DE2622374A1 - FIBROUS STRUCTURES OF OLEFINIC POLYMERS AND THE PROCESS FOR THEIR PRODUCTION - Google Patents

Description

PATENT LAWYERS

DipL-lng. P. WIRTH Dr. V. SCHMIED-KOWARZ! K DipUng. G. DAN N EN BERG Dr. P. WEiNHOLD Dr. D. GUDEL

2S1134 β FRANKFURT AM MAIN

TELEPHONE (0311)

2870K IiR. ESCHENHEIMER STRASSE 30

SK / SK

Case FC. 2131

Montedison S.p.A. Fora Buonaparte 31 Milan / Italy

Fibrous structures of olefinic polymers and methods of making them

The present invention relates to fibrous structures of olefin polymers with improved bonding properties in the manufacture of synthetic or semi-synthetic paper and a process for the manufacture of such structures as well as paper and paper-like products made from these structures alone or in a mixture with cellulose fibers.

It is well known that synthetic polymers can be used to produce fibrous, also as fibrils, fibrids, plexofilamentary fibrids or microflakes known structures with similar morphology and cellulose fibers obtained as a partial or complete replacement of the latter in the manufacture of paper or paperboard Products are suitable for the processes used to manufacture conventional paper »

These fibrous structures do not have a granular shape, whereby is at least one dimension smaller than the other two;

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besides being in the shape of a real fiber, they can also have the of a movie.

These fiber-like structures (hereinafter also referred to as "fiber structures" called) have geyenä about liquids, especially water, a very high absorption coefficient and can after spontaneous mechanical interlacing self-supporting felts and form plates which have a specific surface area above 1 m / g as an essential property. Usually they have sine Length or larger dimension between 1-50 mm and an obvious (average) diameter or a smaller one Dimension to / ical 1-400, u.

According to British patent specification 868 651, such structures prepared by adding a solution of a synthetic polymer to a non-solvent of the polymer and at the same time the precipitated or swollen polymer is subjected to the action of shear forces. A similar process is also described in German Patent No. 2,208,553.

According to British Patent 1,287,917, structures are obtained similar morphology, which can also be used as a replacement for cellulose fibers can be used in papermaking, by polymerizing o ^ -olefins in the presence of coordination catalysts under the action of shear forces active in the reaction medium.

Other methods of manufacturing fibrous structures with the above properties and uses in the state of more or less coherent aggregates or fibrillated

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filamentary structures (plexofilaments) consist in that one Solutions, emulsions, dispersions or suspensions of synthetic Polymers in solvents, emulsifiers or dispensers media or mixtures thereof under conditions of a f ^ st immediate evaporation of the solvent or dpr present liquid phase extruded through an opening ("flash spinning process") · Such methods are described, for example, in U.S. Patents 891,943 and 1,262,531, in U.S. Patents 3,402,231, 3,08 *. 519, 3 222 784, 3 227 794.3 808 091, 3 770 856, and 3,740,383, Irish patent 789,808, French Patent 2 176 858 and German Patent 2 343 543 are described.

The fibrous aggregates or plexofilaments obtained by this process can easily be split open by cutting and whipping.

(divided)
until the elementary fiber structures with a specific surface area above 1 m / g, which are suitable for the manufacture of paper and similar products, are obtained.

For example, British Patent 891,945 describes the manufacture such fiber structures (plexofilament fibrids) by fragmentation of the plexofilaments obtained by flash spinning polymeric solutions.

Finally, fibrils or fiber structures with similar pollution properties can be obtained by adding a solution, suspension, Emulsion or dispersion of a polymer in solvents and / or emulsifying or dispersing media during the

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Extrusion under conditions of rapid evaporation of the liquid phase of the cutting effect of a gaseous flowable Exposing high velocity material directed at an angle to the direction of extrusion. Such procedures are in the Italian patent 947 919 and in the Italian

(= P 2 ^C 51 532.6)

Patent application 29594 A / 74 / by the same applicant.

The possible use of the above fiber structures, however are obtained from a polyolefinic material, as partial / iron Replacement of cellulosic fibers in papermaking faces the main disadvantage of poor adhesion between the fibers different fibers within the formed paper texture.

Therefore, the papers obtained show mechanical properties; whose values increase with the increased content of polyolefinic fibers to decrease.

If one assumes the value of the breaking length ("breaking length" = BL) as the characteristic parameter of the mechanical properties of a paper, it turns out that this value can drop to less than a third of the value of a paper consisting only of cellulose if a content of 30 Ge \ ii .-% polyolefinic fibers is present in the paper.

According to the invention it has now been found that such polyolefinic Fiber structures with better usability in papermaking due to an increased mutual adhesiveness with cellulose fibers if they have at least one or more nitrogen-containing polymeric compounds on their surface contain one of the following general formulas:

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(I) __Α _Γ Β - (A '- D)

in which · ρ = O or T;

Α., B and A can have different meanings depending on * / om V.'ert from ρ, and in particular when ρ = 1, A ,. and A ₂ independently of one another for radicals

RRR RRRR RRR

Ml MM IM

-C-C-C-, -C-C-C-C-, -C-C-C-,

RRR R: l RRRR ₁ R '

or

RRRR MM C

M.
RR

also still, stand; or they can / if B has a meaning other than a

Piperazine residue, for residues of the type

R R

I I

-C-C-

I I

R R stand, while B is a nitrogen-containing radical of the formula -IM-,

-N-X-N- or (piperazine)

if, on the other hand, ρ = D, then A. means a remainder

means;

-CH.

or

R R

while B = A. or the following remainder

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-CH-CR- where in the latter case the molar

CCII ) Ratio of A / B in the macromolecule between

I 2 ^y yl 1

I is 1:20 and 4: 1;

Furthermore are

R = H, an aliphatic C. "" radical or a cycloaliphatic or aromatic C ^ .. η radical;

R = II, -OH, -QR, -0-CR, -CN ^ ^R , -N ^, - (CH) -1 I 0 I '^ - ^X ~

Cl, Br, 3: °

D = -N-, -N-X-F-, -N

I i

R ₂ = a C. A.lkylgruppu; R = H or -CH ₃ ;

X = a C _2D alkylene radical in which one or more H atoms can be replaced by a hydroxyl, alkyl, amine or alkylamine group; X can also stand for the following remainder:

m is an integer between 0 and 4;

y is an integer between 1 and 3;

ζ is an integer between 1 and 20;

n is an integer between 5 and 100 when ρ = 1, and

between 5 and 1000 when ρ = 0;

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- ^C V ^CH 2

O O -C-B-C-I

thereby i.st

B and D = -N-K-N- or sin ~ N RR

rest

2 m

K = a C., alkylene radical; I -o

R = H, an aliphatic C ₁

Remainder or a cycloaliphatic sr

or aromatic C, ^ _n radical; R ₂ = C., alkyl radical m = an integer between O and 2; η = an integer between 5 and 500; (TII)

O O

U) ODBi 6, D and η have the meaning given for formula (II)

to have;

(IV)

CH CH

CH

where Rj = a C. Alkyl group and

η = an integer between 10 and 300.

The compounds of the formula (i) are known and can by Polycondensation of epichlorohydrin or 4-chloro-1,2-epoxybutane (or their R-derivatives substituted in the chain) with one or more primary amines and / or secondary amines of

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R-NH ₀ , HNXNH, HN ^ SH,

² I ι

R R,

and by possible subsequent modification by substitution of the hydrogen bonded to the carbon atoms of the chain ato.ne with R residues in accordance with customary organic methods and / or by etherification of at least a part of the hydroxyl groups originating from the polycondensation with ROH residues, or their esterification with R-COOH acids or at least some of them Substitution with chlorine, bromine or 3odatoms or

/ R / R R

Amide -CO-N ', Arain -WC or alkylamine - (CH ₀ ) l \ l'

RR * ■ ^Z R

Remains produced according to the usual practice of organic chemistry u / earth.

The above polycondensation is known. It can, for example, according to the method of C. Caldo in "Chimica e Industria", Vol. 49, [\ lr. 10, October 1967, pages 915 and 1047, and "Die Makromolekulare Chemie", 116 (1968), pages 158-172 and in the US patents 3,475,518 and 3,527,846.

Preferred primary and secondary amines for the polycondensation are ethylamine, propylamine, n-butylamine, n-pentylamine, n-hexylamine, n-octylamine, n-decylamine, n-dodecylamine, n-dctadecylamine, n-hexadecylamine, n-dioctadecylamine, laurylamine , Cyclohexylamine, aniline, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,2-propylenediamine, dipropylenediamine, diethylenetriamine, di-triethylenediamine, tetraethylene pentaamine, N, M ^f -diisopropylhexamethylenediamine, 1,3-bis- (n-dodecylamino) -2 I, N'-dibutylhex ^ methylenediamine, 4,4'-bis (methyl-

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amino) -diphanylmethane, l \ l, f \! '- dicyclohexylhtixamethylenediamine, pipe razine, trans-2,5-dimethylpiperazine, 2-methylpiperazine, 4,4 '~ bis ~ (ethylamino) -3,3'-dimethyldiphenylmethane.

The compounds of the formula (I) can continue to be given by the known reaction between cx, W-dihalogen derivatives voi, ethane, propane and butane or their corresponding R-substituted derivatives with primary and / or secondary amines of the formulas

r_NH, H-N-X-N-H and H-N

² Il s-

R R (Rj

^v 2 ni

receive u / earth. General information about this manufacture can be found in "feth.d.Grg.Chem.", Houben Weil, vol. 14/2, page 455, 477, 487 and 590.

Preferred dihalogen derivatives include 1,2-dichloroethane, 1,3-di ~ chloropropane and 1,4-dichlorobutane.

When ρ = 0, the compounds of formula (i) fall under following classes:

(a) polyvinyl pyridines;

(b) mixed polymers between vinylpyridine and amides of 06ß-unsaturated acids with 3-6 carbon atoms, u / ie acrylic, methacrylic, vinyl acetic acid and vinyl _propionic acid;

(c) Reduction products of these copolymers, obtained by the method of F.Danusso and P.Ferruti in "Chimica e Industrie" (1968), jjjD, 71, through which the reduction of the amide group into a primary Anjingruppe takes place; and

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(d) the reduction products of homopolymeres of the amides 0 \, G-unsaturated Acids with 3-6 carbon atoms according to the above publication by F. Danusso and P.Ferrut-i.

With regard to the products of classes (b) and (d), the preferred th amides e.g. N-isopropylacrylamide, Ν, Ν-dimethylacrylamide, i \ I-Phcnylacrylamid, N-Cyclohexylacrylamid, N-Isopropylmethacrylamid, N-methyl-N-phenylacrylamide, N-p (-naphthylacrylamide, f \ i-dodecylacrylamide and N-benzyl acrylamide.

The compounds d & v formula (II), (HI) and (IV) are also known. Compounds of the formula (II) are obtained by reaction of an ester of an acrylic acid with one or more secondary diamines of the formulas

H-N-K-NH or H-N N-H

^{R R} (R)

according to the method of F.Danusso and P-Ferruti in "Polymer", 88_, Vol. 11 (2), (1970).

The products of the general formula (III) can be prepared by reacting divinyl sulfone with one or more disecondary diamines of the last-mentioned formulas according to F. Danusso and P-Ferruti in "Chemica Industriale" (1967), 49 , 826.

Preferred diamines for the preparation of compounds of the formulas (Il) and (Hl) are, for example, ethylenediamine, propylenediamine, hexamethylenediamine and piperazine.

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The compounds of the formula (IV) are obtained by polymerization of diallylamines according to the method of Youji Negi, Susurno Harade, Osamu Ishuzuka in "3ourn.Polym.Sci.", Vol. 5 A (1) (1967), p 1951-65.

The possibility of using fibrils or analogous glyolefinic ones, fiber structures containing nitrogenous compounds in papermaking depends on the ability of nitrogenous Compound, during the mechanical mixing treatments with water and, if possible, with cellulose, which are used to produce the corresponding aqueous pulps are necessary to adhere to the surface of the fibrids and the presence of sirer cohesive energy, which is at least equal to the cohesive energy of the fibrils themselves.

It is advisable to disconnect the nitrogenous compound of the fibrils during these treatments because their presence as a non-fibrous, separate phase in the aqueous pulp the surface properties and mechanical resistance of the paper formed proportional to Crowd would worsen.

According to the invention, the nitrogen-containing Compound not in an amount exceeding 400 ppm per treatment stage of the fibers in a beater (beater) of the Lorentz Wettres type under the striking conditions according to

70 standards
TAPPI T-200 os./ can be removed with a load of 0.

Depending on the type of nitrogenous compound, their amount and thickness on the fiber surface as well as the method of suspension it happens that the outer parts of the connection are easier and faster to remove than parts near the Fiber surface. In the case of the Dutch treatment as above Conditions, an initial loss of nitrogenous compound in excess of 400 ppm / h can occur, but this increases stabilizes below this value more or less quickly during treatment,

The aim of the present invention is therefore to create fiber structures olefinic polymers that can completely or partially replace cellulose fibers in paper manufacture, whereby the Fiber structure at least on its outer surface one or more nitrogen-containing polymeric compounds of one of the following general formulas

_m Γ, "i_

(Ti / i_p _ ffl _ η ι ι ,, ¹

^{K J} 1 ^K 2 ^U) p ί

Jn

in which ρ = 0 or 1;

Α., B and A ₉ can have different meanings depending on the value of ρ, and in particular when ρ = 1, A. and A _{9 can} independently of one another for radicals such as

RRR RRRR ^RRR RRRR

I j I IiII IM I I I I

-C-C-C-, -C-C-C-C-, -C-C-C-, or "C-C-C-C-,

I I I MM ill I I M

RRR RRRR RR ₁ R * ^ k R ^

stand; or

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- 13 they can also, if B has a meaning other than one Piperazine residue has, for residues v / ora type

R R

It

-C-C-

I I

R R

stand, while B is a nitrogen-containing radical of the formula -N-,

-NXN- or (piperazine) - ^Ν χ - β- ;

R R <V. -

if, on the other hand, ρ = 0, then A. means a remainder

or ^ ^CH 2 ^ y RR

while B = A. or the following remainder

i in the latter case the molar

(CH) Ratio of A, / B in the macromolecule between ^v - | 2 ^y yl ¹

J ^ ₀ 1:20 and 4: 1;

'continue to be

R = H, an aliphatic C * on R ^9G ^ or a cycloaliphatic or aromatic C, _1Q radical;

RH, -OH, / -OR, -0-CR, ~ CN. ^ ^R , -N ^ ^R , - (CH) - ^

0 P \ R Nl ^{l Z}

Cl, B ₁ -, 3:.

· "· XT \ T Y XT

^R k ^ ^(R 2'm

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R ₂ = a C ₁ . Alkyl groups in R ₃ = H or -CH ^; X = a C _{1? Q} alkylene radical. in which a ODSR more H atoms may be replaced by a hydroxyl _f alkyl, Amir.- or alkylamine group, ·, X may be on for the following radical:

-CH

SJ is an integer between 0 and 4j y is an integer between 1 and 3; 2: is an integer between 1 and 20 j η is an integer between 5 and 100, uienn ρ -between 5 and 100tf when ρ = 0;

= 1, and

(ID

O 0 -CH -CH-C-F-C-

B uad D = -N-K-N- or a

•, is there

rest

K = a C. _c alkylene radical;

R = H, an aliphatic C ^ _ _2Q radical or a cycloaliphatic

odor aromatic C, ^ radical; R ₂ = a C ^ ₅ alkyl radical

m = an integer between 0 and 2; η = an integer between 5 and 500;

(III)

0 O

II I!

CH -CH -S-CH-CH-B-CH ₀ -CH-S-Ch-CH -D 2 2 η 2 2 2 2 Ji 2

O O

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in which B and D independently represent nitrogen-containing radicals of the type

N-K-N-

A d

or - * [\ l '

IN THE-

stand

K = a C. Alkyl radical means 1 -6

R = H, a C residue or a aliphatsichen Cycloaliphatic see C. or aromatic. _n means remainder

o - I U

R = a C alkyl radical, m = an integer between 0 and 2 η = an integer between 5 and 500;

(IV)

.CH

CH

CH

XH.

where R ₃ = a C ^ _ ^ alkyl group and

η = an integer between 10 and 300.

These Fasyr structures are characterized by the fact that they are a specific surface over 1 m / g and that at least one

the nitrogenous compound present on its surface not in amounts above 400 ppm / h treatment in one i.orentz wet race Dutchman in impact conditions according to TAPPI T-200 os 70 standards can be removed under a load of 0.

Barrel structures which on the surface have quantities of nitrogen-containing compounds of the type that cannot be removed under the conditions mentioned above, up to about 0.5% of the total weight of fibers and nitrogen compounds, can already be regarded as satisfactory according to the invention, with quantities of nitrogen-containing compound between 0.5-10 % on the fiber surface are preferred.

Although amounts above 10 / α in certain cases and in some nitrogen-containing compounds provide a further improvement in the utility of the fibers, they are from an economic point of view and because of application difficulties generally not appropriate to the fibers.

The olefinic which makes up the fiber structures according to the invention Polymers can be low or high density polyethylene, a polypropylene consisting essentially of isotactic macromolecules, Poly-4-methylpentene-1 or a random or block copolymer be made of ethylene and propylene.

Containing the nitrogen-containing compounds according to the invention Fibrils or fiber structures can be produced in various ways. One method is to mix the polyol

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Finnish fiber material (regardless of its manufacture, as long as it has a specific surface area above 1 m / g) with a concentrated Solution or suspension of one or more nitrogen-containing compounds in water or another liquid diluent and then filtering and drying the fibers at temperatures below the softening temperature of the Polyolefins. Satisfactory results are achieved by using solutions or suspensions made up of several nitrogenous substances Genetic compounds with different degrees of softening, the lower temperature being at least 10 C. below the softening temperature of the polyolefin and then drying the fibers treated in this way at this lower temperature. Depending on the nitrogen compound used and the amount that one wishes to deposit on the fibers, can the treatment of the fibers should be repeated a few times. The fibers are light after drying with slight agitation dispersible in water.

A convenient method for quickly achieving the inventive Fiber structures, the nitrogenous compound shows exceptional adhesion to the fiber surface is to be found under conditions of almost instantaneous evaporation the liquid phase (flash spinning) a solution, emulsion, dispersion or suspension of the olefinic polymer in one or more liquid medium extruded through an opening, wherein the solution, emulsion, dispersion or suspension one or contains several of the above nitrogen-containing compounds.

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According to the invention it was found that the above-mentioned nitrogen-containing compounds lay on the surface of every fibril or every elementary fiber structure under these working conditions and thus form the aggregates or plexofilamants known to be obtainable by such extrusion. The quantitative analysis carried out on the fibrils obtained in this way, as described later, has shown that at least 60 % by weight of the nitrogenous compound bound to the fiber lie outside the barrel surface, while the remainder lies in the surface zone of the fiber is incorporated "

This is achieved by processes that involve the conversion of the QIefinpolymeren in fibrous structures either in the form of individual fibrils or in the form of more or less complex and stable ones Aggregates result by adding solutions, suspensions, emulsions or dispersions of the polymer in one or more liquid Media is extruded through an orifice under such temperature and pressure conditions that there is almost instantaneous evaporation of the Effect systems present liquid phase in the extrusion environment.

Some of these l / experienced are in the above mentioned patents and relate to the production of fibrillated fiber structures by "flash spinning processes", starting from systems with different compositions and using suitable working conditions (see e.g. the above-mentioned Italian Patent specification 947 919 and the Italian patent application 29594 / A / 74).

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When the extruded products are made from fibril aggregates or plexus filaments exist, these can be divided up in a dutchman or by some other suitable method, until elementary fibrils are obtained or fiber structures of such dimensions that they are directly can be used to make paper.

According to this second production process, the nitrogen-containing compound is added to the polyolefin preparation to be extruded in an amount of at least 0.5% by weight , based on the total weight of polyolefin and nitrogen-containing compound, preferably in an amount between 0.5-10 % of the total weight.

The nitrogenous compound can in the system under the temperature and pressure conditions for performing extrusion can be soluble or insoluble.

Inorganic fillers and wetting agents of various types can be present in the mass to be extruded.

Another object of the present invention is to provide a process for the production of fibrils or fiber structures which contain nitrogen-containing compounds as defined above, which is characterized in that under conditions of almost instantaneous evaporation of the liquid phase, a solution, emulsion, suspension or dispersion of a olefinic polymers in one or more liquid medium containing about 0.5-50% by weight , based on the total weight of polyolefin and nitrogen compound, of a polymeric nitrogen-containing compound of the above

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Containing formulas (i) to (IU), extruded through an orifice.

As mentioned above, the fiber structures according to the invention show improved use properties in papermaking by conventional methods.

L) S patent 3 669 829 describes the production of semi-synthetic paper by conventional methods, starting from aqueous suspensions of cellulose fibers, conventional mono-stretched polypropylene fibers and amounts of 0.1-10 % by weight binders in the form of polycondensation polymers from epichlorohydrin with primary and secondary aliphatic, aromatic, or heterocyclic amines. However, the use of the nitrogen-containing polymers according to the US patent mentioned does not allow the fiber structures according to the invention to be achieved, since when working according to the method of this patent, the nitrogen-containing compounds (due to the high adsorption capacity of cellulose with respect to these compounds) lay on the cellulose fibers, which causes their surface is modified substantially, while the polyolefinic fibers remain practically uncovered.

That wholly or partly from the polyolefinic according to the invention Fibrilized paper shows better mechanical properties than a paper that has the same polyolefinic fiber structures is established per se.

According to the invention it was surprisingly found ^ that the mechanical properties can be further improved if at least some of the macromolecules on the fiber

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Surface nitrogenous compound present about '-.' In or several basic nitrogen atoms contained therein with a polyacid, such as polyacrylic, polymethacrylic, polyitaoon or alginic acid? lets react. According to this reaction, one atom of basic nitrogen reacts with at least one carbonyl group the polyacid to form the corresponding salt; the reaction however, secondary bonds can also be formed between the basic nitrogen atoms themselves and various carboxyl groups of the polyesters (usually up to 5 carboxyl groups).

The reaction between the polyacid and the nitrogen-containing compound can be carried out by treating the fibrils containing the nitrogen-containing compound with an aqueous solution of the polyacid. The concentration of the solution and its temperature can vary within wide ranges. For practical reasons, a solution usually uiird from 0.05-5 - preferred polyacid%. however, higher concentrations can also be used if one wishes to reduce the reaction time, which, however, depends on the molecular weight, the viscosity and the solubility of the polyacid in water. The reaction can take place at room temperature, temperatures between 0-80 ° C. in practice. can be applied. Under the above general conditions, the reaction time, ie the residence time of the fibrils in the polyacid solution, is between a few seconds and 5 minutes and gives satisfactory results. Longer reaction times offer only limited advantages due to the slower rate at which the polyacid reacts with the immediately underlying portions of the nitrogenous compound.

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- 22 -

After the watering, the fiorile can be filtered and washed with water washed to eliminate excess polyacid and recovered as plates j or they can, if necessary after Mixing with cellulose drum, more than usual for papermaking Method used -j

The reaction with the polyacid can also be carried out on the paper, which consists of the fibrils according to the invention or comprises them, or on the corresponding leading plates according to the process known as "sizing ^{presses 11} ; the paper or the plate is treated under the above conditions with the Polyacid solution wetted or soaked, whereupon the excess polyacid is eliminated by squeezing and, if necessary, washing with water and the film is then ^{dried at a temperature preferably between 95-11O 0} C. The treatment can be carried out continuously by removing the sheet of paper formed or one of the Fibrous plate coming from the deformation container, preferably with a moisture content of 20-180 %, is placed in vats with the polyacid solution, which leads sheets or plates soaked with this solution between nip rollers - if necessary after washing with water beforehand - and finally between conventional, to 95-11O ⁰ C. nt cylinders dries.

A modification of the above process which gives similar results is the impregnation of the nitrogenous Compound containing fibrils or the corresponding arches or

such, plates with an aqueous solution of an acidic substance or / which

an acid, such as aluminum sulfate, can form the subsequent

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Treatment of the products impregnated in this way with an aqueous polyacid solution with a pH of about 7-9, some of which has been converted into salt form with an inorganic or organic base, such as NaOH, an amine or ammonia, and the process is terminated by squeezing and / or Wash and dry as above.

The present invention provides fascrartige structures or fibrils, the nitrogen-protean compounds is as defined above contain, in uielchep at least a portion of the macromolecules of the nitrogen compound present on the überfläch ¹ = · the fiber structures chemically by a plurality of basic nitrogen atoms or carboxyl groups of a polyacid, such as polyacrylic , Polymethacrylic, polyitacon odex alginic acid, are bound.

In addition, the present invention provides a paper which is formed in whole or in part from the above fibrous structures,

The following examples illustrate the production of the fibrils or fiber structures according to the invention. The fibrils each For example, for the usual production of synthetic or semi-synthetic paper, its properties have then been used are listed in the attached table.

In the examples, the properties and amounts of the nitrogen-containing compound bound to the fibers were as follows certainly:

Immediately after their production, the nitrogen-containing * - term compound containing fibers of a treatment in a Lorentz Wettres Dutchman under the working conditions according to T-200 os. 70 standards subjected to a load of 0 to the presence of non-removable nitrogenous

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To determine compounds in amounts above 400 ppn / h treatment « During the treatment, the amount of nitrogen-containing bound to the fibers and present in the liquid phase became Compound by azidimetric titration of basic nitrogen and / or azatnmetic analysis according to the KjaLdhal method of the corresponding samples taken from the Hollander.

Usually it was found that the loss of nitrogenous Connection from the fibers very quickly after an initial, more or less high loss on the above Values stabilized - almost immediately in some cases.

The acidimetric analysis of the fibers was carried out on a conductivity meter of type F 39 from Wies.Techn.Werkstätten, Weilheim / Obb., On samples from etu / a 1 g fibers, in 100 ecm dist. Water dispersed, by adding 0.002N HCl.

Through the azidimetric analysis the whole, on the fiber surface basic nitrogen present is titrated, the end of the reaction being indicated when the pointer of the conductivity meter suddenly moves to the position corresponding to the color change and remains there for about 30 seconds.

By special, previously prepared, for each nitrogenous Compound specific calibration curves then became the amount of nitrogenous compound present on the fiber surface calculated. The amount of nitrogenous compound possibly trapped in the surface zone of the fiber, their determination by the azidimetric method takes an extremely long time could be determined by the difference between the amount of total basic compound bound to the fiber

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by the Kjeldhal method.

Cellulose from a mixture of equal parts of bleached birch cellulose and Scandinavian spruce cellulose with a blow measure ( ¹ SR) = 30 was used to produce the semi-synthetic paper.

In the examples, the paper was produced on the basis of u-aqueous pulps with 20 g / l fibrous material, which consisted entirely of the fiber structures according to the invention or a mixture thereof with cellulose; The pulps were converted in the usual manner on a continuous papermaking machine into sheets and dried between heated at 100-11O ⁰ C. cylinders at a pressure of 50 kg / cm 5-60 seconds. The treatment with the polyacid was carried out by impregnation of the sheets thus obtained with an aqueous solution at room temperature, the 2 wt -.% Polyacid. contained, a pH value between 4-5 and a viscosity measured at 20 C. of about 20 centipoises. About 1 minute after impregnation were conducted, the sheets between nip rolls and dried at 100-11O ⁰ C.

The fourths of the breaking length (BL) mentioned in the attached table were measured according to ATICELCA MC2 / 68 standards; You need to can be compared with the value of sheets of paper that have only been produced from cellulose of the type described here using the same process? were presented. Before treatment with a polyacrylic acid solution they were about 6500 and after this treatment about 6800,

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Example 1_

Preparation of the nitrogen-containing compound of the formula:

-CH -CH-CH ~ N 2 J 2

OH

K -CH -CH-CH-N OH

η = 14

10 mol of diglycidylpiperazine (obtained by condensation of piperazine with epichlorohydrin in a molar ratio of 1: 2 in a known manner) and 1 g mol of cyclohexylamine together with 6 l of isopropanol were introduced into a reactor provided with a stirrer and reflux condenser. The mixture is heated and / uide 5 hours to about 82 ⁰ C, then the solvent was distilled off under Murde impeded pressure to dryness. The product thus obtained was a solid with a Eriueichungstemperatur of about 50 ⁰ C. In azotometrischer analysis (Kjeldhal) showed the product has a nitrogen content of 14 Geu) .- / o (theoretical = 14.7%). Its osmometric average molecular weight was 4x10, hence η =

Production of the fiber-like structures according to the invention. For this purpose, the method and apparatus of the Italian patent application were used 29594 A / 74 used; a diagram of this device is shown in the accompanying drawing.

Following the general procedure of this patent application, a Solution, emulsion or dispersion of the polymer in a liquid medium under conditions of almost instantaneous evaporation liquid phase extruded through nozzles (5) in a zone, which by the diverging section (4) of a nozzle from the converging-diverging Type (1) is formed.

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The gaseous flowable material (6) flows through the converging Section (2) and the (crucial) narrowing part (3) of this nozzle and collide at an angle and at high Speed with that in the divergent section Preparation. In the case of aiiftr-pff ^ n on the extruded substance the flowable material has a temperature below the solution and / ο the softening temperature of the system composed of polymer and residual liquid in the polymer. The one used for this manufacture Nozzle has an annular narrow (critical) section 6.5 mm in diameter and a maximum (terminal) section in the diverging part of 15.42 mm in diameter. The distance between the critical section and the maximum section is 31.8 mm.

10.4 kg of high-density polyethylene (MI = 5, melting temperature = 132 ° C.) Together with 0.31 kg of previously prepared nitrogen-containing compound (corresponding to about 2.9 Ge \ n .-% nitrogen-containing compound, based on the total weight with the polyethylene) and 80 1 η-hexane introduced.

The container was heated to obtain a solution of the olefinic polymer in solvent under pressure to 12.3 at ⁰ C. 18D. Under these conditions, the solution (7) was extruded into the above-described diverging section (4) through 8 cylindrical nozzles with a diameter of 1.5 mm each, which were arranged orthogonally around the terminating section of the diverging part. The gaseous flowable material was water vapor at the entrance of the converging section (2) with about 10 At and about 200 ° C. used.

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The flow rate of the solution was 100 l / h for each nozzle; the water vapor pressure at the final diverging section is etu / a atmospheric pressure.

The product thus obtained passed JaJt analysis by means of an optical microscope of individual fibrils with a length between 3-6 mm with a average length of 5.8 mm and an average apparent diameter of 27 / U. Your specific surface was 5 m / g.

500 g of the fibers thus obtained showed lancer after 10 minutes Treatment in a Dutchman under conditions according to TAPII T-200 os.70 standards under a load of 0 indicates a loss nitrogenous compound below 400 ppm- each successive Hour.

The azotometric (Kjeldhal) analysis of these fibers after the treatment showed a total amount of nitrogen-containing compound present of 2.8 % by weight, based on the total weight of fibers and nitrogen-containing compound.

In the analysis, the azidimetrischen present on the fiber surface amount of nitrogen-containing compound was 2.5% of the total weight of fibers and nitrogen compound, corresponding to 90 wt -.% Of the total n-Fasex by the gene on ο mineral s, nitrogenous compounds.

The fibrils coming from the treatment in the Hollander had a specific surface area of 5 m / g and were made according to those described above Process used for making sheets of paper.

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example

0.8 kg of polyethylene according to Example 1, 0.04 kg of nitrogenous compound according to Example 1 (corresponding to 4.7 % _t based on the total with the polyethylene) and 8 liters of η-hexane were placed in a 24 l autoclave. The car theft was at Autog ^ neiin at pressure of 15 to 185 C. _f heated to prepare a solution of the polyolefin to obtain in hexane; Under these conditions, the contents of the autoclave were extruded into the surrounding atmosphere through a nozzle 1.5 mm in diameter and 1.5 mm in length *

This is how you get a highly fibrillated filament from a very large numbers' .'on fibrils, joined together by their ends: and were attached at different heights (plexofilament). This filament was in a Lorentz Wettres Dutchman divided under 2.5 kg load in a concentration of 50 g filament per 1 water. 20 minutes after the start of the procedure the filament was completely separated into individual fibrils that were about 3 mm in length, an average diameter

of 22 / U and a specific surface area of 5 m / g.

According to Kjeldhal's analysis, the total amount of nitrogen-containing compound bound to a single fiber was 2.6 % of the total weight of the fibers containing the nitrogen compound. The loss of nitrogen-containing compound through treatment of these fibrils in a Lorentz-Wettres-Hollander under a load of 0 according to TAPPI T-200 os.70 standards was below 400 ppm / h. The amount of nitrogen-containing compound present on the fiber surface was 2.4 % of the total weight of the fibers (= 92 % of the total nitrogen compound present) »

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example

Preparation of a compound of the following formula: 0 0

2 2

(H)

n = 25

3 mol of diacryloylpiperazine, 3 mol of N, N'-diisopropyldimethylenediamine and viasser were placed in a reactor in such an amount that a monomer concentration of about 30% by weight was obtained. The mixture was allowed to react for 8 hours at 100 ° C. with constant stirring, the reaction mixture was cooled and the formed polymer was separated off by crystallization; it had an F. of 97 ⁰ C.

Making the Fibrils

In the pressure vessel of Example 1 there are 9 kg of high density Polyethylene (M.I. = 4, F. = 132 ° C.) Together with 0.6 kg of nitrogenous polymer prepared above and 210 1 η-hexane introduced. The mixture was heated to 178 ° C. and a pressure of 14.6 at brought and then through the device mentioned in Example 1 at an hourly flow rate of 100 liters per extrusion die using a flowable water vapor cutting stream extruded under the above conditions.

This gave individual fibrils between 2-4 mm in length, an average length of 2.8 mm, an obvious one Diameter of 16 / U and a specific surface area of

6.1 m / g. The total amount of the nitrogen-containing polymer bound to the fibers was 5.98 % of the total weight

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Fibers and nitrogen polymer. 90 % of the polymer present - corresponding to 5.38 %, based on the total weight of the fibers, was present on the fiber surface. After treatment for 20 minutes in a Lorentz-W'ettres-Hollander with the above ΪΑΡΡΙ standards under a load of 0, the losses of nitrogen-containing compound were below 4Dfj ppm / h, corresponding to an amount of nitrogen bond present on the fiber surface of 2.8 %, based on the total weight of the fibers. After the hol. ¹ Mnder treatment, the specific surface area of the fibers was 6.1 m / g.

Example 4

Preparation of a compound of the formula:

CH-CH

(D-

= 60

A polyacrylamide with a viscometric molecular weight

4th
of 1.2 χ 10, produced by polymerization of acrylamide in the presence of azob-his-isobutyronitrile according to known processes, u / urde dissolved in methyl alcohol in a concentration of 20 g / l and due to the addition of NaBH. and CoCl ₂ χ 6H ₂ O in concentrations of 57 g / l or 71 g / l brought to a temperature of 25 ^° C.

The reaction product purified by dialysis showed an in 5.0 milliequivalents KOH / g expressible amine group content

I f

corresponding to the molar ratio C = O: -CH of about 2: 1.

• ι ι

NH,

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Making the Fibrils

The device of Example 1 was 8 kg of a similar one Polyethylene in 80 1 η-hexane and 0.80 kg dps jaio produced above reduced polyacrylamides charged, luorauf the polymer solution at 170 C. and under autogenous pressure of 10.4 at a flow rate of 100 l / h per nozzle extruded ujurds. As a flowable material, water vapor was used under the above conditions described in Example 1 were used.

The fibrils thus obtained had a length of between 2.1-3 mm, mm, an average length of 2.3, an average diameter of 22, u and a specific surface area of 4.6 tr. / G

After about 1 minute long Hollander treatment under normal conditions, the fibrils showed a loss of nitrogenous l / compound below 400 ppm / h, the latter in 9% by weight ,

and of which 92 %

based on the total weight, / (= 8.28 % abs.) was present on the fibrilobar surface. After this treatment, the specific surface area of the fibrils was unchanged.

Example 5

Making a l / compound of the formula:

CPi CH-

i I

^(IV)

_ 3 3 Jn = 50
8 moles of dimethylamine in 40% aqueous solution, 4 moles of allyl chloride and 10 moles of NaOH in 50% aqueous solution were simultaneously placed in a 5-1 flask at room temperature in 1.5 hours

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introduced. After the mixture was held for 30 minutes at room temperature, it was heated for 5 hours at 62 ⁰ C., the oily layer formed was separated and recovered therefrom by distillation, the Dime ^ hylallylamin.

Then followed the quater <iis:>. E.v; jng des Di; "et hy la lly lamina through Dissolve in anhydrous acetone along with a stoichiometric Merigo allyl chloride and let stand for 40 hours. Then became

-Chloride

the precipitate consisting of dimethyldiallylammonium / is filtered off.

335 g of this chloride were dissolved in a nitrogen-free atmosphere along with 5 cc of tert-butyl hydroperoxide in 194 g water and the solution heated for 45 hours 6O ⁰ C. and evaporated under reduced pressure to dryness. The product obtained was a polymer of quaternized dimethyldiallylamine of the above formula,

Making the Fibrils

In the container of Example 1, 8.5 kg of that used in Example 1 was added Polyethylene given together with 0.5 kg of the polymer prepared above and η-hexane in such an amount that one Solution with a polyethylene concentration of 44.0 g / l was obtained. This was extruded as in Example 1 and produced fibrils with a length between 3-5mm, an average length of 3.5mm, an apparent diameter of 22 / U and one specific surface of 4.3 m / g.

After about 15 minutes of Dutch treatment in the usual way the fibrils showed a loss of nitrogenous compound

609S49 / 0999

under 400 pprn / h treatment corresponding to a total amount of nitrogen compound bound to the fibrils of 2.58 %, of which 90 % (= 2.27 % nitrogen compound, based on the total weight of the fibrils) were on the surface. After

Holländsr treatment was the specific surface of the Ρίο
brile 4.3 m / g.

Example 6

Preparation of a compound of the formula:

(D

CH-CK-CH-N ² I ² OH

N-CH-CH-CH -NH-2 j 2 j

OH (CHj

CH.

1.8 mol of l, N-bis (2,3-epoxypropyl) piperazine together with 1.8 mol of octadecylamine and 10 l of isopropanol were introduced into a reactor equipped with a stirrer and reflux condenser. The mixture was allowed to react for 5 hours at 82.4 ° C., the isopropanol was distilled off in vacuo, and a solid residue containing 9.00% N and consisting of the polycondensate of the above formula was obtained.

Making the Fibrils

The device mentioned in Example 1 was treated with a solution of 8 kg of high-density polyethylene (M.I. = 4.5j F. 132 ° C), 0.24 g of the polycondensate prepared above and 80 l of η-hexane charged and this solution at 175 ° C, a pressure of 11 at and a Flow rate of 100 l / h per nozzle extruded.

609849/0599

Steam under the conditions of Example 1 was used as the flowable gaseous material. The fibrils thus obtained had a length between 3-5 mm, an average diameter of 30 <u and a specific surface of 4 m / g.

50Ü g of the fibrils were placed in a Lorentz Wettres Dutchman treated the above TAPPI conditions at a load of 0. After about 10 minutes, the loss of nitrogen had increased Compound stabilized below 400 ppm / hr; the specific surface area of the fibrils was 3.9 m / g.

Under these conditions, according to analysis, a total of 1.5% nitrogen compound, based on the total weight of the fibers containing it, was bound, of which about 93 % (= 1.4 %, based on the total weight of the fibers) was on the fiber surface.

Example 7

Making eJLaer compound of the formula:

-CH-CH-CH-N N

η = 26

OH

In a three-necked flask equipped with a stirrer and reflux condenser 2.2 moles of anhydrous piperazine and 2 moles of epichlorohydrin were introduced along with 600 ecm of ethanol. The mixture was taking Stirred cooling for 1.5 hours, then at 78 ° C. for 8 hours. and finally Heated for 3 hours with the slow addition of 2 mol of NaOH. The sodium chloride thus formed was filtered off and the filtrate with 1800 ecm of acetone precipitated. The white precipitate was

0 C. dried.

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separates and at 100-110 ° C. dried. The product obtained was

- 36 resin-like with a softening temperature above 200 ⁰ C.

manufacture of the fibrils

In the apparatus of Example 1, a solution of 8 kg of the polyethylene van Example 1, dissolved in 80 1 η-hexane and with eirem content of 0.40 kg of the above nitrogen-containing compound at 170 ⁰ C. and a pressure of 10 4 at at a flow rate of 100 l / h per nozzle. Steam under the conditions of Example 1 was used as the edible cutting material. This gave fibrils 2-4 mm in length, an average diameter of 23 / u and a specific upper

area of 5.5 m / g.

After about 20 minutes of Hollander treatment under normal conditions, the resulting fibrils showed a loss of nitrogenous compound under 400 ppm / hour treatment, corresponding to a total nitrogen compound content of 2.2% by weight , 95 % of which was present on the fiber surface . The specific surface area of the fibrils treated in this way was 5.4 m ² / g.

Example 8

8 kg of polypropylene (FuI. = 6.7, F. 165 C.) and n-pentane in such an amount that one Solution with a polypropylene concentration of 50 g / l was obtained. This was brought to 160 C. and under autogenous pressure from 17.6 at converted to fibrils in the device of Example 1. The flow rate of the solution was 100 l / h per nozzle. Steam was used as the cutting material under the conditions mentioned in Example 1.

6098 4 9/0999

The fibrils obtained in this way had a length of 3-5 mm, an average Length of 4.2 mm, an apparent diameter won about 20 / U and a specific surface area of 4. B m / g.

The fibrils were in a concentrate of 3Qg / l in

suspended sulfuric acid to pH 4.1, acidified water / and to the suspension a reduced, the follow Example 4 similar polyacrylamide in an amount of 1.5 g / l suspension added "The polyacrylamide was as a salt in a 1, 5-geu, .- Solution of ü, 2N Schiffelsäure before.

A 5% aqueous NaOH solution was then slowly added to this suspension up to a pH of 6.8; the suspension was filtered and the fibrils washed with water in an amount of 1 1/30 g fibrils, whereupon the latter, dried at 80 ⁰ C. were. They had a specific surface area of 4.2 m ² / g. 500 g of the same were treated in a Lorenzt Wettres Dutchman under a load of 0 according to the above TAPPI conditions. After 5 minutes of this treatment, the polyacrylamide loss had stabilized at below 400 ppm / h; the total amount of polyacrylamide bound to the fibers was 4.5 % _t based on the weight of fibers and polyacrylamide. According to azidimetric and azometric analysis, all of the polyacrylamide present was distributed over the fiber surface. After the Hollander treatment, the fibers had a specific surface area of 4.1 m / g * Example 9

Preparation of a compound of the formula:

0 9 8 4 9/099 9

-CH _n -CH ₀ -S-CII-CH-N

^{2 2} I.

Cm)

n = 3S

347.7 q divinyl sulfone together nrit dtiua 4800 ecm of a mixture of methanol and knife with a ratio of 10: 6 were introduced into eight three-necked flasks. Then 294.6 g of 2-methylpiperazine were added in a stream of nitrogen. The mixture was cooled to room temperature and allowed to react for about -24 seconds. The reaction product was poured into a 1: 1 vol. Mixture of acetone and ether, whereupon the polymer deposited in the form of a rubber-like product, which was decanted and washed with anhydrous ether and dried *

Making the Fibrils

The fibrils were made as in Example 3 under the same conditions made using the nitrogen-containing compound prepared above in an amount of 0.6 kg; they had a length between 3-5 mm, an apparent diameter of 30 µm and a specific surface area of 5.8 m / g.

After Hollander treatment at a load of 0, the fibrils showed a loss of nitrogen-containing compound below 400 ppm / h, this compound being present on the surface in an amount of 4.8 wt .- / b, based on the total weight of the fibrils was. The total nitrogen compound bound to the fibrils was 5.3 % of the total weight. The fibrils had a specific surface area of 5.8 m / g "

609849/0999

Example 1_0

The reduced polyacrylamide from Example 4 was used «

Manufacture of the- fibrils

The device was of the type described in Example 1 a diameter of the critical section v / on i1, '*> well, a maximum diameter in the final section of the divergent Nozzle parts of 15.7 mm and a distance between the critical and maximum section of 21 mm.

In a pressure vessel a 300-1 prepared at 155 ⁰ C. and 21.4 atm pressure emulsion of a solution of polypropylene in n-Psntan, water and the reduced polyacrylamide of Example 4 was added. The polypropylene had a melt index of 10. Its concentration in the emulsion was 50 g / l, while the concentration of the nitrogen-containing compound was 2 g / l of the emulsion. The weight ratio of n-pentane: water in the emulsion was 1.

The emulsion flowed under the above conditions at a total flow rate of 2200 kg / h extruded through 8 cylindrical nozzles with a diameter of 2 mm each, the orthogonal around the final section of a converging-diverging one Nozzle were attached. As a gaseous flowable material, dry saturated water vapor with a pressure of 6 atü and 200 C. Temperature at the entrance of the converging section (2) used.

This gave fibrils with an average length of 2.5 mm, an average diameter of about 16 M and a specific surface area of about 3.9 m / g.

609849/0999

After Hollander treatment for 20 minutes at a load of 0, the fibrils showed a loss of nitrogen-containing compound below 400 ppm / h, corresponding to an amount on the fiber surface of 3% by weight , based on the total weight of the fibrils, while the total of the Fibril-bound amount of the nitrogen compound 3.7 % of the total weight of bt ^ rug. After the Hollander treatment, the specific surface area of the fibrils was 3.9 m ² / g.

Example Y \ _

Reduced polyacrylamide was used as the nitrogenous compound of Example 4 used.

Making the Fibrils

The container of Example 1 was filled with 9.75 kg of polyethylene (M.I. = 6) and 0.250 kg of nitrogen-containing compound from Example 4 and 100 liters of η-hexane. The mixture was under pressure from 17 atü to 200 ° C. heated. In this way a liquid phase of molten polyethylene was formed; dieces remains in a second Phase homogeneously dispersed, which is formed by liquid η-hexane containing a small amount of dissolved polyethylene «

The mass thus obtained was extruded under the above conditions in the apparatus of Example 10 at a total flow rate of 1200 kg / h, using steam of 205 ° C. and 18 atm as the flowable material at the entrance of the converging nozzle section. This gave individual fibrils with an average length of 2.1 mm, an apparent diameter of 20.5 microns and a specific surface area of 4.1 m / g.

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After 15 minutes of intense Hollander treatment under a load of D, the fibrils showed a loss of nitrogenous compound below 400 ppm / scd, corresponding to an amount on the fiber surface of 2.0 Geuj.-fo of the total amount. A total of 2.35 % based on da. Total weight, the nitrogen burn bound to the fibers. After the Hollander treatment, the specific fibril surface area was 4 m / g.

609849/0999

Tabel

Relative / .Ratio . Of Ge \ u. ~% N-

Cellulose / nolyole containing urine

fin.Fibrilen in bind.auf Fi

At. Paper lens surface

BL (in m) before treatment with PolysEure

BL (in m) neon Bshand] jng with polyacid

70/30 2.5 4300 63OO i 50/50 2.5 26OO 3690 1 0/100 2.5 762 1310 1 70/30 2.4 4500 6640 2 o / ioo 2.4 550 10 Go 2 70/30 2.8 3925 5890 - • 3 '50/50 2.8 26OO 3450 3 70/30 8.28 385O 6580 4th 50/50 8.28 2O4O 4350 4th 70/30 2.27 4I5O 6380 5 70/30 1.4 4000 5050 J5 70/30 2.09 3400 6020 7th 70/30 4.5 3586 4580 8th 70/30
70/30
70/30 4.8
3.0
2.0 38OO
3,750
3,510 5720
5,430
5,370 9
IO
11

609849/0999

In the above formulas "mean, among other things, the radicals

R: as long as they are generally defined as alkyl groups or, for example, as alkyl C _{1 2} n radicals, in particular alkyl C ₁ <-, preferably alkyl C ₁ .4 radicals, e.g. methyl, ethyl, propyl, I ^c .opropyl, butyl, pentyl eggs Jleryl, cycloaliphatic or aromatic radicals having 6 to 10 carbon atoms are in particular cyclopentyl, cyclohexyl, _s is phenyl, tolyl or Eaphthyl;

Rp and R, if defined as alkyl groups, are preferred Methyl, ethyl, propyl, isopropyl or butyl;

X is, inter alia, preferably an optionally branched alkyl radical with 1 to 10, in particular 1 to 6 carbon atoms, such as methylene, ethylene, 1,3- or 1,2-propylene, 1,2-1,3- or 1,4-butylene;

the substituents he can carry are, as far as alkyl or alkylamino groups are concerned, as defined under R;

K is a C.j_g alkylene radical as it is defined e.g. for X.

6098 49/0999

Claims (1)

1, - Fibrous structure of Gn or fibril of olefinic polymer, which in the manufacture of paper can replace cellulose fibers in whole or in part and minriasteno on their outer surface one or more nitrogen-containing polymeric compounds of the following formulas: (D A ₁ -B - (A - D) y n in u / which ρ = 0 or 1; A, B and A can have different meanings depending on the value of ρ, especially when ρ = 1. can A. and A ₂ independently of one another for residues RRR RRRR 'RRR I I t Mil I I I -C-C-C-, -C-C-C-C-, -C-C-C-, RRR RRRR RR ₁ R ' RRRR ¹¹¹¹ or -CCCC-, IIII RRR ₁ R also,
stand; or they can / if B has a meaning other than a Piperazine residue, for residues of the type -C-C- R R stand, Tushrend B is a nitrogen-containing radical of the formula -N-, -N-X-N- or (piperazine) means; 609849/0999 if, on the other hand, ρ = D, then A. means a riest " ^CH or - ^CH 2 -f ^R 3- ' <™ 2> y while B = A ₁ or the following residue (CH r 'r ^ ^ ^M the latter case, the molar ratio of A./B in the macromolecule between 1:20 and 4: 1 is? N * 'furthermore R = H, an aliphatic C. _? “Remainder or a cycloaliphatic or aromatic C ^. ^ Remainder, · - H, -OH,.-OR, -0-C-R, 0 Cl, Br, 3: D = -N-, -NXN-, -N RRR U- ₂ R ₂ = a C ^ ₄ alkyl groupj R ₃ = H or -CH ₃ J X = a ^ _1-2 Q alkylene radical in which one or more H atoms can be replaced by a hydroxyl, alkyl, amine or alkylamine group; X can stand for the following remainder: 609849/0999 m is an exne integer between 0 and 4;
y is an integer between 1 and J; ζ is an integer between 1 and 20; η is an integer between 5 and 100, u / enn ρ 5 and 1000, tuenn ρ = 0; = 1, and (T-I) ' ^C V ^CH 2 O O -C-B-C-I 13 URd D = -N-K-N - R-R od ^ r sin - -, is there / J- rest 2 m K = a C., alkylene radical; I -O R = H, a monophatic C _1-20 radical or a cycloaliphatic or aromatic C,. _Q remainder; R ₂ = a C ^ _ ^ alkyl radical m = an integer between 0 and 2; η = an integer between 5 and 500; (in) Ii II -CH-CH ₂ -S-CH ₂ -Ch ₂ -E-CH ₂ -CH ₂ -S-CH ₂ -CK ₂ -D - in which B and D independently represent a nitrogenous one Rest of the formulas _i \ i_K_N- or stand;
K = a C 1 - D R R Alkylene radical N - R = H, an aliphatic C _Q radical or a cycloaliphatic or aromatic C, _ _/ , g radical; 609849/0999 R ₂ = a ¹ ^ _1-5 alkyl radical j m = an integer between 0 and 2; η = an integer between 5 and 500; (IV) CU CH CH CH. in which R = a C,. Alkyl radical and η = an integer between 10 and 300, the fiber-like structures having a specific surface area over 1 m / g and characterized in that at least some of the nitrogenous Compound not in amounts above 400 ppm / h. Treatment in a Lorentz-Wettres-Holländsr under conditions corresponding to the TAPPI 1-200 os.70 standards removed at 0 load can be. 2.- fiber structures according to claim 1, characterized in that the present on the surface thereof, nitrogen-containing polymeric compound which is not entferntbar by said treatment, 0.5-10 wt -.% Of the total weight of fiber structure and polymsrer nitrogen compound. 3. Fiber structures according to claim 1 and 2, characterized in that the olefinic polymer is a high or low density Poly ™, ethylene, polypropylene from predominantly isotactic macromoles- '6 0 9 8 4 9/0999 cool, poly-4-methyl-pentene-i or a random or block copolymer is made up of ethylene and propylene. 4.- fiber structures according to claim 1 to 5, characterized in that that at least part of the nitrogenous compound, which is appropriate on the surface of the structures, constituting macromolecules chemically by one or more basic Nitrogen atoms on carboxyl radicals of a polyacid from the group consisting of polyacrylic acid, polymethacrylic acid, and polyitaconic acid or alginic acid is bound " 5.- A method for producing the fiber-like structures according to claim 1, characterized in that one under conditions an almost instantaneous evaporation of the liquid phase into the extrusion environment a solution, emulsion, dispersion or suspension an olefinic polymer in one or more liquid media, which is at least 0.5 wt .- ^, based on the total weight of the polyolefin, one or more nitrogen-containing polymeric compounds of the general formulas (i) to (IV) of Claim 1 contains extruded through an opening. 6.- The method according to claim 5, characterized in that the nitrogen-containing polymeric compound in the solution, emulsion, Dispersion or suspension in amounts between 0.5-10 Getu .- ^ o, based on the total weight of polyolefin and nitrogen compound, is present. 7.- Paper and similar products, characterized in that they consist of the fiber structures according to Claims 1 to 4. 609849/0999 - 4T8 * - ■ 8 _t - paper and similar products according to claim 7, characterized in that they also contain cellulose fibers in addition to the fiber structures according to claims 1 to 4. . The patent attorney. 6098 4 9/0999 so Blank page