WO2011063630A1 - 可生物降解的香烟用纤维及其制备方法 - Google Patents

可生物降解的香烟用纤维及其制备方法 Download PDF

Info

Publication number
WO2011063630A1
WO2011063630A1 PCT/CN2010/073094 CN2010073094W WO2011063630A1 WO 2011063630 A1 WO2011063630 A1 WO 2011063630A1 CN 2010073094 W CN2010073094 W CN 2010073094W WO 2011063630 A1 WO2011063630 A1 WO 2011063630A1
Authority
WO
WIPO (PCT)
Prior art keywords
acid
polymer
tobacco fiber
biodegradable
chain
Prior art date
Application number
PCT/CN2010/073094
Other languages
English (en)
French (fr)
Inventor
季君晖
Original Assignee
北京中科高意引擎技术有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 北京中科高意引擎技术有限公司 filed Critical 北京中科高意引擎技术有限公司
Publication of WO2011063630A1 publication Critical patent/WO2011063630A1/zh

Links

Classifications

    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00General methods for the manufacture of artificial filaments or the like
    • D01F1/02Addition of substances to the spinning solution or to the melt
    • AHUMAN NECESSITIES
    • A24TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24DCIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D3/00Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
    • A24D3/06Use of materials for tobacco smoke filters
    • A24D3/067Use of materials for tobacco smoke filters characterised by functional properties
    • A24D3/068Biodegradable or disintegrable
    • AHUMAN NECESSITIES
    • A24TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24DCIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D3/00Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
    • A24D3/06Use of materials for tobacco smoke filters
    • A24D3/08Use of materials for tobacco smoke filters of organic materials as carrier or major constituent
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L35/00Compositions 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
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88Monocomponent 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
    • D01F6/92Monocomponent 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
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00Applications
    • C08L2203/12Applications used for fibers

Definitions

  • the invention relates to a tobacco fiber material and a cigarette filter rod made of the fiber material, wherein the tobacco fiber material and the cigarette filter rod are used for polybutylene succinate (PBS) polymer and poly
  • PBS polybutylene succinate
  • the alloy material composed of the lactic acid polymer is a base resin and has excellent biodegradability.
  • the cigarette filter has the function of filtering, blocking and adsorbing harmful components such as nicotine and tar in the flue gas.
  • the good filter material should also improve the taste of the flue gas, reduce the irritation of the flue gas and the human body. Health damage.
  • the materials currently used in the manufacture of cigarette filters are generally made of cellulose acetate fibers and polypropylene fibers. From the viewpoint of processing properties and the comprehensive performance of the final production filter, cellulose acetate fibers are preferred. More cellulose acetate fiber filters are used in medium and high-grade cigarettes.
  • the remaining part of the filter after the cigarette is sucked is discarded, and the cellulose acetate fiber and the polypropylene fiber are difficult to be biodegraded in the natural environment.
  • the cigarette is also harmful to human health and causes environmental pollution. . Human beings cannot completely leave cigarettes. In addition to reducing the harm of cigarettes themselves to the human body, solving the environmental pollution problem caused by filter disposal has become a problem that the cigarette industry must face.
  • cellulose acetate fiber is a chemical product obtained from high-quality wood.
  • the cellulose acetate from wood to cellulose to esterification consumes a large amount of wood raw materials, and many pollution problems are accompanied by production.
  • the production process of the cigarette filter rod mainly includes the process of melt-spinning the raw material into a tobacco tow, and the process of plasticizing the shaped rod to be finally processed into a filter rod, and the spinnability of the raw material, that is, whether it is easy to be spun into a suitable smoke.
  • Cellulose acetate fiber is selected as the main processing material for cigarette filters due to its excellent properties. When looking for alternative materials, it is biodegradable and must meet the requirements of filter rod processing. It is the indispensable condition.
  • Lactic acid-based polymers such as polylactic acid (PLA) or related copolymers, are fully biodegradable under natural conditions or under human conditions and are well known as degradable materials.
  • a technique for producing a cigarette filter tow fiber and a filter rod for tobacco using a lactic acid-based polymer resin is disclosed in Chinese Patent Application No. 200610131699.0 and No. 200710055310.3.
  • lactic acid-based polymers can be used in the processing of cigarette filters, and compared to commercially available cellulose acetate filter rods and polypropylene filter rods, the polylactic acid cigarette filter rods not only have It has the advantages of complete biodegradation and low production cost, and the filter rods produced have good results in terms of filtration performance and physical and mechanical properties, but the main resin used in the technical solution can be seen from the description of the specification. Is a mixture of polylactic acid in one size or multiple specifications, or a copolymer of lactide and caprolactone, lactide, or lactide with caprolactone and glycolide. These resins are all from lactones.
  • the prepared polymer is a random polymer.
  • This material is brittle and easily hydrolyzed.
  • the water content of the material is required to be less than 10,000 parts per million, and the heat resistance of the material is poor.
  • the temperature is very low (only 58 ° C). Since tobacco tows require a certain degree of flexibility and good deformation, and require high heat resistance, there is still a lot of unsatisfactory for the cigarette companies to promote the production of the above-mentioned previously disclosed lactic acid polymer cigarette mouthstock materials. And where to improve.
  • Polybutylene succinate is a fully biodegradable polymer that can be degraded to carbon dioxide and water under the action of bacteria or enzymes, so it is currently used in the plastics sector to ease The pollution caused by traditional plastics to the environment.
  • PBS plastics can be used to prepare film packaging materials, such as degradable plastic bags, sheets of disposable tableware. Materials, etc.; PBS plastics can also be applied in agricultural mulch and some daily groceries.
  • a biodegradable composite and modified resin, a preparation method thereof and use of the composite modified resin are disclosed in Chinese Patent No. 200610026044.7.
  • the biodegradable composite and modified resin provided by this patent consists of 10-73.5% polybutylene succinate (PBS), 5-60% polylactic acid (PLA), 5-35% modified starch, 9-29.85 % Activated inorganic filler and 0.15-1.5% additive auxiliary composition, and extruded granulation by setting conditions, can be prepared into a special resin for blow molding.
  • PBS and PLA are compounded in a specific ratio, and have good heat resistance and rigidity under the action of certain processing aids, are suitable as blow molding special resins, and are biodegradable due to their biodegradability. Sex, can replace existing plastic products.
  • the textile industry also has research on mixed spinning of PBS and PLA, such as direct mixing of PLA and PBS granules into conjugated fibers, but this method is even due to the large difference in compatibility between PLA and PBS and melting temperature. It can be implemented, and only the coarse fiber with a fiber diameter of more than 15 ⁇ (after the traction orientation) can be spun, and it is not possible to use the PBS PLA alloy material to spin a fine and useful fiber.
  • the technical problem to be solved by the present invention is to provide a biodegradable tobacco fiber.
  • the raw material used is a polymer blend of polybutylene succinate and polylactic acid.
  • the tobacco fiber of the present invention has the present
  • the universal cigarette filter uses cellulose diacetate for its comparable adsorption and processing properties. It can be used to prepare cigarette filter rods and cigarette products. After the filter is discarded, it can be decomposed by microorganisms in the environment, which is beneficial to the environment.
  • the invention also provides a preparation method for manufacturing the above biodegradable tobacco fiber, and for the properties of the polybutylene succinate and the polylactic acid composite product, explores and proposes the determination of the conditions and parameters of the manufacturing process, and ensures The properties of the fibers produced meet the current standards for the use of cigarette filters.
  • the present invention provides a biodegradable tobacco fiber material having a raw material composition of 1-99 wt% polybutylene succinate polymer, 1-99 wt% polylactic acid polymer, and 0-3 wt% a stabilizer, and a product of extrusion extrusion of the component through an extruder, the tobacco fiber being processed by the melt spinning process.
  • the applicant of the present invention organically recombines two kinds of biodegradable polymer materials as a basic raw material, appropriately adjusts and changes the processing technology, and provides a tobacco fiber material, which can produce a cigarette filter.
  • the rod and the filter which replace the existing cellulose acetate or acrylic fiber for the cigarette filter, the cigarette provided with the filter has the comprehensive performance to reach the level of the cellulose acetate filter cigarette, and the filter can be degraded as soon as possible after being discarded, the application In the cigarette industry, more significant social benefits will be created for the protection of the environment.
  • the content of the polybutylene succinate polymer and the polylactic acid polymer in the raw material composition is from 5 to 95% by weight, respectively.
  • the tobacco fiber and the filter material of the present invention can be completely homopolymerized polybutylene succinate and polylactic acid, and polymerization can also be used.
  • Polymer materials suitable for other monomeric polymeric segments are present in the molecular chain to facilitate improved processing of the starting materials and associated indicators of the final filter plug and filter product.
  • the composite material for producing tobacco fibers provided by the present invention may satisfy one or all of the following definitions:
  • the polytetramethylene glycol succinate polymer is a high molecular weight polymer having a butylene succinate chain in the molecular chain of not less than 70% of the total chain number of the polymer, and the weight average thereof
  • the molecular weight is 50,000-35 thousand, and the dispersion index is 1.2-3.0;
  • the polylactic acid polymer is a high molecular polymer having not less than 70% of the total number of chain links of the lactic acid chain in the molecular chain, and has a weight average molecular weight of 50,000 to 300,000 and a dispersion index of 1.2 to 3.0.
  • the polybutanediol succinate polymer has a molecular chain of succinic acid
  • the amount of the butylene glycol ester chain is not less than 70% of the total number of links, and the balance is a dibasic acid diol polymer chain of the non-succinic acid butylene glycol chain.
  • the dibasic acid is selected from the group consisting of C2-C12 aliphatic two. a monobasic acid, an aromatic dibasic acid or a mixture thereof; the dihydric alcohol is selected from the group consisting of C2-C12 aliphatic diols or mixtures thereof.
  • the dibasic acid includes oxalic acid, 1,2-malonic acid, 1, 3-malonic acid, glutaric acid, adipic acid, sebacic acid, sebacic acid, eleven a carbonic acid, a dodecanedicarboxylic acid, a fumaric acid, a maleic acid, a phthalic acid, a naphthalenedicarboxylic acid, or the like or a mixture thereof;
  • the glycol includes ethylene glycol, propylene glycol, pentanediol, and hexane Alcohol, decanediol, etc. or a mixture thereof.
  • the dibasic acid forming a polymeric chain other than butylene succinate is selected from the group consisting of oxalic acid, malonic acid, adipic acid, fumaric acid, phthalic acid, etc. or one of them
  • the glycol is selected from ethylene glycol, propylene glycol or hexanediol, etc. or a mixture of one or more thereof.
  • the amount of the lactic acid chain in the molecular chain of the polylactic acid polymer is not less than 70% of the total number of links of the polymer, and the rest is a monomer chain which can be copolymerized with lactic acid.
  • the monomer when the molecular chain of the polylactic acid polymer contains a monomer chain other than a lactic acid chain link, the monomer may include glycolide, ⁇ -caprolactone, ethylene glycol. , propylene glycol, glycolic acid, or ethylene glycol monomethyl ether, or the like, or any mixture thereof.
  • the above two kinds of high molecular polymer raw materials for producing tobacco fibers can be produced by a known method or commercially available.
  • Chinese Patent No. 01144133.X discloses a method for preparing polybutylene succinate (PBS) by using succinic acid and butanediol as monomer raw materials, and often by pressure esterification (condensation) and then vacuum polymerization.
  • PBS polybutylene succinate
  • Method, Chinese Patent Application No. 200710049370.4 also discloses a preparation of high molecular weight PBS.
  • the method, the polybutylene succinate polymer prepared according to these prior art methods can satisfy the raw material requirements of the present invention, and thus the above disclosure is incorporated into the present invention.
  • the PBS polymer containing the polymer chain of the dibasic acid diol can also be produced very conveniently by a chemical process such as a polymerization reaction or a chain extension reaction.
  • a predetermined ratio of the selected dibasic acid and/or diol is added to the condensation reaction system of succinic acid and butanediol, and the polymerization product can be subjected to polymerization to obtain a desired ratio.
  • Polymer chain links are examples of polymer chain links.
  • polylactic acid or a polylactic acid polymer containing selected monomeric copolymeric links may also be prepared according to known methods or commercially available, the former being a commonly known and used polymeric material for many years, a
  • the polymer product can be conveniently synthesized or synthesized according to a mature method, and the polylactic acid polymer containing the selected monomer copolymer chain can be obtained by polymerizing a monomer raw material mixed in a certain ratio according to many published methods, thereby It is easy to prepare a copolymerized product having a desired chain ratio, and it can also be conveniently prepared by a chemical process such as a polymerization reaction or a chain extension reaction under the basic theory of the publication and related polymerization.
  • lactic acid and the selected polymerizable monomer are copolymerized in a desired ratio.
  • the raw material utilized for the tobacco fiber material provided by the present invention in addition to the above-mentioned pure homopolymer or PBS polymer and polylactic acid polymer material containing different copolymerized links (the invention is referred to as polybutylene succinate polymerization)
  • a suitable stabilizer may be added, which means a substance which improves the stability of the PBS and the polylactic acid and the copolymer during processing, storage and use, including but not limited to heat.
  • Stabilizers, light stabilizers and acid inhibitors may include phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, ammonium phosphate, trimethyl phosphate, dimethyl phosphate, triphenyl phosphate, diphenyl phosphate, sub Triphenyl phosphate, diphenyl phosphite, ammonium phosphite, ammonium dihydrogen phosphate, antioxidant 1010 (tetrakis[methylene-3-(3',5'-di-tert-butyl-4-hydroxyphenyl)) Propionate] formazan), antioxidant 1222 (3,5-di-tert-butyl-4-hydroxyphenyl phosphate), antioxidant 1076 ( ⁇ -(3,5-di-tert-butyl-) 4-hydroxyphenyl)propionic acid n-octadecyl alcohol ester), antioxidant 1425 (bis(3,5-di-tert-butyl-4-hydroxybenz
  • the stabilizer comprises trimethyl phosphate, triphenyl phosphate, triphenyl phosphite, antioxidant 1010, antioxidant 1076, H-MOD, epoxy linseed oil, epoxidized soybean oil, 1 , 2-epoxy-3-phenoxypropane, magnesium hydroxide, amino resin, etc. or any mixture thereof.
  • the inventors' research results show that the composite material of the polybutylene succinate polymer and the polylactic acid polymer satisfying the above definition has good molding processability, and thus can be used in the current polypropylene fiber spinning process and equipment.
  • the fiber can prepare a biodegradable cigarette filter rod and a corresponding cigarette product, and the filter discarded by the smoker can be decomposed in a short time in the natural environment, and the cigarette production can be solved while solving the current environmental pollution of the cigarette waste. influences.
  • the process for producing the biodegradable tobacco fiber of the present invention may include: uniformly mixing the dried raw materials, performing blending and extruding granulation by a screw extruder, and the temperature of the extruder barrel is 140-230 during granulation. °C, after pelletizing, granulating, drying, and obtaining the special material for tobacco fiber;
  • the produced tobacco fiber material is melt-spun to form a biodegradable tobacco fiber tow.
  • the extruder selected for extrusion granulation is provided with a melt filtration device and filters particles having a particle size greater than 100 mesh.
  • SP in the extrusion process, it is preferred to provide a filter device with a screen of 100 mesh or more in the extruder.
  • the process of melt-spinning the produced tobacco fiber special material to form the biodegradable tobacco fiber tow comprises the following steps: melt-spinning the special material obtained by the above granulation
  • the screw temperature of the spinning machine is set to 170 °C-250 °C, so that the extruded material flows through the filter, the box, the metering pump and the straight pipe, and is spun through the spinneret, and the filter is controlled in the process.
  • the oil agent is an aqueous solution of a fiber surface treatment agent (for example, polyethylene glycol, ethanolamine methyl ester, nonylphenol surfactant, etc.) having a concentration of 0.8% to 1%.
  • a fiber surface treatment agent for example, polyethylene glycol, ethanolamine methyl ester, nonylphenol surfactant, etc.
  • the speed of the roller of the slow tractor is 200-1500m/min
  • the speed of the roller of the fast tractor is 400-2500r/min
  • the frequency is 25-50HZ
  • the feeding speed of the belt conveyor is 200-1500 r/min
  • the frequency is 30- 60HZ
  • the tow drawn from the belt conveyor is drawn in a water bath in a water tank having a water temperature of 40 ° C - 85 ° C, and then crimped and dried, and the obtained tow is used for the biodegradable tobacco. Fiber tow.
  • the raw materials should be dried first, and the raw materials are preferably dried separately to a moisture content of less than 1% by weight. , and then extrude and granulate.
  • the drying conditions of the raw materials can be determined as follows: The polybutylene succinate polymer is dried at 50-85 ° C for 2-3 hours, and the polylactic acid polymer and the stabilizer are dried at 40-60 ° C. 8 hours, you can meet the requirements.
  • the setting of each parameter can be adjusted within the defined range according to the specific properties of the material and the operation of the equipment.
  • a twin-screw extruder can generally be used to set a suitable barrel temperature in the above temperature range according to the melting characteristics of the material, and the melt is preferably filtered through a melt filter device before extrusion.
  • the pellets are extruded after extrusion to provide a special material for the manufacture of degradable fibers for cigarette filter rods.
  • the present invention has specifically determined a method for manufacturing a fibrous material for tobacco, and the specific scheme can be appropriately adjusted according to the material selection.
  • the screw temperature of the extruder is 180-21 CTC
  • the cooling temperature of the discharge wire is 10-5 CTC
  • the winding traction process the roll winding of the slow tractor Speed 400-900 m/min
  • fast tractor speed is 1000-2000 r/min, frequency is 35-40 HZ
  • belt conveyor feed wheel speed is 500-1000 r/min, frequency is 38-42 HZ .
  • the combination of the polybutylene succinate polymer and the polylactic acid polymer provided by the invention has good biodegradability, and the fiber material can ensure that the performance in terms of mechanics and appearance is basically unchanged within 3 years under normal storage and transportation conditions, and fully meets the requirements of cigarettes.
  • the degradable tobacco fiber of the present invention has significant advantages over the existing polypropylene tobacco fiber and cellulose acetate fiber:
  • the raw materials come from a wide range of sources, both traditional fossil-based resources and biomass can be obtained through biotechnology. This avoids the problem of the dependence of cellulose acetate on the resources of wood pulp, and can be truly derived from nature (biomass). Return to natural (degradation) green production.
  • the fiber tow of the nozzle bar made of the alloy raw material of PBS+PL of the invention can meet the industry standard of the production of the nozzle for the mouth of the cigarette in terms of quality and properties, and can be used for processing into a cigarette filter rod and a cigarette, and is used.
  • the waste filter can achieve complete biodegradation. Compared with the current acetate nozzle, it has an incomparable advantage from the environmental point of view.
  • the biodegradable nozzle provided by the present invention utilizes PBS, PLA or their Copolyester raw materials can be synthesized by chemical methods.
  • the raw materials are abundant, and it is no longer necessary to import high-quality wood, which is more conducive to industrial production. Therefore, the implementation of the present invention can completely replace the cellulose acetate and polypropylene fibers currently used, and at the same time have very broad economic and social benefits.
  • the stirred mixture was blended and extruded into a ⁇ 57 twin-screw extruder with an aspect ratio of 32.
  • the temperature of the barrel was set to 190 ° C for the first stage and 200 ° C for the second stage.
  • the section is 200 ° C
  • the fourth section is 200 ° C
  • the fifth section is 195 ° C
  • the filter on the head melt filter is 100 mesh.
  • the extruding strand is pelletized by a pelletizer, dried by hot air on the line, and packaged to obtain a special material for the tobacco fiber of the present invention.
  • the above-mentioned special fiber for tobacco is spun on a ⁇ 65 melt spinning machine with a screw length to diameter ratio of 28, and the screw temperature setting of the spinning machine is: 190 ° C in the first stage and 205 ° C in the second stage,
  • the three sections are 210 ° C
  • the filter temperature is 205 ° C
  • the cabinet temperature is 205 ° C
  • the straight tube temperature is 205 ° C
  • the temperature range is (15 ⁇ 5) ° C after being sprayed from the spinneret with a size of 1050 ⁇ 3.
  • the dry air side is blown to cool.
  • the cooled tow is coated with an oil agent in the oil sump, and the oil agent in the oil sump is an aqueous solution of the fiber surface treatment agent of the following composition: polyethylene glycol 1700, concentration 0.2%, triethanolamine dimethyl sulfate, concentration 0.15 , nonylphenol polyethylene oxide, concentration of 0.1%.
  • the tow is wound by a slow tractor, and the winding speed of the roller is 800m/min.
  • the fast traction roller rotates at 1500r/min, the frequency is 38HZ, and then is transported through the belt.
  • Machine conveyor, belt conveyor feed wheel speed 800r / min, frequency is 40HZ.
  • the tow drawn from the belt conveyor was drawn by a multi-roll drafter, the drafting medium was water, and the water temperature was 65 °C. After drawing, the tow was crimped in a crimper, the number of crimps was 24/25 mm, and the crimped tow was dried by a steam dryer. After drying, the tow is placed in a silk container by a pendulum machine, and the biodegradable tobacco fiber (tow) of the present invention is obtained by packaging.
  • both resin materials were added to a high-speed mixer, and 1 kg of a long-chain phosphorus-containing sulfur compound H-MOD and 1 kg of triphenyl phosphite were added to the mixer, and the mixture was stirred at a high speed.
  • the above mixture was blended and extruded into granules on a ⁇ 65 twin-screw extruder with a length to diameter ratio of 28.
  • the first stage of the barrel temperature setting was 195 ° C
  • the second stage was 205 ° C
  • the third stage was 215.
  • the fourth section is 210 °C
  • the fifth section is 205 °C
  • the filter on the head melt filter is 120 mesh.
  • the extruding strand is pelletized by a pelletizer, dried by hot air on the line, and packaged to obtain a special material for the tobacco fiber of the present invention.
  • the above-mentioned special material for tobacco fiber is spun on a ⁇ 65 melt spinning machine with a screw length to diameter ratio of 28, and the screw temperature of the spinning machine is set to be: 205 ° C in the first stage and 210 ° C in the second stage, The three sections are 225 °C, the filter temperature is 215 °C, the tank temperature is 215 °C, and the straight tube temperature is 215 °C. After being sprayed from a spinneret having a size of 1050 x 3, it is cooled by a dry air side having a temperature range of 20 to 30 °C.
  • the cooled tow is coated with an oil agent in the oil sump, and the oil agent in the oil sump is an aqueous solution of the fiber treatment agent of the following composition: polyethylene glycol 1700, concentration 0.2%, triethanolamine dimethyl sulfate, concentration 0.15% , nonylphenol polyethylene oxide, concentration of 0.1%.
  • the tow is wound by a slow tractor, and the winding speed of the roller is 1000 m/min.
  • the fast traction roller rotates at 1800 r/min, the frequency is 40HZ, and then passes.
  • Belt conveyors Conveying, belt conveyor feed wheel speed 1000r/min, frequency is 40HZ.
  • the tow drawn from the belt conveyor was drawn by a multi-roll drafter, and the drafting medium was water at a water temperature of 75 °C. After drawing, the tow was crimped in a crimper, the number of crimps was 25 / 25 mm, and the crimped tow was dried by a steam dryer. After drying, the tow is placed in a silk container by a pendulum machine, and the tow of the biodegradable tobacco fiber of the present invention is obtained by packaging.
  • the copolymerized PBS substrate resin used in this embodiment is synthesized according to the method described in CN 01144133.X, and terephthalic acid is added to the reaction system of succinic acid and butanediol, wherein terephthalic acid accounts for binary in the system.
  • the molar ratio of the total amount of the acid was 18%, and then polymerization was carried out to obtain a desired copolymerized polybutylene succinate copolymer.
  • the copolymerized polylactic acid used in the present embodiment can be obtained by a copolymerization reaction in which a lactic acid and an ethylene glycol monomethyl ether monomer are mixed in a molar ratio of 99:1 by a polymerization reaction method disclosed in the invention patent application CN 200610016643.0.
  • the two resin materials after drying were added to a high-speed mixer and stirred uniformly, and blended and extruded into a ⁇ 65 twin-screw extruder with a length to diameter ratio of 28, and the first stage of the barrel temperature setting was 215 ° C.
  • the second section is 220 ° C
  • the third section is 230 ° C
  • the fourth section is 220 ° C
  • the fifth section is 215 ° C
  • the filter on the head melt filter is 100 mesh.
  • the extruding strand is pelletized by a pelletizer, dried by hot air on the line, and packaged to obtain a special material for the tobacco fiber of the present invention.
  • the above special material is spun on a ⁇ 65 melt spinning machine with a screw length to diameter ratio of 28, and the spinning is performed.
  • Machine screw temperature setting the first section is 230 ° C, the second section is 240 ° C, the third section is 250 ° C, the filter temperature is 245 ° C, the cabinet temperature is 245 ° C, the straight tube temperature is 245 ° C .
  • the cooled tow is coated with an oil agent in the oil sump, and the oil in the oil sump is an aqueous solution of the fiber treatment agent of the following composition: polyethylene glycol 1700, concentration 0.6%, triethanolamine dimethyl sulfate, concentration 0.2 %, nonylphenol polyethylene oxide, concentration 0.2%.
  • the tow is wound by a slow tractor, and the winding speed of the roller is 1500 m/min.
  • the steam box it enters the fast traction machine, and the speed of the fast traction roller is 2500 r/min, the frequency is 50HZ, and then passes.
  • Conveyor belt conveyor, belt conveyor feed wheel speed 1500r/min, frequency is 60HZ.
  • the tow drawn from the belt conveyor was drawn by a multi-roll drafter, and the drafting medium was water at a water temperature of 40 °C. After drawing, the tow was crimped in a crimper, the number of crimps was 22 / 25 mm, and the crimped tow was dried by a steam dryer. After drying, the tow is placed in a silk container by a pendulum machine, and the tow of the biodegradable tobacco fiber of the present invention is obtained by packaging.
  • the copolymerized PBS substrate resin used in this embodiment can be synthesized by referring to the method described in CN 01144133.X, and hexanediol is added to the reaction system of succinic acid and butanediol, wherein hexanediol accounts for binary in the system.
  • the molar ratio of the total amount of alcohol was 30%, and then polymerization was carried out to obtain a desired copolymer.
  • the copolymerized polylactic acid used in the present embodiment can be obtained by a copolymerization reaction in which a lactic acid and an ⁇ -caprolactone monomer are mixed at a molar ratio of 70:30 in accordance with a polymerization reaction method disclosed in the invention patent application CN200610016643.0.
  • the above-mentioned special material for tobacco fiber is spun on a ⁇ 60 melt spinning machine with a screw length to diameter ratio of 28, and the screw temperature setting mode of the spinning machine is: the first stage is 170 ° C, and the second stage is 185 ° C.
  • the third stage is 195 ° C, the filter temperature is 185 ° C, the cabinet temperature is 185 ° C, and the straight tube temperature is 185 ° C.
  • the cooled tow is coated with an oil agent in the oil sump, and the oil agent in the oil sump is an aqueous solution of the fiber surface treatment agent of the following composition: polyethylene glycol 1700, concentration 0.8%, triethanolamine dimethyl sulfate, concentration 0.1 %, nonylphenol polyethylene oxide, at a concentration of 0.1%.
  • the tow is wound by a slow tractor, and the winding speed of the roller is 200m/min ; then the traction steam box is used to enter the fast traction machine, the fast traction roller rotates at 400r/min, the frequency is 25HZ, and then passes through the belt.
  • Conveyor conveyor, belt conveyor feed wheel speed 200r / min, frequency is 30HZ.
  • the tow drawn from the belt conveyor was drawn by a multi-roll drafter, and the drafting medium was water at a water temperature of 85 °C. After drawing, the tow was crimped in a crimper, the number of crimps was 25 / 25 mm, and the crimped tow was dried by a steam dryer. After drying, the tow is placed in a silk container by a pendulum machine, and the tow of the biodegradable tobacco fiber of the present invention is obtained by packaging.
  • the copolymerized PBS resin used in this embodiment can be in accordance with the method described in CN 01144133.X. Synthesis, in the reaction system of succinic acid and butanediol, respectively, adding hexanediol and ethylene glycol, wherein the adipic acid accounts for 10% of the total amount of the dibasic acid in the system, and ethylene glycol accounts for the diol in the system. A total of 10% by mole of the molar ratio is then subjected to polymerization to obtain the desired copolymer.
  • copolymerized polylactic acid resin used in this embodiment can be referred to the invention patent application.
  • the polymerization reaction method disclosed in CN200610016643.0 is obtained by copolymerizing lactic acid with glycolide and ethylene glycol monomer in a molar ratio of 80:10:10.
  • the above two dried resins were added to a high speed mixer, and a weight of 0.1 kg of antioxidant 1010 was added to the mixer, and the weight was 0.2 kg of antioxidant 1076, 0.2 kg of 1,2-epoxy-3-benzene.
  • the oxypropane is fully stirred in a high-speed mixer.
  • the mixture was blended and extruded into a ⁇ 35 twin-screw extruder with a length to diameter ratio of 28, and the temperature of the barrel was set to 180 ° C for the first stage and 190 ° C for the second stage. It is 200 ° C, the fourth section is 205 ° C, the fifth section is 195 ° C, and the filter on the head melt filter is 130 mesh.
  • the extruded strand is pelletized by a pelletizer, dried by hot air on the line, and packaged to obtain a special material for the present invention.
  • the above-mentioned tobacco fiber special material is spun on a ⁇ 60 melt spinning machine with a screw length to diameter ratio of 28, and the temperature setting mode of the spinning machine screw is: 200 ° C in the first stage and 210 ° C in the second stage.
  • the third stage is 215 ° C
  • the filter temperature is 210 ° C
  • the tank temperature is 210 ° C
  • the straight pipe temperature is 210 ° C.
  • the cooled tow is coated with an oil agent in the oil sump, and the oil agent in the oil sump is an aqueous solution of the fiber surface treatment agent of the following composition: polyethylene glycol 1500, concentration 0.2%, triethanolamine dimethyl sulfate, concentration 0.15 %, nonylphenol polyethylene oxide, at a concentration of 0.1%.
  • the tow is wound by a slow tractor, and the winding speed of the roller is 700m min.
  • the fast traction roller rotates at 1200r/min, the frequency is 38HZ, and then passes through the belt conveyor. Conveying, belt conveyor feed wheel speed 700r/min, frequency is 40HZ.
  • the tow is pulled out from the belt conveyor and drafted by a multi-roll drafter.
  • the drafting medium is water, and the water temperature is 75 °C.
  • the tow was crimped in a crimper, the number of crimps was 24/25 mm, and the crimped tow was dried by a steam dryer. After drying, the tow is placed in a silk container by a pendulum machine, and the biodegradable tobacco fiber tow of the present invention is obtained by packaging.
  • the copolymerized PBS substrate resin used in the present embodiment was synthesized according to the method described in CN 01144133.X, and 1,3-propanediol was added to the reaction system of succinic acid and butanediol, wherein the amount of 1,3-propanediol was 15% of the molar ratio of the total amount of the diol in the system, followed by polymerization to obtain the desired copolymer.
  • the non-lactone monomer copolymer-modified polylactic acid base resin used in the embodiment can be mixed with the glycolide monomer in a molar ratio of 85:15 according to the polymerization method disclosed in the invention patent application CN 200610016643.0. It is obtained by copolymerization.
  • Agent 1425 (calcium bis(3,5-di-tert-butyl-4-hydroxybenzylphosphonate)) 0.2 kg, 0.1 kg of titanium oxide.
  • the raw materials were stirred uniformly in a high speed mixer.
  • the obtained mixture was blended and extruded into granules by a ⁇ 60 twin-screw extruder with an aspect ratio of 38.
  • the temperature setting of the barrel was 180 ° C in the first stage and 190 ° C in the second stage.
  • the third section is 200 ° C
  • the fourth section is 210 ° C
  • the fifth section is 200 ° C.
  • the extruding strand is pelletized by a pelletizer, dried by hot air on the line, and packaged to obtain a special material for the tobacco fiber of the present invention.
  • the above-mentioned special material for tobacco fiber is spun on a ⁇ 65 melt spinning machine with a screw length to diameter ratio of 28, and the screw temperature setting mode of the spinning machine is: 200 ° C in the first stage and 205 ° C in the second stage, The three sections are 215 ° C, the filter temperature is 205 ° C, the cabinet temperature is 205 ° C, and the straight tube temperature is 205 ° C. After being sprayed from a spinneret of size 1050x3, it is cooled by a dry air side with a temperature range of (20 ⁇ 10) °C.
  • the cooled tow is coated with an oil agent in the oil sump, and the oil agent in the oil sump is an aqueous solution of the fiber surface treatment agent of the following composition: polyethylene glycol 1700, concentration 0.2%, triethanolamine dimethyl sulfate, concentration 0.15 , nonylphenol polyepoxide, at a concentration of 0.1%.
  • the tow after passing through the oil sump is wound by a slow tractor, and the winding speed of the roller is 800m/min. Then, by pulling the steam box, it enters the fast traction machine, and the speed of the fast traction roller is 1500 r/min, the frequency is 38HZ, and then passes. Conveyor belt conveyor, belt conveyor feed wheel speed 800r/min, frequency is 40HZ.
  • the tow was pulled out from the belt conveyor and drafted by a multi-roll drafter.
  • the drafting medium was water and the water temperature was 65 °C.
  • the tow was crimped in a crimper, the number of crimps was 24 / 25 mm, and the crimped tow was dried by a steam dryer. After drying, the tow is placed in a silk container by a pendulum machine, and the tow of the biodegradable tobacco fiber of the present invention is obtained by packaging.
  • the copolymerized PBS resin used in this embodiment is synthesized according to the method described in CN 01144133.X, and terephthalic acid is added in the reaction system of succinic acid and butanediol, wherein terephthalic acid accounts for the total amount of dibasic acid in the system.
  • the molar ratio is 10%, and then polymerization is carried out to obtain the desired copolymer.
  • the above-mentioned nozzle has good biodegradability and fully meets the degradation standard according to ISO 14855, and the degradation rate reaches 96% in 90 days. Material biosafety meets tobacco fiber requirements.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biodiversity & Conservation Biology (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Artificial Filaments (AREA)
  • Cigarettes, Filters, And Manufacturing Of Filters (AREA)

Description

可生物降解的香烟用纤维及其制备方法 技术领域
本发明涉及一种烟用纤维材料及利用该纤维材料所制成的香烟过滤嘴 棒, 所述烟用纤维材料和香烟过滤嘴棒釆用以聚丁二酸丁二醇酯(PBS)聚 合物与聚乳酸聚合物组成的合金材料为基材树脂, 具有优良的生物降解性。 背景技术
香烟过滤嘴具有过滤、 阻挡和吸附烟气中烟碱、 焦油等有害成分的作 用, 好的过滤嘴材料除具有上述作用外, 还应该能改善烟气的口感, 减少 烟气对口腔的刺激及对人体健康的伤害。 作为一个比较成熟的技术, 目前 用于制造香烟过滤嘴的材料一般是以醋酸纤维素纤维和聚丙烯纤维为原 料, 从加工性能和最终生产过滤嘴的综合使用性能考虑, 以醋酸纤维素纤 维为首选, 在中高档卷烟中多使用醋酸纤维素纤维滤嘴。
香烟吸完后剩下的过滤嘴部分是要丢弃的, 而醋酸纤维素纤维和聚丙 烯纤维在自然环境中很难被生物降解, 香烟在背负有害人体健康的罪名的 同时还造成了对环境的污染。 人类不能完全离开香烟, 除了减少香烟本身 对人体的危害以外, 解决滤嘴丢弃带来的环境污染问题就成为香烟行业必 须面对的课题。
另一方面, 醋酸纤维素纤维是以优质木材为原料得到的化工产品, 从 木材到纤维素再到酯化的醋酸纤维素需要消耗大量的木材原料, 而生产环 节中也伴随着很多污染问题。
所以, 无论是从木材资源匮乏, 还是从改善环境污染角度出发, 寻找 替代现有的醋酸纤维素和聚丙烯纤维原料的可生物降解材料, 制造出可降 解的香烟过滤嘴棒, 至少在环境保护方面降低香烟生产所带来的危害, 是 香烟生产行业急需解决的问题。 香烟过滤嘴棒的生产工艺主要包括对原料实施熔融纺丝制成烟用丝 束, 以及增塑定型制棒最终加工成过滤嘴棒的工艺过程, 原料的可纺性能, 即, 是否容易纺成适合烟用的细旦纤维, 以及纤维丝束的牵伸性能和粘合 效果, 最终都将影响滤棒和滤嘴的综合性能, 包括滤过性能, 以及外观、 硬度和空阻等机械性能。 醋酸纤维素纤维就是由于这些性质的优异, 才被 选择成为香烟过滤嘴的主要加工原料。 在寻找其替代材料时, 既具有生物 降解性, 还必须满足过滤嘴棒加工要求, 是缺一不可的二个条件。
乳酸类聚合物,例如聚乳酸(PLA)或相关共聚物在自然条件下或人体 条件下可完全生物降解, 早已是公知的可降解材料。 中国专利申请 200610131699.0和 200710055310.3中公开了一种利用乳酸类聚合物树脂制 造香烟过滤嘴丝束纤维以及烟用滤棒的技术。 虽然该在先公开的专利申请 教导了乳酸类聚合物可以用于香烟过滤嘴的加工, 且与已经商业化的醋酸 纤维素滤棒和聚丙烯滤棒相比, 所述聚乳酸香烟滤棒不仅具有可完全生物 降解和生产成本低廉的优势, 而且制成的滤棒在滤过性能和物理机械性能 方面都显示良好的结果, 但是从其说明书记载内容可以看到, 该技术方案 中采用的主体树脂是聚乳酸的一个规格或多个规格的混合物, 或是丙交酯 与己内酯、 丙交酯, 或丙交酯与己内酯和乙交酯的共聚物, 这些树脂都是 由内酯聚合而成, 制备的聚合物是无规聚合物, 这种材料脆性大, 易水解, 加工时要求材料的含水量低于万分之零点五, 而且这种材料耐热性能差, 热变型温度很低 (只有 58°C ) 。 由于烟用丝束需要一定的柔性和较好的形 变, 以及要求具有较高的耐热性, 对于香烟企业, 推广生产上述在先公开 的乳酸类聚合物香烟嘴棒原料仍有很多不尽人意和有待改进的地方。
聚丁二酸丁二醇酯(PBS)是一种可完全生物降解的聚合物, 它可以在 细菌或酶的作用下最终降解为二氧化碳和水等物质, 所以目前开始在塑料 领域使用, 以缓解传统塑料对环境造成的污染。 根据目前的研究和报道, PBS 塑料可制备膜类包装材料, 例如可降解塑料袋、 一次性餐具的片材原 料等; PBS塑料还可以在农用地膜方面以及一些日用杂品方面应用。
中国专利 CN 200610026044.7中公开了一种可生物降解的复合及改性 树脂及其制备方法以及该复合改性树脂的用途。 该专利提供的可生物降解 的复合及改性树脂由 10-73.5%聚丁二酸丁二醇酯 (PBS) 、 5-60%聚乳酸 (PLA)、 5-35%变性淀粉、 9-29.85%活化无机填料和 0.15-1.5%添加助剂组 成, 经设定条件的螺杆挤出造粒, 可制备成吹塑专用树脂。 根据该专利提 供的方案,将 PBS和 PLA按照特定的比例复合, 并在确定的加工助剂作用 下, 具有很好的耐热性和刚性, 适合作为吹塑专用树脂, 并且由于其生物 可降解性, 可以取代现有塑料产品。 另一方面, 纺织行业也有关于 PBS与 PLA混合纺丝的研究,例如将 PLA和 PBS颗粒直接混合纺制复合纤维,但 由于 PLA和 PBS相容性和熔融温度的较大差别,这种方法即使能实施, 也 只能纺制纤维直径大于 15μ (牵引取向后) 的粗纤维, 还不能实现利用 PBS PLA合金材料纺制较细的具有应用价值的纤维。
由于香烟过滤嘴的特殊要求,在本发明以前,有关 PBS或 PBS与 PLA 复合材料及其纺制的能用于香烟过滤嘴的材料应用还没有记载。 发明内容
本发明主要解决的技术问题在于提供一种可生物降解的烟用纤维, 所 用原料为聚丁二酸丁二醇酯和聚乳酸复合的高分子共混物, 本发明的烟用 纤维具有与目前通用的香烟过滤嘴用纤维素二醋酸酯相当的吸附性能和加 工性能, 可用于制备香烟过滤嘴棒及香烟产品, 过滤嘴丢弃后可被环境中 微生物分解, 利于对环境的保护。
本发明还提供了制造上述可生物降解的烟用纤维的制备方法, 针对聚 丁二酸丁二醇酯与聚乳酸复合产品的性质, 摸索和提出了对制造工艺的条 件和参数的确定, 确保所制造的纤维性能达到目前通用的香烟过滤嘴使用 的标准。 本发明提供了一种可生物降解的烟用纤维材料,其原料组成为 l-99wt% 的聚丁二酸丁二醇酯聚合物、 l-99wt%的聚乳酸聚合物和 0-3wt%的稳定剂, 且为所述组分经过挤出机挤出共混的产物, 该烟用纤维是所述原料经熔融 紡丝工艺加工而成。
根据本发明的方案, 本案申请人将二种均具有生物降解性的聚合物材 料有机地复合后作为基本原料, 对加工工艺进行适当调整和改变, 提供一 种烟用纤维材料, 可以生产香烟滤棒和过滤嘴, 进而取代现有的醋酸纤维 素或丙烯酸纤维用于香烟过滤嘴, 设置这种过滤嘴的香烟在综合性能达到 醋酸纤维素过滤嘴香烟的水平同时, 该过滤嘴在丢弃后能尽快被降解, 应 用在香烟行业, 对于保护环境将产生更显著的社会效益。 申请人的研究结 果显示, 在聚乳酸材料中加入适量的聚丁二酸丁二醇酯(PBS), 可以有效 地提高聚乳酸的韧性和耐水性。而在 PBS材料中加入适量的 PLA材料, 也 利于后期过滤嘴棒的加工制作。 所以, 根据本发明的优选方案, 所述原料 组成中, 聚丁二酸丁二醇酯聚合物和聚乳酸聚合物的含量分别为 5-95wt%。
结合烟用纤维和过滤嘴棒的特定技术要求, 发明人的研究结果显示, 本发明的烟用纤维和过滤嘴原料可以采用完全均聚的聚丁二酸丁二醇酯和 聚乳酸, 也可以使用聚合物分子链中存在适当其它单体聚合链节的聚合物 材料, 以利于提高原料的加工性能和最终滤棒和过滤嘴产品的相关指标。 具体地, 本发明提供的用于制造烟用纤维的复合材料可以满足以下定义之 一或全部:
所述聚丁二醇丁二酸酯聚合物为分子链中丁二酸丁二醇酯链节的量不 少于该聚合物总链节数的 70%的高分子聚合物,且其重均分子量为 5-35万, 分散指数 1.2-3.0;
所述聚乳酸聚合物为分子链中乳酸链节的不少于该聚合物总链节数的 70%的高分子聚合物, 且其重均分子量为 5-30万, 分散指数 1.2-3.0。
根据本发明的方案, 所述聚丁二醇丁二酸酯聚合物的分子链中丁二酸 丁二醇酯链节的量不少于总链节数的 70%, 其余为非丁二酸丁二醇酯链节 的二元酸二元醇聚合链节。
根据本发明的优选方案, 当所述聚丁二酸丁二醇酯聚合物分子链含有 除丁二酸丁二醇酯以外的聚合链节时, 二元酸选自 C2-C12 的脂肪族二元 酸、芳香族二元酸或它们的混合物; 二元醇选自 C2-C12的脂肪族二元醇或 它们的混合物。
作为非限制性示例, 所述二元酸包括乙二酸、 1,2—丙二酸、 1,3—丙二 酸、 戊二酸、 己二酸、 壬二酸、 癸二酸、 十一碳二元酸、 十二碳二元酸、 富马酸、 马来酸、 苯二甲酸、 萘二甲酸等或其混合物; 所述二元醇包括乙 二醇、 丙二醇、 戊二醇、 己二醇、 癸二醇等或其混合物。 由于这些二元酸 和 /或二元醇单体的引入, 在上述聚丁二酸丁二醇酯聚合物分子链中包含了 除丁二酸丁二醇酯外的二元酸二元醇聚合链节, 可以理解, 这些聚合链节 是来自体系中二元酸与二元醇形成的聚合酯链节。
更优选地, 所述形成除丁二酸丁二醇酯以外的聚合链节的二元酸选自 乙二酸、 丙二酸、 己二酸、 富马酸、 苯二甲酸等或它们中一种以上的混合 物, 二元醇选自乙二醇、 丙二醇或己二醇等或它们中一种以上的混合物。
根据本发明的方案, 所述聚乳酸聚合物的分子链中乳酸链节的量不少 于该聚合物总链节数的 70%, 其余为能与乳酸进行共聚的单体链节。
根据本发明的优选方案, 当所述聚乳酸聚合物的分子链上含有除乳酸 链节以外的单体链节时, 所述单体可包括乙交酯、 ε—己内酯、 乙二醇、 丙 二醇、 乙醇酸、 或乙二醇单甲醚等、 或其任意的混合物。
上述用于制造烟用纤维的二种高分子聚合物原料均可按照公知的方法 制备或商购得到。
例如,中国发明专利 01144133.X中公开了一种利用丁二酸和丁二醇为 单体原料, 经常压酯化 (缩合)再减压聚合制备聚丁二酸丁二醇酯 (PBS) 的方法, 中国专利申请 200710049370.4中也公开了一种制备高分子量 PBS 的方法, 按照这些现有技术的方法制备得到的聚丁二酸丁二醇酯聚合物均 可满足本发明原料要求, 因此将上述公开内容并入本发明。 对于含有所述 二元酸二元醇聚合链节的 PBS聚合物, 也可以通过聚合反应、 扩链反应等 化学过程实现非常方便地制备得到。 例如按照以上文献记载的方法, 在丁 二酸与丁二醇的缩合反应体系中加入确定比例的选定二元酸和 /或二元醇, 经聚合反应即可使聚合产物中含有所要求比例的聚合物链节。
另一种聚合物材料, 聚乳酸或含选定单体共聚链节的聚乳酸聚合物也 可以按照公知方法制备或来自商购, 前者已经是普遍公知并且使用多年的 聚合物材料, 是一种可以方便商购或按照成熟方法合成得到的聚合物产品, 而含选定单体共聚链节的聚乳酸聚合物则可以按照很多已经公开的方法使 按一定比例混合的单体原料聚合得到, 从而很容易地制备具有所要求的链 节比例的共聚产物, 也可以在公开文献及相关聚合反应的基础理论教导下 通过聚合反应、 扩链反应等化学过程实现非常方便地制备得到。 例如按照 发明专利申请 CN 200610016643.0中公开的聚合反应方法,将乳酸与所选择 确定的聚合单体按照要求的比例实现共聚。
本发明提供的烟用纤维材料所利用的原料中, 除上述纯均聚或含有不 同共聚链节的 PBS聚合物和聚乳酸聚合物材料 (本发明均称为聚丁二酸丁 二醇酯聚合物和聚乳酸聚合物) 外, 还可以添加适当的稳定剂, 所述的稳 定剂指能提高 PBS和聚乳酸及共聚物在加工、 储存和使用过程中稳定性的 物质, 包括但不限于热稳定剂、 光稳定剂和抑酸剂, 例如可以包括磷酸、 亚磷酸、 次亚磷酸、 焦磷酸、 磷酸铵、 磷酸三甲酯、 磷酸二甲酯、 磷酸三 苯酯、 磷酸二苯酯、 亚磷酸三苯酯、 亚磷酸二苯酯、 亚磷酸铵、 磷酸二氢 铵、 抗氧剂 1010 (四 [亚甲基 3- (3',5'-二叔丁基 -4-羟苯基)丙酸酯]甲垸) 、 抗氧剂 1222 (3,5-二叔丁基 -4-羟苯基磷酸二乙酯) 、 抗氧剂 1076 (β- (3,5- 二叔丁基 -4-羟基苯基)丙酸正十八碳醇酯) 、 抗氧剂 1425 (双 (3,5-二叔丁 基 -4-羟基苄基磷酸单乙酯)钙) 、 长链含磷硫化合物 Η— MOD、 环氧聚丁 二烯、 环氧亚麻子油、 环氧大豆油、 1,2-环氧基 -3-苯氧基丙垸、 氢氧化镁、 氢氧化铝、 氧化钙、 氨基树脂等或它们的任意混合物。 优选地, 所述稳定 剂包括磷酸三甲酯、磷酸三苯酯、亚磷酸三苯酯、抗氧剂 1010、抗氧剂 1076、 H— MOD、环氧亚麻子油、环氧大豆油、 1,2-环氧基 -3-苯氧基丙烷、氢氧化 镁、 氨基树脂等或它们的任意混合物。
发明人的研究结果显示, 满足以上定义的聚丁二酸丁二醇酯聚合物和 聚乳酸聚合物的复合材料具有良好的成型加工性能, 因而可以在目前聚丙 烯烟用纤维纺制工艺和设备基础上通过一定的工艺研究调整实现制造满足 香烟过滤嘴标准的烟用纤维, 尤其是单丝直径小于 20微米的的烟用纤维。 该纤维可以制备可生物降解的香烟过滤嘴棒以及相应的香烟产品, 吸烟者 丢弃的过滤嘴在自然环境中能短时间内被分解, 在满足香烟生产的同时也 解决了目前香烟遗弃物对环境的污染影响。
制造本发明可生物降解的烟用纤维的工艺过程可以包括: 将干燥的原 料混合均匀, 用螺杆挤出机实施共混并挤出制粒, 制粒时挤出机螺筒温度 在 140-230°C, 挤出后切粒, 干燥, 得到的烟用纤维专用料;
对所制造的烟用纤维专用料进行熔融纺丝, 制成可生物降解的烟用纤 维丝束。
优选地,挤出制粒时选用的挤出机设有熔体过滤装置并对粒径大于 100 目的颗粒进行过滤。 SP, 在挤出过程优选在挤出机中设置带 100 目以上滤 网的过滤装置。 根据本发明的具体实施方案, 对所制造的烟用纤维专用料 进行熔融纺丝, 制成可生物降解的烟用纤维丝束的过程包括如下步骤: 将上述制粒得到的专用料进行熔融纺丝时, 设定纺丝机的螺杆温度 170°C-250°C , 使挤出物料流经过滤器、箱体、计量泵和直管后, 通过喷丝板 喷丝, 该过程中控制过滤器温度 170°C-250°C, 箱体温度 170°C-25(TC, 直管 温度 170°C-250°C,然后对喷出的丝以干燥空气冷却,冷却温度为 0°C-50°C ; 冷却后的丝束经涂覆油剂后, 进行慢牵引机绕卷、 蒸汽箱牵引、 快牵 引机绕卷以及皮带输送机的卷绕牵引, 油剂为浓度 0.8%-1%的纤维表面处 理剂(例如: 聚乙二醇、 乙醇胺甲酯、 壬基酚类表面活性剂等) 的水溶液, 慢牵引机的辊卷绕速度 200-1500m/min, 快牵引机的辊转速 400-2500r/min, 频率 25-50HZ, 皮带输送机喂入轮速度 200-1500 r/min, 频率为 30-60HZ; 将从皮带输送机牵引出来的丝束在水温为 40°C-85°C的水槽中水浴牵 伸, 然后经卷曲和干燥定型, 得到的丝束即为所述可生物降解的烟用纤维 丝束。
根据本发明的制造工艺, 原料应先干燥, 优选将原料分别干燥至含水 率低于 lwt%。, 再挤出制粒。具体地, 对原料的干燥条件可以确定为: 聚丁 二酸丁二醇酯聚合物于 50-85°C干燥 2-3 小时, 聚乳酸聚合物和稳定剂于 40-60°C干燥 4-8小时, 即可满足要求。
以上制粒和纺丝工艺中, 各参数的设定可以在所定义范围内根据物料 的具体性质以及设备运转情况进行调整。 原料的挤出制粒时, 一般可使用 双螺杆挤出机, 根据物料的熔融特性在上述温度范围内分段设定合适的螺 筒温度, 挤出前熔体优选通过熔体过滤装置过滤, 挤出后切粒, 以提供制 造香烟过滤嘴棒用可降解纤维的专用料。
同样地,根据所采用的 PBS聚合物和聚乳酸或它们的共聚酯原料的性 质, 本发明有针对性地确定了制造烟用纤维材料的方法, 其具体方案可以 根据物料选择情况适当调整, 例如, 熔融纺丝工序中, 其中, 熔融纺丝 工序中, 挤出机螺杆温度 180-21CTC ; 对喷出丝的冷却温度为 10-5CTC ; 卷绕牵引工艺中, 慢牵引机的辊卷绕速度 400-900 m/min; 快牵引机的辊 转速为 1000-2000 r/min, 频率为 35-40 HZ; 皮带输送机喂入轮速度为 500-1000 r/min, 频率为 38-42 HZ。
上述混料制粒、 纺丝及卷绕牵伸的具体操作和设备以及没有特别说明 的处理剂均为烟用丝束生产中的公知和常规技术。
利用本发明提供的聚丁二酸丁二醇酯聚合物和聚乳酸聚合物组成的合 金材料制造的烟用过滤嘴棒用纤维丝束具有良好的生物降解性能, 纤维材 料在正常的储存和运输条件下可以保证在 3年内力学、 外观等方面性能基 本没有变化, 完全符合香烟要求。 本发明的可降解烟用纤维较现有聚丙烯烟用纤维和纤维素醋酸酯纤维 具有显著优点:
1 具有生物降解性能, 更加环保;
2对烟气具有更好的吸附性能;
3 原料来源广泛, 既可采用传统的化石基资源, 又可采用生物质通过 生物技术得到, 既避免了醋酸纤维素嘴棒依赖木浆的资源问题, 又可真正 实现源自自然 (生物质) 又回归自然 (降解) 的绿色生产。 综上所述,本发明采用 PBS+PLA的合金原料制造的嘴棒用纤维丝束在 质量和性质上均能达到烟用嘴棒生产的行业标准, 可用于加工成香烟过滤 嘴棒及香烟, 使用后的废弃过滤嘴能实现完全生物降解, 与目前的醋酸纤 维嘴棒相比, 从环保角度具有不可比拟的优势; 另一方面, 本发明提供的 可生物降解嘴棒利用的 PBS、 PLA或它们的共聚酯原料可以通过化学方法 合成制备, 原料来源丰富, 不再需要进口优质木材, 更利于工业化生产。 所以, 本发明的实施完全可以取代目前使用的醋酸纤维和聚丙烯纤维, 同 时具有非常广阔的经济效益和社会效益。 具体实施方案
以下通过具体实施例进一步详细说明本发明的实施过程以及所产生的 有益效果, 以帮助阅读者更好地理解本发明, 但不能对本发明的可实施范 围构成任何限定。
除特别说明外, 本发明权利要求书和说明书中出现的比例或浓度均应 理解为重量比或以重量为基准的百分浓度, 以下实施例中所用稳定剂均为 食品添加剂级。 实施例 1
称取 50公斤重均分子量为 (15±1 )万, 分散指数为 1.7的均聚丁二酸 丁二醇酯 (PBS) , 在 65°C烘箱中烘干 2小时。 称取 49公斤重均分子量为
( 15±1 )万, 分散指数为 1.5的均聚聚乳酸, 在 55°C烘箱中烘干 5小时。 二个原料干燥后都加入到高速搅拌机中,并在搅拌机中加入 0.5公斤磷酸三 苯酯和 0.5公斤抗氧剂 1222(3,5-二叔丁基 -4-羟苯基磷酸二乙酯), 高速搅拌 均匀。
将搅拌后的混合物料在长径比为 32的 Φ57双螺杆挤出机上共混并挤出 制粒, 螺筒温度设定第一段为 190°C, 第二段为 200°C, 第三段为 200°C, 第四段为 200°C, 第五段为 195°C, 机头熔体过滤器上滤网为 100目。 挤出 料条用切粒机切粒, 在线热风干燥, 包装, 得到本发明烟用纤维专用料。
将上述烟用纤维专用料在螺杆长径比为 28的 Φ65熔融纺丝机上进行纺 丝, 纺丝机螺杆温度设定是: 第一段为 190°C, 第二段为 205°C, 第三段为 210°C , 过滤器温度 205°C, 箱体温度 205°C, 直管温度 205°C, 从规格为 1050x3的喷丝板喷出后用温度范围为 (15士5) °C的干燥空气侧吹风冷却。
上述冷却后的丝束在上油槽中涂覆油剂, 上油槽中油剂为以下组成的 纤维表面处理剂水溶液: 聚乙二醇 1700, 浓度为 0.2%, 三乙醇胺硫酸二甲 酯, 浓度为 0.15, 壬基酚聚环氧乙烷, 浓度为 0.1%。 经过上油槽后丝束通 过慢牵引机绕卷, 辊卷绕速度为 800m/min; 然后通过牵引蒸汽箱, 进入快 牵引机绕卷, 快牵引辊转速 1500r/min, 频率 38HZ, 然后通过皮带输送机 输送, 皮带输送机喂入轮速度 800r/min, 频率为 40HZ。
从皮带输送机牵引出来的丝束用多辊牵伸机牵伸, 牵伸介质为水, 水 温为 65°C。 牵伸后丝束在卷曲器中进行卷曲, 卷曲数为 24个 /25mm, 卷曲 后的丝束通过蒸气干燥器干燥。 干燥后通过摆丝机将丝束在盛丝容器中摆放好, 打包即得到本发明的 可生物降解烟用纤维(丝束) 。
上述纤维具有良好的生物降解性能,按照 ISO 14855要求完全达到降解 标准要求, 90天降解率达到 91%。 材料生物安全性符合烟用纤维要求。 实施例 2
称取 30公斤重均分子量为 (10±1 )万, 分散指数为 1.2, 分子链上含 有 18% (链节数) 随机分布的对苯二甲酸丁二醇酯链节的共聚聚丁二酸丁 二醇酯 (PBS),在 60 °C烘箱中烘干 3小时。称取 68公斤重均分子量为( 10±1 ) 万, 分散指数为 1.2, 分子链上含有 1% (链节数) 随机分布的乙二醇单甲 醚链节的共聚聚乳酸, 在 45°C烘箱中烘干 8小时。 干燥后将两种树脂原料 都加入到高速搅拌机中, 并在搅拌机中加入 1公斤长链含磷硫化合物 H— MOD和 1公斤亚磷酸三苯酯, 高速搅拌均匀。 上述混合料在长径比为 28 的 Φ65双螺杆挤出机上共混并挤出制粒, 螺筒温度设定第一段为 195°C, 第二段为 205°C, 第三段为 215°C, 第四段为 210°C, 第五段为 205°C, 机 头熔体过滤器上滤网为 120 目。 挤出料条用切粒机切粒, 在线热风干燥, 包装, 得到本发明烟用纤维专用料。
将上述烟用纤维专用料在螺杆长径比为 28的 Φ65熔融纺丝机上进行纺 丝, 纺丝机螺杆温度设定为: 第一段为 205°C, 第二段为 210°C, 第三段为 225 °C , 过滤器温度 215°C, 箱体温度 215°C, 直管温度 215°C。 从规格为 1050x3的喷丝板喷出后用温度范围为 20〜30°C的干燥空气侧吹风冷却。
上述冷却后的丝束在上油槽中涂覆油剂, 上油槽中油剂为以下组成的 纤维处理剂水溶液: 聚乙二醇 1700, 浓度为 0.2%, 三乙醇胺硫酸二甲酯, 浓度为 0.15%, 壬基酚聚环氧乙烷, 浓度为 0.1%。 经过上油槽后丝束通过 慢牵引机绕卷, 辊卷绕速度为 1000 m/min; 然后通过牵引蒸汽箱, 进入快 牵引机绕卷, 快牵引辊转速 1800 r/min, 频率 40HZ, 然后通过皮带输送机 输送, 皮带输送机喂入轮速度 1000r/min, 频率为 40HZ。
从皮带输送机牵引出来的丝束用多辊牵伸机牵伸, 牵伸介质为水, 水 温为 75°C。 牵伸后丝束在卷曲器中进行卷曲, 卷曲数为 25个 /25mm, 卷曲 后的丝束通过蒸气干燥器干燥。 干燥后通过摆丝机将丝束在盛丝容器中摆 放好, 打包即得到本发明的可生物降解烟用纤维丝束。
本实施例所采用的共聚 PBS基材树脂参照 CN 01144133.X中记载的方 法合成, 在丁二酸与丁二醇的反应体系中加入对苯二甲酸, 其中对苯二甲 酸占体系中二元酸总量的摩尔比为 18%, 然后进行聚合反应, 得到所要求 的共聚聚丁二酸丁二醇酯共聚物。
本实施例所采用的共聚聚乳酸可参照发明专利申请 CN 200610016643.0 中公开的聚合反应方法, 将乳酸与乙二醇单甲醚单体按照 99 : 1的摩尔比混合发生共聚反应而得到。
上述纤维具有良好的生物降解性能,按照 ISO 14855要求完全达到降解 标准要求, 90天降解率达到 89%。 材料生物安全性符合烟用纤维要求。 实施例 3
称取 70公斤重均分子量为 35万, 分散指数为 3.0, 分子链上含有 30% (链节数)随机分布的丁二酸己二醇酯链节的共聚聚丁二酸丁二醇酯 (PBS ) 在 75°C烘箱中烘干 3小时。 称取 30公斤重均分子量为 30万, 分散指数为 3.0, 分子链上含有 30% (链节数) 随机分布的 ε—己内酯链节的共聚聚乳 酸, 在 50°C烘箱中烘干 8小时。 将干燥后的两种树脂材料都加入到高速搅 拌机中搅拌均匀, 在长径比为 28的 Φ65双螺杆挤出机上共混并挤出制粒, 螺筒温度设定第一段为 215°C, 第二段为 220°C, 第三段为 230°C, 第四段 为 220°C, 第五段为 215°C, 机头熔体过滤器上滤网为 100目。 挤出料条用 切粒机切粒, 在线热风干燥, 包装, 得到本发明烟用纤维专用料。
将上述专用料在螺杆长径比为 28的 Φ65熔融纺丝机上进行纺丝,纺丝 机螺杆温度设定: 第一段为 230°C, 第二段为 240°C, 第三段为 250°C, 过 滤器温度 245°C,箱体温度 245°C, 直管温度 245°C。从规格为 1250>< 1的喷 丝板喷出后用温度范围为 20〜40°C的干燥空气侧吹风冷却。
冷却后的丝束在上油槽中涂覆油剂, 上油槽中的油剂为以下组成的纤 维处理剂水溶液: 聚乙二醇 1700, 浓度为 0.6%, 三乙醇胺硫酸二甲酯, 浓 度为 0.2%, 壬基酚聚环氧乙烷, 浓度为 0.2%。经过上油槽后丝束通过慢牵 引机绕卷, 辊卷绕速度为 1500 m/min; 然后通过牵引蒸汽箱, 进入快牵引 机绕卷, 快牵引辊转速 2500 r/min, 频率 50HZ, 然后通过皮带输送机输送, 皮带输送机喂入轮速度 1500r/min, 频率为 60HZ。
从皮带输送机牵引出来的丝束用多辊牵伸机牵伸, 牵伸介质为水, 水 温为 40°C。 牵伸后丝束在卷曲器中进行卷曲, 卷曲数为 22个 /25mm, 卷曲 后的丝束通过蒸气干燥器干燥。 干燥后通过摆丝机将丝束在盛丝容器中摆 放好, 打包即得到本发明的可生物降解烟用纤维丝束。
本实施例所采用的共聚 PBS基材树脂可参照按照 CN 01144133.X中记 载的方法合成, 在丁二酸与丁二醇的反应体系中加入己二醇, 其中己二醇 占体系中二元醇总量的摩尔比为 30%, 然后进行聚合反应, 得到所要求的 共聚物。
本实施例所采用的共聚聚乳酸可按照发明专利申请 CN200610016643.0 中公开的聚合反应方法, 将乳酸与 ε-己内酯单体按照 70 : 30的摩尔比混 合发生共聚反应而得到。
上述纤维具有良好的生物降解性能,按照 ISO 14855要求完全达到降解 标准要求, 90天降解率达到 91%。 材料生物安全性符合烟用纤维要求。 实施例 4
称取 10公斤重均分子量为 5万, 分散指数为 2.4, 分子链上含有 10% (链节数) 随机分布的含己二酸的酯链节和 10% (链节数) 随机分布的含 乙二醇的酯链节的共聚聚丁二酸丁二醇酯 (PBS) , 在 60°C烘箱中烘干 3 小时。称取 97公斤重均分子量为 5万,分散指数为 1.3的分子链上含有 10% (链节数) 随机分布的乙交酯和 10% (链节数) 随机分布的乙二醇的共聚 聚乳酸, 在 45°C烘箱中烘干 8小时。 称取 1.5公斤氢氧化镁, 0.5公斤氧化 钛, 在 75°C烘箱中烘干 2小时。 干燥后将两种树脂和助剂都加入到高速搅 拌机中,并在搅拌机中加入重量为 0.2公斤的 1010,重量为 0.3公斤的 1076, 搅袢均匀。混合物料用长径比为 36的 Φ60双螺杆挤出机上共混并挤出制粒, 螺筒温度设定第一段为 140°C, 第二段为 160°C, 第三段为 175°C, 第四段 为 185°C, 第五段为 175°C, 机头熔体过滤器上滤网为 150目。 挤出料条用 切粒机切粒, 经在线热风干燥, 包装, 得到本发明烟用纤维专用料。
将上述烟用纤维专用料在螺杆长径比为 28的 Φ60熔融纺丝机上进行纺 丝, 纺丝机螺杆温度设定方式为: 第一段为 170°C, 第二段为 185°C, 第三 段为 195°C, 过滤器温度 185°C, 箱体温度 185°C, 直管温度 185°C。 从规 格为 2210x4的喷丝板喷出后,用温度范围为 10〜20°C的干燥空气侧吹风冷 却。
上述冷却后的丝束在上油槽中涂覆油剂, 上油槽中油剂为以下组成的 纤维表面处理剂水溶液: 聚乙二醇 1700, 浓度为 0.8%, 三乙醇胺硫酸二甲 酯, 浓度为 0.1%, 壬基酚聚环氧乙烷, 浓度为 0.1%。 经过上油槽后丝束通 过慢牵引机绕卷, 辊卷绕速度为 200m/min; 然后通过牵引蒸汽箱, 进入快 牵引机绕卷, 快牵引辊转速 400r/min, 频率 25HZ, 然后通过皮带输送机输 送, 皮带输送机喂入轮速度 200r/min, 频率为 30HZ。
从皮带输送机牵引出来的丝束用多辊牵伸机牵伸, 牵伸介质为水, 水 温为 85°C。 牵伸后丝束在卷曲器中进行卷曲, 卷曲数为 25个 /25mm, 卷曲 后的丝束通过蒸气干燥器干燥。 干燥后通过摆丝机将丝束在盛丝容器中摆 放好, 打包即得到本发明的可生物降解烟用纤维丝束。
本实施例所采用的共聚 PBS树脂可按照 CN 01144133.X中记载的方法 合成, 在丁二酸与丁二醇的反应体系中分别加入己二醇和乙二醇, 其中己 二酸占体系中二元酸总量的摩尔比 10%, 乙二醇占体系中二元醇总量的摩 尔比的 10%, 然后进行聚合反应, 得到所要求的共聚物。
本实施例所采用的共聚聚乳酸树脂可参照发明专利申请
CN200610016643.0中公开的聚合反应方法, 将乳酸与乙交酯和乙二醇单体 按照 80 : 10 : 10的摩尔比混合发生共聚反应而得到。
上述纤维具有良好的生物降解性能,按照 ISO 14855要求完全达到降解 标准要求, 90天降解率达到 97%。 材料生物安全性符合烟用纤维要求。 实施例 5
称取 89.5公斤重均分子量为(25±2)万, 分散指数为 1.4, 分子链上含 有 15% (链节数)随机分布的丁二酸 1,3—丙二醇酯链节的共聚聚丁二酸丁 二醇酯, 在 60°C烘箱中供干 3小时。 称取 10公斤重均分子量为 18万, 分 散指数为 1.5, 分子链上含有 15% (链节数)随机分布的乙交酯链节的共聚 聚乳酸, 在 50°C烘箱中烘干 6小时。 将上述两种干燥后的树脂加入到高速 搅拌机中,并向搅拌机中加入重量为 0.1公斤抗氧剂 1010,重量为 0.2公斤 抗氧剂 1076, 0.2公斤 1,2-环氧基 -3-苯氧基丙烷,在高速搅拌机中充分搅拌 均勾。 该混合物料用长径比为 28的 Φ35双螺杆挤出机上共混并挤出制粒, 螺筒温度设定方式: 第一段为 180°C, 第二段为 190 °C, 第三段为 200°C, 第四段为 205°C, 第五段为 195°C, 机头熔体过滤器上滤网为 130目。 挤出 料条用切粒机切粒, 在线热风干燥, 包装, 得到的本发明烟用专用料。
将上述烟用纤维专用料在螺杆长径比为 28的 Φ60熔融纺丝机上进行纺 丝, 纺丝机螺杆的温度设定方式: 第一段为 200°C, 第二段为 210°C, 第三 段为 215°C, 过滤器温度 210°C, 箱体温度 210°C, 直管温度 210°C。 从规 格为 2210x4的喷丝板喷出后用温度范围为(15±5) °C的干燥空气侧吹风冷 却。 上述冷却后的丝束在上油槽中涂覆油剂, 上油槽中油剂为以下组成的 纤维表面处理剂水溶液: 聚乙二醇 1500, 浓度为 0.2%, 三乙醇胺硫酸二甲 酯, 浓度为 0.15%, 壬基酚聚环氧乙烷, 浓度为 0.1%。 经过上油槽后丝束 通过慢牵引机绕卷, 辊卷绕速度为 700m min; 然后通过牵引蒸汽箱, 进入 快牵引机绕卷, 快牵引辊转速 1200r/min, 频率 38HZ, 然后通过皮带输送 机输送, 皮带输送机喂入轮速度 700r/min, 频率为 40HZ。从皮带输送机牵 引出来等丝束用多辊牵伸机牵伸, 牵伸介质为水, 水温为 75°C。 牵伸后丝 束在卷曲器中进行卷曲, 卷曲数为 24个 /25mm, 卷曲后的丝束通过蒸气干 燥器干燥。 干燥后通过摆丝机将丝束在盛丝容器中摆放好, 打包即得到本 发明的可生物降解烟用纤维丝束。
本实施例所采用的共聚 PBS基材树脂按照 CN 01144133.X中记载的方 法合成, 在丁二酸与丁二醇的反应体系中加入 1,3-丙二醇, 其中 1,3-丙二醇 的量为体系中二元醇总量的摩尔比的 15%, 然后进行聚合反应, 得到所要 求的共聚物。
本实施例所采用的非内酯单体共聚改性聚乳酸基材树脂可参照发明专 利申请 CN 200610016643.0中公开的聚合反应方法,将乳酸与乙交酯单体按 照 85 : 15的摩尔比混合发生共聚反应而得到。
上述纤维具有良好的生物降解性能,按照 ISO 14855要求完全达到降解 标准要求, 90天降解率达到 93%。 材料生物安全性符合烟用纤维要求。 实施例 6
称取 94.5公斤重均分子量为 16万, 分散指数为 2.1的均聚乳酸, 在 50°C 供箱中烘干 8小时。 称取 5公斤重均分子量为 15万, 分散指数为 1.8, 分 子链上含有 10% (链节数) 随机分布的对苯二甲酸丁二醇酯链节的共聚聚 丁二酸丁二醇酯 (PBS) , 在 70°C烘箱中烘干 2小时。 将两种树脂干燥后 加入到高速搅拌机中,并在高速搅拌机中加入亚磷酸三乙酯 0.2公斤,抗氧 剂 1425 (双 (3,5-二叔丁基 -4-羟基苄基磷酸单乙酯)钙) 0.2 公斤, 氧化钛 0.1公斤。 在高速搅拌机中将所述原料搅拌均匀。 将得到的混合物料用长径 比为 38的 Φ60双螺杆挤出机共混并挤出制粒, 螺筒温度设定方式,第一段 为 180°C, 第二段为 190°C, 第三段为 200°C, 第四段为 210°C, 第五段为 200°C。 挤出料条用切粒机切粒, 在线热风干燥, 包装, 得到本发明烟用纤 维专用料。
将上述烟用纤维专用料在螺杆长径比为 28的 Φ65熔融纺丝机上进行纺 丝, 纺丝机螺杆温度设定方式: 第一段为 200°C, 第二段为 205°C, 第三段 为 215°C, 过滤器温度 205°C, 箱体温度 205°C, 直管温度 205°C。 从规格 为 1050x3的喷丝板喷出后用温度范围为 (20±10) °C的干燥空气侧吹风冷 却。
上述冷却后的丝束在上油槽中涂覆油剂, 上油槽中油剂为以下组成的 纤维表面处理剂水溶液: 聚乙二醇 1700, 浓度为 0.2%, 三乙醇胺硫酸二甲 酯, 浓度为 0.15, 壬基酚聚环氧乙垸, 浓度为 0.1%。 经过上油槽后的丝束 通过慢牵引机绕卷, 辊卷绕速度为 800m/min; 然后通过牵引蒸汽箱, 进入 快牵引机绕卷, 快牵引辊转速 1500 r/min, 频率 38HZ, 然后通过皮带输送 机输送, 皮带输送机喂入轮速度 800r/min, 频率为 40HZ。
从皮带输送机牵引出来等丝束用多辊牵伸机牵伸, 牵伸介质为水, 水 温为 65°C。 牵伸后丝束在卷曲器中进行卷曲, 卷曲数为 24个 /25mm, 卷曲 后的丝束通过蒸气干燥器干燥。 干燥后通过摆丝机将丝束在盛丝容器中摆 放好, 打包即得到本发明的可生物降解烟用纤维丝束。
本实施例所采用的共聚 PBS树脂按照 CN 01144133.X中记载的方法合 成, 在丁二酸与丁二醇的反应体系加入对苯二甲酸, 其中对苯二甲酸占体 系中二元酸总量的摩尔比 10%, 然后进行聚合反应, 得到所要求的共聚物。
上述嘴棒具有良好的生物降解性能,按照 ISO 14855要求完全达到降解 标准要求, 90天降解率达到 96%。 材料生物安全性符合烟用纤维要求。

Claims

权利要求书
1、 一种可生物降解的烟用纤维, 其原料组成为 l-99wt%的聚丁二酸丁 二醇酯聚合物、 l-99wt%的聚乳酸聚合物和 0-3wt%的稳定剂, 且为所述组 分经过挤出机挤出共混的产物, 该烟用纤维是所述原料经熔融纺丝工艺加 工而成。
2、 如权利要求 1所述的可生物降解的烟用纤维, 其中, 所述聚丁二醇 丁二酸酯聚合物为分子链中丁二酸丁二醇酯链节的量不少于该聚合物总链 节数的 70%的高分子聚合物, 且该聚合物的重均分子量为 5-35万, 分散指 数 1.2-3.0。
3、 如权利要求 2所述的可生物降解的烟用纤维, 其中, 所述聚丁二醇 丁二酸酯聚合物的分子链中丁二酸丁二醇酯链节的量不少于该聚合物总链 节数的 70%, 其余为非丁二酸丁二醇酯链节的二元酸二元醇聚合链节。
4、 如权利要求 3所述的可生物降解的烟用纤维, 其中, 所述二元酸选 自 C2-C12 的脂肪族二元酸、 芳香族二元酸或它们的混合物; 二元醇选自 C2-C12的脂肪族二元醇或它们的混合物。
5、 如权利要求 4所述的可生物降解的烟用纤维, 其中, 所述二元酸包 括乙二酸、 1,2—丙二酸、 1,3—丙二酸、戊二酸、 己二酸、 壬二酸、癸二酸、 十一碳二元酸、 十二碳二元酸、 富马酸、 马来酸、 苯二甲酸、 萘二甲酸或 其混合物; 所述二元醇包括乙二醇、 丙二醇、 戊二醇、 己二醇、 癸二醇或 其混合物。
6、 如权利要求 5所述的可生物降解的烟用纤维, 其中, 所述二元酸选 自乙二酸、 丙二酸、 己二酸、 富马酸、 苯二甲酸或它们中一种以上的混合 物, 所述二元醇选自乙二醇、 丙二醇或己二醇, 或它们中一种以上的混合 物。
7、 如权利要求 1所述的可生物降解的烟用纤维, 其中, 所述聚乳酸聚 合物为分子链中乳酸链节不少于该聚合物总链节数的 70%的高分子聚合 物, 且该聚合物的重均分子量为 5-30万, 分散指数 1.2-3.0。
8、 如权利要求 7所述的可生物降解的烟用纤维, 其中, 所述聚乳酸聚 合物的分子链中乳酸链节的量不少于该聚合物总链节数的 70%, 其余为能 与乳酸进行共聚的单体聚合链节。
9、 如权利要求 8所述的可生物降解的烟用纤维, 其中, 所述能与乳酸 进行共聚的单体包括乙交酯、 ε—己内酯、 乙二醇、 丙二醇、 乙醇酸、 或乙 二醇单甲醚、 或其任意混合物。
10、如权利要求 1-9任一项所述的可生物降解的烟用纤维,其中,所述 稳定剂包括磷酸、 亚磷酸、 次亚磷酸、 焦磷酸、 磷酸铵、 磷酸三甲酯、 磷 酸二甲酯、 磷酸三苯酯、 磷酸二苯酯、 亚磷酸三苯酯、 亚磷酸二苯酯、 亚 磷酸铵、 磷酸二氢铵、 抗氧剂 1010 、 抗氧剂 1222、 抗氧剂 1076、 抗氧剂 1425、 长链含磷硫化合物 Η— MOD、 环氧聚丁二烯、 环氧亚麻子油、 环氧 大豆油、 1,2—环氧基一 3—苯氧基丙垸、氢氧化镁、氢氧化铝、氧化钙、氨 基树脂或它们的任意混合物。
11、 如权利要求 10所述的可生物降解的烟用纤维, 其中, 所述稳定剂 包括磷酸三甲酯、 磷酸三苯酯、 亚磷酸三苯酯、 1010、 1076、 H— MOD、 环氧亚麻子油、环氧大豆油、 1,2-环氧基 -3-苯氧基丙烷、氢氧化镁、氨基树 脂或它们的任意混合物。
12、 如权利要求 1-11任一项所述的可生物降解的烟用纤维, 其为单丝 直径小于 20微米的烟用纤维。
13、 权利要求 1-12任一项所述的可生物降解的烟用纤维的制造方法, 该方法包括如下步骤:
将干燥的原料混合均匀, 用螺杆挤出机实施熔融共混并挤出制粒, 制 粒时挤出机螺筒温度在 140-230°C, 挤出后切粒, 干燥, 得到的烟用纤维专 用料;
对所制造的烟用纤维专用料进行熔融紡丝,制成可生物降解的烟用纤维。
14、 如权利要求 13所述的可生物降解的烟用纤维的制造方法, 其中, 将原料分别干燥至含水率低于 lwt%。, 再送入挤出机实施共混和挤出制粒。
15、 如权利要求 14所述的可生物降解的烟用纤维的制造方法, 其中, 对原料的干燥条件为: 聚丁二酸丁二醇酯聚合物于 50-85Ό干燥 2-3小时, 聚乳酸聚合物和稳定剂于 40-60 °C干燥 4-8小时。
16、 如权利要求 13所述的可生物降解的烟用纤维的制造方法, 其中, 所述挤出制粒时选用的挤出机设有熔体过滤装置并对粒径大于 100 目的颗 粒进行过滤。
17、如权利要求 13-16中任一项所述的可生物降解的烟用纤维的制造方 法, 其中, 对所制造的烟用纤维专用料进行熔融纺丝, 制成可生物降解的 烟用纤维的过程包括如下步骤:
将烟用纤维专用料进行熔融紡丝时, 设定纺丝机的螺杆温度 170°C-250°C, 使挤出物料流经过滤器、 箱体、 计量泵和直管后, 通过喷丝 板喷丝, 该过程控制过滤器温度 170°C-250°C, 箱体温度 170°C-250°C, 直管 温度 170°C-250°C,然后对喷出的丝以干燥空气冷却,冷却温度为 0°C-50°C ; 冷却后的丝束经涂覆油剂、 慢牵引机绕卷、 蒸汽箱牵引、 快牵引机绕 卷以及皮带输送机的卷绕牵引, 油剂为浓度 0.8%-1%的纤维表面处理剂的 水溶液, 慢牵引机的辊卷绕速度 200-1500m/min, 快牵引机的辊转速 400-2500r/min, 频率 25-50HZ, 皮带输送机喂入轮速度 200-1500 r/min, 频 率为 30-60HZ;
将从皮带输送机牵引出来的丝束在水温为 40°C-85°C的水槽中水浴牵 伸, 然后经卷曲和干燥定型, 得到的丝束即为所述可生物降解的烟用纤维。
PCT/CN2010/073094 2009-11-30 2010-05-21 可生物降解的香烟用纤维及其制备方法 WO2011063630A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN200910241645.3A CN102080278B (zh) 2009-11-30 2009-11-30 可生物降解的烟用纤维材料及香烟过滤嘴
CN200910241645.3 2009-11-30

Publications (1)

Publication Number Publication Date
WO2011063630A1 true WO2011063630A1 (zh) 2011-06-03

Family

ID=44065843

Family Applications (2)

Application Number Title Priority Date Filing Date
PCT/CN2010/073094 WO2011063630A1 (zh) 2009-11-30 2010-05-21 可生物降解的香烟用纤维及其制备方法
PCT/CN2010/073096 WO2011063632A1 (zh) 2009-11-30 2010-05-21 可生物降解的香烟过滤嘴棒及香烟

Family Applications After (1)

Application Number Title Priority Date Filing Date
PCT/CN2010/073096 WO2011063632A1 (zh) 2009-11-30 2010-05-21 可生物降解的香烟过滤嘴棒及香烟

Country Status (2)

Country Link
CN (1) CN102080278B (zh)
WO (2) WO2011063630A1 (zh)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013019616A3 (en) * 2011-07-29 2013-03-28 R. J. Reynolds Tobacco Company Plasticizer composition for degradable polyester filter tow
JP2014519839A (ja) * 2011-06-23 2014-08-21 ブリティッシュ アメリカン タバコ (インヴェストメンツ) リミテッド フィルター材
JP2015063672A (ja) * 2013-08-29 2015-04-09 三菱化学株式会社 脂肪族ポリエステル樹脂組成物

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9289012B2 (en) 2011-07-29 2016-03-22 R. J. Reynolds Tobacco Company Plasticizer composition for degradable polyester filter tow
CN102318898B (zh) * 2011-08-20 2014-05-21 云南瑞升烟草技术(集团)有限公司 一种滤嘴用天然植物颗粒材料的制备方法
CN102499478B (zh) * 2011-11-04 2013-10-09 马鞍山同杰良生物材料有限公司 一种过滤嘴棒及其制备方法
CN103088458A (zh) * 2013-01-27 2013-05-08 彭荣淮 纯聚乳酸丝束及其制备方法以及卷烟过滤嘴
CN103409837B (zh) * 2013-08-02 2015-10-28 东华大学 一种熔融纺丝制备水溶性聚乙烯醇纤维的方法
KR102410167B1 (ko) 2014-02-24 2022-06-20 필립모리스 프로덕츠 에스.에이. 개선된 경도 및 여과 효율을 갖는 필터
CN111087581B (zh) * 2018-10-23 2022-07-12 中国石油化工股份有限公司 聚乙醇酸的制备方法
CN110306258A (zh) * 2019-07-18 2019-10-08 深圳市大沣生物科技有限公司 一种吸阻可调且高过滤的香烟过滤嘴及其制备方法
CN112251845A (zh) * 2020-10-28 2021-01-22 深圳市华远新材料有限公司 一种用于香烟过滤嘴具有皮芯结构的可降解丝束及其制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05227939A (ja) * 1992-02-18 1993-09-07 Nippon Kayaku Co Ltd タバコフィルター
CN1224737A (zh) * 1997-12-15 1999-08-04 Ykk株式会社 可生物降解树脂的成形制品
CN1961765A (zh) * 2006-11-30 2007-05-16 中国科学院长春应用化学研究所 一种香烟过滤嘴丝束及其制备方法
CN1995135A (zh) * 2005-12-28 2007-07-11 海尔科化工程塑料国家工程研究中心股份有限公司 由聚二元酸二元醇酯改性的聚乳酸合金

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6194483B1 (en) * 1998-08-31 2001-02-27 Kimberly-Clark Worldwide, Inc. Disposable articles having biodegradable nonwovens with improved fluid management properties
JP2003213529A (ja) * 2002-01-11 2003-07-30 Chisso Corp 生分解性複合繊維及びこれを用いた繊維構造物、吸収性物品
JP4650206B2 (ja) * 2005-10-25 2011-03-16 チッソ株式会社 生分解性複合繊維、および、これを用いた繊維構造物と吸収性物品
JP2007216041A (ja) * 2006-01-16 2007-08-30 Ito:Kk 創傷治癒用高分子組成物
CN101023811A (zh) * 2007-02-05 2007-08-29 中国科学院长春应用化学研究所 一种烟用滤棒及其制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05227939A (ja) * 1992-02-18 1993-09-07 Nippon Kayaku Co Ltd タバコフィルター
CN1224737A (zh) * 1997-12-15 1999-08-04 Ykk株式会社 可生物降解树脂的成形制品
CN1995135A (zh) * 2005-12-28 2007-07-11 海尔科化工程塑料国家工程研究中心股份有限公司 由聚二元酸二元醇酯改性的聚乳酸合金
CN1961765A (zh) * 2006-11-30 2007-05-16 中国科学院长春应用化学研究所 一种香烟过滤嘴丝束及其制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ZHANG WEN.: "Study on the Spinning Process and Structure Performance about PLA Fiber and the Blends Fiber.", CHINESE MASTER'S THESES FULL-TEXT DATABASE ENGINEERING SCIENCE AND TECHNOLOGY I., no. 07, 15 July 2009 (2009-07-15), pages 24 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014519839A (ja) * 2011-06-23 2014-08-21 ブリティッシュ アメリカン タバコ (インヴェストメンツ) リミテッド フィルター材
WO2013019616A3 (en) * 2011-07-29 2013-03-28 R. J. Reynolds Tobacco Company Plasticizer composition for degradable polyester filter tow
JP2015063672A (ja) * 2013-08-29 2015-04-09 三菱化学株式会社 脂肪族ポリエステル樹脂組成物

Also Published As

Publication number Publication date
CN102080278A (zh) 2011-06-01
WO2011063632A1 (zh) 2011-06-03
CN102080278B (zh) 2014-11-12

Similar Documents

Publication Publication Date Title
WO2011063630A1 (zh) 可生物降解的香烟用纤维及其制备方法
WO2011063629A1 (zh) 可生物降解的烟用纤维
WO2011063628A1 (zh) 可生物降解的烟用纤维材料及香烟过滤嘴棒
EP1280948B1 (en) Copolyesters and fibrous materials formed therefrom
EP0802942B1 (de) Biologisch abbaubare polymere, verfahren zu deren herstellung sowie deren verwendung zur herstellung bioabbaubarer formkörper
JP5589377B2 (ja) 樹脂組成物、フィルム、袋製品、および、樹脂組成物の製造方法
DE60224530T3 (de) Fasern aus stärke und bioabbaubaren polymeren
EP0802940B1 (de) Biologisch abbaubare polymere, verfahren zu deren herstellung sowie deren verwendung zur herstellung bioabbaubarer formkörper
JP2002146170A (ja) 結晶性ポリ乳酸樹脂組成物、これを用いたフィルムおよびシート
JPH08510782A (ja) セルロースエステルブレンド
JP2001261797A (ja) 脂肪族ポリエステル樹脂および成形品
CN113773626B (zh) 一种环保型可降解母料及其制备方法和应用
CN101168617A (zh) 聚乳酸增韧改性的方法
WO2022202397A1 (ja) マルチフィラメント及びその製造方法、並びに、ステープル及びその製造方法
CN115679474A (zh) 一种抗水解聚乳酸纤维复合材料及其制备方法
CN105177737A (zh) 一种可降解烟用过滤嘴丝束及其制备方法
JP2000017153A (ja) 樹脂組成物および成形体
DE60010856T2 (de) Verfahren zur herstellung eines aliphatischen polyester mit ausgezeichneter stabilität
JP2002105750A (ja) 草刈り機用モノフィラメント及びその製造方法
KR101013446B1 (ko) 셀룰로오스 유도체 및 화학섬유를 포함하는 생분해성 수지 조성물
CN115380060A (zh) 热塑性树脂组合物的制造方法、成型体的制造方法及膜
JP2006045366A (ja) ポリ(3−ヒドロキシブチレート−コ−3−ヒドロキシヘキサノエート)組成物およびその成形体
JP5170359B2 (ja) 樹脂組成物及び成形体
JP2000345012A (ja) 樹脂組成物
JP2024104658A (ja) モノフィラメント、及び、その製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10832537

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 10832537

Country of ref document: EP

Kind code of ref document: A1