CN115449120A - Preparation method of flame-retardant and heat-insulating sea squirt nano cellulose-based aerogel - Google Patents

Preparation method of flame-retardant and heat-insulating sea squirt nano cellulose-based aerogel Download PDF

Info

Publication number
CN115449120A
CN115449120A CN202211005483.5A CN202211005483A CN115449120A CN 115449120 A CN115449120 A CN 115449120A CN 202211005483 A CN202211005483 A CN 202211005483A CN 115449120 A CN115449120 A CN 115449120A
Authority
CN
China
Prior art keywords
tcncs
based aerogel
sea squirt
suspension
neutral
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202211005483.5A
Other languages
Chinese (zh)
Inventor
黄方
林伟杰
宁登文
邹秋霞
武帅
徐德忠
成雅楠
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujian Agriculture and Forestry University
Original Assignee
Fujian Agriculture and Forestry University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fujian Agriculture and Forestry University filed Critical Fujian Agriculture and Forestry University
Priority to CN202211005483.5A priority Critical patent/CN115449120A/en
Publication of CN115449120A publication Critical patent/CN115449120A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/02—Foams characterised by their properties the finished foam itself being a gel or a gel being temporarily formed when processing the foamable composition
    • C08J2205/026—Aerogel, i.e. a supercritically dried gel
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2301/02—Cellulose; Modified cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/07—Aldehydes; Ketones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/26—Silicon- containing compounds

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)

Abstract

The invention provides a preparation method of flame-retardant and heat-insulating sea squirt nano cellulose-based aerogel, belonging to the field of application of environment-friendly materials and preparation of aerogel. According to the method, TCNCs are used as precursors, sepiolite (SP) clay and Graphene Oxide (GO) are added for crosslinking, and then the sea squirt nanocellulose-based aerogel is prepared through freeze drying. According to the invention, TCNCs which are wide in source, natural, renewable and biodegradable are used as precursors, SP nano clay which is low in price, non-toxic and harmless and carbon material GO which is excellent in performance are used for preparing the sea squirt nano cellulose-based aerogel composite material. The preparation process is simple, easy to enlarge production and has obvious ecological and environmental protection benefits. The prepared sea squirt nano cellulose-based aerogel has excellent biocompatibility, high porosity, high specific surface area, low thermal conductivity and good flame retardant and heat insulation effects. The invention widens the application of TCNCs in the field of biomass flame-retardant materials.

Description

Preparation method of flame-retardant and heat-insulating sea squirt nano cellulose-based aerogel
Technical Field
The invention relates to the field of application of environment-friendly materials and preparation of aerogel, in particular to preparation of sea squirt nano cellulose-based aerogel with flame retardant and heat insulation properties.
Background
The nano-cellulose has a great amount of demands in the industries of medical bionic materials and biosensors, but the traditional nano-cellulose is obtained by a hydrolysis method of inorganic acid, organic acid and cellulose, or is prepared by physical and biological methods such as a high-pressure homogenizer, a grinder and the like, and the finally obtained nano-cellulose product generally has the length of about 1-100nm, the length-diameter ratio of only 10-15, low crystallinity, complexity and instability.
Cellulose in nature is widely available, mainly from natural plants, bacteria, algae or animals, wherein the cellulose of the animals is rarely available, and only exists in sea animals of sea squirts with tunicates. The name of the 'tunica capsulata' is derived from a unique epidermal tissue 'tunica capsulata', the tunica capsulata covers the whole epidermal tissue of the marine animals, is a thick and tough shell, the tunica capsulata is a main source of animal cellulose, the tunica capsulata is wrapped by the tough epidermal tissue and can play a role of a good skeleton structure, and the cellulose in the tunica capsulata is synthesized by the marine organisms by using a biomass enzyme complex in the epidermis. The sea squirt nano-cellulose (TCNCs) is derived from epidermal tissues in marine animal tunic, has the advantages of clean components, natural reproducibility, no toxicity, biodegradability and the like, and is a potential raw material for preparing medical bionic materials, optical materials, reinforced composite materials, template materials and biosensors. And the nanocellulose generated by the sea squirt tunic has wide length distribution, the length-diameter ratio of the nanocellulose between 500nm and 2 mu m is about more than 75, the Young modulus is as high as 143GPa, and the nanocellulose has good mechanical properties such as biocompatibility, high crystallinity and the like. Based on the advantages of TCNCs, in recent years, the preparation of various composite materials with excellent properties from TCNCs has become one of the research hotspots with potential application value. TCNCs extracted from sea squirt biological tunic have strong toughness and high porosity, thus providing large skeleton structure for preparing composite material.
At present, the pure aerogel prepared by taking TCNCs as raw materials has the disadvantages of poor mechanical property, low porosity, poor heat conductivity, easy combustion characteristic and the like. In order to avoid the combustion of the material in the transportation process, organic or inorganic flame retardant is required to be added for safe transportation, and the traditional flame retardant material plays a role due to the excellent fire extinguishing performance. However, the traditional organic/inorganic aerogel preparation process is complex, and the defects of high equipment requirement, more added materials, high energy consumption and the like exist, so that the production cost is high, and the scale-up production and application of the sea squirt nano cellulose-based aerogel material field are severely limited.
According to the invention, the large skeleton structure of TCNCs is used as a precursor, sepiolite clay (SP) and Graphene Oxide (GO) are added, and the sea squirt nano cellulose-based aerogel with flame retardant and heat insulation properties is prepared by a freeze drying technology, so that the application prospect of TCNCs in the field of biomass materials is further expanded.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of flame-retardant and heat-insulating sea squirt nano cellulose-based aerogel.
The invention is realized by the following steps:
the invention firstly provides a preparation method of flame-retardant and heat-insulating sea squirt nano cellulose-based aerogel, which comprises the steps of adding sepiolite clay (SP) and Graphene Oxide (GO) for crosslinking by taking TCNCs as precursors, and then preparing the sea squirt nano cellulose-based aerogel through freeze drying.
The cross-linking agent adopted for cross-linking is glutaraldehyde.
The invention specifically comprises the following steps:
(1) Cleaning the sea squirt tunic, soaking in an alkali solution for 8-12h, and washing the tunic to be neutral by using deionized water;
(2) Bleaching the neutral tunic obtained in the step (1) with bleaching liquid for 6-10h, replacing fresh bleaching liquid every 2h, and thoroughly washing with deionized water to be neutral to obtain ascidian cellulose;
(3) Hydrolyzing the ascidian cellulose in the step (2) with acid to prepare TCNCs, adding excessive deionized water to stop reaction, centrifuging, and dialyzing with deionized water until the pH value of the solution becomes neutral to finally obtain TCNCs;
(4) Dispersing the TCNCs in the step (3) into a CNC suspension, adjusting the pH value of the CNC suspension to be neutral, and mixing the TCNCs suspension with SP, GO and glutaraldehyde to form a mixed suspension;
(5) Performing ultrasonic treatment and degassing on the mixed suspension liquid in the step (4);
(6) And (4) freezing and drying the mixture obtained in the step (5) to prepare the TCNCs/SP/GO aerogel with flame retardant and heat insulation properties.
Further:
the concentration of the alkali solution in the step (1) is 5-10wt%.
The bleaching solution in the step (2) is obtained by dissolving 5-10g of sodium chlorite and 5-10ml of glacial acetic acid in 300-500ml of deionized water, and the bleaching temperature is 40-70 ℃.
Step (3) the acid hydrolysis is carried out by using 64% H 2 SO 4 And continuously heating and stirring at 40-65 ℃.
Mixing the suspension of step (4) with 1-10wt% TCNCs, 10-30wt% SP, 1-10wt% GO and 1-10wt% glutaraldehyde.
And (4) mixing the TCNCs suspension with SP, GO and glutaraldehyde in a cylindrical sample bottle.
And (5) carrying out ultrasonic treatment on the mixed suspension for 30-55min.
And (5) degassing and standing the mixed suspension for 5-30min.
The invention also provides the flame-retardant and heat-insulating sea squirt nano cellulose-based aerogel prepared by the preparation method.
The invention has the following advantages: according to the invention, TCNCs which are wide in source, natural, renewable and biodegradable are used as precursors, SP nano clay which is low in price, non-toxic and harmless and carbon material GO which is excellent in performance are used for preparing the sea squirt nano cellulose-based aerogel composite material. The composite material is prepared by utilizing a simple freeze drying technology, the technology is simple to operate, the cost is low, the framework structure is kept relatively complete, the aerogel prepared by the technology is green, renewable, non-toxic and pollution-free, and has biodegradability, the process preparation flow is simple and convenient, the large-scale production is easy, and the obvious ecological and environment-friendly benefits are achieved. The prepared sea squirt nano cellulose-based aerogel has excellent biocompatibility, high porosity, high specific surface area, low thermal conductivity and good flame retardant and heat insulation effects. The invention expands the application of TCNCs in the field of biomass flame-retardant materials.
Drawings
The invention will be further described with reference to the following examples and figures.
FIG. 1 is a TG curve (L) for different aerogels; DTG curves (R) for different aerogels.
FIG. 2 is an XRD plot (L) of different aerogels; crystallinity index (R) of different aerogels.
FIG. 3 is a photograph (L) of a pure aerogel (C) and a composite aerogel (CSG 1, CSG 10) in a flammability test; photograph (R) in combustion test of ethanol-soaked composite aerogel (CSG 10).
Detailed Description
Example 1
(1) After the sea squirt tunic is treated, the sea squirt tunic is placed in 5wt% of alkali solution (potassium hydroxide) for 12 hours at room temperature, and then the sea squirt tunic is washed by deionized water to be neutral;
(2) And (2) heating and bleaching the neutral quilt bag in the step (1) for 10 hours by using bleaching liquid, wherein the heating temperature is 40 ℃, and replacing fresh bleaching liquid every 2 hours. After the color of the tunica becomes white, thoroughly washing the tunica vaginalis by deionized water to be neutral to obtain ascidian cellulose;
(3) Preparing TCNCs by acid hydrolysis of the sea squirt cellulose described in step (2), weighing 10g of TCNCs, adding 362ml of 64% H 2 SO 4 The mixture is continuously heated and stirred for 2 hours at the temperature of 40 ℃. Adding excessive deionized water to terminate the reaction, centrifuging at 8000r/min for 30min, and collecting precipitate. Dialysis was then performed with deionized water until the solution pH became neutral. After dialysis, subjecting the obtained product to ultrasound for 30min to obtain TCNCs, and refrigerating in a refrigerator for later use;
(4) Preparing the TCNCs in the step (3) into 1% CNC suspension by using a high-speed disperser, adjusting the pH value to 7, and putting 5ml of the TCNCs suspension into a 10ml cylindrical sample bottle;
(5) Putting the mixed suspension in the step (4) into an ultrasonic cleaner, and carrying out ultrasonic treatment for 30min;
(6) Degassing and standing the mixture subjected to ultrasonic treatment in the step (5) for 5min;
(7) Placing the degassed sample bottles in the step (6) into a liquid nitrogen bath at-196 ℃, a refrigerator at-79 ℃ and a refrigerator at-4 ℃ in sequence for freeze forming;
(8) And (5) putting the sample pre-frozen in the step (7) into a freeze dryer for freeze drying to prepare the aerogel C.
Example 2
(1) After the sea squirt tunic is treated, the sea squirt tunic is placed in 6wt% alkali solution for about 11 hours at room temperature, and then the tunic is washed to be neutral by deionized water;
(2) Heating and bleaching the neutral tunic in the step (1) for 9h by using bleaching liquid, wherein the heating temperature is 50 ℃, replacing fresh bleaching liquid every 2h until the tunic becomes white, and thoroughly washing the tunic to be neutral by using deionized water to obtain sea squirt cellulose;
(3) Preparing TCNCs by acid hydrolysis of sea squirt cellulose as described in step (2), weighing 10g of TCNCs and adding 362ml of 64% H 2 SO 4 The mixture is continuously heated and stirred for 2 hours at the temperature of 45 ℃. Adding excessive deionized water to stop the reaction, and centrifuging for 30min at 8000r/minAnd collecting the precipitate. Dialysis was then performed with deionized water until the solution pH became neutral. After dialysis, subjecting the obtained product to ultrasound for 30min to obtain TCNCs, and refrigerating in a refrigerator for later use;
(4) Preparing the TCNCs in the step (3) into 1% CNC suspension by using a high-speed disperser, adjusting the pH value of the CNC suspension to be neutral, putting 5ml of the TCNCs suspension into a 10ml cylindrical sample bottle, adding SP and glutaraldehyde in a mass ratio of 10, and mixing together;
(5) And (4) putting the mixed suspension in the step (4) into an ultrasonic cleaner, and carrying out ultrasonic treatment for 35min.
(6) Degassing and standing the mixture subjected to ultrasonic treatment in the step (5) for 10min;
(7) Putting the sample bottle degassed in the step (6) into a liquid nitrogen bath at the temperature of-196 ℃, a refrigerator at the temperature of-79 ℃ and a refrigerator at the temperature of-4 ℃ in sequence for freeze forming;
(8) And (5) freeze-drying the sample pre-frozen in the step (7) to prepare aerogel CS.
Example 3
(1) After the sea squirt tunic is treated, the sea squirt tunic is placed in 7wt% alkali solution for about 10 hours at room temperature, and then the sea squirt tunic is washed by deionized water until the sea squirt tunic is neutral;
(2) Heating and bleaching the neutral quilt bag in the step (1) with bleaching liquid for 8 hours at 55 ℃, replacing fresh bleaching liquid every 2 hours until the quilt bag becomes white in color, and thoroughly washing the quilt bag with deionized water to be neutral to obtain sea squirt cellulose;
(3) Preparing TCNCs by acid hydrolysis of sea squirt cellulose as described in step (2), weighing 10g of TCNCs and adding 362ml of 64% H 2 SO 4 The mixture is continuously heated and stirred for 2 hours at the temperature of 50 ℃. Adding excessive deionized water to terminate the reaction, centrifuging at 8000r/min for 30min, and collecting precipitate. Dialysis was then performed with deionized water until the solution pH became neutral. After dialysis is finished, subjecting the obtained substance to ultrasound for 30min to finally obtain TCNCs, and placing the TCNCs in a beaker and a refrigerator for later use;
(4) Preparing the TCNCs in the step (3) into CNC suspension with the concentration of 3% by using a high-speed disperser, adjusting the pH value to be neutral, putting 5ml of the TCNCs suspension into a 10ml cylindrical sample bottle, adding SP, GO and glutaraldehyde (the GO content accounts for 1wt% of the suspension) in a mass ratio of 10;
(5) Putting the mixed suspension liquid in the step (4) into an ultrasonic cleaner, and carrying out ultrasonic treatment for 40min;
(6) Degassing and standing the mixture subjected to ultrasonic treatment in the step (5) for 15min;
(7) Placing the degassed sample bottles in the step (6) into a liquid nitrogen bath at-196 ℃, a refrigerator at-79 ℃ and a refrigerator at-4 ℃ in sequence for freeze forming;
(8) And (5) freeze-drying the sample pre-frozen in the step (7) to prepare aerogel CSG1.
Example 4
(1) After the sea squirt tunic is treated, the sea squirt tunic is placed in 8wt% alkali solution for about 9 hours at room temperature, and then the tunic is washed to be neutral by deionized water;
(2) Heating and bleaching the neutral tunic in the step (1) with bleaching liquid for 7h at 60 ℃, replacing fresh bleaching liquid every 2h until the tunic becomes white in color, and thoroughly washing the tunic with deionized water to be neutral to obtain sea squirt cellulose;
(3) Preparing TCNCs by acid hydrolysis of the sea squirt cellulose described in step (2), weighing 10g of TCNCs, adding 362ml of 64% H 2 SO 4 The mixture is continuously heated and stirred for 2 hours at the temperature of 55 ℃. Adding excessive deionized water to stop the reaction, centrifuging for 30min at 8000r/min, and collecting precipitate. Dialysis was then performed with deionized water until the solution pH became neutral. After dialysis, subjecting the obtained product to ultrasound for 30min to obtain TCNCs, and placing the TCNCs in a beaker and a refrigerator for later use;
(4) Preparing the TCNCs in the step (3) into 5% CNC suspension by using a high-speed disperser, adjusting the pH value of the CNC suspension to be neutral, putting 5ml of the CNC suspension into a 10ml cylindrical sample bottle, adding SP, GO and glutaraldehyde (GO content accounts for 3wt% of the suspension) in a mass ratio of 10;
(5) Putting the mixed suspension in the step (4) into an ultrasonic cleaner, and carrying out ultrasonic treatment for 45min;
(6) Degassing and standing the mixture subjected to ultrasonic treatment in the step (5) for 20min;
(7) Putting the sample bottle degassed in the step (6) into a liquid nitrogen bath at the temperature of-196 ℃, a refrigerator at the temperature of-79 ℃ and a refrigerator at the temperature of-4 ℃ in sequence for freeze forming;
(8) And (4) freeze-drying the sample pre-frozen in the step (7) to prepare aerogel CSG3.
Example 5
(1) After the sea squirt tunic is treated, the sea squirt tunic is placed in 9wt% alkali solution for about 8 hours at room temperature, and then the tunic is washed to be neutral by deionized water;
(2) Heating and bleaching the neutral tunic in the step (1) for 6 hours by using bleaching liquid, wherein the heating temperature is 70 ℃, replacing fresh bleaching liquid every 2 hours until the tunic is whitened in color, and then thoroughly washing the tunic to be neutral by using deionized water to obtain sea squirt cellulose;
(3) Preparing TCNCs by acid hydrolysis of the sea squirt cellulose described in step (2), weighing 10g of TCNCs, adding 362ml of 64% H 2 SO 4 Continuously heating and stirring for 2h at the temperature of 60 ℃. Adding excessive deionized water to stop the reaction, centrifuging for 30min at 8000r/min, and collecting precipitate. Dialysis was then performed with deionized water until the solution pH became neutral. After dialysis, subjecting the obtained product to ultrasound for 30min to obtain TCNCs, and placing the TCNCs in a beaker and a refrigerator for later use;
(4) Preparing the TCNCs in the step (3) into 7% CNC suspension by using a high-speed disperser, adjusting the pH value of the CNC suspension to be neutral, putting 5ml of the TCNCs suspension into a 10ml cylindrical sample bottle, adding SP, GO and glutaraldehyde (GO content accounts for 7wt% of the suspension) in a mass ratio of 10;
(5) Putting the mixed suspension in the step (4) into an ultrasonic cleaner, and carrying out ultrasonic treatment for 50min;
(6) Degassing and standing the mixture subjected to ultrasonic treatment in the step (5) for 25min;
(7) Putting the sample bottle degassed in the step (6) into a liquid nitrogen bath at the temperature of-196 ℃, a refrigerator at the temperature of-79 ℃ and a refrigerator at the temperature of-4 ℃ in sequence for freeze forming;
(8) And (4) freeze-drying the sample pre-frozen in the step (7) to prepare aerogel CSG7.
Example 6
(1) After the sea squirt tunic is treated, the sea squirt tunic is placed in 10wt% alkali solution for about 8 hours at room temperature, and then the tunic is washed to be neutral by deionized water;
(2) Heating and bleaching the neutral tunic in the step (1) for 7h by using bleaching liquid, wherein the heating temperature is 50 ℃, replacing fresh bleaching liquid every 2h until the tunic becomes white, and thoroughly washing the tunic to be neutral by using deionized water to obtain sea squirt cellulose;
(3) Preparing TCNCs by acid hydrolysis of the sea squirt cellulose described in step (2), weighing 10g of TCNCs, adding 362ml of 64% H 2 SO 4 Continuously heating and stirring for 2h at the temperature of 60 ℃. Adding excessive deionized water to stop the reaction, centrifuging for 30min at 8000r/min, and collecting precipitate. Dialysis was then performed with deionized water until the solution pH became neutral. After dialysis, subjecting the obtained product to ultrasound for 30min to obtain TCNCs, and placing the TCNCs in a beaker and a refrigerator for later use;
(4) Preparing the TCNCs in the step (3) into 10% CNC suspension by using a high-speed disperser, adjusting the pH value of the CNC suspension to be neutral, putting 5ml of the CNC suspension into a 10ml cylindrical sample bottle, adding SP, GO and glutaraldehyde (the GO content accounts for 10wt% of the suspension) in a mass ratio of 10;
(5) Putting the mixed suspension in the step (4) into an ultrasonic cleaner, and carrying out ultrasonic treatment for 55min;
(6) Degassing and standing the mixture subjected to ultrasonic treatment in the step (5) for 30min;
(7) Placing the degassed sample bottles in the step (6) into a liquid nitrogen bath at-196 ℃, a refrigerator at-79 ℃ and a refrigerator at-4 ℃ in sequence for freeze forming;
(8) And (4) freeze-drying the sample pre-frozen in the step (7) to prepare aerogel CSG10.
Example 7
Thermal stability of pure TCNCs aerogel (C), SP-added aerogel (CS), and composite TCNCs aerogels (CSG 1, CSG3, CSG7 and CSG 10) prepared with 1-10% GO were determined using a simultaneous thermal analyzer (fig. 1) using thermogravimetric analysis. As can be seen from FIG. 1, the thermal degradation temperatures of both the pure TCNCs aerogel (C) and the composite TCNCs aerogel occurred predominantly in the range of 200-400 ℃. The thermal weight loss at temperatures <150 ℃ is mainly the hydrolytic absorption process of the physical adsorption of cellulose. According to the TG curve, the initial thermal decomposition temperature of the pure aerogel (C) and the aerogel (CS) is 276 ℃, and the initial thermal decomposition temperatures of the CSG7 and the CSG10 are respectively about 220 ℃ and 210 ℃, so that the thermal decomposition of the aerogel is far lower than that of the pure aerogel and the aerogel with low GO loading, which is related to GO introduction in the process of preparing the composite aerogel, and GO can be degraded at a lower temperature. While the incorporation of GO results in accelerated primary decomposition, an increase in GO content may contribute to the thermal stability of the overall composite aerogel. The peak of the DTG curve represents the temperature at which the aerogel decomposition rate is highest. As can be seen from the DTG curves, all aerogel samples showed a peak around 317 ℃ associated with the breakdown of the glycosidic bond between the glucose units. Therefore, the aerogel prepared from pure cellulose can generate 17% of carbon residue, and the carbon residue of the composite aerogel (CSG 10) can reach 28%. Therefore, the carbon residue of the composite aerogel (CSG 10) is 11 percent more than that of the pure cellulose aerogel, and more residues can be remained, which shows that the thermal stability effect of the composite aerogel (CSG 10) is better.
Example 8
As shown in fig. 2, the peak positions of the pure ascidian nanocellulose (C), the aerogel (CS) containing SP and the composite aerogels (CSG 1, CSG3, CSG7 and CSG 10) with different GO ratios in the XRD chart remained unchanged, and the peaks appeared at 2 θ =22.56 °, 16.74 ° and 14.90 ° respectively as with the pure aerogel (C), and the crystallinity indexes were all substantially around 89%. Has higher crystallinity, wherein the crystallinity is closely related to TCNCs, and is beneficial to improving the mechanical property of the composite aerogel.
Example 9
The weight and volume of the aerogel were measured using an electronic balance and vernier caliper to determine the apparent density of the aerogel. The weight of the aerogel was measured using a one-ten-thousandth electronic balance and the diameter and height were measured using a digital vernier caliper, as can be seen from table 1, the porosity decreased slightly with the addition of SP and GO, but both above 99%.
Table 1: density and porosity of different aerogels
Figure BDA0003809028610000091
Example 10
The heat transport characteristics were evaluated using a Hot Disk thermal constant analyzer (Hot plate AB) in transient mode using an output power of 20 mw. As can be seen from Table 2, the thermal conductivity values of the composite aerogels CSG7 and CSG10 are 0.04135 W.m, respectively, with increasing GO content -1 ·K -1 And 0.04125 W.m -1 ·K -1 Compared with pure aerogel, the composite aerogel CSG10 is reduced by 23%, which shows that the heat-insulating performance effect of the composite aerogel is improved along with the increase of GO content.
Table 2: thermal conductivity of different aerogels
Figure BDA0003809028610000092
Example 11
The samples were subjected to a vertical burn test using a laboratory 150ml glass alcohol burner, and the combustion of the neat aerogel (C) started immediately after contact with the flame and continued for 9 seconds until it was burnt out. The composite aerogel (CSG 1) is in contact with flame for combustion, and the combustion is extinguished after 6 s. Whereas the composite aerogel (CSG 10) shows self-extinguishing behavior within 0.42 s. After being soaked in ethanol, the same composite aerogel (CSG 10) is directly placed on an evaporating dish to be ignited, and self-extinguishment also occurs in 12s, and the composite aerogel (CSG 10) basically keeps the original form and does not collapse after being extinguished. (FIG. 3)
According to the invention, GO and nontoxic and harmless SP nano clay are added into TCNCs by using simple experimental operation of a freeze drying technology, the TCNCs/SP/GO composite aerogel material with high specific surface area, high mechanical property, low thermal conductivity and good flame retardant and heat insulation effects is prepared in one step, and a new strategy is developed for the development of a composite material which is environment-friendly, easy to operate, green, efficient and safe in road transportation.
While specific embodiments of the invention have been described above, it will be understood by those skilled in the art that the specific embodiments described are illustrative only and are not limiting to the scope of the invention, as those skilled in the art will recognize equivalent modifications that can be made in accordance with the spirit of the invention.

Claims (9)

1. A preparation method of flame-retardant and heat-insulating sea squirt nano cellulose-based aerogel is characterized by comprising the following steps: the method comprises the following steps:
(1) Cleaning the sea squirt tunic, soaking in an alkali solution for 8-12h, and washing the tunic to be neutral by using deionized water;
(2) Bleaching the neutral tunicas obtained in the step (1) with bleaching liquid for 6-10h, replacing fresh bleaching liquid every 2h, and thoroughly washing with deionized water until the neutral tunicas are neutral to obtain sea squirt cellulose;
(3) Hydrolyzing the ecteinascidin cellulose in step (2) with acid to prepare TCNCs, adding excessive deionized water to stop the reaction, centrifuging, and dialyzing with deionized water until the pH of the solution becomes neutral to obtain TCNCs;
(4) Dispersing the TCNCs in the step (3) into a CNC suspension, adjusting the pH value of the CNC suspension to be neutral, and mixing the TCNCs suspension with SP, GO and glutaraldehyde to form a mixed suspension;
(5) Performing ultrasonic treatment and degassing on the mixed suspension liquid in the step (4);
(6) And (4) freezing and drying the mixture obtained in the step (5) to prepare the TCNCs/SP/GO aerogel with flame retardant and heat insulation properties.
2. The method for preparing a flame-retardant and heat-insulating ascidian nanocellulose-based aerogel according to claim 1, wherein:
the concentration of the alkali solution in the step (1) is 5-10wt%.
3. The method for preparing a flame retardant and heat insulating ascidian nanocellulose based aerogel according to claim 1, wherein:
the bleaching solution in the step (2) is obtained by dissolving 5-10g of sodium chlorite and 5-10ml of glacial acetic acid in 300-500ml of deionized water, and the bleaching temperature is 40-70 ℃.
4. The method for preparing a flame-retardant and heat-insulating ascidian nanocellulose-based aerogel according to claim 1, wherein:
step (3) the acid hydrolysis is carried out by using 64% H 2 SO 4 And continuously heating and stirring at 40-65 ℃.
5. The method for preparing a flame retardant and heat insulating ascidian nanocellulose based aerogel according to claim 1, wherein:
mixing the suspension of step (4) with 1-10wt% of TCNCs, 10-30wt% of SP, 1-10wt% of GO and 1-10wt% of glutaraldehyde.
6. The method for preparing a flame retardant and heat insulating ascidian nanocellulose based aerogel according to claim 1, wherein:
and (4) mixing the TCNCs suspension with SP, GO and glutaraldehyde in a cylindrical sample bottle.
7. The method for preparing a flame retardant and heat insulating ascidian nanocellulose based aerogel according to claim 1, wherein:
and (5) carrying out ultrasonic treatment on the mixed suspension for 30-55min.
8. The method for preparing a flame retardant and heat insulating ascidian nanocellulose based aerogel according to claim 1, wherein:
and (5) degassing and standing the mixed suspension for 5-30min.
9. Flame retardant and heat insulating ascidian nanocellulose based aerogel prepared by the preparation method as claimed in any one of claims 1-8.
CN202211005483.5A 2022-08-22 2022-08-22 Preparation method of flame-retardant and heat-insulating sea squirt nano cellulose-based aerogel Pending CN115449120A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202211005483.5A CN115449120A (en) 2022-08-22 2022-08-22 Preparation method of flame-retardant and heat-insulating sea squirt nano cellulose-based aerogel

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202211005483.5A CN115449120A (en) 2022-08-22 2022-08-22 Preparation method of flame-retardant and heat-insulating sea squirt nano cellulose-based aerogel

Publications (1)

Publication Number Publication Date
CN115449120A true CN115449120A (en) 2022-12-09

Family

ID=84299243

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202211005483.5A Pending CN115449120A (en) 2022-08-22 2022-08-22 Preparation method of flame-retardant and heat-insulating sea squirt nano cellulose-based aerogel

Country Status (1)

Country Link
CN (1) CN115449120A (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108395578A (en) * 2018-01-23 2018-08-14 武汉理工大学 A kind of preparation method of cellulose nano-fibrous/graphene oxide composite membrane
US20190077667A1 (en) * 2017-05-31 2019-03-14 Central South University Of Forestry And Technology High-strength network structured nano-carrier material and preparation method and application thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20190077667A1 (en) * 2017-05-31 2019-03-14 Central South University Of Forestry And Technology High-strength network structured nano-carrier material and preparation method and application thereof
CN108395578A (en) * 2018-01-23 2018-08-14 武汉理工大学 A kind of preparation method of cellulose nano-fibrous/graphene oxide composite membrane

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
宁登文: ""海鞘纳米纤维素气凝胶的制备及其性能研究"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》, pages 016 - 2297 *

Similar Documents

Publication Publication Date Title
CN108975794B (en) Clay/sodium alginate composite aerogel flame-retardant material and preparation method thereof
CN104558677A (en) Preparation method of nano cellulose/chitosan composite foam
CN103790248B (en) A kind of preparation method of thermal-insulation heat-resistant plate for building
CN103302708B (en) Preparation method of novel hydrophobic wood
CN112175232A (en) Preparation method of conductive hydrogel based on nano-cellulose-graphene-polyvinyl alcohol-polyethylene diamine
Candra Study on bioethanol production using red seaweed Eucheuma cottonii from Bontang sea water
CN113388151B (en) Preparation method of nano cellulose fiber-sodium alginate-hydroxyapatite flame-retardant aerogel
CN106750550A (en) A kind of fire retardant elastic nano-cellulose aerogel and preparation method thereof
CN115180622B (en) Method for preparing high specific surface area active carbon with assistance of ball milling
CN113248097A (en) Excess sludge pretreatment method
CN109777138A (en) The method that fire protection flame retarding, ultralight high-strength paper pulp foam are prepared using lignocellulose raw material
CN101665588B (en) Biodegradable flame resistance material and preparation method thereof
CN115636954A (en) Super-elastic double-layer photo-thermal hydrogel with high mechanical strength and preparation method and application thereof
CN107501615A (en) A kind of preparation method of high strength regenerative cellulose film
CN115449120A (en) Preparation method of flame-retardant and heat-insulating sea squirt nano cellulose-based aerogel
CN114055580A (en) Preparation method of sol-gel-layer-by-layer self-assembled silicon dioxide fireproof film coated wood
CN109777169A (en) A kind of preparation method of the antibacterial toy coating of high heat resistance
CN111303492A (en) Ultra-light plant fiber composite material with waterproof function and applied to degradable dinner plate and preparation method thereof
CN111875342A (en) Novel nano aerogel building thermal insulation material and preparation method thereof
CN115368618B (en) Method for preparing light phenolic resin heat-insulating material from biomass
CN114874504A (en) Light and heat-insulating polysaccharide-based composite aerogel taking wood waste as raw material and preparation method thereof
CN112898615A (en) Mesona chinensis polysaccharide/nano TiO2Dolichos starch multifunctional composite film and preparation method thereof
CN109867815B (en) Method for preparing ultra-light high-elasticity, fireproof and waterproof paper pulp foam by adopting wood fiber raw material
CN116144105B (en) Preparation method of high-temperature-resistant biodegradable polypropylene
CN112778579A (en) Hemicellulose-based conductive composite film and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination