FI106046B - Spin oxidation of polymers in the molten state by applying a skin-core thermobondible polyolefin-fiber type fabrication and control method to be prepared as well as a control method for the strength properties of this nonwoven fabric. - Google Patents

Abstract

The first object of the new innovation is both to improve and regulate the production conditions for skin-core type polyolefin fibers so that the product fibers have better physical characteristics than before. The second object of the innovation is to manufacture from the said fibers nonwoven-fabrics with strength and softness characteristics that are better than before. The method is especially adapted for large-scale productional melt spinning apparatuses having a short cooling system. One part of the method is aimed at controlled molten-state polymer oxidation and the other part at the control and modification of the molecular weight distribution of the said polymer, by adding thereto, if necessary, prior to the spinning nozzle, a very short chain polymer of the same quality. Characteristic features of the regulation method are in addition a low draw ratio, temperature and nozzle diameter at spinning, measurement of the dynamic deformation of the molten filament as a function of time and distance, in order to ensure the supply of oxygen to the filament in the correct place, quantity and temperature, carrying out the oxidation of the filament using an oxidation nozzle separate from the quenching nozzle as a targeted oxidation and, if necessary, using oxygen enriched air increase of the dispersion value of the molecular weight distribution of the product filament when the molecular weights decrease as the oxidation degree increases, decrease of the thermobonding temperature for the product fibers, regulation of the product fabric strengths and their relationship as a function of the degradation degree of the polymer.

Description

106046

A method for manufacturing and adjusting skin-core type thermosetting polyolefin fibers produced by melt spinning oxidation of polymers, and a related method for adjusting the strength properties of nonwoven fabrics.

The first objective of this innovation is to both improve, adjust and control the manufacturing conditions of skin-core type polyolefin-10 fibers so that the product fibers have improved physical properties. Another object of the invention is to produce nonwoven fabrics with better strength and softness properties from said polyolefin fibers.

15

The novel innovation in the production and adjustment of polyolefin fibers is based on the essential improvement and adjustment of the polymeric molecular chain degradation method of spin-fiber surface layer autogenous oxidation. The process is particularly advantageously applied to large-scale melt spinning equipment with a short cooling system. The features of the invention are set forth in the appended claims.

25

The new control method is thus a combination / combination of several sub-methods and is based on numerous measurements and observations. The adjustment method is divided into main and side sections. One part is directed to the melt-controlled, controlled oxygenation of the polymer, and the other part, to control and alter the molecular weight distribution of said polymer, if necessary prior to spinning, e.g. in the radial direction of the nozzle filament by doping it with a very short chain homopolymer of the same polyolefin grade before spinning the nozzle. Characteristic features of the new process include: - The short spinning system has a cooling distance of about 25 mm from the 106046 molten polymer filament from the spinning nozzle (about 1500 mm in the long spinning system). At this short distance and within a few milliseconds, the filament is spun (cold drawing ratio: 150-1600) from a mouth diameter (0.25-0.80 mm) to an almost final fiber diameter (15-30 μτα), i.e. its volume and surface deformation and the like the speed changes are very large. Simultaneously with the said dynamic deformations of the filament, the filament temperature 10 (with polypropylene about 150-200 ° C) decreases, the polymer solidifies and crystallization begins.

- The new method aims to ensure a high quality of fine fibers with a low spinning ratio, i.e. a low spinning nozzle diameter. The number of nozzles of the spinning apparatus must then be increased in order to achieve sufficient production capacity, whereby controlled, homogeneous oxidation and quenching of the filament jet at said very short distances becomes technologically difficult.

20 - The new method measures the size and changes of the dynamic deformation surface of a filament as a function of distance and time so that the oxygen supply to the molten filament at the correct amount, temperature, and location can be obtained. The deformation measurement must also take into account the tensile stress on the filament as well as the corresponding orientation changes of the molecular filament of the molten filament polymer (after disorientation of the chains due to shear forces relaxation), as well as the effects of oxygen supply on filament deformations.

- Studies show that the diffusion of oxygen into the filament surface and matrix is determinant of the rate of degradation of the molecular chains, since the oxidation of the 35 thermal radicals is extremely rapid and the resulting oxidation results (including hydroperoxides) are largely non-reactive. Primarily not the overall speed.

Controlled by deformation measurements, the filament oxidation 3 106046 should always be directed to the beginning of the largest filament deformation area, with the highest filament oxidation area, the lowest filament stress, the filament temperature decrease as long as the strain delay time and the polymeric double-strand orientation.

Due to said very short extinguishing distance and the low amount of oxygen required, a separate oxidation nozzle with a very small free surface area located directly above the extinguishing nozzle, which is adjustable in position, is used for oxidation. A separate oxidation nozzle system allows for customized gas targeting at the correct amount, temperature and location of the filament jet from the spinning nozzle, if necessary, spraying the oxidation gas through the quench zone without substantially mixing the gases, heating or cooling, in the gas phase and in the surface of the filament, utilizing the net heat between the oxidation product quality control, the endothermic evaporation reactions and the exothermic oxidation reactions, the oxygen concentration control, etc.

The direction of the oxidation nozzle relative to the surface of the spinning nozzle and its distances from the nozzle surface and filament jet are essential for carrying out the oxidation process. By positioning the oxidation nozzle on one or two sides (i.e., oxidizing one or both sides of the filament jet) directly on the surface of the spinning nozzle, the oxidation gas jet may over-cool the nozzle surface, whereupon a low-power electrical resistance is provided to the nozzle surface.

When measuring the amount of oxidative degradation by filament melt index, the filament's melt oxidation control equation is of the form 4 MFI = 0 ^ 02 - c2Vi + c3, where 106046 v02 = the partial oxygen velocity or oxidation gas velocity multiplied by the partial pressure of its oxygen, v * velocity and clf c2 and c3 are constant for each polymer (with constant spin conditions).

Increasing the rate of extinguishing air decreases and increasing the partial pressure of oxygen increases the amount of degradation.

The value of constant c2 is substantially influenced by the position of the oxidation nozzle and the dimensions of the oxidizing gas jet and the value of constant c2 by the position of the nozzle nozzle and the dimensions of the extinguishing gas jet, gas temperatures etc. The constant c3 is a function of the amount of oxidizing degradation of the quenching gas.

Naturally, the amount of oxidative degradation can be directly measured by changes in the molecular weights or viscosities of the polymer, whereby the constants of the control equations change. The control equation constants are determined experimentally for the polymer to control the production spinning process.

20 - When large nozzle diameters are used in spinning, the resulting delayed filament cooling, and the corresponding high delay times, the amount of oxidative degradation in the polymer due to quenching air is greatly increased. The amount of this degradation can be controlled by the spin temperature and also by the choice of polymer additive, each of which also affects the control function. At low nozzle diameters, the filament becomes thinner and its temperature decreases so rapidly that the lag time for quenching degradation is too low. In order to keep the spun polymer preferably long-chain, and the rate and oxygen content of the actual oxidation gas to be reasonable, the novel process introduces a slight doping of the spun polymer with a very short-chain polymer as a partial process. The ratio of melt index indices of the 35 short and long chain polymers used in this alloy increased to a high of about 100-200. Here, it was found that at low velocities corresponding to the production capacity, the shear forces on the filament at low nozzle diameters are sufficient to enrich at least the portion of the short-chain polymer to the surface portion of the filament, 5106046 mm. in this surface area, both quenching and controlled oxidation degradation are sufficiently enhanced.

An important result of doping for the oxidation and control process is that the already low addition of short-chain polymer-5 allows for lowering of the spinning temperature (up to 20-50 ° C), thereby reducing thermal degradation in the filament matrix and maintaining the molecular weight of the polymer due to degradation, 10 decreases sharply.

Further, it can be noted that under the spinning conditions of the mixture of homopolymers of interest, the oxidized product filament can be readily solidified as a smectic structure, which can be utilized, in particular in fiber thermoforming, as a significant enhancer of bonding strength. This part of the new adjustment method is very suitable and useful especially for low spinning nozzle spinning, especially for high quality nonwoven fabrics.

20 - According to the new method, changes in the polymer (number and weight average) molecular weights and dispersion during the extruder process are conventional and known for multiextrudations, i.e. all of these values decrease regularly (by approximately 25 logarithms linearly) as the melt index increases. In nozzle oxidation after extrusion, the molecular weights continue to decrease as the melt index increases, but unlike previous changes. Unlike the standard shifting behavior, the dispersion value increases as the melt index increases. This behavior is characteristic of the molecular weight distribution, particularly by the action of the peripheral short chain stratification, as can easily be deduced from the statistical distribution values.

- The polymer-specific bonding equation 35 simulating the thermal bond strength values (0) of the fiber web has the form 0 = c x T 2 x exp [-E / RT], where 0 is (here) the tensile strength or elongation value.

For or against carding of nonwovens. the activation energy values of the bond 40 corresponding to the vertical thermal bond strength values are the same.

6 106046

The values of activation energy corresponding to tensile strength and elongation are usually different.

The thermal bond strength values have maximum values for temperature. The temperature ranges above and below these maximum values have their own equations of the same form. The theoretical maximum value of Sidon's strength is at the intersection of these equations. The same polymer has, within the limits of measurement accuracy, the same bonding equation for binding values corresponding to different degrees of degradation, for temperature ranges above the maximum bonding strength values, i.e., the strength values are within the same common envelope. Under the influence of oxidative degradation, the values of the strength values and the maximum strength values are shifted towards low binding temperatures, and thus the binding strengths increase as the degradation equilibrium increases, correspondingly per polymer, and to a limited extent.

The equations that simulate the strength values provide a direct, polymer-specific control equation for tensile strength (σ) and elongation (€) as a function of melt index ratio and temperature-20 na: σιι / £ ιι = [MFI / (MFI) orn x c4 x exp [-AE / RT] , where the value of the melt index ratio is exponential, n <1.0. A similar type of equation is also obtained for transverse strength values.

25 The key relationships between the elongation and the strength of the production fabrics contribute to the regulation of eg. the feel qualities of the fabrics (softness, elasticity, elasticity, etc.) and the fracture work.

In the process according to the invention, a starting polymer stabilized in a manner known per se is used, in particular peroxy-disintegrants, such as phosphite-phosphonite mixtures, are typically used in an amount up to about 0.5%.

35

In order to clarify the state of the art in polymeric filament spinning oxidation, the scientific grounds for both polymeric melt spinning and its thermal oxidation are considered. In many cases e.g. the innovations presented in recent years in the spinning and oxidation of molten filament 40 blanks utilize 7,106,646 among others. the effects of raising the temperature of the spinning melt, delayed cooling of the molten filament, increasing the diameter of the spinning nozzle, and increasing the capacity of the spinning process. Therefore, we briefly review the results of 5 well-known experimental spinning models on the nature and effect of the factors.

The differential equations (before crystallization) for polymer melt spinning dynamics (S. Kase, T. Matsuo, 1965, .67) for thermal, power, and material balances are / 1 /: 10 v (6T / 6y) + (6T / 6t) = (2 ^ nh / ^ ~ A p CP) (T-Tx) / 1 / (6v / 6y) = F / βΑ / 2 / v (6A / 6y) + (6A / Öt) = -A (δν / öy) ) / 3 /

The independent variables in the equations are time: t, s and position: y, cm, measured from the spinning end; dependent variables 15 are temperature: T, ° C, filament speed: v, cm / s, and cross-sectional area: A, cm 2.

The tensile viscosity: β, gf * s / cm2 is assumed to be a function of temperature and intrinsic viscosity only, | η | and spinning tension: F, gf function only of time. Filament 20 density: p, g / cm 3 and isobaric specific heat: Cp, cal / g * degree are assumed to be constant.

Several studies per mm of fiber filament formation have been presented over the last decades. 2 /. However, the above equations and their solutions / 1 / are accompanied by 25 comparative experimental comparative data, covering quite a number of the most important spinning phenomena and technical applications.

The solutions of the differential equations / 1 / - / 3 / stationary state give changes in the surface area, A (y) and temperature, T (y) of the cross-section of the molten filament as a function of the distance spun from the spinning end under a variety of spinning conditions. The resulting solutions are then correlated with the properties of the filament yarn. Among the relevant results of the spinning model equation solution [IBM 1401] in the melt spinning of polypro-35 penis are: - Increasing the diameter of the spinning nozzle without changing the winding speed or titer shifts the A (y) and T (y) functions towards the y axis and thereby slows down 8 106046 hot filament tension (measuring range: Ds = 0.4-1.6 mm).

- Increasing the tensile viscosity, β-thermal activation energy, causes the T (y) function to shift in the y-axis growth direction and the A (y) function in the opposite direction.

Lowering or increasing the quench air temperature causes a shift of the A (y) and T (y) functions toward decreasing values in the y-axis, i.e., faster filament thinning and filament tension increase.

- Increasing the flow rate (capacity) of the polymer at a constant winding rate greatly increases the distance required for the filament to solidify, i.e., delays the cooling and thinning of the polymer.

Placing an insulating cylinder below the spinning head, around the fiber optic cable, causes the A (y) and T (y) functions to shift, as a function of the insulating cylinder length, toward high γ values, i.e. the insulating cylinder delays the cooling and thinning of the polymer · - The barus effect and temperature distribution in the direction of the filament cross-section become significant with respect to the functions A (y), T (y) and F (y) only at very high polymer flow rates.

Polypropylene filament yarns crystallize rapidly in melt spinning, which makes crystallinity and orientation important. As the filament becomes thinner, the Δη 30 increases rapidly. It can be shown that the birefringence of the wire is directly proportional to the tensile stress at the freezing point, (F / A). In melt spinning, the crystallization of the filament occurs under molecular orientation under non-isothermal conditions. However, the kinetics of the crystallization mechanism 35 can be described by the Avrami-type equation K (t) = 1-exp {- [/ K (T (t)) dt] n) used in isothermal kinetics, where the / 14 / time exponet corresponds to the isothermal case and (t)] is a simple relation to Avram's speed constant of 40 (Ziabicki / 2 /).

• · ·.

9 106046

The degree of crystallinity (κ) at a given time can be obtained from the equation if the temperature dependence of the velocity and the cooling function of the system are known. The temperature function of the isothermal crystallization rate is a nearly symmetrical clock curve with respect to the maximum velocity value. The maximum crystallization rate for polyolefins is below the solidification temperature of the polymer.

The crystallinity of the filament yarn depends not only on the crystallization rate, but also on the amount of time the polymer consumes in the temperature range where it has the highest crystallization rate.

This can be quantified by the length of time the polymer needs to cool down to one degree,

Dt / DT = (pA / P) (dy / dT)) T "where / 5/15 Dt / DT is the" cooling time "and (dy / dT) T * is the temperature change along the spinning filament near the maximum crystallization rate temperature.

Assuming that the temperature of the maximum crystallization rate of the polymer, T *, is a material constant, the degree of crystallinity (density) of the filament can be calculated. There are some correlations between the properties of the polypropylene yarn and the stationary solutions of the spinning equations: - As the nozzle temperature rises, the birefringence, Δη decreases with F / \ (maximum) and density, ρ (κ) decreases with Dt / DT cooling time.

- The insulating cylinder placed below the spinning head causes the high air temperature and near-zero air velocity to remain inside the cylinder and reduces all values: ρ (κ), Δη, Dt / DT and F / \. By delaying the cooling of the molten polymer and thereby providing a lower crystallinity, (equation 5) is explained by the fact that as the insulating cylinder slows down cooling, the filament becomes thinner while achieving a high speed while the filament cools to about 100 ° C. This makes the filament cool-down time low and at the same time the filaments less crystalline.

- As the cooling air speed increases, all values: p, Δη, F / A „and Dt / DT increase.

The information required to examine the melt oxidation of the polymer filament and the subsequent · · 10106046 chain digestion, as well as the temperature change of the filament cross-section (and mantle) and the time of filament solidification as a function of nozzle distance and time.

Autogenous oxidation of the polymer at low temperatures 10 (<140 ° C) has been extensively studied / 5 /. However, in-depth studies of the polymer melting range are almost completely below linear pyrolysis temperatures. The oxidation of polypropylene with molecular oxygen can be represented by the following sub-scheme 15 Κχ ROOH - + RO · + OH · (01) K2 RO · + RH - »products + R · (02) 20 K3 R · + 02 -» R02 · (03) R02 · + RH - »ROOH + R · (04) K5 25 2R02 · -» products (05)

Molecular oxygen oxidizes polymers by the mechanism of free radicals. In the 30 cases under consideration, free radicals are formed mainly by the action of both thermal and mechanical energy.

Carbon radicals react very quickly with the oxygen molecule (302 radical) (K03 ~ 108 - 109 M ^ s "1). However, the oxidation reaction is reversible and the back reaction becomes important when the oxygen pressure is low, the temperature is high or the carbon radical is stabilized. .

An important partial reaction that determines the rate and product (Scheme 04) is the formation of hydroperoxides as a product of abstraction of hydrogen atoms of peroxy radicals. Hydroperoxides are the primary major products of the oxidation of polymers in most cases, and they, as initiators of autogenous oxidation, play an important role in oxidative degradation. The rate constants of the main reactions of the oxidation scheme, in the temperature range 71 ° -140 ° C, are: K (01), s "1 = 5.45 x 1010 x exp (-25000 / RT) 5 K (04), 1M-Is-1 = 1.61 x 107 x exp (-12080 / RT) K (05), 1M-Is-1 = 1.11 x 1013 x exp (-11600 / RT)

The oxidation of polypropylene follows kinetically the first order. The apparent rate of oxidative pyrolysis is given by: 10 -d [RH] / dt = K04 (K01 [ROOH] e / K05) 1/2 x [RH] / 6 /

The concentration of hydroperoxide at steady state is [ROOH] 8 = Kq42 [RH] 2 / (KqjKoj) / 7 /

Placing the values of the rate constants into equation / 6 / gives the apparent rate constant of oxidative degradation: 15 K = 1.128 x 106 x exp [-18780 / RT] x [ROOH] B / 6 /

The equation for simulating the change in hydroperoxide concentration in the temperature range 110 ° -289 ° C is given by: [ROOH] s, Ml-1 = 2.981 x 10 -5 x exp [7381 / RT] / 7/20 First order of oxidative pyrolysis of thermogenometric / 5 / polypropylene melt the reaction rate constant corresponding to the kinetics is in the temperature range 240 ° -290 ° C as iPP: K, s * 1 = 7, 75 x 103x exp (-15240 / RT) 25/61 / aPP: K, s'1 = 4, 83 x 104x exp (-17190 / RT) / 62 /

> M

Comparing the numerical values calculated from the rate constants (/ 6, 7 /) of the solid polypropylene sample at the melting range temperature (30) and the corresponding melting range results (/ 61, 62 /), the values of both series are within the measurement accuracy. . From this it can be assumed that the reaction mechanisms in oxidation are also the same in the 35 melt and solid phase regions of polypropylene.

Experimentally, in the case of solid polypropylene, it has been shown (8) that the maximum oxidation rate is directly proportional to the oxygen pressure in the oxidizing gas phase. Similarly, it has been shown that the concentration of the primary oxidation product, hydroperoxide, is directly proportional to the concentration of oxygen. In flat cases, this results in thick samples [02] = [O2] 0 x exp [- (KD) 1/2 x X] / 81/5 [ROOH] = [ROOH] 0 x exp [- (KD) 1/2 x X ], / 82 / where index 0 refers to the western concentration, X is the distance from the sample surface and D is the diffusion constant of oxygen.

The distribution of oxygen and hydroperoxide concentrations 10 then plays a role in the distribution of the quantity and quality of oxidation products in the oxidation system. Similar phenomena appear to occur in melt phase oxidation as well.

The products of oxidative pyrolysis of polypropylene at 15,289 ° C were determined by δ / IR spectrophotometry from GC fractions and partially by mass spectrometry. The semiquantitative order of product yields was: ethanol, acetone, butanol, methyl vinyl ketone, C6-ketone, propylene, methanal, methanol, propanol, 2-methyl-20-propanol, 2-pentanone, C5-aldehyde, 3-methyl-3,5-hexadiene .

Among the first components is mutual variation as a function of pyrolysis time.

Ethane, propane, propylene, etc. of hydrocarbon products

The presence of oxidative degradation indicates that the process is restricted by oxygen diffusion. Many hydrocarbon components are conventional polypropylene pyrolysis products in an inert atmosphere. When the atmosphere contains sufficient oxygen, the primary oxidation products are further oxidized, with the order of occurrence and product quality changing as a function of the oxygen content of the oxidation gas: 5% O2: H3C-CO-CH3, H3C-CHO, H2O, H3C-CH = CH2, H3C-CH-CHO, co2 ...

20% O 2: H 2 O, CO 2, H 3 C-CO-CH 3, H 3 C-CHO, H 3 C-CH = CH 2 ...

35 50% O 2: CO 2, H 2 O, H 3 C-CH = CH 2, H 3 C-CHO, H 3 C-CO-CH 3 100% O 2: CO 2, H 3 C-CH = CH 3, H 2 O

As the atmospheric oxygen concentration increases, ethanol, acetone, butanol and water are reduced to negligible quantities and carbon uptake is increased.

) · «40 13 106046

The effect of thermal and thermal oxidative degradation on the molecular weights of polypropylene and their distribution will be briefly considered.

Thermal (non-oxidative) degradation of polypropylene to Kine-5 teak and changes in molecular weights and their distribution corresponding to degradation have shown a strong theoretical and practical relationship in studies (Chan & Balke, / 6 /). For practical purposes of this review, the 10 equations that simulate the results of molecular weight changes in the study are (My) 0 - M ′ = 1.3662 x 10 x x T ° 1316 x exp [-8056 / RT] / 9 / (MJ0 - M ′ = 1.1646 x 109 x T ° '1972 x exp [-12646 / RT], / 10 / where the weight and number mean molecular weights were from: (My) 0 = 234000, (M ") 0 to 59300, (My / M") 0 = 15 3.94, x, h is the time Measurements were made in the time and temperature ranges: τ = 0-48h and T = 548-598K.

From the equations, it is to be noted that in production, often very short extrusion delay times, the effect of the processing temperature on the degradation of polypropylene is essential.

The effect of multiple extrusion of polypropylene under oxidative conditions (air) on the polymer melt index, molecular weight, dispersion and low shear melt viscosity has been investigated in a recent study (H. Hinsken et al. / 7 /). The equations that approximate the results of the study to the molecular weights and melt indexes are:

My = 532300 x [MFI] -0'2890 / 11/30 Μ "= 73510 x [MFI] · 0 1026/12 / The molecular weight and melt index values of the starting polymer were: M" = 418400, M "= 78350, My / M" = 5.34 and MFI = 3.1. The measurement results correspond to an extrusion temperature of 260 ° C.

From the results of the research it can be stated that as a result of multiple Randommin degradation under oxidative conditions, the molecular weights and dispersion values are reduced in a conventional and regular manner as a function of the melt index.

The effect of the molecular weight of the polymer crystal on its melting temperature, which is e.g. an essential factor for thermo-binding of peripheral oxidized fibers. It can be shown (e.g., HG. Elias, / 23 / that the melting point (TM) of the finite molecular weight non-perfect polymer crystal 5 implements the equation TM = TM ° - [2RTmTm ° / (AHm) u] [(lnX) / X) + f (X), / 13 / where TM ° is the melting point of the perfect crystal of finite molecular weight, (ÄHM) u is the melting third of the polymer monomer unit, and X is the degree of polymerization you placed) by approximating the values for polypropylene: = 460-507.5 [(lnX) / X].

From the equation, it can be stated that the melting point decrease becomes significant only at the degree of polymerisation of λ-15 X ≤ 103.

Further development of the state of the art in the manufacture of skin-core fibers 20, by means of a few patents, both old and new, is contemplated.

The processes of U.S. Pat. Nos. 2,335,922, 2,715,077, 3,907,957, 4,303,606, 4,347,206 and 4,909,976 involve several awareness of the kinetic and other problems associated with the preparation of peripheral acidified fibers, polymer processing, and their solutions.

The process according to US 2,335,922 / 060341, / 11 /, produces a synthetic textile material by extrusion of a high polymeric material. The polymer to which the air at the extrusion temperature has a destructive effect is extruded into an inert gas or vapor chamber and cooled to a temperature where the air has no adverse effect on the extrudate. Thus, in the process, the effect of air on the polymer at extrusion-35 temperature, its inhibition, and both effects, besides "chemistry", are also known kinetically.

The process of U.S. Pat. No. 2,715,077 / 291152, / 12 /, improves the adhesion of the polyethylene structure (film) to printing inks, metals, paper and various kinds of polymers. In the process, the polymer is exposed to nitrogen oxide-containing air (5-20% N 2 O), preferably in the presence of UV light (λ S 3900 A), and quenched in an extrusion temperature range (150-325 ° C). The description demonstrates knowledge of the kinetics of nitrous oxide treatment and provides information on treatment rate and time.

The process according to U.S. Pat. No. 3,907,957 / 180,474, / 13, reduces or prevents the formation of oxidative layers on the outlet surface of filament extrusion filaments during rapid spinning, which impede processing. In the method, a vapor blanket is introduced into the space closest to the nozzle surface, and a small amount of non-condensable, if necessary preheated inert gas is applied below it (before air quenching). The height of the gases in the direction of the cable is optimized.

The processes of U.S. Pat. Nos. 4,303,606 / 011281 and 4,347,206 / 310882, / 14 /, aim to prevent harmful tensile resonance caused by (one or more) relaxation pulp (Baruse effect) in the spun polypropylene immediately after the nozzle. 20 si. In the method, the filaments are extruded into a short hot zone, extruded or below, before they encounter cooling air. By doing so, the extrusion temperature can also be lowered without increasing the relaxation bulge. The extrusion temperature 25 in the former process was 204 ° C and in the latter process 177 ° C.

The process of U.S. Pat. No. 4,909,976 / 090588, / 15 /, improves the rapid spinning process of synthetic fibers by adding on-line zone heating to the conventional method. In the method, the filament from the spinning end is quenched to a temperature above the glass transition temperature (e.g., smectic structure of the product phase) and then led to a heating zone where the desired improved fiber properties (crystallinity, orienation, strength) are produced. Finally, the filament is turned off again and rewound. In the specification, zone length and temperature values corresponding to a given winding speed are given.

Techniques for Conventional Composite Polymer Structures.

16 106046 level developments are indicated by e.g. patents: US 4,680,156, 4,632,861, 4,634,739, 5,066,723, 4,840,847, 5,009,951 and EP 0,662.533A1.

The process according to U.S. Pat. No. 4,680,156 / 140787, / 16 /, raises the device-specific manufacturing capacity and product quality of skin-core composite fibers. In the method, the molten, molecularly oriented, fibrous core-forming material is surrounded by a molten, skin-forming material. The resulting combination 10 goes into a nozzle tool having a temperature gradient such that the outermost portion of the fiber core solidifies while still in the tool. The molten surface layer forms an anti-fracture barrier layer on the surface of a brittle, high molecular weight, oriented core layer and acts as a lubricant.

The processes of US 4,632,861 / 240386 and US 4,634,739 / 221085, / 16 /, improve the spinning speed and capacity of the bicomponent fiber quick spinning process above the values of the terminal components. In the resulting product fiber, polyethylene forms a continuous phase in the matrix and a polypropylene dispersion phase. Product fibers have good thermal bonding properties.

In the process according to US 5,066,723 / 211290, / 16 /, high impact polymer compositions are prepared in the presence of a Ziegler catalyst. These contain polypropylene as a continuous phase and as a discontinuous phase a thermoplastic polymer containing 90% of polymerized ethylene and the remainder of the other α-olefins. Moon 30 is blended in the presence of free radical to reduce the viscosity of the system.

U.S. Patent 4,840,847 / 020588. / 16 /, by melt spinning, both conjugate fibers of excellent thermal adhesion and absorption capacity are prepared.

The fibers contain, as a second component, a crystalline α-olefin and a second ethylene-dialkylaminoalkylacrylamide copolymer. The process according to U.S. Pat. No. 4,115,620 / 190177, / 16 /, produces conjugate fibers of spontaneous curling as well as high strength properties. One component of the structure comprising at least 40 two-component • · <1 '106046 is composed of polypropylene and 5-50% hard plastic (catalyzed by a hydrocarbon or rosin derivative of at least four carbon atoms) and the other polypropylene and a different amount of hard plastic.

In the process according to patent application EP 0.662.533 A1 / 040195, / 16 /, multicomponent polymers are prepared and, by placing a high speed side-spin unit near the bottom surface of one or more high-spin spinning heads, to prevent the filaments and / or melt filaments from . A spinning head suitable for simultaneous spinning of several different filaments can be used in the process (US 4,406,850, 5,162,074). The methods thus incorporate a short-spin system into a complicated multi-component multi-component spin system of polymers.

The processes of US 3,437,725 and US 3,354,250 seek to reduce thermal degradation by reducing processing time and temperature of the polymer.

In the process according to US 3,437,725 / 290867, / 17 /, the spinning nozzle device has an insulating space between the filter holding plate and the actual nozzle plate through which the polymer flows, at a significantly lower temperature of melting, to the guide tubes through the nozzle plates. . The nozzle plate is electrically heated to produce a steep temperature gradient (> 60 ° C) in the polymer (guide tube and capillary) such that the shear stress is momentarily reduced on the capillary wall without degradation of the polymer.

In the process of U.S. Patent No. 3,354,250 / 260264, / 17 /, the polymer powder is pressed against a melting diaphragm with a perforated electrical resist plate by a screw. The screw tube is surrounded by a water-cooled jacket that maintains the temperature of the polymer powder below the lowest melting point of its components. After thawing, the polymer is introduced into the nozzles immediately after the filter. By the process, the polymer has a low melting time in the molten state.

40 • · 18 106046

The processes according to U.S. Pat. No. 5,281,378 and patent applications FI 943072 and FI 942889 describe the development work carried out during the present decade in the manufacture of skin-core structured fibers using oxidative surface degradation.

The main object of the process according to U.S. Pat. No. 5,281,378 / 200592, / 18 /, is to improve the control of the polymer degradation, spinning and quenching stages and to produce a fiber capable of providing a nonwoven product with increased strength, toughness and uniformity values. A further object of the process is to develop the thermo-bonding properties of a fiber spun from a polyolefin-containing melt.

According to the method, high strength spinning fiber is produced by utilizing oxidative chain degradation of the molten spinning filament surface 15 and a slow melt filament quenching step applied to polypropylene having a broad molecular weight distribution. According to the disclosure, the method is suitable for use in a quick spinning system. According to the description of the method and the requirements, the essential functions of the method 20 are:

In the first step of the process, the polypropylene-containing melt is extruded under conditions of: - a wide molecular weight distribution of the feed polymer, i.e., values of the dispersion of 5.5 to 7.75.

The 25-polymer contains a member of the group antioxidants, stabilizers or mixtures thereof, and optionally degra-. doing component.

- said additives are used in an amount sufficient to prevent or control the degeneration of the polymer components in the extruder.

- the polymeric material (MFI: 5-35) is extruded at 250-325 ° C.

In a second step of the process, quenching the hot extrudate under an oxygen-containing atmosphere to effect oxidative molecular chain degradation of the surface 35 is performed under controlled conditions:

19 106046 - Controlled Quenching Includes Delayed Quenching of Hot Extrudate.

the oxygen-containing quenching atmosphere comprises cross-fire quenching and the upper portion of the cross-blowing is blocked to 5.4% (i.e. quenching and cross-blowing are not performed in the zone in question).

Controlled quenching further comprises maintaining the extrudate at a temperature above 250 ° C for a period of time which produces oxidative degradation on its surface.

10 - The product fiber contains an inner zone: * 100,000-450,000, an outer zone: M '= 5,000-10,000, and an inter-zone having molecular weights within the above ranges.

- 15 duplexes are high in the inner zone and low in the outer zone.

It is difficult to find support for the content of numerous claims in the process description.

From a central comparison of fiber series A, B, C, and D of the process description (Tables I-III), fiber strengths obtained from polymer having le-20 chain distribution are reduced under slow quench conditions. What is different is the reduction of the dispersion values of the polymers of test series B, C and D from different initial values, at the very beginning of oxidation (also not with delayed quenching), to virtually the same final value, from which it does not change as oxidation increases. Statistical analysis of molecular weight distributions does not support the patent concept of enrichment of short molecular chains on the surface of filamen-30 t. It should be noted that the process description does not specify the diameter of the spinning nozzle, the amount or speed of the extinguishing gases, nor the length of the extinguishing zone. Essential information on the tensile strength of the fibers for thermosetting strength is missing from the description.

35 For fabrics of test series fibers (Table IV): - Expression of transverse strength values of fabrics without longitudinal or median strengths shows little or no indication of thermal bonding and actual fabric strengths 40, since even the cardboard adjustment of 20 106046 alone can achieve transverse strengths.

- In the scoreboard, the strength values of the fabrics are given at only two temperatures (not well defined) 5, which is inadequate. It is generally known that the strength values of the thermosetting fabric pass through the maximum as a function of the bonding temperature.

- the weight variation of the fabric samples in the table is too great to make the necessary comparisons. However, on the basis of the fabric strengths given, it cannot be found that they exhibit a significant improvement in the effect of slowing down the fiber filament or widening the molecular weight distribution of the feed polymers. The process of patent application FI 943072/230694 produces skin-core, peripheral oxidized fibers for fabrics with high transverse strength properties in combination with uniformity and elasticity. The method demonstrates different spinning nozzle structures for producing method 20. The method is particularly applicable to short spinning systems. In the process, the polymer composition (e.g., polypropylene: MFI = 0.5-40, M ^ Mn> 4.5) is heated in or near the spinning die (e.g., inductively heated) (e.g., by means of an electrically heated orifice plate located directly above the die). ) so that the composition is partially degraded. The partially degraded polymer composition is extruded to form molten filaments. The molten filaments are immediately quenched in an oxygen-containing atmosphere (oxygen, ozone, air) to at least effect surface chain degradation. The process description and claims state that the fibers produced by the process are capable of forming fabric mass * · * materials (23.9 g / m2, web speed 76.2 m / min.) With a transverse strength of at least 12.6 N / 50. mm.

With respect to the process according to the application, the description of the process does not, in the absence of many relevant information, support the extensive claims claimed. The explanation of the ambiguities and shortcomings is: 40 - no information is available on the fiber 106046, strength values, structure, crystallinity, chain orientation, periodic values, etc., of the fibers produced by the method.

- the indication of the minimum transverse strength of the fabrics 5 does not give any information on the strength of the fabrics, since the corresponding length strengths and elongations are not indicated. By employing conventional homogeneous polypropylene fibers, it is possible to achieve the above-mentioned standard solely by adjusting the carding. boasted tensile strengths.

The microfusion method used in the 10 method is not sufficient to demonstrate the thermosetting properties of the fibers or fiber braids or the strength values of the resulting fabrics because the correlation between the method and the results of direct strength measurements is not demonstrated.

The absence of the aforementioned and some other relevant information prevents the application of the oxidation method of the patent application from being compared to the state of the art in almost all prior art.

The process 20 of patent application FI 942889/160694, / 20 /, produces heat-weldable polyolefin fibers which are particularly suitable for the production of nonwoven fabrics by hot-rolling processes. The method is based on the observation that an increase in the nozzle channel diameter of the nozzle channel of the melt spinning processes to 25 £ 0.5 mm (0.5 to 2.0 mm) causes a significant increase in the thermal weldability of the product fibers.

According to the process description, the process is suitable for use in the manufacture of staple fibers as well as in spunbonding processes. In the production of staple fibers, in a roll-forming range of 30 to 500 m / min., The cooling distance of the melt filaments is preferably between 10 and 350 mm. According to the explanation, the spinning temperature is in the range of 240 to 310 ° C and the spin following the spinning (<100 °) in the pull ratio ** is 1.1 to 3.5. The method is applied to polyolefins in the melt index range, MFI = 5-25.

In the exemplary section of the process description there are several examples of staple fiber production and spinning bonding under conditions: nozzle channel diameter: 0.4-0.9 mm, spinning temperature: 280-310 ° C, cooling distance: 5-30 mm and 40 winding speeds 60-2400 m / min.

22 106046

The method description discloses a novel method for measuring the thermal adhesion of fibers, e.g. the examples are exclusively used. The correlation between the results of the new measurement method and the results of the conventional direct method of measuring the tensile strength, elongation 5 and toughness of fabrics is not given in the description. It should be noted that the result obtained by said measuring method is ambiguous in hot roll bonding of fiber webs involving high shear processing. It should be noted that for example-10, the fiber produced by the mechanical tensile strength of 3.5 and 6 according to claims 5 and 6 of the application, the measuring method provides a good thermal weldability value of a fiber which is known to be extremely poorly heat-welded.

15 The results of the thermal welding provided by the process description cannot be compared to the conventional state of the art of thermal bonding of nonwoven fabrics, as shown by the patent regulations.

It should also be noted that the processes described in US 5,281,378 20 and FI 942889 are directly derived from known molten spinning models (e.g., Kase & Matsuo, / 1 /) and both have the same scientific basis.

In a brief review of publications related to oxidative degradation of polymer spin filament surface portions, no comprehensive method or control model relative to the new method was found for the new method.

Some of the operating principles of the novel melt-spinning-30 process employing oxidative degradation are further explored in the examples below.

Example 1.

Example 1 demonstrates, by means of detailed examples, the rationale for the new invention and the relevant findings therein.

23 106046

Part example 1.1

Part example 1.1 shows the exemplary fabrics and functions of fabrics and fabrics used in method development corresponding to the exemplary section of the disclosure.

In the method description of the new invention, so-called fiber samples were used to prepare the series of fiber samples. shortspin-10 Ning method (herein called short spinning method) and similar equipment.

Spinning and tensile test kits were performed predominantly on pilot-scale installations that differed from production-scale installations only in the number of spinning units 15, but not in their size. Pilot equipment was better equipped with production technology than measuring equipment.

The nozzle diameters (mm) and number of spinning nozzle plates used in the test kits were: 0.25 and 0.30 / 30500, 20 0.40 / 22862 and 0.70 / 12132.

The spinning apparatus capacity (g / min) was P = 45.88 x p x nr, where p (= F (T)) is the polymer density (g / cm 3) and nr is the speed of the polymer pump (min "1).

For the comparison of hot and cold speeds (nozzle and galettes) 25 (including spin pull ratio), the hot speed is calculated as the cold speed (cm / min), i.e.: v = 45.88 xp (T) x N / d (298) x N x As / 14 / where p (T) is the hot density (g / cm 3), N is the number of nozzles-30 and As is the cross-sectional area of the nozzle (cm 2). The hot density of the polymer is obtained from the equation p-1 = 8.1383 x 10 -4 v + 1.1525 and the cold density is p (298) = 0.903.

The partial equipment tests of the short-spin traction drive used in the Pilot tests, 35 Fig. 1, are: 1. extruder, 2. melt-spinning device, 3. 1-gallet, 4. tensile oven, 5. 2-gallet, 6.

2-Avivating, 7th Curl, 8th Stabilizing & Dry Furnace & 9th Staple Fiber Cutter.

• · · 40 The deformation of the molten spun filament after the nozzle 24 106046, under varying spinning conditions, was photographed with a CCD camera and the information was recorded on a magnetic tape. Storage observation and measurements were performed by image analysis methods. Some of the samples used to elucidate details of the invention were prepared under controlled conditions on a Haake-Rheocord-90 apparatus, which was also equipped with a mechanical drive unit with furnace.

X-ray WAXS and SAXS (Philips PW 1730/10, PW 1710/00, Kratky-KCSAS), AFM (TME-rasterscope 2000), and electron microscopy (Cambridge 360 and Cameca Camevax Microbeam) were utilized to determine the fiber structure.

A schematic diagram of a conventional apparatus used in the manufacture and bonding of fiber webs is shown in Figure 2. The components of the system are: 1. Opener, 2. Fine opener, 3. Reservoir, 4. Feeder, 5. Cardstock, 6. Binding rollers, and 7. Coil machine.

All the equipment in the diagram is production-scale.

20 The banding line gauze web production and banding speeds were adjustable between 25 and 100 m / min. The top or bottom of the binder with a diamond or round embossing pattern was temperature and pressure controlled. The diameter of the tying rolls was that of a production tower, but only 2.2 m wide.

Fiber-binding mechanism studies carried out so-called. fiber-link bonding and direct bonding experiments with a mechanical and dynamic mechanical thermoanalyser (Mettler 30 3000 / TMA40 and Seiko 5600 / DMS-200). Isothermal and dynamic oxidation-evaporation experiments were performed using a thermogravometer (Mettler 3000 / T650).

/: The key positions of the 35 quenching, oxidizing, and spinning nozzles used in the Pilot tests (2-figure 1) are shown in Figure 3.

The position of the extinguishing nozzle was determined by the best spinning result. The angle between the center of the extinguishing nozzle (1) and the surface of the spinneret was about 24 ± 1 °. The longitudinal centerline of the longitudinal center of the braze-shaped nozzle opening was 42 106046 cm from the level of the spinning nozzle and its distance from the central plane of the cable jet (6) to the nozzle direction angle was approximately 49 ± 2 mm with a spinning nozzle diameter of 0.70 mm. At a spinning nozzle diameter of 0.25 to 5 mm, the distance values were only 0-10 mm shorter than the above. The size of the nozzle orifice of the extinguishing nozzle was kept constant during the tests, i.e. 11.2 x 478 mm.

The positions of the oxidation nozzle (2) during the test runs were a, b and c (Fig. 3). Directional angle values corresponding to the nozzle positions were 10 7.5 ± 0.5 °, 17.5 ± 0.5 ° and 2 ± 1 °, the distance values in the nozzle direction were 62 ± 5, 64 ± 5 and 32 ± 5 mm and in the height direction ( measured at the longitudinal centerline of the rectangular nozzle hole) 27.5 ± 3, 27.5 ± 3 and 1 ± 2 mm. The size of the orifice nozzle orifice was 0.6 x 460 mm. 15 Precise oxidation from nozzle station c at low nozzle distance values and high gas velocities caused a decrease in the surface temperature of the spinning nozzle plate as well as collectors on the nozzle plate surface. For this reason, especially at low nozzle diameter values (0.30 mm), electric heating of the 20 nozzles was used to keep its temperature equal to that of the spinning melt. The electric heating comprised placing the adjusting resistor (5) in the groove of the spinning nozzle. The resistor package used (4 pieces) was 3.3 x 485 mm and 270 W power.

25

Part example 1.2

In Example 1.2, the dynamic deformation of the molten polymer filament from the spinning nozzle under quenching in a production-scale spinning system is considered.

In a process based on thermal oxidative degradation of the filament surface layer, it is essential * to obtain oxygen to the surface of the molten filament at the correct amount, temperature, and location. With respect to the formation of oxygen surface concentration, its diffusion transport, and its regulation, it is important to know the size of the surface of the molten filament suitable for oxygen transport and its changes. In the present case, the short-spin methods • 40 are extremely rapid due to the short quench interval 26 106046. To determine the surface changes, the deformation of the molten spinning filament as a function of the distance from the nozzle surface to the filament axis was measured using video camera imaging.

5

The spinning conditions of the specimens used in one set of melt filament deformation measurements are shown in Table 1 and the corresponding results calculated from the filament profile are shown in Figure 4. The measurements determined the cross-sectional and envelope surfaces (A (y) and A * (y)), temperature (θ (y) )) as well as changes in the spin delay time (T (y)) as a function of the distance (y) from the nozzle to the filament axis.

15 From the results of measurements in Table 2 and Figure 4, it can be seen that they correspond to the behavior of the Kase & Matsuo spinning model / 1 / presented in the explanation of the method. From the measured values of the melt filaments, the increase of the winding speed (vx), the borehole temperature (O '), the nozzle diameter (Da) and the nozzle capacity (P) (with other conditions unchanged) shifts functions (A (y)). and ^ (y) in the ascending direction of the y-axis and, for example, the rate of extinguishing air velocity (vL) in the descending direction of the y-axis (measured from nozzle level, y = 0 25). and Φ (y) changes. When comparing, the spin model / 1 / simulates the long spinning system as a reference, the short spinning system being used. : 8.185 (no 1) = 10.2 x 0.8040 (no 319); y mm: 200 = 31.7 x 6.3; 102.4 cm @ 2: 105.2 = 23.0 x 4.58 and r. , ms: 945 = 1.71 x 552.

35

The table below shows some gauge values from the measurement values of the filament profiles in Figure 4 in the freezing region of the filaments (O '' 115 ° C, A (y) constant). The values in parentheses are the filament values corresponding to y = 0.6. 40 27 106046

High - no 3 319 14 18 105A ,, cm2 615 4582 348 662 106A, cm2 5.04 6.16 4.53 7.07 x, ms 75 552 41 80 5 ^ / ^ (319) 0.143 1,000 0.076 0.144 104Pb, cm3 / s 3.12 8.04 2.06 2.06 λ 274 1305 181 181 104 KI, mN / cm2 13.4 41.7 24.9 11.5 mm 2.1 6.3 1.2 2.1 10 D ', mm 0.30 0.70 0.30 0.30

According to the table, the increase in nozzle aperture (no. 3 to no. 319) causes strong cooling and retardation of filament thinning, which results in a significantly larger difference between the nozzle capacities during melt melt deformation (in the samples, the same production capacities but different nozzle capacities). Then the total delay time of the filament deformation also increases substantially. The increase in nozzle aperture 20 thus has a very favorable effect on the advantageous oxygen transfer and oxidative degradation in the filament.

The power balance equation (2) for the melt spinning equations was of the form 6v / 6y 25 = F / Αβ, ie the deformation rate is directly proportional to

cable tension and inversely proportional to the tensile viscosity of the polymer melt. The equations for F ~ βνη7 / ρορ are still dependent on the equations, ie the stress acting on the filament is directly proportional to the tensile viscosity and the quenching air velocity. The equations also give a dependence on dA / dy = v ^ / OpP 'p FA / pG, i.e. the gradient of the filament's A (y) function is directly proportional to the cable tension force and inversely proportional to the nozzle capacity (G = p Av) and tensile viscosity (also 35 pi is the activation energy for tensile viscosity (β = K

exp (E / RT)), the closer the A (y) to the y = 0 position and the faster the filament becomes thinner below the spinneret). The equations can still be used to show that the birefringence and at the same time the orientation of the polymer chains are directly proportional to the

• «K

28 106046 in tea) to the cable tension or Δη = (F / A) (K / T). According to the tables, samples no. 14-18 have a constant nozzle capacity, with varying extinguishing air volume and speed. In samples no. 14-16, the cable tension decreases as the step-5 air velocity decreases, thereby decreasing the deformation rate (6v / 6y) and the gradient dA / dy (Figure 4). Sample No. 18 uses a separate oxygen nozzle, which results in filament-soluble oxygen reducing melt viscosity and hence cable tension force, strain rate, dA / dy gradient as well as orientation of polymer chains (Table 2, Figure 4).

Let us briefly consider the diffusive transport of oxygen through the spun-filamentous filament surface deformed over time. The lack of sufficiently accurate oxygen solubility and diffusion values in the molten polymer prevents quantitative treatment of diffusion. In diffusion oxygen transport, the amount of substance transported per unit time (dm / dt) is directly proportional to the dif-20 fusion constant (D), the surface perpendicular to the diffusion current (A) and the concentration gradient (dc / dx) = D x A x (dc / dx).

The melt spinning thus has a diaphragm surface formed in a deformation zone extending from the nozzle temperature to the solidification temperature, which is suitable for diffusion.

• «- * From Table 2 and Figure 4, the surface areas of the filament surfaces can be observed as a function of time, temperature, and distance from the nozzle to about 30 cm. In this connection, the values of the filament surface and the corresponding deformation time obtained at a distance of y = 0.6 and at the solidification point are compared by means of a table and a picture. The reference filaments correspond to nozzle diameter values of 0.70 mm (no. 319) and 0.30 mm (no. 14). 35 A sample corresponding to the effect of oxygen 0.30 mm (no 18) is included for comparison. The product N x Av x τ (cm 2 · s), which is proportional to the amount of oxygen transported, gives the values: N x Av x r / no: 3.426 / 319 - 0.327 / 14 -0.742 / 18 and (115 ° C) 30.69 / 319 - 0.436 / 14-1615 / 18.

40 From the result, it can be seen that the effect of the difference in deformation surfaces of the filaments corresponding to the high and low nozzle diameters on the oxygen displacement is very large. Also, the effect of oxygen through alteration of the deformation surface on the diffusion system may increase significantly.

It should also be noted that the difference between the spinning and solidification temperature and the corresponding oxygen diffusion constants is about 1.5 to 2 decades. The diffusion constant was roughly taken as the low temperature amorphous polypropylene phase value of 10 (/ 5 /, Jellinek: D0 = 1.5, E = 8700 cal / mol) without corrections for ore concentration, oxygen concentration, etc.

The results of sub-example 1.2 clearly indicate, based on changes in filament areas, deformation time and molecular chain orientation, that the oxidation nozzle 15 must be placed in the immediate vicinity of the spinning nozzle surface. In order to increase the values of oxygen surface concentration (solubility) and concentration gradient (diffusion driving force), the oxygen partial pressure of the oxidizing gas phase should be as high as possible.

20

Part example 1.3

In Example 1.3, the implementation of the autogenous oxidation degradation process of the molten spinning filament surface and the corresponding adjustment method by pilot series are considered.

«·>

From the measurements of the spun profile of the molten filament (Part Example 1.2), it is evident that the oxidation is directional to the very beginning of the largest filament deformation area, with the highest filament oxidation area, lowest cable stress (SLT), low temperature reduction, longest deformation time, and polymer orientation. after the nozzle at its lowest.

35

In the short spinning system, the filament extinguishing distance after the spinning nozzle is only about 25 mm, which is very short compared to the extinguishing distance of the long spinning system of about 250 to 1500 mm. Due to the very low processing space 40, the oxidation and quenching nozzles of filament 30 106046 are separated from one another in the process of the invention. In the process, the oxidation is carried out by precision oxidation by means of a very narrow nozzle slot (0.60 x 460 mm) and at a speed sufficiently high to allow the oxidation gas phase to penetrate through the flame of the quenching gas jet into the filament space. The blasting method is based on the poor miscibility of the gases in question. in circumstances / 22 /. The position of the oxidation nozzle is precisely adjustable with respect to the filament jets and the surface of the spinning nozzle (Fig. 3) for successful oxidation.

Although the amount of oxygen required for filament oxidation, and thus flowing from the nozzle, is low, oxygen-rich earth is used in the oxidation and adjustment, if necessary. Raising the oxygen content of the blowing air affects the radial oxygen concentration gradient of the filament / 21 / and thus the amount and position of the molecular chain degradation.

Reducing the deficiency of oxygen at the surface of the filament and outside it also affects the quality and quantity of volatile oxygen compounds. Under difficult spinning conditions (low nozzle diameter, fine filament production, etc.), the net heat between the oxidation and endothermic evaporation reactions (which is a function of oxygen concentration) can be utilized strongly in the spinning to heat the surface portions of the polymer filament.

Several pilot spinning sets were made for spinning oxidation and the development of its control system. The measurement results of these test series are shown in Table 3 and Figure 5.

The behavior of the control system according to the invention with respect to the operation of the quench and oxidation nozzles was investigated by means of 35 test series no. 309. The initial molecular weights and melt index of the polymer of the test series were: Mw = 255000, = 49250, D = 5.25 and MFI = 13.5. Extruder heating zones and spin log temperatures were: 255-265-265-280-290-290 ° C and 295 ° C. The temperature of the spinning melt 40 was 286 ° C. The spin pump capacity was, P = 42.78 31106046 dm 3 / h. The diameter of the spinning nozzle, De = 0.70 mm, and the corresponding nozzle positions of the quenching and oxidizing nozzles are given in Part Example 1.1 and Figure 3. The sample numbers 7-16 and 5a sample numbers 21-25 in Table 2, respectively.

The measurement results in Table 2 give the equation for the control of oxidation for quench air and oxygen velocities: 309-b: MFI = 1.914 x vc2 - 2.427 x vt + 93.248 / 16/309-a: MFI - -0.165 x v02 - 2.427 x vt + 93.248 / 17 / 10 The volume and flow rates in Table 3 are not STP states but correspond to production conditions (v 24 ± 1 ° C, p = 1.0 bar). The obtained simple control equation was found to be sufficiently accurate when using the so-called oxygen flow rate. partial velocity, i.e., vo 2 = 15 PO 2 x v, where v is the velocity of the oxygen enriched air. Samples no. 7-12 of the test series had approximately the same extinguishing gas velocities and corresponding cable voltages (SLTs), but samples no. the values differ significantly. The values calculated from the equation-20 in all samples quite well correspond to those obtained by direct measurement. From Figure 3 in Part Example 1.1, it can be noted that at position a of the oxidation nozzle (samples: 309-21-25), the oxidation jet cuts the main part of the extinguishing jet. According to Table 2, the jet flow rates do not exceed the jet jet speeds, so the control equation changes from the previous one to equation / 17 /. A slightly negative coefficient of oxygen flow indicates the cooling effect of oxygen in the system.

30 The same test conditions as in series 309 were used in test series 314, but the spinning nozzle diameter was only, Ds = 0.25 mm. The oxidation nozzle was in position b. Figure 5 shows the resulting oxidation function [MFI = 29.8 + 0.376 x vO2], which, as in Table 3, shows inefficient oxidation of sar-35 samples (corresponding to spinning deformation). The initial or quenching oxidation of the samples was also quite low.

In test kits # 325 and 326, the diameter of the spinneret • · * 40 was used, D2 = 0.30 mm. The oxidation nozzle was moved to position 32106046 to ground c (Fig. 3) and could be used with either 1 or 2 sides (series 325 and 326). Since the oxidizing nozzle, while operating at the surface of the spinning nozzle, cools this, small electrical resistors are mounted on the spinning nozzle in a series of tests to increase the surface temperature of the spinning nozzle to match the spinning temperature and at the same time remove polymeric surface tumors. Under the influence of nozzle and temperature corrections, the oxidation control system approximates the result of test series no 309, but the oxidation of the step-10 is still very low (Figure 5). The oxidation equation for test series no. 325 has the form MFI = 1.914 x v02 - 0.7363 cf. + 62.645 / 18 /

The use of a two-sided oxidation nozzle improves the oxidation result. Reducing the free aperture of the oxidizing nozzle increases the flow rates and the oxidative degradation, respectively, which must be taken into account, in particular, as the reduction of oxidizing gas in the 2-sided nozzle operation.

The basic factors affecting the amount of quenching oxidation and degradation are temperature, nozzle size and corresponding spindle deformation, feed rate, oxygen content of quenching gas, molecular weight distribution, etc.

The use of oxygen-enriched air to extinguish degradation is not economically viable to the extent 25 required on a production scale.

At spin conditions similar to Test Series No. 309, with the total capacity corresponding to the nozzle-plate, the effect on the melt index is approximately: De, mm / MFI: 0.25 / 27 - 0.30 / 30 - 0.40 / 35 - 0.70 / 41. The use of a large through-30-inch nozzle, due to the high spinning ratio, causes quality problems in the production of fine titer fibers on a production scale.

The high temperature of the spinning melt promotes quenching degradation, but its use determines the Theological properties of the polymer and the quality requirements of the spinning product. High temperature also causes strong thermal degradation in the extruder, which reduces the mechanical properties of the fiber and also the importance of well-implemented peripheral degradation.

40 • · · 33 106046

The economical commercial production of high quality fine titer fibers requires e.g. use of the lowest possible amount of oxidation air, low oxygen enrichment, low nozzle diameter, low 5 spinning temperature.

In further development of the control method of the invention, test kits were made to modify the feed polymers to be suitable for peripheral oxidation of filament system filaments. The starting point was then to mix propylene polymers of very low molecular weight and high molecular weight, assuming enrichment of the short chain polymer at the filament surface area, even at low nozzle speeds of the short spinning system due to the high viscosity difference. At the same time, the short chain polymer would act as a plasticizer in the blend, especially during extrusion. Successful doping could also take advantage of the non-random increase in the rate of degradation of the system caused by chain initiation of molecules. Likewise, the temperature of the spinning melt 20 could be lowered, thereby reducing and providing a proportion of thermal degradation during extrusion, without significantly reducing the mechanical properties of the product fiber with good surface-degraded fiber.

In test series no. 331, melt-like filament oxidation of a mixture of two widely differing propylene polymers is carried out. A 1-sided oxidation nozzle at position c., A spinning temperature of 265 (270) ° C, and a spinning nozzle of 0.25 to 30500 were used in the test set. 5 and 10% by weight of 30 polymers (no 032) having a melt index of 400 polymer (No. 031). In the results of Table 2, the former mixture corresponds to sample numbers 5-10 and the latter to 1-3 (also Figure 5 and Part Example 1.4). The control equation for spinning oxidation is obtained (here ignoring shutdown-35 speed) as a function of the partial flow rate of oxygen flow 5% no 32: MFI - 1.293 vQ2 + 28.61 / 19/10% no 32: MFI = 4.026 vQ2 + 47.89 / 20 /

From the results, it can be seen that at 5 P% PP-32 increments of -40 do not significantly increase quenching degradation (compared to other 34 106046 low nozzle diameter sets, but with larger increments, quenching degradation increases rapidly (with logarithms of shear viscosities nearly linear to concentration). Suitable modifications of the -5 mers can achieve very inexpensive and necessary control values when operating at low nozzle diameter values and productive feed rates.

10 Part example 1.4

In Example 1.4, changes in the molecular distribution of the polymers and in the melt index of the filaments of the Experimental Series of Example 1.3 are examined.

The results of some melt oxidized spinning filaments as well as feed polymer GPS assays (solvent TCB, 135 ° C and co-20 lbs TS 9S & TS 10S) and melt index values (ASTM D 1238: 21.6) in Part Example 1.3, Test Series No. 309 (and 331) N / 230 ° C) is indicated in the table below

Sample M * M „M, MFI

no g / mol g / mol g / mol - g / 10 min 25 0 255000 49250 109000 5.25 13.5 7 192000 43400 160500 4.40 41.5 11 196000 44500 163500 4.40 47.2 15 189000 42700 157500 4.50 51.3 9 171000 33400 142500 5.00 59.8 30 12 186500 35000 154000 5.50 76.3 031 407500 58200 320500 7.00 4.4 032 124450 32280 105480 3.86 400 033 98412 22149 82180 4 , 44 800 035 277900 53210 - 5.33 12.1 35

The equations simulating the mainly thermo-mechanical and simultaneous mild chemical degradation product of extraction under normal atmospheric conditions were obtained in a series of experiments # 309: Mn = 6.602 40 x ΙΟ4 X (MFI) -0'1126 and Μ ,, / Μ » MFI) - ° · 1485. The 35 106046 results obtained can be compared with the extrusion results obtained under both shielding gas and air atmosphere.

From the time-temperature functions simulating the results of the Chan & Balken thermal degradation study, the / 6 / get-5 d (at 309-series dwell time and melt temperature: τ = 5 min, θ = 286 ° C) with only a slight series of 309 lower molecular weight decreases (Δ and Δ M ^ C & B: 69485 and 8111, i.e. -29.8 and -13.7%? 309: 63000 and 5850, or -24.7 10 and -11.9%). Thus, the conventional amount of antioxidant (Phosphite-Phosphorite Blend + Anti-Acid: 0.2%) of Test Series No. 309 is of little importance as a means of reducing thermal degreasing.

The degradation results in extruder basket No. 309 correspond to the conventional multiple extrusion results obtained in the presence of e.g. H. Hinsken et al. / 7 / MWD-MFI measurements. The slopes of the In M „, In M„ and In (Μ ,, / MjJ / In MFI) functions simulating the measurement results are approximately the same in both series.

20

The amount of chemical degradation after the extruder due to the quenching air is dependent on the spinning conditions (Part Example 1.3). In the spinning conditions under consideration, this amount is low compared to thermal and mechanical degradation. Under the influence of the oxidation nozzle (side nozzle) corresponding to the new method, the slope of the MFI functions of In = ♦ * M / ln simulating the degradation results significantly changes compared to the above functions obtained from the Hinsken / 7 / measurement values. The In Mw values of the samples of Series No. 309 fall more steeply and the In Μη values more steeply as a function of the degree of oxidation than the aforementioned measured values. However, the most significant change occurs in the dispersion values, which * grow instead of old-fashioned oxidative degradation. The Side Nozzle Oxidation of Test Series No. 309 provides numerical average molecular weight and dispersion results to simulate:

Mn = 2.159 x 105 x (MFI) -0.420 and Mw / Mn = 0.925 x (MFI) * 0'411; (/ 7 /: Mn = 7.351 x 104 x (MFI) -0103 and Mw / Mn = 6.700 x 40 (MFI) -0.1635). / 21/36 106046

Widening of the molecular weight distribution of the polymer by oxidation is not conventional. However, by MWD balance calculations, it can be shown that, in random degeneration, the surface-to-oxidation degradation of 5 also represents the total dispersion of filament distribution increases as the oxidation increases (the dispersion values of the particles simultaneously decrease in the radial direction of the filament). It should be noted that a similar increase in dispersion values has been observed in solid state surface degradation (S. Girois et al.

10/10 /, J.E. Brown et al. / 9 /).

In the examples of the method description according to U.S. Pat. No. 5,281,378 / 18 / relating to peripheral oxidation, only Mw / Mn and MFI values are provided for the oxidized samples (Mn and Mw-15 values are absent). The Bw, C and D Mw / Mn ratios in the claimed test series were 7.75, 6.59 and 7.14. The Mw / Mn ratios of the test series after oxidation are almost equal (5.3 ± 0.3) and independent of MFI values (or slightly decreased with melt index increase). The behavior of test series A is similar to the previous ones, but the starting and ending values are: Mw / Mn = 5.35 and 4.49 ± 0.08. The distribution values given in the method behave anomalously and do not confirm the occurrence of layered surface degradation.

25

It should also be mentioned that the widening of the molecular weight distribution according to the new oxidation-degradation process is also known to promote the thermo-binding of product fibers.

30

Figure 6 shows the differential molecular weight diagram corresponding to the distributions in the above table. From this, one can observe the shift of the distributions by the action of oxidation towards low molecular weights. However, based on the distribution pattern, the changes in Mn and Mw / Mn during oxidation cannot be estimated since especially the Mn values. the effect of the change on the total distribution is small. Figure 7 is an AFM image of a cross-sectional view of a etched (Cr03 + H2SO4) filament sample.

• · '40 The image shows a dissolution of the radial surface layer of the fiber 37 106046, which at the same time indicates structural degradation due to oxidation of the filament surface layer and change in molecular weight distribution.

Figure 8 is a BSE image of a cross-section of an oxidized filament sample. The image shows a lighter surface layer diffusion yard than oxidation-induced filament. The surface layers of the sample did not withstand electron gun bombardment sufficiently to perform line analysis (equipment: SEM, 360 Cambridge 10 and ΕΡΜΑ, Cameca-camevax microbeam).

Part example 1.5

Part Example 1.5 deals with the thermal bonding of staple fibers formed by melt-in-periphery-acidified polypropylene filaments produced by the process of the invention.

The grounds for thermosetting 20 of the cardboard gauze formed by the synthetic fibers and the determinants of the binding adjustment equation are described in detail in patent application FI 961252 / 18.03.96 (EP 97660030.4 / 14.03.96).

The standard terms for the tensile strength and elongation equations of fabrics that quite accurately simulate the obtained test results are shown in Table 4. The logarithmic graphs corresponding to the tensile strengths of the test fabrics are plotted in Figure 9. The fibers corresponding to Tables 1-7 and 12 are oxidized to different degrees of degradation. The fabrics corresponding to Nos. 8, 9, 10 30 and 11 are for comparison purposes. Fiber No 11 is a conventional production fiber produced by the short spinning process. Fibers # 8, 9 and 10 are skin-co, re-structured imported fibers. These fibers are made by the long spinning process and their conditions of manufacture are not well known.

The properties of the test fibers in Table 4 are summarized in Table 6.

From the theoretical maximum values of fabric strengths in Table 4 and from Figure 9, it can be noted that as the periphery> 40 «increases (as MFI values increase and Mw-38 106046 and Μη values decrease: Part 1.4), the fabric strength functions shift towards low bonding temperatures. . The values of the activation energies (E) for fabric binding are within the limits of the measurement accuracy for fibers of the same starting polymer. The tensile strength and elongation (allrelz) bonding equations corresponding to the high bonding temperature of the gauze corresponding to these fibers appear to converge to form a maximum strength envelope (Figure 9: no. 00 and equations no. 1-7, 12). At full strength values (σχ, 6A) with respect to the firing direction, the equations are not accurate, which may be due to the larger dispersion of the measured values.

The envelope clearly shows the increasing strength values of the fabrics as the bonding temperature decreases as the degree of fiber surface layer degradation increases. Improvement in binding can be attributed to an increase in fiber surface melt, easier relaxation of tensile orientation as chain length decreases (thereby decreasing orientation-oriented shrinkage that adversely binds), improvement in melt-solid moistening, etc. It is also to be noted that in order to increase the yield strength, the surface degraded fibers also need to be subjected to rigorous heat treatment.

25 From the values in Table 4, the difference in the maximum tensile strength of the fabrics corresponding to the fiber samples no. 1 and no. 5 is 28.3% (σΧΙ) and 175.7% (€ „). Increase in tensile strength thus, the increase in elongation 30 is remarkable. The tensile strength ratio is the shape of the same series of fabrics

Ou / Gj! = [MFI / (MFI) 0] - ° '794 x 3.235 x 106 x exp [-12390 / RT] / 22 / thus decreases the σ ^ / G ^ ratio in the test series. an increase in the melt index and bonding temperature, whereby the effect of the change in the melt index ratio is greater than the effect of temperature.

With respect to the elongation and tensile strength ratios, it can be noted from the test results that in the aforementioned series of tests, the elongation ratio, 6 ± / 6XI, decreases slightly and the tensile strength ratio, σ1 / σ11, remains constant or slightly increases with MF1 values.

39 106046

It should be noted that the σ ^ / β ^ ratio of the fabrics corresponding to reference fibers 10 and 11 is of the form: 5 σιι / ειι = 2,443 x 107 x exp [-13780 / RT] and o ^ / e ^ = 0,808 / 23 / ( i.e. T = 433ek, (σ „/ € χ1) / ηο: 1.04 / 1, 2.70 / 10 and 0.81 / 11).

From the thermal bonding results of fiber webs, it can generally be stated that the tensile strength and elongation results obtained with fabrics are highly polymer specific. The increase in the tensile strength of fabrics due to the oxidative surface degradation of the fibers is quite limited (both limited by the polymeric properties as well as the textile adhesive properties of the resulting fabrics). Adjustment of the elongation of fabrics by surface degradation is possible within a fairly wide range. By changing the polymer grade (Mw, MWD, plasticizers and other auxiliaries and additives), an analog drive system with control ranges but with different strength values is obtained for fiber surface degradation.

Part Example 1.6 25 Part 1.6 is a study of the behavior of certain peripheral oxidized product fibers by the process of the invention in oxidative evaporation and Lenk bonding. The aim is to detect possible kinetic differences of 30 mm in the oxidized fibers as the filament. due to changes in molecular weight.

The oxidizing evaporation follows the first order reaction kinetics, i.e. the equation simulating the evaporation result is * 1 - a - exp (-kxt), where / 24/35 a is the evaporated weight fraction and the reaction rate constant, (K, min '1), is of the form K = k0 x exp [ -E0 / RT] / 25 /

Table 5 shows constant values of the reaction rate equations for oxidative evaporation 40 of some peripheral oxidized fibers (as well as the starting polymer) in isothermal evaporation. According to the table, the activation energy of the overall process is constant (within measurement accuracy) for both polymer and fiber evaporation. From the results it can be observed that the evaporation rate reduction is significant between the starting polymer and the peripheral oxidized samples. In contrast, the major differences between the filament oxidized samples are quite small, although the rate of the latter decreases as the melt index increases.

The change in oxidative evaporation rate as a function of melt index change is of the form K = 2.1945 x 107 x [MFI / (MFI) 0] -0'172 x exp [-22392 / RT] / 26 /

Table 5 shows equation constants for oxidative evaporation of a polymer having a melt index, MFI = 30, for both air and oxygen oxidation (not: 0-1 and 0-2) for comparison purposes. The molecular weights of the polymers being compared (Nos: 0-0 and 0-1) differed significantly and were (before oxidation): Mw-Mn-D: 254000-49700-5.1 and 193399-34930-5.53. According to the table, the values of activation energies (within the limits of measurement accuracy) for oxidizing evaporation for polymers 20 are not equal to 0-0 and 0-1. With oxygen oxidation, the evaporation process is only four times faster than with air oxidation (different polymers have produced up to 12-fold differences in air and oxygen oxidation rates). After the incubation period, the mechanism of the oxidation-evaporation process is the same for all samples. The oxidation of the surface portion of the molten filaments is so low that its effect on oxidative evaporation in the studied system is quite mild.

30 It should be noted that the kinetic equation for oxidative evaporation of the reference polymer, especially at high α values, was better suited to the Avrami kinetic equation (1-a = [exp - * (kt) "]) implementing a low time exponent (n <1.20). than pure 1-d format.

35 Both the starting polymer and the series of surface-oxidized fibers corresponded to the incubation time equation t0, min = 1.584 x 10 -3 x exp for the oxidizable evaporation [8163 / RT] / 27 /

Also, during the incubation time, which is a function mainly of the antioxidant and stabilizer of polymer 40, the surface effect of peripheral oxidation is observed (i.e., most of the stabilizer content of the polymer is still retained due to the extremely low delay time of peripheral oxidation).

The incubation times for oxidative evaporation of the reference polymer in air and oxygen oxidation were: to, min = 7.112 x 10-5 x exp [12149 / RT / 28 / to, min = 1.755 x 10-2 x exp [5450 / RT] / 29 /

Oxygen oxidation thus reduces the temperature dependence of the incubation time and shortens the incubation times.

Further, from the results of oxidative evaporation, the kinetics of peripheral oxidation of the molten filament are polymer-specific and are affected not only by molecular weight loss but also by the polymer additive content.

15

The effect of nitrogen and carbon dioxide-containing gas phases on the non-oxidative evaporation of polypropylene will be further examined by means of dynamic thermogravimetric measurement series. At the same time, a series of experiments show the effect of bound oxygen contained in the fossil fuel 20s in the oxygen-free evaporation of the filament quenching step. The molecular weight of the conventional spinning polymer used in the experiments was: = 206000, M M = 33450 and D = 6.15.

25 The results of dynamic measurements are not accurate, but a comparison of the results gives a qualitative indication of the direction of the reactions. In the result comparison, the results have been extrapolated to temperature. This is due to the increase in evaporation rate as the oxidation rate of the carrier gas phase increases, whereby the optimum temperatures for evaporation of the different test series fall within different temperature ranges of 250-500 ° C.

The equation simulating the change in the volatile fraction (a) of the polymer as a function of temperature (dT / dt = 20 ° C / min.) Is of the form o = x T 2 x exp (-E / RT).

35 The equations for the different compartments of the carrier gas phase are: The constants a and E (cal / mol) are: N 2: 3.058 x 104/35499, CO 2: 5.317 / 22072, 2102 + 79N 2: 1.904 x 10 4/15434, and 4902 + 51N 2: 8.352 x 10 -1 / 16148. Compared to the evaporation values of nitrogen, temperatures of 300 ° C and 390 ° C are obtained for the corresponding series of evaporation-40 values: 4902 - 2102 - 'CO2 - N2: 658 - 42 106046 281 - 23 - 1 and 66 - 26 - 5 - 1.

The result thus shows that the quenching of the molten filament performed on the combustion gases (CO 2 + N 2) compared to the values of oxidative evaporation corresponds almost to the values of non-oxidative evaporation.

Table 5 shows the high temperature (index 2) and low temperature (index 1) loop bonding tests of a few peripheral oxidized fibers (FI application No. 10 961252/180396: p. 29, r. 20 - p. 30, r. 9; EPO). -no 0799922) results.

The loop bonding equation has the form of tensile strength σ, mN = cL2 x T2 x exp [-E1> 2 / RT] / 30/15 The results of the table show that the bonding strengths of the peripherally oxidized fibers do not differ significantly as a function of temperature, despite different melting indexes. This may be due to the low temperature rise rate (10 ° C / min) used in the assays, whereby the short-chain, low-temperature particle melt will solidify again before bonding. This assumption is also supported by the position of the strength function corresponding to the relatively high bonding temperature. The reference function of the spun fiber (8-735), which is a reference fiber, settles at a lower bonding temperature of the oxidation fibers, despite the higher molecular weight (12-309: 186000 - 5.2 and 8-735: 220000 - 5.5). Compared to conventional fibers, a high temperature bonding region is also found in the thermoforming of peripheral oxidized fibers, where the change in tensile strength is low as a function of temperature but significant increase in elongation (%) and fracture (mN x mm). This is due to better wetting and spreading of the bonding melt along the solid surfaces of the fiber body.

35 The method description demonstrates the implementation of a new adjustment method for both fiber and fabric. It should be noted that the highly complicated method of adjusting the processes for manufacturing fibers and nonwoven fabrics made from them according to the invention can be varied very well in many ways, while still remaining within the scope indicated by the given examples and claims.

In the examples, attempts have been made to theorize phenomena related to the control method in order to provide a clear scientific picture of the method according to the new invention. However, it is self-evident that not all phenomena related to the method have been explained, either because of their unknown nature or due to the lack of sufficient scientific and scientific results, 10 so that the criteria given in the explanation of the new method cannot be relied solely on.

Based on the description of the invention as well as the examples provided, the following claims are set forth: 15 44 · 0 6 0 4 6

^ OOOOCOmrHLOCOO

'OOOO' ^ O'TrHrHOI

OrHrHOgCgrHrH ^ r H

moooooooooor-oo 3h coooLnmmmcooo M d Ό ^ 'v v' 'v Φ ^ idcmoooooooocmlo

<u A

jj ® a a

m ^ tOCOCDCDCDCOrH

Q Η, —I v — ί CNJ \ —l H τ — 1 CO τ — l q co r-cofOcoco ^ Dco I Γ-Ι o

M t — t t — 1 i—! tH LO

0) c <rHr-COCOCOCOO ^

O r-iCMrHc-ίτ— I rH 00 VO

^ _______ ^ __ "« 8> ° 5- 4J **

'-H g. C

d P <· η * rt 3

2 I

(0 m y

ro CM CM 00 OO rH 00 CM

CQ Ή O O 00 O CM 00 CD

V »3 Ci5 £ '- -" ""

0) 4J ** CD CD Lf) CD CM CM CM

T3 3 cr cr in cr oo after eg S 1

”CQ

* 2, -. Γ ^ - Γ- CD 00 rH 00 CD

§> <Γθ0 00 Γ „CO CM CM 00

ro «CO 00 O 00 VO VO

S _i__u______> 1> · T3

• W

e! 4-> .Coo ^ rr - ^^ coco • H gj \

4- * <D / v0lr-lt-HOOOOt-l <H

C © JbiOOOOCMCMCMCMOOOO

Φ 4->

g -H

(0 to> H (0 • <H Ö, e LO LO IT) IT) 44 (rtM-HiHtHOOOOmcr) ι0

3 \ UOLOOOOOUOIO

** V-f H H rH i— (* —l i — I i — I * —I H

A ---------

(D

^ e

> 0 OOOOOOCMCM

Tjooooooroco e * -H ICO LO lO) LO lO lO. — L t — i 2 * z0 <oooooocmcm

• ^^ AiOOOOCOrOOOOOrHrH

D

3 · £ oooooooo O Ä «ΟΟΟΟΟΟΟΟΟΟΟΟΓ-Γ- V ^ Q g -. -. -. -. -. -. > - g goooooooo

D

D rHOOM'COCOOOChO

0. — I 1 —i rH rH rH 1—1 {H 'z oo oo «106046

S

^ ZL r- Joj ^ ho ^ fÖ

•B

CO _ ^ ° VO «£ £ ^ g °° 3 -i - - v ininHN - 2 ^ 5 ^ - o o ^ -10--1 tO * -" "

fO

-P

-p ---------

-B

S

3 S 3S "- S o '" ^ 4J ^ 2.10 ~' X * CM --1 CM * -H 1 4_) o o "__

-B

g c _________ o

•B

4-> Λ g _, oood [T? n ^ —I ^ ^ cm M 2 0 ^ o CO Jr ^ 1-

O - nCMJT ^ Ci ^ -rv7 «* -« ^ m H

4-t - ^ O O 0x1 0000 0) - “Ό β Φ --------- to

•B

g _ β Λ cm ίη o o g ^ £ en> i m cm v. g g ° ° · »en —i v, q Ό m« e <-i vo 1/1 - ^ ^ co — t ^ ro ^ 5 β

•B

-P

β _________ g to i — i, -.

-h - »tn <3 · _, _ ~ z: S <n ££ o g« S * "-ο- Λ -“ Φ

• N

, n 6

tO O

o ^ g i 'z § cm Φ o υ s σ, o κ o E ^ ^ *! B ^ x C «DS Φ t-, g ^ ^ \ —J r ^» pJ OO g · g · <Λ 30 o> oo E- · Ϊ5 CO H ri I- »pij <-! R * st — I ^> i 46 1 0 6 0 4 6 ΙΟΙ CO "00 ^ = 515 ^ 10 ^ ο to 'OO'" "^ o 00 m ^ in r- nou> g» h cd '-' oo1 "^ ™" 0 'ro' 'i — i ro cm ^ _ ^ ^ oo ^ ^ ^ τΗ $ Γ "" 2 2 ^^

10 CM m ^ <-l CM CD

u-> CM o CD i — I Γ0 li) S § r- io.

rH ^ ^ ° ^ T - O «H

^ CM CD CO m „CD <*> O O ^ ^" »2 S ^ S 5 ω H S CD * g ^ CM ^^^ COCMr- 0) ft -----------

C/O

Λ ^ CO ~ O CO 00 00 ö O »t-4" o'-1 - - CO v -h 01 Ij c-c "cd ^ en en

-P CM Γ-l CM CM lO

e d) g -----------

c/o

• Tl, _j CO λ * I i I CD

ii_j -. v n H ΓΟ ^ v

M 00 -H ° CO v CO v tH

3 ^ CM 00 t «~ - CM CM CD

P

Λ __________ Φ

rV

rl o ^ O rH iH {N

* S * HZ, «77 rH 00 ^ ^ <hg cm v t- ^ ® CM CO CM - = r * Π {Ö (- | I ....... -......... .--- .. Ml I— - ——— M .. .. - I ......— ....,

•B

g, 04 cH 00 ^ 9 ° ^ CD

M 7 O t — 1 JT OOOJ - ^^ 'OO

P r ~ m _ „tH T-H *.«. T-i CO ^ CM CO CM o ^ »· e" ——————— ^ "" "" "" "" 1 1 1 "——

CO M S *** N. "-H

3 ^ »s e '. ^ s | fi o ^ rt · £ ”e s - ΐ -H s i £ 1 2 ° O U g 3 ° ö> ^ <ö 2 -p tsej n p 0) 9 φ Φ 1 ^ 0. I — I p4 E- <r4? Ί 4-> tl 5 »T * * ^> fö {N O T T-t Q ^

LT Γ Lj {U> PJ; 0> ^ Tl W

5 ^ 3 CO K ^ Ξ W Ό h EH% CO Ä 106046, Ο rH „> Ο ° <£>

ro O 'lo 1 I CO

10 «^ ™ ^ £ O ^ o £ t m 00 r ^ ° i o 1

10 CM Μ r ^ CM

n «o pj« w 2 CM ° V CM 1

^ CM Γ- CM

, O CO ™ O £ ^ Λ pj 2 rH O .LO 1

^^ CM Ν I- CO

I {Tl CM ^ O. 00 ^^

5GS t-H? VD CO H VO

N 11 ^ {N 10 HM · CO

- CM ^ O ^ ^ ^ ^ CM S- · -1 2co ^ <cr> r ~

CM H (O CO

_ CM ^ O.0-1 00 CO, ^ ώιΗ ·. ^ *.

CM ^ vH ^ COrH ^ CD

^ CM '-H «3 * CO

CM O t — I CO CO., LTD

CM 2 n H n CM S. * - 1 n ^ - 10 σ '”cm N r- co co I e * o00 ^? 10 cd

tH O r-c _T OOO ^^^ 'CO

CÖ CM CO ^ CM CO CM O 'T ^

O

Oh. ·. + j ----------- -'Λ ^ β ~ A ^ € ”13 '. -? - 5S | Eo "S 2» "E B ΐ ί" 8 1 3 1 S · §. J5 § 3 5 * ^ S. W s <u B 21 | £ m ^ S ^ ^ q «£

£ il> | 1 | 1 1 H

48 ^ 106046 is s Sj% · s s w ^ m ^ co n o n ^ _. ctv m vo

^ H CO

. L-O «* i — I 1 — I

'a * * 3 * oo vo σν m oo in ί ™ r- ° ° ° η 11 1 oo * r o cm Ivo m 00 o. ° ^ 2m m ^ ^ vo ^ to - σν t-im 03 ^ () lo cm o oo o ID <H Ή

is n H VO V

ι-h r, vo .. r ~ cm CO CM ^. o o 2 00 ^ * - [LO O 10 _ * · '

H '* 0 ~ OO

^ CM 00

_ (Tv 00 O

01 ^ {M ^ VO 00 H {M ^

'r- CM CM

00 o'-10'1 ® S CM - r ~, - ·

lN <-H CM OO

.VO CO 00 «° ^ VO

^^ ° ° ° «" * ®

to σ> CM O CM tN

O

.. _P ----------- _ · (0. £ *

HO {0 M 5 · ** Ί ... -H

• r-v. — I \ \ * Ί \ \ Qj g U

§ 5 §% 3 w 3 $ 1 ^ t? m ".3 3 h q„ <£ g I 1> Γ M 11 f 1 49 1 0 6 0 4 6

IrH Γ- °° OOq ° ^ °° LO

O ro 00 o 10 ° S. cC - r- ^

H 1.1 H H OI N O O tM

00 ^ o o § ^^ LO

<J \ 00 'O O v. T ™ ^ LO

^ ™ rH CM £ O Ξ «® ° H 2 S ^« - VO * £ ο ° «3ΐ ri ri mno co ^ CM ^ oo 2 ^ ® o _. V λ ä O ^ CVJ ^ ^ ^ LO ° ° VH. «. LO ^ ^ CO 'T LO CM O CO ™ CM0' o t-σι LOC00.

LO 2h o H N CM- 'W £ LO OfM ^ O - O £

1 CO ^ H CM O CO VN

CM ® ® «N O

m r! lo «° ° ° m ™ ^ £

~ CO. -I O CO

r-10 oo ^ ^ ™ m "£ ^ ° 2 °" - ci e °° -νΓ ^ ^ LO .H or-- ™ r- ^ o rr- iolo CM £ 5 ^ ™ ^ 'vo S w ® ^ £ cm ^ t-η t — io • rH Γ ~ ^ ^ ^ _ Λ ™ ^ oooq ^^^ lo

- ^ m CD ™ ^ lOJ

CCS 1 CM CM O> = Τ lN

o Λί .. _μ ----------- * CCS.

• I- »CCS ^ 5 09 N -rH

~ rt g- ^ wgg r.

· »'S 8 -s" ss 9 "a 3 B is 8 s ° s SM 2%» X s, W g rt B 5 l ^> rt ^ o ^ ^ Q c £ g> I r so 106046 Ε- ι

Pi

CM

W

"E ___ ____

HffiH O i — I O t— 1 00 CO OcHO ^ TO ^ TO

o Tr ^ srvomo ^ ro ^ cMsro ^ oSolJO * ϋ Γο <N CTi CM CD CM ΙΟ {Μ Γ- M1 CD CM CO MC CD L \ CO

ω Cl ^ CO H m c-HOOHCOCTiCM HOO H

H V ^ K V V V K V S S V ^ V v.

. x I _ 7 oo oo r ~ cm co cm oo r- r- cm co cm ^ cj ms cm „cm m m cm cm cm cm m m cm cm cm cm ^ cm

Eh "x __.___; _____

CM

o

"B

Il O r-, co oo r- r- r- r- co co r- r- r- r- r ^ · r- * · r- · ^ τΗ Ο Ο t — 1 tH r-1 t — IOO t —I tH tH rH t— I tH t — l - m—. different different CT »<r> cr> σ \ σ \ σ \ σ \ σ \ σ \ σ \ c \ σ \ σ \ σ \ (0« Η τΗ, CM CM rH tH »H tH CM CM« H tH tH τΗ rH τΗ γΗ flj tH. ^ 31 tH t— \ rH tH ^ ^ tH τΗ τΗ γΗ γΗ τΗ τΗ ϋ ο ^ g -------- Η Λ CMq ^ c-ΙΓ- 0 CST ^ CO γο η η Η CM Μ1 ω

V Ο. V V «h, VV VV VV VV V

r_ * ^^ - νΓ στ Τ 'r- στ om lo oo ^ ro oo o C-, 00 MC 00 ro CM «CM X CM 00 CM CM CM CM CM CM 00 5-1 ίιί L! ^ m' im ^ ^ w \ ^ \ ^ wwww \ Mr. E 2 O m H OO DM- LO IM -LT CD CM CD O 'O' CM mo S ° σϊ ^ σιΓ- οο ^ ιη ^, οον com ion ηλ t

X X XX X X X CD x x x x XX X

rt ^ _τ · o i-π h J · oo Joo m r- o oo <-h <-h <h en W Lo mu ootH mn φη -pi -H 1—1 g o .------- - P xd) (1) 4_> in y) ίο oo co ω om m1 n ooo ^ r-π στ r ~~ o oo ox. m o co co r-ioomoor-H 'jm1 oyi om oooi

H O LO CM O in CM O Γ- Γ „CD CM O) U) CM H OO M1 OOO

^ (M β I (Ο Ί O) ΙΟ H CM 00 M1 O CO 0) 00 HM1 0) 0)

Eh i XXXX XX XXX X X X X X X X XX

K, CO * LT <—I CM Mn Mn 00 OO r ~ -CO Γ "CO OOCO CO M · X <3 * ^ ro oo 'j1 m · n oo» r «r ^ Ö ω o ----- --- o 11 ^ rtx. 1-1 • nj "TV o στ στ r ~ στ στ στ στ r- r ~ - στστστστστστστστ! px— .E o- r- oo oo rrrr-coco 0-0- r- ~ r— γ- γ ~ r- r ~ rj bm M t — I t — 1 t ’Γ x — I x — 1 i—! »H Γ O« i — I x — I x — I x — ltlt— I tH rl>, h »y * * 3 * r- r- r- ι ~ - ^ ^ rrr ^ nr ^ rrr ^ nj ... rt ^^ ooro 'xT ^^^ ooco + J g 0 S En

O

Ό V --------

•B

en h 3 o • · - '5¾ I {—I _I * - · _J ·' · _J »—C _. _ | * —1 _I» - · | * —1 1 • fir * • -Η ^ Γ ' ΐ-ΐΤ'ΚΗ / Γ'ΕΗ ^ Γ'Μ.ΗΗΗ ^ Ι-ΙιΓ'Ι-ί, Γ'ΕΗιΓ ', ρ, Η bt> cowe> Ötit> w "öfc> fc) t> e> t> bÖ 3 rt 1-3 xT________ 0 «, rt j—) 3 h3 9 h cm oo ^ Tincor- K * nb 1 a si 106046 vo cn ^ vo vo σ> ιο ro en r- t-π μ mooo ^ THo ο οο o en cm oo οο ιο o 0 ooo nnnn> = i> ^ vo cm o vo ro ro

Cl QO VO O 00 00 CM Φ O 31 ro H M1 o M1 00

I — I ^^ ^ ^ ^ ·> V V V V V V V V V

1 ΙΟ m ro M1 {VI CM t-H Γ f cm ro CM H r- ~ cm lo ro ro lo lo ro ro ^ ^ cm cm cm cm cm

O CM 00 'T • M' CM CM H H M1 T <T \ 0 \ 0 \ <T \ CM

E ion loio ^^ r cm cm r ~ r- h h h h en m'— o ^ cm cm o o lo lo t ~ - r- en en en en lo

"rl ΌΟ H i — I 00 00 OOCOCO rl H H H VO

Id h ί cm cm ro ro cm cm ro ro hhhh γ-η o r-CM öl ^ VDH CM ^ r- CO ° ^ ^ ^ ^

V S V V. V U V V V V

eno oo ^ r- oo "* '-T ^ vocmh ri r. cm ro cm zi cm cm ~ co m rococoro ro ^ Si m1 * = r S2 ^ t = r 22 ro 22 12 ^^^^ W ww \ E 2 ioo ^ ^ r-ι rH o lo ro oo ° Γ- VO VO 2 00 - LO 0 CM VO csj ^ «g.

^ · «. v ^ CM _, s rvj rvi ^ ** O

Γ «LO VOODOO 00 ^ CO VO I'riHO ^

LO -Ljt LO LO rM 03 LIVO rH LO t-H CO

* cr to o cm vo o en oo vo vo vo vo ro ^ vo

O t-H t-H 00 OO O rl I O 00 t-H O LO CO LO

n vo oo to oo en t-π o vo en h cm ro oo r- to jji en vo cm ro ro en en ro oo lo o ro cm o ^

> v s V V V V V V V V S V * k S V

cm cm m * cm ^ ^ ro t-π vo r- h σι h cm co roro cm cm cm cm ro ro h h ^ ro ^^

•. "-B

0 VO VO CM CM CM CM CM Vfl VO tj tj OOOO O

g CM CM LO LO LO LO • q'tq'VOVO OOOO

ω— o o io to lo lo- en en ιοιοιοιο r ~ rl Li) lO Γ'- Γ- Γ "LO LO t-H t-H CM CM CM CM 00 rt ro ro cm cm cm ro ro cm cm ^

O

the so-called

O L

W 0 • * 1 * 4J 5 S M HH ♦ _i »—I 1 ►— <_J * —I I _I I — I 1 * - *« 5 EU 6

D 3 <C

^ ______________ 0 g i § Ϊ8 * »S 3 Ϊ1 1 s 52 106046 c ι_ι g on σι oor-moo

P_, V V I V S V <k V

Swo co cn 1 m ιο n o o rH r- in cm h n \ 0>

B

O o o N e ΓΗ \ CM ΓΗ CM Γ-

flj H CM

O

cm m n r- ° ö is C I LO ΓΗ V s I {Τι ΓΗ n

B

O n n n c— g in n in o μ \ σι cn cn in

H H H t — I O

rt in in n m o

-P

<u Φ ----------

V

o cm cn co oo • h cn cn cn co

o CM 00 CM H

-V g I cn cn o co

Ch (_I ^ ^ ¢) n n ^ cm 1-3 n n in in CO __________ 3

-P

2 H

^ O o CMOOOO

-5 ö g cn cn cn cn σι m., M t- nt-r-Hoo

£ H CM CM CM CM CM CM CM

flj CM CM CM CM CM CM CM

05 0

> _ iti -p -P

as ο. <= r σ m- r- o ^

to 0 r- nin- ^ rcMH

re oo ο- ^ ΗΓ-η «2 I cn r- h co o o

I V V V V V V

♦. Cocor-r-COOO

«H i — 1, —I 1 —I {—I, —I

in Ο <d m 9) r- m <3 * ^

^ jJ-iOori ^ nininoHCM

^> 1 S CM, CM Γ- CM CM I I I

D iiiiooo PI% nijcMootnn

B

53 106046 <3 <^ ο ιο ro ο ιο ιο,,,, -H,,,

V V V V V V V V V

i-I i-I i-I t-I i-I% -1 (M r ~ H

^ o

C/O

• · «H

: tÖ {Ö --------------- ö a m t> i · *. -H p

C # r-1 P

Φ> 1 P® 'X' 00 X t — I LO VO

** * £ a «* <* ^ ^ 1 ^ 1 * 1 to" ^ 1 »> · <

• -Φ ** C LO lO LO ^ 1-H

X ··. rH -H

φ CO O g

4J> t Ö O

Ό> i _______________ \ w fi JZ -H Q) H <U Ö

-P -H

* * rj: ί ° gooooooooooooooo I: (Ö 1-1 · <CO: (Ö 3 ä .§ 3 S -X ________________ -i — im · *> 0) nrv _i ohg ^ P £ S ^ 00 OS 3 m ' rtirt LOLOLO ^ 10 <D vp ro> «H rH | QIII 1 1 * v ·· {d ^ qoo ^

m ^ 1-1 rt O rH ° m S

<D 2 Λ λ \. ηη / Tv rn ^ + J 3 i ijSJ r-Scoojro Ό -H o rt © Ä (om '' 3'00 -HC -n *, ^ ro ** ex * h 3 [I i ^ -H X5 i3 ro -ro aw 4-1 £., P Jsf OO o S 2

• χ ·· -h a o ^ o 2 S

£ 3 · Η · 3 · * W r ~ -C3V o ^ ® rH rH LO 2 ^ • Η4-, · ^ * · μ es, <m CM ^ ^

<fl 4-J g Φ VM VN VN

C -H g T3 "----------------- • H -H Xi 2 g

§ y X S m g. ^ OlOlOLOlOlOlOCJOOr-C-r-lOCD

υ, ^ I> [- fOVDVOVOCOOLOlOO ^ O <N

J S. J <U Z 'iJrOC'JCMrHrHrH'TCOOD-g'r-rHrHCri

§ pS <DÖ4 1 * I CNJ * -H t li I <l t 1 04 * I * li I 04 04 * I

'5 * · * ^> -H t-j I, I I I I I I I I I I I I I I

y **. ?, 73 2, dp ^ oor-or-o ^ crir-ir-icom ^ r-x S il .11 Ϊ; -v d 1 L.oDt ^ ioovrorHint ^ roov ^ n ^ ro 5 r H e «no'i'in ^ 'TNNriMmnnn

rH e r> 1 * H 2 W VN

5-Horo ^ Hig.111 .......... 1 "d tl t! JS R h -P ^ ovro- ^ r-io ^ oooocorovocMCNjco

J .. ^. . SSVVVVVVSVVVVV

Ϊ 2 SJ d 1 \ S ^ oovr-oot ^ r-VoitOLO ^ r-ocncri

ω KKK.2, g 2 lNCSIrHrHrHrHrHrHC \ irOrHrH (\] rHrH

^ 1 1 f I I I I I I I I I I I I I

., 'dcjVLOVDavno ^ rrHOVLOocNjoon

; X ^ ^ rHOOOrHCMCM rHOCTlOrHOV

P tN <\] C \) CS] {MC \] C \ l {M (MCNC \] rHC \] C \ lrH

• No

VO

§ 3 3 g ^ tl Ö S HNn ^ iOWh <om ° [i »ncooi to -d rt C iH rH ^, g 8 - ·« <EH ___ 54 1 0 6 0 4 6 lOlOlOlOlOlOlOlDlOlO »I j III Λ ^ T - ^ 1—1 λ — lt — I t — 4 r-4 i — I r-4 * k * 1 »k. *> k «k. * K. »K. * K.

tH rH% —I rH t —i t —I i — I r-4 τ— {t-H

«> 2 m lo to rH <3 * n 3 ti ** 1 1 1 1 r ~ ^ 1 co 1 io 1 1 'roro

* β * -H i — I * —I CM CM

B

I ______________ .go ooooooooooooo l —'g'a *

LO ο ο ο rH

^^ ν ν LO 00> νΓ ^

Ε _ I III I

3 α -Ρ ο ο ο ο ο 3 I ο ο ο ο ο rt η n en lo lo ο λ; fc: «cf ^ οι oe» ο m Β Α n ^ ^ m η Α - 3 ι ιιι ι + J ^ ο ο ο ο φ ο ο ο ο ο c fccj om ιο ιο ο γ ~~ J — ι (Π “ΝΡ ^ οο t- ~ ιο σ * ο

τ — I χ — I ι — I ι — 1 CM

jf fOOO'C'COr'LO - OLOOOi-IOCD

L. r-t-i ^ rHoniiic ^ -csion ^ o

? ri Ot ^ oo ^ r ^^ lJc-aDLO ^ LOLO

^ τ — I f — 1 «—I rH i — 1 i — 1 ^ _ι rH rH rH rH i — I rH

^ 1 1 I I I I I I 1 I I I I I I I

2. dP 9) iHr-rOlOlOCOrJlOlOr-OrHO '3 1 r; o ^ cnoorH '. OrHr ^ cnr-oo ω ι 'n <M {\ innnlNooncM <\ jcMcj

5 ι X 1 I I I I I I 1 I I I I I I

r-1 1 φ

pj l_ 4-> 10 CMOtOOCMlO ^ VOOrHr-CSJLO

«4J O ww4« »V

. O.n 2, - zl οοοοοοσ> οο *, θιΗοσιοο

'ίο 2 § HCMfMHHH ^^ CNWHCMCM

° * ° 1 I I I I I I 1 I I I I I I

· <MmnmNinjfliTfflOMfl • ro X OCMOOOOCO ^ OOCTlOOOCri -H? ® {NJ «.k. *. *.». *.

-P N CMCMCMrHrHrH ^ CMCMTHrHCMrH

TJ

LO

0 * 3 * ^ rH

I -ti I c ^ 3 2 ι io '£ ϋ H «H -H ^

B

106046

Peer reviewed literature / 1 / S. Kase, T. Matsuo: 5 J. Appl. Polymer Sci., 3, 1965, 2541; 11, 1967, 251/2 / A. Ziabicki:

Fundamentals of Fiber Formation, New York 1976,

Wiley 10 Z.K. Walczak:

Formation of Synthetic Fibers, New York 1977, Gordon & Breach M.M. denn:

The Mechanics of Viscoelastic Fluids, AMD-Vol.

15 22, ed. R.S. To the Line, 1977, ASME, New York, 101-124

Ann. Rev. Fluid Mech., 1980, 12, 365 Computers in Polymer Processing, ed. J.RA. Pearson, S.M. Richardson, Ch 6, 179, Fiber Spin-20 Ning, 1983 A. Ziabicki, K. Kawai:

High-Speed Fiber Spinning, New York 1985, Wiley & Sons, 67 J.R. Dees, J.E. Spruiell: 25 J. Appl. Polymer Sci., 18, 1974, 1053 R.R. Lamonte, C.D. He:

Trans. Soc. Rheol., 16, 1972, 447 J. Appl. Polymer Sci., 16, 1972, 3285, 3307 C.J.S. Patric: 30 Elongational flows, Aspects of the behavior of model elastoviscous fluids, London 1979, Pitman A. Prastaro, P. Parrini:

Textile Research Journal, 1975, 118 A.C. Smith, W.W. Roberts Jr .: 35 INJ, 6, 1, 31-41 C.H. Chen, J.L. White, J.E. Spruiell:

Textile Research Journal, 1983, 44 H.H. George:

Polymer Engr. Sci., 22, 1982, 5, 292 ... 40 A. Ziabicki:

Kolloid-Zeitschrift, B175, 1960, 1, 14/3 / A. Ziabicki: / 2 /, Fundamentals ...

Appl. Polymer Symp., 6, 1967.1 K. Nakamura, T. Watanabe, T. Amano, K. Katayama: 45 J. Appl. Polymer Sci., 16, 1972, 1077; 17, 1031 (1973); 18, 1974, 615/4 / A. Ziabicki: / 2 /, Fundamentals ..., 112; /3/,A.P.S..3 J.N. Hay: 50 Br. Polym. J., 3, 1971, 74-82 / 5 / J.C.W. Chien, J.K.Y. Kiang:

Macromol. Chem., 181, 1980, 47 J.C.W. Chien, C.R. Boss: J. Polym. Sci., Al, 5, 1967, 3091 55 J.C.W. Chien, D.S.T. Wang:

Macromolecules, 8, 1975, 920 56 106046 H.H.G. Jellinek:

Degradation and Stabilization of Polymers, Amsterdam 1983,

Elsevier: S.S. Stivala, J. Kimura, L. Reich: 20-5 36; I. What, K. Horie: 254-263, 274-285? AS.

Khalturinskii, AL. AL. Berlin: 307-333; Y. Ka-Miya, E. Niki: 337-357 L. Reich, S.S. Stivali:

Rew. Macromol. Chem., 1, 1969, 249 10 Elements of Polymer Degradation, New York, 1971,

Me Graw-Hill, 54-57, 64-69, 230-277, 296-307, 334-341 ./6/ J.H. Chan, S.T. Balke: Dust. Degrat. Stab., 2, 1980, 113/5/7 / H. Hinsken, S. Moss, J-R. Pauquet, H. Zweifel:

Polym. Degrad. Stab., 34, 1991, 279/8 / G.S. Kiryushkin, Yu. Shlyapnikov:

Polym. Degrad. Stab., 1989, 185/9 / J.E. Brown, T. Kashiwagi: 20 Polym. Degrad. Stab., 52, 1-10 / 10/1996, S. Girois, L. Audouin, J. Verdu, P. Delprat, G. Marot:

Polym. Degrad. Stab., 51, 1996, 125/11 / H. Dreyfus: US 2,335,922 / 1943 25/12 / L.E. Wolinski: US 2,715,077 / 1955/13 / D.E. Shaffer: US 3.907.957 / 1975

/ 14 / J.S. Roberts: US 4,303,606 / 1981, US

4.347.206 / 1982/15 / J.A. Cuculo, P.A. Tucker, G-Y. Chen, C-Y. Lin, 30 J. Denton, F. Lundberg: US 4,909,976 / 1990/16 / J.R. Collier: US 4,680,156 / 1985 G. Vassilatos: US 4,632,861 / 1986, US 4,634,739 / 1987 T. Ohmae, T. Sakurai, K. Asao: US 35,4840,847 / 1989, US 5,009,951 / 1991 RK Gupta, G. Jurkiewitsch, L.J. Logan: US 4.115.620 / 1978 [C.J. Wust Jr .: EP 0.662.533Al / priority.

40 US 177749/050194] / 17 / N.C. Pierce: US 3,437,725 / 1969 J.L. Killorau, W.K. Barnett: I.A. Guay: US 3,354,250 / 1967/18 / R.E. Kozulla: US 5,281,378 / 1994, 45/19 / R.J. Coffin, R.K. Gupta, S. Sibal, K. Takeuchi: FI-A 943.072 / 23.06.94; priors. US 080849/240993/20 / L. Pinoca, R. Africano, L. Spagnoli: FI-A 942.889 / 16.06.94; priors. I. / 21 / J · Crank, G.S. Park: * 50 Diffusion in Polymers, London 1968, Academic

Press A.K. Taraiya, G.A. Orchard, I.M. Ward: J. Appl. Polym. Sci., 41, 1990, 1659-1671 L.S. Darken, R.W. Gurry: 55 Physical Chemistry of Metals, London 1953,

McGraw-Hill, 437 D.W. van Kreleven, P.J. Hoflyzer:

Properties of Polymers, Amsterdam 1976, Else-Vier, IV, 403 60/22 / M.A. Patrick: 57 106046

Trans. Instn. Chem. Engrs., 45, 1966, 516 H. Kremer:

Gaswärme, B15, 1, 1966, 3; 2, 1966, 39/23 / H-G. Ellas: Macromolecules 1, Plenum Press, 5 New York 1984, 400-403 P.J. Flory: J. Chem. Phys. 17, 1949, 223-240 P.J. Flory, A. Vrij: J. Am. Chem. Soc., 85, 3548-3553, 1963

Claims (24)

1. Regulatory process for oxidative degradation of polyolefins, in particular the molecular chains in the surface portions of molten polymer filaments of polypropylene suitable for a card spinning system, in a filament manufacturing process in which a stabilized polymer is extruded and the melt spinning and spinning filaments are oxidized and characterized in that the oxidation of the molten spin filament is carried out as a precision oxidation by directing against the filament beam an oxidation gas from a extinguishing nozzle with a separate oxidation nozzle - as a control equation which characterizes the amount of oxidative degradation used in the precision oxidation. spin ratio is an equation of the form MFI = c 2 o - c 2 v 2 + c 3, in which MFI is the value of the polymer melt index, which can be replaced by the value of the viscosity of spin melt corresponding to layer shear rate, v02 is the oxidation gas velocity multiplied by the jerk of oxygen, ie The partial pressure velocity, vx is the velocity of the extinguishing gas, c3, c2 and c3 are experimentally determinable polymeric factors and in which the factor cx is a function of the position of the oxidation nozzle bed in relation to the spin nozzle and the filament jet, of the oxidation gas jet dimension and temperature, ; the factor c, is • ^? a function of the position of the extinguishing nozzle, the dimension of the extinguishing gas jet, its composition, temperature; The factor c3 is a function of the amount of oxidative degradation of the filament caused by the extinguishing gas phase, the nozzle diameter, the spin temperature, the polymer matrix molecular weight distribution, the amount and quality of the blend carried out, and wherein the 35 degree of oxidation is controlled by the partial pressure rate. for oxygen, in addition to the degradation of the molecular chains in the surface portion of the polymeric filament, the size of the dispersion of its molecular mass distribution. 40 2. A method according to claim 1, characterized in that a short-chain polyolefin of the same polymer grade, in particular polypropylene, is involved in the polyolefin. 3. A method according to claim 1 or 2, characterized in that the degradation of the molecular chains that occur during quenching of molten polymer filaments is controlled in addition to conventional temperature and velocity adjustments of the extinguishing gas by controlling the partial pressure for oxygen in the extinguishing gas phase. 10 Method according to any of claims 1-3, characterized in that the thermal degradation of the molecular chains in the molten polyolefin is controlled in the extruder by controlling the temperature of the melt and the delay time of the extrusion 15, in particular, that the polyolefin is extruded within the temperature range 250-290. ° C, with the spin melt delay time in the extruder and pipeline being 5 - 15 minutes. 20 5. A method according to any one of claims 1-4, characterized in that the value of the melt index of the extruder feed polymer is between 1.5 - 15, and the values of the molecular mass distributions are between ΜΜ = 500,000 -240,000, M = = 65,000 - 50,000 and D = 7.0 - 5.0. 25 Method according to any of claims 2-5, characterized in that the feed polypropylene of the extruder is diluted with polypropylene, whose melt index is between 350 - 800 and molecular mass distributions between = 125 000 - 30 95 000, M 2 = 35 000 - 20 000 and D = 3.5 - 5.0, the amount of admixing being at most 15% by weight of the amount of feed polymer. Method according to any of claims 1-6, characterized in that the molten filament is extinguished under conditions where the volume, velocity and temperature of the extinguishing gas are respectively between 400 - 1100 Nm3 / h, 20-60 m / s. and 25 ± 5 ° C, with the polymer feed rate per nozzle disk being 20 - 40 kg / h. '40 66 1 0 6 0 4 6 8. A process according to any one of claims 1-7, characterized in that as a extinguishing gas, a mixture of an air and free oxygen poor gas, such as combustion gas, in which the partial pressure of the oxygen is between 0.01 - 0.21 bar. 9. A method according to any one of claims 1-8, characterized in that after the quenching, the values of the melting index and molecular masses of the product filament are between 10 - 50, and M 2 = 185 000 - 200 000, M n = 40 000 - 50 000. Process according to any of claims 1-9, characterized in that the amount, speed, temperature and oxygen partial pressure of the oxidizing gas to be fed to the oxidation nozzle are respectively 0.01 - 0.8 Nm3 / h, 0.1 - 48 m / s, 25 -60 ° C and 0.21 - 0.98 bar. 11. A method according to any of claims 1 to 10, characterized in that the experimentally determined angular coefficient of the control calculation, cf for the partial pressure velocity of the oxygen, is poured between C₂ = ,20.2 - 2.0. Method according to any one of claims 1-11, characterized in that the amount and velocity of the extinguishing gas are preferably controlled so that the tensile stress acting on the melting filament at the setting point is adjusted below the value approx. 30 mN / m2, depending on the cross-sectional diameter (0.70 - 0.25 mm) of the nozzle nozzles, with a capacity per nozzle disk of 30 - 32 kg / h and at a temperature of the nozzle melt of 285 - 290 ° C, the quantities and velocities of the extinguishing gas (25 ° C) 350 - 750 Nm3 / h and 20 - 45 m / s and in other spinning conditions proportional to,. these values, and wherein the polymeric factor of the control equation varies within the range of C2 = 0 - 3. 13. A process according to any one of claims 1-12, characterized in that for producing the desired thickness and very low molecular weight having and at very low temperature melting layers on the surface of the spun filament, the values for the molecular mass of the filament polymer are reduced. average number of no more than 30% and the values of its dispersion are increased by no more than 40% of the values before the nozzle oxidation, by increasing the oxygen partial pressure velocity and at the same time the oxygen partial pressure in the oxidation gas and within the value range 0.1 - 25 m / s and 40-100 vol% 02 and also by preventing, by controlling the rate of the extinguishing air, that the maximum values of the filament voltage rise above approx. 30 mN / m2. 10 Method according to any of claims 1 "- 13, characterized in that the oxidation nozzle of the filaments is controlled in a position: a = 5-20 °, x = 60 ± 5 mm, y = 25 ± 5 mm, where a is the angle between the center plane of the oxidation gas jet 15 and the spin nozzle's pitch, x and y are the distance of the free orifice nozzle's center line from the vertical center plane (x) of the polymer jet and the spin nozzle's y (y). 20 15. A method according to any one of claims 1 to 14, characterized in that the extinguishing nozzle of the filament is controlled in a position: a = 25 ± 3 °, x = 50-75 mm, y = 40-50 mm, where a is the angle between the median plane of the extinguishing jet and the spin nozzle's pitch, x and y are the distance of the extinction nozzle's free orifice surface midline from the vertical jet plane (x) of the polymer jet and the spin nozzle (y). Method according to any of claims 1-13 or 15, characterized in that, upon oxidation corresponding to the position of the oxidation nozzle a = 2 ± 1 °, x = 32 ± 5 mm, y = 2 ± 1 mm just in the pane with the surface of the nozzle nozzle, the spinning nozzle is heated internally, to prevent its '· ·' cooling, with an output per unit weight of nozzle disk of 0.25 kW / kg. Apparatus for controlling the oxidative degradation of polyolefins, in particular the molecular chains in the surface portions of molten polymer filaments of polypropylene, in a filament manufacturing process, which apparatus discloses a melt spinning device having a spinning nozzle, a sear member, and in particular a quenching device. for extinguishing the polymer filaments, characterized in that for the oxidation of the polymer filaments, the device has a separate oxidation means from the extinguishing means, in particular an oxidation nozzle. 18. Device according to claim 17, characterized in that the positions of the extinguishing and oxidation nozzles of the filaments are the extinguishing nozzle: a = 25 ± 3 °, x = 50-75mm, y = 40-50mm the oxidizing nozzle: a = 5-20 ° , x = 60 ± 5mm, y = 25 ± 5mm, where a is the angle between the median plane of the extinguishing and oxidation gas jets and the spine nozzle's pane, x and y are the free orifice nozzles of the extinguishing and oxidation nozzles from the vertical plane of the polymer beam (x) and the spider nozzle (y). 19. Apparatus according to claim 17, characterized in that, upon oxidation corresponding to the position of the oxidation nozzle a = 2 ± 1 °, x = 32 ± 5 mm, y = 2 ± 1 mm just in the pane with the surface of the nozzle nozzle, the nozzle nozzle -draw its cooling, provided with internal electric heating with a power per unit weight of nozzle plate of 0.25 kW / kg. 25 Device according to any one of claims 17 - 19, characterized in that the dimensions of the free openings of the extinguishing and oxidation nozzles are respectively (10-20) x 480 mm and (0.5-1.5) x 460 mm or the ratio between their areas are 7 - 42. Use of the method according to any one of claims 1-16 for controlling the temperatures of the thermosetting process and the bonding strengths of fibers produced by the method, in particular the melting point and the melting rate of the partial melts which rise from the filament surface layer upon their thermal bonding, and for the regulation of the quality properties of the fabric corresponding to the filaments. 40 69 106046 22. A method of thermo-binding of skin-core type fibers made of polyolefins, in particular of polypropylene with a controlled autogenoxidation of spin filaments in the molten state, based on the degradation process of the molecules in the filament surface layer, characterized in that a. to be thermobonded by the control method according to claims 1-16, such that the fibers exhibit desired surface layer structures and melt ranges which can be determined bed by melt index and with the degree of degree of molecular degradation shown by the molecular masses b. simulates the product fabric pour strength values, where the equations for tensile strength and elongation are 15 o (e) = Coi X [MFI / (MFI) 0] no1 x T2 x exp (-Eo: / RT) and after reaching the maximum values for the pour strength is the common envelope equation o (e) = c02 x T2 x exp [+ E02 / RT] c. the ratio between the features of the product fabric strength and elongation are controlled by a polymeric control equation for the bond σπ / 6π = c03 x [MFI / (MFI) 0] no3 x exp [-E03 / RT]. 23. A process according to claim 22, characterized in that 25 a. Of the feed polymer: Mw = 255,000, Mn = 49,250, Mv = 209,000, D = 5.15, is prepared by using an oxidation process for melt-state filaments. -ber series, in which the ratio of the melt index varies between 2 - 4.5. B. Of said fibers are made thermobonded product fabrics (about 22 g / m2) against whose pour strength values and proportions corresponding to factors in the control equations for the bond (Oi ^ Ou / eu) are obtained respectively: c01 = 5.444 x 1019, n01 = 1.811, Eoi = 47180; c02 = 2.377 X 10 "10, E02 = 35 11920; c03 = 3.235 x 106, n03 = -0.794, E03 = 12390, for the transverse pour strength values, corresponding control equations are formed by corresponding parameters, c. and as the difference between the maximum pour-fastness values of the fabrics are obtained, using bond control, with the setting of melt index 7 ° 106046 MFI = 1.98 and 2.90; Δ6 ″ = 105%, Δ6Χ = 73%, Δτ = 4.5 ° C MFI = 1.98 and 4.07; Δσ „= 8%, Δσχ = 39%, Δτ = 11.1 ° C.