CN109749023A - A kind of preparation method of pH response modified lignin resin nano-micelle - Google Patents
A kind of preparation method of pH response modified lignin resin nano-micelle Download PDFInfo
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- CN109749023A CN109749023A CN201910103932.1A CN201910103932A CN109749023A CN 109749023 A CN109749023 A CN 109749023A CN 201910103932 A CN201910103932 A CN 201910103932A CN 109749023 A CN109749023 A CN 109749023A
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Abstract
The invention belongs to lignin modification and utilize field, and in particular to a kind of preparation method of pH response modified lignin resin nano-micelle.The specific method is as follows: being modified using acryloyl chloride to lignin, prepares acrylated lignin；Acrylated lignin is carried out free radical grafting copolymerization with methacrylic acid to react, prepares acrylated lignin grafted methacrylic acid copolymer；Acrylated lignin grafted methacrylic acid copolymer is dissolved in organic solvent, distilled water is slowly added dropwise under stirring, ultrasonic wave, which is uniformly dispersed, responds modified lignin resin nano-micelle to get pH.Grafting degree of the modified lignin resin nano-micelle methacrylic acid on lignin is high, and the modified lignin resin medicament-carried nano micelle of preparation shows good pH responsiveness in terms of drug release, has a good application prospect in medicament slow release controlled release field.
Description
Technical field
The invention belongs to lignin modification and utilize field, and in particular to a kind of pH response modified lignin resin nano-micelle
Preparation method.
Background technique
Lignin is a kind of natural high-molecular compound, is widely present in plant, is that second is most rich in the world
Rich organic matter.To produce the lignin more than 60,000,000 tons every year in the world in pulp and paper industry, but it is most of
It is used only as the fuel of slurrying boiler or enters refuse landfill directly as waste dumps, the serious wasting of resources and environment is caused to be asked
Topic.Lignin source is wide, renewable, biodegradable, as the exhaustion of fossil fuel is asked with the environmental pollution got worse
Topic, modification and utilization to lignin seem quite important.
Lignin is to connect the complicated virtue formed with irregular form with carbon-carbon bond by ether by phenylpropyl alcohol alkyl structure unit
Fragrant race's polymer.There are phenolic hydroxyl group, alcoholic extract hydroxyl group, methoxyl group isoreactivity group in the molecular structure of lignin, can carry out a variety of
The chemical reaction of type.Graft copolymerization is the important method of chemical modification of lignin, can assign the new function of lignin or more
High performance.The modification of most of lignin is all related with the reactivity of hydroxyl, but phenolic hydroxyl group intramolecular hydrogen easy to form
Key, and reactivity is lower, or even studies have found that the phenolic hydroxyl group on lignin has inhibition to make vinyl monomer free radical polymerization
With which limits the applications of lignin graft modification.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of pH to respond modified lignin resin nano-micelle
Preparation method, it can effectively solve the phenolic hydroxyl group intramolecular hydrogen bond easy to form of lignin, and the problem that reactivity is lower,
And raw material sources are abundant, preparation process is simple, have good application prospect in medicament slow release controlled release field.
A kind of preparation method of pH response modified lignin resin nano-micelle, includes step in detail below:
Lignin and sodium bicarbonate are added in acryloyl chloride, 0.5 ~ 3h is stirred to react at 20 ~ 40 DEG C, reactant is filtered,
It is successively respectively washed three times with 10 ~ 20% sodium bicarbonate aqueous solutions, distilled water and ethyl alcohol, removes unreacted complete acryloyl chloride and carbon
Sour hydrogen sodium, is then dried in vacuo for 24 hours, obtains acrylated lignin；Acrylated lignin is pressed to the weight of 1~50g/100ml
Amount volumetric concentration is dissolved in n,N-Dimethylformamide, and the initiator of methacrylic acid and 0.1 ~ 3% is added, is warming up to 40 ~ 80
DEG C, it is stirred to react 1 ~ 6h, is filtered by vacuum, for 24 hours with water Soxhlet extraction, 50 DEG C of vacuum drying for 24 hours, obtain acrylated lignin and connect
Branch methacrylic acid copolymer；By acrylated lignin grafted methacrylic acid copolymer by 0.001~0.1g/100ml's
Bulking value concentration is dissolved in organic solvent, and stirring is lower to be slowly added dropwise distillation by the volume ratio of water and organic solvent for 1:2 ~ 10:1
Water, ultrasonic 1h are made pH and respond modified lignin resin nano-micelle.
The lignin are as follows: alkali lignin, sulfate-reducing conditions, kraft lignin or organosol lignin.
The mass ratio of the acryloyl chloride and lignin are as follows: 1:2 ~ 50:1.
The mass ratio of the sodium bicarbonate and acryloyl chloride are as follows: 1:3 ~ 3:1.
The mass ratio of the acrylated lignin and methacrylic acid are as follows: 1:1 ~ 1:1000.
The initiator are as follows: benzoyl peroxide, lauroyl peroxide, azodiisobutyronitrile, or by the above initiator
The composite initiation system of composition.
The organic solvent are as follows: N,N-dimethylformamide or dioxane.
The positive effect of the present invention is: 1, by lignin first through acrylated modified, then carrying out with methacrylic acid
Free radical grafting copolymerization reaction can first slough the hydrogen atom of phenolic hydroxyl group and alcoholic extract hydroxyl group on lignin and introduce carbon-to-carbon unsaturation
Double bond, the reactivity that unsaturated double-bond participates in free radical polymerization is more much bigger than the activity of phenolic hydroxyl group or alcoholic extract hydroxyl group, therefore can
To improve grafting rate of the methacrylic acid on lignin, to improve the PH responding ability of modified lignin resin nano-micelle.2,
By acrylated lignin, lignin macromonomer is prepared, then carries out graft copolymerization with methacrylic acid, poly- first can be made
Distribution of the base acrylic acid branch on lignin is more uniform.3, the preparation method have raw material sources abundant, simple process, at
This cheap advantage has good application prospect in medicament slow release controlled release field.
Detailed description of the invention
Fig. 1 is 1 lignin of embodiment, lignin grafted methacrylic acid and acrylated lignin grafted methacrylic acid
Infrared spectrogram.
Fig. 2 is the transmission electron microscope picture that pH responds modified lignin resin nano-micelle in embodiment 1.
Fig. 3 is drug release patterns of the 1 modified lignin resin medicament-carried nano micelle of embodiment in different pH value media.
Specific embodiment
For a better understanding of the present invention, below with reference to embodiment and attached drawing, invention is further described in detail, but
It is that the scope of protection of the invention is not limited to range represented by embodiment.
Embodiment 1
2g alkali lignin and 8g sodium bicarbonate are added in 20ml acryloyl chloride, 2h is stirred to react at 30 DEG C, by reactant mistake
Filter is successively respectively washed three times with 10% sodium bicarbonate aqueous solution, distilled water and ethyl alcohol, and unreacted complete acryloyl chloride and carbon are removed
Sour hydrogen sodium, is then dried in vacuo for 24 hours, obtains acrylated lignin；The acrylated lignin of 1g is dissolved in 10ml N, N- diformazan
In base formamide, the benzoyl peroxide of 2g methacrylic acid and 2% is added, is warming up to 50 DEG C, is stirred to react 3h, is filtered by vacuum,
For 24 hours with water Soxhlet extraction, 50 DEG C of vacuum drying for 24 hours, obtain acrylated lignin grafted methacrylic acid copolymer；By 5mg
Acrylated lignin grafted methacrylic acid copolymer is dissolved in 10ml n,N-Dimethylformamide, is slowly added dropwise under stirring
10ml distilled water, ultrasound 60 minutes are made pH and respond modified lignin resin nano-micelle.
Fig. 1 is the infrared of lignin, lignin grafted methacrylic acid and acrylated lignin grafted methacrylic acid
Spectrogram.Used sample all passes through purification process, eliminates the homopolymer of methacrylic acid and the methyl-prop that unreacted is complete
Acrylic monomer.Lignin grafted methacrylic acid in figure be by alkali lignin without acrylated modification directly and methyl-prop
Olefin(e) acid carry out graft copolymerization be made, the condition of preparation with more than acrylated lignin grafted methacrylic acid it is identical.It can be with
Find out, compared to lignin, lignin grafted methacrylic acid copolymer is in 3714 cm-1Neighbouring hydroxyl vibration absworption peak and
1724 cm-1Neighbouring carbonyl vibration absorption peak is reinforced, and illustrates that methacrylic acid successfully grafts on lignin.And it compares
For lignin grafted methacrylic acid, acrylated lignin grafted methacrylic acid is in 3714 cm-1With 1724 cm-1
The absorption intensity at place is greatly improved again, illustrates that grafting rate of the methacrylic acid on acrylated lignin will be significantly greater than
Its grafting rate on lignin.
Fig. 2 is the transmission electron microscope picture of pH response modified lignin resin nano-micelle.Figure it is seen that micella is spherical in shape, grain
Diameter is located within the scope of 10 ~ 40nm.
Using brufen as model drug, 10mg brufen and the acrylated lignin grafted methacrylic acid copolymerization of 10mg are taken
Object is dissolved in 1ml n,N-Dimethylformamide, is slowly added dropwise 10ml distilled water under stirring, ultrasound 60 minutes, under 10000rpm from
Heart 15min, pours out supernatant, and lower sediment thing is taken to be added in 20ml distilled water, ultrasonic 30min, then obtained by freeze drying pH
Respond modified lignin resin medicament-carried nano micelle.Fig. 3 is drug release patterns of the medicament-carried nano micelle in different pH value media.
As seen from Figure 3, under the neutral environment of pH=7.4, drug accumulation burst size of the carrier micelle in 72h is about 91%, and
In the acid medium of pH=1.0, the cumulative release amount in 72h only has 54%, shows good pH responsiveness.
Embodiment 2
2g alkali lignin and 8g sodium bicarbonate are added in 20ml acryloyl chloride, 2h is stirred to react at 30 DEG C, by reactant mistake
Filter is successively respectively washed three times with 10% sodium bicarbonate aqueous solution, distilled water and ethyl alcohol, and unreacted complete acryloyl chloride and carbon are removed
Sour hydrogen sodium, is then dried in vacuo for 24 hours, obtains acrylated lignin；The acrylated lignin of 1g is dissolved in 10ml N, N- diformazan
In base formamide, the benzoyl peroxide of 1.75g methacrylic acid and 2% is added, is warming up to 50 DEG C, be stirred to react 3h, vacuum is taken out
Filter, for 24 hours with water Soxhlet extraction, 50 DEG C of vacuum drying for 24 hours, obtain acrylated lignin grafted methacrylic acid copolymer；It will
The acrylated lignin grafted methacrylic acid copolymer of 5mg is dissolved in 10ml n,N-Dimethylformamide, stirs lower slowly drop
Add 10ml distilled water, ultrasound 60 minutes is made pH and responds modified lignin resin nano-micelle.
PH is made by the same method of embodiment 1 and responds modified lignin resin medicament-carried nano micelle, tests it in different pH value
Drug release in medium.As a result are as follows: under the neutral environment of pH=7.4, drug accumulation burst size of the carrier micelle in 72h
About 88%, and in the acid medium of pH=1.0, the cumulative release amount in 72h only has 49%, shows good pH responsiveness.
Embodiment 3
2g alkali lignin and 8g sodium bicarbonate are added in 20ml acryloyl chloride, 2h is stirred to react at 30 DEG C, by reactant mistake
Filter is successively respectively washed three times with 10% sodium bicarbonate aqueous solution, distilled water and ethyl alcohol, and unreacted complete acryloyl chloride and carbon are removed
Sour hydrogen sodium, is then dried in vacuo for 24 hours, obtains acrylated lignin；The acrylated lignin of 1g is dissolved in 10ml N, N- diformazan
In base formamide, the benzoyl peroxide of 1.5g methacrylic acid and 2% is added, is warming up to 50 DEG C, be stirred to react 3h, vacuum is taken out
Filter, for 24 hours with water Soxhlet extraction, 50 DEG C of vacuum drying for 24 hours, obtain acrylated lignin grafted methacrylic acid copolymer；It will
The acrylated lignin grafted methacrylic acid copolymer of 5mg is dissolved in 10ml n,N-Dimethylformamide, stirs lower slowly drop
Add 10ml distilled water, ultrasound 60 minutes is made pH and responds modified lignin resin nano-micelle.
PH is made by the same method of embodiment 1 and responds modified lignin resin medicament-carried nano micelle, tests it in different pH value
Drug release in medium.As a result are as follows: under the neutral environment of pH=7.4, drug accumulation burst size of the carrier micelle in 72h
About 89%, and in the acid medium of pH=1.0, the cumulative release amount in 72h only has 38%, shows good pH responsiveness.
Embodiment 4
2g alkali lignin and 8g sodium bicarbonate are added in 20ml acryloyl chloride, 2h is stirred to react at 30 DEG C, by reactant mistake
Filter is successively respectively washed three times with 10% sodium bicarbonate aqueous solution, distilled water and ethyl alcohol, and unreacted complete acryloyl chloride and carbon are removed
Sour hydrogen sodium, is then dried in vacuo for 24 hours, obtains acrylated lignin；The acrylated lignin of 1g is dissolved in 10ml N, N- diformazan
In base formamide, the benzoyl peroxide of 1g methacrylic acid and 2% is added, is warming up to 50 DEG C, is stirred to react 3h, is filtered by vacuum,
For 24 hours with water Soxhlet extraction, 50 DEG C of vacuum drying for 24 hours, obtain acrylated lignin grafted methacrylic acid copolymer；By 5mg
Acrylated lignin grafted methacrylic acid copolymer is dissolved in 10ml n,N-Dimethylformamide, is slowly added dropwise under stirring
10ml distilled water, ultrasound 60 minutes are made pH and respond modified lignin resin nano-micelle.
PH is made by the same method of embodiment 1 and responds modified lignin resin medicament-carried nano micelle, tests it in different pH value
Drug release in medium.As a result are as follows: under the neutral environment of pH=7.4, drug accumulation burst size of the carrier micelle in 72h
About 86%, and in the acid medium of pH=1.0, the cumulative release amount in 72h only has 58%, shows good pH responsiveness.
Claims (7)
1. a kind of preparation method of pH response modified lignin resin nano-micelle, it is characterised in that include step in detail below:
Lignin and sodium bicarbonate are added in acryloyl chloride, 0.5 ~ 3h is stirred to react at 20 ~ 40 DEG C, reactant is filtered,
It is successively respectively washed three times with 10 ~ 20% sodium bicarbonate aqueous solutions, distilled water and ethyl alcohol, removes unreacted complete acryloyl chloride and carbon
Sour hydrogen sodium, is then dried in vacuo for 24 hours, obtains acrylated lignin；Acrylated lignin is pressed to the weight of 1~50g/100ml
Amount volumetric concentration is dissolved in n,N-Dimethylformamide, and the initiator of methacrylic acid and 0.1 ~ 3% is added, is warming up to 40 ~ 80
DEG C, it is stirred to react 1 ~ 6h, is filtered by vacuum, for 24 hours with water Soxhlet extraction, 50 DEG C of vacuum drying for 24 hours, obtain acrylated lignin and connect
Branch methacrylic acid copolymer；By acrylated lignin grafted methacrylic acid copolymer by 0.001~0.1g/100ml's
Bulking value concentration is dissolved in organic solvent, and stirring is lower to be slowly added dropwise distillation by the volume ratio of water and organic solvent for 1:2 ~ 10:1
Water, ultrasonic 1h are made pH and respond modified lignin resin nano-micelle.
2. a kind of preparation method of pH response modified lignin resin nano-micelle according to claim 1, it is characterised in that institute
The lignin stated are as follows: alkali lignin, sulfate-reducing conditions, kraft lignin or organosol lignin.
3. a kind of preparation method of pH response modified lignin resin nano-micelle according to claim 1, it is characterised in that institute
The mass ratio of the acryloyl chloride and lignin stated are as follows: 1:2 ~ 50:1.
4. a kind of preparation method of pH response modified lignin resin nano-micelle according to claim 1, it is characterised in that institute
The mass ratio of the sodium bicarbonate and acryloyl chloride stated are as follows: 1:3 ~ 3:1.
5. a kind of preparation method of pH response modified lignin resin nano-micelle according to claim 1, it is characterised in that institute
The mass ratio of the acrylated lignin and methacrylic acid stated are as follows: 1:1 ~ 1:1000.
6. a kind of preparation method of pH response modified lignin resin nano-micelle according to claim 1, it is characterised in that institute
The initiator stated are as follows: benzoyl peroxide, lauroyl peroxide, azodiisobutyronitrile, or be made of the above initiator compound
Initiation system.
7. a kind of preparation method of pH response modified lignin resin nano-micelle according to claim 1, it is characterised in that institute
The organic solvent stated are as follows: N,N-dimethylformamide or dioxane.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114672031A (en) * | 2022-04-15 | 2022-06-28 | 苏州市焕彤科技有限公司 | PH response polymer nano-drug and preparation method thereof |
| CN114933785A (en) * | 2022-04-29 | 2022-08-23 | 上海昶法新材料有限公司 | Modified lignin/PBAT biodegradable plastic and preparation method thereof |
| CN116120587A (en) * | 2023-02-02 | 2023-05-16 | 广东工业大学 | PH response lignin and preparation method and application thereof |
| CN116120587B (en) * | 2023-02-02 | 2024-04-26 | 广东工业大学 | PH response lignin and preparation method and application thereof |
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| US20160222151A1 (en) * | 2015-02-03 | 2016-08-04 | Florida State University Research Foundation, Inc. | Lignin-Containing Polymers |
| CN104974355A (en) * | 2015-07-27 | 2015-10-14 | 华南理工大学 | pH-responsive amino sodium lignosulphonate as well as preparation method and application thereof |
| WO2018161165A1 (en) * | 2017-03-09 | 2018-09-13 | Fpinnovations | Process for producing an anionic lignin copolymer under aqueous acid conditions |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114672031A (en) * | 2022-04-15 | 2022-06-28 | 苏州市焕彤科技有限公司 | PH response polymer nano-drug and preparation method thereof |
| CN114933785A (en) * | 2022-04-29 | 2022-08-23 | 上海昶法新材料有限公司 | Modified lignin/PBAT biodegradable plastic and preparation method thereof |
| CN116120587A (en) * | 2023-02-02 | 2023-05-16 | 广东工业大学 | PH response lignin and preparation method and application thereof |
| CN116120587B (en) * | 2023-02-02 | 2024-04-26 | 广东工业大学 | PH response lignin and preparation method and application thereof |
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