CN101838348B - Hemicellulose derivative with two functional groups as well as preparation method and application thereof - Google Patents
Hemicellulose derivative with two functional groups as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN101838348B CN101838348B CN2010101811195A CN201010181119A CN101838348B CN 101838348 B CN101838348 B CN 101838348B CN 2010101811195 A CN2010101811195 A CN 2010101811195A CN 201010181119 A CN201010181119 A CN 201010181119A CN 101838348 B CN101838348 B CN 101838348B
- Authority
- CN
- China
- Prior art keywords
- hemicellulose derivative
- hemicellulose
- semicellulose
- functional groups
- wheat straw
- 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.)
- Expired - Fee Related
Links
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention discloses a hemicellulose derivative with two functional groups as well as a preparation method and application thereof. The preparation method comprises the following steps of: treating delignified wheat straws by using a KOH solution, and then carrying out purification and separation on alkali-soluble hemicellulose dissolved in filtrate; carrying out activating treatment on dried hemicellulose by using distilled water, cooling, adding NaOH, reacting for 10 to 30min at 20 to 40 DEG C, then adding butanol and acrylamide, and reacting for 4 to 48h at 20 to 50 DEG C; neutralizing, filtering, washing with ethanol, freezing and drying to obtain the novel hemicellulose derivative with two different functional groups. The invention has simple process, mild reaction conditions and easy industrialization; the obtained product contains ethyl-formamide and carboxyl groups and has degradability; and the modified hemicellulose has greatly-improved hydrophilcity and can be applied to papermaking industry as a papermaking wet-end auxiliary agent.
Description
Technical field
The present invention relates to the modification semicellulose, be specifically related to have hemicellulose derivative and the method for making and the application of two kinds of functional groups.
Background technology
Stalk is as one type of important agricultural organic waste resource, we can say to be accompanied by infant farming and livestock industry has just produced.Agricultural crop straw is one of the abundantest in the world physical resources.China's crop seeding area ranks first in the world, and stalk output reaches 5.7 hundred million tons every year, accounts for 20%～30% of whole world stalk ultimate production, and wherein rice straw is about 1.8 hundred million tons, 1.1 hundred million tons of wheat straws, 2.0 hundred million tons of corn stalk, 0.13 hundred million tons of cotton straw (bavin).These agricultural wastes are mainly used in direct burning heat production, and some is as the raw material of feed, fertilizer and pulp and paper industry, but the not enough agricultural wastes total amount of the utilization in this field 50%.A large amount of agricultural wastes are thrown aside in physical environment or open fire, have both caused the pollution of environment, cause the significant wastage of resource again.Therefore, how to utilize this huge green resource economically, increasingly serious in state of ecological environment, today that petrochemical industry resources such as oil are nervous relatively, have important practical significance and theoretical investigation value.
Containing 25%～35% semicellulose in the agricultural solid residue, is one of high sponge of a few hemicellulose level.How effectively the semicellulose of trans-utilization enormous amount becomes the chemical, novel material, function food additive of industrial significance etc., develops in a healthy way and has positive meaning realizing the industrial or agricultural sustainability.
The chemical modification of glycan is one of a kind of important channel that can give new functional group of glycan and change glycan physical and chemical performance.Present research mainly be with improve the quality of products, the exploitation of the proposition of new synthesis route and product innovation and can the synthetic theory of displaced green be main.Over past ten years; Domestic and international many scholars are devoted to the semicellulose that from reproducible agriculture and forestry organic waste material resource, extracts is carried out the research of chemical modification; Thereby propose many new synthetic routes and prepare dissimilar novel hemicellulose derivatives, for example: acetylizad hemicellulose derivative, methylated hemicellulose derivative, acylations get hemicellulose derivative and quaternised hemicellulose derivative or the like.General esterification can improve hydrophobic nature, the macromolecular film elasticity of increase semicellulose of semicellulose itself, can be applied to industries such as plastics, packing.Quaterisation can improve the wetting ability of semicellulose itself, can be applied to industries such as papermaking, food, weaving, WWT.Yet up to the present also there is not synthetic report about the novel hemicellulose derivative that has two kinds of different functionalities groups; Have ethyl-formamide and carboxylic group simultaneously on this hemicellulose derivative macromolecular chain; Improved the wetting ability of semicellulose greatly, and had degradability, technology is simple; Reaction conditions is gentle, is easy to industriallization.
Summary of the invention
The object of the invention is exactly the deficiency that exists to prior art, and a kind of hemicellulose derivative and method for making and application that has two kinds of functional groups is provided.The inventive method has the hemicellulose derivative of ethyl-formamide and carboxylic group simultaneously through the one-step synthesis preparation under mild conditions.
The object of the invention is realized through following technical scheme:
A kind of hemicellulose derivative that has two kinds of functional groups, structural formula is following:
Wherein,
or-H.
Total substitution value of hemicellulose derivative is 0.10～0.92, and hemicellulose derivative has ethyl-formamide and carboxylic group simultaneously, and the ethyl-formamide on the hemicellulose derivative and the mol ratio of carboxylic group are 1.0～4.3.
A kind of preparation method who has the hemicellulose derivative of two kinds of functional groups may further comprise the steps:
(1) with the wheat straw of KOH solution extraction delignification, the semicellulose to dissolved in filtrate carries out isolation and purification again;
(2) semicellulose adds entry, at 60～85 ℃ of heating 5～30min;
(3) add sodium hydroxide, react 10～30min down at 20～40 ℃;
(4) add butanols, the volume ratio of butanols and water is 2: 3～4: 1, adds acrylic amide then, at 20～50 ℃, and reaction 4～48h;
(5) neutralization is filtered, washing precipitation, and lyophilize promptly gets the hemicellulose derivative that has two kinds of functional groups.
The wheat straw of the said delignification of step (1) is to obtain through following method: using earlier volume ratio is the wheat straw waste 6h that 2: 1 acetone and ethanol extracting 50g in Soxhlet extractor ground; Use 1000ml water at 75 ℃ of extracting 2h then; Residual substance and 75g Textone are joined in the 1000ml water at 75 ℃ of heating 2h, with the acetic acid adjust pH 3.8～4.0.
The wheat straw of the said use of step (1) KOH solution extraction delignification be use concentration be 8～10% weight KOH at 20～30 ℃ of extracting 8～12h, the amount ratio of the wheat straw of delignification and KOH solution is 1: 20～1: 25gml
-1,
The unitary mol ratio of xylan was 0.5: 1～4.0: 1 during said sodium hydroxide and semicellulose were formed.
The unitary mol ratio of xylan was 2: 1～20: 1 during said acrylic amide and semicellulose were formed.
Said neutralization is that to use the acetum of 6M to be neutralized to the pH value be 6.0～8.0.
A kind of application of hemicellulose derivative in papermaking that has two kinds of functional groups.
The principle of the invention:
The present invention compared with prior art has following advantage and beneficial effect:
1. this method technology is simple, and reaction conditions is gentle, and is easy to operate, is easy to industriallization.
2. through single step reaction, can two kinds of different functions property groups be grafted on the semicellulose macromolecular chain simultaneously, give semicellulose new performance, for example water-soluble, zwitter-ion property etc.
3. be 0.10～0.92 hemicellulose derivative through changing reaction conditions, can obtaining two kinds of total substitution values of different functionalities group, and the ethyl-formamide on the semicellulose macromolecular chain and carboxylic group ratio are 1.0～4.3.
4. the semicellulose wetting ability after the chemical modification improves greatly, and ionic raising greatly can be used as wet end adjuvant and is applied to paper industry.
Embodiment
In order to understand technical characterstic of the present invention better, below in conjunction with the present invention being done explanation further through embodiment.
Embodiment 1
The wheat straw waste that the first step 50g grinds earlier with 1000ml acetone-ethanol (2: 1, v/v) extracting 6h in Soxhlet extractor.Then resistates is added 1000ml water and remove water miscible semicellulose at 75 ℃ of extracting 2h.With heating 2h at 75 ℃ in residual substance and the 75g Textone adding 1000ml water,, obtain the wheat straw of delignification with acetic acid adjust pH to 3.8.Use concentration as 10wt%KOH at 23 ℃ of extracting 10h, the amount ratio of the wheat straw of delignification and KOH solution is 1: 20gml
-1The filtrating that obtains is used 95% ethanol (volume(tric)fraction) deposition of 3 times of filtrate volumes then with 6mol/l acetic acid adjust pH to 5.5, filters, and uses acidifying 70% (volume(tric)fraction) washing with alcohol at last, and dry air 12h dries by the fire 16h down at 60 ℃.
Semicellulose after second step was purified 6.6g (be equivalent to semicellulose form in the xylan unit be 0.05 mole) place three mouthfuls of reaction flasks of 250ml, add 72ml water, 85 ℃ of temperature down heating 15min dissolve to complete.
The 3rd step added 1.6g NaOH, under 25 ℃, and reaction 30min.
The 4th step added the 48ml butanols, slowly added the acrylic amide of 21.3g, under 25 ℃, and reaction 12h.
After the reaction of the 5th step finishes, add the acetic acid adjust pH to 7.0 of 6M, filter, use 95% washing with alcohol, then lyophilize 24h.
Process
1H NMR with
13CNMR measures, and total substitution value of resulting novel hemicellulose derivative is 0.67, and wherein the substitution value of ethyl-formamide is 0.54, and the substitution value of carboxylic group is 0.13.
Embodiment 2
Wheat straw waste that the first step 50g ground earlier with 1000ml acetone-ethanol (2: 1, v/v) extracting 6h in Soxhlet extractor.Then resistates is added 1000ml water and remove water miscible semicellulose at 75 ℃ of extracting 2h.Residual substance and 75g Textone are joined in the 1000ml water at 75 ℃ of heating 2h, 3.6, obtain the wheat straw of delignification with the acetic acid adjust pH.Use concentration as 10wt%KOH at 20 ℃ of extracting 10h, the amount ratio of the wheat straw of delignification and KOH solution is 1: 20gml
-1The filtrating that obtains is used 95% volume(tric)fraction ethanol sedimentation of 3 times of filtrate volumes then with 6mol/l acetic acid adjust pH to 5.5, filters, and uses acidifying 70% volume(tric)fraction washing with alcohol at last, and dry air 12h dries by the fire 16h down at 60 ℃.
Semicellulose after second step was purified 6.6g (be equivalent to semicellulose form in the xylan unit be 0.05 mole) place three mouthfuls of reaction flasks of 250ml, add 48ml water, at 60 ℃ of temperature heating 30min down.
After the cooling of the 3rd step, add 2.0g NaOH, under 20 ℃, reaction 30min.
The 4th step slowly added the 72ml butanols then, slowly added the acrylic amide of 56.8g then, under 20 ℃, and reaction 48h.
(5) after reaction finishes, add the acetic acid adjust pH to 7.0 of 6M, filter, with 95% volume(tric)fraction washing with alcohol, lyophilize 24h then.Promptly obtain total substitution value and be 0.92 novel hemicellulose derivative, wherein the substitution value of ethyl-formamide is 0.75, and the substitution value of carboxylic group is 0.17.
Embodiment 3
The wheat straw waste that the first step 50g grinds earlier with 1000ml acetone-ethanol (2: 1, v/v) extracting 6h in Soxhlet extractor.Then resistates is added 1000ml water and remove water miscible semicellulose at 75 ℃ of extracting 2h.Residual substance and 75g Textone are heated 2h at 75 ℃ in 1000ml water, 3.6, obtain the wheat straw of delignification with the acetic acid adjust pH.Use concentration as 10wt%KOH at 20 ℃ of extracting 10h, the amount ratio of the wheat straw of delignification and KOH solution is 1: 25gml
-1The filtrating that obtains is used 95% volume(tric)fraction ethanol sedimentation of 3 times of filtrate volumes then with 6mol/l acetic acid adjust pH to 5.5, filters, and uses acidifying 70% volume(tric)fraction washing with alcohol at last, and dry air 12h dries by the fire 16h down at 60 ℃.
Semicellulose after second step was purified 6.6g (be equivalent to semicellulose form in the xylan unit be 0.05 mole) place three mouthfuls of reaction flasks of 250ml, add 24ml water, at 75 ℃ of temperature heating 5min down.
After the cooling of the 3rd step, add 1.6g NaOH, under 40 ℃, reaction 10min.
The 4th step slowly added the 96ml butanols then, slowly added the acrylic amide of 21.3g then, under 50 ℃, and reaction 4h.
After the reaction of the 5th step finishes, add the acetic acid adjust pH to 7.0 of 6M, filter, with 95% volume(tric)fraction washing with alcohol, lyophilize 24h then.Promptly obtain total substitution value and be 0.46 novel hemicellulose derivative, wherein the substitution value of ethyl-formamide is 0.28, and the substitution value of carboxylic group is 0.18.
The hemicellulose derivative that has two kinds of functional groups of the present invention preparation is owing to contain ethyl-formamide and carboxylic group simultaneously, so the semicellulose wetting ability after the chemical modification improves greatly, can be used as the paper making wet part toughener and is applied in the papermaking.
Claims (5)
1. a hemicellulose derivative that has two kinds of functional groups is characterized in that, semicellulose repeat unit structure formula is following:
Wherein, R=-CH
2-CH
2-C (=O)-NH
2,-CH
2-CH
2-COONa or H;
Total substitution value of hemicellulose derivative is 0.10～0.92, and hemicellulose derivative has ethyl-formamide and carboxylic group simultaneously, and the ethyl-formamide of hemicellulose derivative and the mol ratio of carboxyl are 1.0～4.3;
The preparation method of described hemicellulose derivative may further comprise the steps:
(1) with the wheat straw of KOH solution extraction delignification, the semicellulose to dissolved in filtrate carries out isolation and purification again;
(2) semicellulose adds entry, at 60～85 ℃ of heating 5～30min;
(3) add sodium hydroxide, react 10～30min down at 20～40 ℃;
(4) add butanols, the volume ratio of butanols and water is 2: 3～4: 1, adds acrylic amide then, at 20～50 ℃, and reaction 4～48h;
(5) neutralization is filtered, washing precipitation, and lyophilize promptly gets the hemicellulose derivative that has two kinds of functional groups;
The unitary mol ratio of xylan was 0.5: 1～4.0: 1 during said sodium hydroxide and semicellulose were formed;
The unitary mol ratio of xylan was 2: 1～20: 1 during said acrylic amide and semicellulose were formed.
2. hemicellulose derivative according to claim 1; It is characterized in that; The wheat straw of the said delignification of step (1) is to obtain through following method: using earlier volume ratio is the wheat straw waste 6h that 2: 1 acetone and ethanol extracting 50g in Soxhlet extractor ground; Use 1000ml water at 75 ℃ of extracting 2h then, residual substance and 75g Textone joined in the 1000ml water at 75 ℃ of heating 2h, with the acetic acid adjust pH 3.8～4.0.
3. hemicellulose derivative according to claim 1; It is characterized in that; The wheat straw of the said use of step (1) KOH solution extraction delignification be use concentration be 8～10% weight KOH at 20～30 ℃ of extracting 8～12h, the amount ratio of the wheat straw of delignification and KOH solution is 1: 20～1: 25gml
-1
4. hemicellulose derivative according to claim 1 is characterized in that: said neutralization is that to use the acetum of 6M to be neutralized to the pH value be 6.0～8.0.
5. the described a kind of application of hemicellulose derivative in papermaking that has two kinds of functional groups of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101811195A CN101838348B (en) | 2010-05-18 | 2010-05-18 | Hemicellulose derivative with two functional groups as well as preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101811195A CN101838348B (en) | 2010-05-18 | 2010-05-18 | Hemicellulose derivative with two functional groups as well as preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101838348A CN101838348A (en) | 2010-09-22 |
| CN101838348B true CN101838348B (en) | 2012-06-20 |
Family
ID=42742045
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010101811195A Expired - Fee Related CN101838348B (en) | 2010-05-18 | 2010-05-18 | Hemicellulose derivative with two functional groups as well as preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101838348B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106268949B (en) * | 2016-08-10 | 2019-07-16 | 华南理工大学 | A kind of modified hemicellulose gel supported precious metal catalyst and preparation and application |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1200952C (en) * | 2002-12-10 | 2005-05-11 | 华南理工大学 | Homogeneous chemical modification of hemicellulose of stalks |
-
2010
- 2010-05-18 CN CN2010101811195A patent/CN101838348B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN101838348A (en) | 2010-09-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Gismatulina et al. | Chemical composition of five Miscanthus sinensis harvests and nitric-acid cellulose therefrom | |
| US8038840B2 (en) | Process for refining and producing cellulose, lignin and xylose from biomass material | |
| CN101503865B (en) | Method for preparing mlcrocrystalline cellulose by corps straw | |
| JP2012512658A5 (en) | ||
| JP2012512657A5 (en) | ||
| CN100558749C (en) | A kind of method of preparing acetylated hemicellulose by employing catalysis of iodine | |
| CN102154876B (en) | Method for extracting and separating components in ramulus mori skin | |
| Abuhay et al. | Opportunities for new biorefinery products from Ethiopian ginning industry by-products: Current status and prospects | |
| CN103397554B (en) | A kind of new technology preparing lignocellulose-like biomass microcrystalline Cellulose | |
| CN105625073A (en) | Raw material pretreatment method for straw-based seedling raising pot, product and production method of seedling raising pot | |
| CN102180977A (en) | Method for preparing antibacterial fiber material by using bagasse | |
| CN104164801A (en) | Method for separating and recycling cellulose, semicellulose and lignin in lignocellulosic biomass at one time | |
| CN105713050B (en) | A kind of method that degradation selectivity corncob hemicellulose improves xylose yield | |
| CN103467751B (en) | The extracting method of humic acids in alcohol tank liquid fermented sludge | |
| Putri et al. | Effect of sodium chloroacetate towards the synthesis of CMC (carboxymethyl cellulose) from durian (Durio zibethinus) peel cellulose | |
| CN114197233B (en) | Method for separating and extracting cellulose nanofibers from agricultural and forestry solid wastes | |
| CN101838348B (en) | Hemicellulose derivative with two functional groups as well as preparation method and application thereof | |
| CN102720089A (en) | Method for preparing straw cellulose membrane by using rice straws as raw materials | |
| MY181466A (en) | Acetic acid based refining process of biomass | |
| CN101838349B (en) | Method for preparing carboxymethyl hemicellulose by microwave radiation | |
| CN106995939A (en) | The method that Jujun grasses fibrillation is produced using chemical method | |
| ITNO20120002A1 (en) | PROCESS FOR THE PRODUCTION OF ORGANIC COMPOUNDS FROM VEGETABLE SPECIES | |
| CN101029459A (en) | Technology for producing ligin by crop straw refuse | |
| CN106702805A (en) | Degradable plant fiber paper preparation method | |
| CN108530546B (en) | Synthesis and application of pseudochitosan and derivatives thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120620 Termination date: 20210518 |