CN107400184A - A kind of preparation method of bagasse xylan g LME/AA/AM tetrabasic graft copolymers - Google Patents
A kind of preparation method of bagasse xylan g LME/AA/AM tetrabasic graft copolymers Download PDFInfo
- Publication number
- CN107400184A CN107400184A CN201710830890.2A CN201710830890A CN107400184A CN 107400184 A CN107400184 A CN 107400184A CN 201710830890 A CN201710830890 A CN 201710830890A CN 107400184 A CN107400184 A CN 107400184A
- Authority
- CN
- China
- Prior art keywords
- lme
- solution
- bagasse xylan
- xylan
- bagasse
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Biological Depolymerization Polymers (AREA)
- Laminated Bodies (AREA)
Abstract
The invention discloses a kind of preparation method of bagasse xylan g LME/AA/AM tetrabasic graft copolymers.Using the bagasse xylan of mechanical activation as initiation material, the L ascorbic acid monoesters of maleic acid 6（LME）, acrylic acid (AA), acrylamide (AM) be grafted monomers, in crosslinking agentN,NIn the presence of di-2-ethylhexylphosphine oxide propyl amides, bagasse xylan g LME/AA/AM tetrabasic graft copolymers are obtained through initiator ammonium persulfate initiation grafting copolyreaction.The present invention is directed to the architectural feature of bagasse xylan molecule, and tetrabasic graft copolymer bagasse xylan g LME/AA/AM have been synthesized by polymerisation in solution.The process conditions are easily controllable, grafting rate is high, steady quality, and terminal olefinic link is contained in strand, and product has good biocompatibility, have larger application potential in the field such as biological medicine and functional material.
Description
Technical field
The present invention relates to technical field of polymer materials, particularly a kind of bagasse xylan-g-LME/AA/AM quaternarys grafting
The preparation method of copolymer.
Background technology
Xylan is a kind of complicated heterogeneous pentose, accounts for the 20%~35% of grass dry weight, is nature
The renewable resource of rich reserves, has a variety of activity related to living organism, such as immunological regulation, anti-oxidant, antitumor.
Its physicochemical property is strengthened by the structural modification to xylan molecule, can further widen it in medicine, food, new function
The application in the fields such as material.
Graft copolymerization is that the important channel of structural modification is carried out to xylan, and main technology and principle include wood and gathered
Macromolecular radical is produced on sugared skeleton so trigger the polymerization of another monomer, the reactive functional groups on xylan strand with
Other polymer molecular chains are coupled two ways.Research both at home and abroad is had focused largely in binary grafting, utilizes double bond group
Unsaturation, addition easily occurs and graft copolymerization prepares functional compounds, but by separate base bioactivity and species
Limitation, the deficiencies of generally existing grafting rate is low, reactivity is poor, product quality difficult control so that the utilization of xylan
By certain limitation.Acrylic acid (Acrylic Acid, AA), acrylamide (Acrylic Amide, AM), maleic two
Acid -6-L ascorbic acid monoesters (6-L-Ascorbyl cis-Butenedioic Acid Monoester, LME) is living in biology
Property, to suppress growth of tumour cell, anti-oxidant etc. performance excellent, graft modification is carried out to xylan according to various of monomer,
And retain the multiple characteristic of xylan and monomer, can obtain physicochemical property and antitumor activity it is more excellent xylan grafting altogether
Poly- product.
The present invention introduces mixed grafting monomer AA, AM and LME, triggered using the bagasse xylan of mechanical activation as raw material
In the presence of agent ammonium persulfate and crosslinking agent N, N- di-2-ethylhexylphosphine oxide propyl amides, it is poly- that bagasse wood has been synthesized using solution polymerization process
Sugar-g-LME/AA/AM tetrabasic graft copolymers.
The content of the invention
It is an object of the invention to provide a kind of preparation method of bagasse xylan-g-LME/AA/AM tetrabasic graft copolymers.
The present invention's concretely comprises the following steps：
(1) weigh 5~10g bagasse xylans, mechanical activation 1 is carried out with ND7-2L type frequency conversion planetary ball mills under normal temperature
~2 hours.
(2) 1.5~2.0g maleic anhydrides are weighed and 2.8~3.6g L-AAs are added to the four-hole bottle of 250mL dryings
In, 0.8~1.0g catalyst p-methyl benzenesulfonic acid is added, it is anti-bad to maleic anhydride and L- in 45 DEG C of stirred in water bath 10~20 minutes
Hematic acid is completely dissolved, and reaction obtains LME solution in 2.5 hours.
(3) LME solution rotary evaporation at 0.09MPa, 30~35 DEG C obtained by step (2) is obtained into clear yellow viscous material,
6~8 hours are dried in 50 DEG C of vacuum drying ovens to constant weight, obtains LME solid products.
(4) weigh 0.01~0.03g N, N '-di-2-ethylhexylphosphine oxide propyl amides, 0.2~0.6g analysis pure acrylic acid (AA),
0.2~0.6g acrylamides (AM) and 0.8~2.2g steps (3) LME solid products in 50mL beakers, are configured to mix monomer
Solution.
(5) take the NaOH solution that 20~50mL mass fractions are 10% that the mixed monomer solution in step (4) is adjusted into pH
To 7~8, it is then added in constant pressure funnel.
(6) ammonium persulfate solution that 8~15mL concentration is 0.5mol/L and the sulfurous that 9~16mL concentration is 0.3mol/L are taken
Acid sodium solution, add mixing in another constant pressure funnel and be used as initiator solution.
(7) weigh the bagasse xylan of the activation obtained by 4~8g steps (1) and 10~15mL distilled water is added to be equipped with and stirred
In the 250mL four-hole boiling flasks for mixing device, thermometer and reflux condenser, 40~70 DEG C are warming up to after being mixed evenly, 3~6
Synchronously the initiator solution of step (5) mixed monomer solution and step (6) is added dropwise in hour, continues reaction and obtains for 1 hour
To reaction mixture.
(8) step (7) products therefrom solution is filtered, is that 80%~95% ethanol solution washs with 20~30mL volume fractions
2~3 times, 6~8 hours are dried in 60 DEG C of vacuum drying oven to constant weight, obtains final product tetrabasic graft copolymer
Bagasse xylan-g-LME/AA/AM.
(9) calculating of tetrabasic graft copolymer bagasse xylan-g-LME/AA/AM grafting rate, grafting efficiency：
Grafting rate：
Grafting efficiency：
In formula：
W0--- activate former bagasse xylan quality, g；
W1--- crude product bagasse xylan-g-LME/AA/AM tetrabasic graft copolymer quality, unit g；
W2--- pure bagasse xylan-g-LME/AA/AM tetrabasic graft copolymer quality, unit g.
The present invention is directed to the architectural feature of bagasse xylan molecule, and tetrabasic graft copolymer sugarcane has been synthesized by polymerisation in solution
Slag xylan-g-LME/AA/AM.The process conditions are easily controllable, grafting rate is high, steady quality, and end alkene is contained in strand
Key, product have good biocompatibility, have larger application potential in the field such as biological medicine and functional material.
Brief description of the drawings
Fig. 1 is the SEM shape appearance figures of former bagasse xylan.
Fig. 2 is tetrabasic graft copolymer bagasse xylan-g-LME/AA/AM SEM shape appearance figures.
Fig. 3 is that the IR of former bagasse xylan schemes.
Fig. 4 is the IR of activation bagasse xylan (a) and tetrabasic graft copolymer bagasse xylan-g-LME/AA/AM (b)
Figure.
Fig. 5 is the XRD of former bagasse xylan.
Fig. 6 is tetrabasic graft copolymer bagasse xylan-g-LME/AA/AM XRD.
Fig. 7 is tetrabasic graft copolymer bagasse xylan-g-LME/AA/AM TG and DTG curves.
Embodiment
Embodiment：
(1) 6g bagasse xylans are weighed, it is small with ND7-2L type frequency conversion planetary ball mills to carry out mechanical activation 2 under normal temperature
When.
(2) 2.0g maleic anhydrides are weighed and 3.6g L-AAs are added in the four-hole bottle of 250mL dryings, are added
0.8g catalyst p-methyl benzenesulfonic acid, it is completely dissolved in 45 DEG C of stirred in water bath 15 minutes to maleic anhydride and L-AA, instead
Answer 2.5 hours and obtain LME solution.
(3) LME solution rotary evaporation at 0.09MPa, 35 DEG C obtained by step (2) is obtained into clear yellow viscous material, at 50 DEG C
8 hours are dried in vacuum drying oven to constant weight, obtains LME solid products.
(4) 0.02g N, N '-di-2-ethylhexylphosphine oxide propyl amides are weighed, 0.5g analyzes pure AA, 0.5g AM and 2.0g steps (3)
LME solid products are configured to mixed monomer solution in 50mL beakers.
(5) take 20mL mass fractions be 10% NaOH solution by step (4) mixed monomer solution adjust pH be about
8, it is then added in constant pressure funnel.
(6) take the ammonium persulfate solution that 10mL concentration is 0.5mol/L and the sodium sulfite that 12mL concentration is 0.3mol/L molten
Liquid, add mixing in another constant pressure funnel and be used as initiator solution.
(7) 4g is activated in step (1) bagasse xylan and 10mL distilled water is weighed to be added to equipped with agitator, thermometer
In the 250mL four-hole boiling flasks of reflux condenser, 50 DEG C are warming up to after being mixed evenly, synchronously will step in 4.5~5 hours
Suddenly (5) mixed monomer solution and the initiator solution of step (6) are added dropwise, and continue reaction and obtain reaction mixture in 1 hour.
(8) step (7) products therefrom solution is filtered, is that 80%% ethanol solution washs 3 times with 25mL volume fractions, in 60
DEG C vacuum drying oven in dry 8 hours to constant weight, obtain final product quaternary and connect
(9) tetrabasic graft copolymer BX-g-LME/AA/AM is measured, obtains its grafting rate as 19.88%, grafting
Efficiency is 82.37%.
Product is analyzed through IR, 1718.69cm-1Locate as carboxylic acids C=O stretching vibration absworption peaks, 1457.52cm-1Locate as carboxylic
Acids-OH in-plane bending vibration absworption peaks；1400.17cm-1There is moderate strength absworption peak in place, is shaken for primary amide C-N is flexible
Dynamic absworption peak；3563.15cm-1There is weaker ester bond C=O stretching vibration absworption peaks, 1138.16cm in place-1Place occurs stronger
Ester bond C-O-C stretching absorbance vibration peaks, AA, AM, LME described above are successfully grafted in xylan chain.Through XRD analysis,
Occur new diffraction maximum at 12.02 °, 18.61 °, 24.22 °, 31.36 °, it is amorphous to illustrate that graft crosslinking modification not only occurs on
Area also occurs at new crystal region.TG-DTG analysis shows, three phases are 350 DEG C~750 DEG C, and mass loss constitutes about production
The 5%~10% of quality, it may be possible to caused by modified side chain fracture.Understood with reference to XRD, as graft skeleton
Interpenetrated between rigid xylan molecular backbone and flexible polypropylene acid amides side chain, be cross-linked with each other to be formed couple hardness with softness it is netted
Macromolecular structure can preferably thermal degradation resistance, therefore the stability of tetrabasic graft copolymer improves.Through sem analysis, mechanical activation 2
The xylan particle of hour is mixed monomer-polymer covering, and surface becomes coarse, amorphous state increase, illustrates to pass through machine
Tool activation is destroyed bagasse xylan particle surface and crystal structure, and chemical reactivity improves, and is enhanced with mixing list
The graft copolymerization of body.
Claims (1)
- A kind of 1. preparation method of bagasse xylan-g-LME/AA/AM tetrabasic graft copolymers, it is characterised in that specific steps For：（1）Weigh 5 ~ 10g bagasse xylans, it is small with ND7-2L type frequency conversion planetary ball mills to carry out mechanical activation 1 ~ 2 under normal temperature When；（2）Weigh 1.5 ~ 2.0g maleic anhydrides and 2.8 ~ 3.6g L-AAs are added in the four-hole bottle of 250mL dryings, add Enter 0.8 ~ 1.0g catalyst p-methyl benzenesulfonic acid, it is complete to maleic anhydride and L-AA in 45 DEG C of stirred in water bath 10 ~ 20 minutes Fully dissolved, reaction obtain LME solution in 2.5 hours；（3）By step（2）Gained LME solution rotary evaporation at 0.09MPa, 30 ~ 35 DEG C obtains clear yellow viscous material, at 50 DEG C 6 ~ 8 hours are dried in vacuum drying oven to constant weight, obtains LME solid products；（4）Weigh 0.01 ~ 0.03gN, N'-di-2-ethylhexylphosphine oxide propyl amides, 0.2 ~ 0.6g analyses pure acrylic acid, 0.2 ~ 0.6g third Acrylamide and 0.8 ~ 2.2g steps（3）LME solid products are configured to mixed monomer solution in 50mL beakers；（5）The NaOH solution that 20 ~ 50mL mass fractions are 10% is taken by step（4）In mixed monomer solution regulation pH to 7 ~ 8, It is then added in constant pressure funnel；（6）Take the ammonium persulfate solution that 8 ~ 15mL concentration is 0.5mol/L and the sulfurous acid that 9 ~ 16mL concentration is 0.3mol/L Sodium solution, add mixing in another constant pressure funnel and be used as initiator solution；（7）Weigh 4 ~ 8g steps（1）The bagasse xylan and 10 ~ 15mL distilled water of gained activation are added to equipped with agitator, temperature In 250 mL four-hole boiling flasks of degree meter and reflux condenser, 40~70 DEG C are warming up to after being mixed evenly, it is same in 3 ~ 6 hours Walk step（5）Mixed monomer solution and step（6）Initiator solution be added dropwise, continuing reaction, to obtain product within 1 hour molten Liquid；（8）Filter step（7）Products therefrom solution, it is that 80% ~ 95% ethanol solution washs 2 ~ 3 times with 20 ~ 30mL volume fractions, in 6 ~ 8 hours are dried in 60 DEG C of vacuum drying oven to constant weight, obtain final product tetrabasic graft copolymer bagasse xylan- g-LME/AA/AM。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710830890.2A CN107400184B (en) | 2017-09-15 | 2017-09-15 | A kind of preparation method of bagasse xylan-g-LME/AA/AM tetrabasic graft copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710830890.2A CN107400184B (en) | 2017-09-15 | 2017-09-15 | A kind of preparation method of bagasse xylan-g-LME/AA/AM tetrabasic graft copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107400184A true CN107400184A (en) | 2017-11-28 |
| CN107400184B CN107400184B (en) | 2019-11-26 |
Family
ID=60388648
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710830890.2A Active CN107400184B (en) | 2017-09-15 | 2017-09-15 | A kind of preparation method of bagasse xylan-g-LME/AA/AM tetrabasic graft copolymer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107400184B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110698595A (en) * | 2019-10-22 | 2020-01-17 | 桂林理工大学 | Synthesis method of bagasse xylan-g-GMA derivative with anticancer activity |
| CN110713569A (en) * | 2019-10-22 | 2020-01-21 | 桂林理工大学 | Preparation method of active bagasse xylan-g-BMA derivative |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106496420A (en) * | 2016-10-26 | 2017-03-15 | 桂林理工大学 | A kind of preparation method of bagasse xylan epicatechol gallate g AA/AM/LME complex denaturation derivants |
| CN106632856A (en) * | 2016-10-26 | 2017-05-10 | 桂林理工大学 | Preparation method of active bagasse xylan ferulate-g-LME/AA/AM |
-
2017
- 2017-09-15 CN CN201710830890.2A patent/CN107400184B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106496420A (en) * | 2016-10-26 | 2017-03-15 | 桂林理工大学 | A kind of preparation method of bagasse xylan epicatechol gallate g AA/AM/LME complex denaturation derivants |
| CN106632856A (en) * | 2016-10-26 | 2017-05-10 | 桂林理工大学 | Preparation method of active bagasse xylan ferulate-g-LME/AA/AM |
Non-Patent Citations (1)
| Title |
|---|
| 陈绍民: "《医药知识》", 31 October 2013, 山东科学技术出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110698595A (en) * | 2019-10-22 | 2020-01-17 | 桂林理工大学 | Synthesis method of bagasse xylan-g-GMA derivative with anticancer activity |
| CN110713569A (en) * | 2019-10-22 | 2020-01-21 | 桂林理工大学 | Preparation method of active bagasse xylan-g-BMA derivative |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107400184B (en) | 2019-11-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107417857B (en) | Synthesis method of anti-cancer active derivative bagasse xylan syringic acid ester-g-AM/MMA | |
| CN101638458B (en) | Method for preparing super absorbent resin by using carboxymethyl potato starch as raw material | |
| CN103724555B (en) | A kind of process for preparation of thermoplastic elastomer | |
| CN107400184B (en) | A kind of preparation method of bagasse xylan-g-LME/AA/AM tetrabasic graft copolymer | |
| CN101935380A (en) | Method for preparing potassium- and nitrogen-containing high water-absorbent resin from carboxymethyl potato starch serving as raw material | |
| CN101638457B (en) | Method for preparing super absorbent resin containing covalent nitrogen by using potato starch as raw material | |
| Khullar et al. | Grafting of acrylonitrile onto cellulosic material derived from bamboo (Dendrocalamus strictus) | |
| CN104761673B (en) | A kind of carbomer and preparation method thereof | |
| CN108752542A (en) | There is weary oxygen, pH dual responsiveness Amphipathilic block polymers and preparation method thereof with what azo bond made connecting key | |
| CN106188404A (en) | The formula of a kind of Technologies of Water-absorbing Resin: Corn Starch Grafting and preparation technology | |
| CN101481435B (en) | Preparation of self-diffusion salt tolerant acroleic acid high hydroscopicity resin | |
| CN106928414A (en) | A kind of preparation method of polymeric sorbent predecessor di-block copolymer | |
| CN1896112A (en) | Random and copolymer cation macromolecular emulsion and its preparation | |
| CN106749850A (en) | A kind of preparation method of damage resistant, high-impact PMMA materials | |
| Mishra et al. | Synthesis of graft copolymers of xyloglucan and acrylonitrile | |
| CN109971001B (en) | Macroporous temperature-sensitive amphiphilic hydrogel material and preparation method thereof | |
| CN110062774A (en) | For producing the preparation method of the acrylonitrile polymers of carbon fiber | |
| CN102675541A (en) | Sodium polyacrylate/polyacrylamide composite moisture-absorption resin and preparation method thereof | |
| CN108299659B (en) | preparation method of pH/temperature double-sensitive hydrogel | |
| CN101654521A (en) | Method for preparing copolymeric hydrogel containing maleylation chitosan structure by electron beam irradiation | |
| Trivedi et al. | Modification of sodium salt of partially carboxymethylated tamarind kernel powder through grafting with acrylonitrile: Synthesis, characterization and swelling behavior | |
| CN106632856A (en) | Preparation method of active bagasse xylan ferulate-g-LME/AA/AM | |
| Yoshida et al. | Graft copolymerization of methyl methacrylate onto curdlan | |
| CN108586676A (en) | Heat resistance graft copolymer and preparation method | |
| CN101724125A (en) | Hydrophobic association polymer with cation surface active monomer and synthesis 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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20171128 Assignee: Guilin Qi Hong Technology Co.,Ltd. Assignor: GUILIN University OF TECHNOLOGY Contract record no.: X2022450000106 Denomination of invention: Preparation of bagasse xylan-g-LME/AA/AM quaternary graft copolymer Granted publication date: 20191126 License type: Common License Record date: 20221121 |
|
| EE01 | Entry into force of recordation of patent licensing contract |