WO2008122497A2

WO2008122497A2 - Organopolysiloxane-containing fibre

Info

Publication number: WO2008122497A2
Application number: PCT/EP2008/053348
Authority: WO
Inventors: Elisabeth Gonthier; Mabrouk Ouederni; Konrad Alfons Wierer
Original assignee: Wacker Chemie Ag
Priority date: 2007-04-04
Filing date: 2008-03-20
Publication date: 2008-10-16
Also published as: DE102007016291A1; WO2008122497A3

Abstract

The invention relates to a fibre which can be produced from a composition containing an organopolysiloxane/polyurea/polyurethane block copolymer (A) of general formula (1), where R is a monovalent hydrocarbon radical having 1 to 20 carbon atoms which is optionally substituted by fluorine or chlorine, X is an alkylene radical having 1 to 20 carbon atoms, in which methylene units not adjacent to one another may have been replaced by -O- groups, A is an oxygen atom or an amino group -NR`-, Z is an oxygen atom or an amino group -NR`-, R` is hydrogen or an alkyl radical having 1 to 10 carbon atoms, Y is a divalent hydrocarbon radical having 1 to 20 carbon atoms which is optionally substituted by fluorine or chlorine, D is an alkylene radical having 1 to 700 carbon atoms which is optionally substituted by fluorine, chlorine, C1-C6 alkyl or C1-C6 alkyl ester and in which methylene units not adjacent to one another may have been replaced by -O-, -COO-, -OCO-, or -OCOO- groups, n is a number from 1 to 4000, a is a number which is at least 1, b is a number from 0 to 40, c is a number from 0 to 30 and d is a number greater than 0, and at least one thermoplastic material (B).

Description

Organopolysiloxane-containing fiber

The invention relates to an organopolysiloxane-containing fiber and a process for their preparation.

WO 99/28540 describes fibers of polydiorganosiloxane polyurea copolymers and fibers of blends of these copolymers with other polymers (added between 1% and 99% by weight) and nonwovens and adhesives composed of these fibers.

EP 0 332 719 A describes a polyfluorosilicone urea block copolymer spinnable into fibers.

WO 96/33029 claims a polydiorganosiloxane polyurea copolymer which is used in a melt spinning process i.a. is spinnable to fibers.

These described fibers containing a silicone moiety have no clear advantage over fiber without additive.

EP 1 431 429 claims a process for the preparation of polyurethane fibers with interspinning additives, namely polydimethylsiloxane, alkoxylated PDMS and metal salts of a saturated or unsaturated fatty acid. The aim of the invention is to enable constant textile yarn data and increased productivity over the entire spinning process.

Patent EP 0 643 159 describes the production of elastane fibers with a combination of PDMS and ethoxylated PDMS. In the examples, an improvement of the optical property of the warp knitted fabric obtained by staining method is proved.

Liquid Organopolysiloxanadditive, especially with higher and higher viscosities, however, have the disadvantage that they can be difficult and only with the use of special technical equipment during the extrusion process in thermoplastic melts can be introduced. Preferably are used in extrusion processes solid components and particularly preferably solid components in conventional plastic granules or pellets. The prior art discloses the following disadvantages. When melt spinning is a high energy input to

Melting and conveying necessary. Furthermore, the internal friction during extrusion can lead to polymer degradation and byproducts resulting in spinneret clogging and lower strengths. The products produced according to the prior art have inadequate properties, such as unsatisfactory softness and hydrophobicity; in particular, the processes described in the prior art are complicated, since the siloxanes are present only as liquids, which makes their processing more difficult.

The object of the invention is therefore to improve the state of the art, in particular to provide fibers and their production process, in particular a decrease in the pressure in the extruder and in the spinneret, reducing the torque during the extrusion, decrease in friction in the

Extrusion, melt viscosity lowering, temperature required for processing, improved throughput, lower energy consumption, reduced degradation of the polymer resulting in less spinneret deposition and less cleaning effort, increased fiber mechanics, improved fiber drawing through improved Crystallization of the polymer, reduced wear, easier processability, lower rejects and improvement of the properties of textile fabrics made from the fibers such as, optimizing the visual appearance of the surface (eg gloss), changing the surface grip, improved grip properties, increased softness, good water repellency, achieving hydrophobic, oleophobic or alcohol repellent Surface, dirt repellency and that the textiles are printable with standard colors can be achieved.

The object is achieved by the invention.

The invention relates to a fiber producible by a composition containing

Organopolysiloxane / polyurea / polyurethane block copolymer (A) of the general formula (1)

R

I

A-X-Si-O-SSii-X-A-C-N-Y-N-C-Z-D-Z-C-N-Y-N-C i I H H M M H H I l

R O O O O n

wherein a monovalent, optionally substituted by fluorine or chlorine hydrocarbon radical having 1 to 20

Carbon atoms, an alkylene radical having 1 to 20 carbon atoms, in the non-adjacent methylene units by groups

-O- can be replaced,

A is an oxygen atom or an amino group -NR ^λ -, Z is an oxygen atom or an amino group -NR ^λ -, R ^{λ is} hydrogen or an alkyl radical having 1 to 10

Carbon atoms, Y is a divalent, optionally substituted by fluorine or chlorine hydrocarbon radical having 1 to 20 carbon atoms,

D is an optionally substituted by fluorine, chlorine, C] _- Cg-alkyl or C _] _-Cg-alkyl ester substituted alkylene radical having 1 to 700

Carbon atoms in which non-adjacent methylene units can be replaced by groups -O-, -COO-, -OCO-, or -OCOO-, n is a number from 1 to 4000, a is a number of at least 1, b is a number of 0 to 40, c is a number from 0 to 30 and d is a number greater than 0.

and at least one thermoplastic (B).

The organopolysiloxane / polyurea / polyurethane block copolymer (A) can be prepared by a process comprising two steps wherein

in the first step, a cyclic silazane of the general formula

(2)

X ₁ N-X-Si-R H ₂ N Si "1 / \ RRR

with organosilicon compound of the general formula (3),

(HO) (R ₂ SiO) _n -! [H]

to aminoalkylpolydiorganosiloxane of the general formula (4)

H ₂ NX- [SiR ₂ O] _n SiR ₂ -X-NH ₂ is reacted, and in the second step, the Aminoalkylpolydiorganosiloxan the general formula (4) with diisocyanate of the general formula (5)

OCN-Y-NCO

is polymerized, wherein R is a monovalent, optionally substituted by fluorine or chlorine hydrocarbon radical having 1 to 20

X, an alkylene radical having 1 to 20 carbon atoms, in which non-adjacent methylene units may be replaced by groups -O-,

Carbon atoms, Y is a bivalent, optionally substituted by fluorine or chlorine hydrocarbon radical having 1 to 20

Carbon atoms, D is optionally substituted by fluorine, chlorine, C] _- Cg-alkyl or

C _] _-Cg-alkyl esters substituted alkylene radical having 1 to 700 carbon atoms, in which not adjacent to each other

Methylene units may be replaced by groups -O-, -COO-, -OCO-, or -OCOO-, n is a number from 1 to 4000, a is a number of at least 1, b is a number from 0 to 40, c is a number from 0 to 30 and d is a number greater than 0. The preparation of the aminoalkylpolydiorganosiloxane of the general formula (4) is inexpensive, proceeds under the gentlest conditions and leads to products which are colorless and odorless. Aminoalkylpolydiorganosiloxane of the general formula (4) contains neither cyclic silicone compounds, since they were already removed at the stage of silanol-terminated starting materials of the general formula (3), nor

Equilibration catalysts or their radicals, since the reaction of silanol groups with the heterocycle of the general formula (2) takes place uncatalyzed in a very short time. Therefore, these functionalized silicone oils and their derivatives are odorless and colorless.

Ideally, in the first step, the heterocycles of the general formula (2) and the reactants containing silanol groups are used in equimolar ratios, since the removal of excess heterocycle can thus be omitted. For this purpose, the content of active H in the silanol-terminated starting material is preferably used, for example. determined by titration so as to be able to add an at least equimolar amount of heterocycles. Bisaminoalkyl-terminated siloxanes of the general formula (4) are obtained in high purity, which are likewise suitable for the preparation of high molecular weight siloxane-urea block copolymers.

To achieve shorter reaction times in the preparation of highly pure bisaminoalkyl-terminated silicones of the general formula (4), a slight excess of the heterocyclic compound of the general formula (2) is preferably used, which can then be removed in a simple additional process step such as the addition of small amounts of water , Preferably, R is a monovalent, hydrocarbon radical having 1 to 6 carbon atoms, in particular unsubstituted. Particularly preferred radicals R are methyl, ethyl, vinyl and phenyl.

Preferably, X is an alkylene radical having 2 to 10 carbon atoms. Preferably, the alkylene radical X is not interrupted.

Preferably, A is an NH group.

Preferably Z is an oxygen atom or an NH group. Preferably, Y is a hydrocarbon radical having 3 to 13 carbon atoms, which is preferably unsubstituted. Preferably, Y is an aralkylene, linear or cyclic alkylene radical.

Preferably, D is an alkylene radical having at least 2, in particular at least 4 carbon atoms and at most 12 carbon atoms.

Also preferably, D is a polyoxyalkylene radical, in particular polyoxyethylene radical or polyoxypropylene radical having at least 20, in particular at least 100 carbon atoms and at most 800, in particular at most 200 carbon atoms.

Preferably, the radical D is not substituted.

n is preferably a number of at least 3, in particular at least 25 and preferably at most 800, in particular at most 400, particularly preferred at most 250.

Preferably, a is a number of at most 50. When b is not 0, b is preferably a number of at most 50, especially at most 25.

c is preferably a number of at most 10, in particular at most 5.

The polydiorganosiloxane-urea copolymer of the general formula (1) shows high molecular weights and good mechanical properties with good processing properties.

Above all, by the use of chain extenders such as dihydroxy compounds or water in addition to the urea groups, a significant improvement in the mechanical properties can be achieved. Thus, materials can be obtained which are in the mechanical

Properties with conventional silicone rubbers are quite comparable, but have increased transparency and in which no additional active filler must be incorporated.

If b is at least 1, in the second step up to 95 percent by weight, based on all components used, of chain extenders which are selected from diamines, isocyanate-blocked hydroxy compounds, dihydroxy compounds or mixtures thereof, can be used.

Preferably, the chain extenders have the general formula (6)

HZ-D-ZH,

wherein D and Z have the above meanings. If Z has the meaning O, the chain extender of the general formula (6) can also be reacted with diisocyanate of the general formula (5) before the reaction in the second step become. Optionally, water can also be used as a chain extender.

Preferably, in the copolymer of the general formula (1), based on the sum of the urethane and urea groups, at least 50 mol%, in particular at least 75 mol% of urea groups.

Examples of the diisocyanates of the general formula (5) to be used are aliphatic compounds such as

Isophorone diisocyanate, hexamethylene-1, 6-diisocyanate, tetramethylene-1, 4-diisocyanate, and methylenedicyclohexyl-4, 4 ^λ - diisocyanate, or aromatic compounds such as methylenediphenyl 4, 4 ^λ diisocyanate, 2, 4-toluene diisocyanate, 2, 5-toluenediisocyanate , 2, 6-toluene diisocyanate, m-phenylene diisocyanate, p-

Phenyl diisocyanate, m-xylene diisocyanate, tetramethyl-m xyloldiisocyanat or mixtures of these isocyanates. An example of commercially available compounds are the diisocyanates of the DESMODUR® series (H, I, M, T, W) of Bayer AG, Germany. Preferred are aliphatic diisocyanates in which Y is an alkylene radical, as these lead to materials exhibiting improved UV stabilities, which is advantageous in outdoor application of the polymers. The CC, CO-OH-terminated alkylenes of the general formula (6) are preferably polyalkylenes or polyoxyalkylenes. These are preferably substantially free of contaminants from mono-, tri- or higher-functional polyoxyalkylenes. Polyether polyols, polytetramethylene diols, polyester polyols, polycaprolactone diols but also CC, CO-OH-terminated polyalkylenes based on polyvinyl acetate,

Polyvinylacetatethylencopolymere, polyvinyl chloride copolymer, polyisobutlydiols are used. Preference is given here polyoxyalkyls are used, more preferably polypropylene glycols. Such compounds are as Base materials, inter alia, for flexible polyurethane foams and for coating applications commercially available with molecular masses Mn up to more than 10,000. Examples of these are the BAYCOLL® polyether polyols and polyester polyols from Bayer AG, Germany or the Acclaim® polyether polyols from Lyondell Inc., USA. It is also possible to use monomeric CC, CO-alkylene diols, such as ethylene glycol, propanediol, butanediol or hexanediol. Furthermore, dihydroxy compounds in the context of the invention are also to be understood as meaning bishydroxyalkyl silicones, as sold, for example, by Goldschmidt under the name Tegomer H-Si 2111, 2311 and 2711.

The preparation of the above-described copolymers of the general formula (1) can be carried out both in solution and in solid substance, continuously or discontinuously. It is essential that for the selected polymer mixture under the reaction conditions an optimal and homogeneous mixing of the components takes place and phase incompatibility is optionally prevented by solubilizers. The production depends on the used

Solvent off. If the proportion of hard segments such as urethane or urea units is large, it may be necessary to choose a solvent having a high solubility parameter such as dimethylacetamide. For most syntheses, THF has proven to be sufficiently well suited. Preferably, all ingredients are dissolved in an inert solvent. Particularly preferred is a synthesis without solvent.

For the reaction without solvent, the homogenization of the mixture is of crucial importance in the reaction. Furthermore, the polymerization can also be controlled by the choice of the reaction sequence in a step synthesis. For better reproducibility, it should generally be produced with the exclusion of moisture and under protective gas, usually nitrogen or argon.

The reaction preferably takes place, as usual in the preparation of polyurethanes, by adding a catalyst. Suitable catalysts for the preparation are dialkyltin compounds, such as, for example, dibutyltin dilaurate, dibutyltin diacetate, or tertiary amines, such as, for example, N, N-

Dimethylcyclohexanamine, 2-dimethylaminoethanol, 4-dimethylaminopyridine.

Another object of the invention is a process for producing fibers, characterized in that

Organopolysiloxane / polyurea / polyurethane block copolymer (A) of the general formula (1) is extruded with a thermoplastic material.

The thermoplastic material is preferably polyvinyl alcohol, copolymers of vinyl acetate, polyolefins such as polypropylene and polyethylene, polyesters such as polyethylene terephthalate and polytrimethyl terephthalate, polyacrylonitrile, polyurethane, polyamide, polylactate, acetate, triacetate

Polyester, polyamide and polyolefin, particularly preferred are polyamide and polyolefin.

The organopolysiloxane / polyurea / polyurethane block copolymer (A) is used in amounts of preferably 0.001 to 50 wt .-%, particularly preferably from 0.01 to 15 wt .-%, particularly preferably 0.01 to 10 wt .-% based on the Total weight of the organopolysiloxane / polyurea composition / Polyurethane block copolymer (A) and the thermoplastic used.

The addition of components (A) and (B) is carried out at elevated temperature by conventional methods for the distribution of solid additive components in thermoplastics. Examples of suitable equipment for subsequent incorporation are single-screw and twin-screw extruders. Temperature and other conditions for incorporation are dependent on the particular fiber raw material and known to the skilled person or to be determined by routine experiments.

The additives can be added directly in the extruder to the thermoplastic granulate in front of the spinneret head. But this can also be done as a prefabricated masterbatch. In this case, the additives are added to the thermoplastic granules in an independent extruder. The compound thus obtained can still be added in a dry mixer to the thermoplastic granules to achieve the desired amount of addition. This mixture or the compound itself is then added in the extruder in front of the spinneret head to make fibers.

In a preferred embodiment, the process for producing fibers is carried out such that

Organopolysiloxane / polyurea / polyurethane block copolymer (A) and the thermoplastic material (B) are processed into a granulate, which is a compound and in a second step, the compound with the thermoplastic material (B) to the desired ratio of (A) (B) can be adjusted and the compound with the appropriate amount of thermoplastic material (B) is extruded.

By the granulation of the organopolysiloxane / polyurea / polyurethane block copolymer (A) and the thermoplastic Plastics (B), a compound is prepared which contains the organopolysiloxane / polyurea / polyurethane block copolymer (A) generally in a more concentrated form, so that they easily and without much effort to the desired ratio organopolysiloxane / polyurea / polyurethane block copolymer for various purposes (A) can be adjusted to thermoplastic material (B) by appropriate addition of a certain amount of thermoplastic material (B), which is possible with only a correspondingly highly concentrated compound. Of course, such a compound can also be prepared with the desired amount ratio of components (A) and (B), and then processed further.

The advantage of making the compound is its better processability and better quality products. The targeted use of mixing units in compounding a very uniform and finely divided distribution (dispersion) of the additive (A) in the polymer (B) is achieved and significantly increased the efficiency of (A) in the spinning process. Further, a possible thread breakage, spinning disturbances and unequal fiber diameter are prevented.

In the process of the present invention, extrusion may occur at a die pressure reduced by up to 75% over a process which does not include an organopolysiloxane / polyurea / polyurethane block copolymer (A), with pressure reduction starting at 0.5%.

From the fibers according to the invention, it is possible to produce fabrics such as woven fabrics, knitted fabrics, scrims, knitted fabrics, nonwovens, felts, etc.

With the compounds according to the invention, all fibers can be used as filaments and staple fibers in the form of fibers, threads, yarns, Nonwovens, mats, strands, woven, knitted or knitted fabrics and tufted fabric packages are produced.

The fabrics made from the fibers of the invention may be used for technical applications such as e.g. Conveyor belts, compensators, protective clothing, awnings, carpets, tablecloths, curtains, baby diapers, seats insulation area or airbags are used.

But also for use in the high-performance textile sector, such as paragliders, hot air balloons, parachutes, outdoor clothing, sports textiles, casual wear, leisure items such as tents or backpacks, sails and streetwear the fibers of the invention can come.

The invention has the following advantages, such as internal lubricity, a decrease in the pressure in the extruder and in the spinneret, a reduction of the torque in the extrusion, a decrease in the friction in the extrusion, a lowering of the melt viscosity, a lowering of the temperature required for processing , improved throughput, lower energy consumption, the reduced degradation of the polymer resulting in less deposit on the spinnerets and less cleaning effort, increased fiber mechanics, improved fiber orientation through improved crystallization of the polymer, reduced wear, lighter weight Processability and lower rejection. Furthermore, the fibers and textiles according to the invention have the following advantages, such as optimizing the visual impression of the surface (eg gloss), changing the surface grip, improved grip properties, increased softness, good water repellency, achievement of hydrophobic, oleophobic, alcohol or dirt repellent Surface, with the effects achieved permanently in the wash and in dry cleaning, the textiles are printable with standard colors, the surface smoothness is increased and leads to a reduction of the fiber-fiber friction and the fiber-metal friction during processing, whereby all other process steps are simplified, such as

Sewability is improved, the yarns are more easily unwound from the bobbin, etc. At the surface of the fiber is always an accumulation of silicone components, even if the original surface is chafed, since the silicone units in the fiber on the surface increased tensile and tear strength of the fiber and fabric, increased impact strength, increased modulus of the fiber, reduced splicing of the ends of the fiber, improved flexibility and fiber recoil force

In the following examples, unless stated otherwise, all amounts and percentages are by weight and all pressures are 0.10 MPa (abs.). All viscosities were determined at 20 ⁰ C. The molecular weights by GPC were dissolved in toluene (0.5 ml / min) at 23 ⁰ C (column: PLgel Mixed C + PLgel 100 A, detector: RI ERC7515)

example 1

1500 g of bishydroxy-terminated polydimethylsiloxane (mol. Subsequently, 116 g of 1- (3-aminopropyl-l, 1-dimethylsilyl) -2, 2-dimethyl-1-aza-2-sila-cyclopentane was added dropwise at room temperature and then allowed to stand for 1 hour. This gave a crystal-clear bisaminopropyl-terminated polydimethylsiloxane with a

Molecular weight of 3200 g / mol, which according to 29Si NMR was free of Si-OH groups and had no inherent odor. Example 2

In a 2000 ml flask equipped with dropping funnel and reflux condenser, 1080 g bishydroxy-terminated polydimethylsiloxane (molecular weight 10800 g / mol) were charged. Then, at a temperature of 60 ⁰ C 23.2 g of 1- (3-aminopropyl-l, 1-dimethylsilyl) -2, 2-dimethyl-l-aza-2-sila-cyclopentane was added dropwise and then at 60 ⁰ 5 hours C stirred. Upon cooling, a clear bisaminopropyl-terminated polydimethylsiloxane having a molecular weight of 11,000 g / mol was obtained, which, according to 29Si NMR, was free of Si-OH groups and had no inherent odor.

Example 3

In a 250 ml flask equipped with dropping funnel and reflux condenser, 40 g of bisaminopropyl-PDMS (molecular weight 3200) were initially charged in a solvent mixture of 80 ml of dry THF and 20 ml of dimethylacetamide. Subsequently, a solution of 2.33 g of methylenedi-p-phenyldiisocyant in 20 ml of dry THF was added dropwise at room temperature and then refluxed for 1 hour. After cooling the solution, the polymer was precipitated by dropwise addition to hexane. A clear copolymer was obtained with a molecular weight Mw of 161000 g / mol, which showed a softening in the TMA at 154 ⁰ C and exhibited no odor.

Examples 4-9:

Analogously to Example 3, a bisaminopropyl PDMS having a molecular weight of 3200 g / mol or 11000 g / mol was reacted with other diisocyanates.

Example 13:

In a twin-screw kneader from Collin, Ebersberg with 4 heating zones, the diisocyanate was metered in a nitrogen atmosphere in the first heating zone and the aminopropyl-terminated silicone oil in the second heating zone. The temperature profile of the heating zones was programmed as follows: Zone 1 30 ⁰ C, Zone 2 100 ⁰ C, Zone 3 150 ° C, Zone 4 140 ⁰ C. The speed was 50 rpm. The diisocyanate (methylene bis (4-isocyanatocyclohexane)) was metered into zone 1 at 304 mg / min and the amine oil (3200 g / mol) was metered into zone 2 at 3.5 g / min. At the nozzle of the extruder, a clear polydimethylsiloxane-polyurea block copolymer having a molecular weight of 110,000 g / mol and a softening temperature of 126 ° C, which had no odor, could be removed. Example 14:

Analogously to Example 13 were in a twin-screw mixer from Collin, Ebersberg (Teach -Line) with 4 heating zones under nitrogen atmosphere at the following temperature profile (zone 1 30 ⁰ C, zone 2 90 ⁰ C, zone 3 120 ° C, zone 4 130 ⁰ C. , Speed = 50 rpm), the diisocyanate (isophorone diisocyanate) in zone 1 was metered at 179 mg / min and the amine oil (3200 g / mol) in zone 2 at 3.5 g / min. At the nozzle of the extruder, a clear, odorless polydimethylsiloxane polyurea block copolymer with a softening temperature of 58 ⁰ C was removed. It had a molecular weight of 52,000 g / mol.

Example 15

Analogously to Example 13 were in a twin-screw mixer from Collin, Ebersberg (Teach-Line) with 4 heating zones under nitrogen atmosphere at the following temperature profile (zone 1 30 ° C, zone 2 100 ° C, zone 3 170 ⁰ C, zone 4 180 ° C. , Speed = 50 rpm), the diisocyanate (toluene 2,4-diisocyanate) in zone 1 was metered at 111 mg / min and the amine oil (11,000 g / mol) in zone 2 at 5.2 g / min. At the nozzle of the extruder could a

Polydimethylsiloxane polyurea block copolymer having a softening temperature of 87 ⁰ C are removed. It had a molecular weight of 195,000 g / mol.

Example 16

In a 250 ml flask with dropping funnel and reflux condenser, 32 g of bisaminopropyl-PDMS (molecular weight 3200) and 5 g of bishydroxypropyl-PDMS (Tegomer 2711, Th. Goldschmidt AG, molecular weight 5200) in a solvent mixture of 80 ml of dry THF and 20 ml Submitted dimethylacetamide. After adding 3 drops of dibutyltin dilaurate, a solution of 2.5 g of isophorone diisocyanate in 20 ml of dry THF was added dropwise at room temperature and then refluxed for 2 hours. After this Cooling the solution, the polymer was precipitated by dropwise addition to hexane.

This gave a copolymer having a molecular weight of M w 78000 g / mol, which has a softening point at 42 ⁰ C.

Example 17

In a 250 ml flask equipped with dropping funnel and reflux condenser, 32 g of bisaminopropyl-PDMS (molecular weight 3200) and 0.9 g of butanediol were initially charged in a solvent mixture of 80 ml of dry THF and 20 ml of dimethylacetamide. After adding 3 drops of dibutyltin dilaurate, a solution of 4.5 g of isophorone diisocyanate in 20 ml of dry THF was added dropwise at room temperature and then refluxed for 2 hours. After cooling the solution, the polymer was precipitated by dropwise addition to hexane. A copolymer having a molecular weight of 63,000 g / mol was obtained.

Example 18

In a 250 ml flask equipped with dropping funnel and reflux condenser, 32 g of bisaminopropyl-PDMS (molecular weight 3200) and 1.2 g of hexamethylenediamine were initially charged in a solvent mixture of 80 ml of dry THF and 20 ml of dimethylacetamide. After adding a solution of 4.5 g of isophorone diisocyanate in 20 ml of dry THF was refluxed for 2 hours. After cooling the solution, the polymer was precipitated by dropwise addition to hexane.

This gave a copolymer having a molecular weight of Mw 73000 g / mol. Application example 1

Production of a Compound of Polypropylene (PP) and Organopolysiloxane / Polyurea / Polyurethane Block Copolymer (A) and subsequent Fiber-spinning

The following raw materials are used:

Polypropylene: Moplen HP561S (Basell). Melt Flow Rate (MFR) (230 ° C / 2.16Kg) ISO 1133 33 g / 10 min Organopolysiloxane: Example 7 having a melt viscosity of 50-100 Pa. s at 150 ⁰ C.

To prepare the compound, the polypropylene granules and the organopolysiloxane / polyurea / polyurethane block copolymer (A) granules are first described below

Mixed proportions: 90% by weight of polypropylene, 10% by weight of organopolysiloxane / polyurea / polyurethane block copolymer (A). Subsequently, this granulate mixture is extruded on a twin-screw extruder ZE-25 (Berstorff). The process parameters are described below:

- Throughput: 10 kg / h

- Screw speed: 300 revolutions per minute

- Temperature profile: 150 ⁰ C to 160 ° C

To carry out the spinning experiments, mixtures having an additive content of in each case 0.1% by weight, 1% by weight and 10% by weight are prepared from the commercial polypropylene and the respective masterbatch granules. A control fiber of polypropylene without additive is also spun. To spin out the granules mixtures

- A Haake extruder with 19 mm screw diameter (25D, conical, 2: 1) with 2 heating zones at 240 ⁰ C.

- a pump with 0.6 cm / turn - a 13 hole spinneret with a hole diameter of 300 microns - Used a BARMAG winder for a winding at 2000 m / min.

Due to the set speed and the delivery volume of the melt spinning pump on Haake extruder under the winding conditions mentioned a Gesamtfilamentgarntiter of about 110-115 dtex spun.

An antistatic, hydrophilic preparation, Limanol LB 25 (Schill & Seilacher), is applied to the fiber prior to rewinding in small quantities.

The two-stage stretching of the filament to about 25% residual elongation after their production on a pilot plant Streckspul (Fa. ZINSER) via two heating rails (100 ⁰ C) and three godets (80 ⁰ C) is performed. This requires stretch ratios of about 1: 2.6-2.8.

The fibers are characterized on a text techno Statimat M. Twenty-five single tear tests are carried out and an average calculation is determined.

In the final processing step, the production of tubular knitwear takes place on a circular knitting machine from LUKAS. The drawn threads are first stitched three times to make them (total titer approx. 125dtex). With these threads, the production of a circular knit takes place on the above-mentioned single-system circular knitting machine with ZyI. -2! 5 ³ / i6 '' and 18s division.

Fiber and textile properties

hydrophobia

On an absorbent paper, the knits with 0 wt.%, 0.1 wt.%, 1 wt.% And 10 wt.% Additive are placed. distilled Water is dripped onto the knit with a pipette. At 0% by weight, 0.1% by weight, 1% by weight of additive, the drops quickly sink into the tissue, since the hydrophilic preparation Limanol LB 25 is located on the surface of the fibers. With an additive addition of 10% by weight, the water remains in a round drop form on the knitted fabric despite hydrophilic preparation. The wetting of the fabric with 10% by weight of additive is determined, in that the contact angle assumed by the water on the fabric is measured over 10 minutes. The larger this angle, the more hydrophobic is the knitted fabric. As a control, the contact angle is also measured on the surface of the pure polypropylene knit. The measurements are repeated four times and an average value is determined. The results of these measurements are summarized in the following table.

Even after 10 minutes, the contact angle of the water droplet on the surface of the fabric with 10 wt.% Additive 30% greater than the contact angle of the water droplet on the surface of the fabric without additive after immediate measurement.

Handle

A part of the knits are washed 5 times in a conventional washing machine with mild detergent at 40 ⁰ C (color code setting).

The washed and unwashed fabrics are conditioned in a climate-controlled room at 23 ° C and 50% humidity for 24 hours and judged manually by 3 people by the handle (dryness, softness, slipperiness). For this purpose, the samples were strung together after the handle judgment and set a grading scale of 1-5 with 5 as the softest, most slippery handle and 1 as a dry, hard grip. The results are summarized in the following table.

The more additive is in the fibers, the softer the knits become. This property remains even after 5 washes. Tear resistance and modulus

The following table summarizes the mechanical properties of the fiber.

The tensile strength and modulus values are 0.1% by weight and 1% by weight additive addition significantly above the values of the untreated polypropylene. The additive can cause a clear improvement in the mechanical properties of the fiber.

The incorporated organopolysiloxane compounds assist in the stretching process; The polymer chains can slide together more easily and can crystallize faster and better and orient themselves. Even with a 10% by weight addition, the values of the untreated polypropylene are achieved. The presence of this additive, even in relatively high amounts, does not adversely affect fiber properties.

Process properties

The addition of the organopolysiloxane-containing additive has a great influence on the spinning of polypropylene. The additive improves the extrusion of the polypropylene by significantly reducing extruder and spinner nozzle pressures and screw torque; the more additive, the more pressure and torque are reduced. The polypropylene can be faster and with less

Energy consumption melted and pumped through the spinneret holes. The thread formation at the nozzle and the removal of the fiber remain undisturbed.

The melt flow becomes better, therefore the fibers can be spun at a lower temperature (240 ^° C. instead of 260 ^° C.) with a similar speed. The polypropylene degradation (continued fracture and oxidation) is also reduced.

Application Example 2

Preparation of a Compound of Polyamide 6 (PA 6) and Organopolysiloxane / Polyurea / Polyurethane Block Copolymer (A) and subsequent Spinning to Fibers

The following raw materials are used:

Polyamide 6: Ultramid B 2715 (BASF). Viscosity number (VN)

(0.5% (w / v) in 96% (w / w) sulfuric acid) ISO 307

146-151 ml / g.

Organopolysiloxane: Example 7 having a melt viscosity of

50-100 Pa. s at 150 ° C. To prepare the compound, the polyamide 6 granules and the organopolysiloxane / polyurea / polyurethane block copolymer (A) granules are first mixed in the following proportions: 90% by weight polyamide 6, 10% by weight organopolysiloxane / polyurea / polyurethane block copolymer (A ). Subsequently, this granulate mixture is extruded on a twin-screw extruder ZE-25 (Berstorff). The process parameters are described below:

- Throughput: 10 kg / h

- Screw speed: 400 revolutions per minute

- Temperature profile: 250 ⁰ C to 255 ° C

To carry out the spinning experiments, mixtures having an additive content of in each case 0.1% by weight, 1% by weight, 5% by weight and 10% by weight are prepared from the commercial polyamide 6 and the respective masterbatch granules. A control fiber of polyamide 6 without additive is also spun.

To spin out the granulate mixtures are: a 30 mm extruder with 3 zone screw (25D)

- a pump with 2.4 cm ³ / turn

- A 13-hole spinneret with a hole diameter of 300 microns

- Used a BARMAG winder for a winding at 4000 m / min. Due to the set speed and the delivery volume of the melt spinning pump at the extruder a Gesamtfilamentgarntiter of about 100fl3 dtex is spun under said winding conditions.

The two-stage drawing of the filament yarns to about 25% residual elongation is carried out after their preparation on a pilot stretch-train installation (ZINSER). The fibers are characterized on a text techno Statimat M. Twenty-five single tear tests are carried out and an average calculation is determined.

In the last processing step, the production of

Hose knit on a circular knitting machine from LUKAS. The drawn threads are first stitched twice to make them (total titer about 130-160 dtex). With these threads, the production of a circular knit takes place on the above-mentioned single-system circular knitting machine with ZyI. -2! 5 ³ / i6 '' and 18s division.

Fiber and textile properties

Handle

A part of the knits are washed 5 times in a conventional washing machine with mild detergent at 40 ⁰ C (color code setting). The washed and unwashed fabrics are conditioned in a climate-controlled room at 23 ° C and 50% humidity for 24 hours and judged manually by 3 people by the handle (dryness, softness, slipperiness). For this purpose, the samples were strung together after the handle judgment and set a grading scale of 1-5 with 5 as the softest, most slippery handle and 1 as a dry, hard grip. The results are summarized in the following table.

The more additive is in the fibers, the softer the knits become. This property remains even after 5 washes.

Tear resistance and modulus

The following table summarizes the mechanical properties of the fiber.

The tensile strength and modulus values are significantly higher than those of the untreated polyamide 6 at 5% by weight and 10% by weight additive addition. The additive can bring about a clear improvement in the mechanical properties of the fiber. The incorporated organopolysiloxane compounds assist in the stretching process; The polymer chains can slide together more easily and can crystallize faster and better and orient themselves.

Process properties

The addition of the organopolysiloxane-containing additive has a great influence on the spinning of polyamide 6. The additive improves the extrusion of the polyamide 6 by significantly reducing the extruder and spinneret pressures and the torque of the screws; the more additive, the more pressure and torque are reduced.

The polyamide 6 can be melted faster and with less energy consumption and pumped through the spinneret holes. The thread formation at the nozzle and the removal of the fiber remain undisturbed.

The melt flow becomes better, therefore the fibers can be spun at a lower temperature (250 ^° C. instead of 270 ^° C.) with similar speed. The polypropylene degradation (continued fracture and oxidation) is also reduced.

Claims

claims

1. Fiber producible by a composition comprising organopolysiloxane / polyurea / polyurethane block copolymer (A) of the general formula (1)

R

I

A-X-Si-O-SSii-X-A-C-N-Y-N-C-Z-D-Z-C-N-Y-N-C i I H H M M H H I l

R O O O O n

-0- can be replaced,

Carbon atoms, a bivalent, optionally substituted by fluorine or chlorine hydrocarbon radical having 1 to 20

Carbon atoms, D is an optionally substituted by fluorine, chlorine, C] _- Cg-alkyl or C _] _-Cg-alkyl ester substituted alkylene radical having 1 to 700

and at least one thermoplastic (B).

2. Fiber according to claim 1, characterized in that the organopolysiloxane / polyurea / polyurethane block copolymer (A) in an amount of 0.001 to 50 wt.% Based on the total weight of the composition

Organopolysiloxane / polyurea / polyurethane block copolymer (A) and thermoplastic material is included.

3. A fiber according to claim 1 or 2, characterized in that the thermoplastic material is selected from the group consisting of polyvinyl alcohol, copolymers of vinyl acetate, polyolefins, polyesters, polyacrylonitrile, polyurethane, polyamide, polylactate, acetate, triacetate.

4. A process for producing fibers, characterized in that organopolysiloxane / polyurea / polyurethane block copolymer (A) of the general formula (1) - Y - N -

H I l

If

-0- can be replaced,

Carbon atoms, optionally by fluorine, chlorine, C] _g-alkyl or

C _] _-Cg-alkyl ester substituted alkylene radical having 1 to 700

Carbon atoms in which non-adjacent methylene units may be replaced by groups -O-, -COO-, -OCO-, or -OCOO-, n is a number from 1 to 4000, a is a number of at least 1, b is a number from 0 to 40, c is a number from 0 to 30 and d is a number greater than 0

is extruded with a thermoplastic material.

5. A process for producing fibers according to claim 4, characterized in that the organopolysiloxane / polyurea / polyurethane block copolymer (A) in an amount of 0.001 to 50 wt.% Based on the total weight of the composition

Organopolysiloxane / polyurea / polyurethane block copolymer (A) and thermoplastic material is extruded.

6. A process for producing fibers according to claim 4 or 5, characterized in that in a first step, a compound is prepared, wherein organopolysiloxane / polyurea / polyurethane block copolymer (A) and the thermoplastic material (B) are processed into granules, the is a compound and in a second step, the compound with the thermoplastic material (B) to the desired ratio of (A) to (B) can be adjusted and the compound with the appropriate amount of thermoplastic material (B) is extruded.

7. A process for the production of fibers according to claim 4 to 6, characterized in that the thermoplastic material is selected from the group consisting of polyvinyl alcohol, copolymers of vinyl acetate, polyolefins, polyester,

Polyacrylonitrile, polyurethane, polyamide, polylactate, acetate, triacetate exists.

8. The method according to claim 4 to 7, characterized in that the extruding reduced by up to 75% Nozzle pressure compared to a process in which no organopolysiloxane / polyurea / polyurethane block copolymer (A) is included takes place.

9. Textile fabric, characterized in that it comprises fibers according to one or more of claims 1 to 3 or produced according to one or more of claims 4 to 8.