CN113444200A - Anti-freezing hydrogel and preparation method and application thereof - Google Patents
Anti-freezing hydrogel and preparation method and application thereof Download PDFInfo
- Publication number
- CN113444200A CN113444200A CN202110644255.1A CN202110644255A CN113444200A CN 113444200 A CN113444200 A CN 113444200A CN 202110644255 A CN202110644255 A CN 202110644255A CN 113444200 A CN113444200 A CN 113444200A
- Authority
- CN
- China
- Prior art keywords
- hydrogel
- freezing
- percent
- antifreeze
- gel
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
- C08F220/585—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine and containing other heteroatoms, e.g. 2-acrylamido-2-methylpropane sulfonic acid [AMPS]
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Dispersion Chemistry (AREA)
- Physics & Mathematics (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses an antifreeze hydrogel and a preparation method and application thereof, wherein the preparation raw materials of the antifreeze hydrogel comprise: polymerized monomers, organosilicon materials, chain transfer agents and alcohols. According to the invention, the organosilicon material, the chain transfer agent and the alcohol are added into the hydrogel, so that the elasticity of the hydrogel in a frozen state can be effectively improved, and the thawing time is prolonged. The anti-freezing hydrogel has better bending property and stretchability, can be frozen in a freezing box of a refrigerator, ice crystals in a crushed ice shape are formed on the surface of the frozen gel, the gel body is milk white, the gel can be bent, the breaking elongation of the gel can reach more than 200 percent, and the retention time at low temperature can reach more than 1 hour.
Description
Technical Field
The invention relates to the technical field of hydrogel, in particular to anti-freezing hydrogel and a preparation method and application thereof.
Background
Hydrogels are composed of a network of crosslinked hydrophilic polymers dispersed in water. The polymer network imparts solid-like mechanical properties to the hydrogel, while the large amount of water in the hydrogel imparts liquid-like transport properties. Many hydrogels are biocompatible and thus have a wide range of uses in the biomedical field. The hydrogel contains a large amount of water, the water has higher specific heat capacity, and the latent heat of fusion after freezing is higher, so the hydrogel can be used as a cold storage and human body cryotherapy material. However, when the temperature of the hydrogel is lowered to below the freezing point, the hydrogel, which originally has elasticity and toughness, becomes hard to freeze, lacks elasticity and toughness, and is difficult to curl. The hard frozen hydrogel is difficult to be attached to the surface of a human body, the fixing effect is not good, and the comfort level and the effect of hydrogel cryotherapy are greatly reduced. The hydrogel system is designed to have better flexibility at low temperature, so that the application range of the hydrogel under the low temperature condition can be expanded.
In recent years, many reports on anti-freezing hydrogel have been made, and the general idea is to add an anti-freezing protective agent such as organic solvents of glycerol, ethylene glycol and sorbitol, and ionic salts such as calcium chloride, ammonium chloride, zinc sulfate and lithium chloride into the hydrogel, so as to reduce the freezing point of the hydrogel and improve the anti-freezing performance of the hydrogel, so that the hydrogel has good flexibility in a wide temperature range from low temperature to high temperature, and the practicability and durability of the hydrogel in practical application are effectively improved.
Although the freezing point of the antifreeze hydrogel is lowered, the antifreeze hydrogel is not frozen when in use, the gel is relatively soft, and the fitness and comfort are relatively high when in use, the antifreeze hydrogel has poor effect when being used as a cold therapy material. The main reason is that the freezing point of the anti-freezing gel is greatly reduced, the anti-freezing hydrogel is higher than the freezing point when being used as a cryotherapy material (if reaching the freezing point, the anti-freezing hydrogel is frozen and becomes a hard frozen material), the anti-freezing hydrogel is not frozen when being used, the refrigeration duration of the cryotherapy is kept short, and the refrigeration duration is far shorter than that of the hydrogel adopting ice blocks and non-anti-freezing hydrogel. The non-antifreeze hydrogel is used as a cryotherapy material, the gel is in an icing state when in use, and the cryotherapy material can be melted only by absorbing a large amount of body heat in the process of cryotherapy, so that the phase transition process is generated, and the cryotherapy time is longer. The anti-freezing gel is not frozen when in use, and does not have a phase transition process in the cold therapy process, so that the temperature of the material can rise quickly after the material absorbs the heat of a human body, and the cold therapy time is far shorter than that in the frozen state, thereby the cold therapy time is shorter.
Glycerol-Gel cryotherapy materials (represented by commercial products such as Elasto-Gel) currently on the market belong to the class of anti-freezing materials, and the Gel is elastic and soft during cold compress, but the cryotherapy time is short. The ideal elastic gel cold therapy material is relatively soft and elastic during cold compress, and has phase transition state during cold compress, large cold storage amount and long cold therapy time.
The related art reports a new type of antifreeze hydrogel (Advanced Materials, 2018, 30: 1801541) that can maintain high stretchability, toughness and electrical conductivity at temperatures as low as-57 ℃. The technology is to add an ionic compound (calcium chloride CaCl) into the tough polyacrylamide-sodium alginate double-network hydrogel2) Thereby lowering the freezing point of the liquid phase to obtain the anti-freezing hydrogel. The study found that at a temperature of-15 ℃, the gel, which was not soaked with calcium chloride solution, was in a frozen state (frozen state), completely whitened, and could hardly withstand any stretching; the gel soaked in 10 wt% calcium chloride solution is in a slurry state and still highly stretchable, but loses transparency only with detachment of ice crystals on the surface of the material. Although this study does not relate to the use of gels as cold packs, the gels remain soft even in frozen conditions and can be developed as an ideal cold pack. However, the gel contains salt substances, and has certain side effects on a human body or a cold therapy device when being used as a cold compress material.
Disclosure of Invention
The invention aims to at least solve the problems that the existing hydrogel is inelastic after being frozen and the thawing time is short, and provides the anti-freezing hydrogel which has good elasticity after being frozen, can be curled and stretched and has long low-temperature retention time.
The invention also provides a preparation method and application of the anti-freezing hydrogel.
Specifically, the invention adopts the following technical scheme:
the first aspect of the invention provides a freeze-resistant hydrogel, which is prepared from the following raw materials: polymerized monomers, organosilicon materials, chain transfer agents and alcohols.
The antifreeze hydrogel according to the first aspect of the invention has at least the following beneficial effects:
according to the invention, by adding the organosilicon material chain transfer agent and alcohols into the hydrogel, in the process of forming a gel network by polymerizing a polymerization monomer, the organosilicon material can enter the hydrogel through participating in polymerization reaction, so that a hydrophilic structure of the hydrogel contains a hydrophobic organosilicon component, and the hydrophobic organosilicon component has an anti-freezing function, therefore, most of structures of the hydrogel contain a part which is not easy to freeze. By introducing an organosilicon component into the hydrogel structure, a wholly hydrophilic, locally hydrophobic hydrogel structure can be formed.
Some branching structures are formed in the gel by adding chain transfer agents. Thus, most of the polymer chain segments in the obtained hydrogel are of a cross-linked network structure with two fixed ends, and one part of the chain segments are of a branched structure with two fixed ends, so that the number of cross-linked points in the gel is reduced by the branched structure with two fixed ends, and the tensile property and the like in a frozen state are influenced.
The introduction of alcohols can promote the solubility of the organic silicon material in the aqueous solution, and the existence of the alcohols can increase the frost resistance of the aqueous solution and reduce the freezing point of the aqueous solution. Specifically, a part of the alcohol solution in the gel seeps out to the surface of the gel during the freezing process of the gel, a crystalline state is easily formed on the surface of the gel, the surface of the gel is in a crushed ice-like crystal state, the hydrogel is wholly changed into a completely opaque state, and the surface of the hydrogel is not hardened, so that the elasticity of the gel at low temperature is further improved. Through the synergistic effect of the organosilicon material, the chain transfer agent and the alcohol, the elasticity of the hydrogel in a frozen state can be effectively improved, the hydrogel can be curled and stretched in the frozen state, and the low-temperature retention time is prolonged.
In some embodiments of the invention, the raw materials for the preparation of the antifreeze hydrogel also include nanoclay. The nano clay is a substance with a layered silicate structure, during the synthesis process of the hydrogel, a polymerized monomer is firstly adsorbed on the surface of a lamellar structure of the nano clay and polymerized to form a macromolecular chain, and finally a unique three-dimensional network structure is formed through the physical crosslinking effect of nano clay particles, so that the gel has better mechanical property, compression resistance and tensile resistance.
In some embodiments of the invention, the starting materials for the preparation of the antifreeze hydrogel also comprise an initiator.
In some embodiments of the invention, the starting materials for the preparation of the antifreeze hydrogels also comprise polymerization promoters.
In some embodiments of the invention, the starting material for the preparation of the antifreeze hydrogel also comprises water.
In some embodiments of the invention, the antifreeze hydrogel comprises the following preparation raw materials in percentage by mass:
3 to 30 percent of polymerized monomer
0.5 to 10 percent of organosilicon material
0.1 to 1 percent of chain transfer agent
1 to 20 percent of alcohol
1 to 10 percent of nano clay
0.05 to 1 percent of initiator
0.05 to 1 percent of polymerization accelerator
27 to 94.3 percent of water.
In some embodiments of the invention, the antifreeze hydrogel comprises the following preparation raw materials in percentage by mass:
5 to 20 percent of polymerized monomer
2 to 6 percent of organic silicon material
0.1 to 1 percent of chain transfer agent
5 to 15 percent of alcohol
2 to 5 percent of nano clay
0.1 to 0.5 percent of initiator
0.1 to 0.5 percent of polymerization accelerator
27 to 94.3 percent of water.
In some embodiments of the invention, the polymerized monomers include any one or more of acrylamide, hydroxyethyl methacrylate, acrylic acid (and salts thereof), methacrylic acid (and salts thereof), and 2-acrylamido-2-methylpropanesulfonic acid (and salts thereof).
In some embodiments of the invention, the silicone material comprises any one or more of a silane coupling agent, a silicone oil, a silicone resin, and composites thereof, preferably a silane coupling agent. The silane coupling agent has double bonds and includes any one or more of gamma-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltris (beta-methoxyethoxy) silane, and vinyltriethoxysilane.
In some embodiments of the invention, the chain transfer agent comprises any one or more of dodecyl mercaptan, aliphatic mercaptans including any one or more of mercaptoethanol, thioglycolic acid and isooctyl 3-mercaptopropionate.
In some embodiments of the invention, the alcohol comprises any one or more of ethanol, ethylene glycol, propylene glycol, and propylene glycol.
In some embodiments of the invention, the nanoclay includes magnesium lithium silicate nanoparticles, preferably Laponite nanolithioan, montmorillonite, and the like.
In some embodiments of the invention, the initiator includes various types of water-soluble free radical polymerization initiators such as ammonium persulfate, potassium persulfate, azobisisobutylamidine hydrochloride, azobisisobutylimidazoline hydrochloride, and the like.
In some embodiments of the present invention, the polymerization accelerator comprises any one or a combination of N, N-tetramethylethylenediamine, triethanolamine.
A second aspect of the present invention provides a process for the preparation of the above freeze-resistant hydrogel, comprising the steps of:
and mixing the preparation raw materials of the anti-freezing hydrogel, and reacting to obtain the anti-freezing hydrogel.
In some embodiments of the invention, the preparation method is more specifically that the polymerized monomers, nanoclay, chain transfer agent and initiator are dissolved in water to obtain component a; dissolving an organic silicon material and a polymer accelerator in alcohol to obtain a component B; and mixing the component A and the component B, and reacting to obtain the anti-freezing hydrogel.
In some embodiments of the present invention, the reaction time is 10 to 50 ℃ and the reaction time is 10 to 60 min.
The third aspect of the invention provides the application of the anti-freezing hydrogel in the preparation of ice bags, ice pads, cold compress physiotherapy devices and shock absorption devices as a cold therapy dressing material or as a filling material.
Compared with the prior art, the invention has the following beneficial effects:
the antifreeze hydrogel has better bending property and tensile property, can be frozen in a freezing box of a refrigerator, ice crystals in a crushed ice shape are formed on the surface of the frozen gel, the gel body is milk white, the gel can be bent, and the elongation at break can reach more than 200%.
After being frozen, the anti-freezing hydrogel can be bent, wound and fixed on the leg, the arm and the like for cold therapy, the cold therapy time can reach 1 hour, and the anti-freezing hydrogel is a cold therapy material with excellent performance. Hydrogels also bend when frozen, and are not hard, frozen, which is a synergistic result of multiple factors related to the unique composition of the hydrogel.
The antifreeze hydrogel is a hydrogel with a hybrid structure, a hydrophilic structure contains a hydrophobic silane component, and the hydrophobic silane component has an antifreeze effect, so that most of structures in the hydrogel which are easy to freeze contain parts which are difficult to freeze. In the preparation process of the hydrogel, a chain transfer reagent is adopted, so that a plurality of branched structures are formed in the gel, most of high molecular chain segments are cross-linked network structures with fixed two ends, and one part of molecular chain segments are branched structures with non-fixed two ends, and different fixing modes can cause different icing and freezing states. The components are introduced with an alcohol solution, so that the solubility of the silane coupling agent in an aqueous solution can be promoted, the existence of the alcohol increases the frost resistance of the aqueous solution, the freezing point of the aqueous solution is reduced, a part of the alcohol solution seeps to the surface of the gel in the freezing process of the gel, and a crystalline state is formed on the surface of the gel, so that the surface of the gel presents crushed ice-shaped crystals. Under the synergistic action of multiple factors, the hydrogel provided by the invention has freezing resistance and certain flexibility in a frozen state, and is similar to a slurry state. Moreover, compared with the gel which can keep soft in the frozen state in the prior art, the system of the invention does not adopt any salt substance.
Detailed Description
The technical solution of the present invention is further described below with reference to specific examples.
Example 1
Dissolving 6g of nano-Laponite (Laponite) in 565.8g of water, stirring for a period of time to form a uniform and transparent solution, weighing 18g of polymerization monomer acrylamide, 0.3g of initiator ammonium persulfate and 0.6g of chain transfer agent dodecyl mercaptan, stirring, and dissolving in the solution to form a solution, wherein the solution is a component A; 0.3g of polymerization accelerator N, N, N, N-tetramethylethylenediamine and 3g of silane coupling agent gamma-methacryloxypropyltrimethoxysilane were added to 6g of ethanol to form a solution, which was component B. And blending the component A and the component B to form a solution, quickly pouring the solution into a plastic sealing bag, sealing the bag after air is exhausted, and standing the bag at normal temperature for 30 minutes to obtain the gel.
The sealed bag is placed in a freezing chamber of a refrigerator, frozen at minus 15 ℃ overnight and then taken out, and the stretching length, the low-temperature retention time and the crimping performance are measured.
Example 2
60g of montmorillonite is dissolved in 162g of water and stirred for a period of time to form a uniform transparent solution, 180g of 2-acrylamide-2-methylpropanesulfonic acid sodium salt as a polymerization monomer, 6g of potassium persulfate as an initiator and 6g of mercaptoethanol as a chain transfer agent are weighed and stirred and then dissolved in the solution to form a solution, and the solution is a component A; 6g of triethanolamine as a polymerization accelerator and 60g of vinyltrimethoxysilane as a silane coupling agent were added to 120g of propylene glycol to form a solution, which was component B. And blending the component A and the component B to form a solution, quickly pouring the solution into a plastic sealing bag, sealing the bag after air is exhausted, and standing the bag at normal temperature for 30 minutes to obtain the gel.
The sealed bag is placed in a freezing chamber of a refrigerator, frozen at minus 15 ℃ overnight and then taken out, and the stretching length, the low-temperature retention time and the crimping performance are measured.
Example 3
Dissolving 18g of nano-Laponite (Laponite) in 428.4g of water, stirring for a period of time to form a uniform and transparent solution, weighing 60g of polymerization monomer acrylic acid, 1g of initiator azodiisobutyl amidine hydrochloride and 2g of chain transfer agent thioglycolic acid, stirring, and dissolving in the solution to form a solution, wherein the solution is a component A; 0.6g of triethanolamine as a polymerization accelerator and 30g of vinyltrimethoxysilane as a silane coupling agent were added to 60g of ethylene glycol to form a solution, which was component B. And blending the component A and the component B to form a solution, quickly pouring the solution into a plastic sealing bag, sealing the bag after air is exhausted, and standing the bag at normal temperature for 30 minutes to obtain the gel.
The sealed bag is placed in a freezing chamber of a refrigerator, frozen at minus 15 ℃ overnight and then taken out, and the stretching length, the low-temperature retention time and the crimping performance are measured.
Comparative example 1
This comparative example prepared a gel without a chain transfer agent in the feed.
Dissolving 18g of nano-Laponite (Laponite) in 430.4g of water, stirring for a period of time to form a uniform transparent solution, weighing 60g of polymerized monomer methacrylic acid and 1g of initiator azodiisobutyl imidazoline hydrochloride, stirring, and dissolving in the solution to form a solution, wherein the solution is a component A; 0.6g of triethanolamine as a polymerization accelerator and 30g of vinyltriethoxysilane as a silane coupling agent were added to 60g of glycerol to form a solution, which was component B. And blending the component A and the component B to form a solution, quickly pouring the solution into a plastic sealing bag, sealing the bag after air is exhausted, and standing the bag at normal temperature for 30 minutes to obtain the gel.
The sealed bag is placed in a freezing chamber of a refrigerator, frozen at minus 15 ℃ overnight and then taken out, and the stretching length, the low-temperature retention time and the crimping performance are measured.
Comparative example 2
This comparative example prepared a gel without silane in the starting material.
Dissolving 18g of nano-Laponite (Laponite) in 457.9g of water, stirring for a period of time to form a uniform transparent solution, weighing 60g of a polymerization monomer methacrylic acid, 1g of an initiator azobisisobutyrimidazoline hydrochloride, 0.5g of a cross-linking agent N, N' -methylene bisacrylamide and 2g of a chain transfer agent thioglycolic acid, stirring, and dissolving in the solution to form a solution, wherein the solution is a component A; 0.6g of triethanolamine as a polymerization accelerator was added to 60g of glycerol to form a solution, which was component B. And blending the component A and the component B to form a solution, quickly pouring the solution into a plastic sealing bag, sealing the bag after air is exhausted, and standing the bag at normal temperature for 30 minutes to obtain the gel.
The sealed bag is placed in a freezing chamber of a refrigerator, frozen at minus 15 ℃ overnight and then taken out, and the stretching length, the low-temperature retention time and the crimping performance are measured.
Comparative example 3
This comparative example prepared a gel without alcohol in the starting material.
Dissolving 18g of nano-Laponite (Laponite) in 428.4g of water, stirring for a period of time to form a uniform and transparent solution, weighing 60g of polymerization monomer acrylic acid, 1g of initiator azodiisobutyl amidine hydrochloride and 2g of chain transfer agent thioglycolic acid, stirring, and dissolving in the solution to form a solution, wherein the solution is a component A; 0.6g of triethanolamine as a polymerization accelerator and 30g of vinyltrimethoxysilane as a silane coupling agent were added to 60g of water to form a solution, which was component B. And blending the component A and the component B to form a solution, quickly pouring the solution into a plastic sealing bag, sealing the bag after air is exhausted, and standing the bag at normal temperature for 30 minutes to obtain the gel.
The sealed bag is placed in a freezing chamber of a refrigerator, frozen at minus 15 ℃ overnight and then taken out, and the stretching length, the low-temperature retention time and the crimping performance are measured.
Comparative example 4
Compared with the antifreeze hydrogel prepared in the embodiment 1-3, the preparation raw materials of the common antifreeze elastomer gel do not contain a chain transfer agent and an organic silicon material, and a crosslinking agent is added.
Dissolving 12g of nano-Laponite (Laponite) in 225.9g of water, stirring for a period of time to form a uniform transparent solution, weighing 60g of polymerization monomer acrylamide, 1g of initiator ammonium persulfate and 0.5g of cross-linking agent N, N' -methylene bisacrylamide, stirring, and dissolving in the solution to form a solution, wherein the solution is a component A; 0.6g of triethanolamine as a polymerization accelerator was added to 300g of glycerol to form a solution, which was component B. And blending the component A and the component B to form a solution, quickly pouring the solution into a plastic sealing bag, sealing the bag after air is exhausted, and standing the bag at normal temperature for 30 minutes to obtain the gel.
The sealed bag is placed in a freezing chamber of a refrigerator, frozen at minus 15 ℃ overnight and then taken out, and the stretching length, the low-temperature retention time and the crimping performance are measured.
Comparative example 5
Compared with the antifreeze hydrogel prepared in the embodiment 1-3, the antifreeze hydrogel prepared by the comparative example does not contain chain transfer agent, organic silicon material and alcohol, and the crosslinking agent is added.
Dissolving 12g of nano-Laponite (Laponite) in 465.9g of water, stirring for a period of time to form a uniform and transparent solution, weighing 60g of polymerization monomer acrylamide, 1g of initiator ammonium persulfate and 0.5g of cross-linking agent N, N' -methylene bisacrylamide, stirring, and dissolving in the solution to form a solution, wherein the solution is a component A; 0.6g of triethanolamine as a polymerization accelerator was added to 60g of water to form a solution, which was component B. And blending the component A and the component B to form a solution, quickly pouring the solution into a plastic sealing bag, sealing the bag after air is exhausted, and standing the bag at normal temperature for 30 minutes to obtain the gel.
The sealed bag is placed in a freezing chamber of a refrigerator, frozen at minus 15 ℃ overnight and then taken out, and the stretching length, the low-temperature retention time and the crimping performance are measured.
The hydrogel raw material formulation of examples 1 to 3 and comparative examples 1 to 5 is shown in table 1 below.
TABLE 1 hydrogel raw material ratio
The performance test results of the hydrogels of examples 1 to 3 and comparative examples 1 to 5 after freezing are shown in the following table 2.
TABLE 2 hydrogel Performance test results
| Serial number | Whether or not to freeze | Elongation at break | Hold time at zero degree | Soft condition of |
| Example 1 | Is that | 200％ | 75 minutes | Can be folded and curled |
| Example 2 | Is that | 205％ | 68 minutes | Can be folded and curled |
| Example 3 | Is that | 210％ | 70 minutes | Can be folded and curled |
| Comparative example 1 | Is that | 20％ | 80 minutes | Can be curled and easily broken |
| Comparative example 2 | Is that | 50％ | 72 minutes | Crimpable and relatively hard |
| Comparative example 3 | Is that | 60％ | 65 minutes | Can be folded and easily broken |
| Comparative example 4 | Whether or not | 400％ | 20 minutes | Can be folded and curled |
| Comparative example 5 | Is that | About 0 percent | 90 minutes | Non-crimpable |
The test results show that the hydrogel prepared in examples 1 to 3 can be frozen after being frozen in a refrigerator, the elongation at break in the frozen state can reach 200% or more, the hydrogel can be folded and curled, the hydrogel has good elasticity, the retention time at 0 ℃ exceeds 1 hour, and the thawing time is long. In contrast, the hydrogels of comparative examples 1 to 3, which have a long retention time at 0 ℃, have a hard material and a low elasticity, since the elongation at break after freezing is reduced to 60% or less. Meanwhile, the hydrogel of comparative example 4 could not be frozen at-15 ℃ and the retention time at 0 ℃ was only 20 minutes; whereas the hydrogel of comparative example 5 did not have any elasticity after freezing. In conclusion, by adding the organosilicon material, the chain transfer agent and the alcohol into the hydrogel, the elasticity of the hydrogel in a frozen state can be effectively improved, and the thawing time is prolonged.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A freeze resistant hydrogel characterized by: the preparation raw materials of the anti-freezing hydrogel comprise: polymerized monomers, organosilicon materials, chain transfer agents and alcohols.
2. The antifreeze hydrogel of claim 1, wherein: the raw materials for preparing the anti-freezing hydrogel also comprise nano clay.
3. The antifreeze hydrogel of claim 2, wherein: the raw materials for preparing the anti-freezing hydrogel also comprise an initiator.
4. The antifreeze hydrogel of claim 3, wherein: the raw materials for preparing the anti-freezing hydrogel also comprise a polymerization accelerator; preferably, the raw material for preparing the anti-freeze hydrogel also comprises water.
5. The antifreeze hydrogel of claim 4, wherein: the anti-freezing hydrogel comprises the following preparation raw materials in percentage by mass:
3 to 30 percent of polymerized monomer
0.5 to 10 percent of organosilicon material
0.1 to 1 percent of chain transfer agent
1 to 20 percent of alcohol
1 to 10 percent of nano clay
0.05 to 1 percent of initiator
0.05 to 1 percent of polymerization accelerator
27 to 94.3 percent of water.
6. The antifreeze hydrogel of any of claims 1 to 5, wherein: the organic silicon material comprises any one or more of silane coupling agent, silicone oil, silicone resin and compound thereof, and the silane coupling agent is preferred; preferably, the silane coupling agent includes any one or more of gamma-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltris (beta-methoxyethoxy) silane, and vinyltriethoxysilane.
7. The antifreeze hydrogel of any of claims 1 to 5, wherein: the chain transfer agent comprises any one or more of dodecyl mercaptan and aliphatic mercaptan; preferably, the fatty thiol comprises any one or more of mercaptoethanol, thioglycolic acid and isooctyl 3-mercaptopropionate.
8. The antifreeze hydrogel of any of claims 1 to 5, wherein: the alcohols include any one or more of ethanol, ethylene glycol, propylene glycol and propylene glycol.
9. A method of producing a freeze resistant hydrogel according to any of claims 1 to 8, characterized in that: the method comprises the following steps:
mixing the preparation raw materials of the anti-freezing hydrogel, and reacting to obtain the anti-freezing hydrogel;
preferably, the preparation method comprises the steps of dissolving the polymerization monomer, the nanoclay, the chain transfer agent and the initiator in water to obtain component A; dissolving an organic silicon material and a polymer accelerator in alcohol to obtain a component B; and mixing the component A and the component B, and reacting to obtain the anti-freezing hydrogel.
10. Use of the antifreeze hydrogel of any one of claims 1 to 8 in the manufacture of ice bags, ice pads, cold compress physiotherapy devices, and shock absorbing devices.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110644255.1A CN113444200B (en) | 2021-06-09 | 2021-06-09 | Anti-freezing hydrogel and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110644255.1A CN113444200B (en) | 2021-06-09 | 2021-06-09 | Anti-freezing hydrogel and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113444200A true CN113444200A (en) | 2021-09-28 |
| CN113444200B CN113444200B (en) | 2022-09-09 |
Family
ID=77811129
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110644255.1A Active CN113444200B (en) | 2021-06-09 | 2021-06-09 | Anti-freezing hydrogel and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113444200B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114292483A (en) * | 2021-11-24 | 2022-04-08 | 四川大学 | Polyacrylamide/organosilicon blended hydrogel and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070037898A1 (en) * | 2005-08-10 | 2007-02-15 | Phelan John C | Silicone hydrogels |
| WO2008033462A2 (en) * | 2006-09-13 | 2008-03-20 | Hemcon Medical Technologies, Inc. | Supple tissue dressing assemblies, systems, and methods formed from hydrophilic polymer sponge structures such as chitosan |
| ZA200801930B (en) * | 2006-04-28 | 2009-09-30 | Zeltiq Aesthetics Inc | Cryoprotecant for use with a treatment device for improved cooling of subcuteneous lipid-rich cells |
| CN107641179A (en) * | 2017-09-30 | 2018-01-30 | 西南交通大学 | A kind of preparation method of the self-adhesion attached water gel with freeze proof/heat resistanceheat resistant performance |
| CN111269354A (en) * | 2020-02-29 | 2020-06-12 | 湖南大学 | Anti-freezing conductive hydrogel for photocuring 3D printing and preparation method thereof |
| US20200207927A1 (en) * | 2018-12-26 | 2020-07-02 | Ypf Tecnología S.A. | Hydrogels derived from acrylamide for controlling circulation losses and methods of fabrication thereof |
-
2021
- 2021-06-09 CN CN202110644255.1A patent/CN113444200B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070037898A1 (en) * | 2005-08-10 | 2007-02-15 | Phelan John C | Silicone hydrogels |
| ZA200801930B (en) * | 2006-04-28 | 2009-09-30 | Zeltiq Aesthetics Inc | Cryoprotecant for use with a treatment device for improved cooling of subcuteneous lipid-rich cells |
| WO2008033462A2 (en) * | 2006-09-13 | 2008-03-20 | Hemcon Medical Technologies, Inc. | Supple tissue dressing assemblies, systems, and methods formed from hydrophilic polymer sponge structures such as chitosan |
| CN107641179A (en) * | 2017-09-30 | 2018-01-30 | 西南交通大学 | A kind of preparation method of the self-adhesion attached water gel with freeze proof/heat resistanceheat resistant performance |
| US20200207927A1 (en) * | 2018-12-26 | 2020-07-02 | Ypf Tecnología S.A. | Hydrogels derived from acrylamide for controlling circulation losses and methods of fabrication thereof |
| CN111269354A (en) * | 2020-02-29 | 2020-06-12 | 湖南大学 | Anti-freezing conductive hydrogel for photocuring 3D printing and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 俞丽萍: "肿瘤化疗过程中所用冰袋的改进", 《上海护理》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114292483A (en) * | 2021-11-24 | 2022-04-08 | 四川大学 | Polyacrylamide/organosilicon blended hydrogel and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113444200B (en) | 2022-09-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Huang et al. | Research progress on double-network hydrogels | |
| US6960617B2 (en) | Hydrogels having enhanced elasticity and mechanical strength properties | |
| CN113444200B (en) | Anti-freezing hydrogel and preparation method and application thereof | |
| Omidian et al. | Swelling and mechanical properties of modified HEMA-based superporous hydrogels | |
| CN109851817B (en) | Preparation method of urushiol co-crosslinked anti-freezing/heat-resistant adhesive hydrogel | |
| CN101724384B (en) | Preparation method of high strength elastic slow-expansion water-absorption particle diverting agent | |
| CN112225910B (en) | Organic hydrogel with adjustable anti-freezing and water-locking properties and preparation method and application thereof | |
| CN110408053A (en) | A kind of high tough freeze proof heat-resistance polypropylene amide organic hydrogels and preparation method thereof | |
| EP3221386A1 (en) | Polyphosphate hydrogels and methods of making and using thereof | |
| US20150136144A1 (en) | Compositions and methods relating to an occlusive polymer hydrogel | |
| WO2021238112A1 (en) | High-stability composite phase-change gel for medicine cold-chain transportation at 2-8℃ | |
| AU2014337073A1 (en) | Compositions and methods relating to an occlusive polymer hydrogel | |
| CA2249719C (en) | Freeze-preventing material and method for preventing pavement surface from freezing | |
| CN113527714B (en) | Anti-freezing conductive hydrogel, preparation method thereof and force response sensing application | |
| EP1659143A1 (en) | Temperature-responsive hydrogel | |
| CN108530652A (en) | A kind of converted starch plural gel and its preparation method and application | |
| CN110408052B (en) | Fish antifreeze protein bionic freeze-resistant adhesive tough hydrogel and preparation method thereof | |
| CN115554462B (en) | Anti-swelling injectable hydrogel adhesive and preparation method thereof | |
| CN114437373B (en) | Amino acid composite free radical polymerization type hydrogel and preparation method and application thereof | |
| CN101912633A (en) | Hyaluronic acid sponge and preparation method thereof | |
| CN114478923B (en) | High-toughness antifreezing conductive hydrogel and preparation method thereof | |
| JPH0665560A (en) | Water-containing gel composition for cold-reserving agent excellent in shape retention, and cold-reserving agent | |
| JPH0425297B2 (en) | ||
| CN116102769B (en) | Carboxymethyl chitin hemostatic sponge material, preparation method and application | |
| CN113476643B (en) | Preparation method of hydrogel dressing capable of quickly gelling and slowly reinforcing after injection |
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 |