CN108373553A - A kind of response type antimicrobial macromolecule hydrogel - Google Patents
A kind of response type antimicrobial macromolecule hydrogel Download PDFInfo
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- CN108373553A CN108373553A CN201711479135.0A CN201711479135A CN108373553A CN 108373553 A CN108373553 A CN 108373553A CN 201711479135 A CN201711479135 A CN 201711479135A CN 108373553 A CN108373553 A CN 108373553A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
Abstract
The present invention provides a kind of response type antimicrobial macromolecule hydrogel, which is characterized in that includes the component of following parts by weight：8 22 parts of polyvinyl alcohol, 12 19 parts of hydroxyl butyl chitosans, 15 parts of non-ionic celluloses ethers, 4 11 parts of chitins, 37 parts of sodium potassium tartrate tetrahydrates, 29 parts of gluconic acid polyhexamethylene guanides, 0.8 2.5 parts of reinforcing fibers, 39 Atlantic halibut antibacterial peptides, 68 88 parts of pure water.The present invention has good bio-compatible type, mechanical property and mechanical strength, it more importantly can be high to thermotonus responsiveness in 37 50 DEG C of section, biological slow-released material, fast cooling material etc. are can be applied to, demand of the fields such as information, life, environment, aerospace for functional material is can adapt to.
Description
Technical field
The invention belongs to technical field of polymer materials, and in particular to a kind of response type antimicrobial macromolecule hydrogel.
Background technology
Hydrogel can be defined as being swollen and keep large quantity of moisture in water and undissolved polymer, hydrophilic small molecules energy
It is enough to be spread in hydrogel.Hydrogel has good biocompatibility, compared with hydrophobic polymer, the enzyme that is immobilized or thin
Born of the same parents only have weaker interaction, and being fixed on the activity of biomolecule in hydrogel can be maintained for a long time.Therefore, hydrogel
In fields such as biochemistry, medicine, there are many purposes.
According to hydrogel to the response situation of environmental stimuli, hydrogel can be divided into two major classes:(1) " traditional " hydrogel,
This kind of hydrogel is insensitive to the variation of variation such as temperature and the pH of environment;(2) " environment sensitive " hydrogel, this kind of hydrogel
Stimulation caused by variation in quite wide degree to temperature or pH etc. has different degrees of response." traditional " water
Gel is the hot topic studied before people's the mid-80, and " environment sensitive " hydrogel has been then people since 1985 most
For interested project.
In addition, people are also especially interested in the hydrogel having the following properties that:(1) it environment can be decomposed in vivo
Hydrogel, such as the hydrogel that can be ablated under weak basic condition in vivo, the hydrogel that can be enzymatically decomposed;(2) can with from
The hydrogel of sub- exchanging form release protein;(3) hydrogel etc. with " memory ".Although the hydrogel type of people's research
It is various, but final purpose is desirable to hydrogel and plays a role in practical applications by different purposes and requirement.
In recent years, with the rapid development of the fields such as information, life, environment, aerospace science and technology, people are to material
The requirement of performance is higher and higher.Therefore, the functional polymer hydrogel material for being badly in need of having a collection of performance special comes out, existing to adapt to
For the trend of scientific technological advance.
Invention content
In view of this, the present invention provides a kind of response type antimicrobial macromolecule hydrogel, the present invention has good biofacies
Appearance type, mechanical property and mechanical strength, it is often more important that can be high to thermotonus responsiveness in 37-50 DEG C of section, it can
Applied to biological slow-released material, fast cooling material etc., the fields such as information, life, environment, aerospace are can adapt to for work(
The demand of energy material.
The technical scheme is that：A kind of response type antimicrobial macromolecule hydrogel, which is characterized in that including following weight
The component of number：8-22 parts of polyvinyl alcohol, 12-19 parts of hydroxyl butyl chitosans, 1-5 parts of non-ionic celluloses ethers, 4-11 parts of first
Shell element, 3-7 parts of sodium potassium tartrate tetrahydrates, 2-9 parts of gluconic acid polyhexamethylene guanides, 0.8-2.5 parts of reinforcing fibers, the Atlantic Ocean 3-9 are mediocre
Flounder antibacterial peptide, 68-88 part pure water.
Further, the response type antimicrobial macromolecule hydrogel includes the component of following parts by weight：11-16 parts of poly- second
Enol, 14-17 parts of hydroxyl butyl chitosans, 2-4 parts of non-ionic celluloses ethers, 6-9 parts of chitins, 4-6 parts of sodium potassium tartrate tetrahydrates, 4-
7 parts of gluconic acid polyhexamethylene guanides, 1.2-2.1 parts of reinforcing fibers, 5-8 Atlantic halibuts antibacterial peptide, 75-85 parts of pure water.
Further, the response type antimicrobial macromolecule hydrogel includes the component of following parts by weight：14 parts of polyethylene
Alcohol, 15 parts of hydroxyl butyl chitosans, 3 parts of non-ionic celluloses ethers, 8 parts of chitins, 5 parts of sodium potassium tartrate tetrahydrates, 6 parts of gluconic acids are poly-
Hexa-methylene guanidine, 1.5 parts of reinforcing fibers, 7 Atlantic halibut antibacterial peptides, 80 parts of pure water.
Further, the reinforcing fiber is D-lactic acid-caprolactone nanofiber.
Further, a diameter of 200-500um of the reinforcing fiber.
Particularly, the present invention can be prepared by this field any prior art.
The components such as heretofore described polyvinyl alcohol, hydroxyl butyl chitosan can be achieved by the prior art.Nonionic
Fiber type element ether can be any one or mixing in hypromellose ether, hydroxypropylcelluloether ether.
Chitin also known as chitin, chitin, chitin.A kind of biopolymer of chitin.Extensively
In the mycelium and protozoan and certain green algas of the general shell for being present in invertebrate and fungi.Produce the master of chitin
It is shrimp, crab shell to want raw material, and preferable with shrimp shell.It is mainly used as actinomyces culture and chromatographic material.The chemical constitution of chitin and
Plant cellulose is closely similar.All it is the polymer of hexose, molecular weight is all 1,000,000 or more.The base unit of cellulose is
Glucose, it is to pass through polymer made of β-Isosorbide-5-Nitrae glucoside chain link by 300~2500 glucose residues.The base of chitin
Our unit is acetylglucosamine, it is to pass through p1, the interconnection of 4 glucoside chains by 1000~3000 acetyl glucoseamin residues
Into polymer.And the base unit of chitosan is gucosamine.The molecular weight of chitin more high absorption capacity is stronger, is suitble to
Industry, field of environment protection application.
Gluconic acid polyhexamethylene guanide has broad-spectrum；Effective concentration is low；Work fast；Property is stablized；It is readily soluble
In the excellent performance of water；It can use at normal temperatures；It is long-term antibacterial, without side-effects；It is non-corrosive；It is colourless, odorless；It is nontoxic；Non-ignitable,
It is not quick-fried, safe to use；It is moderate；Convenient transportation, it may be said that be best fungicide.
In the present invention, chitin and sodium potassium tartrate tetrahydrate synergistic can promote polyvinyl alcohol, hydroxyl butyl chitosan and nonionic
The polymerization of fiber type element ether, crosslinking, be allowed to pure water in conjunction with and form hydrogel.Gluconic acid polyhexamethylene guanide, increasing simultaneously
In the presence of strong fiber, stability when synergistic effect can improve moisture low temperature in macromolecule hydrogel system, and at 50 DEG C
The a large amount of release water outlets in left and right, to realize fast cooling；In addition gluconic acid polyhexamethylene guanide can with Atlantic halibut antibacterial peptide
Synergistic effect significantly improves the anti-microbial property of the present invention, the microorganisms such as bacterium is can effectively avoid when applied to biomedicine field
Infection.
The macromolecule hydrogel structure of the present invention passes through poly- second using chitin and sodium potassium tartrate tetrahydrate synergistic as crosslinking agent
Enol, hydroxyl butyl chitosan and non-ionic celluloses ether crosslinking are blended, and the macromolecule with temperature response characteristics is prepared
Hydrogel.Meanwhile being blended in crosslinking and being added to reinforcing fiber, the mechanical property and mechanical strength of the present invention can be significantly improved；
The polyhexamethylene guanide of addition, as natural antimicrobial substance, can significantly improve the antibacterial of the present invention with Atlantic halibut antibacterial peptide
Performance.
Inside of the invention has the three-dimensional net structure formed with chemical bond and/or physical force between macromolecular chain,
It is with good stability.Present invention can apply to the controlled release carrier of chemical sensor, drug or function ingredients, substances to detach,
The fields such as rapid cooling.
The mechanism that the present invention absorbs water is：The synergistic effects such as capillary attraction and dilating effect, chemistry and physisorption
As a result, wherein physical absorption accounts for leading role, the permeable pressure head inside and outside hydrogel cross-linked network is the key that its water swelling
Factor.
In the present invention, hydrone can form hydrogen bond with the functional group of core component, and high-sequential is formed in polymer surrounding
Water molecule layer, polymer is in extended configuration, when temperature is increased to 37-50 DEG C of temperature range（Lowest critical solution temperature
LCST）When, hydrogen bond is destroyed, and the hydrone being wrapped in around polymer is reduced, the heat resistance and salt tolerance between hydrophobic grouping
Enhancing, water are discharged from hole, gel sudden contraction, and deswelling occurs.The above change procedure is reversible, and the gel of contraction can be with
The reduction of temperature and be swollen again, restore to the original state.To realize that the rapid evaporation of moisture takes away heat, achieve the effect that cooling；
Or reach the drug component of internal carrying or function ingredients are released when the temperature rises, the effect etc. of long-acting slow-release.
The present invention has good bio-compatible type, mechanical property and mechanical strength, it is often more important that can be at 37-50 DEG C
Section it is high to thermotonus responsiveness, can be applied to biological slow-released material, fast cooling material etc., can adapt to information,
Demand of the fields such as life, environment, aerospace for functional material.
Specific implementation mode
Technical scheme of the present invention is clearly and completely described below in conjunction with embodiment, it is clear that described reality
It is only a part of the embodiment of the present invention to apply example, instead of all the embodiments.
Embodiment 1
A kind of response type antimicrobial macromolecule hydrogel, which is characterized in that include the component of following parts by weight：8 parts of polyethylene
Alcohol, 12 parts of hydroxyl butyl chitosans, 1 part of non-ionic celluloses ether, 4 parts of chitins, 3 parts of sodium potassium tartrate tetrahydrates, 2 parts of gluconic acids are poly-
Hexa-methylene guanidine, 0.8 part of reinforcing fiber, 3 Atlantic halibut antibacterial peptides, 68 parts of pure water.
Further, the reinforcing fiber is D-lactic acid-caprolactone nanofiber.
Further, a diameter of 200um of the reinforcing fiber.
Embodiment 2
A kind of response type antimicrobial macromolecule hydrogel, which is characterized in that include the component of following parts by weight：22 parts of polyethylene
Alcohol, 19 parts of hydroxyl butyl chitosans, 5 parts of non-ionic celluloses ethers, 11 parts of chitins, 7 parts of sodium potassium tartrate tetrahydrates, 9 parts of gluconic acids
Polyhexamethylene guanide, 2.5 parts of reinforcing fibers, 9 Atlantic halibut antibacterial peptides, 88 parts of pure water.
Further, the reinforcing fiber is D-lactic acid-caprolactone nanofiber.
Further, a diameter of 500um of the reinforcing fiber.
Embodiment 3
A kind of response type antimicrobial macromolecule hydrogel includes the component of following parts by weight：11 parts of polyvinyl alcohol, 14 parts of hydroxyl butyl
Chitosan, 2 parts of non-ionic celluloses ethers, 6 parts of chitins, 4 parts of sodium potassium tartrate tetrahydrates, 4 parts of gluconic acid polyhexamethylene guanides,
1.2 parts of reinforcing fibers, 5 Atlantic halibut antibacterial peptides, 75 parts of pure water.
Further, the reinforcing fiber is D-lactic acid-caprolactone nanofiber.
Further, a diameter of 250um of the reinforcing fiber.
Embodiment 4
A kind of response type antimicrobial macromolecule hydrogel includes the component of following parts by weight：16 parts of polyvinyl alcohol, 17 parts of hydroxyl butyl
Chitosan, 4 parts of non-ionic celluloses ethers, 9 parts of chitins, 6 parts of sodium potassium tartrate tetrahydrates, 7 parts of gluconic acid polyhexamethylene guanides,
2.1 parts of reinforcing fibers, 8 Atlantic halibut antibacterial peptides, 85 parts of pure water.
Further, the reinforcing fiber is D-lactic acid-caprolactone nanofiber.
Further, a diameter of 400um of the reinforcing fiber.
Embodiment 5
A kind of response type antimicrobial macromolecule hydrogel includes the component of following parts by weight：14 parts of polyvinyl alcohol, 15 parts of hydroxyl butyl
Chitosan, 3 parts of non-ionic celluloses ethers, 8 parts of chitins, 5 parts of sodium potassium tartrate tetrahydrates, 6 parts of gluconic acid polyhexamethylene guanides,
1.5 parts of reinforcing fibers, 7 Atlantic halibut antibacterial peptides, 80 parts of pure water.
Further, the reinforcing fiber is D-lactic acid-caprolactone nanofiber.
Further, a diameter of 300um of the reinforcing fiber.
Comparative example 1
A kind of response type antimicrobial macromolecule hydrogel includes the component of following parts by weight：14 parts of polyvinyl alcohol, 15 parts of hydroxyl butyl
Chitosan, 3 parts of non-ionic celluloses ethers, 8 parts of chitins, 5 parts of sodium potassium tartrate tetrahydrates, 6 parts of gluconic acid polyhexamethylene guanides,
1.5 parts of reinforcing fibers, 7 Atlantic halibut antibacterial peptides, 80 parts of pure water.
Further, the reinforcing fiber is D-lactic acid-caprolactone nanofiber.
Further, a diameter of 300um of the reinforcing fiber.
Comparative example 2
A kind of response type antimicrobial macromolecule hydrogel includes the component of following parts by weight：14 parts of polyvinyl alcohol, 15 parts of hydroxyl butyl
Chitosan, 3 parts of non-ionic celluloses ethers, 8 parts of chitins, 5 parts of sodium potassium tartrate tetrahydrates, 6 parts of gluconic acid polyhexamethylene guanides,
1.5 parts of reinforcing fibers, 7 Atlantic halibut antibacterial peptides, 80 parts of pure water.
Further, the reinforcing fiber is D-lactic acid-caprolactone nanofiber.
Further, a diameter of 350um of the reinforcing fiber.
Macromolecule hydrogel performance test
The macromolecule hydrogel for choosing embodiment 1-5 and comparative example 1-2, the cm of 20 cm × 10 are prepared by the prior art
Shape（Water content is 100g）.Macromolecule hydrogel is heated with 30 DEG C, 40 DEG C, 50 DEG C of temperature respectively, records its 12 points
Mass change in clock.Its result is as shown in table 1-3.
1. macromolecule hydrogel mass change value of table（30℃）
| Experimental group/mass change（g） | 3min | 6 min | 9 min | 12 min |
| Embodiment 1 | -1.3 | -2.5 | -3.0 | -3.1 |
| Embodiment 2 | -1.1 | -2.3 | -2.8 | -2.8 |
| Embodiment 3 | -2.5 | -3.0 | -3.1 | -3.4 |
| Embodiment 4 | -1.6 | -2.9 | -3.0 | -3.1 |
| Embodiment 5 | -0.4 | -1.2 | -2.3 | -3.8 |
| Comparative example 1 | -4.4 | -7.3 | -14.4 | -29.5 |
| Comparative example 2 | -4.8 | -8.2 | -17.6 | -26.0 |
2. macromolecule hydrogel mass change value of table（40℃）
| Experimental group/mass change（g） | 3min | 6 min | 9 min | 12 min |
| Embodiment 1 | -1.1 | -2.5 | -2.9 | -3.0 |
| Embodiment 2 | -1.2 | -2.5 | -2.8 | -3.0 |
| Embodiment 3 | -2.5 | -3.1 | -3.8 | -4.9 |
| Embodiment 4 | -2.8 | -3.0 | -3.4 | -4.7 |
| Embodiment 5 | -1.6 | -3.1 | -4.2 | -5.6 |
| Comparative example 1 | -4.8 | -8.2 | -17.0 | -32.9 |
| Comparative example 2 | -4.9 | -9.0 | -26.2 | -38.8 |
3. macromolecule hydrogel mass change value of table（50℃）
| Experimental group/mass change（g） | 3min | 6 min | 9 min | 12 min |
| Embodiment 1 | -21.1 | -28.6 | -40.3 | -51.2 |
| Embodiment 2 | -20.0 | -25.2 | -36.7 | -48.1 |
| Embodiment 3 | -17.0 | -26.9 | -35.3 | -47.2 |
| Embodiment 4 | -16.4 | -26.5 | -36.7 | -46.7 |
| Embodiment 5 | -19.7 | -29.8 | -43.3 | -49.3 |
| Comparative example 1 | -6.4 | -13.2 | -25.2 | -34.3 |
| Comparative example 2 | -10.2 | -19.2 | -28.2 | -41.6 |
It is obvious to a person skilled in the art that invention is not limited to the details of the above exemplary embodiments, and do not carrying on the back
In the case of spirit or essential attributes from the present invention, the present invention can be realized in other specific forms.Therefore, no matter from which
From the point of view of a bit, the present embodiments are to be considered as illustrative and not restrictive, and the scope of the present invention is wanted by appended right
Ask rather than above description limit, it is intended that by all changes that come within the meaning and range of equivalency of the claims
It is included within the present invention.
In addition, it should be understood that although this specification is described in terms of embodiments, but not each embodiment is only wrapped
Containing an independent technical solution, this description of the specification is merely for the sake of clarity, and those skilled in the art should
It considers the specification as a whole, the technical solutions in the various embodiments may also be suitably combined, forms those skilled in the art
The other embodiment being appreciated that.It is noted that the technical characteristic not being described in detail in the present invention, can pass through this
Field any prior art is realized.
Claims (5)
1. a kind of response type antimicrobial macromolecule hydrogel, which is characterized in that include the component of following parts by weight：8-22 parts poly-
Vinyl alcohol, 12-19 parts of hydroxyl butyl chitosans, 1-5 parts of non-ionic celluloses ethers, 4-11 parts of chitins, 3-7 parts of potassium tartrates
Sodium, 2-9 parts of gluconic acid polyhexamethylene guanides, 0.8-2.5 parts of reinforcing fibers, 3-9 Atlantic halibuts antibacterial peptide, 68-88 parts it is pure
Water.
2. response type antimicrobial macromolecule hydrogel according to claim 1, which is characterized in that including following parts by weight
Component：11-16 parts of polyvinyl alcohol, 14-17 parts of hydroxyl butyl chitosans, 2-4 parts of non-ionic celluloses ethers, 6-9 parts of chitins,
4-6 parts of sodium potassium tartrate tetrahydrates, 4-7 parts of gluconic acid polyhexamethylene guanides, 1.2-2.1 parts of reinforcing fibers, 5-8 Atlantic halibut antibacterials
Peptide, 75-85 part pure water.
3. response type antimicrobial macromolecule hydrogel according to claim 2, which is characterized in that including following parts by weight
Component：14 parts of polyvinyl alcohol, 15 parts of hydroxyl butyl chitosans, 3 parts of non-ionic celluloses ethers, 8 parts of chitins, 5 parts of potassium tartrates
Sodium, 6 parts of gluconic acid polyhexamethylene guanides, 1.5 parts of reinforcing fibers, 7 Atlantic halibut antibacterial peptides, 80 parts of pure water.
4. according to claim 1-3 any one of them response type antimicrobial macromolecule hydrogels, which is characterized in that the enhancing is fine
Dimension is D-lactic acid-caprolactone nanofiber.
5. response type antimicrobial macromolecule hydrogel according to claim 4, which is characterized in that the diameter of the reinforcing fiber
For 200-500um.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112125569A (en) * | 2020-08-28 | 2020-12-25 | 同济大学 | Response type concrete antifreeze agent and preparation method and application thereof |
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