CN111545139B - Reversible phase-change atomized liquid gel containing glycosyl-amido-aryl-alkyl four-section glycosyl gelling agent and preparation method and application thereof - Google Patents
Reversible phase-change atomized liquid gel containing glycosyl-amido-aryl-alkyl four-section glycosyl gelling agent and preparation method and application thereof Download PDFInfo
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- CN111545139B CN111545139B CN202010501953.1A CN202010501953A CN111545139B CN 111545139 B CN111545139 B CN 111545139B CN 202010501953 A CN202010501953 A CN 202010501953A CN 111545139 B CN111545139 B CN 111545139B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0052—Preparation of gels
- B01J13/0065—Preparation of gels containing an organic phase
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- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
- A24B15/00—Chemical features or treatment of tobacco; Tobacco substitutes, e.g. in liquid form
- A24B15/10—Chemical features of tobacco products or tobacco substitutes
- A24B15/16—Chemical features of tobacco products or tobacco substitutes of tobacco substitutes
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- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
- A24B15/00—Chemical features or treatment of tobacco; Tobacco substitutes, e.g. in liquid form
- A24B15/10—Chemical features of tobacco products or tobacco substitutes
- A24B15/16—Chemical features of tobacco products or tobacco substitutes of tobacco substitutes
- A24B15/167—Chemical features of tobacco products or tobacco substitutes of tobacco substitutes in liquid or vaporisable form, e.g. liquid compositions for electronic cigarettes
Abstract
The invention discloses a reversible phase-change atomized liquid gel containing glycosyl-amido-aryl-alkyl four-section glycosyl gelling agent, which comprises the following components in percentage by mass: 0.1-3.0 wt% of sugar-based gelling agent; 97.0-99.9 wt% of atomized liquid; the chemical structural formula of the glycosyl gelling agent is as follows:
Description
Technical Field
The invention belongs to the technical field of gel, and particularly relates to an atomized liquid gel which is derived from saccharides and contains a glycosyl-amido-aryl-alkyl four-stage glycosyl gelling agent and has reversible phase change characteristics, and a preparation method and application thereof.
Background
Supramolecular organogels are non-glassy, non-crystalline, thermoreversible solid materials comprising a three-dimensional network (solid phase) made of entangled and self-assembled gelling agent fibers and an organic continuous phase (liquid phase) immobilized thereon. The supramolecular organogel contains organic liquids as the main component, with rheological behavior and solid appearance. The continuous organic phase comprises organic solvent, vegetable oil or mineral oil, wherein the organic solvent capable of gelation comprises aliphatic hydrocarbon and aromatic hydrocarbon, alcohols, silicone oil, dimethyl sulfoxide, etc. The gelling agent is a low molecular weight organic gelling agent with relatively small molecular weight (3000 Da), the organic gelling agent is derived from long-chain alkane or steroid derivative, amino acid derivative, urea, saccharide system, metal complex, charge transfer complex, macrocyclic substance, organic salt (ionic liquid) and the like, and the organic gelling agent is also called molecular building block and is a basic structural skeleton forming the low molecular weight organic gelling agent. The small molecular weight organic gelling agent self-assembles to obtain a three-dimensional network through non-covalent interactions such as hydrogen bonds, pi-pi stacking, van der waals forces, electrostatic interactions, etc., and organic solvent molecules are trapped and fixed to the three-dimensional network through interfacial forces to form a viscoelastic gel material, and such gels are called supramolecular gels or physical gels due to the complex supramolecular structures.
Organogels are currently used mainly in the fields of topical drug delivery, dermal drug delivery, transdermal drug delivery, parenteral drug delivery, buccal drug delivery, in situ organogels as mucoadhesives, tablets and suppositories, and in the culture of microorganisms.
In recent years, small molecular weight organogelators derived from saccharides have been attracting much attention for reasons including: the saccharides contain a plurality of hydroxyl functional groups and have wide hydrogen bonding action, and the hydrogen bonding has reversibility, specificity, directionality and cooperativity, so the saccharides can utilize abundant intramolecular and intermolecular hydrogen bonding action to self-assemble and manufacture a complex organization system, and the advantage of the self-assembly of the hydrogen bonding is far greater than that of organic gelling agents such as amino acid derivatives, urea and the like; the characteristics of structural richness, diversity of sugar units, sequences and connection sites, anomeric structure, chemical modification and/or substitution of different positions, interconversion of conformational isomers, etc. are suitable for creating a variety of unique organic gelling agents, water-based gelling agents and general gelling agents; the gelation property can be easily adjusted by simply protecting or deprotecting a plurality of hydroxyl groups of the saccharide; the precursor saccharide raw material is cheap and available on the market, and can be derived from abundant renewable resources; carbohydrates are generally biodegradable, non-toxic and environmentally friendly. Precursor materials for the preparation of sugar-based small molecule gelling agents are typically: d-maltose, D-sorbitol, L-ascorbic acid, trehalose, amygdalin, D-lactose, D-allose, D-mannose, D-galactose and D-glucose.
In the currently popular electronic nicotine delivery systems (e-cigarettes), liquid tobacco liquid is usually atomized into aerosol by means of electrothermal or ultrasonic atomization to deliver nicotine and flavor substances. And tobacco juice seepage is ubiquitous problem in present electron cigarette, feels to cause very adverse effect to user experience, and the reason of electron cigarette tobacco juice seepage has: 1. an electronic cigarette liquid storage device (atomizer) filled with cigarette liquid often leaks due to air pressure, temperature or vibration and the like in the transportation and storage processes; 2. the nicotine and the aroma components are dissolved in the atomizing agent which takes the glycerol and the propylene glycol as main components to form uniform viscous liquid tobacco juice, the viscosity of the tobacco juice is obviously reduced, the fluidity is enhanced in the electric heating high-temperature or ultrasonic atomizing process, in addition, the influence of a gas circuit system communicated with the outside is added, the assembly clearance of the electronic cigarette smoking set is increased due to the thermal expansion in the smoking process, and the tobacco juice is easy to leak from the atomizer in the smoking process and after the smoking is finished.
In order to solve or improve the problem of electronic cigarette tobacco juice leakage, two measures are mainly taken at present: firstly, the leakage risk of liquid smoke liquid is reduced by considering the aspects of the design of structures and air paths of smoking tools and atomizers, the development of new liquid storage and guide materials, novel induction devices and the like; and secondly, the solid (semi-solid) tobacco juice is used for replacing the existing liquid tobacco juice and developing a matched smoking set, so that the risk of tobacco juice leakage is reduced while the tobacco juice is stored and transported conveniently. The former brings practical problems of increased research and development cost and complex structure and manufacturing process, and in addition, the atomizer needs air circulation in the using process and cannot be completely isolated from the external atmosphere, so that the leakage of smoke liquid is still difficult to control; the solid (semi-solid) tobacco liquid related to the latter is not only complex in preparation process, but also has no reversible phase change performance or low phase change temperature, namely the solid (semi-solid) tobacco liquid can be melted only when being heated but can not be recovered or can be recovered only when being cooled to a low temperature (such as 40 ℃), so that the solid (semi-solid) tobacco liquid can improve the leakage problem of the tobacco liquid even when being stored and transported, but the solid (semi-solid) tobacco liquid is liquefied and is difficult to recover to the original solid (semi-solid) tobacco liquid when meeting practical conditions of slightly high environmental temperature, slight vibration, repeated rise and fall of the using temperature of the electronic cigarette and the like, and the problem of the leakage of the tobacco liquid still exists.
The present invention has been made to solve the above problems.
Disclosure of Invention
In a first aspect, the present invention provides a reversible phase-change aerosol gel comprising a glycosyl-amido-aryl-hydrocarbyl quarternary glycosyl gelling agent, comprising:
0.1-3.0 wt% of sugar-based gelling agent;
97.0-99.9 wt% of atomizing agent;
the chemical structural formula of the glycosyl gelling agent is as follows:
wherein:
s is glycosyl;
a (R) n is an aryl group having an alkyl group or an alkoxy group, and 1. ltoreq. n.ltoreq.5.
Wherein, glycosyl refers to a group left after one hydrogen atom in a sugar molecule is removed; arylene refers to a group remaining after removal of two hydrogen atoms from an aromatic ring molecule, the two removed hydrogens being on different atoms.
Preferably, S is a monosaccharide radical, a maltosyl radical, a cellobiosyl radical, or a lactose radical;
a (R) n is
The atomized liquid gel with the reversible phase change characteristic comprises a supermolecular three-dimensional network consisting of a small molecular weight organic gelling agent and liquid atomized liquid fixed in the network. The organic gelling agent with small molecular weight in the atomized liquid gel is a glycosyl gelling agent, a three-dimensional network is obtained through self-assembly of non-covalent action (hydrogen bonds, pi-pi stacking, van der waals force, electrostatic action and the like), atomized liquid substance molecules are captured and fixed in the three-dimensional network through interfacial force to form a viscoelastic material, and the material has a complex supermolecular structure, so that the atomized liquid gel can be called as supermolecular gel or physical gel. The driving force for self-assembly to form a three-dimensional network is reversible non-covalent action, so the atomized liquid gel has reversible phase change characteristics.
In the present invention, the atomized liquid gel having a reversible phase transition characteristic means that the atomized liquid gel has a thermally reversible phase transition characteristic and/or a shear reversible phase transition characteristic. The gel-sol phase transition temperature of the atomized liquid gel is 188-248 ℃; the gel-sol phase transition critical shear stress of the atomized liquid gel is 110-800 Pa. Wherein, the thermal reversible phase transition characteristic is that: below the gel-sol phase transition temperature (T) of the atomized liquid gelgel) When the atomized liquid gel is in a gel state; when the atomized liquid gel is heated and the temperature exceeds the gel-sol phase transition temperature (T)gel) When the sugar-based gelling agent is used, the non-covalent interaction between molecules of the sugar-based gelling agent is destroyed, the atomized liquid gel is rapidly melted and changed into a sol state, wherein the liquid atomized liquid fixed in the sugar-based gelling agent is evaporated and atomized, and the atomized agent is released to form inhalable aerosol; when the temperature drops below the sol-gel transition temperature (T) of the atomized liquid gelgel) When the glycosyl gelator is not covalently bondedThe liquid atomized liquid without atomization is fixed in the supermolecule gel network again, and the atomized liquid gel is restored to the gel state. Also, the shear reversible phase transition characteristic means: at a shear stress below the gel-sol critical stress of the atomized hydrogel, the atomized hydrogel is in a gel state; when the sugar-based gelling agent is oscillated and the shear stress is increased, the non-covalent interaction between the molecules of the sugar-based gelling agent is destroyed, the atomized liquid gel is changed into a sol state from a gel state, the liquid atomized liquid fixed in the sugar-based gelling agent is evaporated and atomized, and the atomizing agent is released to form inhalable aerosol; when the oscillation is stopped and the shearing stress is reduced, the glycosyl gelling agent molecules are driven by non-covalent interaction to self-assemble to form a supramolecular gel network, the sol state is rapidly cooled and solidified to recover the gel state, the liquid atomized liquid which is not atomized is re-fixed in the supramolecular gel network, and the atomized liquid gel recovers to the gel state.
In the invention, the chemical structural formula of the glycosyl gelling agent is as follows:
s is glycosyl; a (R) n is an aryl group having an alkyl group or an alkoxy group, and 1. ltoreq. n.ltoreq.5.
The advantages and the problems to be solved of the sugar-based gelling agent of the present invention are:
1. the atomizing agent as the main component of the atomizing liquid is glycerol and propylene glycol, the glycerol and the propylene glycol belong to polar media, the hydrogen bond donor and the acceptor fragment of the traditional glycosyl gelling agent containing a large amount of hydroxyl are easy to perform solvation action, so that the intermolecular hydrogen bond strength of the glycosyl gelling agent is obviously reduced, the stability of a gelled three-dimensional network is influenced, and even the glycosyl gelling agent is mixed with the atomizing liquid and cannot form atomizing liquid gel.
In order to solve the problem, the hydrophobic aliphatic long chain and aromatic ring are introduced into the glycosyl gelling agent, so that the effects of van der Waals force, hydrophobic (solvophobic) effect, pi-pi stacking and the like in the glycosyl gelling agent are improved, the intermolecular hydrogen bond strength in the glycosyl gelling agent is improved, and the intermolecular self-assembly capacity of the glycosyl gelling agent is further improved. In addition, the long fatty chains are hydrophobic, which can improve the hydrophobic (solvophobic) effect of the glycosyl gelling agent, thereby weakening the influence of the solvation effect of glycerol and propylene glycol on the hydrogen bonding effect between molecules of the gelling agent.
2. The hydrogen bonding between molecules of the glycosyl gelling agent is a main driving force for self-assembly, and glycerol and propylene glycol which are main components of the atomized liquid contain a large amount of alcohol hydroxyl groups, and the hydrogen bonding between the alcohol hydroxyl groups and the sugar hydroxyl groups in the glycosyl gelling agent can be in strong competition with the hydrogen bonding between molecules of the sugar hydroxyl groups of the glycosyl gelling agent, so that the hydrogen bonding between molecules of the glycosyl gelling agent is weakened, the rigidity and the thermal stability of the gel are poor, and the atomized liquid gel with reversible phase change characteristics suitable for high-temperature conditions is difficult to prepare.
In order to solve the problem, the invention adopts a glycosyl raw material with more oriented hydroxyl groups (such as cyclic sugar) or introduced with additional hydrogen bond donor and acceptor groups (such as amide groups) to prepare the glycosyl gelling agent, and the glycosyl gelling agent molecules can form a strong synergistic hydrogen bond network besides the original intermolecular hydrogen bond action, so that the hydrogen bond action is enhanced, the self-assembly hydrogen bond driving capability is increased, the hydrogen bond competitive power of the alcoholic hydroxyl groups in the glycerol and the propylene glycol is weakened, the formed network structure is more rigid, the stability and the rigidity are improved, and the atomized liquid gel with the reversible phase change characteristic and higher phase change shear stress and higher phase change temperature is obtained.
In light of the above, the sugar-based gelling agent of the present invention preferably has the chemical formula:
the structure of the sugar-based gelling agent comprises sugar groups, amide groups, aromatic groups and hydrophobic hydrocarbon chains of a cyclic sugar structure. The sugar-based gelling agent of the present invention has the following advantages: 1. the five-membered ring intramolecular hydrogen bond formed between the amino group (-NH) and the 2-position hydroxyl group (2-OH) will polarize the second hydrogen bond (i.e., the six-membered ring intramolecular hydrogen bond between the two bi-axial hydroxyl groups 2-OH and 4-OH), resulting in the hydroxyl group at the 4-position (4-OH) being an effective cooperative donor, i.e., a cooperative hydrogen bonding network of 2-OH → 4-OH → 6-OH is formed. As a result, 4-OH, acting as a co-donor, may form additional intramolecular hydrogen bonds with 6-OH, possibly establishing strong intermolecular hydrogen bonds. In this way, the thermal stability and rigidity of the gel will be significantly improved. The cyclic sugar structure can improve the hydrogen bond action among the molecules of the sugar-based gelling agent, weaken the hydrogen bond competitiveness of the alcoholic hydroxyl in the glycerol and the propylene glycol, enable the formed network structure to have higher rigidity, and improve the stability and the rigidity. 2. The introduction of aromatic groups can improve the pi-pi stacking effect, increase the corresponding van der Waals force of the length of a hydrocarbon chain, and the two can improve the intermolecular hydrogen bond strength of the glycosyl gelling agent, and the hydrophobic effect of the hydrocarbon chain can also improve the hydrophobic (solvophobic) effect of the glycosyl gelling agent, so that the influence of the solvation effect of glycerol and propylene glycol on the intermolecular hydrogen bond effect of the gelling agent is weakened. 3. By introducing a hydrogen bond donor and an acceptor (an amide group) into the glycosyl ligand, the hydroxyl hydrogen bond of the glycosyl ligand can be oriented and polarized to form a hydrogen bond cooperative network and a cooperative center, so that the intermolecular hydrogen bond action of the gelling agent is greatly enhanced, the competition of the hydrogen bond action between the glycerol/propylene glycol hydroxyl group and the hydroxyl group of the gelling agent in the atomized liquid on the intermolecular hydrogen bond of the gelling agent is effectively inhibited, the structure of a gel network is stabilized, and the thermal stability and the gel phase transition temperature of the gel are greatly improved. The configuration isomerization enables the atomized liquid to have the capability of gelatinizing the atomized liquid, so that the atomized liquid gel with higher phase transition temperature and higher phase transition shear stress and reversible phase transition characteristic is obtained.
Preferably, based on the mass percentage of the atomized liquid, the atomized liquid comprises: an atomizing agent, which accounts for 90-100 wt% of the atomized liquid; nicotine in an amount of 0-10 wt% of the atomized liquid; a fragrance which comprises 0-10 wt% of the atomized liquid;
the atomizing agent is a mixture of glycerol and propylene glycol, wherein the volume ratio of the glycerol to the propylene glycol is 3:7-7: 3.
In this case, the atomized liquid in the atomized liquid gel is a solution containing an atomizing agent as a main component or a carrier and further containing or not containing a substance such as nicotine and/or a flavor component (perfume).
Under heating and/or vibration, the atomized liquid gel is changed from gel state to sol state, and the atomized agent fixed in the gel carries dissolved nicotine, aroma components and other substances to be released together to form inhalable aerosol; when the heating and/or shaking is stopped, the sol gel returns to the gel state and the non-atomized molecules of the aerosol, nicotine and aroma are re-immobilized in the gel network.
In a second aspect, the invention provides a method for preparing the atomized liquid gel, wherein the sugar-based gelling agent is heated and dissolved in the atomized liquid, and after the sugar-based gelling agent is stirred until the sugar-based gelling agent is completely dissolved, the heated mixed solution is slowly cooled to form the atomized liquid gel.
By employing different types and amounts of sugar-based gelling agents and adjusting the types and proportions of the various components of the atomized liquid, a balance can be established between the gelling agent-gelling agent and gelling agent-atomized liquid interactions to drive the formation of a gel without forming precipitates, crystals, or a homogeneous solution.
The third aspect of the invention provides an application of the atomized liquid gel, wherein the atomized liquid gel is directly injected into a liquid storage bin of an electronic cigarette atomizer, and the atomized liquid gel cartridge suitable for an electronic cigarette is prepared after the solution is cooled and gelatinized.
Under the conditions of heating, high shearing and violent oscillation, the non-covalent action of the self-assembled three-dimensional network structure is relatively weak, so that the network structure is destroyed, the viscosity of the gel is reduced, and the trapped atomized liquid is released; when heating is stopped, the shear rate is reduced or high-speed shearing is stopped, the gel has quick visco-elastic creep recovery and good thixotropic behavior, can be quickly self-assembled to form gel, and the viscosity of the gel is increased again. Therefore, the gel has good reversibility to a sol state when heated or vigorously shaken (sheared); when cooled or at rest (shear stopped), a gel can form rapidly. The above process may be repeated a number of times. In conclusion, the atomized liquid gel of the invention can be applied to devices for oscillating and atomizing by electric heating or non-electric heating (such as high-frequency bulk acoustic waves and surface acoustic waves).
The gel can be directly filled into a liquid storage bin of a commercially available electronic cigarette atomizer, and specifically, a molten gel hot solution is directly injected into the liquid storage bin of the atomizer, and the sol is cooled and gelatinized. The preferred type of atomizer is disposable (pre-filled).
The gel can be made into atomized liquid gel cartridges with different shapes and independently stored and packaged according to market demands, shape adaptability of the heating device of the electronic cigarette smoking set and operation modes. The aerosol gel cartridge may be in the form of a tablet, a granule, a column, or the like. The method specifically comprises the following steps: for the oil cup heating type electronic cigarette, the atomized liquid gel cigarette cartridge with the matched size and shape can be manufactured according to the structure of the oil cup, and the gel cigarette cartridge can be placed in the oil cup when in use. The atomized liquid gel cartridge is suitable for a refillable electronic cigarette atomizer.
In a fourth aspect, the present invention provides an application of the atomized liquid gel, wherein a melted atomized liquid gel solution is directly injected into an aerosol generating device made of a porous material, and the solution is fixed in the porous material after being cooled and gelatinized.
The supermolecule gel can be poured into an aerosol generating device made of a porous material due to excellent creep recovery and thixotropy. The aerosol generating device may incorporate heating and/or oscillatory atomisation and a reservoir of atomised liquid gel. Types of the porous material include, but are not limited to, single materials or composite materials of metals, alloys, ceramics, micro-electro-mechanical system (MEMS) elements, carbon-based materials, high molecular polymers, and the like. Under heating and/or oscillation, the gel is changed from a gel state to a sol state, atomized liquid fixed in the gel is atomized after being released from a gel network, and generated aerosol is released from micropores of the porous material; when the heating and/or shaking is stopped, the sol gel returns to the gel state, the atomized liquid is re-immobilized in the gel network, and the solidified gel losing fluidity is confined in the porous material. According to the consumption and product requirements, the aerosol generating device can be replaced integrally after the gel stored in the porous material is used up, and the aerosol generating device can also be used after the gel is used up, the sol-state thermal gel is injected into the pores of the porous material, and the aerosol generating device is cooled and solidified.
In this case, the atomized liquid is firstly fixed in the three-dimensional grid of the gel to form atomized liquid gel, then the atomized liquid gel is fixed in the porous material, and double locking is carried out, so that the problem of liquid leakage of the electronic cigarette atomizer is solved.
According to the fifth aspect of the invention, the atomized liquid gel is applied to the inner surface of the cigarette paper of a cigarette which is not burnt under heating through glue application, and the atomized liquid gel is fixed in the fiber porous of the cigarette paper after the solution is cooled and gelatinized.
The atomized liquid gel can be coated on the inner surface of the cigarette paper suitable for heating non-combustion cigarettes by sizing, and can penetrate into fiber pores of the cigarette paper when being heated in a sol state and be fixed in the pores after being cooled into gel due to good creep recovery property and thixotropy of the gel. When the cigarette is baked and heated at low temperature and does not burn, the gel in the cigarette paper is subjected to sol phase change, the fixed atomized liquid is atomized by heating, and the generated aerosol of the atomizing agent, nicotine and aroma components and substances evaporated by heating of cigarette fillers are released together, so that the effects of increasing the smoke quantity, enhancing the strength and increasing the aroma are achieved; due to the thermal and chemical stability of the gel supramolecular structure, the gel immobilized in the cigarette paper remains stable in its properties during cigarette production and storage.
Compared with the prior art, the invention has the following beneficial effects:
1. the atomized liquid gel has reversible phase transition characteristics, the glycosyl gelling agent in the atomized liquid gel is self-assembled to obtain a three-dimensional network through non-covalent action (hydrogen bonds, pi-pi stacking, van der waals force, electrostatic action and the like), atomized liquid substance molecules are captured and fixed in the three-dimensional network through interfacial force to form the atomized liquid gel, and the driving force for forming the three-dimensional network through self-assembly is the reversible non-covalent action, so the atomized liquid gel has reversible phase transition characteristics. Under heating and/or vibration, the atomized liquid gel is changed from gel state to sol state, and the fixed atomizing agent (or the atomizing agent carrying dissolved nicotine, aroma component and other substances) in the gel is released to form inhalable aerosol; when heating and/or shaking is stopped, the sol gel rapidly returns to the gel state and the non-aerosolized nebulant (or nebulant, nicotine and aroma) molecules of the substance in the gel are re-immobilized in the gel network. The atomized liquid gel of the invention can be applied to devices for oscillating and atomizing by electric heating or non-electric heating (such as high-frequency bulk acoustic waves and surface acoustic waves).
2. In the invention, the chemical structural formula of the glycosyl gelling agent is as follows:
wherein: s is monosaccharide group, maltose group, cellobiase group or lactose group; a (R) n is an aryl group having an alkyl group or an alkoxy group, and 1. ltoreq. n.ltoreq.5. The prepared atomized liquid gel has higher gel-sol phase transition temperature (188 ℃ -248 ℃), which is close to the evaporation atomization temperature of the atomized liquid, so that the sol phase transition of the atomized liquid gel and the evaporation atomization of the atomized liquid in the atomized liquid gel tend to be synchronous, and the advantages are that: on one hand, the liquid leakage risk caused by long-time non-atomization due to the release of the atomized liquid from the gel because the gel phase transition temperature of the low-phase-transition temperature (such as 60-80 ℃) gel is lower than the evaporation atomization temperature (200-250 ℃) of the atomized liquid in the heating process in the prior art is greatly reduced, meanwhile, the atomization waiting time is greatly shortened, the utilization efficiency of heat is improved, and the atomized liquid is rapidly atomized; on the other hand, it is more important to ensure the temperature (T) due to the sol-gel phase transition when the heating or cooling is stoppedgel) The temperature of the gel is higher, the molten sol can be rapidly solidified, and the atomized liquid which is not atomized can be rapidly fixed in the gel network to form gel, so that the risk of leakage of the atomized liquid caused by long time for the sol to be solidified into the gel or incapability of being gelled again at all in the cooling process of the gel with low phase-transition temperature is greatly reduced. The glycosyl gelling agent network in the atomized liquid gel has excellent chemical stability, thermal stability and structural rigidity, and is suitable for products needing high-temperature atomization of atomized liquid, such as electronic cigarettes, heated and non-combustible cigarettes and the like.
3. The atomized liquid is different from common organic solvents and mainly characterized by containing a large amount of polar glycerol and propylene glycol, the structure of the atomized liquid contains polyol hydroxyl, and the competition effect of the solvation and the alcohol hydroxyl provides great challenges for the selection of an organic gelling agent for fixing the atomized liquid, the gel stability of the atomized liquid and the realization of high phase transition temperature. The glycosyl gelling agent with different functional groups obtained by modification is adopted, the strength of non-covalent action in a gelling agent network is greatly increased, and the advantages of fixing atomized liquid are as follows: (1) the glycosyl ligand of the gelling agent contains a large amount of hydroxyl, can form strong intramolecular and intermolecular hydrogen bond action, and becomes a main driving force for self-assembly to form a three-dimensional gel network; (2) by introducing aromatic rings and long-chain hydrocarbon groups into the glycosyl ligand, the non-hydrogen bond actions such as pi-pi stacking and van der waals force are added on the basis of the existing intermolecular hydrogen bond action, the adjustment of the non-hydrogen bond action force is realized by adjusting the electron cloud density of the aromatic rings and the length of the alkane chain, the hydrophobic action of the glycosyl ligand is also increased, and the weakening action of the solvation of polar polyol such as glycerol/propylene glycol and the like in atomized liquid on the intermolecular hydrogen bond of the glycosyl gelling agent is compensated; (3) by introducing a hydrogen bond donor and an acceptor (an amide group) into the glycosyl ligand, the hydroxyl hydrogen bond of the glycosyl ligand can be oriented and polarized to form a hydrogen bond cooperative network and a cooperative center, so that the intermolecular hydrogen bond action of the gelling agent is greatly enhanced, the competition of the hydrogen bond action between the glycerol/propylene glycol hydroxyl group and the hydroxyl group of the gelling agent in the atomized liquid on the intermolecular hydrogen bond of the gelling agent is effectively inhibited, the structure of a gel network is stabilized, and the thermal stability and the gel phase transition temperature of the gel are greatly improved.
4. The atomized liquid gel stored in the porous material can effectively reduce the mass loss of the atomized liquid caused by throwing, leakage or volatilization, and the storage capacity of the atomized liquid can be adjusted according to the pore size, the pore volume and the rheological property of the gel of the porous material. The atomized liquid gel is stored in the porous material, so that the probability of contact of the atomized liquid with the external environment or air is greatly reduced, and the risks of pollution, oxidation, volatilization loss and the like of the atomized liquid are reduced. Adopt collection heating and/or vibration atomizing and storage atomizing liquid gel function aerosol generating device as an organic whole, the integrated level is high, avoids using special stock solution storehouse, has reduced the volume of atomizer by a wide margin, has increased the portability of electron cigarette.
5. The atomized liquid gel provided by the invention has a firm supermolecular network structure and relatively harsh phase change conditions (such as the outside temperature needs to exceed the phase change temperature, violent oscillation and the like), and can keep a stable gel state under the same transportation and storage conditions as the liquid atomized liquid, so that the liquid leakage problem of an atomizer caused by air pressure change in the air transportation process and air pressure change in areas with different altitudes is particularly greatly reduced, and the leakage risk caused by external force action such as slight collision oscillation and the like is also greatly reduced.
6. The atomized liquid is fixedly encapsulated in the gelling agent three-dimensional network with stable properties, and the gelling agent three-dimensional network can lock the atomized liquid in the atomized liquid, so that the atomized liquid is equivalent to a protective barrier of the atomized liquid, and the risks of pollution, oxidative deterioration, volatilization loss and the like of the atomized liquid are reduced.
Detailed Description
For the convenience of understanding, the technical scheme of the invention is further illustrated by the specific embodiments. Other persons will appreciate that the illustrated embodiments are only to assist understanding of the invention and therefore should not be seen as a specific limitation of the invention.
Example 1
This embodiment is an atomized liquid gel 1 having a thermally reversible phase transition characteristic, comprising: 0.8 wt% of sugar-based gelling agent; 99.2 wt% of atomized liquid; based on the mass percentage of the atomized liquid, the atomized liquid comprises: an atomizing agent comprising 92.0 wt% of the atomized liquid; nicotine, which constitutes 2.0 wt% of the atomized liquid; a fragrance comprising 6.0 wt% of the atomized liquid; the atomizing agent is a mixture of glycerol and propylene glycol, wherein the volume ratio of the glycerol to the propylene glycol is 5: 5.
The chemical structural formula of the glycosyl gelling agent is as follows:
directly injecting the solution of the atomized liquid gel 1 into a liquid storage bin of an electronic cigarette atomizer, cooling and gelling the solution to obtain an atomized liquid gel cartridge 1 suitable for an electronic cigarette, applying the atomized liquid gel cartridge 1 to the electronic cigarette, wherein the gel-sol phase transition temperature is 225 ℃, the temperature is close to the atomization temperature of the atomized liquid, heating the atomized liquid gel cartridge to 220 ℃, the atomized liquid gel is changed from a gel state to a sol state, the atomized agent fixed in the gel carries dissolved nicotine and aroma component substances to release to form inhalable aerosol, after several mouths of smoking, heating is stopped, when the temperature of the electronic cigarette is reduced to below the gel-sol phase transition temperature, the sol gel is restored to the gel state, and the atomized agent, nicotine and aroma component substance molecules which are not atomized in the gel are re-fixed in a gel network, so that the atomized liquid gel 1 prepared in the embodiment has obvious thermal reversible phase transition characteristics, after repeated smoking, the phase change performance of the atomized liquid gel 1 is still obvious, so that the atomized liquid gel 1 prepared by the embodiment is suitable for products of electronic cigarettes requiring high-temperature atomization of atomized liquid.
In this example, the gel-sol phase transition temperature was measured by the following method: the method is characterized by comprising the following steps: placing the gel in a test tube with the diameter of 10mm, placing a glass bead with the diameter of 5mm and the mass of 0.24g on the top of the gel, placing the test tube in a constant-temperature oil bath, heating at the heating rate of 1.5 ℃/min, wherein the temperature when the glass bead is completely submerged in the solution corresponds to the gel-sol phase transition temperature. The test was repeated twice to take an average.
The gel-sol phase transition critical shear stress is 690Pa, under high shear and violent oscillation (acoustic frequency of 2.4MHz), the gel network structure is destroyed, the gel viscosity is reduced, the collected atomized liquid is released, and the aerosol which can be sucked is generated; after several mouths of suction, stopping vibration, rapidly self-assembling to form gel, and increasing the viscosity of the gel again. The above process may be repeated a number of times. In conclusion, the atomized liquid gel provided by the invention can be applied to a device for high-frequency bulk acoustic wave oscillation atomization.
In this example, the gel-sol phase transition critical Shear stress is measured by the International Standard method of Plastics-Polymers/Resins in the Liquid State or as Emulsions or Dispersions-Determination of Viscosity Using a Rotational Viscometer with Defined Shear Rate.
Claims (10)
1. A reversible phase-change atomized liquid gel comprising a glycosyl-amido-aryl-hydrocarbyl, four-segment glycosyl gelling agent, characterized in that it comprises, on a mass percent basis:
0.1-3.0 wt% of sugar-based gelling agent;
97.0-99.9 wt% of atomized liquid;
the chemical structural formula of the glycosyl gelling agent is as follows:
wherein:
s is glycosyl;
a (R) n is an aryl group having an alkyl group or an alkoxy group, and 1. ltoreq. n.ltoreq.5.
2. The aerosolized liquid gel of claim 1,
s is monosaccharide group, maltose group, cellobiase group or lactose group;
a (R) n is
3. The atomized liquid gel of claim 1, wherein the sugar-based gelling agent has the chemical formula:
4. the aerosolized liquid gel of claim 1, wherein the aerosolized liquid comprises, based on a mass percentage of the aerosolized liquid:
an atomizing agent, which accounts for 90-100 wt% of the atomized liquid;
nicotine in an amount of 0-10 wt% of the atomized liquid;
a fragrance which comprises 0-10 wt% of the atomized liquid;
the atomizing agent is a mixture of glycerol and propylene glycol, wherein the volume ratio of the glycerol to the propylene glycol is 3:7-7: 3.
5. The atomized liquid gel of claim 1, wherein the atomized liquid gel having a reversible phase change characteristic is an atomized liquid gel having a thermally reversible phase change characteristic and/or a shear reversible phase change characteristic; the gel-sol phase transition temperature of the atomized liquid gel is 188-248 ℃; the gel-sol phase transition critical shear stress of the atomized liquid gel is 110-800 Pa.
6. A method of preparing the atomized liquid gel of claim 1, wherein the sugar-based gelling agent is dissolved in the atomized liquid under heating, stirred until completely dissolved, and cooled to form the atomized liquid gel.
7. The use of the atomized hydrogel of claim 1, wherein the atomized hydrogel solution is directly injected into the reservoir of the electronic cigarette atomizer, and the atomized hydrogel cartridge suitable for an electronic cigarette is prepared after the solution is cooled and gelled.
8. Use of an atomized liquid gel according to claim 1 wherein the atomized liquid gel solution is directly injected into an aerosol generating device made of a porous material and the solution is fixed to the porous material after gelation by cooling.
9. Use according to claim 8, wherein the porous material is selected from a single material or a composite of a metal, a ceramic, a carbon-based material, a high molecular polymer.
10. The use of an atomized liquid gel according to claim 1, wherein the molten atomized liquid gel solution is applied by size application to the inner surface of a paper wrapper of a cigarette that is not burning when heated, and is fixed in the porosity of the fibers of the paper wrapper after the solution is gelled by cooling.
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| CN113197327B (en) * | 2021-05-13 | 2022-11-04 | 云南中烟工业有限责任公司 | Gel based on long-chain alkyl dibasic fatty acid nicotine salt gelling agent |
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| CN102391429A (en) * | 2011-09-15 | 2012-03-28 | 西北工业大学 | PH-sensitive xylan hydrogel and preparation method thereof |
| CN103960783A (en) * | 2014-05-15 | 2014-08-06 | 湖北中烟工业有限责任公司 | Gel type solid-liquid electronic cigarette cartridge and manufacturing method thereof |
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