CN114075427A - Composite antifreezing agent and preparation method thereof - Google Patents
Composite antifreezing agent and preparation method thereof Download PDFInfo
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- CN114075427A CN114075427A CN202010839605.5A CN202010839605A CN114075427A CN 114075427 A CN114075427 A CN 114075427A CN 202010839605 A CN202010839605 A CN 202010839605A CN 114075427 A CN114075427 A CN 114075427A
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- 239000002131 composite material Substances 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 229920001661 Chitosan Polymers 0.000 claims abstract description 83
- -1 hydroxybutyl Chemical group 0.000 claims abstract description 71
- 239000002105 nanoparticle Substances 0.000 claims abstract description 60
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000007864 aqueous solution Substances 0.000 claims abstract description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 14
- 230000002528 anti-freeze Effects 0.000 claims description 42
- 239000003795 chemical substances by application Substances 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 16
- 239000007798 antifreeze agent Substances 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 10
- 238000007710 freezing Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000001879 gelation Methods 0.000 claims description 8
- 230000008014 freezing Effects 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 5
- 229940094522 laponite Drugs 0.000 claims description 4
- XCOBTUNSZUJCDH-UHFFFAOYSA-B lithium magnesium sodium silicate Chemical compound [Li+].[Li+].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3 XCOBTUNSZUJCDH-UHFFFAOYSA-B 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 239000003365 glass fiber Substances 0.000 claims description 3
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 3
- 230000000640 hydroxylating effect Effects 0.000 claims description 3
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims description 3
- 239000003444 phase transfer catalyst Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 230000007423 decrease Effects 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 9
- 230000008859 change Effects 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 7
- 230000009467 reduction Effects 0.000 abstract description 7
- 230000002441 reversible effect Effects 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 239000000499 gel Substances 0.000 description 17
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 238000000315 cryotherapy Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000000017 hydrogel Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000002087 whitening effect Effects 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 208000001034 Frostbite Diseases 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 210000001789 adipocyte Anatomy 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000037213 diet Effects 0.000 description 1
- 235000005911 diet Nutrition 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000007443 liposuction Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 210000004003 subcutaneous fat Anatomy 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
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- 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
- C09K5/20—Antifreeze additives therefor, e.g. for radiator liquids
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B18/00—Surgical instruments, devices or methods for transferring non-mechanical forms of energy to or from the body
- A61B18/02—Surgical instruments, devices or methods for transferring non-mechanical forms of energy to or from the body by cooling, e.g. cryogenic techniques
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- Chemical & Material Sciences (AREA)
- Surgery (AREA)
- Engineering & Computer Science (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Life Sciences & Earth Sciences (AREA)
- Heart & Thoracic Surgery (AREA)
- Veterinary Medicine (AREA)
- Medical Informatics (AREA)
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Abstract
The invention provides a composite antifreezing agent and a preparation method thereof, wherein the composite antifreezing agent is prepared from hydroxybutyl chitosan and inorganic nanoparticles according to a set proportion, wherein the inorganic nanoparticles have hydroxyl groups and/or can generate hydroxyl groups in an aqueous solution. The composite antifreezing agent prepared by the invention keeps a gel state at room temperature, is convenient to operate, reversibly converts from the gel state to a sol state along with the reduction of temperature, and can realize the effect of continuous supply; the composite antifreezing agent prepared by the invention realizes reversible change of viscosity through sol-gel reversible change, has high sol viscosity in the treatment process, can reduce the position movement between the treatment device and the skin, has low gel state viscosity after treatment is finished, and is beneficial to the disassembly of the treatment head.
Description
Technical Field
The invention relates to the technical field of medical treatment, and particularly relates to a composite antifreezing agent and a preparation method thereof.
Background
Liposuction is the most effective treatment for fat removal, but it is traumatic and carries a certain surgical risk. In order to remove excessive subcutaneous fat tissue in a non-invasive way, traditional non-invasive treatment comprises external medicines, weight-losing medicines, exercise, diet or a combination of the methods, but the methods are mostly used for losing weight generally or systemically and cannot achieve the effect of eliminating fat in local regions of a human body. New devices available for local fat reduction are becoming the focus of research, and various frozen fat reduction devices are disclosed, and frozen fat dissolution is considered as a method for effectively reducing the number of fat cells. In the frozen fat dissolving technology, the antifreezing agent can prevent the fat reducing device from freezing on the skin or the moisture seeped from the skin from freezing so as to frostbite the skin, and also has the function of transferring heat. During the cooling treatment, the treatment head and the tissue area need to be in stable contact to keep the treatment head fixed in position relative to the skin, the treatment effect cannot be influenced by the position deviation of the treatment head caused by the movement of the patient during the treatment, and therefore better adhesion is also needed for the antifreezing agent. However, the conventional antifreeze is liquid, has low viscosity, is easy to flow, is not easy to operate, is easy to be squeezed away by negative pressure in the treatment process, and is easy to cause whitening on the surface of the skin.
Disclosure of Invention
The invention aims to provide a composite antifreezing agent and a preparation method thereof, and aims to solve one or more problems in the prior art.
In order to solve the technical problem, the invention provides a preparation method of a composite antifreezing agent, which comprises the following steps:
mixing hydroxybutyl chitosan and inorganic nanoparticles according to a set proportion to prepare a composite antifreezing agent;
wherein the inorganic nanoparticles have hydroxyl groups and/or are capable of generating hydroxyl groups in aqueous solution.
Optionally, in the preparation method of the composite antifreeze agent, the inorganic nanoparticles include one or more of laponite, silica, hydroxyapatite, glass fiber, and calcium carbonate.
Optionally, in the preparation method of the composite antifreeze, the method for preparing the composite antifreeze by mixing hydroxybutyl chitosan and inorganic nanoparticles according to a set ratio comprises the following steps:
mixing the hydroxybutyl chitosan with the mass of m1, the deionized water with the mass of m2 and the inorganic nanoparticles with the mass of m3, and stirring to form the composite antifreeze agent;
wherein m1/m2 is 10-15%, and m3/m2 is 0.1-4%.
Optionally, in the preparation method of the composite anti-freezing agent, the method for mixing the hydroxybutyl chitosan with the mass m1, the deionized water with the mass m2 and the inorganic nanoparticles with the mass m3 comprises:
mixing the hydroxybutyl chitosan with a mass m1 and deionized water with a mass m2 to prepare an aqueous hydroxybutyl chitosan solution;
adding the inorganic nanoparticles with the mass m3 into the hydroxybutyl chitosan aqueous solution.
Optionally, in the preparation method of the composite antifreeze, before the inorganic nanoparticle solution is added to the hydroxybutyl chitosan aqueous solution, potassium persulfate is further added.
Optionally, in the preparation method of the composite antifreeze, the hydroxybutyl chitosan and the inorganic nanoparticles are mixed according to a set ratio to prepare the composite antifreeze, and the preparation is carried out under an ice bath condition.
Optionally, in the preparation method of the composite antifreeze, hydroxybutyl chitosan is prepared; when the hydroxybutyl chitosan is prepared, the alkalized chitosan is used as a raw material, butylene oxide is used as a hydroxylating agent, and sodium dodecyl sulfate is used as a phase transfer catalyst.
The invention also provides a composite antifreezing agent, which is prepared by the preparation method of the composite antifreezing agent, wherein the composite antifreezing agent is in a gel state at the temperature higher than the gelation temperature, and the composite antifreezing agent is reversibly converted from the gel state to the sol state along with the reduction of the temperature.
Optionally, in the composite antifreezing agent, the bonding strength of the composite antifreezing agent in a sol state is 20-32 kPa.
Optionally, in the composite antifreeze, under standard atmospheric pressure, the freezing point of the composite antifreeze is-20 to-25 ℃, and the gelation temperature is 15 to 20 ℃.
Compared with the prior art, the antifreeze prepared by the preparation method of the antifreeze provided by the invention has the following advantages:
(1) at room temperature, the conventional antifreezing agent is liquid, has small viscosity and easy flowing, and is not beneficial to operation; the composite antifreeze prepared by utilizing hydroxybutyl chitosan and inorganic nanoparticles can realize reversible change of viscosity through sol-gel reversible change, the sol viscosity is high in the treatment process, the position movement between a treatment device and the skin is reduced, and the composite antifreeze is changed to a gel state along with the rise of temperature after treatment is finished, so that the viscosity is low, and the treatment head is convenient to disassemble;
(2) in the treatment process, the conventional antifreezing agent is easily squeezed away by negative pressure, and the prepared antifreezing agent can be converted from gel to sol along with the reduction of temperature, so that the effect of continuously supplying the antifreezing agent can be realized;
(3) the inorganic nano particles adopted by the invention have hydroxyl groups and/or can generate hydroxyl groups in an aqueous solution, so that the mechanical property of the hydroxybutyl chitosan can be improved through intermolecular hydrogen bond combination between the inorganic nano particles and the hydroxybutyl chitosan, and the prepared composite antifreezing agent can have a good adhesion effect in a sol state;
(4) when the preparation method of the antifreeze is used for preparing the antifreeze, the proportion of the hydroxybutyl chitosan and the inorganic nanoparticles is controlled, so that the prepared antifreeze has the bonding strength of 20 k-32 kPa in a sol state, has excellent adhesion, has the freezing point of-20 to-25 ℃, meets the requirements of the cryotherapy temperature of-9 to-11 ℃ and the gelation temperature of 15 to 20 ℃, and exists in a gel state at room temperature, thereby greatly improving the convenience of operation;
(5) the raw materials are simple to select, and the inorganic nanoparticles can be used for preparing the composite antifreezing agent without special treatment.
Drawings
FIG. 1 is a flow chart of a method for preparing an antifreeze provided by an embodiment of the present invention;
FIG. 2 is a diagram of the mechanism of hydroxybutyl chitosan in the examples of the present invention.
Detailed Description
The antifreeze and the preparation method thereof provided by the invention are further explained in detail by combining the attached drawings and specific examples. The advantages and features of the present invention will become more apparent from the following description. It is to be noted that the drawings are in a very simplified form and are not to precise scale, which is merely for the purpose of facilitating and distinctly claiming the embodiments of the present invention. Further, the structures illustrated in the drawings are often part of actual structures. In particular, the drawings may have different emphasis points and may sometimes be scaled differently.
The core idea of the invention is to prepare an antifreeze which has better adhesiveness and can generate sol-gel interconversion under a certain temperature mechanism.
In view of this, an embodiment of the present invention provides a preparation method of a composite antifreeze, including: and preparing the hydroxybutyl chitosan and the inorganic nanoparticles into the composite antifreezing agent according to a set proportion, wherein the inorganic nanoparticles have hydroxyl groups and/or can generate hydroxyl groups in an aqueous solution.
As described above, in the cryolipolysis operation, the anti-freezing agent needs to have good adhesion in order to prevent the treatment head from being displaced during the treatment and thus affecting the treatment effect. However, the conventional antifreeze is liquid, has low viscosity, is easy to flow, is not easy to operate, is easy to be squeezed away by negative pressure in the treatment process, and is easy to cause whitening on the surface of the skin. The antifreeze prepared by the preparation method of the composite antifreeze provided by the implementation can realize reversible change of viscosity through sol-gel reversible change, has high sol viscosity in the treatment process, reduces the position movement between the treatment device and the skin, can realize continuous supply, has low gel state viscosity after treatment, and is beneficial to the disassembly of the treatment head.
In this embodiment, the hydroxybutyl chitosan may be prepared from chitosan, that is, the preparation method of the composite antifreeze provided in this embodiment includes the following steps:
s1, preparing hydroxybutyl chitosan by using chitosan;
s2, mixing the hydroxybutyl chitosan and the inorganic nano particles according to a set proportion to prepare the composite antifreezing agent.
The above steps are described in further detail below.
The Hydroxybutyl chitosan (Hydroxybutyl chitosan) has unique temperature sensitivity and good biological activity, is easy to dissolve in water, can be gelled without crosslinking by a crosslinking agent in an aqueous solution, and has temperature and PH value sensitivity. However, the hydroxybutyl chitosan hydrogel has poor mechanical properties, stability and adhesion, which greatly limits its application range.
In view of this, the present embodiment improves the mechanical properties, stability and adhesion of hydroxybutyl chitosan through the inorganic nanoparticles, and the inorganic nanoparticles have rigidity, play a role in structural support of hydroxybutyl chitosan, and can improve the storage modulus of hydroxybutyl chitosan. The composite antifreezing agent is prepared by the hydroxybutyl chitosan and the inorganic nanoparticles according to a set proportion, so that the composite antifreezing agent has good mechanical property and adhesion while the temperature sensitivity is kept.
In step S1, in the preparation of hydroxybutyl chitosan, alkalizable chitosan is used as the raw material, butylene oxide is used as the hydroxylating agent, and sodium dodecyl sulfate is used as the phase transfer catalyst. Specifically, the preparation of the hydroxybutyl chitosan may comprise the following steps:
a. alkalization: ice-cooling Chitosan (Chitosan) with NaOH solution to prepare alkalized Chitosan;
b. hydroxybutylation: as shown in fig. 2, the alkalized chitosan is dissolved in a mixed solution of isopropyl alcohol and distilled water, and a certain amount of Sodium Dodecyl Sulfate (SDS) is added, and butylene oxide is dropped, and reacted to prepare hydroxybutyl chitosan.
In step S2, since the inorganic nanoparticles have hydroxyl groups and/or can generate hydroxyl groups in an aqueous solution, the inorganic nanoparticles can be bonded to the hydroxybutyl chitosan in a hydrogen bonding manner, so that the finally prepared composite antifreeze agent has good adhesion and mechanical properties. Wherein the inorganic nanoparticles may be selected from one or more of Laponite (Laponite), silica, hydroxyapatite, glass fiber, and calcium carbonate. Besides being capable of being combined with the hydroxybutyl chitosan in a hydrogen bonding mode, the nanoparticle without the nanoparticle also has certain electronegativity and certain adsorption capacity on the hydroxybutyl chitosan, so that the combination effect between the hydroxybutyl chitosan can be further improved. In addition, the inorganic nano particles can be used for preparing the composite antifreezing agent without special treatment, so that the difficulty of the whole preparation process of the composite antifreezing agent is reduced.
It should be noted here that besides the above list, the inorganic nanoparticles may also be attapulgite, kaolin, etc., and the specific selection of the inorganic nanoparticles is not limited enough for the application, and only needs to ensure that the inorganic nanoparticles can be combined with hydroxybutyl chitosan to prepare the composite antifreeze agent and have a certain adhesiveness. Inorganic nanoparticles that do not have adhesion, like graphene oxide, are not within the scope of the present application.
In this embodiment, step S2 specifically includes the following steps:
mixing the hydroxybutyl chitosan with the mass of m1, the deionized water with the mass of m2 and the inorganic nanoparticles with the mass of m3, and stirring to form the composite antifreeze agent; wherein m1/m2 is 10-15%, and m3/m2 is 0.1-4%.
Wherein, the stirring can be carried out by a homogenizing emulsifying machine so as to improve the stirring uniformity and ensure that the hydroxybutyl chitosan and the inorganic nano-particles can be fully contacted. In addition, since hydroxybutyl chitosan may be transformed into gel state at higher temperature, which is not favorable for mixing with inorganic nanoparticles, it is preferable that step 2 is performed under ice bath condition.
Further, the mixing of the hydroxybutyl chitosan with mass m1, the deionized water with mass m2 and the inorganic nanoparticles with mass m3 may employ the following steps:
mixing the hydroxybutyl chitosan with a mass m1 and deionized water with a mass m2 to prepare an aqueous hydroxybutyl chitosan solution; adding the inorganic nanoparticles with the mass m3 into the hydroxybutyl chitosan aqueous solution.
In other embodiments, the inorganic nanoparticles may be dispersed in deionized water, followed by the addition of hydroxybutyl chitosan and stirring to form the composite antifreeze agent. The sequence of adding the hydroxybutyl chitosan and the inorganic nanoparticles is not limited, and the hydroxybutyl chitosan and the inorganic nanoparticles are only required to be mixed to meet the conditions that m1/m2 is 10% -15% and m3/m2 is 0.1% -4%, so that the finally formed composite antifreezing agent has a freezing point of-20 to-25 ℃ under the standard atmospheric pressure, meets the cryotherapy temperature of-9 to-11 ℃, has a gelation temperature of 15 to 20 ℃, and exists in a gel state at room temperature, and can greatly improve the convenience of operation.
The inorganic nano particles are used as a cross-linking agent to provide physical cross-linking points for the hydroxybutyl chitosan, so that the hydroxybutyl chitosan forms a gel and the cohesive force of the hydroxybutyl chitosan is enhanced, and further the bonding strength of the composite antifreeze agent is increased. The hydroxybutyl chitosan is in a gel state through physical crosslinking, so the cohesive force of the composite antifreeze can be adjusted through the addition amount of the inorganic nanoparticles, and the adhesive force of the composite antifreeze can also change along with the change of the addition amount of the inorganic nanoparticles. Therefore, further preferably, when the mass ratio m1/m2 of the hydroxybutyl chitosan to the deionized water in the prepared hydroxybutyl chitosan aqueous solution is 10-15%, the inorganic nanoparticles are added to make m3/m2 be 0.5-1%, and the bonding strength of the prepared composite antifreeze agent can reach 20-32 kPa.
In addition, when the inorganic nanoparticles are added into the hydroxybutyl chitosan aqueous solution, a certain amount of potassium persulfate can be added, and the potassium persulfate is used as a catalyst, so that the hydrogen bonding effect of the hydroxybutyl chitosan and the inorganic nanoparticles can be improved.
The embodiment also provides a composite antifreeze prepared by the preparation method of the antifreeze provided by the embodiment, the composite antifreeze is in a gel state at the temperature higher than the gelation temperature, and the composite antifreeze is reversibly converted from the gel state to a sol state along with the reduction of the temperature.
The bonding strength of the composite antifreezing agent in a sol state is 20-32 kPa, the freezing point is-20 to-25 ℃ under the standard atmospheric pressure, and the gelation temperature is 15-20 ℃.
The preparation method of the antifreeze provided by the embodiment of the invention is illustrated below.
(1) Preparation of hydroxybutyl chitosan
Measuring 10mL of 50% NaOH solution, adding 2-5 g of chitosan powder, stirring for 24h under the protection of nitrogen atmosphere and ice bath condition, filtering, and extruding out redundant alkali liquor. Adding a certain amount of isopropanol aqueous solution (isopropanol: water is 1: 1) into the alkalized chitosan, fully stirring at normal temperature until the alkalized chitosan is completely dispersed in the system, adding a trace amount of sodium dodecyl sulfate, heating the system to 60 ℃, dropwise adding 40-50 mL of butylene oxide, and stirring for reacting for 12 hours. After the reaction is finished, adding 10% HCI solution dropwise to adjust the pH of the product to be neutral, filtering out insoluble substances when the product becomes transparent, dialyzing for 3d, centrifuging, and freeze-drying the precipitate to obtain hydroxybutyl chitosan powder.
(2) Preparation of hydroxybutyl chitosan/inorganic nano particle hydrogel
Weighing a certain amount of hydroxybutyl chitosan, adding deionized water to prepare 10-15% w/v water solution, and dissolving for 24h at 4 ℃. After the mixture is fully dissolved, 0.5-1% w/v of inorganic nanoparticles and a trace amount of potassium persulfate are added into the solution, the mixture is stirred vigorously by a homogenizing emulsifying machine to be uniform, the hydroxybutyl chitosan/inorganic nanoparticle composite hydrosol is formed, and the mixture is placed at room temperature to form the composite antifreezing agent spontaneously.
In summary, in the antifreeze and the preparation method thereof provided by the invention, hydroxybutyl chitosan and inorganic nanoparticles are prepared into the composite antifreeze according to a set proportion, and the inorganic nanoparticles have hydroxyl groups and/or can generate hydroxyl groups in an aqueous solution. At room temperature, the conventional antifreezing agent is liquid, has small viscosity and easy flowing, is not beneficial to operation, and is easy to be squeezed away by negative pressure in the treatment process, and the skin surface is easy to be whitened; the composite antifreeze agent disclosed by the invention keeps a gel state at room temperature, is convenient to operate, can be converted from gel to sol along with the reduction of temperature, and can realize the effect of continuously supplying the antifreeze agent.
The above description is only for the purpose of describing the preferred embodiments of the present invention, and is not intended to limit the scope of the present invention, and any variations and modifications made by those skilled in the art based on the above disclosure are within the scope of the appended claims.
Claims (10)
1. The preparation method of the composite antifreezing agent is characterized by comprising the following steps:
mixing hydroxybutyl chitosan and inorganic nanoparticles according to a set proportion to prepare a composite antifreezing agent;
wherein the inorganic nanoparticles have hydroxyl groups and/or are capable of generating hydroxyl groups in aqueous solution.
2. The method of claim 1, wherein the inorganic nanoparticles comprise one or more of laponite, silica, hydroxyapatite, glass fiber, and calcium carbonate.
3. The preparation method of the composite antifreeze agent according to claim 1, wherein the method for preparing the composite antifreeze agent by mixing hydroxybutyl chitosan and inorganic nanoparticles according to a set ratio comprises the following steps:
mixing the hydroxybutyl chitosan with the mass of m1, the deionized water with the mass of m2 and the inorganic nanoparticles with the mass of m3, and stirring to form the composite antifreeze agent;
wherein m1/m2 is 10-15%, and m3/m2 is 0.1-4%.
4. The method for preparing the composite antifreeze of claim 3, wherein the method for mixing the hydroxybutyl chitosan with the mass m1, the deionized water with the mass m2 and the inorganic nanoparticles with the mass m3 comprises:
mixing the hydroxybutyl chitosan with a mass m1 and deionized water with a mass m2 to prepare an aqueous hydroxybutyl chitosan solution;
adding the inorganic nanoparticles with the mass m3 into the hydroxybutyl chitosan aqueous solution.
5. The method of claim 4, wherein potassium persulfate is further added before the inorganic nanoparticle solution is added to the hydroxybutyl chitosan aqueous solution.
6. The preparation method of the composite antifreeze agent as claimed in claim 1, wherein the preparation of the composite antifreeze agent is carried out by mixing hydroxybutyl chitosan and inorganic nanoparticles according to a predetermined ratio under ice bath conditions.
7. The method for preparing the composite antifreeze of claim 1, further comprising preparing hydroxybutyl chitosan; when the hydroxybutyl chitosan is prepared, the alkalized chitosan is used as a raw material, butylene oxide is used as a hydroxylating agent, and sodium dodecyl sulfate is used as a phase transfer catalyst.
8. A composite antifreeze prepared by the method for preparing a composite antifreeze according to any one of claims 1 to 7, wherein the composite antifreeze is in a gel state above a gelation temperature, and reversibly changes from the gel state to a sol state as the temperature decreases.
9. The composite antifreeze of claim 8, wherein the bonding strength of the composite antifreeze in a sol state is 20 to 32 kPa.
10. The composite antifreeze of claim 8, wherein the freezing point of the composite antifreeze is between-20 and-25 ℃ and the gelation temperature is between 15 and 20 ℃ under standard atmospheric pressure.
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| CN105107008A (en) * | 2015-09-16 | 2015-12-02 | 中南民族大学 | Hydroxybutyl chitosan/oxidized sodium alginate/nano-silver composite hydrogel dressing plaster |
| CN106110323A (en) * | 2016-07-06 | 2016-11-16 | 安徽理工大学 | A kind of gold hydroxyl butyl aquagel and its preparation method and application |
| CN107915787A (en) * | 2016-10-11 | 2018-04-17 | 中国海洋大学 | A kind of preparation method of pH temperature dual-sensitivity chitosan nano particle |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105107008A (en) * | 2015-09-16 | 2015-12-02 | 中南民族大学 | Hydroxybutyl chitosan/oxidized sodium alginate/nano-silver composite hydrogel dressing plaster |
| CN106110323A (en) * | 2016-07-06 | 2016-11-16 | 安徽理工大学 | A kind of gold hydroxyl butyl aquagel and its preparation method and application |
| CN107915787A (en) * | 2016-10-11 | 2018-04-17 | 中国海洋大学 | A kind of preparation method of pH temperature dual-sensitivity chitosan nano particle |
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