CN108641003A - A kind of heterogeneous method for preparing acetoacetate cellulose material - Google Patents
A kind of heterogeneous method for preparing acetoacetate cellulose material Download PDFInfo
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- CN108641003A CN108641003A CN201810332960.6A CN201810332960A CN108641003A CN 108641003 A CN108641003 A CN 108641003A CN 201810332960 A CN201810332960 A CN 201810332960A CN 108641003 A CN108641003 A CN 108641003A
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- acetoacetate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B3/00—Preparation of cellulose esters of organic acids
- C08B3/08—Preparation of cellulose esters of organic acids of monobasic organic acids with three or more carbon atoms, e.g. propionate or butyrate
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- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
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- 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
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
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- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The present invention relates to a kind of heterogeneous methods for preparing acetoacetate cellulose material, including：Acetoacetate reagent is added in cellulosic material, diluent is added, is stirred to react, cooling, washing purifying, drying to get.Present invention eliminates to cellulose dissolution process, it is selectively low to cellulose substrate material, purification process is simple, the modified primary morphology and mechanical performance that can preferably keep cellulosic material, and method of modifying is simple, does not need the electrochemical conditions of additional catalyst, numerous reaction reagents and harshness；Modified cellulosic material surface introduces a large amount of acetoacetic acid groups, and the active site for providing more reaction paths is modified for its follow-up functionalized modification, expands its application range.
Description
Technical field
It is the invention belongs to functional fiber element derivant material preparation field, more particularly to a kind of heterogeneous to prepare acetyl second
The method of acidifying cellulosic material.
Background technology
There are two important active sites for acetoacetate functional group tool：Ketone carbonyl and methylene.Hydrogen on its methylene
Atom is easy to leave away to form stable carbanion, and nucleophilic addition, reaction occurs as core reagent and carbonyls
Mild condition, selectivity are good.In recent years, the application of such reaction also appears in the newspapers repeatly, such as in textile industry, and addition contains work
The compound (acetoacetic ester, diethyl malonate etc.) for sprinkling methylene is used as formaldehyde eliminating agent, reduces due to process
The Formaldehyde that middle fiber is discharged with fabric.In addition, the carbonyl in acetoacetate functional group can under mild conditions, with ammonia
Base functional group reacts, which is widely used in coating enhancing solidification.It is big that acetoacetyl is introduced into hydroxy polymer
Molecule can significantly reduce the viscosity of polymer solution and the glass transition temperature (Tg) of polymer, change the rheology of solution
Mechanical property.Therefore, it using acetoacetate functional group as research object, is introduced into polymer, it is new that polymer can be assigned
Function and value, have certain application prospect.
Cellulose is that a kind of most wide, content is most polysaccharide is distributed in nature, accounts for 50% or more of plant kingdom's carbon content.
The mankind are long-standing to the understanding of cellulose and application, and converted products is in food, coating, environmental protection, film, building, tobacco etc.
Aspect is widely used.In order to meet performance requirement, people are often modified cellulose using the hydroxyl on strand.
It is traditional it is cellulose modified be broadly divided into homogeneously with two methods of heterogeneous modification, homogeneous modified cellulose refers to that cellulose is molten
Functional molecular is recycled to be modified after solving specific dissolution system；And heterogeneous modification is directly in cellulose primary morphology
On the basis of, it is surface modified functionalization.Heterogeneous modification compared with homogeneous modified, be omitted cumbersome dissolving cellulose with
And later separation purification process, and the prototype structure of cellulosic material can be kept.
Invention content
Technical problem to be solved by the invention is to provide a kind of heterogeneous sides for preparing acetoacetate cellulose material
Method, this method are eliminated to cellulose dissolution process, and selectively low to cellulose substrate material, purification process is simple, modified
The primary morphology and mechanical performance of cellulosic material can be preferably kept, and method of modifying is simple, not need additional catalysis
Agent, numerous reaction reagents and harsh electrochemical conditions；Modified cellulosic material surface introduces a large amount of acetoacetic acid groups, is
Its follow-up functionalized modification is modified the active site for providing more reaction paths, expands its application range.
A kind of heterogeneous method for preparing acetoacetate cellulose material of the present invention, the specific steps are：
Acetoacetate reagent is added in cellulosic material, diluent is added, is stirred to react, cooling, washing purifying,
Drying, obtains acetoacetate cellulose material, wherein the mass ratio of cellulosic material and acetoacetate reagent is 1:0.5-
1:10, the mass ratio of cellulosic material and diluent is 1:8-1:11.
The acetoacetate reagent is diketene or acetoacetic ester.
The acetoacetic ester is methyl acetoacetate, ethyl acetoacetate, one kind in tert-butyl acetoacetate or several
Kind.
The cellulosic material is unmodified fibers cellulosic material or the chemically-modified cellulose derivative with hydroxyl.
The unmodified fibers cellulosic material is cotton, cotton yarn, cotton fabric, bamboo fiber products, filter paper, film, bacterial fibers
Plain film, bag filter, microcrystalline cellulose, cellulose nano wire, cellulose micro wire or Cellulose nanocrystal dry powder.
The chemically-modified cellulose derivative with hydroxyl is methylcellulose, carboxymethyl cellulose, hydroxypropyl fibre
Dimension element or hydroxypropyl methyl cellulose.
The diluent is dimethyl sulfoxide (DMSO), N,N-dimethylformamide or DMAC N,N' dimethyl acetamide.
The temperature that is stirred to react is 80-120 DEG C, and it is 1-6h to be stirred to react the time.
The reagent that the washing purifying uses is at least one of water, methanol, ethyl alcohol, acetone；Washing purification time is
1-2h。
The drying is：4-24h is dried in vacuo under the conditions of 60-80 DEG C.
The present invention is using nature abundance, inexpensive, the commercialized cellulosic material of green as raw material, in mild condition
Under, acetoacetate chemical fibre dimension is prepared by ester exchange reaction without dissolving and acetoacetate reagent (i.e. under heterogeneous conditions)
A large amount of acetoacetate functional groups are contained on cellulosic material, modified cellulosic material surface, are traditional follow-up work(of cellulosic material
Energyization modification provides active site, improves pristine fibre cellulosic material added value.
Advantageous effect
The present invention with it is homogeneous it is cellulose modified compared with, eliminate to cellulose dissolution process, cellulose substrate material selected
Selecting property is low, and purification process is simple, the modified primary morphology and mechanical performance that can preferably keep cellulosic material, and modified
Method is simple, does not need the electrochemical conditions of additional catalyst, numerous reaction reagents and harshness；Modified cellulosic material table
Face introduces a large amount of acetoacetic acid groups, and the active site for providing more reaction paths is modified for its follow-up functionalized modification, is expanded
Its application range.
Description of the drawings
Fig. 1 is heterogeneous in the present invention to prepare acetoacetate cellulose MATERIALS METHODS schematic diagram.
Fig. 2 is the infrared spectrogram of cotton fabric and acetoacetate cotton fabric in embodiment 1.
Fig. 3 is the infrared spectrogram of bag filter and acetoacetate bag filter in embodiment 2.
Fig. 4 is the infrared spectrogram of filter paper and acetoacetate filter paper in embodiment 3.
Fig. 5 is the infrared spectrogram of bacterial cellulose film and acetoacetate bacterial cellulose film in embodiment 4.
Fig. 6 is the scanning electron microscope (SEM) photograph of (c, d) after cotton fabric (a, b) and cotton fabric acetoacetate in embodiment 1；Wherein
(a, c) is the scanning electron microscope (SEM) photograph at 200 μm, and (b, d) is the scanning electron microscope (SEM) photograph at 20 μm.
Fig. 7 is the scanning electron microscope (SEM) photograph of (c, d) after filter paper (a, b) and filter paper acetoacetate in embodiment 3；Wherein (a, c)
It is the scanning electron microscope (SEM) photograph at 100 μm, (b, d) is the scanning electron microscope (SEM) photograph at 20 μm.
Specific implementation mode
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, people in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Embodiment 1
Cotton fabric (knitting) 5g is weighed, 10g tert-butyl acetoacetate reagents are added in cotton fabric, 50g is added later
N,N-Dimethylformamide is reacted 4h, is cooled to room temperature, cotton fabric is taken out with anhydrous as diluent, 110 DEG C of constant temperature stirrings
After ethyl alcohol washs 1h, 60 DEG C of vacuum drying are for 24 hours to get to acetoacetate cotton fabric, and infrared spectrum is as shown in Fig. 2, show to produce
Object acetoacetic acid group peak (1700-1760cm-1) to hydroxyl peak (3000-3600cm-1) make integrated peak areas ratio be 0.15.It knits
Rear bursting strength is respectively 414.1N and 414.01N to object before modified, the results showed that mechanical performance does not occur obviously after fabric-modifying
Variation.Scanning electron microscope (SEM) photograph is as shown in Figure 6, the results showed that significant change does not occur for pattern after cotton fabric acetoacetate.
Embodiment 2
Anhydrous fiber element bag filter 5g is weighed, 20g tert-butyl acetoacetate reagents are added in bag filter, are added later
50g n,N-Dimethylformamide is reacted 6h, is cooled to room temperature, bag filter is taken out and is used as diluent, 100 DEG C of constant temperature stirrings
After absolute ethyl alcohol washs 1h, 60 DEG C of vacuum drying 4h are to get to acetoacetate bag filter, and infrared spectrum is as shown in figure 3, show
Product acetoacetic acid group peak (1700-1760cm-1) to hydroxyl peak (3000-3600cm-1) make integrated peak areas ratio be 1.5.
Embodiment 3
Cellulosic filter paper 5g is weighed, 10g ethyl acetoacetate reagents are added in filter paper, 50g N, N- bis- is added later
Methylformamide is mixed slowly as diluent, 110 DEG C of constant temperature, is reacted 6h, is cooled to room temperature, and filter paper is taken out anhydrous second
After alcohol washs 1h, 60 DEG C of vacuum drying are for 24 hours to get to acetoacetate filter paper, and infrared spectrum is as shown in figure 4, show product second
Ethyl acetoacetic acid group peak (1700-1760cm-1) to hydroxyl peak (3000-3600cm-1) make integrated peak areas ratio be 0.2.Paper modification
Front and back fracture elongation is respectively 5.1% and 5.8%, and ultimate strength is 21MPa and 19MPa, the results showed that machine after paper modification
Significant change does not occur for tool performance.Scanning electron microscope (SEM) photograph such as Fig. 7, the results showed that pattern does not occur obviously to become after filter paper acetoacetate
Change.
Embodiment 4
Anhydrous bacterial cellulose film 5g is weighed, 20g tert-butyl acetoacetate reagents are added to bacterial cellulose film
In, 50g n,N-dimethylacetamide is added later as diluent, 90 DEG C of constant temperature stirrings are reacted 6h, are cooled to room temperature, will be thin
After film taking-up washs 1h with absolute ethyl alcohol, 60 DEG C of vacuum drying are infrared for 24 hours to get to acetoacetate bacterial cellulose film
Spectrum is as shown in figure 5, show product acetoacetic acid group peak (1700-1760cm-1) to hydroxyl peak (3000-3600cm-1) accumulate
It is 0.3 to divide peak area ratio.
Claims (10)
1. a kind of heterogeneous method for preparing acetoacetate cellulose material, the specific steps are：
Acetoacetate reagent is added in cellulosic material, diluent is added, is stirred to react, cooling, washing purifying is dried
It is dry, obtain acetoacetate cellulose material, wherein the mass ratio of cellulosic material and acetoacetate reagent is 1:0.5-1:
10, the mass ratio of cellulosic material and diluent is 1:8-1:11.
2. a kind of heterogeneous method for preparing acetoacetate cellulose material described in accordance with the claim 1, which is characterized in that
The acetoacetate reagent is diketene or acetoacetic ester.
3. a kind of heterogeneous method for preparing acetoacetate cellulose material according to claim 2, which is characterized in that
The acetoacetic ester is one or more of methyl acetoacetate, ethyl acetoacetate, tert-butyl acetoacetate.
4. a kind of heterogeneous method for preparing acetoacetate cellulose material described in accordance with the claim 1, which is characterized in that
The cellulosic material is unmodified fibers cellulosic material or the chemically-modified cellulose derivative with hydroxyl.
5. a kind of heterogeneous method for preparing acetoacetate cellulose material according to claim 4, which is characterized in that
The unmodified fibers cellulosic material is cotton, cotton yarn, cotton fabric, bamboo fiber products, filter paper, film, bacteria cellulose film, dialysis
Bag, microcrystalline cellulose, cellulose nano wire, cellulose micro wire or Cellulose nanocrystal.
6. a kind of heterogeneous method for preparing acetoacetate cellulose material according to claim 4, which is characterized in that
The chemically-modified cellulose derivative with hydroxyl is methylcellulose, carboxymethyl cellulose, hydroxypropyl cellulose or hydroxyl
Propyl methocel.
7. a kind of heterogeneous method for preparing acetoacetate cellulose material described in accordance with the claim 1, which is characterized in that
The diluent is dimethyl sulfoxide (DMSO), N,N-dimethylformamide or DMAC N,N' dimethyl acetamide.
8. a kind of heterogeneous method for preparing acetoacetate cellulose material described in accordance with the claim 1, which is characterized in that
The temperature that is stirred to react is 80-120 DEG C, and it is 1-6h to be stirred to react the time.
9. a kind of heterogeneous method for preparing acetoacetate cellulose material described in accordance with the claim 1, which is characterized in that
The reagent that the washing purifying uses is at least one of water, methanol, ethyl alcohol, acetone；Washing purification time is 1-2h.
10. a kind of heterogeneous method for preparing acetoacetate cellulose material described in accordance with the claim 1, feature exist
In the drying is：4-24h is dried in vacuo under the conditions of 60-80 DEG C.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810332960.6A CN108641003A (en) | 2018-04-13 | 2018-04-13 | A kind of heterogeneous method for preparing acetoacetate cellulose material |
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| CN201810332960.6A CN108641003A (en) | 2018-04-13 | 2018-04-13 | A kind of heterogeneous method for preparing acetoacetate cellulose material |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109505124A (en) * | 2018-12-04 | 2019-03-22 | 东华大学 | A kind of antibacterial cotton sticking patch and its preparation and application |
| CN110343214A (en) * | 2019-07-12 | 2019-10-18 | 东华大学 | A method of cellulose graft copolymer is prepared in homogeneous using enzymatic system |
| CN115897231A (en) * | 2022-11-17 | 2023-04-04 | 华南理工大学 | Efficient washable antibacterial and ultraviolet-resistant fabric and preparation method and application thereof |
| CN116285012A (en) * | 2023-03-15 | 2023-06-23 | 广东云启科技研究有限公司 | Cellulose-based antibacterial material, and preparation method and application thereof |
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| US5360843A (en) * | 1991-08-09 | 1994-11-01 | Eastman Chemical Company | Cellulose acetoacetates |
| CN101942088A (en) * | 2010-08-24 | 2011-01-12 | 中山大学 | Method for synthesizing acetoacetate ester compound |
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2018
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US5360843A (en) * | 1991-08-09 | 1994-11-01 | Eastman Chemical Company | Cellulose acetoacetates |
| CN101942088A (en) * | 2010-08-24 | 2011-01-12 | 中山大学 | Method for synthesizing acetoacetate ester compound |
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| K.J.EDGAR等: "Synthesis and Properties of Cellulose Acetoacetates", 《MACROMOLECULES》 * |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109505124A (en) * | 2018-12-04 | 2019-03-22 | 东华大学 | A kind of antibacterial cotton sticking patch and its preparation and application |
| CN110343214A (en) * | 2019-07-12 | 2019-10-18 | 东华大学 | A method of cellulose graft copolymer is prepared in homogeneous using enzymatic system |
| CN110343214B (en) * | 2019-07-12 | 2021-08-10 | 东华大学 | Method for preparing cellulose graft copolymer in homogeneous phase by using enzymatic system |
| CN115897231A (en) * | 2022-11-17 | 2023-04-04 | 华南理工大学 | Efficient washable antibacterial and ultraviolet-resistant fabric and preparation method and application thereof |
| CN115897231B (en) * | 2022-11-17 | 2024-05-03 | 华南理工大学 | Efficient washable antibacterial and ultraviolet-resistant fabric and preparation method and application thereof |
| CN116285012A (en) * | 2023-03-15 | 2023-06-23 | 广东云启科技研究有限公司 | Cellulose-based antibacterial material, and preparation method and application thereof |
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