CN106222822A - A kind of heat-proof polylactic acid cigarette tows and preparation method thereof - Google Patents
A kind of heat-proof polylactic acid cigarette tows and preparation method thereof Download PDFInfo
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- CN106222822A CN106222822A CN201610596534.4A CN201610596534A CN106222822A CN 106222822 A CN106222822 A CN 106222822A CN 201610596534 A CN201610596534 A CN 201610596534A CN 106222822 A CN106222822 A CN 106222822A
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- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
-
- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
- A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
- A24D3/02—Manufacture of tobacco smoke filters
-
- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
- A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
- A24D3/06—Use of materials for tobacco smoke filters
- A24D3/08—Use of materials for tobacco smoke filters of organic materials as carrier or major constituent
- A24D3/10—Use of materials for tobacco smoke filters of organic materials as carrier or major constituent of cellulose or cellulose derivatives
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D11/00—Other features of manufacture
- D01D11/06—Coating with spinning solutions or melts
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/08—Melt spinning methods
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/04—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers
- D01F11/08—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G1/00—Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics
- D02G1/20—Combinations of two or more of the above-mentioned operations or devices; After-treatments for fixing crimp or curl
- D02G1/205—After-treatments for fixing crimp or curl
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02J—FINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
- D02J1/00—Modifying the structure or properties resulting from a particular structure; Modifying, retaining, or restoring the physical form or cross-sectional shape, e.g. by use of dies or squeeze rollers
- D02J1/22—Stretching or tensioning, shrinking or relaxing, e.g. by use of overfeed and underfeed apparatus, or preventing stretch
- D02J1/224—Selection or control of the temperature during stretching
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
- D10B2331/04—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyesters, e.g. polyethylene terephthalate [PET]
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Biological Depolymerization Polymers (AREA)
- Artificial Filaments (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of heat-proof polylactic acid cigarette tows and preparation method thereof, adding the coloring adsorbent that parts by weight are 1～5 part and the crystallization nucleating agent that parts by weight are 0.3～8 part in the polylactic resin that parts by weight are 100 parts, coloring adsorbent is uniformly mixed to form according to weight ratio 1:1:1 by polylactic resin, calcium sulfate and titanium dioxide；Crystallization nucleating agent be particle diameter be 100nm 1500nm zeolite powder, by the meerschaum powder of 100nm 1500nm, the concave and convex rod stone powder of 100nm 1500nm, the aluminium silicate powder of 100nm 1500nm, the kaolin powder of 100nm 1500nm, 100nm 1500nm SiO 2 powder in one or more mixture；Advantage is on the basis of having preferable thermostability, has preferable bulkiness, and elastic-restoring force is the strongest, and that can improve filter stick goes out rod rate.
Description
Technical field
The present invention relates to a kind of cigarette tows, especially relate to a kind of heat-proof polylactic acid cigarette tows and preparation method thereof.
Background technology
Cigarette filter is the important component part of Medicated cigarette, can improve cigarette taste and reduce harmful substances from flue gases pair
The injury of human body.Traditional material preparing cigarette tows is diacetate fiber material, in diacetate fiber material preparation process
Needing to use a large amount of sulphuric acid, oxalic acid or acetone class harmful substance, environmental pollution is extremely serious, and complex manufacturing, production
Cycle length, cost are high.Polylactic acid (PLA) is nonpoisonous and tasteless, and its material comes from nature, is attributed to nature, it may occur that biodegradation, finally
Generate carbon dioxide and water, recyclable regenerative, do not stay any pollutant, be a kind of excellent environmental type biodegradable material
Material.The fibrous material using polylactic acid melt-spun to obtain has excellent wet guilding, breathability and self-absorbing filtering.Use polylactic acid
Cigarette tows surface prepared by the fibrous material that melt-spun obtains has roughening, and inside has seven curved eight fork pore types, to flue gas
Toxin has absorption, the effect stopped and filter.At present, acid fiber by polylactic material the most progressively replaces diacetate fiber materials application
In cigarette tows prepares industry.
The Chinese invention patent of Patent No. 200610131699.0 and 200710055310.3 discloses one respectively adopt
The filter stick prepared with polylactic acid cigarette tows.In these two parts of patents, use lactide caprolactone and Acetic acid, hydroxy-, bimol. cyclic ester class mixture conduct
Matrix resin adds in poly-lactic acid material.Lactide caprolactone and Acetic acid, hydroxy-, bimol. cyclic ester class are all lactone polymers, are random flexibilities
Polymer, mobile performance is the highest, and fusing point low softening point is low, and expansion force is big, and these materials are made after mixing with poly-lactic acid material
The standby cigarette tows thermostability obtained is poor, is susceptible to thermal contraction phenomenon when temperature is higher.During production of cigarettes, filter
When rod is docked in cigarette, filter plug can cause cigarette tows to shrink, at high temperature with the cutting blade friction of high speed rotating
Flue gas is when filter stick, and cigarette tows also can shrink.Public affairs in the Chinese invention patent of Patent No. 201110166814.9
Having opened a kind of heat-proof polylactic acid cigarette tows and preparation method thereof, in this patent, the heatproof by adding in poly-lactic acid material adds
Add the mixture of agent or nucleating agent in polylactic acid production and heat stabilizer and antioxidation auxiliary agent, improve the heat resistance of poly-lactic acid material
And thermal stability, it is to avoid when cigarette is pumped to close to filter stick, filter stick can due to flue-gas temperature is too high and moment drop-head shadow
Ring the resistance to suction of filter stick, well solve the contractility problem of cigarette tows.But this heat-proof polylactic acid cigarette tows bullet
Property restoring force poor, produce filter stick time run into moment heat up suddenly time, cigarette tows is in the nothing of fiber noncrystalline domain
Rule molecular structure moment forms rigid body, fiber generation stiffening phenomenon, causes the bulkiness of filter stick to reduce, so that filter stick
Go out rod rate the highest, go out rod rate be only 1,400,000/ton～1,450,000/ton.
In view of this, design is a kind of on the basis of ensureing to have preferable thermostability, has preferable bulkiness, elastic recovery
Power is the strongest, and heat-proof polylactic acid cigarette tows going out rod rate that can improve filter stick and preparation method thereof is significant.
Summary of the invention
One of the technical problem to be solved is to provide a kind of on the basis of ensureing to have preferable thermostability,
Having preferable bulkiness, elastic-restoring force is the strongest, can improve the heat-proof polylactic acid cigarette tows rod rate of filter stick.
The present invention solves the technical scheme that one of above-mentioned technical problem used: a kind of heat-proof polylactic acid cigarette tows,
Each component including following parts by weight:
Polylactic resin 100
Coloring adsorbent 1～5
Crystallization nucleating agent 0.3～8
Described coloring adsorbent is uniformly mixed according to weight ratio 1:1:1 by polylactic resin, calcium sulfate and titanium dioxide
Formed；Described crystallization nucleating agent be particle diameter be the zeolite powder of 100nm-1500nm, the sepiolite powder of 100nm-1500nm
End, the aluminium silicate powder of the concave and convex rod stone powder of 100nm-1500nm, 100nm-1500nm, the kaolin powder of 100nm-1500nm
End, 100nm-1500nm SiO 2 powder in one or more mixture.
The molecular weight of described polylactic resin is 5-30 ten thousand, and relative viscosity is 2.4-4.0, and fusing point is 160-180 DEG C, glass
Glass conversion temperature is 55-61 DEG C, and crystallization temperature is 70-115 DEG C, and isotactic index is more than 97%, and optical activity is more than 90%, disappears
Curl is less than 5%, and level of residual monomers is less than 1%, and molecular weight distribution is less than 2.21%, and melt index is at 190 DEG C/2.16Kg load
It is down 5g/10min～20g/10min.The polylactic resin of high molecular that this cigarette tows uses, melting peak elongated, hold
Limit narrow, be not required to add antioxidant and lubricant just can obtain relatively thin fine with coloring adsorbent and crystallization nucleating agent melt spinning
Density, and high resilience power, this material has the spinnability of steady extruding in melt spinning process, improves cigarette tows further and produces
The thermostability of product and elastic-restoring force.
The preparation process of described zeolite powder is:
A. zeolite raw material is heated 20-40 minute at a temperature of 1000 DEG C-1500 DEG C；
B. after heating completes, being poured on zeolite by the water under room temperature, the weight of water is zeolite raw material weight
5%-15%, obtains zeolite granule；
C. zeolite granule is carried out ball milling, obtain the zeolite powder of 100nm-1500nm；
Described meerschaum powder, described concave and convex rod stone powder, described aluminium silicate powder, described kaolin powder
The preparation process of last, described SiO 2 powder is identical with the preparation process of described zeolite powder.In this cigarette tows,
The crystallization nucleating agent crystallization effect obtained is good, reduces noncrystalline domain present in cigarette tows further.
Compared with prior art, the advantage of the heat-proof polylactic acid cigarette tows of the present invention is by parts by weight being
The polylactic resin of 100 parts adds the coloring adsorbent that parts by weight are 1～5 part and the crystallization that parts by weight are 0.3～8 part
Nucleator, coloring adsorbent is uniformly mixed to form according to weight ratio 1:1:1 by polylactic resin, calcium sulfate and titanium dioxide；Knot
Brilliant nucleator be particle diameter be the zeolite powder of 100nm-1500nm, the meerschaum powder of 100nm-1500nm, 100nm-
The concave and convex rod stone powder of 1500nm, the aluminium silicate powder of 100nm-1500nm, the kaolin powder of 100nm-1500nm, 100nm-
One or more mixture in the SiO 2 powder of 1500nm, nano level crystallization nucleating agent can improve volume energetically
The degree of crystallinity of tobacco bunch, the noncrystalline domain existed in reducing it, on the basis of having preferable thermostability, elastic-restoring force is also
Relatively strong, greatly reduce and cigarette tows is in atactic molecule structure moment of fiber noncrystalline domain heats up and form what rigid body caused
Fiber stiffening phenomenon, that improves filter stick goes out rod rate, goes out rod rate up to 1,550,000/ton～1,600,000/ton.
The two of the technical problem to be solved are to provide the preparation method of a kind of heat-proof polylactic acid cigarette tows, should
Heat-proof polylactic acid cigarette tows prepared by preparation method, on the basis of having preferable thermostability, has preferable bulkiness,
Elastic-restoring force is the strongest, and that can improve filter stick goes out rod rate.
The present invention solves the technical scheme that the two of above-mentioned technical problem used: a kind of heat-proof polylactic acid cigarette tows
Preparation method, comprises the following steps:
1. each component is got the raw materials ready according to following parts by weight:
Polylactic resin 100
Coloring adsorbent 1～5
Crystallization nucleating agent 0.3～8
Described coloring adsorbent is uniformly mixed according to weight ratio 1:1:1 by polylactic resin, calcium sulfate and titanium dioxide
Formed；Described crystallization nucleating agent be particle diameter be the zeolite powder of 100nm-1500nm, the sepiolite powder of 100nm-1500nm
End, the aluminium silicate powder of the concave and convex rod stone powder of 100nm-1500nm, 100nm-1500nm, the kaolin powder of 100nm-1500nm
End, 100nm-1500nm SiO 2 powder in one or more mixture；
2. it is dried after mix homogeneously after polylactic resin, coloring adsorbent and crystallization nucleating agent being prepared as graininess
Process, obtain the water content mixed material less than 300ppm；
3. mixed material being carried out melt spinning, spinning temperature is 185 DEG C～235 DEG C, obtain single fiber density be 3.8～
The as-spun fibre of 7.8dtex；
4. by as-spun fibre by being placed with the antistatic groove of antistatic additive, resist quiet by drum process in as-spun fibre surface-coated
After electricity agent, as-spun fibre being merged formation fibre bundle, each fibre bundle comprises 6,000～1.4 ten thousand as-spun fibres, fibre bundle close
Degree is 3.0～6.0ktex；
5. by fibre bundle by after the first antistatic solution that temperature is 60 DEG C～67 DEG C, stretching-machine is used to carry out for the first time
Stretching, draw ratio is 1:1.2～1:2.5；
6. by the fibre bundle after for the first time stretching by after the second antistatic solution that temperature is 68 DEG C～78 DEG C, employing is drawn
Stretching machine to carry out stretching for the second time, draw ratio is 1:1.2～1:2.5；
7. the fibre bundle after second time stretching is first passed through steam box and carry out thermal finalization process, then carry out heat by crimping machine
Water crimps, and wherein in steam box, the temperature of steam is 79 DEG C～90 DEG C, and the hot water temperature of hot water curling is 91 DEG C～100 DEG C；
8. the fibre bundle drying plant after being crimped by hot water is dried, and dries temperature 60 C～70 DEG C, drying time be 15～
30 minutes, obtain heat-proof polylactic acid cigarette tows.
The preparation process of described zeolite powder is:
A. zeolite is heated 20-40 minute at a temperature of 1000 DEG C-1500 DEG C；
B. after heating completes, being poured on zeolite by the water under room temperature, the weight of water is the 5%-of zeolite weight
15%, obtain zeolite granule；
C. zeolite granule being carried out ball milling, obtain zeolite powder, the particle diameter of zeolite powder is 100nm-1500nm；
Described meerschaum powder, described concave and convex rod stone powder, described aluminium silicate powder, described kaolin powder
The preparation process of last, described SiO 2 powder is identical with the preparation process of described zeolite powder.
The molecular weight of described polylactic resin is 5-30 ten thousand, and relative viscosity is 2.4-4.0, and fusing point is 160-180 DEG C, glass
Glass conversion temperature is 55-61 DEG C, and crystallization temperature is 70-115 DEG C, and isotactic index is more than 97%, and optical activity is more than 90%, disappears
Curl is less than 5%, and level of residual monomers is less than 1%, and molecular weight distribution is less than 2.21%, and melt index is at 190 DEG C/2.16Kg load
It is down 5g/10min～20g/10min.
The first described antistatic solution is mixed according to weight rate 0.5:100～3:100 by the first antistatic additive and water
Formed, the first described antistatic additive be polyoxypropylene ethylene oxide glycerin ether with aliphatic alcohol polyoxyvinethene phosphate potassium salt and
The mixture of at least one in phosphate kalium salt；The second described antistatic solution by the second antistatic additive and water according to weight
Ratio 0.5:100～3.5:100 is mixed to form, and the second described antistatic additive is polyester POY oil preparation.In the method, by
The continuous cooperation of one antistatic solution and the second antistatic solution processes, and improves the antistatic effect of cigarette tows.
Described steam box includes casing, the stainless steel cloth arranged in described casing and is arranged in described casing
Steam jet, the mesh number of described stainless steel cloth is 60-200 mesh, and described steam jet is positioned at described stainless steel silk
The underface of net, the upper surface uniform intervals of described steam pipe is provided with multiple fumarole, described fumarole a diameter of
3-5mm, the spacing between adjacent two described fumaroles is 4-6mm, and fibre bundle is upper via described stainless steel cloth
Surface is by described casing.In the method, fibre bundle passes through via the upper surface of stainless steel cloth, and steam pipe is from bottom to top
Injection steam, steam contacts with fibre bundle via stainless steel cloth and fibre bundle is carried out heat treatment, and fibre bundle is not easy
Unrest is blown, it is ensured that the heating uniformity of fibre bundle, it is ensured that fibre bundle has higher elastic-restoring force, it is to avoid it is stiff by steam
Hardening.
Compared with prior art, the advantage of the preparation method of the heat-proof polylactic acid cigarette tows of the present invention is by weight
Amount number is to add coloring adsorbent that parts by weight are 1～5 part in the polylactic resin of 100 parts and parts by weight are 0.3～8
The crystallization nucleating agent of part, coloring adsorbent is uniformly mixed according to weight ratio 1:1:1 by polylactic resin, calcium sulfate and titanium dioxide
Formed；Crystallization nucleating agent be particle diameter be the zeolite powder of 100nm-1500nm, the meerschaum powder of 100nm-1500nm,
The concave and convex rod stone powder of 100nm-1500nm, the aluminium silicate powder of 100nm-1500nm, the kaolin powder of 100nm-1500nm,
One or more mixture in the SiO 2 powder of 100nm-1500nm, nano level crystallization nucleating agent can be energetically
Improving the degree of crystallinity of cigarette tows, reduce the noncrystalline domain existed in it, fibre bundle is by temperature is 60 DEG C～67 DEG C the
After one antistatic solution, using stretching-machine to carry out for the first time and stretch, draw ratio is 1:1.2～1:2.5, is being 68 DEG C by temperature
～after second antistatic solution of 78 DEG C, use stretching-machine to carry out second time and stretch, draw ratio is 1:1.2～1:2.5, for the second time
Fibre bundle after stretching first passes through steam box and carries out thermal finalization process, then carries out hot water curling, wherein steam box by crimping machine
The temperature of middle steam is 79 DEG C～90 DEG C, and the hot water temperature of hot water curling is 91 DEG C～100 DEG C；Thus continue through 60 DEG C～67
DEG C, 68 DEG C～78 DEG C, 79 DEG C～90 DEG C and 91 DEG C～100 DEG C of four temperature sections gradually promoted carry out processing and improve fibre bundle
The degree of orientation and degree of crystallinity so that it is have higher heat resistance, improve its bulkiness and elastic-restoring force, thus prepare
Cigarette tows is on the basis of having preferable thermostability, and elastic-restoring force is the strongest, greatly reduces and is in fibre in cigarette tows
The atactic molecule structure moment of dimension noncrystalline domain heats up and forms the fiber stiffening phenomenon that rigid body causes, and improves going out of filter stick
Rod rate, goes out rod rate up to 1,550,000/ton～1,600,000/ton.
Detailed description of the invention
The invention discloses a kind of heat-proof polylactic acid cigarette tows, below in conjunction with the embodiment heat-proof polylactic acid to the present invention
Cigarette tows is described in further detail.
Embodiment one: a kind of heat-proof polylactic acid cigarette tows, including each component of following parts by weight:
Polylactic resin 100
Coloring adsorbent 1.8
Crystallization nucleating agent 0.3
Coloring adsorbent is uniformly mixed to form according to weight ratio 1:1:1 by polylactic resin, calcium sulfate and titanium dioxide；Knot
Brilliant nucleator be particle diameter be the zeolite powder of 100nm-1500nm.
In the present embodiment, the molecular weight of polylactic resin is 5-30 ten thousand, and relative viscosity is 2.4-4.0, and fusing point is 160-180
DEG C, glass transition temperature is 55-61 DEG C, and crystallization temperature is 70-115 DEG C, and isotactic index is more than 97%, and optical activity is more than
90%, racemization degree be less than 5%, level of residual monomers be less than 1%, molecular weight distribution be less than 2.21%, melt index 190 DEG C/
It is 5g/10min～20g/10min under 2.16Kg load.
In the present embodiment, the preparation process of zeolite powder is:
A. zeolite raw material is heated 20-40 minute at a temperature of 1000 DEG C-1500 DEG C；
B. after heating completes, being poured on zeolite by the water under room temperature, the weight of water is zeolite raw material weight
5%-15%, obtains zeolite granule；
C. zeolite granule is carried out ball milling, obtain the zeolite powder of 100nm-1500nm.
Embodiment two: a kind of heat-proof polylactic acid cigarette tows, including each component of following parts by weight:
Polylactic resin 100
Coloring adsorbent 5
Crystallization nucleating agent 8
Coloring adsorbent is uniformly mixed to form according to weight ratio 1:1:1 by polylactic resin, calcium sulfate and titanium dioxide；Knot
Brilliant nucleator be particle diameter be the zeolite powder of 100nm-1500nm, the meerschaum powder of 100nm-1500nm, 100nm-
The concave and convex rod stone powder of 1500nm, the aluminium silicate powder of 100nm-1500nm, the kaolin powder of 100nm-1500nm and
The mixture of the SiO 2 powder of 100nm-1500nm.
In the present embodiment, the molecular weight of polylactic resin is 5-30 ten thousand, and relative viscosity is 2.4-4.0, and fusing point is 160-180
DEG C, glass transition temperature is 55-61 DEG C, and crystallization temperature is 70-115 DEG C, and isotactic index is more than 97%, and optical activity is more than
90%, racemization degree be less than 5%, level of residual monomers be less than 1%, molecular weight distribution be less than 2.21%, melt index 190 DEG C/
It is 5g/10min～20g/10min under 2.16Kg load.
In the present embodiment, the preparation process of zeolite powder is:
A. zeolite raw material is heated 20-40 minute at a temperature of 1000 DEG C-1500 DEG C；
B. after heating completes, being poured on zeolite by the water under room temperature, the weight of water is zeolite raw material weight
5%-15%, obtains zeolite granule；
C. zeolite granule is carried out ball milling, obtain the zeolite powder of 100nm-1500nm；
Meerschaum powder, concave and convex rod stone powder, aluminium silicate powder, kaolin powder, the preparation process of SiO 2 powder
Identical with the preparation process of zeolite powder.
Embodiment three: a kind of heat-proof polylactic acid cigarette tows, including each component of following parts by weight:
Polylactic resin 100
Coloring adsorbent 2.5
Crystallization nucleating agent 6
Coloring adsorbent is uniformly mixed to form according to weight ratio 1:1:1 by polylactic resin, calcium sulfate and titanium dioxide；Knot
Brilliant nucleator be particle diameter be the meerschaum powder of 100nm-1500nm.
In the present embodiment, the molecular weight of polylactic resin is 5-30 ten thousand, and relative viscosity is 2.4-4.0, and fusing point is 160-180
DEG C, glass transition temperature is 55-61 DEG C, and crystallization temperature is 70-115 DEG C, and isotactic index is more than 97%, and optical activity is more than
90%, racemization degree be less than 5%, level of residual monomers be less than 1%, molecular weight distribution be less than 2.21%, melt index 190 DEG C/
It is 5g/10min～20g/10min under 2.16Kg load.
In the present embodiment, the preparation process of meerschaum powder is:
A. meerschaum raw material is heated 20-40 minute at a temperature of 1000 DEG C-1500 DEG C；
B. after heating completes, being poured on meerschaum by the water under room temperature, the weight of water is meerschaum raw material weight
5%-15%, obtains sepiolite particle；
C. sepiolite particle is carried out ball milling, obtain the meerschaum powder of 100nm-1500nm.
The invention also discloses the preparation method of a kind of above-mentioned heat-proof polylactic acid cigarette tows, below in conjunction with embodiment to this
The preparation method of the heat-proof polylactic acid cigarette tows of invention is described in further detail.
Embodiment one: the preparation method of a kind of heat-proof polylactic acid cigarette tows, comprises the following steps:
1. each component is got the raw materials ready according to following parts by weight:
Polylactic resin 100
Coloring adsorbent 1
Crystallization nucleating agent 0.3
Coloring adsorbent is uniformly mixed to form according to weight ratio 1:1:1 by polylactic resin, calcium sulfate and titanium dioxide；Knot
Brilliant nucleator be particle diameter be the zeolite powder of 100nm-1500nm；
2. it is dried after mix homogeneously after polylactic resin, coloring adsorbent and crystallization nucleating agent being prepared as graininess
Process, obtain the water content mixed material less than 300ppm；
3. mixed material being carried out melt spinning, spinning temperature is 185 DEG C～235 DEG C, obtain single fiber density be 3.8～
The as-spun fibre of 7.8dtex；
4. by as-spun fibre by being placed with the antistatic groove of antistatic additive, resist quiet by drum process in as-spun fibre surface-coated
After electricity agent, as-spun fibre being merged formation fibre bundle, each fibre bundle comprises 6,000～1.4 ten thousand as-spun fibres, fibre bundle close
Degree is 3.0～6.0ktex；
5. by fibre bundle by after the first antistatic solution that temperature is 60 DEG C～67 DEG C, stretching-machine is used to carry out for the first time
Stretching, draw ratio is 1:1.2～1:2.5；
6. by the fibre bundle after for the first time stretching by after the second antistatic solution that temperature is 68 DEG C～78 DEG C, employing is drawn
Stretching machine to carry out stretching for the second time, draw ratio is 1:1.2～1:2.5；
7. the fibre bundle after second time stretching is first passed through steam box and carry out thermal finalization process, then carry out heat by crimping machine
Water crimps, and wherein in steam box, the temperature of steam is 79 DEG C～90 DEG C, and the hot water temperature of hot water curling is 91 DEG C～100 DEG C；
8. the fibre bundle drying plant after being crimped by hot water is dried, and dries temperature 60 C～70 DEG C, drying time be 15～
30 minutes, obtaining single fiber density was 2～6dtex, and total fine density is the heat-proof polylactic acid cigarette tows of 2.5～5.8dtex.
In the present embodiment, the preparation process of zeolite powder is:
A. zeolite is heated 20-40 minute at a temperature of 1000 DEG C-1500 DEG C；
B. after heating completes, being poured on zeolite by the water under room temperature, the weight of water is the 5%-of zeolite weight
15%, obtain zeolite granule；
C. zeolite granule being carried out ball milling, obtain zeolite powder, the particle diameter of zeolite powder is 100nm-1500nm.
In the present embodiment, the molecular weight of polylactic resin is 5-30 ten thousand, and relative viscosity is 2.4-4.0, and fusing point is 160-180
DEG C, glass transition temperature is 55-61 DEG C, and crystallization temperature is 70-115 DEG C, and isotactic index is more than 97%, and optical activity is more than
90%, racemization degree be less than 5%, level of residual monomers be less than 1%, molecular weight distribution be less than 2.21%, melt index 190 DEG C/
It is 5g/10min～20g/10min under 2.16Kg load.
In the present embodiment, the preparation process of zeolite powder is:
A. zeolite raw material is heated 20-40 minute at a temperature of 1000 DEG C-1500 DEG C；
B. after heating completes, being poured on zeolite by the water under room temperature, the weight of water is zeolite raw material weight
5%-15%, obtains zeolite granule；
C. zeolite granule being carried out ball milling, obtain zeolite powder, the particle diameter of zeolite powder is 100nm-1500nm.
In the present embodiment, the first antistatic solution by the first antistatic additive and water according to weight rate 0.5:100～3:100
Being mixed to form, the first antistatic additive is polyoxypropylene ethylene oxide glycerin ether and aliphatic alcohol polyoxyvinethene phosphate potassium salt and phosphorus
The mixture of at least one in acid esters potassium salt；Second antistatic solution by the second antistatic additive and water according to weight rate 0.5:
100～3.5:100 are mixed to form, and the second antistatic additive is polyester POY oil preparation.
In the present embodiment, steam box includes casing, the stainless steel cloth arranging in casing and the steam being arranged in casing
Jet pipe, the mesh number of stainless steel cloth is 60-200 mesh, and steam jet is positioned at the underface of stainless steel cloth, the upper surface of steam pipe
Uniform intervals is provided with multiple fumarole, a diameter of 3-5mm of fumarole, and the spacing between adjacent two fumaroles is 4-6mm,
Fibre bundle passes through casing via the upper surface of stainless steel cloth.
Embodiment two: the preparation method of a kind of heat-proof polylactic acid cigarette tows, comprises the following steps:
1. each component is got the raw materials ready according to following parts by weight:
Polylactic resin 100
Coloring adsorbent 5
Crystallization nucleating agent 8
Coloring adsorbent is uniformly mixed to form according to weight ratio 1:1:1 by polylactic resin, calcium sulfate and titanium dioxide；Knot
Brilliant nucleator be particle diameter be the zeolite powder of 100nm-1500nm, the meerschaum powder of 100nm-1500nm, 100nm-
The concave and convex rod stone powder of 1500nm, the aluminium silicate powder of 100nm-1500nm, the kaolin powder of 100nm-1500nm and
The mixture of the SiO 2 powder of 100nm-1500nm.
2. it is dried after mix homogeneously after polylactic resin, coloring adsorbent and crystallization nucleating agent being prepared as graininess
Process, obtain the water content mixed material less than 300ppm；
3. mixed material being carried out melt spinning, spinning temperature is 185 DEG C～235 DEG C, obtain single fiber density be 3.8～
The as-spun fibre of 7.8dtex；
4. by as-spun fibre by being placed with the antistatic groove of antistatic additive, resist quiet by drum process in as-spun fibre surface-coated
After electricity agent, as-spun fibre being merged formation fibre bundle, each fibre bundle comprises 6,000～1.4 ten thousand as-spun fibres, fibre bundle close
Degree is 3.0～6.0ktex；
5. by fibre bundle by after the first antistatic solution that temperature is 60 DEG C～67 DEG C, stretching-machine is used to carry out for the first time
Stretching, draw ratio is 1:1.2～1:2.5；
6. by the fibre bundle after for the first time stretching by after the second antistatic solution that temperature is 68 DEG C～78 DEG C, employing is drawn
Stretching machine to carry out stretching for the second time, draw ratio is 1:1.2～1:2.5；
7. the fibre bundle after second time stretching is first passed through steam box and carry out thermal finalization process, then carry out heat by crimping machine
Water crimps, and wherein in steam box, the temperature of steam is 79 DEG C～90 DEG C, and the hot water temperature of hot water curling is 91 DEG C～100 DEG C；
8. the fibre bundle drying plant after being crimped by hot water is dried, and dries temperature 60 C～70 DEG C, drying time be 15～
30 minutes, obtaining single fiber density was 2～6dtex, and total fine density is the heat-proof polylactic acid cigarette tows of 2.5～5.8dtex.
In the present embodiment, the preparation process of zeolite powder is:
A. zeolite is heated 20-40 minute at a temperature of 1000 DEG C-1500 DEG C；
B. after heating completes, being poured on zeolite by the water under room temperature, the weight of water is the 5%-of zeolite weight
15%, obtain zeolite granule；
C. zeolite granule being carried out ball milling, obtain zeolite powder, the particle diameter of zeolite powder is 100nm-1500nm；
Meerschaum powder, concave and convex rod stone powder, aluminium silicate powder, kaolin powder, the preparation process of SiO 2 powder
Identical with the preparation process of zeolite powder.
In the present embodiment, the molecular weight of polylactic resin is 5-30 ten thousand, and relative viscosity is 2.4-4.0, and fusing point is 160-180
DEG C, glass transition temperature is 55-61 DEG C, and crystallization temperature is 70-115 DEG C, and isotactic index is more than 97%, and optical activity is more than
90%, racemization degree be less than 5%, level of residual monomers be less than 1%, molecular weight distribution be less than 2.21%, melt index 190 DEG C/
It is 5g/10min～20g/10min under 2.16Kg load.
In the present embodiment, the preparation process of zeolite powder is:
A. zeolite raw material is heated 20-40 minute at a temperature of 1000 DEG C-1500 DEG C；
B. after heating completes, being poured on zeolite by the water under room temperature, the weight of water is zeolite raw material weight
5%-15%, obtains zeolite granule；
C. zeolite granule being carried out ball milling, obtain zeolite powder, the particle diameter of zeolite powder is 100nm-1500nm.
In the present embodiment, the first antistatic solution by the first antistatic additive and water according to weight rate 0.5:100～3:100
Being mixed to form, the first antistatic additive is polyoxypropylene ethylene oxide glycerin ether and aliphatic alcohol polyoxyvinethene phosphate potassium salt and phosphorus
The mixture of at least one in acid esters potassium salt；Second antistatic solution by the second antistatic additive and water according to weight rate 0.5:
100～3.5:100 are mixed to form, and the second antistatic additive is polyester POY oil preparation.
In the present embodiment, steam box includes casing, the stainless steel cloth arranging in casing and the steam being arranged in casing
Jet pipe, the mesh number of stainless steel cloth is 60-200 mesh, and steam jet is positioned at the underface of stainless steel cloth, the upper surface of steam pipe
Uniform intervals is provided with multiple fumarole, a diameter of 3-5mm of fumarole, and the spacing between adjacent two fumaroles is 4-6mm,
Fibre bundle passes through casing via the upper surface of stainless steel cloth.
Embodiment three: the preparation method of a kind of heat-proof polylactic acid cigarette tows, comprises the following steps:
1. each component is got the raw materials ready according to following parts by weight:
Polylactic resin 100
Coloring adsorbent 2.5
Crystallization nucleating agent 6
Coloring adsorbent is uniformly mixed to form according to weight ratio 1:1:1 by polylactic resin, calcium sulfate and titanium dioxide；Knot
Brilliant nucleator be particle diameter be the meerschaum powder of 100nm-1500nm.
2. it is dried after mix homogeneously after polylactic resin, coloring adsorbent and crystallization nucleating agent being prepared as graininess
Process, obtain the water content mixed material less than 300ppm；
3. mixed material being carried out melt spinning, spinning temperature is 185 DEG C～235 DEG C, obtain single fiber density be 3.8～
The as-spun fibre of 7.8dtex；
4. by as-spun fibre by being placed with the antistatic groove of antistatic additive, resist quiet by drum process in as-spun fibre surface-coated
After electricity agent, as-spun fibre being merged formation fibre bundle, each fibre bundle comprises 6,000～1.4 ten thousand as-spun fibres, fibre bundle close
Degree is 3.0～6.0kte；
5. by fibre bundle by after the first antistatic solution that temperature is 60 DEG C～67 DEG C, stretching-machine is used to carry out for the first time
Stretching, draw ratio is 1:1.2～1:2.5；
6. by the fibre bundle after for the first time stretching by after the second antistatic solution that temperature is 68 DEG C～78 DEG C, employing is drawn
Stretching machine to carry out stretching for the second time, draw ratio is 1:1.2～1:2.5；
7. the fibre bundle after second time stretching is first passed through steam box and carry out thermal finalization process, then carry out heat by crimping machine
Water crimps, and wherein in steam box, the temperature of steam is 79 DEG C～90 DEG C, and the hot water temperature of hot water curling is 91 DEG C～100 DEG C；
8. the fibre bundle drying plant after being crimped by hot water is dried, and dries temperature 60 C～70 DEG C, drying time be 15～
30 minutes, obtaining single fiber density was 2～6dtex, and total fine density is the heat-proof polylactic acid cigarette tows of 2.5～5.8dtex.
In the present embodiment, the preparation process of meerschaum powder is:
A. meerschaum raw material is heated 20-40 minute at a temperature of 1000 DEG C-1500 DEG C；
B. after heating completes, being poured on meerschaum by the water under room temperature, the weight of water is meerschaum raw material weight
5%-15%, obtains sepiolite particle；
C. sepiolite particle is carried out ball milling, obtain the meerschaum powder of 100nm-1500nm.
In the present embodiment, the molecular weight of polylactic resin is 5-30 ten thousand, and relative viscosity is 2.4-4.0, and fusing point is 160-180
DEG C, glass transition temperature is 55-61 DEG C, and crystallization temperature is 70-115 DEG C, and isotactic index is more than 97%, and optical activity is more than
90%, racemization degree be less than 5%, level of residual monomers be less than 1%, molecular weight distribution be less than 2.21%, melt index 190 DEG C/
It is 5g/10min～20g/10min under 2.16Kg load.
In the present embodiment, the preparation process of zeolite powder is:
A. zeolite raw material is heated 20-40 minute at a temperature of 1000 DEG C-1500 DEG C；
B. after heating completes, being poured on zeolite by the water under room temperature, the weight of water is zeolite raw material weight
5%-15%, obtains zeolite granule；
C. zeolite granule being carried out ball milling, obtain zeolite powder, the particle diameter of zeolite powder is 100nm-1500nm.
In the present embodiment, the first antistatic solution by the first antistatic additive and water according to weight rate 0.5:100～3:100
Being mixed to form, the first antistatic additive is polyoxypropylene ethylene oxide glycerin ether and aliphatic alcohol polyoxyvinethene phosphate potassium salt and phosphorus
The mixture of at least one in acid esters potassium salt；Second antistatic solution by the second antistatic additive and water according to weight rate 0.5:
100～3.5:100 are mixed to form, and the second antistatic additive is polyester POY oil preparation.
In the present embodiment, steam box includes casing, the stainless steel cloth arranging in casing and the steam being arranged in casing
Jet pipe, the mesh number of stainless steel cloth is 60-200 mesh, and steam jet is positioned at the underface of stainless steel cloth, the upper surface of steam pipe
Uniform intervals is provided with multiple fumarole, a diameter of 3-5mm of fumarole, and the spacing between adjacent two fumaroles is 4-6mm,
Fibre bundle passes through casing via the upper surface of stainless steel cloth.
Claims (8)
1. a heat-proof polylactic acid cigarette tows, it is characterised in that include each component of following parts by weight:
Polylactic resin 100
Coloring adsorbent 1～5
Crystallization nucleating agent 0.3～8
Described coloring adsorbent is uniformly mixed to form according to weight ratio 1:1:1 by polylactic resin, calcium sulfate and titanium dioxide；
Described crystallization nucleating agent be particle diameter be the zeolite powder of 100nm-1500nm, the meerschaum powder of 100nm-1500nm,
The concave and convex rod stone powder of 100nm-1500nm, the aluminium silicate powder of 100nm-1500nm, the kaolin powder of 100nm-1500nm,
One or more mixture in the SiO 2 powder of 100nm-1500nm.
A kind of heat-proof polylactic acid cigarette tows the most according to claim 1, it is characterised in that described polylactic resin
Molecular weight is 5-30 ten thousand, and relative viscosity is 2.4-4.0, and fusing point is 160-180 DEG C, and glass transition temperature is 55-61 DEG C, crystallization
Temperature is 70-115 DEG C, and isotactic index is more than 97%, and optical activity is more than 90%, and racemization degree is less than 5%, and level of residual monomers is less than
1%, molecular weight distribution is less than 2.21%, and melt index is 5g/10min～20g/10min under 190 DEG C/2.16Kg load.
A kind of heat-proof polylactic acid cigarette tows the most according to claim 1, it is characterised in that described zeolite powder
Preparation process is:
A. zeolite raw material is heated 20-40 minute at a temperature of 1000 DEG C-1500 DEG C；
B. after heating completes, being poured on zeolite by the water under room temperature, the weight of water is the 5%-of zeolite raw material weight
15%, obtain zeolite granule；
C. zeolite granule is carried out ball milling, obtain the zeolite powder of 100nm-1500nm；
Described meerschaum powder, described concave and convex rod stone powder, described aluminium silicate powder, described kaolin powder, institute
The preparation process of the SiO 2 powder stated is identical with the preparation process of described zeolite powder.
4. the preparation method of a heat-proof polylactic acid cigarette tows, it is characterised in that comprise the following steps:
1. each component is got the raw materials ready according to following parts by weight:
Polylactic resin 100
Coloring adsorbent 1～5
Crystallization nucleating agent 0.3～8
Described coloring adsorbent is uniformly mixed to form according to weight ratio 1:1:1 by polylactic resin, calcium sulfate and titanium dioxide；
Described crystallization nucleating agent be particle diameter be the zeolite powder of 100nm-1500nm, the meerschaum powder of 100nm-1500nm,
The concave and convex rod stone powder of 100nm-1500nm, the aluminium silicate powder of 100nm-1500nm, the kaolin powder of 100nm-1500nm,
One or more mixture in the SiO 2 powder of 100nm-1500nm；
2. it is dried place after mix homogeneously after polylactic resin, coloring adsorbent and crystallization nucleating agent being prepared as graininess
Reason, obtains the water content mixed material less than 300ppm；
3. mixed material being carried out melt spinning, spinning temperature is 185 DEG C～235 DEG C, obtain single fiber density be 3.8～
The as-spun fibre of 7.8dtex；
4. by as-spun fibre by being placed with the antistatic groove of antistatic additive, by drum process at as-spun fibre surface-coated antistatic additive
After as-spun fibre is merged formation fibre bundle, each fibre bundle comprises 6,000～1.4 ten thousand as-spun fibres, and the density of fibre bundle is
3.0～6.0ktex；
5. by fibre bundle by after the first antistatic solution that temperature is 60 DEG C～67 DEG C, use stretching-machine to carry out for the first time and draw
Stretching, draw ratio is 1:1.2～1:2.5；
6. by the fibre bundle after for the first time stretching by after the second antistatic solution that temperature is 68 DEG C～78 DEG C, employing stretching-machine
Carrying out second time to stretch, draw ratio is 1:1.2～1:2.5；
7. the fibre bundle after second time stretching is first passed through steam box and carry out thermal finalization process, then carry out hot water volume by crimping machine
Song, wherein in steam box, the temperature of steam is 79 DEG C～90 DEG C, and the hot water temperature of hot water curling is 91 DEG C～100 DEG C；
8. the fibre bundle drying plant after being crimped by hot water is dried, and drying temperature 60 C～70 DEG C, drying time is 15～30 points
Clock, obtains heat-proof polylactic acid cigarette tows.
The preparation method of a kind of heat-proof polylactic acid cigarette tows the most according to claim 4, it is characterised in that described bubble
The preparation process of zeolite powder is:
A. zeolite is heated 20-40 minute at a temperature of 1000 DEG C-1500 DEG C；
B. after heating completes, being poured on zeolite by the water under room temperature, the weight of water is the 5%-15% of zeolite weight,
To zeolite granule；
C. zeolite granule being carried out ball milling, obtain zeolite powder, the particle diameter of zeolite powder is 100nm-1500nm；
Described meerschaum powder, described concave and convex rod stone powder, described aluminium silicate powder, described kaolin powder, institute
The preparation process of the SiO 2 powder stated is identical with the preparation process of described zeolite powder.
The preparation method of a kind of heat-proof polylactic acid cigarette tows the most according to claim 4, it is characterised in that described is poly-
The molecular weight of lactic acid resin is 5-30 ten thousand, and relative viscosity is 2.4-4.0, and fusing point is 160-180 DEG C, and glass transition temperature is
55-61 DEG C, crystallization temperature is 70-115 DEG C, and isotactic index is more than 97%, and optical activity is more than 90%, and racemization degree is less than 5%, list
Body residual quantity be less than 1%, molecular weight distribution be less than 2.21%, melt index under 190 DEG C/2.16Kg load be 5g/10min～
20g/10min。
The preparation method of a kind of heat-proof polylactic acid cigarette tows the most according to claim 4, it is characterised in that described
One antistatic solution is mixed to form according to weight rate 0.5:100～3:100 by the first antistatic additive and water, and described first resists
Electrostatic agent be polyoxypropylene ethylene oxide glycerin ether with aliphatic alcohol polyoxyvinethene phosphate potassium salt and phosphate kalium salt in extremely
Few a kind of mixture；The second described antistatic solution by the second antistatic additive and water according to weight rate 0.5:100～
3.5:100 is mixed to form, and the second described antistatic additive is polyester POY oil preparation.
The preparation method of a kind of heat-proof polylactic acid cigarette tows the most according to claim 4, it is characterised in that described steaming
Vapour case includes casing, the stainless steel cloth arranged in described casing and the steam jet being arranged in described casing, described
The mesh number of stainless steel cloth be 60-200 mesh, described steam jet is positioned at the underface of described stainless steel cloth, described
The upper surface uniform intervals of steam pipe be provided with multiple fumarole, a diameter of 3-5mm of described fumarole, adjacent two institutes
Spacing between the fumarole stated is 4-6mm, and fibre bundle passes through described case via the upper surface of described stainless steel cloth
Body.
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| CN112674386A (en) * | 2020-12-23 | 2021-04-20 | 武汉市昱宸峰科技有限公司 | Surface treatment method and device for cigarette filter stick |
| CN113455701A (en) * | 2021-08-02 | 2021-10-01 | 苏州金泉新材料股份有限公司 | Cigarette tow and preparation method thereof |
| CN113862818A (en) * | 2021-08-31 | 2021-12-31 | 大韩道恩高分子材料(上海)有限公司 | Preparation and application method of electret material for degradable resin |
| CN114456552A (en) * | 2022-02-25 | 2022-05-10 | 复旦大学 | Method for improving crystallization temperature and toughness of polymer by using two-dimensional zeolite |
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Application publication date: 20161214 |
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