EP1040215A1 - Verfahren zur herstellung von polyurethan-elastomerfäden und danach hergestellte fäden - Google Patents

Verfahren zur herstellung von polyurethan-elastomerfäden und danach hergestellte fäden

Info

Publication number
EP1040215A1
EP1040215A1 EP98959871A EP98959871A EP1040215A1 EP 1040215 A1 EP1040215 A1 EP 1040215A1 EP 98959871 A EP98959871 A EP 98959871A EP 98959871 A EP98959871 A EP 98959871A EP 1040215 A1 EP1040215 A1 EP 1040215A1
Authority
EP
European Patent Office
Prior art keywords
chain extender
temperature
glycol
thread
amino groups
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP98959871A
Other languages
German (de)
English (en)
French (fr)
Inventor
Frank Hermanutz
Peter Hirt
Oliver Oess
Wilhelm Oppermann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rhodianyl SAS
Original Assignee
Rhodianyl SAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Rhodianyl SAS filed Critical Rhodianyl SAS
Publication of EP1040215A1 publication Critical patent/EP1040215A1/de
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/70—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyurethanes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S528/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S528/906—Fiber or elastomer prepared from an isocyanate reactant

Definitions

  • the invention relates to a process for the production of polyurethane elastomer threads and threads produced according to them.
  • Polyurethane elastomers are block copolymers that are made up of regularly arranged soft and hard segments.
  • the soft segments consist of long, disordered and flexible chains, which give the fiber the required rubber-like elasticity.
  • the properties can be varied with regard to the molecular weight and type of the soft segment in terms of elongation and stretching force.
  • the soft segments are fixed over the hard segments. The provision of the molecular chains of the soft segments after the
  • the hard segments consist of short-chain, partially crystalline areas.
  • the main task of the hard segments is to prevent the polymer chains from sliding off when mechanical forces act as fixed points.
  • the resilience forces in the elastomer cause it to contract to almost its original length after stretching. The remaining difference in length will
  • the polyurethane elastomers are generally obtained in one step or by a two-step process.
  • the two-step process in the first reaction step, higher molecular weight diols are reacted with diisocyanates to form prepolymers, which in a second step react with so-called chain extenders to form high molecular weight products. Excess amounts of diisocyanate are used in the first reaction step, so that the prepolymer is terminated at both ends by an isocyanate group.
  • the chain extenders are bifunctional, low-molecular compounds with terminal reactive hydrogen atoms, mostly dihydroxy or diamine compounds.
  • the prepolymers react with the prepolymers to form the corresponding carbamic acid derivatives, ie the polyurethane elastomers Polyureairethane elastomers.
  • the soft segments formed from the higher molecular weight diols alternate with the rigid hard segments formed by the reaction of the chain extender with terminal isocyanate groups.
  • the prepolymer stage is bypassed. The diisocyanate reacts simultaneously with the macrodiol and the chain extender.
  • melt-spun polyurethane elastomer threads predominantly use a polyurethane polymer based on aromatic
  • Diiosocyanates mainly diphenylmethane-4,4'-diisocyanate (MDI).
  • MDI diphenylmethane-4,4'-diisocyanate
  • the fully reacted polymer is melted and processed into a thread using a melt spinning process.
  • polyurethane polymers based on aromatic diisocyanates are increasingly being rejected.
  • Aromatic amines which are suspected of being carcinogenic, appear as degradation products.
  • Polyurethane polymers based on aromatic diisocyanates also tend to yellow. It was therefore an object of the present invention to provide a process with which polyurethane elastomer threads based on non-aromatic diisocyanates with improved properties, in particular with regard to tensile strength, elongation at break, residual elongation and HDT temperature, can be obtained
  • this object is achieved by a method which comprises the following steps
  • Macrodiols having a molecular weight of about 500 to 10,000, (ii) an aliphatic, cycloaliphatic and / or aliphatic-cycloaliphatic diisocyanate and (iii) a chain extender having at least two hydroxyl and / or amino groups, the polymer having a molar excess of isocyanate groups compared to the hydroxyls and amino groups from macrodiol and chain extender, based on the sum of the hydroxyl and amino groups, of at least about 0.2%, (b) melt extruding the polyurethane polymer into a thread, the steps
  • the polyurethane polymer must be melt-flowable at a suitable temperature.
  • the polyurethane polymer is prepared either by reacting macrodiol, chain extender and diisocyanate, optionally with the addition of a catalyst, essentially in the absence of a solvent by the prepolymer or the one-shot process, or by reacting one Polyurethane precursor polymer, which has a stochiometric content or a deficit of isocyanate groups compared to hydroxyl and amino groups, is melted into the melt and, if necessary after cooling the melt, is reacted with a diisocyanate and / or an isocyanate-terminated prepolymer essentially in the absence of a solvent
  • the polyurethane polymer has a molar excess of isocyanate groups over hydroxy and amino groups of about 0.2 to 15%, in particular about 1 to 10%
  • Polyurethane polymer chains can be formed by forming allophanate or biuret formations
  • allophanate In the following only the term "allophanate” is used, it should also include “biuret” depending on the context).
  • an excess isocyanate group reacts with an already formed urethane or urea group to form a branch.
  • the applicant has found that allophanate-crosslinked polyurethane - Polymers based on aliphatic diisocyanates are not satisfactorily melt-spinnable.
  • the spinning temperatures required for spinning the allophanate-crosslinked polyurethanes are in the range of 230 ° C.
  • the spun threads show high stickiness and inadequate strengths. At the high spinning temperatures required, the polymer is also greatly degraded uses the different kinetics of the polyurethane chain formation reaction and the
  • Allophanate formation from The formation of the allophanate bonds takes place more slowly than the build-up of the linear polyurethane chains.
  • the polyurethane polymer is consequently produced with a defined excess of cyanate and melt-spun or extruded before the formation of the allophanate cross-links of the polymer is avoided and the tendency of the threads to stick is reduced. Further treatment of the threads (winding, tempering, etc.) is possible without any problems. Aftertreatment of the threads then forms covalent allophanate cross-links in the hard segments.
  • a chemical network of allophanate cross-links is formed leads to a significant improvement in the thread properties compared to conventional melt-spun elastane thread.
  • a major advantage is that present in the inventively obtained filaments aliphatic allophanate bonds are much more thermostable than aromatic allophanate
  • the extrusion can expediently be carried out on conventional plants for thread thicknesses of approximately 5 to 2000 dtex.
  • the melt extrusion is preferably carried out at a temperature of approximately 80 to 180 ° C., in particular approximately 100 to 150 ° C.
  • the aftertreatment can be carried out by tempering for several hours at temperatures of preferably about 60 to 100 ° C or optionally storing for several days at room temperature. Aftertreatment at temperatures higher than 150 ° C is not recommended.
  • the macrodiols used are preferably essentially linear diols which, apart from the terminal hydroxyl groups, have no further groups which react with isocyanates.
  • the macrodiols have a molecular weight of approximately 500 to 10,000, preferably approximately 700 to 5000, in particular approximately 1000 to 3000 weight average molecular weight If the macrodiol residues are too short, the difference in cohesive energy between the hard and soft segments becomes smaller, which results in a stronger phase mixing and thus poorer elastic properties. Macrodiols with a low glass transition point are preferred. In general, the glass transition points of the macrodiols used are around -35 ° C to -60 ° C.
  • Polyester or polyether glycols are preferably used. Hydroxy group-terminated polyethers are referred to as polyether glycols. Polyalkylene glycols are preferably used. Preferred examples are polyethylene glycol, polypropylene glycol and / or polytetramethylene glycol, the latter of which is particularly preferred.
  • Polytetramethylene glycol is also known as polytetrahydrofuran and can be produced by ionic polymerization of tetrahydrofuran with acidic catalysts. Suitable copolymers are also obtained by copolymerizing tetrahydrofuran with propylene oxide, ethylene oxide and glycols. Elastomers synthesized from polyether glycols are characterized by their advantageous low-temperature behavior and high
  • Suitable polyester glycols are preferably prepared by esterifying an aliphatic and / or cycloaliphatic dicarboxylic acid with excess amounts of a diol.
  • Preferred dicarboxylic acids are succinic acid, glutaric acid, adipic acid,
  • the dicarboxylic acid is esterified with an excess of diol, preferably ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol and / or 1,6-hexanediol.
  • diol preferably ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol and / or 1,6-hexanediol.
  • a polyester of adipic acid and ethylene glycol is particularly preferred. Polyester segments tend to crystallize at low temperatures, which at the expense of elastic
  • a reduction in the tendency of the polyester chains to crystallize is preferably brought about by the incorporation of methyl branches. This can be done by partially replacing the diols mentioned with other diols, such as 1,2-propanediol and 2,3-butanediol, or by using methyl-substituted dicarboxylic acids. By using the longer-chain glycols mentioned, such as 1,4-butanediol, 1,5-
  • Pentanediol and / or 1,6-hexanediol, elastomers are obtained with increased resistance to hydrolysis.
  • Suitable polyester glycols can also be obtained by reacting omega-hydroxycarboxylic acids with small amounts of diols or by ring-opening polymerization of lactones with small amounts of diol. Mixtures of polyether glycols and polyester glycols can also be used.
  • suitable macrodiols see also be used.
  • the aliphatic, cycloaliphatic and / or aliphatic-cycloaliphatic diisocyanate preferably (after deduction of the isocyanate groups) comprises an alkylene group with 2 to 14
  • Hexamethylene diisocyanate and / or dicyclohexylmethane-4,4'-diisocyanate are particularly preferred.
  • the chain extender is a compound with at least two hydroxyl and / or primary amino groups, preferably a diol or a diamine, which has a low molecular weight compared to the macrodiol.
  • diols, diamines or amino alcohols with 2 to 6 carbon atoms are in particular diols, diamines or amino alcohols with 2 to 6 carbon atoms.
  • Preferred examples are ethylene glycol, 1,4-butanediol, cis-2-butene-1,4-diol and 2-butyne-1,4-diol.
  • olefinically unsaturated chain extenders are used. With “olefinic unsaturation” it should be stated that the chain extender has one or more double or triple bonds capable of polymerization reactions.
  • the olefinically unsaturated chain extender can be a diaminoalkene, diaminoalkyne, diaminocycloalkene, alkenediol, alkynediol and / or cycloalkenediol. preferred
  • suitable diamines are cis or trans-1,4-diaminobut-2-ene, cis or trans-4,4'-diaminostilbene, diaminomaleonitrile, 1,4-diaminobut-2-yne and / or 3,6-diaminocyclohexene - (l).
  • Preferred examples of suitable diols are glycerol-1-allyl ether, ice- or trans-2-butene-1, 4-diol, 2-butyne-1, 4-diol and 5,6-bis (hydroxymethyl) bicyclo [2.2. 1.] hepten-2.
  • olefinically unsaturated chain extenders permits a further improvement in the textile-mechanical properties of the fibers formed from the polyurethane elastomers according to the invention by the covalent crosslinking of the Double or triple bonds built into the polymer chains are induced.
  • the shaped threads are exposed to high-energy rays.
  • the threads are preferably treated with electron beams or UV rays
  • Polyurethane elastomers according to the invention can contain additives in the form of matting agents, color pigments, antioxidants, thermal stabilizers, photo or UV stabilizers and / or hydrolysis stabilizers
  • the polyurethane polymer with free isocyanate groups is not stable in storage because it has formed allophanate crosslinks in the course of storage
  • the polymer can be produced directly from the components, the production being carried out by the ohe shot process or the prepolymer process.
  • the macrodiol, the chain extender and the diisocyanate are preferably in the required amounts at one temperature between about 60 and 180 ° C, especially between about 80 and
  • a polyaddition catalyst in particular dibutyltin dilaurate or dibutyltin diacetate, can optionally be added to set a desired reaction level.
  • macrodiol and diisocyanate are first converted to the prepolymer, and this is then extended with the pad extender to the desired polyurethane polymer. The polymer obtained is then extended spun directly
  • a stable polyurethane precursor polymer which has a stoichiometric content or a deficiency of isocyanate groups compared to hydroxyl and amino groups can be prepared first, which can be granulated and temporarily stored if necessary.
  • the precursor polymer is melted if necessary and at a temperature of preferably about 100 to 160 ° C. with an aliphatic, cycloaliphatic and / or alophatic-cycloaliphatic diisocyanate and / or an isocyanate-terminated prepolymer and the mixture is homogenized.
  • the precursor polymer can optionally be at a higher temperature than the preferred reaction temperature be melted, in this case the melt is added before the addition of the diisocyanate and / or isocyanate-terminated prepolymer expediently somewhat cooled
  • isocyanate-terminated prepolymers reaction products of macrodiol with 1.1 to 3 equivalents of diisocyanate are particularly suitable.
  • the precursor polymer can be melted in an extruder, the addition of the diisocyanate and / or the isocyanate terminated prepolymer is advantageously carried out either in the exit area of the extruder or after the extruder in the melt line.
  • the mixture obtained is expediently homogenized and extruded, for example using static mixers in the melt line
  • the ratio of macrodiol to chain extender in the polyurethane polymer is about 1 4 to 1 1
  • melt-spun polyurethane thread obtained by the process according to the invention shows significantly improved thread properties compared to conventional melt-spun polyurethane thread due to the covalent crosslinking of the
  • Hard segments over allophanate bonds achieve a significant improvement in the hysteresis behavior, i.e. a lower residual elongation and less loss of force, an increase in tear strength and a higher HDT temperature
  • PTHF polytetrahydrofuran
  • the spinning temperature was 80 ° C., the residence time was 30 min.
  • the thread obtained was not sticky and could be wound up without problems
  • the thread was annealed for 24 hours at a temperature of 100 ° C.
  • the polyurethane elastomer thread produced according to this example was no longer soluble in DMA / DMF, which indicates the presence of allophanate crosslinking.
  • the thread showed a thread that was conventionally melt-spun significantly improved thread properties (see table)
  • Example 1 was repeated, but only 25.6 g (0.152 mmol) of HDI were used, ie a stochiometric amount without excess, based on PTHF and butenediol
  • the thread properties of the threads obtained in Examples 1 and 2 were determined.
  • the force-elongation measurements were carried out on a Zwick tensile testing machine from Zwick. All measurements were carried out in a standard atmosphere. The measurement methods are based on DIN 53835 for determining the tensile strength and elongation at break the following device parameters were selected: clamping length 50 mm, preload 0 N,
  • Test speed 500 mm / min The determination of the residual elongation was carried out in accordance with DIN 53835 Part 2 The fibers were subjected to repeated repeated loading and unloading between constant yield strengths. The device recorded the first and fifth loading and unloading cycles Residual strains and the textile mechanical key figure b w 5 The residual strain e 5 residual is that
  • Ratio of remaining length change (1 in the first or fifth expansion cycle to original measuring length 1 0 of the sample The dimensionless index b w , s describes the relative drop in force between the first and fifth expansion cycles.
  • the following device parameters were selected: clamping length 100 mm, elongation 300%, preload force 0.01 cN / tex, test speed 500 mm / min, number of
  • the HDT (Heat Distortion Temperature) temperature was determined based on A TMA 7 device from Perkin Elmer with the following settings determines static force 0.002 cN / dtex, 2 K / min. The results are summarized in the table
  • Example 1 was repeated, but the polymer melt was annealed at 80 ° C. for 20 h before spinning in order to form allophanate crosslinks in the polymer.
  • the spinning temperature required for spinning the allophanate crosslinked polyurethane was 230 ° C. (residence time about 1 h).
  • the spinnability was unsatisfactory.
  • the thread obtained showed high stickiness and low strength. Winding up this thread was not possible. Subsequent tempering of individual threads did not lead to any significant
  • the thread obtained according to Example 1 was treated with an electron beam hardening system

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Artificial Filaments (AREA)
EP98959871A 1997-12-10 1998-11-11 Verfahren zur herstellung von polyurethan-elastomerfäden und danach hergestellte fäden Withdrawn EP1040215A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19754886A DE19754886A1 (de) 1997-12-10 1997-12-10 Verfahren zur Herstellung von Polyurethan-Elastomerfäden und danach hergestellte Fäden
DE19754886 1997-12-10
PCT/EP1998/007195 WO1999029939A1 (de) 1997-12-10 1998-11-11 Verfahren zur herstellung von polyurethan-elastomerfäden und danach hergestellte fäden

Publications (1)

Publication Number Publication Date
EP1040215A1 true EP1040215A1 (de) 2000-10-04

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP98959871A Withdrawn EP1040215A1 (de) 1997-12-10 1998-11-11 Verfahren zur herstellung von polyurethan-elastomerfäden und danach hergestellte fäden

Country Status (7)

Country Link
US (1) US6485665B1 (ja)
EP (1) EP1040215A1 (ja)
JP (1) JP2001526328A (ja)
AU (1) AU1561799A (ja)
DE (1) DE19754886A1 (ja)
TW (1) TW422861B (ja)
WO (1) WO1999029939A1 (ja)

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US7763341B2 (en) 2004-01-23 2010-07-27 Century-Board Usa, Llc Filled polymer composite and synthetic building material compositions
CN101111353B (zh) 2004-06-24 2011-09-28 世纪-博得美国公司 用于三维泡沫产品的连续成型设备
US7794224B2 (en) 2004-09-28 2010-09-14 Woodbridge Corporation Apparatus for the continuous production of plastic composites
US20070071972A1 (en) * 2005-09-28 2007-03-29 Mccoy Kay M Textile fibers having soft hand characteristics and methods of making thereof
US8299136B2 (en) 2006-03-24 2012-10-30 Century-Board Usa, Llc Polyurethane composite materials
US20090311529A1 (en) * 2008-06-16 2009-12-17 Voith Patent Gmbh High tenacity thermoplastic polyurethane monofilament and process for manufacturing the same
JP5072910B2 (ja) * 2009-06-30 2012-11-14 ダンロップスポーツ株式会社 ゴルフボール
US9481759B2 (en) 2009-08-14 2016-11-01 Boral Ip Holdings Llc Polyurethanes derived from highly reactive reactants and coal ash
US8846776B2 (en) 2009-08-14 2014-09-30 Boral Ip Holdings Llc Filled polyurethane composites and methods of making same
EP2573215A1 (en) * 2011-09-20 2013-03-27 Mölnlycke Health Care AB Polymer fibers
CA2851349C (en) 2011-10-07 2020-01-21 Russell L. Hill Inorganic polymer/organic polymer composites and methods of making same
WO2014168633A1 (en) 2013-04-12 2014-10-16 Boral Ip Holdings (Australia) Pty Limited Composites formed from an absorptive filler and a polyurethane
US10138341B2 (en) 2014-07-28 2018-11-27 Boral Ip Holdings (Australia) Pty Limited Use of evaporative coolants to manufacture filled polyurethane composites
WO2016022103A1 (en) 2014-08-05 2016-02-11 Amitabha Kumar Filled polymeric composites including short length fibers
US9988512B2 (en) 2015-01-22 2018-06-05 Boral Ip Holdings (Australia) Pty Limited Highly filled polyurethane composites
WO2016195717A1 (en) 2015-06-05 2016-12-08 Boral Ip Holdings (Australia) Pty Limited Filled polyurethane composites with lightweight fillers
WO2017082914A1 (en) 2015-11-12 2017-05-18 Boral Ip Holdings (Australia) Pty Limited Filled polyurethane composites with size-graded fillers

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Also Published As

Publication number Publication date
WO1999029939A1 (de) 1999-06-17
AU1561799A (en) 1999-06-28
JP2001526328A (ja) 2001-12-18
DE19754886A1 (de) 1999-06-17
TW422861B (en) 2001-02-21
US6485665B1 (en) 2002-11-26

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