CN107400184B - A kind of preparation method of bagasse xylan-g-LME/AA/AM tetrabasic graft copolymer - Google Patents
A kind of preparation method of bagasse xylan-g-LME/AA/AM tetrabasic graft copolymer Download PDFInfo
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- CN107400184B CN107400184B CN201710830890.2A CN201710830890A CN107400184B CN 107400184 B CN107400184 B CN 107400184B CN 201710830890 A CN201710830890 A CN 201710830890A CN 107400184 B CN107400184 B CN 107400184B
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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Abstract
The invention discloses a kind of preparation methods of bagasse xylan-g-LME/AA/AM tetrabasic graft copolymer.Using the bagasse xylan of mechanical activation as starting material, maleic acid -6-L ascorbic acid monoesters (LME), acrylic acid (AA), acrylamide (AM) are grafted monomers, in crosslinking agentN,NIn the presence of '-di-2-ethylhexylphosphine oxide propyl amides, bagasse xylan-g-LME/AA/AM tetrabasic graft copolymer is obtained through initiator ammonium persulfate initiation grafting copolyreaction.The present invention is directed to the structure feature of bagasse xylan molecule, has synthesized tetrabasic graft copolymer bagasse xylan-g-LME/AA/AM by polymerisation in solution.The process conditions are easily controllable, grafting rate is high, quality is stable, and terminal olefinic link is contained in strand, and product has good biocompatibility, have biggish application potential in the fields such as biological medicine and functional material.
Description
Technical field
The present invention relates to technical field of polymer materials, especially a kind of bagasse xylan-g-LME/AA/AM quaternary grafting
The preparation method of copolymer.
Background technique
Xylan is a kind of heterogeneous pentose of complexity, accounts for about the 20%~35% of gramineae plant dry weight, is nature
The renewable resource of rich reserves has a variety of activity relevant to living organism, such as immunological regulation, anti-oxidant, antitumor.
Enhance its physicochemical property 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 the important channel that structural modification is carried out to xylan, and main technology and principle include that wood is poly-
Macromolecular radical is generated on sugared skeleton so cause another monomer polymerization, the reactive functional groups on xylan strand with
Other polymer molecular chains are coupled two ways.Research both at home and abroad has focused largely in binary grafting, utilizes double bond group
Unsaturation, Yi Fasheng addition and graft copolymerization prepare functional compounds, but by separate base bioactivity and type
Limitation, the deficiencies of generally existing grafting rate is low, reactivity is poor, product quality is difficult to control, so that the development and 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, inhibit growth of tumour cell, it is anti-oxidant etc. be excellent in, graft modification is carried out to xylan according to various of monomer,
And retain the multiple characteristic of xylan and monomer, can be obtained physicochemical property and anti-tumor activity it is more excellent xylan grafting altogether
Poly- product.
The present invention introduces mixed grafting monomer AA, AM and LME, is causing using the bagasse xylan of mechanical activation as raw material
Under the action 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 copolymer.
Summary of the invention
The object of the present invention is to provide a kind of preparation methods of bagasse xylan-g-LME/AA/AM tetrabasic graft copolymer.
Specific steps of the invention are as follows:
(1) it weighs 5~10g bagasse xylan, carries out mechanical activation 1 with ND7-2L type frequency conversion planetary ball mill under room temperature
~2 hours.
(2) it weighs 1.5~2.0g maleic anhydride and 2.8~3.6g L-AA is added to the dry four-hole bottle of 250mL
In, be added 0.8~1.0g catalyst p-methyl benzenesulfonic acid, 45 DEG C stirred in water bath 10~20 minutes it is anti-bad to maleic anhydride and L-
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 substance, In
LME solid product is obtained to constant weight within drying 6~8 hours in 50 DEG C of vacuum drying ovens.
(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 acrylamide (AM) and 0.8~2.2g step (3) LME solid product in 50mL beaker, are configured to mix monomer
Solution.
(5) take the NaOH solution that 20~50mL mass fraction is 10% that the mixed monomer solution in step (4) is adjusted 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 is added mixing in another constant pressure funnel and is used as initiator solution.
(7) bagasse xylan and 10~15mL distilled water for weighing 4~8g step (1) resulting activation are added to be equipped with and stir
It mixes in the 250mL four-hole boiling flask of device, thermometer and reflux condenser, 40~70 DEG C is warming up to after being mixed evenly, 3~6
The initiator solution of step (5) mixed monomer solution and step (6) is added dropwise for synchronization in hour, the reaction was continued 1 hour
To reaction mixture.
(8) step (7) products therefrom solution is filtered, is that 80%~95% ethanol solution washs with 20~30mL volume fraction
2~3 times, final product tetrabasic graft copolymer is obtained to constant weight within drying 6~8 hours in 60 DEG C of vacuum drying oven
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 structure feature of bagasse xylan molecule, has synthesized tetrabasic graft copolymer sugarcane by polymerisation in solution
Slag xylan-g-LME/AA/AM.The process conditions are easily controllable, grafting rate is high, quality is stable, and end alkene is contained in strand
Key, product have good biocompatibility, have biggish application potential in the fields such as biological medicine and functional material.
Detailed description of the invention
Fig. 1 is the SEM shape appearance figure of former bagasse xylan.
Fig. 2 is the SEM shape appearance figure of tetrabasic graft copolymer bagasse xylan-g-LME/AA/AM.
Fig. 3 is the IR figure of former bagasse xylan.
Fig. 4 is the IR for activating bagasse xylan (a) and tetrabasic graft copolymer bagasse xylan-g-LME/AA/AM (b)
Figure.
Fig. 5 is the XRD diagram of former bagasse xylan.
Fig. 6 is the XRD diagram of tetrabasic graft copolymer bagasse xylan-g-LME/AA/AM.
Fig. 7 is TG the and DTG curve of tetrabasic graft copolymer bagasse xylan-g-LME/AA/AM.
Specific embodiment
Embodiment:
(1) 6g bagasse xylan is weighed, it is small with ND7-2L type frequency conversion planetary ball mill to carry out mechanical activation 2 under room temperature
When.
(2) it weighs 2.0g maleic anhydride and 3.6g L-AA is added in the dry four-hole bottle of 250mL, be added
0.8g catalyst p-methyl benzenesulfonic acid is completely dissolved, instead in 45 DEG C of stirred in water bath 15 minutes to maleic anhydride and L-AA
It answers 2.5 hours and obtains LME solution.
(3) LME solution rotary evaporation at 0.09MPa, 35 DEG C obtained by step (2) is obtained into clear yellow viscous substance, at 50 DEG C
LME solid product is obtained to constant weight within drying 8 hours in vacuum drying oven.
(4) 0.02g N is weighed, N '-di-2-ethylhexylphosphine oxide propyl amides, 0.5g analyze pure AA, 0.5g AM and 2.0g step (3)
LME solid product is configured to mixed monomer solution in 50mL beaker.
(5) take 20mL mass fraction 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 is added mixing in another constant pressure funnel and is 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 blender, thermometer
In the 250mL four-hole boiling flask of reflux condenser, 50 DEG C are warming up to after being mixed evenly, it is synchronous in 4.5~5 hours to walk
Suddenly (5) mixed monomer solution and the initiator solution of step (6) are added dropwise, and the reaction was continued 1 hour obtains reaction mixture.
(8) step (7) products therefrom solution is filtered, is that 80%% ethanol solution washs 3 times with 25mL volume fraction, 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 and is 19.88%, is grafted
Efficiency is 82.37%.
Product is analyzed through IR, 1718.69cm-1Place is carboxylic acids C=O stretching vibration absworption peak, 1457.52cm-1Place is carboxylic
Acids-OH in-plane bending vibration absorption peak；1400.17cm-1There is moderate strength absorption peak in place, for the flexible vibration of primary amide C-N
Dynamic absorption peak；3563.15cm-1There is weaker ester bond C=O stretching vibration absworption peak, 1138.16cm in place-1Place occurs stronger
Ester bond C-O-C stretching absorbance vibration peak, AA, AM, LME described above are successfully grafted in xylan chain.Through XRD analysis, In
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 be 350 DEG C~750 DEG C, mass loss accounts about production
The 5%~10% of quality, it may be possible to caused by modified branch fracture.In conjunction with XRD diagram it is found that as graft skeleton
Interpenetrated between rigid xylan molecular backbone and flexible polypropylene amide branch, 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 raising of tetrabasic graft copolymer.Through sem analysis, mechanical activation 2
The xylan particle of hour is mixed monomer-polymer covering, and surface becomes coarse, and amorphous state increases, and illustrates to pass through machine
Tool activation destroys bagasse xylan particle surface and crystal structure, and chemical reactivity improves, and enhances and mixes list
The graft copolymerization of body.
Claims (1)
1. a kind of preparation method of bagasse xylan-g-LME/AA/AM tetrabasic graft copolymer, it is characterised in that specific steps
Are as follows:
(1) 5 ~ 10g bagasse xylan is weighed, it is small with ND7-2L type frequency conversion planetary ball mill to carry out mechanical activation 1 ~ 2 under room temperature
When；
(2) it weighs 1.5 ~ 2.0g maleic anhydride and 2.8 ~ 3.6g L-AA is added in the dry four-hole bottle of 250mL, add
Enter 0.8 ~ 1.0g catalyst p-methyl benzenesulfonic acid, 45 DEG C stirred in water bath 10 ~ 20 minutes it is complete to maleic anhydride and L-AA
Fully dissolved, reaction obtain 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 substance, at 50 DEG C
LME solid product is obtained to constant weight within drying 6 ~ 8 hours in vacuum drying oven；
(4) 0.01 ~ 0.03g is weighedN, N'-di-2-ethylhexylphosphine oxide propyl amides, 0.2 ~ 0.6g analyze pure acrylic acid, 0.2 ~ 0.6g third
Acrylamide and 0.8 ~ 2.2g step (3) LME solid product in 50mL beaker, are configured to mixed monomer solution；
(5) take the NaOH solution that 20 ~ 50mL mass fraction is 10% that the mixed monomer solution in step (4) is adjusted 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 acid that 9 ~ 16mL concentration is 0.3mol/L are taken
Sodium solution is added mixing in another constant pressure funnel and is used as initiator solution；
(7) it weighs the bagasse xylan activated obtained by 4 ~ 8g step (1) and 10 ~ 15mL distilled water is added to equipped with blender, 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
The initiator solution of step (5) mixed monomer solution and step (6) is added dropwise step, and the reaction was continued, and to obtain product within 1 hour molten
Liquid；
(8) step (7) products therefrom solution is filtered, is that 80% ~ 95% ethanol solution washs 2 ~ 3 times with 20 ~ 30mL volume fraction, in
Final product tetrabasic graft copolymer bagasse xylan-is obtained to constant weight within drying 6 ~ 8 hours in 60 DEG C of vacuum drying oven
g-LME/AA/AM。
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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 |