EP0019950B1 - Verfahren zur Herstellung von Polyolefin-Fibrillen und erzeugte Fibrillen - Google Patents

Verfahren zur Herstellung von Polyolefin-Fibrillen und erzeugte Fibrillen Download PDF

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Publication number
EP0019950B1
EP0019950B1 EP80200389A EP80200389A EP0019950B1 EP 0019950 B1 EP0019950 B1 EP 0019950B1 EP 80200389 A EP80200389 A EP 80200389A EP 80200389 A EP80200389 A EP 80200389A EP 0019950 B1 EP0019950 B1 EP 0019950B1
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EP
European Patent Office
Prior art keywords
polyolefine
weight
grafted
molecular weight
molecular
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP80200389A
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English (en)
French (fr)
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EP0019950A1 (de
Inventor
Jean-Pierre Pleska
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hercules LLC
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Hercules LLC
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Filing date
Publication date
Application filed by Hercules LLC filed Critical Hercules LLC
Priority to AT80200389T priority Critical patent/ATE14458T1/de
Publication of EP0019950A1 publication Critical patent/EP0019950A1/de
Application granted granted Critical
Publication of EP0019950B1 publication Critical patent/EP0019950B1/de
Expired legal-status Critical Current

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Classifications

    • 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
    • D01D5/11—Flash-spinning

Definitions

  • the present invention relates to a process for the production of polyolefin-based fibrils and the fibrils obtained which have excellent compatibility with cellulosic pulp and which therefore lead to the production, from mixtures of these fibrils and cellulosic pulp. , mixed papers with improved characteristics. In addition, these fibrils are easily suspended in water. Therefore, they can easily be implemented by conventional papermaking techniques.
  • the known methods also have a common drawback: the grafted polyolefin is in its entire mass, whereas, to ensure sufficient compatibility between the polyolefin fibrils and the cellulose pulp and the ease of aqueous suspension, it it suffices that the fibrils are grafted to their surface.
  • the known methods therefore involve the use of a large excess, relative to the quantity actually useful, of polar monomer.
  • the present invention aims to provide a process for the direct production of fibrils having excellent compatibility with cellulosic fibers and which can very easily be suspended in water which no longer has the aforementioned drawbacks of the known processes.
  • the Belgian patent uses a grafted polymer, the molecular weight of which is not specified. It does not provide for the use of two polyolefins of different molecular weight, one of which (that of average molecular weight) is not grafted with a polymeric monomer, while the other (of low molecular weight) is grafted of a polar monomer prior to its introduction into the mixture.
  • fibrils is intended to denote elongated fibrillated structures made up of very fine filaments, of thickness on the order of a micron, connected together to form a three-dimensional network.
  • the length of these flaky fibrils varies from 1 mm to 5 cm and their diameter from 0.01 to 5 ⁇ m approximately.
  • the specific surface of these fibrils is greater than 1 m2 / g.
  • the liquid mixture subjected to sudden expansion comprises at least one liquid phase based on organic solvent and on polyolefin which may be unique.
  • the mixture can also consist of a system with two liquid phases (two-phase mixture), namely a continuous phase rich in polyolefin in which are dispersed droplets of a liquid phase poor in polyolefin.
  • the form in which the mixture is presented liquid subjected to sudden expansion depends on pressure, temperature, and polyolefin concentration. It is generally preferred that the liquid mixture is in the form of a two-phase mixture and the pressure, the temperature and the polymer concentration are chosen accordingly.
  • the temperature is generally between 100 and 300 ° C and preferably between 125 and 250 ° C.
  • the polyolefin concentration of the mixture is generally between 1 and 500 g per kg of solvent; it is preferred to use mixtures containing from 10 to 300 g of polyolefin per kg of solvent, the best results being obtained for concentrations of 50 to 200 g / kg.
  • the pressure applied to the mixture is generally between atmospheric pressure and 100 atm. Preferably, it is between 5 and 80 atm.
  • the temperature and the pressure must also be chosen high enough for the expansion of the mixture to cause instant vaporization of the organic solvent and low enough for it to solidify the polyolefins it contains.
  • the mixture in the bisphasic form it is often advantageous to subject a pre-treatment to a mixture consisting of a single liquid phase being at higher pressure.
  • the value to be given to this pre-expansion can be easily determined experimentally by subjecting a portion of the mixture at high pressure to progressive expansion and noting the pressure at which it becomes cloudy.
  • All polyolefins are suitable for preparing the liquid mixture. It is possible to use, for example, high or low density polyethylene, polypropylene, polystyrene, poly-4-methylpentene-1, syndiotactic polybutadiene or 1,4-polybutadiene. However, homo- and copolymers derived from alpha-monoolefins comprising from 2 to 6 carbon atoms in their molecule are preferred. Excellent results have been obtained with polymers derived from ethylene and propylene. The use of several different polyolefins is in no way excluded.
  • the organic solvent used to prepare the mixture can be chosen from the solvents generally used for this purpose. In general, these solvents do not dissolve more than 50 g / I and, preferably, more than 10 g / I of polymer under normal conditions of temperature and pressure (20 ° C, 1 atmosphere). In addition, they have, at normal pressure, a boiling temperature 20 ° C lower and, preferably, more than 40 ° C below the melting or plasticization temperature of the polymer. Finally, they allow the formation of a liquid two-phase mixture under the operating conditions just before the sudden expansion.
  • aliphatic hydrocarbons are used and, in particular, pentane and hexane.
  • the use of mixtures of solvents also falls within the scope of the invention.
  • the pressure applied is brought to a value close to atmospheric pressure, preferably to a pressure less than 3 kg / cm 2 absolute, in a very short time interval, preferably less than 1 second .
  • This expansion is obtained by passing through a preferably cylindrical orifice whose diameter is between 0.1 and 20 mm and preferably between 0.5 and 10 mm and whose length / diameter ratio is between 0 , 1 and 10 and preferably between 0.5 and 2.
  • This sudden relaxation can advantageously be carried out according to the process and using the device described in detail in Belgian patent 824,484 filed on January 17, 1975 in the name of the Applicant .
  • the liquid mixture subjected to sudden expansion contains a polyolefin of normal molecular weight and a polyolefin of low molecular weight.
  • polyolefins of normal molecular weight is intended to denote the polyolefins, as defined above, whose number-average molecular weight (M n ) is greater than 10,000 and preferably greater than 12,000. The best results have been obtained when this molecular weight is greater than 15,000.
  • low molecular weight polyolefins the polyolefins, as defined above, whose number average molecular weight ( M n) is less than 10,000 and preferably less than 8,000. The best results have been obtained when this molecular weight is less than 5,000 and more particularly with crystalline polyolefin waxes.
  • Number average molecular weight is defined by the relationship in which N, represents the number of molecules of molecular weight M ,. This number-average molecular weight is determined in a known manner by the cryoscopic and ebullioscopic methods, by the method of terminal groups or by osmometry.
  • the low molecular weight polyolefin may be of a different nature, but is preferably identical in nature to that of the weight polyolefin. normal molecular entering into the composition of the mixture subjected to the sudden expansion.
  • It can be manufactured, in a known manner, by controlled polymerization of the corresponding alpha-monoolefin (s) or by controlled depolymerization (for example by thermal degradation, by radiation or by oxidation) of the corresponding polyolefins of higher average molecular weight.
  • the low molecular weight polyolefin used according to the invention is grafted with a polar monomer.
  • the grafting monomer is generally a monomer having a double bond and groups capable of reacting with the hydroxyl groups of the cellulose and which are difficult to homopolymerize.
  • the preferred monomers are acrylic and methacrylic monomers such as alkyl and glycidyl acrylates and methacrylates and alpha-chloroacrylic acid, as well as allylic monomers and unsaturated polycarboxylic acids such as maleic, fumaric and itaconic acids and their derivatives such as the corresponding anhydrides.
  • the use of several polar monomers also falls within the scope of the invention.
  • the grafting reaction of the monomer on the polyolefin can be initiated by free radicals generated in a known manner, for example by high energy radiation, by prior oxidation of the polyolefin (by ozonization for example) or even by introduction, into the medium containing the latter, of a compound generating free radicals, the latter method being preferred.
  • free radical generators can be used for this purpose.
  • organic peroxides such as ditert peroxides. butyl, lauroyl, benzoyl, acetylcyclohexanesulfonyl, peroxydicarbonates such as diethyl and diketyl peroxydicarbonates, peresters such as tert perpivalate.
  • butyl and azo-bis-nitriles such as azo - bis - 2,4 - dimethyl - valeronitrile and azo - bis - isobutyronitrile.
  • Preference is given to free radical generators with half-life times of around 10 minutes at 160 ° C.
  • the grafting reaction is carried out so as to obtain a low molecular weight polyolefin generally containing from 0.01 to 10% by weight of polar graft monomer and preferably from 0.1 to 5% by weight.
  • a low molecular weight polyolefin generally containing from 0.01 to 10% by weight of polar graft monomer and preferably from 0.1 to 5% by weight.
  • the best results have been obtained when the content of the grafted polar monomer in polyolefin is between 0.5 and 3%. Too low levels of polar monomer do not ensure sufficient compatibility with the cellulose paper pulp. Too high contents can lead to too short and colored fibrils.
  • the grafting of the polar monomer generally results in depolymerization: in this case, it is therefore not essential to use a low molecular weight polymer since this property is acquired during grafting itself. However, even in this case, it is preferred to carry out the grafting of the polar monomer on low-molecular-weight propylene polymers as defined above because the grafting yield is better and the operation is more economical.
  • the grafting of the polar monomer onto the low molecular weight polyolefin can be carried out according to known methods: it can be carried out in an organic solvent such as those mentioned above in connection with the preparation of the liquid mixture subjected to sudden expansion ; it can be carried out on the polyolefin melted in the kneading zone of an extruder; it can also be carried out in the liquid mixture subjected to sudden expansion, as described in Belgian patent 847,491 mentioned above.
  • grafting of the polar monomer onto the low molecular weight polyolefin is carried out by kneading them in the proportions and for the time required to obtain the contents of the grafted polar monomer mentioned above, at a temperature preferably above the melting point of the polyolefin at low molecular weight, and in the possible presence of a compound generating free radicals, such as those defined above.
  • the mode of incorporation of the low molecular weight polyolefin into the liquid mixture subjected to sudden expansion is not critical. It can be mixed, prior to its grafting with the polar monomer or in the grafted state, with the polyolefin or with the organic solvent used in the composition of the liquid mixture or even directly in the latter, at any time before expansion sudden.
  • the preferred procedure consists, for practical reasons, of directly incorporating the low-molecular-weight polyolefin previously grafted, in the molten state, into the mixture of polyolefin of normal molecular weight and of organic solvent being in the liquid state.
  • This incorporation can be carried out using any suitable device, such as for example a metering pump, the flow rate of which is adjusted as a function of the flow rate of liquid mixture, to ensure the desired ratio between the respective amounts of low molecular weight polyolefin.
  • grafted and liquid mixture containing polyolefin of normal molecular weight Preferably, when the incorporation of the low molecular weight polyolefin into the liquid mixture is carried out, the mixture obtained is homogenized, for example by means of a static mixer.
  • the proportion of grafted low molecular weight polyolefin and weight polyolefin Normal molecular in the liquid mixture subjected to sudden expansion is chosen as a function of the polar monomer content of the low molecular weight polyolefin and of the final content of polar monomer which it is desired to impart to the fibrils produced according to the invention.
  • the amount of low molecular weight polyolefin grafted does not represent more than 50% of the total weight of the polyolefins present in the liquid mixture subjected to sudden expansion. Preferably, this amount is between 5 and 40% by weight.
  • polyolefins of normal molecular weight also modified by grafting of a polar monomer is not excluded from the scope of the invention.
  • the grafting of at least part of the polar monomer onto the polyolefin of normal molecular weight is inevitable when the grafting of the polar monomer onto the low molecular weight polyolefin is carried out in the liquid mixture subjected to sudden expansion.
  • the liquid mixture subjected to sudden expansion can of course contain, in addition to the polyolefins and the organic solvent, other usual additives such as stabilizers with respect to the action of heat or light, reinforcing agents , fillers, pigments, dyes, antistatic agents, nucleating agents, etc.
  • the invention also relates to the fibrils obtained according to the method described above.
  • these fibrils have a heterogeneous structure.
  • the filaments of which they are made have a composition which is not the same at the heart and at the surface.
  • they consist mainly of polyolefin of normal molecular weight.
  • On the surface they mainly consist of low molecular weight polyolefin grafted with a polar monomer.
  • the mixture of fibrils according to the invention with conventional cellulosic pulps leads to papers having properties often superior to those of papers produced only from these cellulosic pulps, which proves that their chemical reactivity with respect to cellulosic fibers is markedly improved.
  • these mixed papers have improved surface properties which make them particularly suitable for use as papers for printing and writing.
  • the papers formed can be subjected to thermal consolidation at a relatively high temperature capable of causing at least a partial fusion of the fibrils.
  • the thermal consolidation treatment can also be avoided if a high mobility hydroxylated coupling agent is incorporated into the mixture of fibrils according to the invention and cellulosic fibers suspended in a liquid.
  • coupling agents which are suitable in the process according to the invention, mention may in particular be made of starch and its derivatives, cellulose derivatives, polyvinyl alcohols with a high hydrolysis rate and of low molecular weight, polyethylene glycol, polypropylene glycol , a nitrogen derivative such as casein.
  • the suspending medium can be water or an organic solvent dissolving the coupling agent.
  • the amount of coupling agent used can vary between 1 and 50% by weight of the dry weight of the fibrils used.
  • dispersing fibrils according to the invention when dispersing fibrils according to the invention or when mixing them with cellulose pulps, it is also possible to incorporate into the dispersion medium compounds capable of reacting with both the hydroxyl groups of the cellulose and with the reactive groups of the grafted monomer (s).
  • the incorporation of a polyamide modified for example by epichlorohydrin or a urea-formaldehyde resin proves to be very advantageous.
  • Example 1 is given for comparison.
  • the maleic anhydride content of the grafted polypropylene wax was approximately 2.5%.

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Textile Engineering (AREA)
  • Artificial Filaments (AREA)
  • Graft Or Block Polymers (AREA)
  • Paper (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Materials For Medical Uses (AREA)
  • Multicomponent Fibers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Developing Agents For Electrophotography (AREA)
  • Diaphragms For Electromechanical Transducers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Silicon Polymers (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
  • Sampling And Sample Adjustment (AREA)

Claims (9)

1. Verfahren zur Herstellung von Polyolefin-Fibrillen durch plötzliches Entspannen im Durchgang eines flüssigen Gemenges des geschmolzenen Polyolefines, eines polaren Monomers und eines Lösungsmittels durch eine Öffnung unter Druck- und Temperaturbedingungen, bei denen die plötzliche Entspannung des flüssigen Gemenges eine sofortige Verdampfung des Lösungsmittels und eine Verfestigung des Polyolefins zur Form von Fibrillen herbeiführt, dadurch gekennzeichnet, daß man dem plötzlichen Entspannen ein Gemenge unterwirft, das im Lösungsmittel enthält:
(a) ein erstes Polyolefin normalen Molekulargewichtes, d.h. eines Molekulargewichtes von zahlenmäßig durchschnittlich oberhalb 10000, wobei diesem ersten Polyolefin kein polares Monomer aufgepfropft ist, und
(b) ein zweites Polyolefin mit kleinerem Molekulargewicht, d.h. einem Molekulargewicht von zahlenmäßig durchschnittlich unterhalb 10 000, wobei diesem zweiten Polyolefin vor seiner Einführung in das Gemenge ein polares Monomer aufgepfropft ist.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man ein Polyolefin kleineren Molekulargewichtes verwendet, das unter den Polymerisaten der von Äthylen und Propylen stammenden Olefine gewählt ist.
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß man ein Polyolefin kleinen Molekulargewichtes verwendet, dessen Molekulargewicht zahlenmäßig durchschnittlich geringer als 8000, vorzugsweise kleiner als 5000 ist.
4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß man ein Polyolefin normalen Molekulargewichtes verwendet, dessen Molekulargewicht zahlenmäßig durchschnittlich größer als 12000, vorzugsweise größer als 15000, ist.
5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß man als Polyolefin kleineren Molekulargewichtes ein kristallines Wachs des Polyäthylens oder des Polypropylens verwendet.
6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß man ein Polyolefin kleineren Molekulargewichtes aufgepfropft mit Maleinsäureanhydride verwendet.
7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß man ein aufgepfropftes Polyolefin kleineren Molekulargewichtes verwendet, dessen Gehalt an polarem Monomer zwischen 0,1 und 5 Gew-% liegt.
8. Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß man ein flüssiges Gemenge verwendet, in dem die Menge des aufgepfropften Polyolefins kleineren Molekulargewichtes zwischen 5 und 40 Gew-% des gesamten im Gemenge enthaltenen Polyolefins beträgt.
9. Verfahren nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß man ein Polyolefin kleineren Molekulargewichtes, gepfropft durch Vermischen eines solchen Polyolefins und eines polaren Monomers, und gegebenenfalls einer Verbindung verwendet, die bei einer Temperatur oberhalb des Schmelzpunktes des Polyolefins kleineren Molekulargewichtes freie Radikale erzeugt.
EP80200389A 1979-05-10 1980-04-28 Verfahren zur Herstellung von Polyolefin-Fibrillen und erzeugte Fibrillen Expired EP0019950B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT80200389T ATE14458T1 (de) 1979-05-10 1980-04-28 Verfahren zur herstellung von polyolefinfibrillen und erzeugte fibrillen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR7912146 1979-05-10
FR7912146A FR2456133A1 (fr) 1979-05-10 1979-05-10 Procede de production de fibrilles a base de polyolefines et fibrilles obtenues

Publications (2)

Publication Number Publication Date
EP0019950A1 EP0019950A1 (de) 1980-12-10
EP0019950B1 true EP0019950B1 (de) 1985-07-24

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EP80200389A Expired EP0019950B1 (de) 1979-05-10 1980-04-28 Verfahren zur Herstellung von Polyolefin-Fibrillen und erzeugte Fibrillen

Country Status (11)

Country Link
US (1) US4332749A (de)
EP (1) EP0019950B1 (de)
JP (1) JPS55152812A (de)
AT (1) ATE14458T1 (de)
BR (1) BR8002771A (de)
CA (1) CA1146316A (de)
DE (1) DE3070897D1 (de)
ES (1) ES8101101A1 (de)
FI (1) FI71957C (de)
FR (1) FR2456133A1 (de)
NO (1) NO155735C (de)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4923646A (en) * 1988-11-08 1990-05-08 James River Corporation Method and apparatus for the manufacture of fibrids
US5051150A (en) * 1989-03-20 1991-09-24 Hercules Incorporated Stabilized synthetic pulp-cellulose blends
US5026745A (en) * 1989-06-12 1991-06-25 Aristech Chemical Corporation Biodeteriable plastics and blends
JPH04130243U (ja) * 1991-05-21 1992-11-30 株式会社精工舎 給紙装置
TW436535B (en) * 1997-04-08 2001-05-28 Danaklon As Drylaid nonwoven materials, methods for producing them and bicomponent fibers for the production thereof
US20090069491A1 (en) * 2007-09-06 2009-03-12 Dow Global Technologies Inc. Peroxide-free direct grafting of polar monomers onto unsaturated polyolefins
CN102224178A (zh) * 2008-09-24 2011-10-19 陶氏环球技术有限责任公司 不含过氧化物直接接枝极性单体到不饱和聚烯烃上
JP6328997B2 (ja) * 2014-05-21 2018-05-23 三井化学株式会社 変性ポリオレフィン合成パルプ、ヒートシール紙および不織布。

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4013751A (en) * 1971-10-29 1977-03-22 Gulf Research & Development Company Fibrils and processes for the manufacture thereof
FR2176843B3 (de) * 1972-03-20 1976-03-12 Gulf Research Development Co
GB1450892A (en) * 1972-09-26 1976-09-29 Ici Ltd Production of fibrils
JPS49118915A (de) 1973-03-26 1974-11-13
US4210615A (en) * 1973-05-23 1980-07-01 Basf Aktiengesellschaft Manufacture of thermoplastics fibrids
IT995549B (it) * 1973-10-02 1975-11-20 Anic Spa Procedimento per la produzione di strutture fibrose
US4110385A (en) * 1973-12-21 1978-08-29 Basf Aktiengesellschaft Manufacture of fibrids of polyolefins
DE2363671C3 (de) * 1973-12-21 1979-09-20 Basf Ag, 6700 Ludwigshafen Verfahren zur Herstellung von Kurzfasern aus Niederdruckpolyäthylen
LU69217A1 (de) * 1974-01-21 1975-12-09
LU73706A1 (de) * 1975-11-03 1977-06-03
US4107243A (en) * 1976-06-10 1978-08-15 Suntech, Inc. Preparation of thermoplastic polymer fibrilla and fibril

Also Published As

Publication number Publication date
NO155735C (no) 1987-05-20
JPS6311444B2 (de) 1988-03-14
DE3070897D1 (en) 1985-08-29
FR2456133B1 (de) 1981-11-27
CA1146316A (fr) 1983-05-17
US4332749A (en) 1982-06-01
FI71957C (fi) 1987-03-09
JPS55152812A (en) 1980-11-28
EP0019950A1 (de) 1980-12-10
ES491185A0 (es) 1980-12-01
ATE14458T1 (de) 1985-08-15
FR2456133A1 (fr) 1980-12-05
BR8002771A (pt) 1980-12-23
FI71957B (fi) 1986-11-28
FI801496A (fi) 1980-11-11
NO801395L (no) 1980-11-11
ES8101101A1 (es) 1980-12-01
NO155735B (no) 1987-02-09

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