EP0053242B1 - Fibrids and fibrils from vinylidene fluoride polymers - Google Patents
Fibrids and fibrils from vinylidene fluoride polymers Download PDFInfo
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- EP0053242B1 EP0053242B1 EP81108023A EP81108023A EP0053242B1 EP 0053242 B1 EP0053242 B1 EP 0053242B1 EP 81108023 A EP81108023 A EP 81108023A EP 81108023 A EP81108023 A EP 81108023A EP 0053242 B1 EP0053242 B1 EP 0053242B1
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- Prior art keywords
- fibrids
- fibrils
- polyvinylidene fluoride
- pvdf
- vinylidene fluoride
- Prior art date
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- 229920000642 polymer Polymers 0.000 title claims description 12
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 title claims description 5
- 239000002033 PVDF binder Substances 0.000 claims description 34
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 34
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- -1 polypropylene Polymers 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims 1
- 239000011888 foil Substances 0.000 claims 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 22
- 239000013078 crystal Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000002904 solvent Substances 0.000 description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000001939 inductive effect Effects 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 1
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 241000282485 Vulpes vulpes Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/08—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of halogenated hydrocarbons
- D01F6/12—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of halogenated hydrocarbons from polymers of fluorinated hydrocarbons
-
- 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
- D01D5/40—Formation of filaments, threads, or the like by applying a shearing force to a dispersion or solution of filament formable polymers, e.g. by stirring
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H5/00—Special paper or cardboard not otherwise provided for
- D21H5/12—Special paper or cardboard not otherwise provided for characterised by the use of special fibrous materials
- D21H5/20—Special paper or cardboard not otherwise provided for characterised by the use of special fibrous materials of organic non-cellulosic fibres too short for spinning, with or without cellulose fibres
Definitions
- the present invention relates to fibrids and fibrils based on polymers of vinylidene fluoride. These fibrids and fibrils are a special form of fibers that have special physical properties.
- Fibrids and fibrils made of polyolefins, polyamides or based on fluorine-containing polymers or copolymers of polyvinylidene fluoride are known. Their manufacture is e.g. B. described in the journal "Angewandte Chemie", 90 (1978), pp. 833-926. in GB-PS 1 491 050, GB-PS 1 530 522 and GB-PS 1 552 313 or FR-PS 2 367 838. These known fibrids are mainly used as substitute products of pulp, such as. B. in papermaking.
- the new fibrids made of polyvinylidene fluoride can also be used in filters for aggressive substances, even at higher temperatures of e.g. B. 120 ° C, such as. B. in the filtration of nitric acid, where the known polyolefin fibrids cannot be used.
- PVDF polyvinylidene fluoride
- the new fibrids have a very large surface area, which can be up to 130 m 2 / g.
- PVDF - both in powder form and as a shaped body - has practically no adhesive properties for water, the new fibrids contain more than 90% by weight of water after their production. Other liquids adhere equally well to the new fibrids. This property is also retained when the new fibrids are dried and then treated with water with the addition of small amounts of surface-active substances.
- the new fibrids of the PVDF can be produced on the one hand analogously to the production of fibrids from polyamides: the polymer is dissolved in a suitable, water-miscible solvent and the polymer precipitates in water under shear-inducing conditions. Suitable shear-inducing conditions are mentioned in the references mentioned above.
- PVDF powder can be dissolved in acetone if the dissolving process is carried out just below the boiling point of acetone or if the PVDF powder is treated with acetone under pressure at temperatures above 52 ° C. In this way, up to 100% solutions of PVDF in acetone can be prepared which are stable at 20 ° C and, depending on the concentration, have a service life of between 10 and 24 hours at this temperature. Fibrids made of PVDF can be produced from these solutions in a manner known per se.
- solvents are the higher homologues of acetone, provided they are liquid and miscible with water at room temperature. If necessary, the PVDF powder must be dissolved in these solvents in the same way as when using acetone. Ethylene and propylene carbonate, y-butyrolactone, dimethylacetamide, tetramethylurea and dimethyl sulfoxide are also suitable as solvents. Depending on the choice of solvent, fibrids with different contents of crystal form I are obtained under the same precipitation conditions.
- the polymer can also contain small amounts (up to 10% by weight) of other monomers copolymerized or grafted on.
- the melt flow index (MFI according to DIN 53 735) should be between 0.1 and 200.
- PVDF with small amounts of copolymerized comonomers and / or compounded additional polymers has further advantages: PVDF with copolymerized tetrafluoroethylene or other monomers from fluorinated olefins, with the same gravitational forces and the same solvents, give fibrids with a larger surface area and a higher PVDF content of crystal form I It has been shown that when the same solvents are used, the content of fibrids of crystal form I is directly dependent on the surface of the fibrids: the larger the surface, the greater the content of crystal form 1.
- Crystal form I is understood to mean the crystal form which has the excellent dielectric properties (cf. J. Polym. Sc .: Part A, Vol. 3, pp. 4263-4278 (1964)). It is therefore possible to produce fibrids with defined dielectric properties by varying the shear forces and the polymerized second monomer.
- the content of fibrids in the crystallization form I can also be determined by varying the content of PVDF in the solutions to be precipitated: the higher this is, the higher the content of crystallization form I.
- PVDF is compounded in quantities of up to 10% by weight with other olefinic polymers, it is still possible to produce the new fibrids in a second way: the compounds are processed into oriented films and these oriented films are mechanically comminuted. Surprisingly, fibrids of crystallization form 1 are also obtained.
- a highly crystalline PVDF (which likewise predominantly consists of crystallization form 11) which is compounded with 0.5 to 10% by weight of an isotactic polypropylene is preferably used for the type of production.
- the production and orientation of the films from such a compound is carried out in a manner known per se, e.g. B. by extruding, then quenching and stretching in two mutually perpendicular directions.
- the stretched film is mechanically shredded at temperatures between ⁇ 20 and ⁇ 60 ° C.
- the shear-induced precipitation of PVDF fibrids from acetone solution is carried out as follows: Varying amounts of water are pumped through a nozzle with an inside diameter of 2 mm and an outside diameter of 3 mm.
- the free-falling water jet has a constant length of 50 cm. After 50 cm the water jet strikes a water surface of constant height; the height is maintained by means of an appropriate overflow.
- the acetone solution according to Example 1 is applied to the water jet at a constant pressure via an annular nozzle.
- the ring nozzle ends about 1 mm above the water outlet.
- fibrids with a specific surface area of 80 m 2 / g are obtained.
- the proportion of fibrids in crystal form I is 65%, calculated according to the formula
- D 510 is the IR absorption for crystal form I and D 530 is the IR absorption for crystal form II.
- Example 2 is repeated with an annular nozzle which has a gap width of 0.4 mm. This measure increases the shear-inducing effect. Fibrids are obtained, the specific surface area of which has risen to 105 and the content of crystal form I was 75%.
- Example 3 The procedure is the same as in Example 3. However, a 7.5% solution in acetone of a polyvinylidene fluoride with 6% by weight of copolymerized tetrafluoroethylene is used as the solution. Fibrids with a specific surface area of 85 and a crystal form I content of 85% are obtained.
- Example 2 The procedure of Example 2 is repeated with the difference that a 7.5% solution of a polyvinylidene fluoride with an MFJ of 20 in dimethyl sulfoxide (dissolving temperature 75 ° C.) is used and the amount of water is 4.0 l / min. Fibrids with a specific surface area of 50 are obtained. These differ from those of Example 2 in that they have practically pure crystal form 1 in the crystalline phase, which was proven by IR absorption and X-ray diffraction.
- the biaxially stretched film obtained in this way contains 75% crystal form I in the crystalline system of polyvinylidene fluoride.
- This film is cooled to ⁇ 50 ° C. and then split with rapidly rotating knives. Fine-fiber polyvinylidene fluoride fibrils with a specific surface area of 95 are obtained.
- the crystal form I remains fully intact after this process.
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Laminated Bodies (AREA)
- Artificial Filaments (AREA)
Description
Gegenstand der vorliegenden Erfindung sind Fibride und Fibrillen auf Basis von Polymeren des Vinylidenfluorids. Diese Fibride und Fibrillen sind eine spezielle Form von Fasern, die besondere physikalische Eigenschaften besitzen.The present invention relates to fibrids and fibrils based on polymers of vinylidene fluoride. These fibrids and fibrils are a special form of fibers that have special physical properties.
Fibride und Fibrillen aus Polyolefinen, Polyamiden oder auf Basis von fluorhaltigen Polymeren oder Copolymeren des Polyvinylidenfluorids sind bekannt. Ihre Herstellung wird z. B. beschrieben in der Zeitschrift »Angewandte Chemie«, 90 (1978), S. 833-926. in GB-PS 1 491 050, GB-PS 1 530 522 und GB-PS 1 552 313 oder FR-PS 2 367 838. Diese bekannten Fibride werden hauptsächlich als Substitutionsprodukte von Zellstoff eingesetzt, wie z. B. bei der Papierherstellung.Fibrids and fibrils made of polyolefins, polyamides or based on fluorine-containing polymers or copolymers of polyvinylidene fluoride are known. Their manufacture is e.g. B. described in the journal "Angewandte Chemie", 90 (1978), pp. 833-926. in GB-PS 1 491 050, GB-PS 1 530 522 and GB-PS 1 552 313 or FR-PS 2 367 838. These known fibrids are mainly used as substitute products of pulp, such as. B. in papermaking.
Es wurde nun gefunden, daß auch einfache Polymere auf Basis von Vinylidenfluorid in Fibride überführbar sind. Dabei stellte sich überraschenderweise heraus, daß diese Fibride des Polyvinylidenfluorids ausgezeichnete dielektrische Eigenschaften besitzen, während das Polymere, aus dem die Fibride gewonnen werden, verminderte dielektrische Eigenschaften besitzt. Die neuen Fibride können demzufolge auf Spezialgebieten in der Elektronik-Industrie eingesetzt werden; so lassen sie sich beispielsweise in Medien mit höherem E-Modul einbetten, so daß eine Verstärkung des piezoelektrischen Effekts erreicht wird.It has now been found that simple polymers based on vinylidene fluoride can also be converted into fibrids. It was surprisingly found that these fibrids of polyvinylidene fluoride have excellent dielectric properties, while the polymer from which the fibrids are obtained has reduced dielectric properties. The new fibrids can therefore be used in special areas in the electronics industry; for example, they can be embedded in media with a higher modulus of elasticity, so that the piezoelectric effect is enhanced.
Weiterhin lassen sich die neuen Fibride aus Polyvinylidenfluorid (PVDF) auch vorzüglich in Filter für aggressive Substanzen, selbst bei höheren Temperaturen von z. B. 120°C einsetzen, wie z. B. bei der Filtration von Salpetersäure, wo die bekannten Fibride aus Polyolefinen nicht verwendbar sind.Furthermore, the new fibrids made of polyvinylidene fluoride (PVDF) can also be used in filters for aggressive substances, even at higher temperatures of e.g. B. 120 ° C, such as. B. in the filtration of nitric acid, where the known polyolefin fibrids cannot be used.
Die neuen Fibride besitzen eine sehr große Oberfläche, die bis zu 130 m2/g betragen kann. Obwohl PVDF - sowohl in Pulverform als auch als Formkörper - praktisch keine Adhäsionseigenschaften für Wasser besitzt, enthalten die neuen Fibride nach ihrer Herstellung über 90 Gew.-% Wasser. Auch andere Flüssigkeiten haften gleich gut an den neuen Fibriden. Diese Eigenschaft bleibt auch erhalten, wenn man die neuen Fibride trocknet und anschließend mit Wasser unter Zusatz von geringen Mengen an oberflächenaktiven Substanzen behandelt.The new fibrids have a very large surface area, which can be up to 130 m 2 / g. Although PVDF - both in powder form and as a shaped body - has practically no adhesive properties for water, the new fibrids contain more than 90% by weight of water after their production. Other liquids adhere equally well to the new fibrids. This property is also retained when the new fibrids are dried and then treated with water with the addition of small amounts of surface-active substances.
Die Herstellung der neuen Fibride des PVDF kann einerseits analog der Herstellung von Fibriden aus Polyamiden erfolgen: Man löst das Polymere in einem geeigneten, mit Wasser mischbaren, Lösungsmittel und fällt das Polymere unter scherinduzierenden Bedingungen in Wasser aus. Geeignete scherinduzierende Bedingungen sind in den oben genannten Literaturstellen genannt.The new fibrids of the PVDF can be produced on the one hand analogously to the production of fibrids from polyamides: the polymer is dissolved in a suitable, water-miscible solvent and the polymer precipitates in water under shear-inducing conditions. Suitable shear-inducing conditions are mentioned in the references mentioned above.
Bei der Herstellung von Fibriden aus PVDF trat jedoch die Schwierigkeit auf, ein geeignetes Lösungsmittel zu finden, das die gewünschten Eigenschaften besitzt. In den meisten gängigen Lösungsmitteln gilt PVDF als unlöslich, oder diese Lösungsmittel sind mit Wasser nicht mischbar. (Vgl. Gnamm/Fuchs »Lösungsmittel, Weichmachungsmittel«, Bd. 1, 8. Auflage (1980), S. 358-361When producing fibrids from PVDF, however, the difficulty arose in finding a suitable solvent that has the desired properties. In most common solvents, PVDF is considered to be insoluble, or these solvents are immiscible with water. (See Gnamm / Fuchs "Solvents, Plasticizers", Vol. 1, 8th Edition (1980), pp. 358-361
Es wurde gefunden, daß sich PVDF-Pulver in Aceton lösen läßt, wenn man den Lösevorgang kurz unterhalb des Siedepunkts von Aceton durchführt oder wenn man das PVDF-Pulver unter Druck bei Temperaturen über 52°C mit Aceton behandelt. Es lassen sich auf diese Weise bis zu 100/oige Lösungen von PVDF in Aceton herstellen, die bei 20°C stabil sind und, je nach Konzentration, bei dieser Temperatur Standzeiten zwischen 10 und 24 Stunden besitzen. Aus diesen Lösungen lassen sich Fibride aus PVDF in an sich bekannter Weise herstellen.It has been found that PVDF powder can be dissolved in acetone if the dissolving process is carried out just below the boiling point of acetone or if the PVDF powder is treated with acetone under pressure at temperatures above 52 ° C. In this way, up to 100% solutions of PVDF in acetone can be prepared which are stable at 20 ° C and, depending on the concentration, have a service life of between 10 and 24 hours at this temperature. Fibrids made of PVDF can be produced from these solutions in a manner known per se.
Andere geeignete Lösungsmittel sind die höheren Homologen des Acetons, sofern sie bei Raumtemperatur flüssig und mit Wasser mischbar sind. Gegebenenfalls muß in diesen Lösungsmitteln das PVDF-Pulver in gleicher Weise wie beim Einsatz von Aceton gelöst werden. Als Lösungsmittel eignen sich weiterhin noch Äthylen- und Propylencarbonat, y-Butyrolacton, Dimethylacetamid, Tetramethylharnstoff und Dimethylsulfoxid. Je nach Wahl des Lösungsmittels erhält man bei gleichen Fällbedingungen Fibride mit unterschiedlichem Gehalt an der Kristallform I.Other suitable solvents are the higher homologues of acetone, provided they are liquid and miscible with water at room temperature. If necessary, the PVDF powder must be dissolved in these solvents in the same way as when using acetone. Ethylene and propylene carbonate, y-butyrolactone, dimethylacetamide, tetramethylurea and dimethyl sulfoxide are also suitable as solvents. Depending on the choice of solvent, fibrids with different contents of crystal form I are obtained under the same precipitation conditions.
Zur Herstellung der Fibride und Fibrillen eignet sich sowohl hochkristallines als auch weniger kristallines Polyvinylidenfluorid. Das Polymere kann auch geringe Mengen (bis zu 10 Gew.-%) weitere Monomere einpolymerisiert oder aufgepfropft enthalten. Der Schmelzflußindex (MFI gemäß DIN 53 735) sollte zwischen 0,1 und 200 liegen.Both highly crystalline and less crystalline polyvinylidene fluoride are suitable for producing the fibrids and fibrils. The polymer can also contain small amounts (up to 10% by weight) of other monomers copolymerized or grafted on. The melt flow index (MFI according to DIN 53 735) should be between 0.1 and 200.
Der Einsatz von PVDF mit geringen Mengen an einpolymerisierten Comonomeren und/oder eincompoundierten zusätzlichen Polymeren hat noch weitere Vorteile: PVDF mit einpolymerisiertem Tetrafluoräthylen oder anderen Monomeren aus fluorierten Olefinen ergeben bei gleichen Schwerkräften und gleichen Lösungsmitteln Fibride mit größerer Oberfläche und höherem Gehalt an PVDF der Kristallform I. Es hat sich nämlich gezeigt, daß bei Verwendung gleicher Lösungsmittel der Gehalt an Fibriden der Kristallform I direkt abhängig von der Oberfläche der Fibride ist: Je größer die Oberfläche, um so größer ist der Gehalt an der Kristallform 1.The use of PVDF with small amounts of copolymerized comonomers and / or compounded additional polymers has further advantages: PVDF with copolymerized tetrafluoroethylene or other monomers from fluorinated olefins, with the same gravitational forces and the same solvents, give fibrids with a larger surface area and a higher PVDF content of crystal form I It has been shown that when the same solvents are used, the content of fibrids of crystal form I is directly dependent on the surface of the fibrids: the larger the surface, the greater the content of crystal form 1.
Weiterhin hat sich herausgestellt, daß der Gehalt an PVDF der Kristallform um so größer ist, je größer die einwirkenden Scherkräfte bei der Ausfällung sind. Unter der Kristallform I ist dabei jene Kristallform zu verstehen, die die ausgezeichneten dielektrischen Eigenschaften besitzt (vgl. J. Polym. Sc.: Part A, Vol. 3, S. 4263-4278 (1964)). Man hat es demzufolge in der Hand, durch Variation der einwirkenden Scherkräfte und des einpolymerisierten zweiten Monomeren Fibride mit definierten dieleketrischen Eigenschaften herzustellen.Furthermore, it has been found that the PVDF content of the crystal form is greater, the greater the shear forces acting during the precipitation. Crystal form I is understood to mean the crystal form which has the excellent dielectric properties (cf. J. Polym. Sc .: Part A, Vol. 3, pp. 4263-4278 (1964)). It is therefore possible to produce fibrids with defined dielectric properties by varying the shear forces and the polymerized second monomer.
Der Gehalt an Fibriden der Kristallisationsform I kann auch noch durch Variation des Gehalts an PVDF in den auszufällenden Lösungen bestimmt werden: je höher dieser liegt, desto höher wird der Gehalt an der Kristallisationsform I.The content of fibrids in the crystallization form I can also be determined by varying the content of PVDF in the solutions to be precipitated: the higher this is, the higher the content of crystallization form I.
Wenn das PVDF mit weiteren olefinischen Polymeren in Mengen bis zu 10 Gew.-% compoundiert vorliegt, hat man weiterhin die Möglichkeit, die neuen Fibride auf eine zweite Art herzustellen: Die Compounds werden zu orientierten Folien verarbeitet und diese orientierten Folien werden mechanisch zerkleinert. Dabei werden überraschenderweise ebenfalls Fibride der Kristallisationsform 1 erhalten. Vorzugsweise wird für die Herstellungsart ein hochkristallines PVDF eingesetzt (das ebenfalls überwiegend aus der Kristallisationsform 11 besteht) das mit 0,5 bis 10 Gew.-% eines isotaktischen Polypropylens compoundiert ist.If the PVDF is compounded in quantities of up to 10% by weight with other olefinic polymers, it is still possible to produce the new fibrids in a second way: the compounds are processed into oriented films and these oriented films are mechanically comminuted. Surprisingly, fibrids of crystallization form 1 are also obtained. A highly crystalline PVDF (which likewise predominantly consists of crystallization form 11) which is compounded with 0.5 to 10% by weight of an isotactic polypropylene is preferably used for the type of production.
Die Herstellung und Orientierung der Folien aus einem solchen Compound erfolgt auf an sich bekannte Weise, z. B. durch Extrudieren, anschließendem Abschrecken und Verstrecken in zwei senkrecht zueinander stehenden Richtungen. Das mechanische Zerkleinern der so gestreckten Folie erfolgt bei Temperaturen zwischen ―20 und ―60° C.Beispiel 1The production and orientation of the films from such a compound is carried out in a manner known per se, e.g. B. by extruding, then quenching and stretching in two mutually perpendicular directions. The stretched film is mechanically shredded at temperatures between ―20 and ―60 ° C. Example 1
In einem Rührkolben werden in 925 cm3 reinem Aceton 75 g Polyvinylidenfluorid (MFJ=20) kurz unterhalb des Siedepunkts unter Rühren gelöst. Die Lösung wird auf 20° C abgekühlt. Die Lösung muß innerhalb von 8 Stunden bearbeitet werden, weil sie sonst zu gelieren beginnt.75 g of polyvinylidene fluoride (MFJ = 20) are dissolved in 925 cm 3 of pure acetone in a stirred flask just below the boiling point with stirring. The solution is cooled to 20 ° C. The solution must be processed within 8 hours, otherwise it will start to gel.
Die scherinduzierte Fällung von PVDF-Fibriden aus acetonischer Lösung wird wie folgt vorgenommen: Durch eine Düse mit einem Innendurchmesser von 2 mm und einem Außendurchmesser von 3 mm werden wechselnde Mengen Wasser pro Minute gepumpt. Der frei fallende Wasserstrahl hat eine konstante Länge von 50 cm. Nach 50 cm prallt der Wasserstrahl auf eine Wasseroberfläche mit gleichbleibender Höhe; die Höhenkonstanz wird mittels eines entsprechenden Überlaufs aufrechterhalten. Über eine Ringdüse wird die acetonische Lösung gemäß Beispiel 1 mit konstantem Druck auf den Wasserstrahl aufgebracht. Die Ringdüse endet etwa 1 mm oberhalb des Wasseraustritts.The shear-induced precipitation of PVDF fibrids from acetone solution is carried out as follows: Varying amounts of water are pumped through a nozzle with an inside diameter of 2 mm and an outside diameter of 3 mm. The free-falling water jet has a constant length of 50 cm. After 50 cm the water jet strikes a water surface of constant height; the height is maintained by means of an appropriate overflow. The acetone solution according to Example 1 is applied to the water jet at a constant pressure via an annular nozzle. The ring nozzle ends about 1 mm above the water outlet.
Bei Verwendung einer Ringdüse mit einer Spaltbreite von 0,8 mm und einer Wassermenge von 10,0 I/min erhält man Fibride mit einer spezifischen Oberfläche von 80 m2/g. Der Anteil der Fibride der Kristallform I beträgt 65%, berechnet nach der FormelWhen using an annular nozzle with a gap width of 0.8 mm and a water quantity of 10.0 l / min, fibrids with a specific surface area of 80 m 2 / g are obtained. The proportion of fibrids in crystal form I is 65%, calculated according to the formula
in welcher D510 die IR-Absorption für die Kristallform I und D530 die IR-Absorption für die Kristallform II bedeuten.in which D 510 is the IR absorption for crystal form I and D 530 is the IR absorption for crystal form II.
Beispiel 2 wird wiederholt mit einer Ringdüse, die eine Spaltbreite von 0,4 mm besitzt. Durch diese Maßnahme wird die scherinduzierende Wirkung vergrößert. Es werden Fibride erhalten, deren spezifische Oberfläche auf 105 angestiegen ist und deren Gehalt an Kristallform I bei 75% lag.Example 2 is repeated with an annular nozzle which has a gap width of 0.4 mm. This measure increases the shear-inducing effect. Fibrids are obtained, the specific surface area of which has risen to 105 and the content of crystal form I was 75%.
Es wird in gleicher Weise wie Beispiel 3 gearbeitet. Als Lösung wird jedoch eine 7,5%ige Lösung in Aceton eines Polyvinylidenfluorids mit 6 Gew.-% einpolymerisiertem Tetrafluoräthylen verwendet. Es werden Fibride mit einer spezifischen Oberfläche von 85 und einem Gehalt an Kristallform I von 85% erhalten.The procedure is the same as in Example 3. However, a 7.5% solution in acetone of a polyvinylidene fluoride with 6% by weight of copolymerized tetrafluoroethylene is used as the solution. Fibrids with a specific surface area of 85 and a crystal form I content of 85% are obtained.
Die Arbeitsweise des Beispiels 2 wird wiederholt mit dem Unterschied, daß eine 7,5%ige Lösung eines Polyvinylidenfluorids mit einem MFJ von 20 in Dimethylsulfoxid (Lösetemperatur 75° C) verwendet wird und die Wassermenge 4,0 1/min beträgt. Es werden Fibride mit einer spezifischen Oberfläche von 50 erhalten. Diese unterscheiden sich von denen des Beispiels 2 dadurch, daß sie in der kristallinen Phase praktisch die reine Kristallform 1 aufweisen, was durch IR-Absorption und Röntgenbeugung bewiesenwurde.The procedure of Example 2 is repeated with the difference that a 7.5% solution of a polyvinylidene fluoride with an MFJ of 20 in dimethyl sulfoxide (dissolving temperature 75 ° C.) is used and the amount of water is 4.0 l / min. Fibrids with a specific surface area of 50 are obtained. These differ from those of Example 2 in that they have practically pure crystal form 1 in the crystalline phase, which was proven by IR absorption and X-ray diffraction.
95 Teile Polyvinylidenfluorid (MFJ =20) und 5 Teile isotaktisches Polypropylen werden bei 255° C und bei einem Druck von 100 kg/cm2 zu einer Bahn mit 0,5 mm Dicke schmelzverpreßt. Die Bahn wird sofort in kaltem Wasser abgekühlt. Dann wird die Bahn bei 50°C um das 4- fache verstreckt und anschließend bei 100°C um das 6-fache verstreckt, und zwar senkrecht zur ersten Streckrichtung.95 parts of polyvinylidene fluoride (MFJ = 20) and 5 parts of isotactic polypropylene are melt-pressed at 255 ° C. and at a pressure of 100 kg / cm 2 to form a sheet with a thickness of 0.5 mm. The web is immediately cooled in cold water. Then the web is stretched 4-fold at 50 ° C and then stretched 6-fold at 100 ° C, perpendicular to the first stretching direction.
Die so erhaltene biaxial verstreckte Folie enthält im kristallinen System des Polyvinylidenfluorids 75% Kristallform I. Diese Folie wird auf ―50° C abgekühlt und anschließend mit schnell rotierenden Messern gespalten. Es werden feinfaserige Polyvinylidenfluorid-Fibrillen mit einer spezifischen Oberfläche von 95 erhalten. Die Kristallform I bleibt nach diesem Prozeß voll erhalten.The biaxially stretched film obtained in this way contains 75% crystal form I in the crystalline system of polyvinylidene fluoride. This film is cooled to ―50 ° C. and then split with rapidly rotating knives. Fine-fiber polyvinylidene fluoride fibrils with a specific surface area of 95 are obtained. The crystal form I remains fully intact after this process.
Claims (3)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3045333 | 1980-12-02 | ||
| DE19803045333 DE3045333A1 (en) | 1980-12-02 | 1980-12-02 | "FIBRIDS AND FIBRILLES MADE OF VINYLIDENE FLUORIDE POLYMERS" |
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| Publication Number | Publication Date |
|---|---|
| EP0053242A1 EP0053242A1 (en) | 1982-06-09 |
| EP0053242B1 true EP0053242B1 (en) | 1984-09-19 |
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ID=6118067
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP81108023A Expired EP0053242B1 (en) | 1980-12-02 | 1981-10-07 | Fibrids and fibrils from vinylidene fluoride polymers |
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| Country | Link |
|---|---|
| EP (1) | EP0053242B1 (en) |
| JP (1) | JPS57121609A (en) |
| DE (2) | DE3045333A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE9014598U1 (en) * | 1990-10-22 | 1991-01-03 | Krahmer, Gerhard M., 5064 Rösrath | Hair implant made of synthetic threads |
| DE4130356C2 (en) * | 1991-09-12 | 1995-01-26 | Bitterfeld Wolfen Chemie | PTFE fiber material and process for its manufacture |
| WO2014026272A1 (en) | 2012-08-14 | 2014-02-20 | Tindale, Jocelyn | Method of treating subterranean formations using blended proppants |
| EP2906615A4 (en) * | 2012-10-12 | 2016-04-13 | Evan Koslow | High dielectric compositions for particle formation and methods of forming particles using same |
| EP2999809A1 (en) | 2013-05-21 | 2016-03-30 | Gabae Technologies, LLC | High dielectric compositions for particle formation and methods of forming particles using same |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1465427A (en) * | 1964-08-14 | 1967-01-13 | Grace W R & Co | Striated films and mixtures of fibrils made up of two incompatible thermoplastic polymers, and their manufacturing process |
| US3693851A (en) * | 1965-06-05 | 1972-09-26 | Polymer Processing Res Inst | Method for fibrillating stretched film |
| IT1012545B (en) * | 1973-03-12 | 1977-03-10 | Solvay | PROCESS FOR THE MANUFACTURE OF DISCONTINUOUS FIBRILS USEFUL FOR THE PRODUCTION OF NON-WOVEN FABRICS AND SYNTHETIC PAPERS |
| DE2646332B2 (en) * | 1976-10-14 | 1979-04-12 | Basf Ag, 6700 Ludwigshafen | Process for the production of fibrils from fluorine-containing polymers |
-
1980
- 1980-12-02 DE DE19803045333 patent/DE3045333A1/en not_active Withdrawn
-
1981
- 1981-10-07 EP EP81108023A patent/EP0053242B1/en not_active Expired
- 1981-10-07 DE DE8181108023T patent/DE3166192D1/en not_active Expired
- 1981-12-01 JP JP56191901A patent/JPS57121609A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57121609A (en) | 1982-07-29 |
| DE3166192D1 (en) | 1984-10-25 |
| DE3045333A1 (en) | 1982-07-01 |
| EP0053242A1 (en) | 1982-06-09 |
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