EP0019950B1 - Verfahren zur Herstellung von Polyolefin-Fibrillen und erzeugte Fibrillen - Google Patents
Verfahren zur Herstellung von Polyolefin-Fibrillen und erzeugte Fibrillen Download PDFInfo
- 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
- Authority
- 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
Links
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title claims description 36
- 239000000203 mixture Substances 0.000 claims abstract description 67
- 239000000178 monomer Substances 0.000 claims abstract description 42
- 239000007788 liquid Substances 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 18
- -1 polyethylene Polymers 0.000 claims description 23
- 229920000642 polymer Polymers 0.000 claims description 11
- 229920001155 polypropylene Polymers 0.000 claims description 9
- 239000004743 Polypropylene Substances 0.000 claims description 7
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 239000000835 fiber Substances 0.000 claims description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000009834 vaporization Methods 0.000 claims description 3
- 230000008016 vaporization Effects 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 238000007711 solidification Methods 0.000 claims description 2
- 230000008023 solidification Effects 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 14
- 239000003960 organic solvent Substances 0.000 description 10
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 8
- 229920002678 cellulose Polymers 0.000 description 7
- 239000001913 cellulose Substances 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 150000003254 radicals Chemical class 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000001993 wax Substances 0.000 description 5
- 229920003299 Eltex® Polymers 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000007822 coupling agent Substances 0.000 description 4
- 229920001903 high density polyethylene Polymers 0.000 description 4
- 239000004700 high-density polyethylene Substances 0.000 description 4
- 238000010348 incorporation Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 238000007596 consolidation process Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- YLGXILFCIXHCMC-JHGZEJCSSA-N methyl cellulose Chemical compound COC1C(OC)C(OC)C(COC)O[C@H]1O[C@H]1C(OC)C(OC)C(OC)OC1COC YLGXILFCIXHCMC-JHGZEJCSSA-N 0.000 description 2
- 125000005634 peroxydicarbonate group Chemical group 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- SZTBMYHIYNGYIA-UHFFFAOYSA-N 2-chloroacrylic acid Chemical compound OC(=O)C(Cl)=C SZTBMYHIYNGYIA-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- XWCDCDSDNJVCLO-UHFFFAOYSA-N Chlorofluoromethane Chemical class FCCl XWCDCDSDNJVCLO-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000000746 allylic group Chemical group 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229920001112 grafted polyolefin Polymers 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical class OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 125000000400 lauroyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 150000002829 nitrogen Chemical class 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 238000002103 osmometry Methods 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical class C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 238000006385 ozonation reaction Methods 0.000 description 1
- 230000003071 parasitic effect Effects 0.000 description 1
- 150000002976 peresters Chemical class 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
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)
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 |
Family
ID=9225410
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
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)
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)
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 |
-
1979
- 1979-05-10 FR FR7912146A patent/FR2456133A1/fr active Granted
-
1980
- 1980-04-23 US US06/142,996 patent/US4332749A/en not_active Expired - Lifetime
- 1980-04-28 EP EP80200389A patent/EP0019950B1/de not_active Expired
- 1980-04-28 DE DE8080200389T patent/DE3070897D1/de not_active Expired
- 1980-04-28 AT AT80200389T patent/ATE14458T1/de not_active IP Right Cessation
- 1980-05-06 ES ES491185A patent/ES8101101A1/es not_active Expired
- 1980-05-06 BR BR8002771A patent/BR8002771A/pt unknown
- 1980-05-08 FI FI801496A patent/FI71957C/fi not_active IP Right Cessation
- 1980-05-09 CA CA000351770A patent/CA1146316A/fr not_active Expired
- 1980-05-09 NO NO801395A patent/NO155735C/no unknown
- 1980-05-09 JP JP6081280A patent/JPS55152812A/ja active Granted
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 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA1079919A (en) | Method for making structural foams with facing sheets | |
EP0852588B1 (de) | Cellulosemicrofibrille mit modifizierter oberfläche-verfahren zur herstellung und verwendung als füllstoff in verbundwerkstoffen | |
EP0890583B1 (de) | Verfahren zur Oxidation von Polyethylenwachsen | |
US4927871A (en) | Process for producing modified ultrahigh-molecular-weight polyolefins | |
EP0019950B1 (de) | Verfahren zur Herstellung von Polyolefin-Fibrillen und erzeugte Fibrillen | |
CA2397673C (fr) | Procede d'obtention d'un latex photochromique | |
EP0394090B1 (de) | Wässrige Emulsion, basierend auf gepfropften Polyolefinen, Verfahren zur Herstellung und Verwendung, insbesondere bei Zusammensetzungen zur Imprägnierung | |
FR2464982A1 (fr) | Dispersions aqueuses de colophane renforcee | |
EP0231699B1 (de) | Äthylenpolymer-Zusammensetzungen, Verfahren zu deren Herstellung und deren Anwendung zum Erhalten industrieller Gegenstände | |
FR2795076A1 (fr) | Dispersions cationiques hydrophobes stabilisees par des copolymeres maleimides de faible masse moleculaire, pour le collage du papier | |
EP0215082B1 (de) | Verfahren zur herstellung von lösungen von lignocellulosehaltigen materialien und die hergestellten lösungen | |
CA1079917A (fr) | Procede pour la production de structures fibrillees en resine synthetique__________________________________________________ | |
FR2627498A1 (fr) | Procede de traitement de polypropylene | |
CH646689A5 (fr) | Emulsion aqueuse de peroxyde destinee au traitement des fibres de verre. | |
US4152317A (en) | Process for improving the water wettability of polyolefins | |
EP0000083A1 (de) | Verwendung von Pulvern aus Vinylchloridpolymeren zur Herstellung von Separatoren für Batterien | |
WO1996003544A1 (fr) | Composition latex pour l'encollage de fils ou de fibres textiles et procede d'encollage | |
FR2695645A1 (fr) | Procédé de préparation de polyaminoborazines. | |
FR2477173A1 (fr) | Agent epaississant contenant de la silice et une polyolefine fibreuse et composition le contenant | |
EP0337873A1 (de) | Wässerige Dispersionen von thermisch härtbare Polymeren auf der Basis von Alkyl(meth)acrylat, Verfahren zu deren Herstellung und deren Verwendung als Bindemittel und/oder Imprägniermittel | |
EP0086123A1 (de) | Verfahren zur Herstellung von Styren-Pfropfpolymeren | |
CH618474A5 (en) | Process for the preparation of hydrophilic polyolefin fibres | |
CH405704A (fr) | Solution de polypryrrolidone et procédé de préparation de celle-ci | |
BE824531A (fr) | Procede de production de fibrilles a base de polyolefines | |
BE559841A (de) |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Designated state(s): AT BE CH DE FR GB IT LI NL SE |
|
17P | Request for examination filed |
Effective date: 19810601 |
|
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: HERCULES INCORPORATED |
|
ITF | It: translation for a ep patent filed | ||
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Designated state(s): AT BE CH DE FR GB IT LI NL SE |
|
REF | Corresponds to: |
Ref document number: 14458 Country of ref document: AT Date of ref document: 19850815 Kind code of ref document: T |
|
REF | Corresponds to: |
Ref document number: 3070897 Country of ref document: DE Date of ref document: 19850829 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: AT Payment date: 19900411 Year of fee payment: 11 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 19900415 Year of fee payment: 11 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 19900418 Year of fee payment: 11 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 19900420 Year of fee payment: 11 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 19900426 Year of fee payment: 11 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 19900502 Year of fee payment: 11 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 19900531 Year of fee payment: 11 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Effective date: 19910428 Ref country code: AT Effective date: 19910428 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Effective date: 19910429 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Effective date: 19910430 Ref country code: CH Effective date: 19910430 Ref country code: BE Effective date: 19910430 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 19910430 Year of fee payment: 12 |
|
BERE | Be: lapsed |
Owner name: HERCULES INC. Effective date: 19910430 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Effective date: 19911230 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee | ||
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Effective date: 19920201 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |
|
ITTA | It: last paid annual fee | ||
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Effective date: 19921101 |
|
NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee | ||
EUG | Se: european patent has lapsed |
Ref document number: 80200389.7 Effective date: 19911108 |