CN107602933A - A kind of resistance to preparation method for shrinking high-strength cellulose aerogels material - Google Patents
A kind of resistance to preparation method for shrinking high-strength cellulose aerogels material Download PDFInfo
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Abstract
The present invention relates to a kind of resistance to contraction high-strength cellulose aerogels material, belong to materials processing technology field.Succinic acid and potassium hydroxide are stirred by the present invention, and heating water bath is still aging, are centrifuged, and collect lower sediment, vacuum freeze drying, and grinding is prepared into matrix powder；Lithium chloride, microcrystalline cellulose and dimethyl acetamide are stirred, heating water bath obtains cellulose solution, and cellulose solution is cooled in room temperature juxtaposition beaker, ageing, obtains cellulose gel；Cellulose gel, matrix powder etc. is weighed to put in flask, insulation is warming up to room temperature, obtains mixed liquor, weighs mixed liquor, isocyanates and 200 mesh bacteria celluloses and puts in flask, hydrolysis heating, standing is cooled in room temperature juxtaposition autoclave, is passed through carbon dioxide, then logical nitrogen, pressurize is simultaneously continually fed into carbon dioxide, it is incubated and removes to be depressed into and communicated with atmospheric pressure, waits to remove being cooled to room temperature after the completion of pressure, you can be prepared into a kind of resistance to contraction high-strength cellulose aerogels material.
Description
Technical field
The present invention relates to a kind of resistance to preparation method for shrinking high-strength cellulose aerogels material, belong to materials processing technology
Field.
Background technology
Aeroge is a kind of new material for possessing porous network structure, has porosity height, specific surface area big and close
Spend the advantages that light.Cellulose aerogels possess the characteristics of many excellent, as biorenewable, biocompatibility and biology can drop
Solution property etc..Substantial amounts of active hydroxyl groups in the molecular structure of cellulose be present, it is prone to chemically react, such as sulfonation, esterification, ether
Change, crosslinking.Cellulose aerogels after modified have extensively at numerous aspects such as catalysis, separation, drug delivery and organizational projects
General research.
Cellulose is the natural polymer of nature, and molecular formula is (C6H10O5)n, it possesses the spies such as distribution is wide, reserves are big
Point, and possess good biorenewable, unique performance such as biocompatibility and biodegradability.
Aeroge is a kind of porous material, have low-density, high porosity, high-specific surface area, low heat conduction coefficient and
The features such as low-k.1931, aeroge was as made from Kistler, with sol-gel at first（sol-gel）Skill
Art develops rapidly, lot of documents inorganic aerogels and polymeric aerogels.Because cellulose aerogels have renewable, toughness
Well, the features such as easy processing, aeroge of new generation has been increasingly becoming it.Because in contemporary society, due to many non-renewable resources
Utilization such as oil, coal and the resource-constrained of natural gas and these resources can produce a series of environmental problem, due to fibre
The many advantages of element, such as recyclability are tieed up, therefore everybody concern is increasingly obtained about cellulose aerogels functional material.
In materials science field, the definition of composite is heterogeneous system, mainly by two or more physics
The solid material that the combinations of substances different with chemical property forms.In composite heterogeneous system, there is a phase matrix, it is to connect
Continuous phase；For another phase reinforcing material, it is dispersed phase.In recent years, this biological material shape of cellulose is added in polymer
Into composite, impart biodegradability, therefore, this enhancing matrix using cellulose as polymer is obtained
Cellulose/polymer composites are widely studied by everybody.
Cellulose aerogels material can be applied on many fields, be such as catalyzed, be separated by filtration, drug delivery and tissue
Engineering etc..Therefore, it can be modified for cellulose aerogels by surface, prepare the material containing different functional groups, so as to
Assign aeroge special performance, such as hydrophobicity, electric conductivity.
The content of the invention
The technical problems to be solved by the invention：After first being dissolved for cellulose in regenerative process, due to there may be fibre
The rearrangement of plain crystal formation is tieed up, cellulose aerogels can be caused to occur that very big contraction and its mechanical property become in preparation process
A kind of the problem of poor, there is provided resistance to preparation method for shrinking high-strength cellulose aerogels material.
In order to solve the above technical problems, the technical solution adopted by the present invention is：
（1）In mass ratio 1：5, succinic acid and the potassium hydroxide of mass fraction 5% are stirred, it is still aging after heating water bath,
Centrifuge and collect lower sediment and obtain, vacuum freeze drying, grinding is prepared into matrix powder；
（2）In mass ratio 1：5：10, lithium chloride, microcrystalline cellulose and dimethyl acetamide are stirred, heating water bath obtains fine
Plain solution is tieed up, cellulose solution standing is cooled into room temperature is placed in beaker, still aging to obtain cellulose gel；
（3）Count in parts by weight, weigh 45~50 parts of cellulose gels, 10~15 parts of matrix powders, 5~8 parts of 3- amino respectively
Propyl-triethylsilicane alkane is placed in three-necked flask, insulation reaction, and standing is warming up to room temperature, obtains mixed liquor；
（4）Count in parts by weight, weigh 45~50 portions of mixed liquors, 10~15 parts of isocyanates and 3~5 part of 200 mesh bacterium respectively
Cellulose is placed in three-necked flask, and hydrolysis heating, standing is cooled to room temperature and is placed in autoclave, in autoclave
It is passed through carbon dioxide, after the completion of carbon dioxide to be led to, stands simultaneously logical nitrogen, pressurize and be simultaneously continually fed into carbon dioxide, be incubated and delay
Slowly remove to be depressed into and communicated with atmospheric pressure, after the completion of pressure to be removed, standing is cooled to room temperature, you can it is fine to be prepared into a kind of resistance to contraction high-strength
Tie up plain aerogel material.
Step（3）Described insulation reaction temperature is -5~0 DEG C.
Step（4）Described standing and logical nitrogen are to lead to nitrogen to 8.5MPa.
Step（4）The described pressure time of removing is 1~2h.
Compared with other method, advantageous effects are the present invention：
（1）The present invention is polybasic carboxylic acid by succinic acid, and cellulose gel is modified, and passes through what is contained inside polybasic carboxylic acid
Polyfunctional compound crosslinks reaction with cellulosic material, due to two carboxyls closed in polybasic carboxylic acid, is first dehydrated shape
Into acid anhydrides, further carry out esterification and crosslinking with the hydroxyl on cellulose molecular chain and form ester bond, be advantageous to improve cellulose net
The stability of network structure, further improves material mechanical performance；
（2）The present invention is modified by amino silane, is entered by it added to aeroge inside and through supercritical carbon dioxide
Row drying process, make the reduction of gel rubber material Investigation of drying shrinkage of high, while polymeric matrix is introduced in material internal, further improve
The globality and mechanical property of aeroge.
Embodiment
In mass ratio 1：5, succinic acid and the potassium hydroxide of mass fraction 5% are stirred, at 45~50 DEG C water-bath add
It is still aging after 2~3h of heat, then 10~15min is centrifuged under 1200~1500r/min, lower sediment is collected, vacuum is cold
Lyophilized dry, grinding is prepared into matrix powder；In mass ratio 1：5：10, lithium chloride, microcrystalline cellulose and dimethyl acetamide are stirred
Mixing is mixed, 25~30min of heating water bath, obtains cellulose solution at 45~50 DEG C, and cellulose solution is stood and is cooled to room temperature
It is placed in beaker, after still aging 6~8h, obtains cellulose gel；Count in parts by weight, weigh 45~50 parts of celluloses respectively
Gel, 10~15 parts of matrix powders, 5~8 parts of 3- aminopropyl triethyl silicanes are placed in three-necked flask, are protected at -5~0 DEG C
After 6~8h of temperature reaction, standing is warming up to room temperature, obtains mixed liquor, counts in parts by weight, weighs 45~50 parts of mixed liquors, 10 respectively
~15 parts of isocyanates and 3~5 part of 200 mesh bacteria cellulose are placed in three-necked flask, 3~5h of hydrolysis heating at 75~80 DEG C
Afterwards, stand and be cooled to room temperature and be placed in autoclave, to being passed through carbon dioxide in autoclave to 0.5~0.6Mpa,
After the completion of carbon dioxide to be led to, then 25~30min is stood at 30~35 DEG C, it is 8.5MPa to lead to nitrogen to pressure, and pressurize is simultaneously held
It is continuous be passed through 20~24h of carbon dioxide after, be incubated and slowly remove to be depressed into and communicated with atmospheric pressure, control and remove that to press the time be 1~2h, wait to remove
After the completion of pressure, standing is cooled to room temperature, you can is prepared into a kind of resistance to contraction high-strength cellulose aerogels material.
Example 1
In mass ratio 1：5, succinic acid and the potassium hydroxide of mass fraction 5% are stirred, it is quiet at 45 DEG C after heating water bath 2h
Ageing is put, then 10min is centrifuged under 1200r/min, collects lower sediment, vacuum freeze drying, grinding is prepared into matrix
Powder；In mass ratio 1：5：10, lithium chloride, microcrystalline cellulose and dimethyl acetamide are stirred, at 45 DEG C water-bath add
Hot 25min, obtains cellulose solution, and cellulose solution standing is cooled into room temperature is placed in beaker, after still aging 6h, obtains fine
Tie up plain gel；Count in parts by weight, weigh 45 parts of cellulose gels, 10 parts of matrix powders, 5 parts of 3- aminopropyl triethyl groups respectively
Silane is placed in three-necked flask, and at 0 DEG C after insulation reaction 6h, standing is warming up to room temperature, obtains mixed liquor, counts in parts by weight,
Weigh 45 portions of mixed liquors, 10 parts of isocyanates and 3 part of 200 mesh bacteria cellulose respectively to be placed in three-necked flask, the water at 75 DEG C
After solution heating 3h, standing is cooled to room temperature and is placed in autoclave, to being passed through carbon dioxide in autoclave extremely
0.5Mpa, after the completion of carbon dioxide to be led to, then 25min is stood at 30 DEG C, logical nitrogen to pressure be 8.5MPa, and pressurize is simultaneously persistently
After being passed through carbon dioxide 20h, it is incubated and slowly removes to be depressed into and communicated with atmospheric pressure, controls and remove that to press the time be 1h, after the completion of pressure to be removed,
Standing is cooled to room temperature, you can is prepared into a kind of resistance to contraction high-strength cellulose aerogels material.
Example 2
In mass ratio 1：5, succinic acid and the potassium hydroxide of mass fraction 5% are stirred, it is quiet at 47 DEG C after heating water bath 2h
Ageing is put, then 12min is centrifuged under 1300r/min, collects lower sediment, vacuum freeze drying, grinding is prepared into matrix
Powder；In mass ratio 1：5：10, lithium chloride, microcrystalline cellulose and dimethyl acetamide are stirred, at 47 DEG C water-bath add
Hot 28min, obtains cellulose solution, and cellulose solution standing is cooled into room temperature is placed in beaker, after still aging 7h, obtains fine
Tie up plain gel；Count in parts by weight, weigh 47 parts of cellulose gels, 12 parts of matrix powders, 6 parts of 3- aminopropyl triethyl groups respectively
Silane is placed in three-necked flask, and at -2 DEG C after insulation reaction 7h, standing is warming up to room temperature, obtains mixed liquor, counts in parts by weight,
Weigh 47 portions of mixed liquors, 12 parts of isocyanates and 4 part of 200 mesh bacteria cellulose respectively to be placed in three-necked flask, the water at 78 DEG C
After solution heating 4h, standing is cooled to room temperature and is placed in autoclave, to being passed through carbon dioxide in autoclave extremely
0.5Mpa, after the completion of carbon dioxide to be led to, then 28min is stood at 32 DEG C, logical nitrogen to pressure be 8.5MPa, and pressurize is simultaneously persistently
After being passed through carbon dioxide 22h, it is incubated and slowly removes to be depressed into and communicated with atmospheric pressure, controls and remove that to press the time be 1h, after the completion of pressure to be removed,
Standing is cooled to room temperature, you can is prepared into a kind of resistance to contraction high-strength cellulose aerogels material.
Example 3
In mass ratio 1：5, succinic acid and the potassium hydroxide of mass fraction 5% are stirred, it is quiet at 50 DEG C after heating water bath 3h
Ageing is put, then 15min is centrifuged under 1500r/min, collects lower sediment, vacuum freeze drying, grinding is prepared into matrix
Powder；In mass ratio 1：5：10, lithium chloride, microcrystalline cellulose and dimethyl acetamide are stirred, at 50 DEG C water-bath add
Hot 30min, obtains cellulose solution, and cellulose solution standing is cooled into room temperature is placed in beaker, after still aging 8h, obtains fine
Tie up plain gel；Count in parts by weight, weigh 50 parts of cellulose gels, 15 parts of matrix powders, 8 parts of 3- aminopropyl triethyl groups respectively
Silane is placed in three-necked flask, and at -5 DEG C after insulation reaction 8h, standing is warming up to room temperature, obtains mixed liquor, counts in parts by weight,
Weigh 50 portions of mixed liquors, 15 parts of isocyanates and 5 part of 200 mesh bacteria cellulose respectively to be placed in three-necked flask, the water at 80 DEG C
After solution heating 5h, standing is cooled to room temperature and is placed in autoclave, to being passed through carbon dioxide in autoclave extremely
0.6Mpa, after the completion of carbon dioxide to be led to, then 30min is stood at 35 DEG C, logical nitrogen to pressure be 8.5MPa, and pressurize is simultaneously persistently
After being passed through carbon dioxide 24h, it is incubated and slowly removes to be depressed into and communicated with atmospheric pressure, controls and remove that to press the time be 2h, after the completion of pressure to be removed,
Standing is cooled to room temperature, you can is prepared into a kind of resistance to contraction high-strength cellulose aerogels material.
It our experiments show that：The high-strength of resistance to contraction cellulose aerogels density of material prepared by this method is 12.3mg/cm3,
Porosity is 99.6%, and water contact angle reaches 160 °, reaches super-hydrophobic degree.The aeroge has stronger mechanical performance, can be with
Reach 62KPa, compression resilience may return to 52.9%, and its specific surface area can reach 11.33cm3/g.And its heat endurance
Improve 23 °.The aeroge can be used for water-oil separating, high by separative efficiency after 6 times, and oil water mixture can reach 100%,
Oil hydrosol separative efficiency also can reach 98.6%.Meanwhile modified material has preferable adsorptivity, maximal absorptive capacity is
For 82.1mg/g moreover, the aeroge after filtering absorption is reusable after being handled through soda acid, the adsorption efficiency after 6 times can
Reach 93.4%.
Claims (4)
1. a kind of resistance to preparation method for shrinking high-strength cellulose aerogels material, it is characterised in that specifically preparation process is：
（1）In mass ratio 1：5, succinic acid and the potassium hydroxide of mass fraction 5% are stirred, it is still aging after heating water bath,
Centrifuge and collect lower sediment and obtain, vacuum freeze drying, grinding is prepared into matrix powder；
（2）In mass ratio 1：5：10, lithium chloride, microcrystalline cellulose and dimethyl acetamide are stirred, heating water bath obtains fine
Plain solution is tieed up, cellulose solution standing is cooled into room temperature is placed in beaker, still aging to obtain cellulose gel；
（3）Count in parts by weight, weigh 45~50 parts of cellulose gels, 10~15 parts of matrix powders, 5~8 parts of 3- amino respectively
Propyl-triethylsilicane alkane is placed in three-necked flask, insulation reaction, and standing is warming up to room temperature, obtains mixed liquor；
（4）Count in parts by weight, weigh 45~50 portions of mixed liquors, 10~15 parts of isocyanates and 3~5 part of 200 mesh bacterium respectively
Cellulose is placed in three-necked flask, and hydrolysis heating, standing is cooled to room temperature and is placed in autoclave, in autoclave
It is passed through carbon dioxide, after the completion of carbon dioxide to be led to, stands simultaneously logical nitrogen, pressurize and be simultaneously continually fed into carbon dioxide, be incubated and delay
Slowly remove to be depressed into and communicated with atmospheric pressure, after the completion of pressure to be removed, standing is cooled to room temperature, you can it is fine to be prepared into a kind of resistance to contraction high-strength
Tie up plain aerogel material.
2. a kind of resistance to preparation method for shrinking high-strength cellulose aerogels material according to claim 1, its feature exist
In：Step（3）Described insulation reaction temperature is -5~0 DEG C.
3. a kind of resistance to preparation method for shrinking high-strength cellulose aerogels material according to claim 1, its feature exist
In：Step（4）Described standing and logical nitrogen are to lead to nitrogen to 8.5MPa.
4. a kind of resistance to preparation method for shrinking high-strength cellulose aerogels material according to claim 1, its feature exist
In：Step（4）The described pressure time of removing is 1~2h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110229307A (en) * | 2019-06-28 | 2019-09-13 | 陕西科技大学 | A kind of poly- polyisocyanates shape memory aeroge of HEC/CNC/ and its preparation method and application |
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| CN101880410A (en) * | 2010-07-21 | 2010-11-10 | 武汉大学 | High-strength transparent cellulose material and preparation method thereof |
| CN103012835A (en) * | 2012-12-19 | 2013-04-03 | 江南大学 | Preparation method of cellulose/ polyurethane composite aerogel |
| CN103554548A (en) * | 2013-10-24 | 2014-02-05 | 华南理工大学 | Preparation method of wood fiber biomass aerogel |
| CN105542218A (en) * | 2016-01-22 | 2016-05-04 | 昆明理工大学 | Preparation method of citric acid cross-linking reinforced cellulose aerogel |
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- 2017-10-10 CN CN201710933539.6A patent/CN107602933A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101880410A (en) * | 2010-07-21 | 2010-11-10 | 武汉大学 | High-strength transparent cellulose material and preparation method thereof |
| CN103012835A (en) * | 2012-12-19 | 2013-04-03 | 江南大学 | Preparation method of cellulose/ polyurethane composite aerogel |
| CN103554548A (en) * | 2013-10-24 | 2014-02-05 | 华南理工大学 | Preparation method of wood fiber biomass aerogel |
| CN105542218A (en) * | 2016-01-22 | 2016-05-04 | 昆明理工大学 | Preparation method of citric acid cross-linking reinforced cellulose aerogel |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110229307A (en) * | 2019-06-28 | 2019-09-13 | 陕西科技大学 | A kind of poly- polyisocyanates shape memory aeroge of HEC/CNC/ and its preparation method and application |
| CN110229307B (en) * | 2019-06-28 | 2021-02-26 | 陕西科技大学 | HEC/CNC/polyisocyanate shape memory aerogel and preparation method and application thereof |
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