CN103102510B - Cellulose acetate foamed porous material and supercritical carbon dioxide auxiliary processing method thereof - Google Patents
Cellulose acetate foamed porous material and supercritical carbon dioxide auxiliary processing method thereof Download PDFInfo
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- CN103102510B CN103102510B CN201210028929.6A CN201210028929A CN103102510B CN 103102510 B CN103102510 B CN 103102510B CN 201210028929 A CN201210028929 A CN 201210028929A CN 103102510 B CN103102510 B CN 103102510B
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- cellulose acetate
- weight part
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- porous material
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Links
- 229920002301 cellulose acetate Polymers 0.000 title claims abstract description 60
- 239000011148 porous material Substances 0.000 title claims abstract description 39
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 12
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 12
- 238000003672 processing method Methods 0.000 title abstract description 5
- 238000002360 preparation method Methods 0.000 claims abstract description 21
- 239000000314 lubricant Substances 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 15
- 239000004014 plasticizer Substances 0.000 claims abstract description 11
- 238000001125 extrusion Methods 0.000 claims abstract description 10
- 239000003381 stabilizer Substances 0.000 claims abstract description 10
- 239000012530 fluid Substances 0.000 claims abstract description 6
- -1 citric acid ester Chemical class 0.000 claims description 24
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 20
- 229920001747 Cellulose diacetate Polymers 0.000 claims description 15
- 239000002594 sorbent Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 9
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 8
- 238000012545 processing Methods 0.000 claims description 8
- 238000005187 foaming Methods 0.000 claims description 6
- 229910021536 Zeolite Inorganic materials 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 5
- 239000010457 zeolite Substances 0.000 claims description 5
- 235000021355 Stearic acid Nutrition 0.000 claims description 4
- 239000006260 foam Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 4
- 238000007493 shaping process Methods 0.000 claims description 4
- 230000003068 static effect Effects 0.000 claims description 4
- 239000008117 stearic acid Substances 0.000 claims description 4
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 claims description 3
- 239000012752 auxiliary agent Substances 0.000 abstract description 8
- 239000003463 adsorbent Substances 0.000 abstract 1
- 235000019504 cigarettes Nutrition 0.000 description 17
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 239000006261 foam material Substances 0.000 description 5
- 239000000779 smoke Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000004902 Softening Agent Substances 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 4
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 4
- 238000009987 spinning Methods 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 241000208125 Nicotiana Species 0.000 description 3
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000013618 particulate matter Substances 0.000 description 3
- 238000002166 wet spinning Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- DOOTYTYQINUNNV-UHFFFAOYSA-N Triethyl citrate Chemical compound CCOC(=O)CC(O)(C(=O)OCC)CC(=O)OCC DOOTYTYQINUNNV-UHFFFAOYSA-N 0.000 description 2
- 208000012886 Vertigo Diseases 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000000578 dry spinning Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002074 melt spinning Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- WEAPVABOECTMGR-UHFFFAOYSA-N triethyl 2-acetyloxypropane-1,2,3-tricarboxylate Chemical compound CCOC(=O)CC(C(=O)OCC)(OC(C)=O)CC(=O)OCC WEAPVABOECTMGR-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229920006239 diacetate fiber Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- AXFBAIOSECPASO-UHFFFAOYSA-N pentacyclo[6.6.2.02,7.04,16.011,15]hexadeca-1(14),2(7),3,5,8(16),9,11(15),12-octaene Chemical compound C1=C(C=C23)C4=C5C3=CC=CC5=CC=C4C2=C1 AXFBAIOSECPASO-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 230000000391 smoking effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000001069 triethyl citrate Substances 0.000 description 1
- VMYFZRTXGLUXMZ-UHFFFAOYSA-N triethyl citrate Natural products CCOC(=O)C(O)(C(=O)OCC)C(=O)OCC VMYFZRTXGLUXMZ-UHFFFAOYSA-N 0.000 description 1
- 235000013769 triethyl citrate Nutrition 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
- B29C48/875—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling for achieving a non-uniform temperature distribution, e.g. using barrels having both cooling and heating zones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92904—Die; Nozzle zone
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
Abstract
The invention relates to a cellulose acetate material, and in particular relates to a cellulose acetate foamed porous material and a supercritical fluid carbon dioxide auxiliary processing method thereof. The cellulose acetate foamed porous material comprises 90 to 99.5 parts by weight of cellulose acetate and 0.5 to 10 parts by weight of auxiliary agent and is prepared through a supercritical carbon dioxide fluid auxiliary extrusion processing method, and 0.5 to 5 parts by weight of supercritical carbon dioxide is added; and the auxiliary agent is selected from one or more of a plasticizer, a stabilizer, a lubricant, and an adsorbent. The invention also relates to a preparation method of the foamed porous material. The prepared cellulose acetate foamed porous material has the porosity of 70-85%, the Elongation at break of 2-5%, the compressive strength of 15-20Mpa and the tensile strength of 10-15MPa.
Description
Technical field
The present invention relates to a kind of cellulose acetate material, specifically, relate to a kind of cellulose acetate foamed porous material and supercritical co assistance processing method thereof.
Background technology
Cellulose acetate, it is a kind of regenerated fiber, be made up of the process of Mierocrystalline cellulose aceticanhydride, different according to gamma value, product comprises a cellulose acetate (MCA), Cellulose diacetate (CA) and cellulosetri-acetate (TCA), the wherein tow that obtains after reeling off raw silk from cocoons of Cellulose diacetate, being generally acknowledged optimal filtering material, is the main raw material world today producing cigarette filter.
Cellulose diacetate (CDA) is widely used in pipe tobacco textile fibres, thermoplastics and various mould material.The spinning processes of current CDA mainly contains dry-spinning, two step wet-spinnings and a step wet-spinning 3 kinds of operational paths, but be that wet-spinning or dry-spinning all exist the organic reagent such as acetone, methylene dichloride in spinning process, have certain hazardness to environment; There is the shortcomings such as spinning speed is slow, spinning property is poor simultaneously.Document " plasticization and modification of Cellulose diacetate and melt-spinning research " (synthetic fiber industry, 2011) propose a kind of method of melt-spinning in, the method needs the softening agent adding about 25% in Cellulose diacetate to carry out speedup modification to Cellulose diacetate.
The present invention proposes a kind of method utilizing supercritical co Dichlorodiphenyl Acetate Mierocrystalline cellulose to carry out extruding preparation.
Summary of the invention
Primary goal of the invention of the present invention is for proposing a kind of cellulose acetate foamed porous material;
Second goal of the invention of the present invention is the supercritical co extruding process thereof proposing this cellulose acetate foamed porous material.
In order to complete object of the present invention, the technical scheme of employing is:
A kind of cellulose acetate foamed porous material, comprising: cellulose acetate 90 ~ 99.5 weight part and auxiliary agent 0.5 ~ 10 weight part, and assists extruding process thereof to be prepared from by supercritical carbon dioxide fluid, add supercritical co 0.5 ~ 5 weight part.
First optimal technical scheme of the present invention is: cellulose acetate is selected from a cellulose acetate, Cellulose diacetate and cellulosetri-acetate.
Second optimal technical scheme of the present invention is: described auxiliary agent is selected from least one in citric acid ester plasticizer, phosphorous acid ester type thermal stabilizing agent, lubricant, sorbent material.
3rd optimal technical scheme of the present invention is: citric acid ester plasticizer is 0.5 ~ 2 weight part, preferably 0.75 ~ 1.75 weight part.Wherein, citric acid ester plasticizer is selected from: triethyl citrate TEC, acetyl triethyl citrate ATEC, tri-n-butyl citrate TBC, ATBC AT-BC etc.
4th optimal technical scheme of the present invention is: phosphorous acid ester type thermal stabilizing agent is 0.05 ~ 0.2 weight part, preferably 0.75 ~ 0.15 weight part.
5th optimal technical scheme of the present invention is: lubricant is 0.05 ~ 1 weight part, preferably 0.1 ~ 0.5 weight part; Described lubricant is selected from oxidized polyethlene wax, stearic acid or stearate.
5th optimal technical scheme of the present invention is: described sorbent material is 1 ~ 5 weight part, preferably 1 ~ 2.5 weight part; Described sorbent material is selected from zeolite or gac class material.
6th optimal technical scheme of the present invention is: a kind of cellulose acetate foamed porous material, and it consists of:
Cellulose diacetate 90 ~ 95 weight part;
Citric acid ester plasticizer 0.75 ~ 1.75 weight part;
Phosphorous acid ester type thermal stabilizing agent 0.75 ~ 0.15 weight part;
Lubricant 0.1 ~ 0.5 weight part;
Sorbent material 1 ~ 5 weight part;
And in preparation process, add supercritical co 0.5 ~ 5 weight part.
The invention still further relates to the preparation method of cellulose acetate foamed porous material, the step of described preparation method is: cellulose acetate is positioned over foaming dedicated extruder, inject whipping agent supercritical co in proportion at inlet simultaneously, after fully being mixed by foam extrusion machine, from die extrusion foaming and shaping; Described dedicated extruder is singe screw or the parallel double-screw extruder of band 5 heating zone, at the static mixer that the output terminal of forcing machine saves with 5 ~ 8; Screw element has the spiral shell rib parallel with hand of spiral; The inlet of liquid carbon dioxide is provided with at the metering zone of forcing machine.
First optimal technical scheme of cellulose acetate foamed porous material preparation method of the present invention is, in proportion cellulose acetate, softening agent, stablizer, lubricant, sorbent material are put into homogenizer mixing 3 ~ 5 minutes, then add in the hopper of forcing machine and carry out extruding processing.
Second optimal technical scheme of cellulose acetate foamed porous material preparation method of the present invention is, each section of temperature of described dedicated extruder is:
First humidity province temperature: 160 ~ 200 DEG C, preferably 165 ~ 180 DEG C;
Second humidity province temperature: 220 ~ 230 DEG C, preferably 220 ~ 225 DEG C;
3rd humidity province temperature: 230 ~ 250 DEG C, preferably 235 ~ 245 DEG C
4th humidity province temperature: 230 ~ 250 DEG C, preferably 235 ~ 245 DEG C
Head temperature: 200 ~ 220 DEG C, preferably 205 ~ 215 DEG C,
Die temperature: 150 ~ 170 DEG C, preferably 160 ~ 165 DEG C.
Further explanation and description of the technical solution of the present invention are carried out below:
The present invention relates to a kind of cellulose acetate foamed porous material, namely the method adopting supercritical co to extrude processing is prepared from, main component is for comprising cellulose acetate and auxiliary agent, and further preferably cellulose acetate 90 ~ 95 weight part, auxiliary agent 1 ~ 5 weight part.
In order to improve the performance of cellulose acetate foam material, described auxiliary agent is selected from one or more in softening agent, stablizer, lubricant, sorbent material.Wherein, add citric acid ester plasticizer, suitably can improve the mobility of material; Add phosphorous acid ester type thermal stabilizing agent, to guarantee that the color of resulting product is for white; Add lubricant, as oxidized polyethlene wax, stearic acid, stearate, the adhesion of cellulose acetate and forcing machine spiral shell bucket or screw rod can be prevented; Add zeolite, gac class material, the adsorption of foam material to polar material can be improved further, as alcohols, phenols, aldehydes, carbon monoxide etc.In actual production process, according to the needs of product, the kind of additive can be determined.
Wherein, citric acid ester plasticizer 0.5 ~ 2 weight part, preferably 0.75 ~ 1.75 weight part in described foamed porous material; Phosphorous acid ester type thermal stabilizing agent 0.05 ~ 0.2 weight part, preferably 0.75 ~ 0.15 weight part; Sorbent material 1 ~ 5 weight part, preferably 1 ~ 2.5 weight part; Described sorbent material is selected from zeolite or gac class material, lubricant 0.05 ~ 1 weight part, preferably 0.1 ~ 0.5 weight part; Described lubricant is selected from oxidized polyethlene wax, stearic acid or stearate.
The invention still further relates to the preparation method of this foamed porous material, in proportion cellulose acetate, auxiliary agent will be put into homogenizer mixing 3 ~ 5 minutes, then add in the hopper of forcing machine and carry out extruding processing, inject whipping agent supercritical co in proportion at inlet simultaneously, after fully being mixed by foam extrusion machine, from die extrusion foaming and shaping; Described dedicated extruder refers to singe screw or the parallel double-screw extruder of band 5 heating zone, at the static mixer that the output terminal of forcing machine saves with 5 ~ 8, improves the cell uniformity of foam material; Screw element has the spiral shell rib parallel with hand of spiral, to improve self-cleaning and the mixed effect of forcing machine, promotes the formation of cellulose acetate/supercritical co homogeneous phase solution; The simultaneously inlet of the metering zone design liquid carbon dioxide of forcing machine, inlet carbon seal ring seals, and the rear end of inlet is the screw element of coarse pitch, to improve the conveying intensity of material and to prevent the escape of carbonic acid gas.
The performance perameter of the Cellulose diacetate foamed porous material using preparation method of the present invention to prepare is:
Percentage of open area: 70 ~ 85%,
Tension set: 2 ~ 5%,
Compressive strength: 15 ~ 20MPa,
Tensile strength: 10 ~ 15MPa.
Cellulose acetate foamed porous materials'use supercritical fluid carbon dioxide of the present invention, can realize the cellulosic internal plasticization of Dichlorodiphenyl Acetate, about reducing processing temperature to 220 DEG C, thus realizes the processing of Dichlorodiphenyl Acetate Mierocrystalline cellulose extrusion foaming.Supercritical fluid carbon dioxide is used to make whipping agent, not only cheap, and be easy to take off and volatilize, safely, efficiently, can obtain hard or the semi-rigid material of opening, percentage of open area can reach more than 80%.Its application is also very extensive, not only can be applicable to the strobe utility of water treatment, for sewage disposal and water purification, can also be used as gas filtering material, as cigarette filter, can improve more than 30% to the filtration efficiency of nuisance CO.
The complete processing of the diacetate fiber that traditional cigarette filter uses is complicated, need a large amount of organic solvents, as acetone etc., the residual meeting of organic solvent causes damage to human body, cellulose acetate foam material of the present invention then environmental protection more, safety is the desirable replacement material of existing cigarette filter tip materials.
The specific embodiment of the present invention is only limitted to further illustrate the present invention, does not limit Composition of contents of the present invention.The present invention is raw materials used be commercially available.
Embodiment
Embodiment 1 ~ 5
A kind of cellulose acetate foamed porous material, its formula is as shown in table 1:
Table 1:
| Embodiment | 1 | 2 | 3 | 4 | 5 |
| Cellulose diacetate (kg) | 90 | 95 | 99 | 96 | 92 |
| Supercritical co (kg) | 10 | 5 | 1 | 4 | 8 |
| Tri-n-butyl citrate (kg) | 0.5 | 0.75 | 2 | 1.75 | 1 |
| Phosphorous acid ester (kg) | 0.05 | 0.75 | 0.2 | 0.15 | 0.1 |
| Oxidized polyethlene wax (kg) | 0.05 | 0.1 | 1 | 0.5 | 0.1 |
| Zeolite (kg) | 1 | 1.5 | 5 | 2.5 | 2 |
In upper table ratio, cellulose acetate, softening agent, stablizer, lubricant, sorbent material are put into homogenizer mixing 3 ~ 5 minutes, then add in the hopper of forcing machine and carry out extruding processing, inject whipping agent supercritical co in proportion at the inlet of forcing machine simultaneously, after fully being mixed by foam extrusion machine, from die extrusion foaming and shaping; Dedicated extruder is singe screw or the parallel double-screw extruder of band 5 heating zone, at the static mixer that the output terminal of forcing machine saves with 5 ~ 8; Screw element has the spiral shell rib parallel with hand of spiral; The inlet of liquid carbon dioxide is provided with at the metering zone of forcing machine.Inlet carbon seal ring seals, and the rear end of inlet is the screw element of coarse pitch.Each section of temperature of dedicated extruder is as shown in table 2:
Table 2
| Embodiment | 1 | 2 | 3 | 4 | 5 |
| First humidity province temperature | 160℃ | 200℃ | 165℃ | 180℃ | 170℃ |
| Second humidity province temperature | 220℃ | 230℃ | 220℃ | 225℃ | 225℃ |
| 3rd humidity province temperature | 230℃ | 250℃ | 235℃ | 245℃ | 240℃ |
| 4th humidity province temperature | 230℃ | 250℃ | 235℃ | 245℃ | 240℃ |
| Head temperature | 200℃ | 220℃ | 205℃ | 215℃ | 210℃ |
| Die temperature | 150℃ | 170℃ | 160℃ | 165℃ | 155℃ |
| Embodiment | 1 | 2 | 3 | 4 | 5 |
| Percentage of open area (%) | 85 | 83 | 82 | 84 | 83 |
| Tension set (%) | 3 | 5 | 4 | 4 | 5 |
| Compressive strength (MPa) | 18 | 19 | 17 | 18 | 19 |
| Tensile strength (MPa) | 14 | 15 | 14 | 15 | 13 |
Experimental example 1
Control group: adopt No. 1 pipe tobacco of Anhui Zhong Yan limited liability company, cigarette tissue, common cigarette filter stick to prepare cigarette 100,
Experimental group 1 ~ 5: No. 1 pipe tobacco, cigarette tissue adopting Anhui Zhong Yan limited liability company, cigarette filter stick (be prepared into and help same size with general fibre element tow filter) prepared by the how empty foam material of cellulose acetate prepared by the embodiment of the present invention 1 ~ 5 prepares cigarette 100;
Cigarette smoke analytical test: according to GB/T 19609-2004 " cigarette routine analysis smoking machine measure total particulate matter and tar " and GB/T 23356-2009 infrared of the mensuration non-scatter of carbon monoxide " in the components in cigarette smoke gas phase " mensuration smoke's total particulate matter (PTM), tar and carbon monoxide content, benzo in main flume (α) pyrene is measured according to the GB/T21130-2007 mensuration of benzo (α) pyrene " in the cigarette smoke condensates ", by YC/T255-2008 " the mensuration high performance liquid chromatography of main carbonyl compounds in main stream cigarette smoke " to measure in main flume can crotonic aldehyde, by the YC/T253-2008 mensuration continuous flow method of prussic acid " in the cigarette mainstream flue gas " to measure in main flume can prussic acid, test-results is as shown in table 4:
Table 4: flue gas analysis result:
From above-mentioned experiment, the cellulose acetate foamed porous material of preparation of the present invention is better than existing Diacetate cellulose tow to the adsorption effect of objectionable constituent in cigarette.
Claims (16)
1. a cellulose acetate foamed porous material, it is characterized in that, described cellulose acetate foamed porous material comprises cellulose acetate 90 ~ 99.5 weight part, citric acid ester plasticizer is 0.5 ~ 2 weight part, phosphorous acid ester type thermal stabilizing agent is 0.05 ~ 0.2 weight part, lubricant is 0.05 ~ 1 weight part, sorbent material is 1 ~ 5 weight part; And by supercritical carbon dioxide fluid auxiliary extruding process thereof preparation continuously, supercritical co 0.5 ~ 5 weight part added.
2. cellulose acetate foamed porous material according to claim 1, it is characterized in that, described cellulose acetate is selected from a cellulose acetate, Cellulose diacetate and cellulosetri-acetate.
3. cellulose acetate foamed porous material according to claim 1, it is characterized in that, described cellulose acetate is selected from two
Cellulose acetate.
4. cellulose acetate foamed porous material according to claim 1, is characterized in that, described citric acid ester plasticizer is 0.75 ~ 1.75 weight part.
5. cellulose acetate foamed porous material according to claim 1, is characterized in that, described phosphorous acid ester type thermal stabilizing agent is 0.075 ~ 0.15 weight part.
6. cellulose acetate foamed porous material according to claim 1, is characterized in that, described lubricant is 0.1 ~ 0.5 weight part; Described lubricant is selected from oxidized polyethlene wax, stearic acid or stearate.
7. cellulose acetate foamed porous material according to claim 1, is characterized in that, described sorbent material is 1 ~ 2.5 weight part; Described sorbent material is selected from zeolite or gac class material.
8. the cellulose acetate foamed porous material according to the arbitrary claim of claim 1 ~ 7, is characterized in that, consisting of of described cellulose acetate foamed porous material:
Cellulose diacetate 90 ~ 95 weight part;
Citric acid ester plasticizer 0.75 ~ 1.75 weight part;
Phosphorous acid ester type thermal stabilizing agent 0.75 ~ 0.15 weight part;
Lubricant 0.1 ~ 0.5 weight part;
Sorbent material 1 ~ 5 weight part;
And in preparation process, add supercritical co 0.5 ~ 5 weight part.
9. the preparation method of cellulose acetate foamed porous material according to claim 1, it is characterized in that, the step of described preparation method is: cellulose acetate, citric acid ester plasticizer, phosphorous acid ester type thermal stabilizing agent, lubricant, sorbent material are put into homogenizer mixing 3 ~ 5 minutes, then add in the hopper of forcing machine and carry out extruding processing, inject whipping agent supercritical co in proportion at inlet simultaneously, after fully being mixed by foam extrusion machine, from die extrusion foaming and shaping;
Described dedicated extruder is singe screw or the parallel double-screw extruder of band 5 heating zone, at the static mixer that the output terminal of forcing machine saves with 5 ~ 8; Screw element has the spiral shell rib parallel with hand of spiral; The inlet of liquid carbon dioxide is provided with at the metering zone of forcing machine.
10. the preparation method of cellulose acetate foamed porous material according to claim 9, is characterized in that, each section of temperature of described dedicated extruder is:
First humidity province temperature: 160 ~ 200 DEG C;
Second humidity province temperature: 220 ~ 230 DEG C;
3rd humidity province temperature: 230 ~ 250 DEG C;
4th humidity province temperature: 230 ~ 250 DEG C;
Head temperature: 200 ~ 220 DEG C;
Die temperature: 150 ~ 170 DEG C.
The preparation method of 11. cellulose acetate foamed porous materials according to claim 10, is characterized in that, the first humidity province temperature 165 ~ 180 DEG C.
The preparation method of 12. cellulose acetate foamed porous materials according to claim 10, is characterized in that, the second humidity province temperature 220 ~ 225 DEG C;
The preparation method of 13. cellulose acetate foamed porous materials according to claim 10, is characterized in that, the 3rd humidity province temperature 235 ~ 245 DEG C.
The preparation method of 14. cellulose acetate foamed porous materials according to claim 10, is characterized in that, the 4th humidity province temperature 235 ~ 245 DEG C.
The preparation method of 15. cellulose acetate foamed porous materials according to claim 10, is characterized in that, head temperature 205 ~ 215 DEG C.
The preparation method of 16. cellulose acetate foamed porous materials according to claim 10, is characterized in that, die temperature 160 ~ 165 DEG C.
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| CN103772927A (en) * | 2014-01-15 | 2014-05-07 | 南通烟滤嘴有限责任公司 | Biodegradable porous foaming material and preparation method thereof |
| CN103772751B (en) * | 2014-01-15 | 2016-04-13 | 南通烟滤嘴有限责任公司 | Porous foamed body cigarette filter tip material and preparation method thereof |
| CN105686074B (en) * | 2016-03-08 | 2019-11-26 | 云南中烟工业有限责任公司 | A kind of biodegradable filter tip perfume bar and preparation method thereof |
| CN105686075B (en) * | 2016-03-08 | 2019-08-09 | 云南中烟工业有限责任公司 | A kind of preparation method of cellulose acetate aperture microcellular foam material filter tip adsorbing bar |
| CN105585740B (en) * | 2016-03-08 | 2018-03-09 | 云南中烟工业有限责任公司 | A kind of preparation method of cellulose acetate perforate microcellular foam material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4507256A (en) * | 1983-05-26 | 1985-03-26 | Eastman Kodak Company | Process for foaming cellulose acetate rod |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4507256A (en) * | 1983-05-26 | 1985-03-26 | Eastman Kodak Company | Process for foaming cellulose acetate rod |
Non-Patent Citations (1)
| Title |
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| production of controlled polymerci foams by supercritical CO2;E.Reverchon et al;《the journal of supercritical fluids》;20071231;第40卷;实验和结论部分 * |
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