CN103102510A - 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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- CN103102510A CN103102510A CN2012100289296A CN201210028929A CN103102510A CN 103102510 A CN103102510 A CN 103102510A CN 2012100289296 A CN2012100289296 A CN 2012100289296A CN 201210028929 A CN201210028929 A CN 201210028929A CN 103102510 A CN103102510 A CN 103102510A
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- cellulose acetate
- weight part
- porous material
- preferred
- foaming porous
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- 229920002301 cellulose acetate Polymers 0.000 title claims abstract description 52
- 239000011148 porous material Substances 0.000 title claims abstract description 33
- 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 17
- 239000000314 lubricant Substances 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 15
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 11
- 238000001125 extrusion Methods 0.000 claims abstract description 10
- 239000004014 plasticizer Substances 0.000 claims abstract description 10
- 239000003381 stabilizer Substances 0.000 claims abstract description 9
- 239000012530 fluid Substances 0.000 claims abstract description 6
- 238000005187 foaming Methods 0.000 claims description 34
- -1 citric acid ester Chemical class 0.000 claims description 22
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 229920001747 Cellulose diacetate Polymers 0.000 claims description 16
- 239000002594 sorbent Substances 0.000 claims description 13
- 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
- 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
- 238000000465 moulding 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
- 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
- 239000003463 adsorbent Substances 0.000 abstract 1
- 235000019504 cigarettes Nutrition 0.000 description 19
- 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 6
- 239000006261 foam material 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
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 4
- 239000013618 particulate matter Substances 0.000 description 4
- 239000000779 smoke Substances 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
- 229920002678 cellulose Polymers 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000003546 flue gas 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
- 229920006239 diacetate fiber Polymers 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
- 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
- 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 foaming porous material and supercritical co assistance processing method thereof.
Background technology
Cellulose acetate, it is a kind of regenerated fiber, process and make with aceticanhydride by Mierocrystalline cellulose, different according to gamma value, product comprises a cellulose acetate (MCA), Cellulose diacetate (CA) and cellulosetri-acetate (TCA), wherein the tow that obtains after reeling off raw silk from cocoons of Cellulose diacetate, be the optimal filtering material of generally acknowledging, is to produce the main raw material of cigarette filter in the world today.
Cellulose diacetate (CDA) is widely used in pipe tobacco textile fibres, thermoplastics and various mould material.The spinning processes of CDA mainly contains dry-spinning, two step wet-spinnings and 3 kinds of operational paths of a step wet-spinning at present, but be that wet-spinning or dry-spinning all exist the organic reagents such as acetone, methylene dichloride in spinning process, environment is had certain hazardness; Exist simultaneously the shortcomings such as spinning speed is slow, spinning property is poor.Document " plasticization and modification of Cellulose diacetate and melt-spinning research " (synthetic fiber industry, 2011) proposed a kind of method of melt-spinning in, the method need to be added 25% left and right in Cellulose diacetate softening agent carries out the speedup modification to Cellulose diacetate.
The present invention proposes a kind of supercritical co Dichlorodiphenyl Acetate Mierocrystalline cellulose that utilizes and extrudes the method for preparation.
Summary of the invention
Primary goal of the invention of the present invention is for proposing a kind of cellulose acetate foaming porous material;
The second goal of the invention of the present invention is to propose the supercritical co extruding process thereof of this cellulose acetate foaming porous material.
In order to complete purpose of the present invention, the technical scheme of employing is:
A kind of cellulose acetate foaming porous material comprises: cellulose acetate 90～99.5 weight parts and auxiliary agent 0.5～10 weight part, and assist extruding process thereof to be prepared from by supercritical carbon dioxide fluid, add supercritical co 0.5～5 weight part.
The first optimal technical scheme of the present invention is: cellulose acetate is selected from a cellulose acetate, Cellulose diacetate and cellulosetri-acetate.
The second optimal technical scheme of the present invention is: described auxiliary agent is selected from least a in citric acid ester plasticizer, phosphorous acid ester type thermal stabilizing agent, lubricant, sorbent material.
The 3rd optimal technical scheme of the present invention is: citric acid ester plasticizer is 0.5～2 weight part, preferred 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.
The 4th optimal technical scheme of the present invention is: the phosphorous acid ester type thermal stabilizing agent is 0.05～0.2 weight part, preferred 0.75～0.15 weight part.
The 5th optimal technical scheme of the present invention is: lubricant is 0.05～1 weight part, preferred 0.1～0.5 weight part; Described lubricant is selected from oxidized polyethlene wax, stearic acid or stearate.
The 5th optimal technical scheme of the present invention is: described sorbent material is 1～5 weight part, preferred 1～2.5 weight part; Described sorbent material is selected from zeolite or gac class material.
The 6th optimal technical scheme of the present invention is: a kind of cellulose acetate foaming porous material, and it consists of:
Cellulose diacetate 90～95 weight parts;
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 add supercritical co 0.5～5 weight part in preparation process.
The invention still further relates to the preparation method of cellulose acetate foaming porous material, described preparation method's step is: cellulose acetate is positioned over the foaming dedicated extruder, simultaneously inject in proportion the whipping agent supercritical co at inlet, after fully being mixed by foam extrusion machine, from die extrusion foaming and moulding; Described dedicated extruder is single screw rod or the parallel double-screw extruder with 5 heating zone, at the output terminal of the forcing machine static mixers with 5～8 joints; Have the spiral shell rib parallel with hand of spiral on screw element; Be provided with the inlet of liquid carbon dioxide at the metering zone of forcing machine.
The first optimal technical scheme of cellulose acetate foaming porous material preparation method of the present invention is, in proportion cellulose acetate, softening agent, stablizer, lubricant, sorbent material are put into homogenizer and mixed 3～5 minutes, then add in the hopper of forcing machine and extrude processing.
The second optimal technical scheme of cellulose acetate foaming porous material preparation method of the present invention is that each of described dedicated extruder section temperature is:
The first humidity province temperature: 160～200 ℃, preferred 165～180 ℃;
The second humidity province temperature: 220～230 ℃, preferred 220～225 ℃;
The 3rd humidity province temperature: 230～250 ℃, preferred 235～245 ℃
The 4th humidity province temperature: 230～250 ℃, preferred 235～245 ℃
Head temperature: 200～220 ℃, preferred 205～215 ℃,
Die temperature: 150～170 ℃, preferred 160～165 ℃.
Below further explanation and description of the technical solution of the present invention are carried out:
The present invention relates to a kind of cellulose acetate foaming porous material, the method that namely adopts supercritical co to extrude processing is prepared from, main component is for comprising cellulose acetate and auxiliary agent, and further preferred cellulose acetate 90～95 weight parts, 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, can suitably improve the mobility of material; Add the phosphorous acid ester type thermal stabilizing agent, take the color of guaranteeing resulting product as white; Add lubricant, as oxidized polyethlene wax, stearic acid, stearate, can prevent the adhesion of cellulose acetate and forcing machine spiral shell bucket or screw rod; Add zeolite, gac class material, can further improve foam material to the adsorption of polar material, as alcohols, phenols, aldehydes, carbon monoxide etc.In actual production process, can according to the needs of product, determine the kind of additive.
Wherein, citric acid ester plasticizer 0.5～2 weight part in described foaming porous material, preferred 0.75～1.75 weight part; Phosphorous acid ester type thermal stabilizing agent 0.05～0.2 weight part, preferred 0.75～0.15 weight part; Sorbent material 1～5 weight part, preferred 1～2.5 weight part; Described sorbent material is selected from zeolite or gac class material, lubricant 0.05～1 weight part, preferred 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 foaming porous material, to in proportion cellulose acetate, auxiliary agent be put into homogenizer mixed 3～5 minutes, then add in the hopper of forcing machine and extrude processing, simultaneously inject in proportion the whipping agent supercritical co at inlet, after fully being mixed by foam extrusion machine, from die extrusion foaming and moulding; Described dedicated extruder refers to single screw rod or the parallel double-screw extruder with 5 heating zone, at the output terminal of the forcing machine static mixers with 5～8 joints, improves the cell uniformity of foam material; Have the spiral shell rib parallel with hand of spiral on screw element, to improve self-cleaning and the mixed effect of forcing machine, promote the formation of cellulose acetate/supercritical co homogeneous phase solution; The inlet of the simultaneously metering zone of forcing machine design liquid carbon dioxide, inlet seals with carbon seal ring, 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.
Use the performance perameter of the Cellulose diacetate foaming porous material that preparation method of the present invention prepares to be:
Percentage of open area: 70～85%,
Tension set: 2～5%,
Compressive strength: 15～20MPa,
Tensile strength: 10～15MPa.
Cellulose acetate of the present invention foaming porous material uses supercritical fluid carbon dioxide, can realize the cellulosic internal plasticization of Dichlorodiphenyl Acetate, reduces processing temperature to 220 ℃ left and right, thereby realizes the processing of Dichlorodiphenyl Acetate Mierocrystalline cellulose extrusion foaming.Use supercritical fluid carbon dioxide 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 perforate, 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, is used for sewage disposal and water purification, can also be used as gas filtering material, as cigarette filter, can improve more than 30% 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 is environmental protection more, safety, is the desirable replacement material of existing cigarette filter tip materials.
The specific embodiment of the present invention only limits to further illustrate the present invention, not to Composition of contents restriction of the present invention.The present invention is raw materials used be commercially available.
Embodiment
Embodiment 1～5
A kind of cellulose acetate foaming 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 being put into homogenizer mixed 3～5 minutes, then add in the hopper of forcing machine and extrude processing, inlet at forcing machine injects the whipping agent supercritical co in proportion simultaneously, after fully being mixed by foam extrusion machine, from die extrusion foaming and moulding; Dedicated extruder is single screw rod or the parallel double-screw extruder with 5 heating zone, at the output terminal of the forcing machine static mixers with 5～8 joints; Have the spiral shell rib parallel with hand of spiral on screw element; Be provided with the inlet of liquid carbon dioxide at the metering zone of forcing machine.Inlet seals with carbon seal ring, and the rear end of inlet is the screw element of coarse pitch.Each of dedicated extruder section temperature is as shown in table 2:
Table 2
| Embodiment | 1 | 2 | 3 | 4 | 5 |
| The first humidity province temperature | 160℃ | 200℃ | 165℃ | 180℃ | 170℃ |
| The second humidity province temperature | 220℃ | 230℃ | 220℃ | 225℃ | 225℃ |
| The 3rd humidity province temperature | 230℃ | 250℃ | 235℃ | 245℃ | 240℃ |
| The 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, cigarette tissue, the common cigarette filter stick of cigarette in Anhui limited liability company to prepare 100 of cigarettes,
Experimental group 1～5: adopt No. 1 pipe tobacco, the cigarette tissue of the limited liability company of cigarette in Anhui, the cigarette filter stick of the how empty foam material preparation of the cellulose acetate of the embodiment of the present invention 1～5 preparation (be prepared into general fibre element tow filter side same size) prepares 100 of cigarettes;
cigarette smoke analytical test: measure flue gas total particulate matter (PTM) according to GB/T 19609-2004 " cigarette is measured total particulate matter and tar with routine analysis with smoking machine " and GB/T 23356-2009 " in components in cigarette smoke gas phase, the non-scattering of the mensuration of carbon monoxide is infrared ", tar and carbon monoxide content, measure benzo (α) pyrene in main flume according to GB/T21130-2007 " mensuration of benzo in the cigarette smoke total particulate matter (α) pyrene ", press YC/T255-2008 " the mensuration high performance liquid chromatography of main carbonyl compounds in main stream cigarette smoke " measure in main flume can crotonic aldehyde, press YC/T253-2008 " the mensuration continuous flow method of prussic acid in cigarette mainstream flue gas " 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 as can be known, the cellulose acetate of preparation of the present invention foaming porous material is better than existing diacetate fiber tow to the adsorption effect of objectionable constituent in cigarette.
Claims (10)
1. cellulose acetate foaming porous material, it is characterized in that, described cellulose acetate foaming porous material comprises cellulose acetate 90～99.5 weight parts and auxiliary agent 0.5～10 weight part, and assist extruding process thereof preparation, supercritical co 0.5～5 weight part that adds by supercritical carbon dioxide fluid.
2. cellulose acetate foaming porous material according to claim 1, is characterized in that, described cellulose acetate is selected from a cellulose acetate, Cellulose diacetate and cellulosetri-acetate, preferred Cellulose diacetate.
3. cellulose acetate according to claim 1 foaming porous material, is characterized in that, described auxiliary agent is selected from least a in citric acid ester plasticizer, phosphorous acid ester type thermal stabilizing agent, lubricant, sorbent material.
4. cellulose acetate foaming porous material according to claim 3, is characterized in that, described citric acid ester plasticizer is 0.5～2 weight part, preferred 0.75～1.75 weight part.
5. cellulose acetate foaming porous material according to claim 3, is characterized in that, described phosphorous acid ester type thermal stabilizing agent is 0.05～0.2 weight part, preferred 0.075～0.15 weight part.
6. cellulose acetate foaming porous material according to claim 3, is characterized in that, described lubricant is 0.05～1 weight part, preferred 0.1～0.5 weight part; Described lubricant is selected from oxidized polyethlene wax, stearic acid or stearate.
7. cellulose acetate foaming porous material according to claim 3, is characterized in that, described sorbent material is 1～5 weight part, preferred 1～2.5 weight part; Described sorbent material is selected from zeolite or gac class material.
8. according to claim 1～7 described cellulose acetates of arbitrary claim foaming porous materials, is characterized in that, the consisting of of described cellulose acetate foaming porous material:
Cellulose diacetate 90～95 weight parts;
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 add supercritical co 0.5～5 weight part in preparation process.
9. the preparation method of cellulose acetate claimed in claim 1 foaming porous material, it is characterized in that, described preparation method's step is: cellulose acetate and auxiliary agent are put into homogenizer mixed 3～5 minutes, then add in the hopper of forcing machine and extrude processing, simultaneously inject in proportion the whipping agent supercritical co at inlet, after fully being mixed by foam extrusion machine, from die extrusion foaming and moulding;
Described dedicated extruder is single screw rod or the parallel double-screw extruder with 5 heating zone, at the output terminal of the forcing machine static mixers with 5～8 joints; Have the spiral shell rib parallel with hand of spiral on screw element; Be provided with the inlet of liquid carbon dioxide at the metering zone of forcing machine.
10. the preparation method of cellulose acetate foaming porous material according to claim 9, is characterized in that, each of described dedicated extruder section temperature is:
The first humidity province temperature: 160～200 ℃, preferred 165～180 ℃;
The second humidity province temperature: 220～230 ℃, preferred 220～225 ℃;
The 3rd humidity province temperature: 230～250 ℃, preferred 235～245 ℃
The 4th humidity province temperature: 230～250 ℃, preferred 235～245 ℃
Head temperature: 200～220 ℃, preferred 205～215 ℃,
Die temperature: 150～170 ℃, preferred 160～165 ℃.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103772751A (en) * | 2014-01-15 | 2014-05-07 | 南通烟滤嘴有限责任公司 | Filtering tip material made of porous foam for cigarettes and preparation method thereof |
| 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 |
| CN105585740A (en) * | 2016-03-08 | 2016-05-18 | 云南中烟工业有限责任公司 | Method for preparing cellulose-acetate open-micro-cell foam material |
| CN105686075A (en) * | 2016-03-08 | 2016-06-22 | 云南中烟工业有限责任公司 | Preparing method for filter tip adsorption bar made of cellulose acetate open-cell micropore foam material |
| CN105686074A (en) * | 2016-03-08 | 2016-06-22 | 云南中烟工业有限责任公司 | Biodegradable filter tip fragrance rod and preparation method thereof |
| CN115003743A (en) * | 2020-01-20 | 2022-09-02 | 伊士曼化工公司 | Biodegradable compositions and articles made from cellulose acetate |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103772751A (en) * | 2014-01-15 | 2014-05-07 | 南通烟滤嘴有限责任公司 | Filtering tip material made of porous foam for cigarettes and preparation method thereof |
| 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 |
| CN105585740A (en) * | 2016-03-08 | 2016-05-18 | 云南中烟工业有限责任公司 | Method for preparing cellulose-acetate open-micro-cell foam material |
| CN105686075A (en) * | 2016-03-08 | 2016-06-22 | 云南中烟工业有限责任公司 | Preparing method for filter tip adsorption bar made of cellulose acetate open-cell micropore foam material |
| CN105686074A (en) * | 2016-03-08 | 2016-06-22 | 云南中烟工业有限责任公司 | Biodegradable filter tip fragrance rod 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 |
| 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 |
| CN115003743A (en) * | 2020-01-20 | 2022-09-02 | 伊士曼化工公司 | Biodegradable compositions and articles made from cellulose acetate |
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