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WO2010079030A2 - Utilisation de copolymères à blocs amphiphiles comme plastifiants pour matières textiles composées de fibres de polypropylène - Google Patents

Utilisation de copolymères à blocs amphiphiles comme plastifiants pour matières textiles composées de fibres de polypropylène Download PDF

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Publication number
WO2010079030A2
WO2010079030A2 PCT/EP2009/066524 EP2009066524W WO2010079030A2 WO 2010079030 A2 WO2010079030 A2 WO 2010079030A2 EP 2009066524 W EP2009066524 W EP 2009066524W WO 2010079030 A2 WO2010079030 A2 WO 2010079030A2
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Prior art keywords
polypropylene
units
use according
polyester
mol
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German (de)
English (en)
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WO2010079030A3 (fr
Inventor
Pia Baum
Klaus Scheuermann
Claudia Sierakowski
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BASF SE
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BASF SE
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
    • D01F6/06—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins from polypropylene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers

Definitions

  • amphiphilic block copolymers as plasticizers for polypropylene fibers comprising textile materials
  • the present invention relates to the use of amphiphilic block copolymers comprising a nonpolar block comprising hydrocarbon units and a polar block comprising oxygen and / or nitrogen atoms as plasticizers for textile materials of polypropylene fibers. It relates in particular to the improvement of the grip of textile materials.
  • Polypropylene is very well suited as a fiber material for textile materials, such as, for example, woven fabrics, knitted fabrics, knits or nonwovens, because of the low density, the low price and the hydrophobicity.
  • WO 2006/128796 discloses a process for coloring polyolefins, in particular textile materials, from polypropylene by means of aqueous dyebaths.
  • the polyolefin is previously veneered with an amphiphilic block copolymer.
  • WO 2006/218795 discloses the use of said block copolymers for the preparation of blends of two different polymers.
  • WO 2006/128507 discloses nonwovens comprising fibers of polypropylene, a polymer immiscible therewith, and said block copolymers as compatibilizers.
  • WO 2008/65185 discloses a process for producing colored textile materials containing polypropylene fibers, wherein the polypropylene fibers are referred to
  • WO 2008/65178 discloses a process for printing polypropylene films, in which the films are additized to facilitate the printability with the abovementioned block copolymer and a thermoplastically processable polymer.
  • WO 2008/65133 discloses a process for producing colored textile materials containing polypropylene fibers, wherein the polypropylene fibers are additized to improve the dyeability with a thermoplastically processable polymer and a block copolymer.
  • the block copolymers may be block copolymers of at least one nonpolar block and at least one polar block or blocks comprising at least one block comprising hydrocarbons and at least one block comprising vinylaromatic units.
  • the object of the invention was to provide suitable additives which lead to softer textile materials made of polypropylene fibers.
  • these should be those additives which improve the feel of textile materials.
  • additives as plasticizers for textile materials wherein the textile materials contain polypropylene or polypropylene blend fibers and the polypropylene has a melt flow index MFR (230 ° C., 2.16 kg) of 0.1 to 60 g / 10 min, wherein the polypropylene with the additives in the melt intensively mixed together, followed by spinning and processing of the resulting fibers into textile materials, wherein the additives to at least one amphiphilic block copolymer (A) comprising at least
  • Hydrocarbon units consists, and
  • Nitrogen atoms to the total number of oxygen and nitrogen and carbon atoms (no + nn) / (nc + no + nn) is 0.1 to 0.5,
  • the amount of the polypropylene is 70 to 99.5% by weight and the amount of the additives is 0.5 to 12% by weight, each in terms of the sum of all
  • Components of the fibers is.
  • the amphiphilic block copolymer is used in combination with a polyester (B), preferably a polyester having a melting point of 50 to 240 ° C.
  • textile materials or “textile fabrics” are intended to encompass all flat textile materials which can be produced starting from textile fibers. These may be semi-finished products, intermediates or end products.
  • textile materials include woven, knitted, knitted, nonwoven or nonwoven fabrics.
  • textile finished goods such as clothing of all kinds, home textiles, such as carpets, curtains, blankets or furniture fabrics or technical textiles for industrial or commercial use or household applications, such as rags or wipes for cleaning or clothing for
  • the textile materials can be modified exclusively from the inventively modified
  • Polypropylene compositions be prepared. But you can of course also in combination with other materials, such as polyester or polyamide Materials or natural fibers are used. A combination can be made at different stages of production. For example, it is already possible to produce filaments of a plurality of polymers with a defined geometric arrangement at the melt-spinning stage. In the manufacture of yarn, fibers of other polymers may be incorporated, or fiber blends may be made of staple fibers. Furthermore, various yarns can be processed together, and finally, fabrics, knits or the like comprising the polypropylene compositions of the present invention can be joined together with chemically dissimilar fabrics.
  • textile materials include clothing or textiles for the production of clothing and home textiles of all kinds, especially textiles for sports and leisure wear, carpets or nonwovens, such as diaper nonwovens.
  • the softening effect of an additive can be recognized by means of various physical properties of the additized polypropylene compared to non-additized polypropylene, such as the modulus of elasticity, the breaking stress or the notched impact strength.
  • the term “handle” refers to the behavior of a textile material when it is grasped by hand or, more generally, when it comes into contact with the skin
  • a textile material has a "good feel” when it is soft and comfortable It is clear to a person skilled in the art that the feel of a textile on the skin also depends on the way in which the fibers are made into a textile material, so it is important to compare two “textile fabrics” Compare materials that are made in an absolutely identical manner, and differ only in that one textile is additiviert according to the invention and the other not.
  • the textile materials include polypropylene fibers which additionally comprise softening additives.
  • the plasticizing additives are amphiphilic block copolymers (A), which can optionally be used in combination with a polyester (B).
  • the polypropylene used may be polypropylene homopolymers. But it may also be polypropylene copolymers, which in addition to the Propylene small amounts of other comonomers include. Suitable comonomers may in particular be other olefins such as ethylene and 1-butene, 2-butene, isobutene, 1-pentene, 1-hexene, 1-heptene, 1-octene, styrene or ⁇ -methylstyrene, dienes and / or Polyenes act. The proportion of comonomers in the polypropylene is generally not more than 20% by weight, preferably not more than 10% by weight. The type and amount of the comonomers are chosen by the skilled person depending on the desired properties of the fiber. Of course, a mixture of several different types of polypropylene can be used.
  • relatively high molecular weight, viscous polypropylene grades are used which are characterized in the usual way by their melt flow index (determined to ISO 1133).
  • At least one polypropylene having a melt flow index MFR (230 ° C., 2.16 kg) used according to the invention is from 0.1 to 60 g / 10 min.
  • Such types of polypropylene are particularly suitable for the production of fibers.
  • polypropylene is also intended to include blends of polypropylene and other polymers
  • polymer alloy is understood in the usual sense to be a solid, homogeneous mixture of two or more different polymers Further details on the meaning of the term “Polymer blend” are, for example, “Ullmann's Encyclopedia of Industrial Chemistry”, VCH-Wiley-Verlag, Weinheim 2005 (A1).
  • polypropylene blends comprise at least 70% by weight of at least one polypropylene of the type mentioned as well as at least one different polymer or copolymer.
  • the other polymers may be, for example, other polyolefins such as polyethylene, polyisobutene or polystyrene, but polyamides or polycarbonates.
  • Preferably used polypropylene blends comprise at least 80% by weight of polypropylene, more preferably at least 90% of polypropylene, and most preferably only polypropylene is used, based in each case on polypropylene and optionally further polymers together.
  • the additives used (A) and optionally (B) are not counted among the constituents of a polypropylene blend listed here.
  • Further polymers of a blend are preferably polyolefins, particularly preferably polyethylene, polyisobutene or polystyrene, and very particularly preferably polyethylene.
  • Amphiphilic block copolymer (A) According to the invention, at least one amphiphilic block copolymer (A) is used as the plasticizer additive. Of course, mixtures of different amphiphilic block copolymers (A) can be used.
  • the amphiphilic block copolymer (A) used comprises at least one nonpolar block (Aa) having a number-average molar mass M n of at least 200 g / mol, which consists essentially of hydrocarbon units and at least one polar block (Ab) having a number-average molar mass M n of at least 1000 g / mol.
  • the blocks (Aa) and (Ab) are interconnected by means of suitable linking groups.
  • the non-polar blocks (Aa) have a number-average molar mass M n of 500 to 10,000 g / mol, preferably 500 to 8,000 g / mol, more preferably 750 to 6000 g / mol and most preferably 750 to 2000 g / mol on.
  • the polar blocks (Ab) each have a number-average molar mass M n of 1000 to 20,000 g / mol.
  • M n is preferably from 1500 to 18000 g / mol, particularly preferably from 2000 to 15000 g / mol and very particularly preferably from 3000 to 8000 g / mol.
  • non-polar blocks (Aa) consist essentially of hydrocarbon units. Particularly noteworthy here are blocks which are unsaturated as monomers
  • Hydrocarbons such as ethylene, propylene, 1-butene, 2-butene, isobutene, higher olefins, styrene or ⁇ -methylstyrene include. Furthermore, they may also be dienes such as butadiene or isoprene. They may each be homopolymeric blocks or copolymeric blocks. In a preferred embodiment of the invention are blocks of ethylene, propylene or isobutene units.
  • the non-polar blocks (Aa) may also be modified polyhydrocarbons, as long as this does not change the non-polar character of the blocks.
  • examples include polyolefins which contain small amounts of not more than 5% by weight of acidic monomers or maleated polypropylene or polybutadiene.
  • the non-polar blocks may also comprise silane or siloxane units.
  • Blocks of polar monomers preferred for carrying out the present invention comprise, in addition to the C and H atoms, at least O and / or N atoms to a sufficient extent to impart polar properties to the block (Ab).
  • the numerical ratio of oxygen and nitrogen atoms to the total number of oxygen and nitrogen and carbon atoms ( ⁇ O + ⁇ N) / (nc + no + nn) is 0.1 to 0.5, preferably 0.2 to 0.45 and more preferably 0.3 to 0.4.
  • Examples include -SO3H, -PO3H2 or -OP (OH) 3 groups.
  • the polar blocks can be, for example, polyether, polyester, polyurethane or polyurea blocks with a corresponding ratio of O and / or N atoms to the C atoms.
  • the polar blocks (Ab) can be straight-chain or branched. They can also be heavily branched. For example, they may also be dendrimeric or hyperbranched blocks with corresponding polar groups.
  • the polar block may be a highly branched polyethyleneimine block.
  • the blocks (Aa) and / or (Ab) may be terminally arranged, i. only be connected to another block, or they may be connected to two or more other blocks.
  • the blocks (Aa) and (Ab) may be linearly linked together in an alternating arrangement.
  • any number of blocks can be used. As a rule, but are no more than 8 blocks Aa or Ab available. This results in the simplest case a
  • Diblock copolymer of the general formula Aa-Ab may be triblock copolymers of the general formula Aa-Ab-Aa or Ab-Aa-Ab. Of course, several blocks can follow each other, for example Aa-Ab-Aa-Ab. If star-shaped blocks Aa or Ab are used, star-shaped block copolymers can also be synthesized.
  • the non-polar blocks (Aa) are preferably blocks comprising essentially monoolefin units. Preference is given to blocks which essentially comprise propylene and / or isobutene units. In a particularly preferred embodiment of the invention, the non-polar blocks (Aa) are constructed essentially of isobutene units.
  • the polyisobutene blocks are functionalized by means of suitable reagents at the chain ends.
  • the functionalized chain ends are chosen so that they can react with suitable polar monomers or alternatively with pre-synthesized polar blocks which have complementary functional groups at the chain ends.
  • suitable polar monomers or alternatively with pre-synthesized polar blocks which have complementary functional groups at the chain ends.
  • a large number of different block copolymers can be synthesized purposefully from a limited number of different polyisobutene blocks and a limited number of different polar blocks, as it were in the modular principle.
  • the length of the block can be varied with the polyisobutene blocks.
  • the polar blocks can each be selected to match the respective polar polymers.
  • non-polar blocks other comonomers can be used in addition to the isobutene units for finely controlling the properties.
  • comonomers are in addition to 1-butene and cis- or trans-2-butene in particular isoolefins having 5 to 10 carbon atoms such as 2-methyl-1-butene or vinyl aromatics such as styrene.
  • the proportion of such comonomers should normally not exceed 20% by weight, based on the amount of all the building blocks of the block.
  • the blocks may also comprise the initiator or starter molecules used to start the polymerization, fragments thereof and the functional groups already mentioned.
  • reactive polyisobutene should be used for the synthesis.
  • reactive polyisobutene is understood by the person skilled in the art to mean polyisobutene which has a very high proportion of terminal ⁇ -olefin end groups.
  • the preparation of reactive polyisobutenes is known and described, for example, in detail in WO 04/9654, pages 4 to 8, or in WO 04/35635, pages 6 to 10.
  • the reactive polyisobutenes may be linear, branched or star-shaped. Depending on the preparation, they can have ⁇ -olefin groups only at one chain end or else at two or more chain ends.
  • Functionalized polyisobutenes can be prepared starting from reactive polyisobutenes by providing them with functional groups in single-stage or multistage reactions which are known in principle to those skilled in the art. Depending on the type of reactive polyisobutene used, functionalized polyisobutenes are obtained which have functional groups only at one chain end or at two or more chain ends.
  • the reactive polyisobutene is functionalized with an alkene having a double bond substituted with electron-withdrawing groups (enophile) in an ene reaction.
  • enophile electron-withdrawing groups
  • maleic anhydride isobutene as the enophile.
  • polyisobutenes polyisobutenyl succinic anhydride, PIBSA
  • succinic anhydride groups are obtained.
  • Particularly preferred polar blocks (Ab) for carrying out the invention can be constructed essentially from oxyalkylene units. This results in polyether blocks.
  • oxyalkylene is in principle known type and Assuming units of the general formula -R 6 -O-.
  • R 6 is a divalent aliphatic hydrocarbon radical which may also optionally have further substituents.
  • a polar block (Ab) may also comprise several different oxyalkylene units.
  • the polar blocks comprise as main components ethylene oxide units - (CH 2) 2-O- and / or propylene oxide units -CH 2 -CH (CH 3) -O-.
  • Alkylene oxide units containing more than 3 carbon atoms can optionally be used in small amounts to fine tune the properties.
  • the blocks may be random copolymers, gradient copolymers, alternating or block copolymers of ethylene oxide and
  • Act propylene oxide units The amount of higher alkylene oxide units should not exceed 10% by weight, preferably 5% by weight. Preference is given to blocks which comprise at least 50% by weight of ethylene oxide units, preferably 75% by weight and particularly preferably at least 90% by weight of ethylene oxide units. Very particular preference is given to pure polyoxyethylene blocks.
  • Such blocks are available in a manner known in principle, for example by
  • 3 C atoms and optionally further components can also be prepared by polycondensation of di- and / or polyalcohols, suitable initiators and optionally further monomeric components. Branched or star-shaped blocks (Ab) are available by using starter molecules with at least 3 arms. Examples of suitable initiators include glycerol, trimethylolpropane, pentaerythritol or ethylenediamine. The synthesis of polyalkylene oxides is known to the person skilled in the art. Details are detailed in, for example, "Polyoxyalkylenes" in Ullmann's Encyclopedia of Industrial Chemistry, 6 th Edition, Electronic Release.
  • the terminal groups of blocks synthesized in this way are OH groups and / or ether groups -OR 7 , where R 7 is a hydrocarbon radical having 1 to 30 C atoms.
  • polyester units which are particularly suitable for carrying out the invention essentially comprise polyester units. These may be PET units, or preferably polyesters in which part of the terephthalic acid units are replaced by aliphatic dicarboxylic acid units, in particular by adipic acid units.
  • the end groups of a polyester block are determined by the person skilled in the art, depending on the type of functionalization of the non-polar block (Aa), for example via the ratio of the reactants.
  • succinic anhydride groups (variant Ni)) polyester blocks are synthesized with OH groups, in the event that the polyisobutene itself has OH groups (variant vi)), COOH-terminated esters can be used.
  • Other preferred polar blocks include blocks each comprising essentially carbonate, urethane, urea or amide units. The synthesis should preferably be carried out in each case such that the products are OH and / or NH 2 -terminated.
  • blocks which comprise both ether units and other polar units, in particular ester, carbonate, urethane, urea or amide units can be obtained, for example, by using a polyester diol as a starter molecule to form blocks comprising oxyalkylene units.
  • a reverse procedure can be used for the synthesis of a polyester diol as the alcohol component, for example di-, tri- or Oligoalkylenglykole.
  • groups comprising groups containing carbonate, urethane, urea or amide units can also be incorporated into corresponding blocks.
  • amphiphilic block copolymers (A) can preferably be carried out by first preparing the polar blocks (Ab) separately and reacting them in a second reaction stage with the functionalized polyisobutenes (Aa) to form block copolymers.
  • the structure of the amphiphilic block copolymers (A) can be influenced by selecting the type and amount of the starting materials for the blocks (Aa) and (Ab) and the reaction conditions, in particular the order of addition. Details on the structure of possible products and the implementation options are detailed in WO 2006/128796, pages 8 to 10.
  • n and m stand independently of each other for natural numbers. They are from the
  • amphiphilic block copolymers (A) may also have residues of starting materials, depending on the preparation conditions.
  • triblock copolymers of the formula Aa-Ab-Aa can still be used Diblock copolymers Aa-Ab and functionalized and unfunctionalized polyisobutene included.
  • these products can be used without further purification for the application.
  • the products can also be cleaned before use. The person skilled in cleaning methods are known.
  • Preferred block copolymers for carrying out this invention are triblock copolymers of the general formula Aa-Ab-Aa, or their mixture with two-block copolymers Aa-Ab and optionally by-products.
  • diblock copolymers Aa-Ab and / or triblock copolymers Aa-Ab-Aa consisting essentially of isobutene nonpolar blocks (Aa) having a number-average molar mass M n of 500 to 10,000 g / mol and substantially consisting of oxyalkylene polar blocks ( Ab) with a number-average molar mass M n of 1000 to 20,000 g / mol.
  • polyester (B) As additive, mixtures of several different polyesters can be used.
  • the polyesters (B) may be conventional PET with a melting point of 255 to 280 0 C. It is particularly advantageous to use modified PET which has additional soft segments and, accordingly, a lower degree of crystallization and / or melting point.
  • the polyester used as a component of the additive (B) generally have a melting point of 50 to 240 0 C.
  • the melting point is 60 to 230 ° C, more preferably 80 to 160 0 C, most preferably 100 to 150 ° C and for example 1 10-130 ° C.
  • polyesters can be obtained by using so-called "soft" monomers as diol components and / or dicarboxylic acid components, ie monomers which lead to polyesters which crystallize worse than PET.
  • Diols which can be mentioned here are in particular aliphatic diols, in particular aliphatic 1, ⁇ Examples are 1,4-butanediol or 1,6-hexanediol.
  • Cycloaliphatic diols such as cyclopentane or cyclohexanediol and also polyether diols such as diethylene glycol, triethylene glycol, polyethylene glycol or polypropylene glycol may also be used.
  • Dicarboxylic acid units to be mentioned are aliphatic dicarboxylic acids, in particular aliphatic 1, ⁇ -dicarboxylic acids having 4 to 10, preferably 4 to 8 carbon atoms.
  • Examples include succinic, glutaric, adipic or sebacic acid.
  • Preferred polyesters comprise as monomers at least one diol selected from the group of aliphatic diols having 3 to 10 carbon atoms, cycloaliphatic diols or Poyletherdiolen the general formula HO - (- CH (R) -CH2-O-) n -H, where n is a Number greater than two, in particular 2 to 150, preferably 2 to 30 and particularly preferably 2 to 10 and the radicals R independently of one another are H or CH3, preferably H and / or at least one aliphatic dicarboxylic acid having 4 to 10 carbon atoms.
  • they may also comprise other monomers, for example terephthalic acid and / or ethylene glycol.
  • the polyester (B) is polybutylene terephthalate.
  • Polybutylene terephthalate has a melting point of about 220 to 225 0 C.
  • polyesters (B) which have at least two different dicarboxylic acid units. They comprise at least 5 to 80 mol%, preferably 20 to 70 mol% of terephthalic acid units and 20 to 95 mol%, preferably 30 to 80 mol% of units of aliphatic 1, ⁇ -dicarboxylic acids having 4 to 10 carbon atoms.
  • the total amount of terephthalic acid units and aliphatic 1, ⁇ -dicarboxylic acids having 4 to 10 carbon atoms is in this case at least 80 mol%, preferably at least 90 mol%, particularly preferably at least 98 mol% and very particularly preferably 100 mol%, wherein the% data in each case the total amount of all dicarboxylic acid units in the polyester are related.
  • the aliphatic 1, ⁇ -dicarboxylic acid units may, for example, be succinic acid, glutaric acid, adipic acid or sebacic acid. It is preferably adipic acid.
  • various dicarboxylic acid units it is also possible for various dicarboxylic acid units to be present therefrom. For example, mention may be made of other aromatic dicarboxylic acid units and / or cycloaliphatic dicarboxylic acid units. Of course, mixtures of different dicarboxylic acid units can be used.
  • the diol units are selected in the second preferred embodiment from the group of aliphatic, cycloliphatic and / or polyether diols, wherein at least 50 to 100 mol% of aliphatic 1, ⁇ -diols are present, wherein the% are based on the total amount of all diols.
  • the aliphatic diols having 4 to 10 carbon atoms may, for example, be 1, 4-butanediol, 1, 5-butanediol or 1, 6-hexanediol. It is preferably 1, 4-butanediol.
  • polyether diols include diethylene glycol, triethylene glycol, polyethylene glycol or Polypropylene glycol.
  • Examples of cycloaliphatic diols include cyclopentane or cyclohexanediols.
  • the polyesters (B) of the second preferred embodiment may of course also comprise further components for fine control of the properties.
  • Examples include building blocks which have additional functional groups. Particular mention should be made here of amino groups. Also to be mentioned are building blocks for chain extension.
  • building blocks for chain extension are also possible to use trifunctional or polyfunctional alcohols or carboxylic acids. As a result, branched products can be obtained.
  • the number-average molecular weight M n of preferred polyesters should generally be 5000 to 50 000 g / mol, preferably 10000 to 30 000 g / mol. Have proven particularly useful 20,000 to 25,000 g / mol.
  • the ratio M w / M n is preferably 3 to 6, for example 4 to 5.
  • the preferred polyester may advantageously have a melt flow rate MFR of 2 to 6 g / 10 min (ISO 1133, 190 ° C., 2.16 kg).
  • a preferred bulk density is 1, 2 - 1, 35 g / cm 3, more preferably 1, 22 - 1. 30 g / cm3
  • the preferred Vicat softening temperature is 75 to 85 ° C, more preferably 78-82 ° C (VST A / 50, ISO 306).
  • polyesters typical reaction conditions and catalysts are known in principle to the person skilled in the art.
  • the dicarboxylic acid units can be used to synthesize the polyesters in a manner known in principle as free acids or in the form of customary derivatives, such as, for example, esters. Typical esterification catalysts can be used.
  • the preferred polyesters are also commercially available.
  • the polypropylene or polypropylene blends may optionally also comprise further typical additives and auxiliaries (C).
  • additives and auxiliaries include antistatic agents, stabilizers, UV absorbers or fillers.
  • Such additives are known in the art. Details of this are, for example, in "Polyolefins" in Ullmann's Encyclopedia of Technical Chemistry, 6 th Edition, 2000, Electronic Release.
  • amphiphilic block copolymers (A) and the polypropylene or the polypropylene blends and optionally polyester (B) and further components (C) are intensively mixed together with heating to the molten liquid by means of suitable equipment.
  • Kneaders, single-screw extruders, twin-screw extruders or other mixing or dispersing units can be used as apparatuses, for example.
  • twin-screw extruders can be used.
  • the polypropylene, the amphiphilic block copolymer (A) and optionally the other components are preferably metered into the mixing unit using appropriate metering devices as granules.
  • appropriate metering devices for example, it is also possible to use a premixed granules.
  • Polypropylene blends can be obtained by already using a polypropylene blend. But it is also possible polypropylene and another
  • amphiphilic block copolymer (A) also acts as a compatibilizer, so that the addition of further compatibilizers is often unnecessary.
  • additives and auxiliaries may already be present in the polypropylene used, or incorporated in the course of the described mixing of the components.
  • the temperature for mixing is selected by the person skilled in the art and depends on the type of components used. On the one hand, the polypropylene and the other components of the mixture should sufficiently soften, so that thorough mixing is possible. On the other hand, they should not be too thin, because otherwise sufficient shear energy input can no longer take place and, under certain circumstances, thermal degradation is also to be feared. As a rule, the mixing is carried out at a product temperature of 160 to 260 0 C, preferably from 160 to 190 0 C, without the invention being limited thereto.
  • the temperature of the heating mantle of the mixing units used is - as the expert in principle known - usually something about it.
  • the melt is spun into fibers.
  • the molten mass is pressed in a manner known in principle by one or preferably a plurality of nozzles, for example a corresponding perforated plate, corresponding filaments being formed.
  • Proven for spinning the inventively used Mixtures has a nozzle temperature of 200 0 C to 260 0 C, preferably 200 ° C to 230 0 C.
  • the fibers or filaments should generally have a diameter of less than 25 microns. Preferably, the diameter is 10 to 15 microns, without the invention being limited thereto.
  • the yarns consist of several filaments, for example 10 to 200 filaments with total yarn counts of 30 to 4000 dtex (dtex ⁇ g / 10 km fiber). For the garment industry, 1-8 dtex per filament, for the carpet industry 10-50 dtex / filament have proven successful.
  • fibers having a total yarn titre of 50 to 100 dtex / 16 to 32 filaments can be produced.
  • the filaments obtained by spinning can also be processed into staple fibers in the usual way.
  • the filaments are first cut into shorter pieces and then processed into yarns.
  • the resulting fibers or yarns can then be processed by methods known to those skilled in the art to the already mentioned textile material materials or textile fabrics.
  • a concentrate of the polypropylene, the amphiphilic block copolymer (A) and optionally the polyester (B) and further components (C) is first prepared.
  • the already described techniques and conditions for mixing can be used.
  • the preparation of the concentrate and the production of the threads can be carried out in the same operation both separately and in-line or in different operations.
  • the concentrate can be manufactured and sold by a raw material supplier, while the further processing takes place at a manufacturer of textile materials.
  • the amount of additives (A) and (B) taken together is 0.5 to 12 wt.% With respect to the total amount of all components, ie the sum of the polypropylene or polypropylene blend, the amphiphilic block copolymer (A) and / or -rank existing of the polyester (B) and the additives and auxiliaries (C).
  • the amount of (A) and (B) is preferably from 1 to 7% by weight and more preferably from 2.5 to 5% by weight. Unless (B) are present, these amounts are of course also (A) alone.
  • the weight ratio of the polyester (B) and the amphiphilic block copolymer (A) (B) / (A) is usually 20: 1 to 1: 1, preferably 12: 1 to 2: 1, more preferably 10: 1 to 2: 1, and most preferably 7: 1 to 3: 1.
  • the amount of the polypropylene is generally from 70 to 99.5% by weight, preferably from 80 to 99.5% by weight, based on the sum of all components of the fibers, preferably from 88 to 99% by weight.
  • the amount of additives and auxiliaries (C) should, if present at all, be less than 20% by weight, preferably less than 10% by weight, more preferably less than 5% by weight and most preferably less than 2% by weight, based on the sum of all components , If present at all, the amount of fillers should be less than 5% by weight, preferably less than 2% by weight and most preferably no fillers should be present.
  • additives (A) and optionally (B) make it possible to obtain softer textile materials.
  • the additives improve in particular the so-called "grip".
  • the textile materials can be undyed, or even be embedded by means of pigments or dyes.
  • Dyeing procedures are disclosed, for example, by WO 2006/128796.
  • the fibers used to make the textile materials may be POY (partially oriented yarns), BCF (bulked continuous filament) or staple fibers. Staple fibers are produced in short lengths and twisted after spinning (like cotton) into a thread. Then they are tufted into a carpet or processed into garment textiles. BCF yarns are long filaments that are bundled into a bundle of fibers.
  • BCF bulk continuous filament threads
  • Melt-spun and crimped BCF yarns can be used for carpet yarn, for example.
  • a plurality of strand-like filaments are extruded, cooled, brought together in bundles to form a thread, stretched, curled and wound into a coil.
  • the bundled filament strands are bundle-wise extruded by means of a spinneret having a nozzle bore on each of the filaments on its underside.
  • spinneret having a nozzle bore on each of the filaments on its underside.
  • multiple filament bundles are extruded through multiple spinnerets.
  • several threads are produced in parallel side by side in such spinning processes, which are then performed together to form filament bundles.
  • a polyester comprising terephthalic acid units (about 40 mol% with respect to the amount of all dicarboxylic acid units), adipic acid units (about 60 mol% with respect to the amount of all dicarboxylic acid units) and 1, 4-butanediol units was used, which according to the in WO 98 / 12242, Example 1 described procedure.
  • the melting point was 110 to 120 0 C.
  • Polybutylene terephthalate having a melt volume rate MVR (250 0 C, 2.16 kg) of 40 cm 3/10 min, melting temperature (DSC) 223 ° C, density 1300 kg / m 3 (Ultradur ® B 2550, Fa. BASF)
  • Polybutylene terephthalate having a melt volume rate MVR (250 0 C, 2.16 kg) of 19 cm 3/10 min, melting temperature (DSC) 223 ° C, density 1300 kg / m 3 (Ultradur B 4250 ®)
  • polypropylene By means of metallocene catalysis, polypropylene, high melt flow index MFR (230 0 C, 2.16 kg) min 30 g / 10 min, melt volume rate MVR (230 ° C, 2.16 kg) 40 cm 3/10 min, melting temperature 145 ° C (Metocene ® HM 562 S, Fa. Basell).
  • Polypropylene P2 By means of metallocene catalysis, polypropylene, high melt flow index MFR (230 0 C, 2.16 kg) min 30 g / 10 min, melt volume rate MVR (230 ° C, 2.16 kg) 40 cm 3/10 min, melting temperature 145 ° C (Metocene ® HM 562 S, Fa. Basell).
  • Polypropylene P2 By means of metallocene catalysis, polypropylene, high melt flow index MFR (230 0 C, 2.16 kg) min 30 g / 10 min, melt volume rate MVR (230 ° C, 2.16 kg) 40 cm
  • polypropylene with a higher crystalline content such as P1 (about 55% instead of 45%) and a higher melting range (about 150 to 160 0 C).
  • the polypropylene was processed in a twin-screw extruder after premixing the components at 210 0 C to a homogeneous melt.
  • the mixture was processed from the melt on the one hand to the specimens described below and on the other hand spun into filaments as also described below.
  • a two-stage procedure was carried out by first preparing in the manner described a concentrate of 50% by weight of polypropylene (P1), 40% by weight of polyester (B1) and 10% by weight of amphiphilic block copolymer (A1).
  • the concentrate (K1) was processed in a second step with additional polypropylene to the additized polypropylene.
  • Test specimens are prepared from variously additized polypropylene melts. On the test specimens, the notched impact strength and the impact properties according to Charpy (elongation at break and breaking stress) were measured as proof of the changed mechanical behavior of the additized polypropylene.
  • the Zwick Z050 1 kN test set was used for the measurement.
  • the modulus of elasticity is a measure of the strength of the materials while the breaking stress EB gives a measure of the elasticity. The higher the breaking stress, the better.
  • Example 1 shows that the use of an amphiphilic block copolymer (A) alone already produces significant effects; in combination with the polyester (B) even better results can be achieved.
  • Both textiles are "felt" by test persons with their eyes closed, with the right and left hand to be exchanged, judged by at least 3 persons who judge the differences according to notes 1-5.
  • the overall rating is better only if at least two people score 4 or 5. With large dispersion of results, i. more than 1 grade difference between the assessing persons), the difference is assessed as undetectable (3). The overall rating is then based on the scale 1, 1-2, 2, 2-3, 4, 4-5, 5.
  • Titanium dioxide masterbatches (37.5% by weight T ⁇ O2, 62.5% by weight of polypropylene)
  • the components were spun on a large industrial spinning machine with a single-screw extruder (temperature about 230 0 C) with three gravimetric dosing devices from the melt and then textured.
  • Garntiter Spinning as POY yarn dtex 50f28. After texturing and stretching, the final fiber denier is dtex 30f28. Knitting is done on a circular knitting machine from a spool.
  • a reference knitted fabric was made of 100% polypropylene under otherwise identical conditions. Both knits were tested as described above. The results are as follows:
  • Table 2 Composition of the samples and evaluation of the handle The example shows that at 1% no difference to the non-additive textile made of polypropylene is obtained. With increasing content of additive mixture, the grip of the textile material is getting better.
  • composition of the additized polypropylene 95% by weight of polypropylene, 4% by weight of polyester B1, 1% by weight of block copolymer A1
  • the components were in granules and were first mixed by hand.
  • a reference knitted fabric was made of 100% polypropylene under otherwise identical conditions. Both knits were tested as described above. The polypropylene knitted fabric was rated grade 4.
  • BCF yarn fiber thickness of fiber thickness 1000 dtex Production of a tufted carpet. Yarn strength: 1000 dtex
  • composition of the additized polypropylene 98.5% polypropylene, 1.2% polyester B1 and 0.3% block copolymer A1; Rating: Grade: 4 Yarn material for Example 2-4:
  • composition of the additized polypropylene 97.5% polypropylene, 2% polyester B1 and 0.5% block copolymer A1; Rating: 5
  • Polypropylene fiber materials are significantly improved by the additives used in the invention.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Artificial Filaments (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne l'utilisation de copolymères à blocs amphiphiles, constitués d'un bloc apolaire comprenant des motifs hydrocarbonés et d'un bloc polaire comportant des atomes d'oxygène et/ou d'azote, comme plastifiants pour matières textiles constituées de fibres de polypropylène, en particulier pour améliorer le toucher de matières textiles.
PCT/EP2009/066524 2008-12-19 2009-12-07 Utilisation de copolymères à blocs amphiphiles comme plastifiants pour matières textiles composées de fibres de polypropylène Ceased WO2010079030A2 (fr)

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EP08172403 2008-12-19
EP08172403.1 2008-12-19

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WO2010079030A2 true WO2010079030A2 (fr) 2010-07-15
WO2010079030A3 WO2010079030A3 (fr) 2010-12-16

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PCT/EP2009/066524 Ceased WO2010079030A2 (fr) 2008-12-19 2009-12-07 Utilisation de copolymères à blocs amphiphiles comme plastifiants pour matières textiles composées de fibres de polypropylène

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10202712B2 (en) 2009-07-31 2019-02-12 Basf Se Producing spinnable and dyeable polyester fibers

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU694983B2 (en) * 1994-06-06 1998-08-06 Johnson & Johnson Consumer Companies, Inc. Novel compositions for dental floss
US5952088A (en) * 1996-12-31 1999-09-14 Kimberly-Clark Worldwide, Inc. Multicomponent fiber
US20050217037A1 (en) * 2002-10-08 2005-10-06 Negola Edward J Dyed polyolefin yarn and textile fabrics using such yarns
US20090039543A1 (en) * 2005-05-30 2009-02-12 Basf Aktiengesellschaft Polymer Composition Comprising Polyolefins And Amphiphilic Block Copolymers And Optionally Other Polymers And/Or Fillers And Method For Dying Compositions Of That Type Or Printing Thereon
DE102005025017A1 (de) * 2005-05-30 2006-12-07 Basf Ag Verwendung von amphiphilen Blockcopolymeren zur Herstellung von Polymerblends
DE102005025055B4 (de) * 2005-05-30 2007-12-06 Fiberweb Corovin Gmbh Verfahren zur Herstellung eines Vlieses mit hoher Dehnbarkeit aus Polymermischungen mit amphiphilen Blockcopolymeren, Vlies mit hoher Dehnbarkeit und Verwendung sowie Polymermischung zur Herstellung eines Vlieses mit hoher Dehnbarkeit
DE102006057221A1 (de) * 2006-12-01 2008-06-05 Basf Se Verfahren zur Herstellung von gefärbten textilen Materialien umfassend Polypropylenfasern

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10202712B2 (en) 2009-07-31 2019-02-12 Basf Se Producing spinnable and dyeable polyester fibers

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