CN102080278B - Biodegradable cigarette fiber material and cigarette filter - Google Patents
Biodegradable cigarette fiber material and cigarette filter Download PDFInfo
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- CN102080278B CN102080278B CN200910241645.3A CN200910241645A CN102080278B CN 102080278 B CN102080278 B CN 102080278B CN 200910241645 A CN200910241645 A CN 200910241645A CN 102080278 B CN102080278 B CN 102080278B
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- acid
- cigarette
- biodegradable
- polymer
- tow
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- 239000000853 adhesive Substances 0.000 description 1
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- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229920001585 atactic polymer Polymers 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
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- 230000005494 condensation Effects 0.000 description 1
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- 235000009508 confectionery Nutrition 0.000 description 1
- 229920006238 degradable plastic Polymers 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002327 glycerophospholipids Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
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- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- GLDOVTGHNKAZLK-UHFFFAOYSA-N n-octadecyl alcohol Natural products CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 229940093430 polyethylene glycol 1500 Drugs 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 230000000391 smoking effect Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 235000019505 tobacco product Nutrition 0.000 description 1
- RJIFVNWOLLIBJV-UHFFFAOYSA-N tributyl benzene-1,2,4-tricarboxylate Chemical compound CCCCOC(=O)C1=CC=C(C(=O)OCCCC)C(C(=O)OCCCC)=C1 RJIFVNWOLLIBJV-UHFFFAOYSA-N 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
-
- 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
- A24D3/06—Use of materials for tobacco smoke filters
- A24D3/067—Use of materials for tobacco smoke filters characterised by functional properties
- A24D3/068—Biodegradable or disintegrable
-
- 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
- A24D3/06—Use of materials for tobacco smoke filters
- A24D3/08—Use of materials for tobacco smoke filters of organic materials as carrier or major constituent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/12—Applications used for fibers
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Textile Engineering (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Biodiversity & Conservation Biology (AREA)
- Medicinal Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Biological Depolymerization Polymers (AREA)
- Polyesters Or Polycarbonates (AREA)
- Artificial Filaments (AREA)
- Cigarettes, Filters, And Manufacturing Of Filters (AREA)
Abstract
The invention provides a biodegradable cigarette fiber material and a cigarette filter. The biodegradable cigarette fiber material comprises the following raw materials of 1-99wt percent of poly(butylene succinate) polymer, 1-99wt percent of polylactic acid polymer and 0-3wt percent of stabilizing agent, and the cigarette fiber material is prepared by processing the raw materials with a melting spinning process. The poly(butylene succinate) polymer and the polylactic acid polymer can be respective homopolymers of the two polymers per se and can also be copolymers containing other monomer materials, which do not exceed 30 percent of the total quantity of respective molecular chain segments of the two polymers. The invention also provides a biodegradable cigarette filter rod prepared from the cigarette fibre material through sizing processing, and a cigarette product. The provided cigarette filter has a property equivalent to the property of the traditional general cigarette filter, a cigarette end discarded by a smoker can be decomposed within shorter time in the natural environment, and the pollution of the cigarette waste to the environment is avoided at present while the requirement of cigarette production is met.
Description
Technical field
The present invention relates to a kind of cigarette fibrous material and utilize the made cigarette filter of this fibrous material, described cigarette adopts the alloy material forming taking poly butylene succinate (PBS) polymer and polylactic acid polymer as substrate resin with fibrous material and cigarette filter, has good biological degradability.
Background technology
Cigarette filter has filtration, stops and adsorbs the effect of the harmful components such as nicotine, tar in flue gas, and good filter-tip material, except having above-mentioned effect, also should be able to improve the mouthfeel of flue gas, reduces the stimulation of flue gas to oral cavity and the injury to health.As the technology of a comparative maturity, at present generally taking cellulose acetate fibre and polypropylene fibre as raw material for the manufacture of the material of cigarette filter, consider from processing characteristics and the filter-tip Integrated using performance of final production, taking cellulose acetate fibre as first-selected, the cellulose acetate fibre filter tips that use in medium-to-high grade cigarette more.
Filter tip part remaining after cigarette sucks will abandon, and cellulose acetate fibre and polypropylene fibre are difficult to be biodegradable in natural environment, and cigarette, on the basis of charge of bearing harmful health, has also been caused the pollution to environment simultaneously.The mankind can not leave cigarette completely, and except reducing cigarette itself to the harm of human body, solution filter tip abandons the problem of environmental pollution bringing just becomes the problem that cigarette industry must be faced.
On the other hand, cellulose acetate fibre is the chemical products that obtain taking high-quality timber as raw material, and from timber to cellulose, the cellulose acetate to esterification need to consume a large amount of wood raw materials again, and in production link, is also accompanied by a lot of pollution problems.
So; no matter be from timber resources scarcity; or from improving environmental pollution angle; find the Biodegradable material that substitutes existing cellulose acetate and polypropylene fibre raw material; produce degradable cigarette filter; at least aspect environmental protection, reducing cigarette and produce the harm bringing, is cigarette production industry urgent problem.
The production technology of cigarette filter mainly comprises that raw material is implemented to melt spinning makes pipe tobacco, and plasticising sizing system rod is finally processed into the technical process of filter stick, the spinning property of raw material,, whether be easily spun into fine count fiber, and drawing-off performance and the bonding effect of fibre bundle, finally all will affect the combination property of filter stick and filter tip, comprise filterability, and the mechanical performance such as outward appearance, hardness and empty resistance.Cellulose acetate fibre is exactly the excellence due to these character, is just selected to mainly processing raw material of cigarette filter.In the time finding its alternative materials, both there is biological degradability, also must meet filter stick processing request, be two indispensable conditions.
Lactide acid polymer, for example PLA (PLA) or related copolymers fully biodegradable under field conditions (factors) or under people's concrete conditions in the establishment of a specific crime, is known degradation material already.A kind of technology of utilizing lactide acid polymer resin manufacture cigarette filter filament fiber and filter stick for cigarettes is disclosed in Chinese patent application 200610131699.0 and 200710055310.3.Although this formerly disclosed patent application has instructed the lactide acid polymer can be for the processing of cigarette filter, and compare with polypropylene filter with business-like cellulose acetate filter stick, described PLA cigarette filter stick not only has the advantage of fully biodegradable and low production cost, and the filter stick of making is all showing good result aspect filterability and physical and mechanical properties, but recording content from its description can see, the matrix resin adopting in this technical scheme is a specification of PLA or the mixture of multiple specifications, or lactide and caprolactone, lactide, or the copolymer of lactide and caprolactone and glycolide, these resins are to be all polymerized by lactone, the polymer of preparation is atactic polymer, this material fragility is large, facile hydrolysis, add and require man-hour the moisture of material lower than 5/10000ths, and this material thermal resistance can be poor, thermal change type temperature very low (only having 58 DEG C).Because pipe tobacco needs certain flexibility and deformation preferably, and require to have higher heat resistance, produce above-mentioned formerly disclosed lactide acid polymer Mouthpiece for cigarette raw material for cigarette business enterprise expand and still have a lot of unsatisfactory places with having much room for improvement.
Poly butylene succinate (PBS) is a kind of polymer of fully biodegradable, it can finally be degraded to the material such as carbon dioxide and water under the effect of bacterium or enzyme, so start at present to use in plastics field, to alleviate conventional plastic pollution on the environment.According to current research and report, PBS plastics can be prepared film based packaging material, the such as sheet stock of degradable plastic pocket, disposable tableware etc.; PBS plastics can also be aspect agricultural mulching and some daily use Sundry goods aspects application.
The purposes of a kind of biodegradable compound and modified resin and preparation method thereof and this composite modified resin is disclosed in Chinese patent CN 200610026044.7.The biodegradable compound and modified resin that this patent provides adds auxiliary agent by 10-73.5% poly butylene succinate (PBS), 5-60% PLA (PLA), 5-35% converted starch, 9-29.85% activated inorganic filler and 0.15-1.5% and forms, Screw Extrusion granulation through imposing a condition, can be prepared into blowing resin dedicated.The scheme providing according to this patent, by compound according to specific ratio to PBS and PLA, and under definite processing aid effect, there is good heat resistance and rigidity, be suitable as blowing resin dedicated, and due to its biodegradability, can replace existing plastic product.
Due to the particular/special requirement of cigarette filter, before the present patent application day, about PBS or PBS and the application of PLA composite in cigarette filter processing are not also recorded.
Summary of the invention
The technical problem that the present invention mainly solves is to provide a kind of biodegradable cigarette fibrous material; and the cigarette filter that utilizes this fibre bundle to process; raw materials used is poly butylene succinate and the compound high molecular polymer of PLA; it is suitable with at present general cigarette filter performance that the cigarette filter providing has; and the stub abandoning can be decomposed by microorganism in environment, be beneficial to the protection to environment.
The present invention also provides the method for manufacturing above-mentioned biodegradable cigarette fibrous material and cigarette filter, for the character of poly butylene succinate and PLA joint product, grope and proposed determining of condition to manufacturing technique and parameter, the cigarette filter product of guaranteeing manufacturing can reach the performance standard of at present general cigarette filter.
The invention provides a kind of biodegradable cigarette fibrous material, its raw material composition comprises poly butylene succinate polymer, the polylactic acid polymer of 1-99wt% and the stabilizing agent of 0-3wt% of 1-99wt%, and this cigarette fibrous material is that described raw material processes through melt-spinning technology.
According to the solution of the present invention, this case applicant is using organically compound rear as base stock two kinds of polymeric materials all with biological degradability, processing technology is suitably adjusted and changed, a kind of fibrous material (tow) and fragrant filter stick for cigarettes for cigarette are provided, can produce cigarette filter stick and filter tip, and then replace existing cellulose acetate or acrylic fiber for cigarette filter, this filter-tip cigarette is set and reaches the filter-tip level of cellulose acetate simultaneously in combination property, this filter tip can be degraded as early as possible after abandoning, be applied in cigarette industry, to produce more significant social benefit for protection of the environment.Applicant's result of study shows, adds appropriate poly butylene succinate (PBS) in poly-lactic acid material, can effectively improve toughness and the resistance to water of PLA.According to preferred version of the present invention, described raw material composition comprises the poly butylene succinate polymer of 5-95wt% and the polylactic acid polymer of 5-95wt%.
In conjunction with fibre bundle and filter-tip particular technology requirement for cigarette, inventor's result of study shows, cigarette of the present invention can adopt poly butylene succinate and the PLA of complete homopolymerization with fiber and filter material rod, also can use in polymer molecular chain and have the suitably polymerization chain link of other monomer, be beneficial to improve the processing characteristics of raw material and the index of correlation of final filter stick and product filters.Particularly, the present invention one of can meet to give a definition for the manufacture of the composite of pipe tobacco or all:
The amount that described PBGS polymer is succinic acid-butanediol ester chain link in strand is no less than 70% high molecular polymer of total chain number, and its weight average molecular weight is 5-35 ten thousand, dispersion index 1.2-3.0;
Described polylactic acid polymer is 70% the high molecular polymer that is no less than total chain number of lactic acid chain link in strand, and its weight average molecular weight is 5-30 ten thousand, dispersion index 1.2-3.0.
According to the solution of the present invention, in the strand of described PBGS polymer, the amount of succinic acid-butanediol ester chain link is no less than 70% of total chain number, and all the other are the copolymerization chain link that binary acid, dihydroxylic alcohols or its polymerization of mixtures form.
According to preferred version of the present invention, in the time that described poly butylene succinate polymer molecular chain contains the copolymerization chain link except succinic acid-butanediol ester, form in the monomer of described copolymerization chain link, form in the monomer of described copolymerization chain link, binary acid is selected from aliphatic dibasic acid, aromatic acid or their mixture of C2-C12; Dihydroxylic alcohols is selected from the aliphatic dihydroxy alcohol of C2-C12 or their mixture.
As non-limiting example, described binary acid comprises ethanedioic acid, 1,2-malonic acid, 1,3-malonic acid, glutaric acid, adipic acid, azelaic acid, decanedioic acid, DC11, SL-AH, fumaric acid, maleic acid, phthalic acid, naphthalenedicarboxylic acid etc. or its mixture; Described dihydroxylic alcohols comprises ethylene glycol, propylene glycol, pentanediol, hexylene glycol, decanediol etc. or its mixture.
More preferably, the monomer of described formation copolymerization chain link is selected from ethanedioic acid, malonic acid, adipic acid, fumaric acid, phthalic acid, ethylene glycol, propylene glycol or hexylene glycol etc., or their multiple mixture.
According to the solution of the present invention, in the strand of described polylactic acid polymer, the amount of lactic acid chain link is no less than 70% of total chain number, and all the other are for carrying out the copolymerization chain link that the monomeric substance of copolymerization is polymerized with lactic acid.
According to preferred version of the present invention, when on the strand of described polylactic acid polymer, contain except lactic acid chain link copolymerization chain link time, described formation copolymerization chain link monomeric substance can comprise glycolide, 6-caprolactone, ethylene glycol, propylene glycol, glycollic acid, glycol monoethyl ether etc. or its mixture.
Above-mentioned two kinds of high molecular polymerization raw materials for the manufacture of fibrous material for cigarette (tow) all can or be commercially available according to known method preparation.
For example, in Chinese invention patent 01144133.X, disclosing one, to utilize succinic acid and butanediol be raw material monomer, prepare the method for poly butylene succinate (PBS) through normal pressure esterification (condensation) polymerization of reducing pressure again, a kind of method of preparing high molecular weight PBS is also disclosed in Chinese patent application 200710049370.4, the poly butylene succinate polymer preparing according to the method for these prior aries all can meet ingredient requirement of the present invention, at this, above-mentioned disclosure is incorporated to the present invention.For the PBS polymer that contains described binary acid and/or dihydroxylic alcohols copolymerization chain link, also can realize and preparing easily by the chemical process such as polymerisation, chain extending reaction, and between different chain link, have at least a chemical bond to connect.The method of for example recording according to above document adds binary acid and/or the dihydroxylic alcohols of determining ratio in the condensation reaction system of succinic acid and butanediol, and further polymerization can make in polymerizate containing the polymer chain link that requires to some extent ratio.
Another kind of polymeric material, PLA or also can be according to known method preparation or from being purchased containing the polylactic acid polymer of copolymerization chain link, the former has been common general knowledge and has used polymeric material for many years, a kind of can conveniently be purchased or according to the synthetic polymeric articles obtaining of maturation method, polylactic acid polymer containing copolymerization chain link can obtain the raw material monomer polymerization mixing by a certain percentage according to a lot of disclosed methods, thereby preparation has the copolymerization product of desired chain link ratio easily, also can under the basic theory instruction of open source literature and relevant polymerisation, pass through polymerisation, the chemical processes such as chain extending reaction realize and preparing easily, and between different chain links, have at least a chemical bond to connect.For example, according to disclosed polymerisation process in application for a patent for invention CN 200610016643.0, lactic acid and selected definite polymerization single polymerization monomer ratio are as requested realized to copolymerization.
In the raw material that for cigarette, fibrous material (tow) utilizes provided by the invention, except above-mentioned pure homopolymerization or the PBS polymer that contains copolyesters chain link and polylactic acid polymer material, can also add suitable stabilizing agent, described stabilizing agent refers to improve mouth bar material and comprises that PBS and PLA and copolymer thing are in processing, in storage and use procedure, the material of stability, includes but not limited to heat stabilizer, light stabilizer and acid inhibitor, for example, can comprise phosphoric acid, phosphorous acid, ortho phosphorous acid, pyrophosphoric acid, ammonium phosphate, trimethyl phosphate, dimethyl phosphate, triphenyl phosphate, diphenyl phosphate, triphenyl phosphite, diphenyl phosphite, ammonium phosphite, ammonium dihydrogen phosphate (ADP), antioxidant 1010 (four [methylene 3-(3 ', 5 '-di-t-butyl-4-hydroxyphenyl) propionic ester] methane), antioxidant 1222 (3,5-di-t-butyl-4-hydroxyphenyl diethyl phosphate), antioxidant 1076 (the positive octadecanol ester of β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid), antioxidant 1425 (two (3,5-di-tert-butyl-4-hydroxyl benzyl monoethyl phosphate) calcium), the phosphorous sulphur compound H-MOD of long-chain, epoxidized polybutadiene, epoxy Linseed oil, epoxidized soybean oil, 1,2-epoxy radicals-3-phenoxypropane, magnesium hydroxide, aluminium hydroxide, calcium oxide, amino resins etc. or their any mixture.Preferably, described stabilizing agent comprises trimethyl phosphate, triphenyl phosphate, triphenyl phosphite, antioxidant 1010, antioxidant 1076, H-MOD, epoxy Linseed oil, epoxidized soybean oil, 1,2-epoxy radicals-3-phenoxypropane, magnesium hydroxide, amino resins etc. or their any mixture.
Inventor's result of study shows, the composite that meets poly butylene succinate polymer defined above and polylactic acid polymer has good moulding processability, thereby according to manufacturing to the similar spinning technique of polypropylene fibre the cigarette fibrous material tow that meets cigarette filter standard at present.On this basis, having the present invention further provides one, to utilize this cigarette fibre bundle be raw material, the biodegradable cigarette filter rod of being processed into through sizing.
The present invention also provides simultaneously and has been provided with the above-mentioned biodegradable filter-tip tobacco product taking homopolymerization PBS or the PBS polymer that contains copolymerization chain link and homopolymerization PLA or the polylactic acid polymer that contains copolymerization chain link as raw material, the filter tip that smoker abandons can be decomposed in the short time in natural environment, in meeting cigarette production, has also solved the pollution effect of current cigarette abandon to environment.
Manufacturing the biodegradable cigarette of the present invention comprises the steps: by the method for fibre bundle
Dry raw material is mixed, use screw extruder extrusion granulator, when granulation, extruding machine barrel temperature, at 140-230 DEG C, is extruded rear pelletizing, dry, the cigarette holder stick PP Pipe Compound obtaining.
The PP Pipe Compound that above-mentioned granulation is obtained is carried out melt spinning, 170 DEG C-250 DEG C of the extruder temperatures of setting spinning machine, extruded material is flowed through after filter, casing, measuring pump and straight tube, spray silk by spinnerets, 170 DEG C-250 DEG C of controlled filter actuator temperatures, 170 DEG C-250 DEG C of spin manifold temperatures, 170 DEG C-250 DEG C of straight tube temperature, silk to ejection is cooling with dry air, and chilling temperature is 0 DEG C-50 DEG C;
Cooled tow is through applying the coiling traction around volume and belt conveyor around volume, steam chest traction, fast hauling machine of finish, slow hauling machine, finish is the aqueous solution of the fiber surface finishing agent (for example: polyethylene glycol, monoethanolamine methyl esters, nonylphenol class surfactant etc.) of concentration 0.8%-1%, the roller winding speed 200-1500m/min of slow hauling machine, the roller rotating speed 400-2500r/min of fast hauling machine, frequency 25-50HZ, belt conveyor feeding-wheel speed 200-1500r/min, frequency is 30-60HZ;
Be water-bath drawing-off the tank of 40 DEG C-85 DEG C by the tow pulling out from belt conveyor in water temperature, then through curling and dryness finalization, the tow obtaining is described biodegradable cigarette fibrous material.
According to manufacturing technique of the present invention, raw material should first be dried, and preferably raw material is dried to respectively to moisture content lower than 1wt ‰, then extrusion granulator.Particularly, can be defined as the drying condition of raw material: poly butylene succinate polymer is in 50-85 DEG C of dry 2-3 hour, and polylactic acid polymer closes stabilizing agent in 40-60 DEG C of dry 4-8 hour, can meet the demands.
More than, in granulation and spinning technique, the setting of each parameter can be adjusted according to the specific nature of material and equipment operation situation in institute's range of definition.When the extrusion granulator of raw material, generally can use double screw extruder, according to the melting characteristic of material, suitable barrel temperature is set in segmentation within the scope of said temperature, realizes and granulating, so that the PP Pipe Compound of manufacturing cigarette filter rod to be provided.
Similarly, according to the character of adopted PBS polymer and PLA or their copolyesters raw material, the method of the manufacture pipe tobacco material that the present invention has determined targetedly, its concrete scheme can select situation suitably to adjust according to material, for example,, in melt spinning operation, wherein, in melt spinning operation, extruder screw temperature 180-210 DEG C; Chilling temperature to ejection silk is 10-50 DEG C; Reel in traction technique, the roller winding speed 400-900m/min of slow hauling machine; The roller rotating speed of fast hauling machine is 1000-2000r/min, and frequency is 35-40HZ; Belt conveyor feeding-wheel speed is 500-1000r/min, and frequency is 38-42HZ.
Concrete operations and the equipment of above-mentioned mixing and granulation, spinning and coiling drawing-off and do not have special instruction finishing agent be pipe tobacco produce in known and routine techniques.
The present invention further provides and adopted above-mentioned PBS+PLA alloy material pipe tobacco to manufacture the method for biodegradable cigarette filter, the method comprises:
Make tow by evenly gluing to spraying the bonding plasticizer of this tow weight 0.5～15% after described tow opening;
Cigarette with mouth rod former in by described the tow of glue rub and be rolled into round bar shaped, with the sizing of plug wrap parcel, become mouth bar bar, the fiber obvolvent in tow together, is torn by hand and can obviously sees that the fiber of tow has formed the three-dimensional network mouth bar bar of connection;
Above-mentioned mouth bar bar is cut into specific length with cutter, obtain described biodegradable Mouthpiece for cigarette;
Above-mentioned bonding plasticizer refers to and can make fiber in poly butylene succinate mouth rod occur crosslinked, bonding, expand or fluffy material, include but not limited to comprise dioctyl phthalate, dibutyl terephthalate, trioctyl trimellitate (TOTM), tributyl trimellitate, tri trimellitate ester in the last of the ten Heavenly stems, trimellitic acid glyceryl ester, phosphoglyceride, triacetyl glycerine, two sweet sour diacetates, propene carbonate, glyceride lactate, ethylene glycol monoethyl ether, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, water base amylan, carboxymethyl starch glue, SGA, polyethylene glycol glue, polyvinyl alcohol glue, protein adhesive, collagen glue etc. or their any mixture.
Preferably, described bonding plasticizer comprises trimellitic acid glyceryl ester, triacetyl glycerine, diethylene glycol acetate, propene carbonate, dibutyl carbonate, carboxymethyl starch glue, polyethylene glycol glue, collagen glue etc. or their any mixture.
In concrete scheme of the present invention, bonding plasticizer used is with suitable dissolution with solvents, and this solvent to be can effectively dissolve bonding plasticizer as choice criteria, preferably taking ethanol or ethanol water as solvent.
The cigarette filter stick that the present invention utilizes the alloy material manufacture of poly-butyric acid butanediol ester polymer and polylactic acid polymer composition to provide has good biodegradability, can ensure after receiving on cigarette in 3 years interior mechanicses, outward appearance under normal storage and transportation conditions.The aspect performances such as mouthfeel do not change substantially, meet cigarette requirement completely, and when after cigarette is used, discarded stub enters rubbish etc. and is rich in microbial environment in three months degradation rate can exceed can be degradable in 70%, six month.The present invention obtains cigarette mouth rod in security performance, and the physical and chemical indexs such as resistance to suction, weight, hardness, circumference meet the requirement of cigarette mouth rod completely.
Through absorption test, cigarette of the present invention is better than for the absorption property of harmful material the polypropylene fibre mouth rod and the cellulose acetate fibre mouth rod (testing result sees the following form) that use at present with filter stick in cigarette aspiration procedure.
The filter stick fume indication contrast of various raw materials
Note: 1, " the fine mouth rod of vinegar " in table is that market brand cigarette is used mouth rod; The statistics of the mouth rod product that the fume indication of " alloy mouth rod " is prepared from the embodiment of the present invention.
2, refer to that above object detection method carries out according to GB5606-2004 " cigarette " standard.
The more existing mouth rod of mouth rod of the present invention has remarkable advantage:
1 has biodegradability, more environmental protection;
2 pairs of flue gases have better absorption property, have reduced harmfulness of smoking;
3 raw material sources are extensive, both can adopt traditional fossil base resource, can adopt again living beings to obtain by biotechnology, both avoid cellulose acetate mouth rod to rely on the resource problem of wood pulp, not only can really realize the green production that is derived from nature (living beings) but also back to nature (degraded).
In sum, the cigarette filter stick of alloy raw material manufacture that the present invention adopts PBS+PLA is in quality and all can reach in nature the industry standard of cigarette mouth rod, and be processed into cigarette, discarded stub after use can be realized complete biodegradable, compared with current acetate fiber mouth rod, there is incomparable advantage from environmental angle; On the other hand, PBS, PLA or their copolyesters raw material that biodegradable mouth rod provided by the invention utilizes can synthesize preparation by chemical method, and raw material sources are abundant, no longer need import high-quality timber, are more conducive to suitability for industrialized production.So enforcement of the present invention can replace acetate fiber mouth rod and the polypropylene fibre mouth rod of current use completely, has boundless economic benefit and social benefit simultaneously.
Specific embodiments
The beneficial effect that is further described implementation process of the present invention and produced by specific embodiment below, to help reader to understand better the present invention, but can not think restriction to of the present invention can practical range formation.
Except special instruction, the ratio occurring in the claims in the present invention book and description or concentration are all interpreted as weight ratio or the percentage concentration taking weight as benchmark.
Embodiment 1
Take 50 kilogram weight average molecular weights for (15 ± 1) ten thousand, the equal poly butylene succinate (PBS) that dispersion index is 1.7 is dried 2 hours in 65 DEG C of baking ovens.Take 49 kilogram weight average molecular weights for (15 ± 1) ten thousand, the homopolymerization PLA that dispersion index is 1.5 is dried 5 hours in 55 DEG C of baking ovens.After two raw material dryings, all join in homogenizer, and in mixer, add 0.5 kilogram of triphenyl phosphate and 0.5 kilogram of antioxidant 1222 (3,5-di-t-butyl-4-hydroxyphenyl diethyl phosphate), high-speed stirred is even.
Extrusion granulator on Φ 57 double screw extruders that are 32 in draw ratio by the mixed material after stirring, barrel Temperature Setting first paragraph is 190 DEG C, and second segment is 200 DEG C, and the 3rd section is 200 DEG C, and the 4th section is 200 DEG C, the 5th section is 195 DEG C.Extrude material strip pelleter pelletizing, online heated-air drying, packaging, obtains cigarette holder stick PP Pipe Compound of the present invention.
On Φ 65 melt spinning machines that are 28 by PP Pipe Compound at screw slenderness ratio by above-mentioned cigarette holder stick, carry out spinning, spinning machine extruder temperature is set: first paragraph is 190 DEG C, second segment is 205 DEG C, the 3rd section is 210 DEG C, 205 DEG C of filter temperatures, 205 DEG C of spin manifold temperatures are that the dry air lateral blowing of (15 ± 5) DEG C is cooling by temperature range the ejection of spinnerets that 205 DEG C of straight tube temperature are 1050 × 3 from specification.
Above-mentioned cooled tow applies finish in finishing bathtray, the fiber surface finishing agent aqueous solution that in finishing bathtray, finish is following composition: polyethylene glycol 1700, and concentration is 0.2%, triethanolamine dimethyl suflfate, concentration is 0.15, nonyl phenol poly(ethylene oxide), and concentration is 0.1%.After finishing bathtray, tow is by slow hauling machine around volume, and roller winding speed is 800m/min; Then by traction steam chest, enter fast hauling machine around volume, fast carry-over pinch rolls rotating speed 1500r/min, frequency 38HZ, then carries by belt conveyor, belt conveyor feeding-wheel speed 800r/min, frequency is 40HZ.
The tow pulling out from belt conveyor multi-roll drafting machine drawing-off, drawing-off medium is water, water temperature is 65 DEG C.After drawing-off, tow carries out curlingly in curler, and crispation number is 24/25mm, and the tow after curling is dried by steam heated oven.
After dry, by yarn swaying machine, tow is well placed in Sheng silk container, packing obtains biodegradable pipe tobacco of the present invention.
From hopper pull-out tow, through roller-way, to send to Y11 tow opening machine and carry out tow opening, after shredding, tow enters casing, sprays the bonding plasticizer of this tow weight 6% with whirl coating dish and nozzle, and makes tow be stained with equably glue.The solvent of bonding plasticizer adopts water: the mixed solvent that the mass ratio of ethanol is 50: 50, and bonding plasticizer composition: acetic acid glyceryl ester, concentration is 20%, polyacrylic acid ester gum, concentration is 4%.The tow of upper glue will be rubbed in mouth rod former and will be rolled into round bar shaped at Y21 type cigarette, wrap up by plug wrap, sizing forms mouth bar bar, with cutter will be from former out mouth bar bar cut into specific length, utilize packaging treating apparatus, pack pack, namely into via tray filling machine and obtain cigarette of the present invention complete biodegradable mouth rod.
Above-mentioned mouth rod has good biodegradability, requires to reach completely degraded standard-required according to ISO 14855, and within 90 days, degradation rate reaches 91%.Material biological safety meets the requirement of cigarette mouth rod.Circumference 24.1mm, out-of-roundness 0.1mm, resistance to suction 3255Pa, hardness 90%, physical property meets the requirement of mouth rod.Through cigarette test, fume indication is that nicotine 1.03mg/ props up, and wet tar 15.6mg/ props up, and CO15.2mg/ props up, and tar 12.4mg/ props up.
Embodiment 2
Take 30 kilogram weight average molecular weights for (10 ± 1) ten thousand, dispersion index is 1.2, on strand, contain the copolymerization poly butylene succinate (PBS) of the terephthalic acid (TPA) connection of 18% (chain number) random distribution, in 60 DEG C of baking ovens, dry 3 hours.Take 68 kilogram weight average molecular weights for (10 ± 1) ten thousand, dispersion index is 1.2, contains the copolymerization PLA of the glycol monoethyl ether chain link of 1% (chain number) random distribution on strand, in 45 DEG C of baking ovens, dries 8 hours.After dry, two kinds of resin raw materials are all joined in homogenizer, and in mixer, add 1 kilogram of phosphorous sulphur compound H-MOD of long-chain and 1 kilogram of triphenyl phosphite, high-speed stirred is even.Extrusion granulator on Φ 65 double screw extruders that above-mentioned compound is 28 in draw ratio, barrel Temperature Setting first paragraph is 195 DEG C, and second segment is 205 DEG C, and the 3rd section is 215 DEG C, and the 4th section is 210 DEG C, the 5th section is 205 DEG C.Extrude material strip pelleter pelletizing, online heated-air drying, packaging, obtains cigarette holder stick PP Pipe Compound of the present invention.
On Φ 65 melt spinning machines that are 28 by PP Pipe Compound at screw slenderness ratio by above-mentioned cigarette holder stick, carry out spinning, spinning machine extruder temperature is set as: first paragraph is 205 DEG C, and second segment is 210 DEG C, the 3rd section is 225 DEG C, 215 DEG C of filter temperatures, 215 DEG C of spin manifold temperatures, 215 DEG C of straight tube temperature.The spinnerets that is 1050 × 3 from specification ejection, be that the dry air lateral blowing of 20～30 DEG C is cooling by temperature range.
Above-mentioned cooled tow applies finish in finishing bathtray, the fibre finish aqueous solution that in finishing bathtray, finish is following composition: polyethylene glycol 1700, and concentration is 0.2%, triethanolamine dimethyl suflfate, concentration is 0.15%, nonyl phenol poly(ethylene oxide), and concentration is 0.1%.After finishing bathtray, tow is by slow hauling machine around volume, and roller winding speed is 1000m/min; Then by traction steam chest, enter fast hauling machine around volume, fast carry-over pinch rolls rotating speed 1800r/min, frequency 40HZ, then carries by belt conveyor, belt conveyor feeding-wheel speed 1000r/min, frequency is 40HZ.
The tow pulling out from belt conveyor multi-roll drafting machine drawing-off, drawing-off medium is water, water temperature is 75 DEG C.After drawing-off, tow carries out curlingly in curler, and crispation number is 25/25mm, and the tow after curling is dried by steam heated oven.After dry, by yarn swaying machine, tow is well placed in Sheng silk container, packing obtains biodegradable pipe tobacco of the present invention.
From hopper pull-out tow, through roller-way, to send to Y11 tow opening machine and carry out tow opening, after shredding, tow enters casing, sprays the bonding plasticizer of this tow weight 2% with whirl coating dish and nozzle, and makes tow be stained with equably glue.The solvent of bonding plasticizer adopts water: the mixed solvent that ethanol mass ratio is 50: 50, and bonding plasticizer composition: diethylene glycol acetate, concentration is 30%, polyethylene glycol glue, concentration is 4%.The tow of upper glue will be rubbed in mouth rod former and will be rolled into round bar shaped at Y21 type cigarette, wrap up by plug wrap, sizing forms mouth bar bar, with cutter will be from former out mouth bar bar cut into specific length, utilize packaging treating apparatus, pack pack, namely into via tray filling machine and obtain cigarette of the present invention complete biodegradable mouth rod.
The copolymerization PBS substrate resin that the present embodiment adopts is synthetic with reference to the method for recording in CN 01144133.X, in the reaction system of succinic acid and butanediol, add terephthalic acid (TPA), wherein to account for the mol ratio of total system be 18% to terephthalic acid (TPA), then carry out polymerisation, obtain desired copolymerization poly butylene succinate copolymer.
The copolymerization PLA that the present embodiment adopts can be with reference to disclosed polymerisation process in application for a patent for invention CN200610016643.0, by lactic acid and glycol monoethyl ether monomer according to the mixed in molar ratio generation copolyreaction of 99: 1 and obtain.
Above-mentioned mouth rod has good biodegradability, requires to reach completely degraded standard-required according to ISO 14855, and within 90 days, degradation rate reaches 89%.Material biological safety meets the requirement of cigarette mouth rod.Circumference 24.1mm, out-of-roundness 0.2mm, resistance to suction 3232Pa, hardness 91%, physical property meets the requirement of mouth rod.Through cigarette test, fume indication is that nicotine 1.03mg/ props up, and wet tar 15.6mg/ props up, and CO15.2mg/ props up, and tar 12.5mg/ props up.
Embodiment 3
Taking 70 kilogram weight average molecular weights is 350,000, and dispersion index is 3.0, and the copolymerization poly butylene succinate (PBS) that contains the hexylene glycol connection of 30% (chain number) random distribution on strand is dried 3 hours in 75 DEG C of baking ovens.Taking 30 kilogram weight average molecular weights is 300,000, and dispersion index is 3.0, contains the copolymerization PLA of the 6-caprolactone chain link of 30% (chain number) random distribution on strand, in 50 DEG C of baking ovens, dries 8 hours.Dried two kinds of resin materials are all joined in homogenizer and stirred, extrusion granulator on Φ 65 double screw extruders that are 28 in draw ratio, barrel Temperature Setting first paragraph is 215 DEG C, second segment is 220 DEG C, the 3rd section is 230 DEG C, and the 4th section is 220 DEG C, and the 5th section is 215 DEG C.Extrude material strip pelleter pelletizing, online heated-air drying, packaging, obtains cigarette holder stick PP Pipe Compound of the present invention.
On Φ 65 melt spinning machines that are 28 at screw slenderness ratio by above-mentioned PP Pipe Compound, carry out spinning, spinning machine extruder temperature is set: first paragraph is 230 DEG C, and second segment is 240 DEG C, the 3rd section is 250 DEG C, 245 DEG C of filter temperatures, 245 DEG C of spin manifold temperatures, 245 DEG C of straight tube temperature.The spinnerets that is 1250 × 1 from specification ejection, be that the dry air lateral blowing of 20～40 DEG C is cooling by temperature range.
Cooled tow applies finish in finishing bathtray, the fibre finish aqueous solution that the finish in finishing bathtray is following composition: polyethylene glycol 1700, and concentration is 0.6%, triethanolamine dimethyl suflfate, concentration is 0.2%, nonyl phenol poly(ethylene oxide), and concentration is 0.2%.After finishing bathtray, tow is by slow hauling machine around volume, and roller winding speed is 1500m/min; Then by traction steam chest, enter fast hauling machine around volume, fast carry-over pinch rolls rotating speed 2500r/min, frequency 50HZ, then carries by belt conveyor, belt conveyor feeding-wheel speed 1500r/min, frequency is 60HZ.
The tow pulling out from belt conveyor multi-roll drafting machine drawing-off, drawing-off medium is water, water temperature is 40 DEG C.After drawing-off, tow carries out curlingly in curler, and crispation number is 22/25mm, and the tow after curling is dried by steam heated oven.After dry, by yarn swaying machine, tow is well placed in Sheng silk container, packing obtains biodegradable pipe tobacco of the present invention.
From hopper pull-out tow, through roller-way, to send to Y11 tow opening machine and carry out tow opening, after shredding, tow enters casing, sprays the bonding plasticizer of this tow weight 0.5% with whirl coating dish and nozzle, and makes tow be stained with equably glue.The solvent that bonding plasticizer adopts is water: the mixed solvent that the mass ratio of ethanol is 50: 50, bonding plasticizer composition: carboxymethyl starch glue, concentration is 5%.The tow of upper glue will be rubbed in mouth rod former and will be rolled into round bar shaped at Y21 type cigarette, wrap up by plug wrap, sizing forms mouth bar bar, with cutter will be from former out mouth bar bar cut into specific length, by packaging treating apparatus, pack pack, namely into via tray filling machine and obtain cigarette of the present invention complete biodegradable mouth rod.
The copolymerization PBS substrate resin that the present embodiment adopts can be synthetic with reference to the method according to recording in CN 01144133.X, in the reaction system of succinic acid and butanediol, add hexylene glycol, wherein to account for the mol ratio of total system be 30% to hexylene glycol, then carry out polymerisation, obtain desired copolymer.
The copolymerization PLA that the present embodiment adopts can be according to disclosed polymerisation process in application for a patent for invention CN200610016643.0, by lactic acid and 6-caprolactone monomer according to the mixed in molar ratio generation copolyreaction of 70: 30 and obtain.
Above-mentioned mouth rod has good biodegradability, requires to reach completely degraded standard-required according to ISO 14855, and within 90 days, degradation rate reaches 91%.Material biological safety meets the requirement of cigarette mouth rod.Circumference 24.1mm, out-of-roundness 0.1mm, resistance to suction 3334Pa, hardness 89%, physical property meets the requirement of mouth rod.Through cigarette test, fume indication is that nicotine 1.04mg/ props up, and wet tar 15.4mg/ props up, and CO15.5mg/ props up, and tar 12.4mg/ props up.
Embodiment 4
Taking 10 kilogram weight average molecular weights is 50,000, dispersion index is 2.4, on strand, contain the copolymerization poly butylene succinate (PBS) of the ethylene glycol of adipic acid and 10% (chain number) random distribution of 10% (chain number) random distribution, in 60 DEG C of baking ovens, dry after 3 hours.Taking 97 kilogram weight average molecular weights is 50,000, dispersion index is the copolymerization PLA of the ethylene glycol of glycolide and 10% (chain number) random distribution that contains 10% (chain number) random distribution on 1.3 strand, in 45 DEG C of baking ovens, dries after 8 hours.Take 1.5 kilograms of magnesium hydroxides, 0.5 kilogram of titanium oxide is dried 2 hours in 75 DEG C of baking ovens.After dry, two kinds of resins and auxiliary agent are all joined in homogenizer, and in mixer, to add 0.2 kilogram of 1010 weight be 0.3 kilogram 1076, to stir.Extrusion granulator on Φ 60 double screw extruders that mixed material is 36 by draw ratio, barrel Temperature Setting first paragraph is 140 DEG C, and second segment is 160 DEG C, and the 3rd section is 175 DEG C, and the 4th section is 185 DEG C, the 5th section is 175 DEG C.Extrude material strip pelleter pelletizing, through online heated-air drying, packaging, obtains cigarette holder stick PP Pipe Compound of the present invention.
On Φ 60 melt spinning machines that are 28 by PP Pipe Compound at screw slenderness ratio by above-mentioned cigarette holder stick, carry out spinning, spinning machine extruder temperature setting means is: first paragraph is 170 DEG C, and second segment is 185 DEG C, the 3rd section is 195 DEG C, 185 DEG C of filter temperatures, 185 DEG C of spin manifold temperatures, 185 DEG C of straight tube temperature.The spinnerets that is 2210 × 4 from specification ejection, be that the dry air lateral blowing of 10～20 DEG C is cooling by temperature range.
Above-mentioned cooled tow applies finish in finishing bathtray, the fiber surface finishing agent aqueous solution that in finishing bathtray, finish is following composition: polyethylene glycol 1700, and concentration is 0.8%, triethanolamine dimethyl suflfate, concentration is 0.1%, nonyl phenol poly(ethylene oxide), and concentration is 0.1%.After finishing bathtray, tow is by slow hauling machine around volume, and roller winding speed is 200m/min; Then by traction steam chest, enter fast hauling machine around volume, fast carry-over pinch rolls rotating speed 400r/min, frequency 25HZ, then carries by belt conveyor, belt conveyor feeding-wheel speed 200r/min, frequency is 30HZ.
The tow pulling out from belt conveyor multi-roll drafting machine drawing-off, drawing-off medium is water, water temperature is 85 DEG C.After drawing-off, tow carries out curlingly in curler, and crispation number is 25/25mm, and the tow after curling is dried by steam heated oven.After dry, by yarn swaying machine, tow is well placed in Sheng silk container, packing obtains biodegradable pipe tobacco of the present invention.
From hopper pull-out tow, through roller-way, to send to Y11 tow opening machine and carry out tow opening, after shredding, tow enters casing, sprays the bonding plasticizer of this tow weight 15% with whirl coating dish and nozzle, and makes tow be stained with equably glue.The solvent that bonding plasticizer adopts is water: the mixed solvent that the mass ratio of ethanol is 50: 50, and bonding plasticizer composition: glyceride lactate, concentration is 20%, collagen glue, concentration is 4%.The tow of upper glue will be rubbed in mouth rod former and will be rolled into round bar shaped at Y21 type cigarette, wrap up by plug wrap, sizing forms mouth bar bar, with cutter will be from former out mouth bar bar cut into specific length, by packaging treating apparatus, pack pack, namely into via tray filling machine and obtain cigarette of the present invention complete biodegradable mouth rod.
The copolymerization PBS resin that the present embodiment adopts can be synthetic according to the method for recording in CN 01144133.X, in the reaction system of succinic acid and butanediol, add respectively hexylene glycol and ethylene glycol, wherein adipic acid accounts for total system mol ratio 10%, ethylene glycol accounts for 10% of total system mol ratio, then carry out polymerisation, obtain desired copolymer.
The copolymerization polylactic resin that the present embodiment adopts can be with reference to disclosed polymerisation process in application for a patent for invention CN200610016643.0, by lactic acid and glycolide and ethylene glycol monomer according to the mixed in molar ratio generation copolyreaction of 80: 10: 10 and obtain.
Above-mentioned mouth rod has good biodegradability, requires to reach completely degraded standard-required according to ISO 14855, and within 90 days, degradation rate reaches 97%.Material biological safety meets the requirement of cigarette mouth rod.Circumference 24.1mm, out-of-roundness 0.2mm, resistance to suction 3334Pa, hardness 90%, physical property meets the requirement of mouth rod.Through cigarette test, fume indication is that nicotine 1.05mg/ props up, and wet tar 15.6mg/ props up, and CO15.5mg/ props up, and tar 12.5mg/ props up.
Embodiment 5
Take 89.5 kilogram weight average molecular weights for (25 ± 2) ten thousand, dispersion index is 1.4, on strand, contain the copolymerization poly butylene succinate of the 1,3-PD chain link of 15% (chain number) random distribution, in 60 DEG C of baking ovens, dry 3 hours.Taking 10 kilogram weight average molecular weights is 180,000, and dispersion index is 1.5, contains the copolymerization PLA of the glycolide of 15% (chain number) random distribution on strand, in 50 DEG C of baking ovens, dries 6 hours.Above-mentioned two kinds of dried resins are joined in homogenizer, and be 0.1 kilogram of antioxidant 1010 to adding weight in mixer, weight is 0.2 kilogram of antioxidant 1076,0.2 kilogram 1,2-epoxy radicals-3-phenoxypropane stirs in homogenizer.On Φ 35 double screw extruders that this mixed material is 28 by draw ratio, extrude and know grain, barrel Temperature Setting mode: first paragraph is 180 DEG C, second segment is 190 DEG C, and the 3rd section is 200 DEG C, and the 4th section is 205 DEG C, and the 5th section is 195 DEG C.Extrude material strip pelleter pelletizing, online heated-air drying, packaging, the cigarette holder stick PP Pipe Compound of the present invention obtaining.
On Φ 60 melt spinning machines that are 28 by PP Pipe Compound at screw slenderness ratio by above-mentioned cigarette holder stick, carry out spinning, the Temperature Setting mode of spinning machine screw rod: first paragraph is 200 DEG C, second segment is 210 DEG C, the 3rd section is 215 DEG C, 210 DEG C of filter temperatures, 210 DEG C of spin manifold temperatures, 210 DEG C of straight tube temperature.The spinnerets that is 2210 × 4 from specification ejection, be that the dry air lateral blowing of (15 ± 5) DEG C is cooling by temperature range.
Above-mentioned cooled tow applies finish in finishing bathtray, the fiber surface finishing agent aqueous solution that in finishing bathtray, finish is following composition: polyethylene glycol 1500, and concentration is 0.2%, triethanolamine dimethyl suflfate, concentration is 0.15%, nonyl phenol poly(ethylene oxide), and concentration is 0.1%.After finishing bathtray, tow is by slow hauling machine around volume, and roller winding speed is 700m/min; Then by traction steam chest, enter fast hauling machine around volume, fast carry-over pinch rolls rotating speed 1200r/min, frequency 38HZ, then carries by belt conveyor, belt conveyor feeding-wheel speed 700r/min, frequency is 40HZ.From tow multi-roll drafting machine drawing-offs such as belt conveyor pull out, drawing-off medium is water, and water temperature is 75 DEG C.After drawing-off, tow carries out curlingly in curler, and crispation number is 24/25mm, and the tow after curling is dried by steam heated oven.After dry, by yarn swaying machine, tow is well placed in Sheng silk container, packing obtains biodegradable pipe tobacco of the present invention.
From hopper pull-out tow, through roller-way, to deliver to Y11 tow opening machine and carry out tow opening, after shredding, tow enters casing, sprays the bonding plasticizer of this tow weight 5% with whirl coating dish and nozzle, and makes tow be stained with equably glue.The solvent that bonding plasticizer adopts is water: the mixed solvent that the mass ratio of ethanol is 50: 50, and bonding plasticizer composition: diethylene glycol acetate, concentration is 30%, carboxymethyl starch glue, concentration is 2%.
The tow of upper glue will be rubbed in mouth rod former and will be rolled into round bar shaped at Y21 type cigarette, wrap up by plug wrap, sizing forms mouth bar bar, the mouth rod of specific length will out be cut into from former with cutter in mouth bar bar, through packaging treating apparatus, pack pack, namely into via tray filling machine and obtain cigarette of the present invention complete biodegradable mouth rod.
The copolymerization PBS substrate resin that the present embodiment adopts is synthetic according to the method for recording in CN 01144133.X, in the reaction system of succinic acid and butanediol, add 1, ammediol, wherein 1, the amount of ammediol be in total system mol ratio 15%, then carry out polymerisation, obtain desired copolymer.
The non-internal ester monomer modification by copolymerization PLA substrate resin that the present embodiment adopts can be with reference to disclosed polymerisation process in application for a patent for invention CN200610016643.0, by lactic acid and glycolide monomer according to the mixed in molar ratio generation copolyreaction of 85: 15 and obtain.
Above-mentioned mouth rod has good biodegradability, requires to reach completely degraded standard-required according to ISO 14855, and within 90 days, degradation rate reaches 93%.Material biological safety meets the requirement of cigarette mouth rod.Circumference 24.1mm, out-of-roundness 0.2mm, resistance to suction 3435Pa, hardness 89%, physical property meets the requirement of mouth rod.Through cigarette test, fume indication is that nicotine 1.05mg/ props up, and wet tar 15.4mg/ props up, and CO15.5mg/ props up, and tar 12.4mg/ props up.
Embodiment 6
Taking 94.5 kilogram weight average molecular weights is 160,000, and the equal PLA that dispersion index is 2.1 is dried 8 hours in 50 DEG C of baking ovens.Taking 5 kilogram weight average molecular weights is 150,000, and dispersion index is 1.8, contains the terephthalic acid (TPA) chain link copolymerization poly butylene succinate (PBS) of 10% (chain number) random distribution on strand, in 70 DEG C of baking ovens, dries 2 hours.To after two kinds of resin dryings, join in homogenizer, and in homogenizer, add 0.2 kilogram of triethyl phosphite, 0.2 kilogram, antioxidant 1425 (two (3,5-di-tert-butyl-4-hydroxyl benzyl monoethyl phosphate) calcium), 0.1 kilogram of titanium oxide.In homogenizer, described raw material is stirred.The Φ that is 38 by draw ratio by the mixed material obtaining 60 double screw extruder extrusion granulators, barrel Temperature Setting mode, first paragraph is 180 DEG C, and second segment is 190 DEG C, and the 3rd section is 200 DEG C, and the 4th section is 210 DEG C, the 5th section is 200 DEG C.Extrude material strip pelleter pelletizing, online heated-air drying, packaging, obtains cigarette holder stick PP Pipe Compound of the present invention.
On Φ 65 melt spinning machines that are 28 by PP Pipe Compound at screw slenderness ratio by above-mentioned cigarette holder stick, carry out spinning, spinning machine extruder temperature setting means: first paragraph is 200 DEG C, second segment is 205 DEG C, the 3rd section is 215 DEG C, 205 DEG C of filter temperatures, 205 DEG C of spin manifold temperatures, 205 DEG C of straight tube temperature.The spinnerets that is 1050 × 3 from specification ejection, be that the dry air lateral blowing of (20 ± 10) DEG C is cooling by temperature range.
Above-mentioned cooled tow applies finish in finishing bathtray, the fiber surface finishing agent aqueous solution that in finishing bathtray, finish is following composition: polyethylene glycol 1700, and concentration is 0.2%, triethanolamine dimethyl suflfate, concentration is 0.15, nonyl phenol poly(ethylene oxide), and concentration is 0.1%.Tow after finishing bathtray is by slow hauling machine around volume, and roller winding speed is 800m/min; Then by traction steam chest, enter fast hauling machine around volume, fast carry-over pinch rolls rotating speed 1500r/min, frequency 38HZ, then carries by belt conveyor, belt conveyor feeding-wheel speed 800r/min, frequency is 40HZ.
From tow multi-roll drafting machine drawing-offs such as belt conveyor pull out, drawing-off medium is water, and water temperature is 65 DEG C.After drawing-off, tow carries out curlingly in curler, and crispation number is 24/25mm, and the tow after curling is dried by steam heated oven.After dry, by yarn swaying machine, tow is well placed in Sheng silk container, packing obtains biodegradable pipe tobacco of the present invention.
From hopper pull-out tow, through roller-way, to deliver to Y11 tow opening machine and carry out tow opening, after shredding, tow enters casing, sprays the bonding plasticizer of this tow weight 10% with whirl coating dish and nozzle, and makes tow be stained with equably glue.The solvent that bonding plasticizer adopts is ethanol, bonding plasticizer composition: trimellitic acid glyceryl ester, and concentration is 20%, polyacrylic acid ester gum, concentration is 6%.The tow of upper glue will be rubbed in mouth rod former and will be rolled into round bar shaped at Y21 type cigarette, wrap up by plug wrap, sizing forms mouth bar bar, with cutter will be from former out mouth bar bar cut into specific length, adopt packaging treating apparatus, pack pack, namely into via tray filling machine and obtain cigarette of the present invention complete biodegradable mouth rod.
The copolymerization PBS resin that the present embodiment adopts is synthetic according to the method for recording in CN 01144133.X, reaction system at succinic acid and butanediol adds terephthalic acid (TPA), wherein terephthalic acid (TPA) accounts for the mol ratio 10% of total system, then carries out polymerisation, obtains desired copolymer.
Above-mentioned mouth rod has good biodegradability, requires to reach completely degraded standard-required according to ISO 14855, and within 90 days, degradation rate reaches 96%.Material biological safety meets the requirement of cigarette mouth rod.Circumference 24.1mm, out-of-roundness 0.1mm, resistance to suction 3445Pa, hardness 96%, physical property meets the requirement of mouth rod.Through cigarette test, fume indication is that nicotine 1.06mg/ props up, and wet tar 15.8mg/ props up, and CO15.7mg/ props up, and tar 12.7mg/ props up.
Claims (13)
1. a biodegradable cigarette fibrous material, its raw material composition comprises poly butylene succinate polymer, the polylactic acid polymer of 1-99wt% and the stabilizing agent of 0-3wt% of 1-99wt%, and this cigarette fibrous material is that described raw material processes through melt-spinning technology;
The manufacture method of fibrous material for described biodegradable cigarette, the method comprises the steps:
Dry raw material is mixed, use screw extruder extrusion granulator, when granulation, extruding machine barrel temperature, at 140-230 DEG C, is extruded rear pelletizing, dry, the cigarette holder stick PP Pipe Compound obtaining;
The PP Pipe Compound that above-mentioned granulation is obtained is carried out melt spinning, 170 DEG C-250 DEG C of the extruder temperatures of setting spinning machine, extruded material is flowed through after filter, casing, measuring pump and straight tube, spray silk by spinnerets, 170 DEG C-250 DEG C of controlled filter actuator temperatures, 170 DEG C-250 DEG C of spin manifold temperatures, 170 DEG C-250 DEG C of straight tube temperature, silk to ejection is cooling with dry air, and chilling temperature is 0 DEG C-50 DEG C;
Cooled tow is through applying the coiling traction around volume and belt conveyor around volume, steam chest traction, fast hauling machine of finish, slow hauling machine; oil concentration is the aqueous solution of the fiber surface finishing agent of 0.8%-1%; the roller winding speed 200-1500m/min of slow hauling machine; the roller rotating speed 400-2500r/min of fast hauling machine; frequency is 25-50Hz; belt conveyor feeding-wheel speed 200-1500r/min, frequency is 30-60Hz;
Be water-bath drawing-off the tank of 40 DEG C-85 DEG C by the tow pulling out from belt conveyor in water temperature, then through curling and dryness finalization, the tow obtaining is described biodegradable cigarette fibrous material;
The amount that described PBGS polymer is succinic acid-butanediol ester chain link in strand is no less than 70% high molecular polymer of total chain number, and its weight average molecular weight is 5-35 ten thousand, dispersion index 1.2-3.0; 70% the high molecular polymer that described polylactic acid polymer is that in strand, lactic acid chain link is no less than total chain number, and its weight average molecular weight is 5-30 ten thousand, dispersion index 1.2-3.0.
2. biodegradable cigarette fibrous material as claimed in claim 1, wherein, in the strand of described PBGS polymer, the amount of succinic acid-butanediol ester chain link is no less than 70% of total chain number, and all the other are the copolymerization chain link that binary acid, dihydroxylic alcohols or its polymerization of mixtures form.
3. biodegradable cigarette fibrous material as claimed in claim 2, wherein, forms in the monomer of described copolymerization chain link, and binary acid is selected from aliphatic dibasic acid, aromatic acid or their mixture of C2-C12; Dihydroxylic alcohols is selected from the aliphatic dihydroxy alcohol of C2-C12 or their mixture.
4. biodegradable cigarette fibrous material as claimed in claim 3, wherein, described binary acid comprises ethanedioic acid, 1,2-malonic acid, 1,3-malonic acid, glutaric acid, adipic acid, azelaic acid, decanedioic acid, DC11, SL-AH, fumaric acid, maleic acid, phthalic acid, naphthalenedicarboxylic acid or its mixture; Described dihydroxylic alcohols comprises ethylene glycol, propylene glycol, pentanediol, hexylene glycol, decanediol or other mixture.
5. biodegradable cigarette fibrous material as claimed in claim 4, wherein, the monomer of described formation copolymerization chain link is selected from ethanedioic acid, malonic acid, adipic acid, fumaric acid, phthalic acid, ethylene glycol, propylene glycol or hexylene glycol, or their multiple mixture.
6. biodegradable cigarette fibrous material as claimed in claim 1, wherein, in the strand of described polylactic acid polymer, the amount of lactic acid chain link is no less than 70% of total chain number, and all the other are for carrying out the copolymerization chain link that the monomeric substance of copolymerization is polymerized with lactic acid.
7. biodegradable cigarette fibrous material as claimed in claim 6, wherein, the monomeric substance of described formation copolymerization chain link comprises glycolide, 6-caprolactone, ethylene glycol, propylene glycol, glycollic acid, glycol monoethyl ether or its mixture.
8. biodegradable cigarette fibrous material as claimed in claim 1, wherein, described stabilizing agent comprises phosphoric acid, phosphorous acid, ortho phosphorous acid, pyrophosphoric acid, ammonium phosphate, trimethyl phosphate, dimethyl phosphate, triphenyl phosphate, diphenyl phosphate, triphenyl phosphite, diphenyl phosphite, ammonium phosphite, ammonium dihydrogen phosphate (ADP), antioxidant 1010, antioxidant 1222, antioxidant 1076, antioxidant 1425, epoxidized polybutadiene, epoxy Linseed oil, epoxidized soybean oil, 1, 2-epoxy radicals-3-phenoxypropane, magnesium hydroxide, aluminium hydroxide, calcium oxide, amino resins or their any mixture.
9. biodegradable cigarette fibrous material as claimed in claim 8, wherein, described stabilizing agent comprises trimethyl phosphate, triphenyl phosphate, triphenyl phosphite, antioxidant 1010, antioxidant 1076, epoxy Linseed oil, epoxidized soybean oil, 1,2-epoxy radicals-3-phenoxypropane, magnesium hydroxide, amino resins or their any mixture.
10. a biodegradable cigarette filter rod, this cigarette filter rod is to utilize the biodegradable cigarette fibrous material described in claim 1-9 any one to process.
11. 1 kinds are provided with filter-tip cigarette, and described filter tip is that biodegradable cigarette filter rod claimed in claim 10 processes.
12. biodegradable cigarette fibrous materials claimed in claim 1, wherein, are dried to respectively moisture content lower than 1wt ‰ by raw material, then extrusion granulator.
Biodegradable cigarette fibrous material described in 13. claims 12, wherein, to the drying condition of raw material is: poly butylene succinate polymer is in 50-85 DEG C of dry 2-3 hour, and polylactic acid polymer and stabilizing agent are in 40-60 DEG C of dry 4-8 hour.
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| CN200910241645.3A CN102080278B (en) | 2009-11-30 | 2009-11-30 | Biodegradable cigarette fiber material and cigarette filter |
| PCT/CN2010/073094 WO2011063630A1 (en) | 2009-11-30 | 2010-05-21 | Biodegradable fiber for cigarette and preparation method thereof |
| PCT/CN2010/073096 WO2011063632A1 (en) | 2009-11-30 | 2010-05-21 | Biodegradable cigarette filter rod and cigarette |
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| CN200910241645.3A CN102080278B (en) | 2009-11-30 | 2009-11-30 | Biodegradable cigarette fiber material and cigarette filter |
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| WO (2) | WO2011063632A1 (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| ES2694424T3 (en) | 2011-06-23 | 2018-12-20 | British American Tobacco (Investments) Ltd | Filtering material comprising polylactide fibers |
| US8973588B2 (en) * | 2011-07-29 | 2015-03-10 | R.J. Reynolds Tobacco Company | Plasticizer composition for degradable polyester filter tow |
| US9289012B2 (en) | 2011-07-29 | 2016-03-22 | R. J. Reynolds Tobacco Company | Plasticizer composition for degradable polyester filter tow |
| CN102318898B (en) * | 2011-08-20 | 2014-05-21 | 云南瑞升烟草技术（集团）有限公司 | Method for preparing natural plant granular materials for filter tips |
| CN102499478B (en) * | 2011-11-04 | 2013-10-09 | 马鞍山同杰良生物材料有限公司 | Filter tip stick and preparation method thereof |
| CN103088458A (en) * | 2013-01-27 | 2013-05-08 | 彭荣淮 | Pure polylactic acid tows as well as preparation method and cigarette filter trip thereof |
| CN103409837B (en) * | 2013-08-02 | 2015-10-28 | 东华大学 | The method of water-soluble polyvinyl alcohol fibers prepared by a kind of melt spinning |
| JP6394181B2 (en) * | 2013-08-29 | 2018-09-26 | 三菱ケミカル株式会社 | Aliphatic polyester resin composition |
| PT3110267T (en) | 2014-02-24 | 2019-06-18 | Philip Morris Products Sa | Filter with improved hardness and filtration efficiency |
| CN111087581B (en) * | 2018-10-23 | 2022-07-12 | 中国石油化工股份有限公司 | Method for preparing polyglycolic acid |
| CN110306258A (en) * | 2019-07-18 | 2019-10-08 | 深圳市大沣生物科技有限公司 | A kind of resistance to suction is adjustable and the cigarette filter and preparation method thereof of high filtration |
| CN112251845A (en) * | 2020-10-28 | 2021-01-22 | 深圳市华远新材料有限公司 | Degradable tow with skin-core structure for cigarette filter tip and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1961765A (en) * | 2006-11-30 | 2007-05-16 | 中国科学院长春应用化学研究所 | A cigarette filter filament and preparation method thereof |
| CN101023811A (en) * | 2007-02-05 | 2007-08-29 | 中国科学院长春应用化学研究所 | Filtering rod for cigarette and preparing method |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2839409B2 (en) * | 1992-02-18 | 1998-12-16 | 日本化薬株式会社 | Tobacco filter |
| TW506894B (en) * | 1997-12-15 | 2002-10-21 | Ykk Corp | A biodegradable resin composition |
| US6194483B1 (en) * | 1998-08-31 | 2001-02-27 | Kimberly-Clark Worldwide, Inc. | Disposable articles having biodegradable nonwovens with improved fluid management properties |
| JP2003213529A (en) * | 2002-01-11 | 2003-07-30 | Chisso Corp | Biodegradable conjugated fiber and fiber structure and absorption article using the same |
| JP4650206B2 (en) * | 2005-10-25 | 2011-03-16 | チッソ株式会社 | Biodegradable conjugate fiber, and fiber structure and absorbent article using the same |
| CN100577731C (en) * | 2005-12-28 | 2010-01-06 | 海尔科化工程塑料国家工程研究中心股份有限公司 | Poly diol binary acid ester modified polylactic acid alloy |
| JP2007216041A (en) * | 2006-01-16 | 2007-08-30 | Ito:Kk | Polymer composition for healing wound |
-
2009
- 2009-11-30 CN CN200910241645.3A patent/CN102080278B/en active Active
-
2010
- 2010-05-21 WO PCT/CN2010/073096 patent/WO2011063632A1/en active Application Filing
- 2010-05-21 WO PCT/CN2010/073094 patent/WO2011063630A1/en active Application Filing
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1961765A (en) * | 2006-11-30 | 2007-05-16 | 中国科学院长春应用化学研究所 | A cigarette filter filament and preparation method thereof |
| CN101023811A (en) * | 2007-02-05 | 2007-08-29 | 中国科学院长春应用化学研究所 | Filtering rod for cigarette and preparing method |
Non-Patent Citations (3)
| Title |
|---|
| JP特开2003-213529A 2003.07.30 * |
| 张文."聚乳酸纤维及其共混纤维的纺制及结构与性能研究".《中国优秀硕士学位论文全文数据库（工程科技I辑）》.2009,(第07期),第24，67页. * |
| 张文."聚乳酸纤维及其共混纤维的纺制及结构与性能研究".《中国优秀硕士学位论文全文数据库(工程科技I辑)》.2009,(第07期),第24,67页. * |
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| CN102080278A (en) | 2011-06-01 |
| WO2011063630A1 (en) | 2011-06-03 |
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