CN109674085A - It is a kind of for reducing the heat accumulation capsule of cigarette mainstream flue gas temperature and its preparation and application - Google Patents
It is a kind of for reducing the heat accumulation capsule of cigarette mainstream flue gas temperature and its preparation and application Download PDFInfo
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- CN109674085A CN109674085A CN201710973892.7A CN201710973892A CN109674085A CN 109674085 A CN109674085 A CN 109674085A CN 201710973892 A CN201710973892 A CN 201710973892A CN 109674085 A CN109674085 A CN 109674085A
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- heat accumulation
- capsule
- accumulation capsule
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- gas temperature
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- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
- A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
- A24D3/02—Manufacture of tobacco smoke filters
- A24D3/0204—Preliminary operations before the filter rod forming process, e.g. crimping, blooming
- A24D3/0212—Applying additives to filter materials
- A24D3/0216—Applying additives to filter materials the additive being in the form of capsules, beads or the like
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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
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
- C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
Abstract
The invention discloses a kind of heat accumulation capsules for reducing cigarette mainstream flue gas temperature, including wall material and core material；The core material includes inorganic phase-changing material；The wall material is polylactic acid.The inorganic phase-changing material is disodium hydrogen phosphate dodecahydrate.Invention additionally discloses the preparation methods of the heat accumulation capsule, inner hole of the core material solution through the coaxial syringe needle of electrostatic spinning, wall material solution are added dropwise in solidification liquid together through the inside and outside interporal lacuna of the coaxial syringe needle of same electrostatic spinning, be separated by solid-liquid separation, wash after stirring, cooled and solidified to obtain the final product.Different from it is existing frequently with chemical method, the cladding of inorganic phase-changing material is realized using physical method.Relative to chemical method, reduces and chemically react many and diverse step, do not need using excessive chemical solvent, device is simple, size tunable.
Description
Technical field
The present invention relates to inorganic hydrous salt phase transition Material Fields, and in particular to a kind of encapsulation inorganic hydrated salt heat accumulation capsule
Preparation method.
Background technique
During the smoking process, the heat that cigarette combustion cone generates can be brought by main flume to filter tip, and with volume
Cigarette aspirates process, is gradually risen by the flue-gas temperature of filter tip.The result of study of forefathers shows the preceding 2- in suction close to end
When 3 mouthfuls of suctions, the flue-gas temperature of filter end reaches as high as 70 DEG C~80 DEG C, the flue-gas temperature of filter end under depth suction mode
Maximum temperature has been even up to 100 DEG C or so, and excessively high filter tip temperature not only influences filter tip and filtering to flue gas aerosol particulate matter
Rejection effect in mouth, while also will affect consumer to the degree of recognition of flue gas aesthetic quality.So flue-gas temperature point in filter tip
Cloth regulation retains efficiency and product quality to filter tip and can play a key effect.
Phase-change material can absorb or discharge a large amount of latent heat in phase transition process, can be widely applied to heat storage and temperature
Control field.Inorganic phase-change material, organic phase-change material can be divided by attribute.There are latent heats of phase change for organic phase change material
Low, the disadvantages of thermal coefficient is low, at high cost, so having using the inorganic hydrated salt of low melting point, Gao Qianre as heat accumulating
Wide application prospect.Such as the Chinese patent literature of Publication No. CN105996121A discloses a kind of filter stick additive, it should
Additive includes at least functional auxiliary agent and phase transformation excipient, can also in addition add plasticizer and solvent；When only comprising function
When auxiliary agent and phase transformation excipient, the weight percent of each component are as follows: function additive 0.1~70%, phase transformation excipient 30~
99.9%.For another example the Chinese patent literature of Publication No. CN104449586A discloses a kind of controllable cigarette filter flue-gas temperature
Organic/inorganic composite phase-change material, which is characterized in that expanded graphite and/or porous silicon are supported on by the alkane of C19~C21
Glue particle surface is constituted；Wherein, the mass percentage content of each raw material component are as follows: the alkane 70~96% of C19~C21；Expansion
Graphite and/or Bio-sil 4~30%.
But the existing capsule-type inorganic-phase variable cooling material for filter stick does not have been reported that also.
Summary of the invention
The present invention provides a kind of inorganic hydrated salt heat accumulation capsules for reducing cigarette mainstream flue gas temperature, it is intended to be made
Millimeter rank, the cooling added material suitable for cigarette filter rod.
It is a second object of the invention to provide the preparation method of the inorganic hydrated salt heat accumulation capsule.
It is a third object of the invention to provide inorganic hydrated salt heat accumulation capsule the answering in cigarette filter rod
With.
Existing cladding organic phase change material report is more, such as the cladding of paraffin, and for inorganic hydrous salt phase transition material
Cladding research it is then less.The cladding of traditional inorganic hydrated salt mainly uses chemical method, such as situ aggregation method, interfacial polymerization
Method etc., wall material use high-molecular organic material, residual harmful substance, and prepare heat accumulation capsule material be it is powdered, can not
Directly make an addition in cigarette filter.To solve prior art problem, the present invention provides one kind for reducing cigarette mainstream flue gas
The heat accumulation capsule of temperature, including wall material and core material；The core material includes inorganic phase-changing material；The wall material is polylactic acid.
The higher problem domain of the last three mouthfuls of temperature of cigarette smoking is being solved, the present invention is originally provided with the nothing
Machine phase-change material is core material, with the cigarette added material for the capsule structure that natural polymer (polylactic acid) is wall material.The material energy
The good requirement for solving cigarette field to cooling material, the supercooling of inorganic phase-changing material can be prevented, mutually separate and leak etc.
Problem.
Preferably, the inorganic phase-changing material is phase transition temperature between 30-60 DEG C of inorganic hydrous salt phase transition material.
Further preferably, the inorganic phase-changing material includes but are not limited to Na2HPO4·12H2O, Zn (NO3)2·
6H2O, Ca (NO3)2·4H2O, Na2SO3·5H2O, Ba (OH)2·8H2O, MgSO4·7H2O, Na2SO4·10H2O, Na2CO3·
10H2O, CaCl2·6H2O, Li2NO3·3H2One or more of O.
Most preferably, the inorganic phase-changing material is disodium hydrogen phosphate dodecahydrate.Present invention preferably employs 12 hydrations
Disodium hydrogen phosphate, 35.5 DEG C of transformation temperature, preparation process is not easy mutually to separate, and is more conducive to form heat accumulation capsule.
Preferably, the core material also includes thickener and nucleating agent.In the present invention, using thickener and nucleating agent pair
The inorganic phase-changing material is modified processing, facilitate with disodium hydrogen phosphate dodecahydrate coordinated, maintain it good
Phase transition performance.
The thickener can be used material well-known to those skilled in the art, preferably sodium alginate, polyethylene glycol,
At least one of carboxymethyl cellulose or polyvinyl alcohol；Particularly preferably sodium alginate.
The material that nucleating agent of the present invention can be well known to those skilled in the art.Further study show that described
Nucleating agent be preferably α-Al2O3、Na2SiO3.9H2O、CH3COONa.3H2O or Na2B4O7.10H2At least one of O；Into one
Step is preferably α-Al2O3。α-Al2O3It is best to disodium hydrogen phosphate dodecahydrate nucleating effect.
Preferably, the mass ratio of thickener and nucleating agent is not less than 1: 1.The study found that the ratio is lower than 1: 1, at
Core agent can settle, and be higher than 1: 1 and contribute to form the heat accumulation capsule.Further preferably, the mass ratio of thickener and nucleating agent
It is 1: 1.
Preferably, the thickener and nucleating agent is the 3~5% of inorganic phase-changing material weight alone；It is further excellent
It is selected as 5%.Studies have shown that nucleating effect is best under 5%, it is higher than 5%, is unfavorable for being nucleated.
Preferably, the molecular weight of polylactic acid is 20000-100000.
The mass ratio of wall material and core material does not specially require, and should ensure that wall material coats the core material completely.The matter
Measuring ratio can also be according to the material concentration and flow control of preparation process.
Preferably, the partial size of heat accumulation capsule of the present invention is 0.5~5mm.Heat accumulation capsule of the present invention reaches
To millimeter rank, more conducively applied in cigarette field.
The partial size of heat accumulation capsule of the present invention, can pass through material concentration and flow control.Preferably, the storage
The partial size of hot glue capsule is 0.5~2mm.
The present invention also provides the preparation methods of the heat accumulation capsule described in one kind, and core material solution is through the coaxial syringe needle of electrostatic spinning
The inside and outside interporal lacuna of inner hole, wall material solution through the coaxial syringe needle of electrostatic spinning (present invention is also referred to as coaxial syringe needle) it is (interior
Gap between the outer wall in hole and the inner wall of exit orifice) it (preferably at different flow rates) is added dropwise in solidification liquid together, it is solid after stirring
Liquid separation, washing, cooled and solidified to obtain the final product.
The method of the present invention realizes the cladding of inorganic phase-changing material using physical method.Relative to chemical method, step letter
It is single, it does not need using excessive chemical solvent, device is simple, size tunable.
Preferably, the solidification liquid is polyvinyl alcohol water solution, concentration is 1~8wt%.
Preferably, in the solidification liquid, the concentration of poly-vinyl alcohol solution is that (concentration of polyvinyl alcohol is 2.5~3wt%
2.5~3g/100mL).Polyvinyl alcohol is used as solidification liquid in an experiment, is dispersion liquid and protection liquid.Concentration is too small to be not achieved point
Scattered effect, concentration is excessive, as the drop of instillation is more and more, causes solution in g., jelly-like, protection is not achieved in capsules break
Effect.The study found that under the preferred content, the more conducively formation of the heat accumulation capsule.
Preferably, the core material solution is the molten liquid of inorganic phase-changing material, thickener and nucleating agent.
Heating melting after inorganic phase-changing material, thickener and nucleating agent are mixed obtains the core material solution.
Preferably, thickener is the 4.5~5% of inorganic phase-changing material weight, further excellent in the core material solution
It is selected as 5%；Nucleating agent is the 4.5~5% of inorganic phase-changing material weight；Further preferably 5%.
Preferably, wall material solution is the solution of polylactic acid dissolution in organic solvent.
Preferably, the organic solvent is low boiling point solvent；Preferably methylene chloride.
Preferably, the concentration of the polylactic acid is that (every 1mL organic solvent is molten by 0.03~0.10g/mL in wall material solution
Solution has the polylactic acid of 0.03~0.10g)；Further preferably 0.09~0.1g/mL.
Preferably, the flow proportional of wall material solution, core material solution is 1.8~2.2: 1.In the wall material solution, core
Under the concentration of material solution, the flow proportional of control wall material solution, core material solution helps to be made the heat accumulation capsule.
Preferably, the flow velocity of wall material solution is 8ml/h~80ml/h.The flow velocity of preferred core material solution be 5mL/h~
50mL/h.Further preferably, the flow velocity of wall material solution is 15~50ml/h；The flow velocity of core material solution is 8ml/h~35ml/h.
Preferably, speed of agitator is 200r/min~400r/min.
In the present invention, the washing is carried out using deionized water, crystallisation by cooling again after washing, the method for crystallisation by cooling can
Existing method is used, for example, the crystallisation by cooling at 4 DEG C.
In the present invention, the coaxial syringe needle of the electrostatic spinning can be existing conventional equipment.
The coaxial double needle of the electrostatic spinning includes that inner hole input terminal, exit orifice input terminal and output end, output end include
The inner hole and exit orifice of coaxial arrangement；The wall material solution is inputted by exit orifice input terminal, and the core material solution passes through inner hole
Input terminal input, and be added dropwise in solidification liquid by output end simultaneously.
A kind of most preferred preparation method of the present invention comprising the steps of:
Step (1): pva powder being added in deionized water, is dissolved at 80 DEG C, obtains poly-vinyl alcohol solution (solidification
Liquid；Concentration is 1~8wt%)；
By disodium hydrogen phosphate dodecahydrate, thickener, nucleating agent, the ten of the agitated modification for obtaining stable homogeneous at 60 DEG C
Two hypophosphite monohydrate disodium hydrogen molten liquids (core material solution)；The nucleating agent of inorganic hydrous salt phase transition material is α-Al2O3, thickener is
Sodium alginate is the 5% of disodium hydrogen phosphate dodecahydrate quality；
It will be dissolved in methylene chloride under particles of polylactic acid room temperature, is made PLA solution (wall material solution)；The molecule of polylactic acid
Measuring is 20000-100000, and in wall material solution, the concentration of polylactic acid is 0.03~0.10g/mL；
Step (2): modified disodium hydrogen phosphate dodecahydrate molten liquid and PLA solution are respectively charged into syringe
(syringe equipped with disodium hydrogen phosphate dodecahydrate molten liquid uses glass syringe, pacifies on syringe and connecting pipe
Temperature-controllable heating mantle is filled, to prevent crystallisation by cooling during the preparation process), and syringe pump is configured, it is same to be all connected with electrostatic spinning
(output end of the syringe equipped with core material solution connects axonometer head with the inner hole input terminal of coaxial double needle；Equipped with wall material solution
The output end of syringe connected with the exit orifice input terminal of coaxial double needle), then with instillation poly-vinyl alcohol solution different in flow rate
In, mechanical stirring after a certain period of time, deionized water washing, collect, cooled and solidified by filtering.
The preparation method of inorganic hydrated salt heat accumulation capsule described above, using the coaxial crosspointer of electrostatic spinning (outside outer syringe needle
Diameter is 2.1mm, and interior syringe needle outer diameter is 1.3mm), preparation polylactic acid is shell material, modified disodium hydrogen phosphate dodecahydrate molten liquid
For core material, the controllable polylactic acid heat accumulation capsule of uniform particle diameter, size.
12 hydration phosphorus of the preparation method of inorganic hydrated salt heat accumulation capsule described above, PLA solution and modification
Sour disodium hydrogen molten liquid is flowed out from coaxial needle tubing ectonexine gap and inner needle tube at different flow rates respectively, and it is molten to instill polyvinyl alcohol
In liquid.
Preferably, PLA solution flow rates are the modified disodium hydrogen phosphate dodecahydrate melting of 15mL/h~50mL/h
Flow velocity is 8ml/h~35ml/h.
The preparation method of inorganic hydrated salt heat accumulation capsule described above uses mechanical stirring, stirring speed in solidification process
Degree is 200r/min~400r/min, to keep invariablenes turning speed during the preparation process, the capsule of uniform particle diameter can be made.
The preparation method of inorganic hydrated salt heat accumulation capsule described above, further includes filtering product, washes through deionization,
The step of being solidified at 4 DEG C.
The invention also includes using heat accumulation capsule made from the preparation method.
Use outer syringe needle outer diameter for 2.1mm, interior syringe needle outer diameter is the coaxial crosspointer of electrostatic spinning of 1.3mm, and partial size can be made
Reach the heat accumulation capsule of 2mm.
The invention also discloses the applications of the heat accumulation capsule described in one kind, are reducing last 1~3 as cigarette cooling material
Application in mouth cigarette mainstream flue gas temperature.
Preferably, the heat accumulation capsule is added in cigarette filter rod.
Preferably, the heat accumulation capsule is added to cigarette filter close to pipe tobacco end.
Preferably, the additive amount of the heat accumulation capsule of every cigarette is 20~60mg.
Further preferably, the additive amount of heat accumulation capsule is 35~40mg/ branch；Most preferably 40mg/ branch.Preferably adding
Under amount, last three mouthfuls of cooling effect is more preferable.
The principle of the invention is explained:
The present invention is gathered according to emulsification-solvent volatilization and orifice-coagulating bath method principle using the coaxial syringe needle of electrostatic spinning
Lactic acid solution and the disodium hydrogen phosphate dodecahydrate molten liquid of modification are respectively at different flow rates between coaxial needle tubing ectonexine
Gap and inner needle tube outflow, instill in polyvinyl alcohol solidify liquid, can curing molding after methylene chloride volatilizees completely.
The present invention has the advantages that
The present invention uses the coaxial syringe needle of electrostatic spinning for the first time, using the bioabsorbable polymer material polylactic acid of non-toxic degradable as wall
Material, disodium hydrogen phosphate dodecahydrate molten liquid are core, are prepared for grade capsule.It does not need to add in experimentation of the present invention
Any surfactant reduces experimental procedure, and can prepare the heat accumulation capsule of different-grain diameter, most by both regulations flow velocity
Big partial size is up to 5mm.
Brief Description Of Drawings
Fig. 1 show the differential scanning calorimeter curve graph of inorganic hydrated salt heat accumulation capsule prepared by embodiment 1.
Fig. 2 show the differential scanning calorimeter curve graph of inorganic hydrated salt heat accumulation capsule prepared by embodiment 2.
It is under 40mg to cigarette filter that Fig. 3, which show inorganic hydrated salt heat accumulation capsule material additive amount prepared by embodiment 1,
The influence relation curve of flue-gas temperature.
It is under 20mg to cigarette filter that Fig. 4, which show inorganic hydrated salt heat accumulation capsule material additive amount prepared by embodiment 1,
The influence relation curve of flue-gas temperature.
It is under 30mg to cigarette filter that Fig. 5, which show inorganic hydrated salt heat accumulation capsule material additive amount prepared by embodiment 1,
The influence relation curve of flue-gas temperature.
Fig. 6 is the outer syringe needle schematic diagram for implementing the coaxial crosspointer of electrostatic spinning of preparation method of the present invention；A is wall material solution；b
For core material solution.
Specific embodiment
The outer syringe needle outer diameter of the coaxial crosspointer of the electrostatic spinning that following embodiment and comparative example use is 2.1mm, interior syringe needle
Outer diameter is 1.3mm.Structural schematic diagram is shown in Fig. 6.
Embodiment 1
12g polyvinyl alcohol is weighed, is dissolved at 80 DEG C in 400mL deionized water, obtains poly-vinyl alcohol solution.
Weigh 20g disodium hydrogen phosphate dodecahydrate, 1g α-Al2O3,1g sodium alginate melts at 60 DEG C, obtains modified
Disodium hydrogen phosphate dodecahydrate molten liquid.
3g particles of polylactic acid is weighed, is dissolved in 30mL methylene chloride, the PLA solution that concentration is 10% is obtained.
PLA solution and modified disodium hydrogen phosphate dodecahydrate molten liquid are respectively charged into syringe, Liang Tai is placed in
On syringe pump, coaxial crosspointer (the coaxial crosspointer of electrostatic spinning) reactor is connected, the flow velocity of two syringe pumps is respectively 15mL/h (poly-
Lactic acid solution), 8mL/h (disodium hydrogen phosphate dodecahydrate molten liquid), instill poly-vinyl alcohol solution in, mechanical stirring 4h, stirring
Speed is 300r/min, and product at reduced pressure is filtered, and is washed with deionized water, and is then collected, and cryocoagulation is at 4 DEG C to get newborn to gathering
The disodium hydrogen phosphate dodecahydrate microcapsules of acid cladding.The partial size for measuring microcapsules is 2mm, and the enthalpy of phase change for measuring microcapsules is
116.3J/g。
Application examples:
It is added in common carbon fiber filter stick by phase transformation capsule described in 20mg/ branch, 30mg/ branch or 40mg/ branch the present embodiment,
Composite filter tip is prepared respectively, and the suction of ISO mode is carried out on one channel smoke sucking machine respectively, and (suction time 2s, puff interval are
60s, every mouthful of pumping volume are 35mL), while with cigarette gas phase temperature detector on-line checking filter tip flue-gas temperature.Additive amount is
The main flume figure of the composite filter of 40mg/ branch is shown in Fig. 3, and the main flume figure for adding the composite filter of 20mg is shown in Fig. 4, additive amount
Main flume figure for the composite filter of 30mg/ branch is shown in Fig. 5, compared with control sample, adds the composite filter tip of phase transformation capsule to cigarette
Temperature degree tool is significantly reduced effect, wherein last two mouthfuls of the temperature for adding the composite filter of 20mg reaches 50 DEG C of left sides
It is right；Addition 30mg promotes cooling effect further, and the temperature of last a bite reaches 50 DEG C or so；40mg is added, last
The temperature of mouth is down to 35 DEG C or less from 70 DEG C of control sample；Cooling effect is obvious.
Embodiment 2
12g polyvinyl alcohol is weighed, is dissolved at 80 DEG C in 400mL deionized water, obtains poly-vinyl alcohol solution.
Weigh 20g disodium hydrogen phosphate dodecahydrate, 1g α-Al2O3,1g sodium alginate melts at 60 DEG C, obtains modified
Disodium hydrogen phosphate dodecahydrate molten liquid.
3g particles of polylactic acid is weighed, is dissolved in 30mL methylene chloride, the PLA solution that concentration is 10% is obtained.
PLA solution and modified disodium hydrogen phosphate dodecahydrate molten liquid are respectively charged into syringe, Liang Tai is placed in
On syringe pump, coaxial crosspointer is connected, the flow velocity of two syringe pumps is respectively 30mL/h (PLA solution), 16mL/h, is instilled poly-
In glycohol solution, product at reduced pressure is filtered, is washed with deionized water, then received by mechanical stirring 4h, mixing speed 300r/min
Collect, cryocoagulation is at 4 DEG C to get the disodium hydrogen phosphate dodecahydrate microcapsules coated to polylactic acid.Measure the partial size of microcapsules
For 0.5mm, the enthalpy of phase change of microcapsules is 96.5J/g.
Comparative example 1
12g polyvinyl alcohol is weighed, is dissolved at 80 DEG C in 400mL deionized water, obtains poly-vinyl alcohol solution.
Weigh 20g disodium hydrogen phosphate dodecahydrate, 1g α-Al2O3, 1g sodium alginate melts at 60 DEG C, obtains modified ten
Two hypophosphite monohydrate disodium hydrogen molten liquids.
0.3g particles of polylactic acid is weighed, is dissolved in 30mL methylene chloride, the PLA solution that concentration is 1% is obtained.
PLA solution and modified disodium hydrogen phosphate dodecahydrate molten liquid are respectively charged into syringe, Liang Tai is placed in
On syringe pump, coaxial crosspointer is connected, the flow velocity of two syringe pumps instills in poly-vinyl alcohol solution, mechanical stirring 4h with example 1,
Mixing speed is 300r/min, and the too low microcapsules molding for causing preparation of the concentration of polylactic acid is few compared with embodiment 1.
Comparative example 2
12g polyvinyl alcohol is weighed, is dissolved at 80 DEG C in 400mL deionized water, obtains poly-vinyl alcohol solution.
Weigh 20g disodium hydrogen phosphate dodecahydrate, 1g α-Al2O3,1g sodium alginate melts at 60 DEG C, obtains modified
Disodium hydrogen phosphate dodecahydrate molten liquid.
4.5g particles of polylactic acid is weighed, is dissolved in 30mL methylene chloride, the PLA solution that concentration is 15% is obtained.
PLA solution and modified disodium hydrogen phosphate dodecahydrate molten liquid are respectively charged into syringe, Liang Tai is placed in
On syringe pump, coaxial crosspointer is connected, the flow velocity of two syringe pumps instills in poly-vinyl alcohol solution, mechanical stirring 4h with example 1,
Mixing speed is 300r/min, and product at reduced pressure is filtered, and is washed with deionized water, and is then collected, and cryocoagulation is at 4 DEG C to get arriving
The disodium hydrogen phosphate dodecahydrate microcapsules of polylactic acid cladding.The excessive concentration of polylactic acid causes to be easy to block up during the preparation process
Syringe needle is filled in, large scale syringe needle is replaced, can avoid syringe needle blocking.
Comparative example 3
2g polyvinyl alcohol is weighed, is dissolved at 80 DEG C in 400mL deionized water, obtains poly-vinyl alcohol solution.
Weigh 20g disodium hydrogen phosphate dodecahydrate, 1g α-Al2O3, 1g sodium alginate melts at 60 DEG C, obtains modified ten
Two hypophosphite monohydrate disodium hydrogen molten liquids.
3g particles of polylactic acid is weighed, is dissolved in 30mL methylene chloride, the PLA solution that concentration is 10% is obtained.
PLA solution and modified disodium hydrogen phosphate dodecahydrate molten liquid are respectively charged into syringe, Liang Tai is placed in
On syringe pump, coaxial crosspointer is connected, the flow velocity of two syringe pumps instills in poly-vinyl alcohol solution, mechanical stirring 4h with example 1,
Mixing speed is 300r/min, and polyvinyl alcohol solidification liquid concentration is too low, and ratio of briquetting is low (being lower than Examples 1 and 2).
Comparative example 4
12g polyvinyl alcohol is weighed, is dissolved at 80 DEG C in 400mL deionized water, obtains poly-vinyl alcohol solution.
Weigh 20g disodium hydrogen phosphate dodecahydrate, 1g α-Al2O3, 1g sodium alginate melts at 60 DEG C, obtains modified ten
Two hypophosphite monohydrate disodium hydrogen molten liquids.
3g particles of polylactic acid is weighed, is dissolved in 30mL methylene chloride, the PLA solution that concentration is 10% is obtained.
PLA solution and modified disodium hydrogen phosphate dodecahydrate molten liquid are respectively charged into syringe, Liang Tai is placed in
On syringe pump, coaxial crosspointer is connected, the flow velocity of two syringe pumps is respectively 25mL/h (PLA solution), 20mL/h, is instilled poly-
In glycohol solution, mechanical stirring 4h, mixing speed 300r/min, the two flow rate is improper, and core material packet is caused not live.
Comparative example 5
12g polyvinyl alcohol is weighed, is dissolved at 80 DEG C in 400mL deionized water, obtains poly-vinyl alcohol solution.
Weigh 20g disodium hydrogen phosphate dodecahydrate, 1g α-Al2O3, 0.5g sodium alginate melts at 60 DEG C, obtains modified
Disodium hydrogen phosphate dodecahydrate molten liquid.
3g particles of polylactic acid is weighed, is dissolved in 30mL methylene chloride, the PLA solution that concentration is 10% is obtained.
PLA solution and modified disodium hydrogen phosphate dodecahydrate molten liquid are respectively charged into syringe, Liang Tai is placed in
On syringe pump, coaxial crosspointer is connected, the flow velocity of two syringe pumps instills in poly-vinyl alcohol solution, mechanical stirring 4h with example 1,
Mixing speed is 300r/min, and the amount of sodium alginate thickener is on the low side, during stirring coagulation forming, α-Al2O3In capsule
Sedimentation.
Claims (26)
1. a kind of heat accumulation capsule for reducing cigarette mainstream flue gas temperature, which is characterized in that including wall material and core material；Described
Core material includes inorganic phase-changing material；The wall material is polylactic acid.
2. as described in claim 1 for reducing the heat accumulation capsule of cigarette mainstream flue gas temperature, which is characterized in that the nothing
Machine phase-change material is phase transition temperature between 30-60 DEG C of inorganic hydrous salt phase transition material, includes but are not limited to Na2HPO4·
12H2O, Zn (NO3)2·6H2O, Ca (NO3)2·4H2O, Na2SO3·5H2O, Ba (OH)2·8H2O, MgSO4·7H2O,
Na2SO4·10H2O, Na2CO3·10H2O, CaCl2·6H2O, Li2NO3·3H2One or more of O.
3. as claimed in claim 1 or 2 for reducing the heat accumulation capsule of cigarette mainstream flue gas temperature, which is characterized in that described
Core material also include thickener and nucleating agent.
4. as claimed in claim 3 for reducing the heat accumulation capsule of cigarette mainstream flue gas temperature, which is characterized in that the increasing
Thick dose is at least one of sodium alginate, polyethylene glycol, carboxymethyl cellulose or polyvinyl alcohol.
5. as claimed in claim 3 for reducing the heat accumulation capsule of cigarette mainstream flue gas temperature, which is characterized in that it is described at
Core agent is α-Al2O3、Na2SiO3.9H2O、CH3COONa.3H2O or Na2B4O7.10H2At least one of O.
6. as claimed in claim 3 for reducing the heat accumulation capsule of cigarette mainstream flue gas temperature, which is characterized in that thickener and
The mass ratio of nucleating agent is not less than 1: 1.
7. as claimed in claim 3 for reducing the heat accumulation capsule of cigarette mainstream flue gas temperature, which is characterized in that the increasing
Thick dose and nucleating agent are the 3~5% of inorganic phase-changing material weight alone.
8. as described in claim 1 for reducing the heat accumulation capsule of cigarette mainstream flue gas temperature, which is characterized in that polylactic acid
Molecular weight is 20000-100000.
9. the heat accumulation capsule as described in any one of claims 1 to 8 for reducing cigarette mainstream flue gas temperature, feature exist
In the partial size of heat accumulation capsule is 0.5~5mm.
10. a kind of preparation method of heat accumulation capsule as described in any one of claims 1 to 9, which is characterized in that core material solution warp
The inner hole of the coaxial syringe needle of electrostatic spinning, wall material solution are added dropwise together through the inside and outside interporal lacuna of the coaxial syringe needle of same electrostatic spinning
Into solidification liquid, after stirring be separated by solid-liquid separation, wash, cooled and solidified to obtain the final product.
11. the preparation method of heat accumulation capsule as claimed in claim 10, which is characterized in that the solidification liquid is polyvinyl alcohol water
Solution, concentration are 1~8wt%.
12. the preparation method of heat accumulation capsule as claimed in claim 11, which is characterized in that in the solidification liquid, polyvinyl alcohol
Concentration be 2.5~3wt%.
13. the preparation method of heat accumulation capsule as claimed in claim 10, which is characterized in that the core material solution is inorganic phase
Become the molten liquid of material, thickener and nucleating agent.
14. the preparation method of heat accumulation capsule as claimed in claim 13, which is characterized in that in the core material solution, thickening
Agent is the 4.5~5% of inorganic phase-changing material weight；Nucleating agent is the 4.5~5% of inorganic phase-changing material weight.
15. the preparation method of heat accumulation capsule as claimed in claim 10, which is characterized in that wall material solution is dissolved in for polylactic acid
Solution in organic solvent.
16. the preparation method of heat accumulation capsule as claimed in claim 15, which is characterized in that the organic solvent is low boiling point
Solvent is methylene chloride.
17. the preparation method of heat accumulation capsule as claimed in claim 15, which is characterized in that in wall material solution, the polylactic acid
Concentration be 0.03~0.10g/mL.
18. such as the preparation method of the described in any item heat accumulation capsules of claim 12~17, which is characterized in that wall material solution, core
The flow proportional of material solution is 1.8~2.2: 1.
19. the preparation method of heat accumulation capsule as claimed in claim 18, which is characterized in that the flow velocity of wall material solution is 8ml/h
~80ml/h.
20. the preparation method of heat accumulation capsule as claimed in claim 18, which is characterized in that speed of agitator be 200r/min~
400r/min。
21. the preparation method of heat accumulation capsule as claimed in claim 12, which is characterized in that described using deionized water progress
Washing, after washing at 4 DEG C cooled and solidified.
22. a kind of application of heat accumulation capsule according to any one of claims 1 to 9, which is characterized in that as cigarette cooling material
Reducing the application in last 1~3 mouthful of cigarette mainstream flue gas temperature.
23. the application of heat accumulation capsule as claimed in claim 22, which is characterized in that the heat accumulation capsule is added to cigarette
In filter stick.
24. the application of heat accumulation capsule as claimed in claim 23, which is characterized in that the heat accumulation capsule is added to cigarette
Filter tip is close to pipe tobacco end.
25. such as the application of the described in any item heat accumulation capsules of claim 22~24, which is characterized in that the heat accumulation glue of every cigarette
The additive amount of capsule is 20~60mg.
26. the application of heat accumulation capsule as claimed in claim 25, which is characterized in that the additive amount of heat accumulation capsule be 35~
40mg/ branch.
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