CN103628253B - A kind of preparation method and applications of filter stick functionalization tow - Google Patents
A kind of preparation method and applications of filter stick functionalization tow Download PDFInfo
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- CN103628253B CN103628253B CN201310577049.9A CN201310577049A CN103628253B CN 103628253 B CN103628253 B CN 103628253B CN 201310577049 A CN201310577049 A CN 201310577049A CN 103628253 B CN103628253 B CN 103628253B
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Abstract
The invention discloses the preparation method and applications of a kind of filter stick functionalization tow, the preparation method of functionalization tow is to be dissolved in by polymer raw material after solvent is made into spinning liquid, is placed in device for storing liquid；After regulation electrostatic spinning voltage, the spinning liquid in device for storing liquid is supplied, by micro pump, the spinning head that device for storing liquid is connected continuously；The tow surface that described spinning liquid sprays to continuous moving by spinning head forms nano fibrous membrane, obtains functionalization tow；This preparation method is simple, can with continuous industrial production, prepared functionalization tow be applied to prepare effectively reduce that cigarette mainstream flue gas is coal-tar middle oil, nitrosamine and HCN burst size, and do not affect the cigarette filter rod of smoking property of cigarette quality.
Description
Technical field
The present invention relates to the preparation method and applications of a kind of filter stick functionalization tow, belong to tobacco filtering material application
Field.
Background technology
Filter tip is harmful to into as the bridge between smoker and main flume, the part that can not only filter in flue gas
Point, and tipped with filters on Medicated cigarette, Jiao can be reduced with the TPM in effectively catching cigarette mainstream flue gas
Oil content, reduces flue gas to health and the harm of environment, be in Tar technology the most directly and
Means intuitively.At present, the exploitation of filter stick for cigarettes material and plug configuration is increasingly paid attention to by countries in the world, makes
To be the trend of tobacco business reducing tar and reducing harm from now on functional type filter stick.Domestic each tobacco enterprise typically uses acetic acid
Fiber or the common filter tip of cellulose propionate, and there is the function fiber tow filter rods application that selectivity is high, absorption property is good
Study less.
Along with growing to even greater heights and the consumer's generally enhancing to smoking with health problem concern of world's Anti-smoking activity,
Market is more and more higher to the requirement of Medicated cigarette, and the pressure that tobacco faces is increasing, the most in recent years some states
Family requires to mark or reduce harmful substance listed in Hoffmann list.How to make Medicated cigarette tar and
Harmful components burst size reduces, and keeps the most again cigarette odor-absorbing to make consumer obtain physiology and meets, is Cigarette design
The ultimate challenge faced, the most common filter tip still can not meet the requirement of this respect.
Electrostatic spinning be utilize the stretching of high-pressure electrostatic make polymer solution or burning melt liquid formed injection thread and from
Spinneret orifice sprays and forms polymer nanofiber process.Electrostatic spinning technique principle sees accompanying drawing 1, from shower nozzle
In pore flow out spinning liquid thread, under electrostatic force accelerated motion and division and form thread bunch, warp
Condense after solvent evaporation or melt cooling or be cured as microfilament, being deposited on reception device with the form of non-woven fabrics
On.Spinning liquid is connected with the positive pole of high-voltage D.C. generator, and receiving device is negative pole ground connection.
By changing the composition of Electrospun nano-fibers, the fiber of different physicochemical properties can be obtained.
This can realize by adding various ingredients in spinning liquid, and every kind of component added can make product have
A kind of specific ideal performance；Can also be by from plurality of raw materials liquid spinning, so that containing the fiber of heterogeneity
Depositing simultaneously forming dressing, the dressing of formation the most just contains the fiber of different materials.Electrostatic spinning nano fiber has
There are special structure and performance, such as: the fibre weight of formation is light, good penetrability, specific surface area are big, porosity
Connectedness high, internal voids is good, easily combine with nano level chemical substance or functional materials, makes
Its filter efficiency is greatly improved than conventional filter materials.
Summary of the invention
It is an object of the invention to the preparation method being to provide filter stick functionalization tow, this preparation method is simple,
Cheaper starting materials, can be continuously produced, and the functionalization tow surface prepared has the tar in flue gas, nitrosamine
With HCN, there is special Selective adsorption.
Another object of the present invention is to be to provide the application of described filter stick functionalization tow, by described filter stick
With functionalization tow be applied to preparation can effectively reduce that cigarette mainstream flue gas is coal-tar middle oil, nitrosamine and HCN, and
Do not affect the cigarette filter rod of smoking property of cigarette quality.
The invention provides the preparation method of a kind of filter stick functionalization tow, this preparation method is that polymer is former
After expecting that being dissolved in solvent is made into spinning liquid, it is placed in device for storing liquid；After regulation electrostatic spinning voltage is 15～30KV,
Spinning liquid in device for storing liquid is supplied, by micro pump, the spinning head that device for storing liquid is connected continuously；Described spinning liquid
Distance spinning head 5～25cm, and the tow of continuous moving is sprayed to the speed of 1.0～5.0mL/h by spinning head
Matrix surface forms nano fibrous membrane, obtains functionalization tow；
Described device for storing liquid is connected with 2～4 groups of spinning heads, and often group is 3～5 spinning heads；
Described polymer raw material is 5～15:95～85 with the mass ratio of solvent；
Described polymer raw material be polyvinyl butyral, cellulose acetate, hydroxyethyl cellulose, polyurethane,
Polyureas, polymine, gelatin, poly-hydroxyl succinic acid valerate, polyaniline, poly terephthalic acid phenylenediamine
One or more.
Needed for described solvent correspondingly selects to dissolve polymer raw material according to the dissolubility of polymer raw material
Solvent.
Described solvent includes ethanol, acetone, water, formic acid, trifluoroethanol, dichloromethane, acetic acid, trifluoro
One or more in acetic acid, oxolane, dimethylformamide, triethanolamine；Described solvent is in preparation
Electrospun fibers process is volatilized, and obtains nanofiber.
In described nano fibrous membrane, nanofiber diameter is 500nm～3 μm.
Described tow matrix is 40～180m/min through receiving the speed of device.
Described nano fibrous membrane is the amount of spraying is tow quality 1/500～the 1/100 of tow matrix surface.
Described tow is placed on reception device as receiving matrix by shredding；Described tow includes that acetic acid is fine
Dimension tow or polypropylene fiber.
Present invention also offers the application of the functionalization tow that described method prepares, this application is by described function
Change tow be applied to preparation reduce that cigarette mainstream flue gas is coal-tar middle oil, nitrosamine and the cigarette filter rod of HCN burst size.
Described electric spinning device mainly includes being connected with the device for storing liquid of spinning head, high voltage power supply and reception device.
The spinning process of the present invention: by after abundant for tow base material shredding, continuously enter plasticizer bringing device
The electrostatic spinning chamber arranged between before, electrostatic spinning apparatus principle is as it is shown in figure 1, spinning liquid joins Static Spinning
In the device for storing liquid being connected with many group spinning heads of silk device, spinning liquid is connected with the positive pole of power supply, the negative pole of power supply
It is connected with receiving plate, regulation spinning head and the distance received between plate, open high voltage power supply, regulating power source voltage
And the fltting speed of spinning liquid, carrying out electrostatic spinning, the tow after shredding continuously enters electrostatic spinning chamber and is received
Plate receives electrostatic spinning nano fiber, sprays one layer of nano fibrous membrane at tow matrix surface, obtains functionalization tow.
Beneficial effects of the present invention: prepared nanofiber is uniformly sprayed by first passage electrostatic spinning technique of the present invention
Overlay on tow surface, it is thus achieved that functionalization tow there is nano fibrous membrane ultra-thin and in uniform thickness, and nanometer film
There is special hole series structure, adsorption effect selective to the tar in flue gas, nitrosamine and HCN, will
Spray the functionalization tow of nano fibrous membrane for preparing filter stick, the premise of smoking property of cigarette quality can not have been affected
Under, effectively reduce that cigarette mainstream flue gas is coal-tar middle oil, nitrosamine and the burst size of HCN.The present invention is by selecting
Suitably polymer raw material and properly mixed spinning liquid, in conjunction with the technological parameter system of preparation method of the present invention
Standby nanofiber diameter out is typically equally distributed between 500nm～3 μm, and nanofiber is intricate
Spray and on the tow matrix surface of shredding, be built into thickness uniformly, and there is the pore structure of certain hole, research
Find that these pore structures have good physical absorption ability to tar, nitrosamine and HCN, use simultaneously
, nitrosamine coal-tar middle oil to flue gas and HCN good intermolecular force can be produced after polymer raw material spinning,
Considerably increase the selective adsorption capacity to the tar in flue gas, nitrosamine and HCN, and to smoking property of cigarette
Quality is without impact；The preparation method of the present invention is simple, can carry out serialization commercial production.Test result indicate that:
Compared with general fibre filter stick control sample, the filter tip that the functionalization tow preparing of the present invention is standby can reduce tarry matters in smoke
0.9～1.6mg/ props up, and the most also can reduce harmful ingredients in flue gas nitrosamine 29～36%, reduces harmful ingredients in flue gas
HCN16～23%, Sensory Quality of Cigarette evaluation result shows the most negative at sucking quality in flue gas
Impact.
Accompanying drawing explanation
[Fig. 1] is the electrostatic spinning apparatus figure of the present invention: 1 is electrospinning room；2 is electrospinning spinnerets；3 be continuously before
The tow of row；4 for receiving plate；5 is high voltage power supply.
Detailed description of the invention
Following example are to further illustrate the present invention rather than limit the scope of the invention.
Embodiment 1
Individually polyvinyl butyral (PVB) solution is carried out spinning.Polyvinyl butyral (PVB) is dissolved in
Ethanol is prepared as the solution of 10% (W/W), is placed in storage tank, by micro pump with each pump 5mL/h
Speed carry out feed liquid supply to 12 electrospinning spinnerets respectively, electrospinning voltages is 25KV, shower nozzle and paper substrate it
Spacing is 15cm, and often group electrospinning spinnerets is 4 shower nozzles, with the acetate silk (speed being continuously traveling
For 50m/min) it is that matrix receives polyvinyl butyral nanofiber online, acetate silk sprays one
Layer diameter is about the white nanofiber of 500nm, and the nano fibrous membrane sprayed and tow mass ratio are 1:100.
Spray modified acetate tow entrance plasticizer bringing device online and then carry out filter stick formation.One end, electrospinning room
Being passed through air continuously, the air being mixed with solvent is carried out solvent recovery after electrospinning room is discharged by the other end.Function is filtered
Then rod carries out the cigarette of Medicated cigarette on cigarette assembler, and equipment operation is normal.The medicated cigarette rolled carries out flue gas and divides
Analysis and harmful components analysis, compared with common cellulose acetate filter rod control sample, by online method of electrostatic spinning at silk
Function fiber tow filter rods Medicated cigarette prepared by one layer of nanofiber is sprayed, it is possible to decrease tarry matters in smoke 0.97mg/ props up on bundle,
The most also can reduce harmful ingredients in flue gas nitrosamine 29.69%, reduce harmful ingredients in flue gas HCN16.78%.Volume
Cigarette sensory quality assessment result shows the most significantly to negatively affect the inherent sucking quality of Medicated cigarette.
Embodiment 2
Individually Dichlorodiphenyl Acetate fiber solution carries out spinning.Acetate fiber is dissolved in acetone and is prepared as 6% (V/V's)
Solution, is placed in storage tank, by micro pump with the speed of each pump 3mL/h respectively to 8 electrospinning spinnerets
Carrying out feed liquid supply, electrospinning voltages is 20KV, and shower nozzle is 18cm with the spacing of paper substrate, often the spray of group electrospinning
Head is 4 shower nozzles.It is that matrix receives vinegar online with the polypropylene fiber (speed is as 100m/min) being continuously traveling
Acid fiber nanofiber, sprays the white nanofiber of one layer of a diameter of about 900nm on polypropylene fiber,
The nano fibrous membrane sprayed and tow mass ratio are 1:300.Spray modified polypropylene fiber online and enter plasticising
Then agent bringing device carries out filter stick formation.One end, electrospinning room is passed through air continuously, and the other end will be mixed with solvent
Air carries out solvent recovery after electrospinning room is discharged., then function filter stick carries out Medicated cigarette on cigarette assembler
Cigarette, equipment operation is normal.The medicated cigarette rolled carries out flue gas analysis and harmful components analysis, fine with common acetic acid
Dimension filter stick control sample is compared, and sprays function prepared by one layer of nanofiber by online method of electrostatic spinning on tow
Fiber tow filter rods Medicated cigarette, it is possible to decrease tarry matters in smoke 1.5mg/ props up, the most also can reduce harmful ingredients in flue gas nitrosamine
35.6%, reduce harmful ingredients in flue gas HCN20.58%, and to the most negative at sucking quality in Medicated cigarette
Impact.
Embodiment 3
Polymine and gelatin are carried out blend spinning.Polymine is dissolved in ethanol and is prepared as 7%
(V/V) solution, is dissolved in gelatin trifluoroethanol and is prepared as the solution of 10% (V/V), with 60:40
Mass ratio two kinds of solution of mixing, are placed in storage tank, are distinguished with the speed of each pump 3mL/h by micro pump
Carrying out feed liquid supply to 8 electrospinning spinnerets, electrospinning voltages is 25KV, and shower nozzle is 15cm with the spacing of paper substrate,
Often group electrospinning spinnerets is 4 shower nozzles.It is that matrix exists with the polypropylene fiber (speed is as 80m/min) being continuously traveling
Line receives polymine and the nanofiber of gelatin, sprays about one layer of a diameter of 3 μm on polypropylene fiber
White nanofiber, the nano fibrous membrane sprayed and tow mass ratio are 1:200.Spray modified online
Polypropylene fiber enters plasticizer bringing device and then carries out filter stick formation.One end, electrospinning room is passed through air continuously, separately
The air being mixed with solvent is carried out solvent recovery after electrospinning room is discharged by one end.Function filter stick is then at cigarette tipping
Carrying out the cigarette of Medicated cigarette on machine, equipment operation is normal.The medicated cigarette rolled carries out flue gas analysis and harmful components analysis,
Compared with common cellulose acetate filter rod control sample, on tow, spray one layer of Nanowire by online method of electrostatic spinning
The function fiber tow filter rods Medicated cigarette of dimension preparation, it is possible to decrease tarry matters in smoke 1.4mg/ props up, the most also can reduce flue gas and be harmful to
Composition nitrosamine 35.6%, reduces harmful ingredients in flue gas HCN22.78%, and the brightest to cigarette smoke evaluation and analysis
Aobvious negative effect.
Embodiment 4
Polyurethane is carried out spinning.Oxolane and dimethylformamide are made into mixed solution with mass ratio 1:1,
Polyurethane is dissolved in mixed solution the spinning liquid being prepared as 10% (W/W), is placed in storage tank, passes through
Micro pump carries out feed liquid supply to 4 electrospinning spinnerets respectively with the speed of each pump 2mL/h, and electrospinning voltages is
30KV, shower nozzle is 25cm with the spacing of paper substrate, and often group electrospinning spinnerets is 4 shower nozzles, be continuously traveling
Diacetate fiber (speed is 120m/min) is the nanofiber that matrix receives polyurethane online, at diacetate fiber
On spray one layer of diameter and be about the white nanofiber of 1 μm, the nano fibrous membrane sprayed with tow mass ratio is
1:400. sprays modified diacetate fiber entrance plasticizer bringing device online and then carries out filter stick formation.Electrospinning
One end, room is passed through air continuously, and the air being mixed with solvent is carried out solvent recovery after electrospinning room is discharged by the other end.
Then function filter stick carries out the cigarette of Medicated cigarette on cigarette assembler, and equipment operation is normal.The medicated cigarette rolled is carried out
Flue gas analysis and harmful components analysis, compared with common cellulose acetate filter rod control sample, by online electrostatic spinning
Method sprays function fiber tow filter rods Medicated cigarette prepared by one layer of nanofiber on tow, it is possible to decrease tarry matters in smoke 1.6mg/
, the most also can reduce harmful ingredients in flue gas nitrosamine 31.36%, reduce harmful ingredients in flue gas HCN18.98%,
Sensory Quality of Cigarette evaluation result shows the most significantly to negatively affect at sucking quality in flue gas.
Claims (6)
1. the application of a functionalization tow, it is characterised in that functionalization tow is applied to preparation and reduces Medicated cigarette master
Flue gas is coal-tar middle oil for stream, nitrosamine and the cigarette filter rod of HCN burst size；
Described functionalization tow is prepared by following methods: polymer raw material is dissolved in solvent and is made into spinning liquid
After, it is placed in device for storing liquid；After regulation electrostatic spinning voltage is 15～30KV, by the spinning in device for storing liquid
Liquid supplies, by micro pump, the spinning head that device for storing liquid is connected continuously；Described spinning liquid by spinning head with
The speed of 1.0～5.0mL/h sprays to distance spinning head 5～25cm, and the tow matrix surface of continuous moving is formed
Nano fibrous membrane, obtains functionalization tow；
Described device for storing liquid is connected with 2～4 groups of spinning heads, and often group is 3～5 spinning heads；
Described polymer raw material is 5～15:95～85 with the mass ratio of solvent；
Described polymer raw material be polyvinyl butyral, cellulose acetate, hydroxyethyl cellulose, polyurethane,
Polyureas, polymine, gelatin, poly-hydroxyl succinic acid valerate, polyaniline, poly terephthalic acid phenylenediamine
One or more；
In described nano fibrous membrane, nanofiber diameter is 500nm～3 μm.
2. the application of functionalization tow as claimed in claim 1, it is characterised in that described solvent according to
The dissolubility of polymer raw material correspondingly selects to dissolve the solvent needed for polymer raw material.
3. the application of functionalization tow as claimed in claim 2, it is characterised in that described solvent includes
Ethanol, acetone, water, formic acid, trifluoroethanol, dichloromethane, acetic acid, trifluoroacetic acid, oxolane, two
One or more in methylformamide, triethanolamine.
4. the application of functionalization tow as claimed in claim 1, it is characterised in that described tow matrix
It is 40～180m/min through receiving the speed of device.
5. the application of functionalization tow as claimed in claim 1, it is characterised in that described nano fibrous membrane
The amount of spraying at tow matrix surface is the 1/500～1/100 of described tow substrate quality.
6. the application of functionalization tow as claimed in claim 1, it is characterised in that described tow matrix
It is placed on reception device as receiving matrix by shredding.
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| CN105887331A (en) * | 2015-01-26 | 2016-08-24 | 重庆联佰博超医疗器械有限公司 | Preparation method for hydroxyethyl cellulose hemostatic gauze |
| CN104923183B (en) * | 2015-05-27 | 2017-12-29 | 河南中烟工业有限责任公司 | The adsorbent of HCN burst sizes in a kind of reduction cigarette mainstream flue gas |
| CN105167189B (en) * | 2015-08-04 | 2019-02-12 | 浙江中烟工业有限责任公司 | A kind of compound tow of molecular engram nanofiber and its preparation method and application |
| CN105002587B (en) * | 2015-08-04 | 2017-03-29 | 浙江中烟工业有限责任公司 | A kind of organic-inorganic nano fiber composite tow and its preparation method and application |
| CN105146753B (en) * | 2015-08-04 | 2019-02-15 | 浙江中烟工业有限责任公司 | The compound tow and its preparation method and application of crotonaldehyde in a kind of reduction flue gas |
| CN105088376B (en) * | 2015-08-04 | 2017-11-17 | 浙江中烟工业有限责任公司 | High compound tow of interfacial-adhesion strength nanofiber and its preparation method and application |
| CN111155358B (en) * | 2018-11-08 | 2022-07-12 | 湖南中烟工业有限责任公司 | Superfine fiber functional paper filter stick base material with fragrance and function of selectively reducing phenol content in smoke and preparation and application thereof |
| CN111150094B (en) * | 2018-11-08 | 2022-03-11 | 湖南中烟工业有限责任公司 | Superfine fiber functional filter stick tow with fragrance carrying and smoke phenol content selectively reducing functions and preparation and application thereof |
| CN111155357B (en) * | 2018-11-08 | 2022-07-12 | 湖南中烟工业有限责任公司 | Superfine fiber functionalized cellulose forming paper with fragrance carrying and smoke phenol content selectively reducing functions and preparation and application thereof |
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