolet, and curing to prepare the high-elastic super-hydrophobic cellulose hybrid aerogel; wherein the curing mode is ultraviolet curing, the curing time is 20-40 s, and the distance is 8-15 cm; preferably, the curing time is 30s and the irradiation distance is 10 cm.
According to the invention, an in-situ grafting chemical bonding mode is adopted, the low-surface-energy PDMS is in-situ grafted on the cellulose aerogel matrix through ultraviolet rapid curing, and chemical bonding is formed between the matrix and the polymer, so that the structural stability and the hydrophobic performance of the hybrid aerogel are greatly improved. Meanwhile, the time consumption of the ultraviolet curing process is short, the process is simple, and the large-scale production is easy to realize; the prepared aerogel material has the advantages of small density, low thermal conductivity, compression recovery performance, good flexibility, integration of waterproof and moisture-permeable performances and excellent hydrophobic durability. The nano-cellulose aerogel prepared by the invention has excellent hydrophobic property, and can be applied to the fields of heat preservation, cold protection, oil absorption and the like.
The prior art and the cellulose-based aerogel hydrophobic modification process and performance parameters of the present invention are shown in table 1 below:
TABLE 1 cellulose-based aerogel hydrophobic modification Process and comparison of Performance parameters
The specific embodiment is as follows:
the nanocellulose used in the following examples was produced by the biotechnology limited for producing xylogen, Tianjin; polydimethylsiloxane (PDMS), cyclohexane and 3-mercaptopropyltrimethoxysilane are produced by chemical reagents of national medicine group limited; 2-hydroxy-2-methyl propiophenone (a light curing agent 1173) is produced by Roen reagent manufactured by Erien scientific and technological development Inc., Shanghai province; the ultrasonic homogeneous disperser is produced by IKA laboratory technology Co., Ltd, T25Ultra-turrax type; the electronic balance is produced by Shanghai Shunhui scientific instruments, Inc., FA2004 type; an Ultraviolet (UV) point light source curing machine is produced by Er Gu photoelectricity technology Co., Ltd, Dongguan, model H34-365.
Comparative example 1:
preparing 100mL of 1 wt.% nano-cellulose dispersion, and mechanically stirring for 5min to obtain a uniform precursor solution; performing oriented freezing on the precursor solution until the precursor solution is completely frozen; and (5) carrying out freeze drying for 48 hours to obtain the nano cellulose aerogel. As shown in a of fig. 1, the aerogel has a porous structure, and as shown in fig. 3, at a compression rate of 80%, the compression rebound rate is 77.6%, the hydrophobic angle is 0 °, and the porosity is 97.64%.
Example 1:
(1) preparing 100mL of 1 wt.% nanocellulose dispersion, adding 0.05g of 3-mercaptopropyl trimethoxy silane cross-linking agent, and mechanically stirring for 5min to obtain a uniform precursor solution; performing oriented freezing on the precursor solution until the precursor solution is completely frozen; and (5) carrying out freeze drying for 48 hours to obtain the nano cellulose aerogel.
(2) 0.2g of Polydimethylsiloxane (PDMS) was dissolved in 100mL of cyclohexane to prepare a 0.2 wt% low surface energy polymer solution, and 0.08g of a light curing agent 1173 was added thereto and subjected to ultrasonic dispersion (100W, 40kHz) for 30min to prepare a uniform low surface energy polymer dispersion.
(3) Soaking the nano cellulose aerogel (1) in the dispersion liquid (2), ultrasonically dispersing, and performing ultrasonic dispersion on the nano cellulose aerogel with the wavelength of 365nm and the intensity of 220mW/cm2And (5) ultraviolet curing for 10s to prepare the high-elasticity super-hydrophobic nano cellulose aerogel. As shown in fig. 1, panel b, the aerogel exhibited a porous honeycomb structure, as shown in fig. 2, a hydrophobic angle of 133.6 °, as shown in fig. 3, a compression rebound of 82.1% at 80% compression, and a porosity of 97.59%.
Example 2:
(1) preparing 100mL of 1 wt.% nanocellulose dispersion, adding 0.1g of KH571 cross-linking agent, and mechanically stirring for 5min to obtain a uniform precursor solution; performing oriented freezing on the precursor solution until the precursor solution is completely frozen; and (5) freeze-drying for 48 hours to obtain the nano-cellulose aerogel.
(2) 0.4g of Polydimethylsiloxane (PDMS) was dissolved in 100mL of cyclohexane to prepare a 0.4 wt% low surface energy polymer solution, and 0.08g of light curing agent TPO was added thereto and ultrasonically dispersed (100W, 40kHz) for 30min to prepare a uniform low surface energy polymer dispersion.
(3) Soaking the nano cellulose aerogel (1) in the dispersion liquid (2), carrying out vacuum filtration, and carrying out 365nm wavelength vacuum filtration to obtain the nano cellulose aerogel with the intensity of 220mW/cm2And (4) ultraviolet curing for 10s, and evaporating the solvent to prepare the high-elasticity super-hydrophobic nano cellulose aerogel. As shown in the graph c in FIG. 1, the porous structure of the aerogel is regular, and as shown in FIG. 2, the hydrophobic angle is148.2 deg., as shown in fig. 3, at 80% compression, the compression rebound was 89.6%, and the porosity was 98.13%.
Example 3:
(1) preparing 100mL of 1 wt.% nanocellulose dispersion, adding 0.15g of 3-mercaptopropyl trimethoxy silane cross-linking agent, and mechanically stirring for 5min to obtain a uniform precursor solution; performing oriented freezing on the precursor solution until the precursor solution is completely frozen; and (5) freeze-drying for 48 hours to obtain the nano-cellulose aerogel.
(2) 0.6g of Polydimethylsiloxane (PDMS) is dissolved in 100mL of acetone to prepare a low surface energy polymer solution with the concentration of 0.6 wt%, 0.08g of light curing agent benzil derivative I-651 is added, and ultrasonic dispersion (100W, 40kHz) is carried out for 30min to prepare a uniform low surface energy polymer dispersion liquid.
(3) Soaking the nano cellulose aerogel (1) in the dispersion liquid (2), carrying out vacuum filtration, and carrying out 365nm wavelength vacuum filtration to obtain the nano cellulose aerogel with the intensity of 220mW/cm2And (5) ultraviolet curing for 20s to prepare the high-elasticity super-hydrophobic nano cellulose aerogel. As shown in fig. 1, d, the aerogel had a three-dimensional porous structure with a reduced pore size, as shown in fig. 2, a hydrophobic angle of 156.8 °, as shown in fig. 3, a compression rebound of 94.3% at 80% compression, and a porosity of 97.96%.
Example 4:
(1) preparing 100mL of 1 wt.% nanocellulose dispersion, adding 0.2gKH571 cross-linking agent, and mechanically stirring for 5min to obtain a uniform precursor solution; performing oriented freezing on the precursor solution until the precursor solution is completely frozen; and (5) freeze-drying for 48 hours to obtain the nano-cellulose aerogel.
(2) 0.8g of Polydimethylsiloxane (PDMS) is dissolved in 100mL of cyclohexane to prepare a low surface energy polymer solution with the concentration of 0.8 wt%, 0.08g of light curing agent benzoin isopropyl ether is added, and ultrasonic dispersion (100W, 40kHz) is carried out for 30min to prepare a uniform low surface energy polymer dispersion liquid.
(3) Soaking the nano cellulose aerogel (1) in the dispersion liquid (2), carrying out vacuum filtration, and carrying out 365nm wavelength vacuum filtration to obtain the nano cellulose aerogel with the intensity of 220mW/cm2Ultraviolet light curing for 30s to prepare high-elastic super-hydrophobic nano-cellulose gasAnd (4) gelling. As shown in fig. 1, e, the aerogel porous structure was broken, the amount of PDMS attached was increased, as shown in fig. 2, the hydrophobic angle was 168.4 °, as shown in fig. 3, the compression spring rate was 98.7% and the porosity was 96.85% at 80% compression rate,
example 5:
(1) preparing 100mL of 1 wt.% nanocellulose dispersion, adding 0.25g of 3-mercaptopropyl trimethoxy silane cross-linking agent, and mechanically stirring for 5min to obtain a uniform precursor solution; performing oriented freezing on the precursor solution until the precursor solution is completely frozen; and (5) freeze-drying for 48 hours to obtain the nano-cellulose aerogel.
(2) 1g of Polydimethylsiloxane (PDMS) is dissolved in 100mL of n-hexane to prepare a low surface energy polymer solution with the concentration of 1.0 wt%, 0.08g of light curing agent OXB-2 is added, and ultrasonic dispersion (100W, 40kHz) is carried out for 30min to prepare a uniform low surface energy polymer dispersion liquid.
(3) Soaking the nano cellulose aerogel (1) in the dispersion liquid (2), carrying out vacuum filtration, and carrying out 365nm wavelength vacuum filtration to obtain the nano cellulose aerogel with the intensity of 220mW/cm2And (5) ultraviolet curing for 30s to prepare the high-elasticity super-hydrophobic nano cellulose aerogel. As shown in fig. 1, f shows that the porous structure of the aerogel is seriously damaged, and the modified aerogel takes the shape of a film, as shown in fig. 2, the hydrophobic angle is 165.8 °, as shown in fig. 3, the compression rebound rate is 99.96% and the porosity is 95.87% at a compression rate of 80%.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention, and are considered to be within the scope of the invention.
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