CN109880026A - A kind of preparation method of the nano lignin hydridization dual network composite hydrogel of high-mechanical property - Google Patents
A kind of preparation method of the nano lignin hydridization dual network composite hydrogel of high-mechanical property Download PDFInfo
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- CN109880026A CN109880026A CN201910202145.2A CN201910202145A CN109880026A CN 109880026 A CN109880026 A CN 109880026A CN 201910202145 A CN201910202145 A CN 201910202145A CN 109880026 A CN109880026 A CN 109880026A
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Abstract
The invention discloses a kind of preparation methods of the nano lignin hydridization dual network composite hydrogel of high-mechanical property, it mainly comprises the steps that first that agar is soluble in water, agar powder is heated to be completely dissolved, addition water-soluble polymer monomer, water-soluble cellulose ether in agar powder solution is stated then up, a little photoinitiator, a little lignin nanoparticle are uniformly mixed, acquired solution place at room temperature a period of time to solution solidify, then place in the UV lamp irradiation cause polymerization.The hydrogel of this method preparation is the characteristic using the sol-gel transition of agar, form the first layer network structure of gel, water-soluble polymer monomer forms second layer network structure, and utilize water-soluble cellulose ether, the characteristic of the multiple interaction of nano lignin and hydrogel network, improve hydrogel mechanical performance, this is a kind of effective ways of toughening enhancing hydrogel, can be used for pharmaceutical carrier, human tissue engineering.
Description
Technical field
The invention belongs to the nano lignin hydridization of hydrogel preparation technical field more particularly to a kind of high-mechanical property is double
The preparation method of network combined hydrogel.
Background technique
Hydrogel is to refer to absorb and keep large quantity of moisture and not soluble in water and having certain three-dimensional structure one
Birds of the same feather flock together condensation material, in the water soluble polymer containing reticular structure, there are hydrophobic groupings and hydrophilic group in water soluble polymer
Hydrone is connected to netted inside by group, hydrophilic radical and water molecules, and hydrophobic grouping water-swellable forms network structure
Skeleton hydrone is lockked, so that it is kept certain water content.Because of the presence of the special three-dimensional network system of hydrogel, make it
Property is soft, is able to maintain certain shape, and water content is higher.It is therefore widely used in pharmaceutical carrier, organizational project, sewage
The fields such as processing.But the mechanical strength and toughness of most of synthetic hydrogels are poor, limit it and are more widely applied.It closes
It is always the direction that scientific research personnel explores, double-network hydrogel, nanometer at novel high-mechanical property and restorative good hydrogel
Composite hydrogel, the hydrogels such as triblock polymer hydrogel are increasingly by everybody concern.
It is current research shows that the double-network hydrogel that two cross-linked networks with strong dissymmetrical structure form can lead to
It crosses to adjust using various polymer and improves mechanical performance with intermolecular interact with structure between two networks.
Double-network hydrogel usually passes through the continuous free radical polymerisation process synthesis of multistep.Firstly, using strong polyelectrolyte (such as poly- third
Olefin(e) acid, polyacrylamide) form the first layer network of height covalent cross-linking.Due to the strong expansion of polyelectrolyte, when will gather
Electrolyte hydrogel, which enters, contains second of neutral second comonomer polymerizeing, and when in the solution of initiator and crosslinking agent, these are anti-
Answer object to will diffuse into the first layer network, and with the first layer network it is loose be cross-linked to form the second network.Multistep polymerization method is
Demonstrate its feasibility for generating different high intensity hydrogels.But the shortcomings that this polymerization, is: polymerization cycle 1 ~ 2 day, consumption
Duration, and since swollen needs a large amount of neutral second comonomer, it is bigger to the consumption of neutral second comonomer.
Summary of the invention
It is an object of the invention to solve deficiency in the prior art, a kind of lignin dual network of high-mechanical property is provided
The preparation method of composite hydrogel forms the first layer network structure of gel using the characteristic of the sol-gel transition of agar,
Water-soluble polymer monomer forms second layer network structure, utilizes water-soluble cellulose ether, nano lignin and hydrogel network
Multiple interaction characteristic, improve the mechanical performance of hydrogel;And the present invention is made using the sol-gel characteristic of agar
Double-network hydrogel can save swollen process, save a large amount of preparation times.
The technical solution of the present invention is as follows: a kind of preparation of high-mechanical property nano lignin hydridization dual network composite hydrogel
Method, specific preparation step are as follows:
1) lignin is soluble in water, it is sonicated, form lignin nanoparticle suspension;
2) agar powder is dissolved in deionized water, is heated to agar powder and is completely dissolved;
3) by water-soluble polymer monomer, water-soluble cellulose ether is added and walks in hot solution, is uniformly mixed;
4) photoinitiator is added into the mixed solution of step 3, lignin nanoparticle suspension stirs, room temperature
It stands to above-mentioned reactant and becomes solid, reactant solid is put into the polymerization a period of time i.e. system of completion hydrogel under ultraviolet lamp
It is standby.
Further, the first network of hydrogel accounts for the 5 ~ 15% of solid content by agar molecule construction, the content of agar.
Further, the second network of hydrogel is built-up by water-soluble polymer monomer polymerization, the content of polymer
Account for the 60 ~ 90% of solid content.
Further, the polymer monomer is including acrylic acid, acrylamide, vinyl alcohol and vinyl pyrrolidone
The strong electrolyte for forming polymer network.
Further, the water-soluble cellulose ether added in hydrogel preparation process includes methylcellulose, ethyl cellulose
Element, propyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, DEAE-cellulose and
Carboxymethyl cellulose.
Further, the partial size of lignin nanoparticle is 80 ~ 1000 nm.
Further, the viscosity profile of water-soluble cellulose ether is in 5000 ~ 8000 mPas.
Further, the water content in the hydrogel of preparation is 75 ~ 87%.
Further, it is 5 ~ 25% that the content of water-soluble cellulose ether and nano lignin, which accounts for the ratio of solid content,.
The invention has the benefit that
1. the raw material using the hydrogel of method disclosed by the invention preparation is water-soluble cellulose ether from a wealth of sources, water-soluble
Property polymer monomer, agar and deionized water, it is low in cost;
2. for enhancing the water-soluble cellulose ether, agar and nano lignin of hydrogel mechanical performance selected by the present invention
With good biocompatibility, advantages of environment protection;
3. composite hydrogel of the present invention has higher mechanical performance compared to traditional hydrogel;
4. composite hydrogel preparation step of the present invention is simple, short preparation period can be promoted the use of on a large scale;
5. composite hydrogel of the present invention does not add crosslinking agent, product is renewable, degradable.
Specific embodiment
Following embodiment further illustrates the contents of the present invention, but should not be construed as limiting the invention.Without departing substantially from
In the case where essence of the present invention, to modification made by the method for the present invention, step or condition and replaces, belong to model of the invention
It encloses.
Embodiment one
The agar of 0.1 ~ 1 g is dissolved in the water of 25 mL, is stirred evenly, solution is heated to agar powder and water complete miscibility, so
3 ~ 10 g acrylamides, 0.1 ~ 1.5 g hydroxyethyl cellulose, a little photoinitiator and a little wooden are added in backward above-mentioned solution
Plain nano granule suspension is uniformly mixed, and is placed a period of time to solution at room temperature and is solidified, rear place polymerize in the UV lamp
50~60 min。
Embodiment two
The agar of 0.1 ~ 1 g is dissolved in the water of 25 mL, is stirred evenly, solution is heated to agar powder and water complete miscibility, so
3 ~ 10 g acrylic acid, 0.1 ~ 1.5 g hydroxyethyl cellulose, a little photoinitiator and a little lignin is added in backward above-mentioned solution
Nano granule suspension is uniformly mixed, and is placed a period of time to solution at room temperature and is solidified, it is rear place polymerization 50 in the UV lamp ~
60 min。
Embodiment three
The agar of 0.1 ~ 1 g is dissolved in the water of 25 mL, is stirred evenly, solution is heated to agar powder and water complete miscibility, so
3 ~ 10 g vinyl alcohols, 0.1 ~ 1.5 g hydroxyethyl cellulose, a little photoinitiator and a little lignin is added in backward above-mentioned solution
Nano granule suspension is uniformly mixed, and is placed a period of time to solution at room temperature and is solidified, it is rear place polymerization 50 in the UV lamp ~
60 min。
Example IV
The agar of 0.1 ~ 1 g is dissolved in the water of 25 mL, is stirred evenly, solution is heated to agar powder and water complete miscibility, so
3 ~ 10 g acrylic acid, 0.1 ~ 1.5 g hydroxypropyl cellulose, a little photoinitiator and a little lignin is added in backward above-mentioned solution
Nano granule suspension is uniformly mixed, and is placed a period of time to solution at room temperature and is solidified, it is rear place polymerization 50 in the UV lamp ~
60 min。
Embodiment five
The agar of 0.1 ~ 1 g is dissolved in the water of 25 mL, is stirred evenly, solution is heated to agar powder and water complete miscibility, so
3 ~ 10 g acrylic acid, 0.1 ~ 1.5 g methylcellulose, a little photoinitiator and a little lignin is added in backward above-mentioned solution to receive
Rice grain suspension is uniformly mixed, and is placed a period of time to solution at room temperature and is solidified, rear place polymerize 50 ~ 60 in the UV lamp
min。
Embodiment six
The agar of 0.1 ~ 1 g is dissolved in the water of 25 mL, is stirred evenly, solution is heated to agar powder and water complete miscibility, so
3 ~ 10 g acrylic acid, 0.1 ~ 1.5 g ethyl cellulose, a little photoinitiator and a little lignin is added in backward above-mentioned solution to receive
Rice grain suspension is uniformly mixed, and is placed a period of time to solution at room temperature and is solidified, rear place polymerize 50 ~ 60 in the UV lamp
min。
Embodiment seven
The agar of 0.1 ~ 1 g is dissolved in the water of 25 mL, is stirred evenly, solution is heated to agar powder and water complete miscibility, so
3 ~ 10 g acrylic acid, 0.1 ~ 1.5 g hydroxypropyl methyl cellulose, a little photoinitiator and a little wood are added in backward above-mentioned solution
Quality nano granule suspension is uniformly mixed, and is placed a period of time to solution at room temperature and is solidified, rear place is gathered in the UV lamp
Close 50 ~ 60 min.
Embodiment eight
The agar of 0.1 ~ 1 g is dissolved in the water of 25 mL, is stirred evenly, solution is heated to agar powder and water complete miscibility, so
3 ~ 10 g acrylamides, 0.1 ~ 1.5 g hydroxymethyl cellulose, a little photoinitiator and a little wooden are added in backward above-mentioned solution
Plain nano granule suspension is uniformly mixed, and is placed a period of time to solution at room temperature and is solidified, rear place polymerize in the UV lamp
50~60 min。
Basic principles and main features and advantage of the invention have been shown and described above.But the foregoing is merely this hairs
Bright specific embodiment, technical characteristic of the invention are not limited thereto, and any those skilled in the art is not departing from this hair
The other embodiments obtained under bright technical solution should all cover within the scope of the patent of the present invention.
Claims (8)
1. a kind of preparation method of the nano lignin hydridization dual network composite hydrogel of high-mechanical property, which is characterized in that tool
The preparation step of body is as follows:
1) lignin is soluble in water, it is sonicated, form lignin nanoparticle suspension;
2) agar powder is dissolved in deionized water, is heated to agar powder and is completely dissolved;
3) by water-soluble polymer monomer, water-soluble cellulose ether is added and walks in hot solution, is uniformly mixed;
4) photoinitiator is added into the mixed solution of step 3, lignin nanoparticle suspension stirs, room temperature
It stands to above-mentioned reactant and becomes solid, solid reactant is put into the polymerization a period of time i.e. system of completion hydrogel under ultraviolet lamp
It is standby.
2. a kind of preparation side of the nano lignin hydridization dual network composite hydrogel of high-mechanical property as described in claim 1
Method, which is characterized in that prepare the first network of the hydrogel of completion by agar molecule construction, the content of agar account for solid content 5 ~
15%。
3. a kind of preparation side of the nano lignin hydridization dual network composite hydrogel of high-mechanical property as described in claim 1
Method, which is characterized in that the second network for preparing the hydrogel of completion is built-up by water-soluble polymer monomer polymerization, polymer
Content account for the 60 ~ 90% of solid content.
4. a kind of preparation side of the nano lignin hydridization dual network composite hydrogel of high-mechanical property as described in claim 1
Method, which is characterized in that the polymer monomer is including acrylic acid, acrylamide, vinyl alcohol and vinyl pyrrolidone
The strong electrolyte of polymer network can be formed.
5. a kind of preparation side of the nano lignin hydridization dual network composite hydrogel of high-mechanical property as described in claim 1
Method, which is characterized in that the water-soluble cellulose ether includes methylcellulose, ethyl cellulose, propyl cellulose, ethoxy fibre
Tie up element, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, DEAE-cellulose and carboxymethyl cellulose.
6. a kind of preparation side of the nano lignin hydridization dual network composite hydrogel of high-mechanical property as described in claim 1
Method, which is characterized in that the partial size of lignin nanoparticle is 80 ~ 1000 nm;Water-soluble cellulose ether and nano lignin contain
The ratio that amount accounts for solid content is 5 ~ 25%.
7. a kind of preparation side of the nano lignin hydridization dual network composite hydrogel of high-mechanical property as described in claim 1
Method, which is characterized in that the viscosity profile of water-soluble cellulose ether is in 5000 ~ 8000 mPas.
8. a kind of preparation side of the nano lignin hydridization dual network composite hydrogel of high-mechanical property as described in claim 1
Method, which is characterized in that the water content in the hydrogel of preparation is 75 ~ 87%.
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CN114752167A (en) * | 2022-05-18 | 2022-07-15 | 安徽大学 | Hydrogel sealing material for electrochemical gas sensor and preparation method thereof |
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CN108546333A (en) * | 2018-03-26 | 2018-09-18 | 中国林业科学研究院林产化学工业研究所 | A kind of preparation of high-mechanical property dual network composite hydrogel |
CN109354656A (en) * | 2018-10-15 | 2019-02-19 | 南京邮电大学 | A kind of preparation method of wooden hydrogel |
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CN108546333A (en) * | 2018-03-26 | 2018-09-18 | 中国林业科学研究院林产化学工业研究所 | A kind of preparation of high-mechanical property dual network composite hydrogel |
CN109354656A (en) * | 2018-10-15 | 2019-02-19 | 南京邮电大学 | A kind of preparation method of wooden hydrogel |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114752167A (en) * | 2022-05-18 | 2022-07-15 | 安徽大学 | Hydrogel sealing material for electrochemical gas sensor and preparation method thereof |
CN114752167B (en) * | 2022-05-18 | 2023-10-03 | 安徽大学 | Hydrogel sealing material for electrochemical gas sensor and preparation method thereof |
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Application publication date: 20190614 |