EP0503421B1 - Polyester fibres modified with carbodiimides and process for their preparation - Google Patents
Polyester fibres modified with carbodiimides and process for their preparation Download PDFInfo
- Publication number
- EP0503421B1 EP0503421B1 EP92103536A EP92103536A EP0503421B1 EP 0503421 B1 EP0503421 B1 EP 0503421B1 EP 92103536 A EP92103536 A EP 92103536A EP 92103536 A EP92103536 A EP 92103536A EP 0503421 B1 EP0503421 B1 EP 0503421B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polyester
- filaments
- fibers
- ppm
- polycarbodiimide
- 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.)
- Expired - Lifetime
Links
- 229920000728 polyester Polymers 0.000 title claims abstract description 90
- 150000001718 carbodiimides Chemical group 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 15
- 230000008569 process Effects 0.000 title claims abstract description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 5
- 239000000835 fiber Substances 0.000 claims description 31
- 238000007792 addition Methods 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 10
- 238000009987 spinning Methods 0.000 claims description 10
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 4
- 229960005215 dichloroacetic acid Drugs 0.000 claims description 4
- 150000001555 benzenes Chemical class 0.000 claims description 2
- 239000012141 concentrate Substances 0.000 claims description 2
- 238000011144 upstream manufacturing Methods 0.000 claims 1
- -1 polyethylene terephthalate Polymers 0.000 description 11
- 230000003301 hydrolyzing effect Effects 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000000155 melt Substances 0.000 description 5
- 230000006641 stabilisation Effects 0.000 description 5
- 238000011105 stabilization Methods 0.000 description 5
- 238000006068 polycondensation reaction Methods 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical class OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000010309 melting process Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920001567 vinyl ester resin Polymers 0.000 description 2
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- 125000003580 L-valyl group Chemical group [H]N([H])[C@]([H])(C(=O)[*])C(C([H])([H])[H])(C([H])([H])[H])[H] 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- IFVTZJHWGZSXFD-UHFFFAOYSA-N biphenylene Chemical group C1=CC=C2C3=CC=CC=C3C2=C1 IFVTZJHWGZSXFD-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000004992 fission Effects 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 229920006253 high performance fiber Polymers 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- CMESPBFFDMPSIY-UHFFFAOYSA-N n,n'-diphenylmethanediimine Chemical compound C1=CC=CC=C1N=C=NC1=CC=CC=C1 CMESPBFFDMPSIY-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- 230000006855 networking Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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
- D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
-
- 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
-
- 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
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
Definitions
- the invention relates to synthetic fibers made of polyesters, prefers polyester monofilaments, which are made by adding a Combination of mono- and polycarbodiimides against the thermal and especially hydrolytic degradation have been stabilized and appropriate procedures for their Manufacturing.
- Polyester molecules are split such that for example, in the case of a polyethylene terephthalate Splitting of the ester bond to form one Carboxyl end group and a vinyl ester takes place, the Vinyl ester then with elimination of acetaldehyde reacted further.
- thermal decomposition will especially by the level of the reaction temperature, the Dwell time and possibly by the nature of the Polycondensation catalyst influenced.
- the hydrolysis resistance is one Polyester strongly by the number of carboxyl end groups per Weight unit pending. It is known to be an improvement to achieve hydrolysis resistance by the fact that this Carboxyl end groups closed by chemical reactions will. As such a "closure" of the carboxyl end groups are already multiple reactions with aliphatic, aromatic, but also cycloaliphatic mono-, bis- or Polycarbodiimides have been described.
- JP-AS 1-15604 / 89 can be removed, it is for the desired thermal and hydrolytic resistance of threads made therefrom of particular importance that in the finished threads or Monofilaments still contain free carbodiimide because otherwise, for example, among the very aggressive Conditions in a paper machine such materials would soon be unusable.
- the JP-AS is still closed see that the use of polycarbodiimides not corresponds to the state of the art already achieved.
- the subject of the invention are therefore Polyester fibers and filaments, in which the closure of the Carboxyl end groups predominantly by reaction with mono- and / or Biscarbodiimiden takes place, the fibers and filaments according to the invention, however, only 30 to 200 ppm of these Contain carbodiimides in free form and the content of free mono-carbodiimides is not 33 ppm.
- polyester content of free mono- and / or biscarbodiimides should in principle be as low as possible, it has now been found that fibers and filaments which do not contain more than 200 ppm of these substances in free form are very suitable for applications in Equipment that is completely closed or that is equipped with systems for cleaning exhaust air and waste water is suitable.
- An example of such an application of the fibers and filaments according to the invention is their use for the production of paper machine screens.
- polyester fibers and filaments still contain at least 0.02% of at least one polycarbodiimide, this polycarbodiimide in free form or with at least some reactive carbodiimide groups.
- the desired polyester fibers and filaments with significantly improved resistance to thermal and / or hydrolytic attack should contain less than 3 meq / kg carboxyl end groups in the polyester. Fibers and filaments in which the number of carboxyl end groups has been reduced to less than 2, preferably even less than 1.5 meq / kg polyester are preferred.
- the content of free mono- and / or bis-carbodiimides should preferably be 30 to 150 ppm, in particular 30 to 100 ppm, based on the weight of the polyester. This applies on the condition that the content of monocarbodiimide is not 33 ppm. It must be ensured that the fibers and filaments still contain polycarbodiimides or their reaction products with groups which are still reactive. Concentrations of 0.05 to 0.6, in particular 0.1 to 0.5% by weight of polycarbodiimide in the polyester fibers and filaments are preferred.
- the molecular weight of suitable carbodiimides is between 2000 and 15000, preferably between 5000 and about 10000.
- polyesters that have a high, medium molecular weight, corresponding to an intrinsic viscosity (intrinsic viscosity) of at least 0.64 [dl / g].
- intrinsic viscosity intrinsic viscosity
- the process according to the invention for producing the claimed stabilized polyester fibers and filaments consists in the addition of mono- and / or biscarbodiimide in an amount of 0.5% by weight or less, based on polyester, and additionally in an amount of at least 0.05% by weight of a polycarbodiimide .
- the amounts of mono- and / or biscarbodiimides and of polycarbodiimides are selected so that the resulting polyester is 30 to 200 ppm, preferably 30 to 150 ppm, in particular 30 to 100 Contains ppm of mono- and / or biscarbodiimides and at least 0.02% by weight of polycarbodiimides and the content of free monocarbodiimide is not 33 ppm.
- This mixture of polyester and carbodiimides can be spun in a known manner to form threads and monofilaments or staple fibers and processed further.
- polyesters to be used are less than 20, preferably even less than 10 meq carboxyl end groups should have per kg. In these values is already the Increase due to melting has also been taken into account.
- Polyesters and carbodiimides are not at high temperatures to store for any length of time. It was already mentioned above noted that when melting polyesters additional Carboxyl end groups arise. Even the ones used Carbodiimides can at high temperatures Decompose polyester melts. It is therefore desirable that Contact or reaction time of the carbodiimide additives with the to limit molten polyesters as much as possible. When in use of melt extruders, it is possible to spend this time in the molten state to less than 5, preferably less less than 3 minutes. A limitation of Melting time in the extruder is only given by the fact that for a perfect reaction between carbodiimide and polyester carboxyl end groups sufficient mixing of the Reactants must take place. This can be done by appropriate Design of the extruder or, for example, by use by static mixers.
- polyesters i.e. aliphatic / aromatic polyesters such as e.g. Polyethylene terephthalate or polybutylene terephthalate, but also completely aromatic and for example Halogenated polyesters can be used in the same way.
- Building blocks of thread-forming polyesters are preferred Diols and dicarboxylic acids, or correspondingly constructed Oxycarboxylic acids.
- the main acid component of the polyester is Terephthalic acid, of course others are also suitable preferably para- or trans-permanent connections such as e.g. 2,6-naphthalenedicarboxylic acid but also p-hydroxybenzoic acid call.
- Typical suitable dihydric alcohols would be for example ethylene glycol, propanediol, 1,4-butanediol also hydroquinone, etc.
- Preferred aliphatic diols have two up to four carbon atoms.
- Ethylene glycol is particularly preferred.
- Longer-chain diols can, however, be used in proportions of up to approx. 20 mol%, preferably less than 10 mol% for modification of the properties are used.
- Polyester fibers and filaments the predominant or consist entirely of polyethylene terephthalate and especially those that have a molecular weight an intrinsic viscosity (intrinsic viscosity) of at least 0.64, preferably at least 0.70 [dl / g].
- the Intrinsic viscosities are in dichloroacetic acid at 25 ° C certainly.
- the stabilization of the filaments according to the invention or fibers by adding a combination of one Mono- and / or biscarbodiimide on one side and one polymeric carbodiimide achieved on the other hand.
- the use of monocarbodiimides is preferred since they are especially by a high reaction rate the reaction with the carboxyl end groups of the polyester award.
- polyesters after the polycondensation remaining carboxyl groups should according to the invention Process mainly by reaction with a mono- or
- Biscarbodiimide be closed. A lower proportion the carboxyl end groups is among these according to the invention Conditions also with carbodiimide groups in addition used polycarbodiimide react.
- the polyester fibers and filaments of the invention therefore contain instead of the carboxyl end groups in essentially their reaction products with those used Carbodiimides.
- Mono- or bis-carbodiimides which only if at all, to a very small extent in free form in the Fibers and filaments may occur are the known, Aryl, alkyl and cycloalkyl carbodiimides.
- Both Diarylcarbodiimides, which are preferably used, the aryl nuclei may be unsubstituted. Preferably however, are substituted in the 2- or 2,6-position and thus sterically hindered aromatic carbodiimides used.
- DE-AS 1 494 009 Variety of monocarbodiimides with steric disabilities the carbodiimide group listed.
- N, N '- (di-o-tolyl) carbodiimide and the N, N '- (2,6,2', 6'-tetraisopropyl) diphenyl carbodiimide are particularly suitable for example, of the monocarbodiimides, the N, N '- (di-o-tolyl) carbodiimide and the N, N '- (2,6,2', 6'-tetraisopropyl) diphenyl carbodiimide.
- Biscarbodiimide, which according to the Invention are suitable, for example, in DE-OS 20 20 330.
- compounds are polycarbodiimides suitable in which the carbodiimide units on or doubly substituted aryl nuclei linked together are, as aryl nuclei phenylene, naphthylene, diphenylene and the divalent radical derived from diphenylmethane in Come into consideration and the substituents according to type and The place of substitution is the substituent in the aryl nucleus correspond to substituted mono-diarylcarbodiimides.
- a particularly preferred polycarbodiimide is the commercially available aromatic polycarbodiimide, which is substituted with isopropyl groups in the o-position to the carbodiimide groups, ie in the 2,6- or 2,4,6-position on the benzene nucleus.
- the polycarbodiimides contained free or bound in the polyester filaments according to the invention preferably have an average molecular weight of from 2000 to 15,000, but in particular from 5,000 to 10,000. As already stated above, these polycarbodiimides react with the carboxyl end groups at a significantly lower rate. If such a reaction occurs, preferably only one group of the carbodiimide will initially react.
- the other groups present in the polymeric carbodiimide lead to the desired depot effect and are the cause of the substantially improved stability of the fibers and filaments obtained.
- the polymeric carbodiimides present in them have not yet been completely reacted, but instead have free carbodiimide groups for trapping further carboxyl end groups.
- polyester fibers and filaments produced according to the invention usual additives such as Titanium dioxide as Matting agents or additives for example for Improve the dyeability or to reduce electrostatic charges included.
- additives such as Titanium dioxide as Matting agents or additives for example for Improve the dyeability or to reduce electrostatic charges included.
- additions or comonomers are of course also suitable the flammability of the fibers and filaments produced can reduce in a known manner.
- Colored pigments, soot or soluble Dyes are incorporated into the polyester melt or already included.
- Polymers e.g. Polyolefins, polyesters, polyamides or polytetrafluoroethylene it is possible, if necessary to achieve completely new textile-technical effects. Also the Addition of cross-linking substances and similar additives can bring advantages for selected areas of application.
- polyester fibers and filaments As already stated above for the production of the polyester fibers and filaments according to the invention Mixing and melting required. Preferably can this melting in the melt extruder directly before actual spinning process take place.
- the addition of the Carbodiimide can be added to the polyester chips, Impregnate the polyester material before the extruder suitable solutions of the carbodiimides, but also by Breading or the like.
- Another type of Additive is especially for the metering of the polymer Carbodiimide, the production of master batches in Polyester (masterbatches). With these concentrates it can Polyester material to be treated directly in front of the extruder or, when using for example one Twin screw extruder, also mixed in the extruder will. If the polyester material to be spun is not is in chip form, but for example continuously as Corresponding melt must be delivered Metering devices for the carbodiimide optionally in melted form, can be provided.
- the amount of the Amount of mono and / or to be added in individual cases Biscarbodiimides according to the carboxyl end group content of the starting polyester taking into account the probable at the Melting process still occurring additional Carboxyl end groups.
- a preferred form of addition for the Polycarbodiimide represents the addition of base batches, which have a higher percentage, e.g. 15% Polycarbodiimide in a conventional polymer Contain polyester granulate.
- the dwell time of the Carbodiimides in the melt preferably less than 5 min, in particular be less than 3 minutes.
- Quantities of mono- or biscarbodiimide largely quantitative, i.e. they are then no longer in free form in the squeezed threads detectable. It also responds to a percentage, albeit a significantly lower one some of the carbodiimide groups used Polycarbodiimides, which primarily function as a depot take over.
- the temperature in the first stage stretching was 80 ° C and in the second stage 90 ° C, the Running speed of the spinning threads after leaving the Quench bath was 32 m / min. Subsequently, one Heat setting in a fixing channel at one temperature of 275 ° C. All spun monofilaments had a final diameter of 0.4 mm.
- Example 1 was also used here for comparison purposes repeated. However, this time an amount of 0.876% by weight of the polycarbodiimide described above in the form of a 15% masterbatch. This attempt was made carried out once again the information in the previous literature check after which even with a noticeable excess of polycarbodiimide, probably due to the low Responsiveness, one over the prior art reduced thermal and hydrolytic resistance can be observed. This example clearly shows that this is actually the case. It is interesting that this is chosen Amount of polycarbodiimide already at a noticeable Crosslinking of the polyester seems to result, as from the significant increase in intrinsic viscosity values can be. Generally, such networking is with thread-forming polymers only within narrow limits permissible if it is strictly reproducible and none Difficulty in spinning or difficulty in drawing the threads made from it are to be expected.
- Example 1 The procedure according to Example 1 or Example 2 was repeated, but now amounts of monocarbodiimide were added, resulting from the stoichiometric calculated value or a 20% excess Monocarbodiimide result. Even those preserved here Results are shown in the table below.
- a run 4a was exactly the stoichiometrically required Amount of monocarbodiimide added while in one run 4b an excess of 1.3 meq / kg of monocarbodiimide was used.
- the relative residual strengths found after a Treatment at 135 ° C in a steam atmosphere after a Time of 80 hours not state of the art. An excess of approx.
- Example 1 was repeated, but this time, in addition to monocarbodiimide, a polycarbodiimide was also used according to the invention. In this experiment, 0.4% by weight of monocarbodiimide and 0.32% by weight of polycarbodiimide, based on polyester, were added.
- the monofilament thus produced was used to manufacture Paper machine screens are ideally suited.
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Artificial Filaments (AREA)
- Polyesters Or Polycarbonates (AREA)
- Paper (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Materials For Medical Uses (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Description
Gegenstand der Erfindung sind Chemiefasern aus Polyestern, bevorzugt Polyestermonofile, die durch den Zusatz einer Kombination von Mono- und Polycarbodiimiden gegen den thermischen und insbesondere den hydrolytischen Abbau stabilisiert worden sind sowie geeignete Verfahren zu ihrer Herstellung.The invention relates to synthetic fibers made of polyesters, prefers polyester monofilaments, which are made by adding a Combination of mono- and polycarbodiimides against the thermal and especially hydrolytic degradation have been stabilized and appropriate procedures for their Manufacturing.
Es ist bekannt, daß bei einer thermischen Belastung Polyestermoleküle derart gespalten werden, daß beispielsweise bei einem Polyäthylenterephthalat die Aufspaltung der Esterbindung unter Ausbildung einer Carboxylendgruppe und eines Vinylesters erfolgt, wobei der Vinylester dann unter Abspaltung von Acetaldehyd weiterreagiert. Eine derartige thermische Zersetzung wird vor allem durch die Höhe der Reaktionstemperatur, die Verweilzeit und möglicherweise durch die Natur des Polykondensationskatalysators beeinflußt.It is known that with thermal stress Polyester molecules are split such that for example, in the case of a polyethylene terephthalate Splitting of the ester bond to form one Carboxyl end group and a vinyl ester takes place, the Vinyl ester then with elimination of acetaldehyde reacted further. Such thermal decomposition will especially by the level of the reaction temperature, the Dwell time and possibly by the nature of the Polycondensation catalyst influenced.
Im Gegensatz dazu ist die Hydrolysebeständigkeit eines Polyesters stark von der Zahl an Carboxylendgruppen pro Gewichtseinheit anhängig. Es ist bekannt, eine Verbesserung der Hydrolysebständigkeit dadurch zu erreichen, daß diese Carboxylendgruppen durch chemische Umsetzungen verschlossen werden. Als derartiger "Verschluß" der Carboxylendgruppen sind bereits mehrfach Umsetzungen mit aliphatischen, aromatischen, aber auch cycloaliphatischen Mono-, Bis- oder Polycarbodiimiden beschrieben worden.In contrast, the hydrolysis resistance is one Polyester strongly by the number of carboxyl end groups per Weight unit pending. It is known to be an improvement to achieve hydrolysis resistance by the fact that this Carboxyl end groups closed by chemical reactions will. As such a "closure" of the carboxyl end groups are already multiple reactions with aliphatic, aromatic, but also cycloaliphatic mono-, bis- or Polycarbodiimides have been described.
So werden beispielsweise in der DE-OS 1 770 495 stabilisierte Polyäthylenglykolterephthalate beschrieben, die durch Zusatz von Polycarbodiimiden erhalten wurden. Aufgrund der allgemein bei Polycarbodiimiden zu becbachtenden langsameren Reaktionsgeschwindigkeit ist es erforderlich, für eine längere Verweilzeit des Polycarbodiimids in der Polyesterschmelze zu sorgen. Aus diesem Grunde wurden Polycarbodiimide bereits bei der Polykondensationsreaktion der Polyester, d.h. bereits in deren Bildungsphase, zugesetzt. Ein derartiges Vorgehen ist jedoch mit einer Reihe von Nachteilen verbunden. Beispielsweise entstehen aufgrund der langen Verweilzeit eine Vielzahl von Nebenprodukten, gegebenenfalls wird auch die eigentliche Polykondensationsreaktion des Polyesters behindert.For example, in DE-OS 1 770 495 described stabilized polyethylene glycol terephthalates, which were obtained by adding polycarbodiimides. Because of the general case of polycarbodiimides Observing slower response speed is it required for a longer dwell time To ensure polycarbodiimide in the polyester melt. Out for this reason, polycarbodiimides were already used in the Polycondensation reaction of the polyesters, i.e. already in their formation phase, added. A however, such an approach is with a number of Disadvantages connected. For example, due to the long dwell time a large number of by-products, if necessary, the actual Polycondensation reaction of the polyester hindered.
Im Gegensatz dazu ist bekannt, daß Monocarbodiimide und Biscarbodiimide deutlich schneller mit Polyesterschmelzen reagieren. Aus diesem Grunde ist es möglich, die Zeit für das Vermischen und Reagieren soweit abzukürzen, daß ein Einsatz dieser Materialien gemeinsam mit den aufzuschmelzenden Polyestergranulaten direkt vor dem Spinnextruder erfolgen kann. Als Beispiele für den Einsatz von Biscarbodiimiden für diesen Zweck sei die DE-OS 20 20 330 genannt, für den Einsatz von Monocarbodiimiden die DE-AS 24 58 701 und die JA-AS 1-15604/89.In contrast, it is known that monocarbodiimides and Biscarbodiimide much faster with polyester melts react. Because of this, it is possible to take the time for to shorten the mixing and reacting to the extent that a Use of these materials together with those to be melted Polyester granules take place directly in front of the spinning extruder can. As examples of the use of biscarbodiimides DE-OS 20 20 330 is mentioned for this purpose, for which Use of monocarbodiimides DE-AS 24 58 701 and JA-AS 1-15604 / 89.
Die beiden letztgenannten Auslegeschriften sind speziell auf die Herstellung von stabilisierten Polyesterfilamenten ausgerichtet, wobei in beiden Fällen ein geringer Überschuß an Carbodiimid im fertigen Faden empfohlen wird. Gemäß DE-AS 24 58 701, Beispiele, soll der Überschuß über der stöchiometrisch benötigten Menge bis zu 7,5 m Val/kg Polyester betragen, während in der JA-AS 1-15604/89 ein Überschuß von 0,005 bis 1,5 Gew.-% an dem dort speziell empfohlenen Monocarbodiimid gefordert wird. Bei der Berechnung der stöchiometrisch notwendigen Menge wird in beiden Fällen berücksichtigt, daß durch das Aufschmelzen des Polymers zum Verspinnen noch ennige zusätzliche Carboxylgruppen durch thermischen Abbau entstehen, die ebenfalls verschlossen werden müssen. Wie insbesondere der JP-AS 1-15604/89 entnommen werden kann, ist es für die gewünschte thermische und hydrolytische Beständigkeit daraus erzeugter Fäden von besonderer Bedeutung, daß in den fertigen Fäden bzw. Monofilamenten noch freies Carbodiimid enthalten ist, da andernfalls beispielsweise unter den sehr agressiven Bedingungen in einer Papiermaschine derartige Materialien bald unbrauchbar sein würden. Der JP-AS ist weiterhin zu entnehmen, daß der Einsatz von Polycarbodiimiden nicht dem bereits erreichten Stand der Technik entspricht.The latter two interpretations are special on the production of stabilized polyester filaments aligned, in both cases a small excess of carbodiimide in the finished thread is recommended. According to DE-AS 24 58 701, examples, the excess should over stoichiometrically required amount up to 7.5 m Val / kg polyester amount, while in the JA-AS 1-15604 / 89 an excess of 0.005 to 1.5% by weight of what is specifically recommended there Monocarbodiimide is required. When calculating the stoichiometrically necessary amount is in both cases takes into account that by melting the polymer to Spinning a few additional carboxyl groups thermal degradation arise, which are also closed Need to become. Like in particular JP-AS 1-15604 / 89 can be removed, it is for the desired thermal and hydrolytic resistance of threads made therefrom of particular importance that in the finished threads or Monofilaments still contain free carbodiimide because otherwise, for example, among the very aggressive Conditions in a paper machine such materials would soon be unusable. The JP-AS is still closed see that the use of polycarbodiimides not corresponds to the state of the art already achieved.
Die ältere, nicht vorveröffentlichte EP-A-0417717 beschreibt Polyesterfasern und -filamente, die durch Umsetzung mit Carbodiimiden verschlossene Carboxylendgruppen enthalten. Beispiel 6 dieser Schrift beschreibt eine Faser, die neben einem Polycarbodiimid ein Mono-carbodiimid in einem Mengenanteil von 33 ppm, bezogen auf das Gesamtgewicht, enthält. The older, unpublished EP-A-0417717 describes polyester fibers and filaments which contain carboxyl end groups blocked by reaction with carbodiimides. Example 6 of this Scripture describes a fiber which, in addition to a polycarbodiimide, is a monocarbodiimide in one Amount of 33 ppm, based on the total weight, contains.
Nachteil aller bisher bekannten Verfahren, die mit einem Überschuß an Mono- oder Biscarbodiimiden arbeiten, ist, daß aufgrund der nicht zu vernachlässigenden Flüchtigkeit dieser Produkte und insbesondere der der thermisch und hydrolytisch erzeugten Spaltprodukte wie z.B. der entsprechenden Isocyanate und aromatischen Amine, mit einer merklichen Belastung von Bedienungspersonal und Umwelt gerechnet werden muß. Der Einsatz stabilisierter Polyesterfäden erfolgt aufgrund ihrer besonderen Eigenschaften üblicherweise bei höheren Temperaturen und meist in Gegenwart von Wasserdampf. Unter diesen Bedingungen ist eine derartige Belastung durch die überschüssigen Zusätze an Carbodiimid und Folgeprodukten zu erwarten. Aufgrund ihrer Flüchtigkeit ist zu erwarten, daß diese Verbindungen aus dem Polyester heraus diffundieren oder auch beispielsweise durch Lösungsmittel oder Mineralöle extrahiert werden können. Eine ausreichende Depotwirkung ist also auf Dauer nicht gewährleistet.Disadvantage of all previously known methods with a Working excess of mono- or biscarbodiimides is that due to the non-negligible volatility of these Products and especially that of thermal and hydrolytically generated fission products such as of the corresponding isocyanates and aromatic amines, with a noticeable strain on operating personnel and the environment must be expected. The use of stabilized Polyester threads are made because of their special Properties usually at higher temperatures and mostly in the presence of water vapor. Under these Conditions is such a burden from the excess additions of carbodiimide and secondary products expect. Due to their volatility, it can be expected that these compounds diffuse out of the polyester or also, for example, by solvents or Mineral oils can be extracted. Adequate The effect of a deposit is not guaranteed in the long term.
Bei diesem Stand der Technik bestand immer noch die Aufgabe, eine Stabilisierung von Polyesterfilamenten aufzufinden, bei der einerseits möglichst alle Carboxylendgruppen innerhalb kurzer Verweilzeiten verschlossen werden, auf der anderen Seite aber die Belästigung durch flüchtige Mono- bzw. Bis-Carbodiimide und ihre Folgeprodukte aufgrund der damit verbundenen Nachteile zumindest auf ein Minimum reduziert wird.With this state of the art there was still the task to find a stabilization of polyester filaments at on the one hand, if possible, all carboxyl end groups within short dwell times are locked on the other But the annoyance caused by volatile mono- or Bis-carbodiimides and their derivatives due to this associated disadvantages reduced to a minimum becomes.
Überraschend wurde gefunden, daß diese Aufgabe durch den Einsatz von Mischungen bestimmter Carbodiimide gelöst werden kann. Gegenstand der Erfindung sind daher Polyesterfasern und -filamente, bei denen der Verschluß der Carboxylendgruppen überwiegend durch Umsetzung mit Mono-und/oder Biscarbodiimiden erfolgt, die Fasern und Filamente gemäß der Erfindung jedoch nur 30 bis 200 ppm an diesen Carbodiimiden in freier Form enthalten und der Gehalt an freien Mono-Carbodiimiden nicht 33 ppm beträgt.It was surprisingly found that this task was accomplished by the Use of mixtures of certain carbodiimides solved can be. The subject of the invention are therefore Polyester fibers and filaments, in which the closure of the Carboxyl end groups predominantly by reaction with mono- and / or Biscarbodiimiden takes place, the fibers and filaments according to the invention, however, only 30 to 200 ppm of these Contain carbodiimides in free form and the content of free mono-carbodiimides is not 33 ppm.
Obwohl der Gehalt der Polyester an freien Mono- und/oder
Biscarbodiimiden grundsätzlich so niedrig wie möglich sein
sollte, hat sich jetzt herausgestellt, daß Fasern und
Filamente, die nicht mehr als 200 ppm dieser Substanzen in
freier Form enthalten, sich sehr gut für Anwendungen in
Apparaturen eignen, die völlig geschlossen sind oder die
mit Anlagen zur Reinigung von Abluft und Abwasser
ausgerüstet sind.
Ein Beispiel für eine derartige Anwendung der
erfindungsgemäßen Fasern und Filamente ist ihr Einsatz für
die Herstellung von Papiermaschinensieben.Although the polyester content of free mono- and / or biscarbodiimides should in principle be as low as possible, it has now been found that fibers and filaments which do not contain more than 200 ppm of these substances in free form are very suitable for applications in Equipment that is completely closed or that is equipped with systems for cleaning exhaust air and waste water is suitable.
An example of such an application of the fibers and filaments according to the invention is their use for the production of paper machine screens.
Um jedoch trotz der relativ geringen Menge an freien Mono-und/oder
Biscarbodiimiden die notwendige Stabilität z.B.
gegen Hydrolyse, zu zeigen ist es erforderlich, daß die
Polyesterfasern und -filamente zumindest noch 0.02 %
wenigstens eines
Polycarbodiimids enthalten, wobei dieses Polycarbodiimid in
freier Form oder mit wenigstens noch einigen
reaktionsfähigen Carbodiimidgruppen vorliegen sollte. Die
gewünschten Polyesterfasern und Filamente mit erheblich
verbesserten Beständigkeiten gegenüber thermischen und/oder
hydrolytischen Angriff sollten weniger als 3 mVal/kg
Carboxylendgruppen im Polyester enthalten. Bevorzugt sind
Fasern und Filamente, bei denen die Zahl der
Carboxylendgruppen auf weniger als 2, vorzugsweise sogar
weniger als 1,5 mVal/kg Polyester reduziert wurde. Der
Gehalt an freien Mono- und/oder Bis-Carbodiimiden sollte
vorzugsweise 30 bis 150 ppm, insbesondere 30 bis 100 ppm,
bezogen auf das Gewicht des Polyesters betragen. Dies gilt
unter der Bedingung, daß der Gehalt an Mono-Carbodiimid nicht 33 ppm beträgt.
Es ist dafür zu sorgen, daß in den Fasern und Filamenten
noch Polycarbodiimide oder deren Reaktionsprodukte mit noch
reaktionsfähigen Gruppen enthalten sind. Bevorzugt sind
Konzentrationen von 0,05 bis 0,6, insbesondere 0,1 bis 0,5
Gew.-% Polycarbodiimid in den Polyesterfasern und
-filamenten. Das Molekulargewicht geeigneter Carbodiimide
liegt zwischen 2000 und 15000, vorzugsweise zwischen 5000
und etwa 10000.
Zur Erzeugung von Hochleistungsfasern ist es erforderlich,
Polyester einzusetzen, die ein hohes, mittleres
Molekulargewicht aufweisen, entsprechend einer Intrinsic-Viskosität
(Grenzviskosität) von mindestens 0,64 [dl/g].
Die Messungen erfolgten in Dichloressigsäure bei 25°C.However, in order to demonstrate the necessary stability, for example against hydrolysis, despite the relatively small amount of free mono- and / or biscarbodiimides, it is necessary that the polyester fibers and filaments still contain at least 0.02% of at least one polycarbodiimide, this polycarbodiimide in free form or with at least some reactive carbodiimide groups. The desired polyester fibers and filaments with significantly improved resistance to thermal and / or hydrolytic attack should contain less than 3 meq / kg carboxyl end groups in the polyester. Fibers and filaments in which the number of carboxyl end groups has been reduced to less than 2, preferably even less than 1.5 meq / kg polyester are preferred. The content of free mono- and / or bis-carbodiimides should preferably be 30 to 150 ppm, in particular 30 to 100 ppm, based on the weight of the polyester. This applies on the condition that the content of monocarbodiimide is not 33 ppm. It must be ensured that the fibers and filaments still contain polycarbodiimides or their reaction products with groups which are still reactive. Concentrations of 0.05 to 0.6, in particular 0.1 to 0.5% by weight of polycarbodiimide in the polyester fibers and filaments are preferred. The molecular weight of suitable carbodiimides is between 2000 and 15000, preferably between 5000 and about 10000.
To produce high-performance fibers, it is necessary to use polyesters that have a high, medium molecular weight, corresponding to an intrinsic viscosity (intrinsic viscosity) of at least 0.64 [dl / g]. The measurements were carried out in dichloroacetic acid at 25 ° C.
Das erfindungsgemäße Verfahren zur Herstellung der
beanspruchten stabilisierten Polyesterfasern und -filamente
besteht in dem Zusatz von Mono- und/oder Biscarbodiimid in
einer Menge von 0.5 Gew.% oder weniger, bezogen auf
Polyester, und zusätzlich einer Menge von mindestens 0.05
Gew.% eines Polycarbodiimids.
Innerhalb dieser Mengenbereiche und unter Berücksichtigung
der Anzahl der im Ausgangspolyester enthaltenen Carboxyl-Endgruppen
werden die Mengen von Mono-und/oder
Biscarbodiimiden und von Polycarbodiimiden so gewählt, daß
der resultierende Polyester 30 bis 200 ppm, vorzugsweise
30 bis 150 ppm, insbesondere 30 bis 100 ppm Mono-und/oder
Biscarbodiimide und mindestens 0.02 Gew.% Polycarbodiimide
enthält und der Gehalt an freiem Mono-Carbodiimid nicht 33 ppm beträgt.
Diese Mischung aus Polyester und Carbodiimiden kann in
bekannter Weise zu Fäden und Monofilamenten oder
Stapelfasern versponnen und weiter verarbeitet werden. The process according to the invention for producing the claimed stabilized polyester fibers and filaments consists in the addition of mono- and / or biscarbodiimide in an amount of 0.5% by weight or less, based on polyester, and additionally in an amount of at least 0.05% by weight of a polycarbodiimide .
Within these quantitative ranges and taking into account the number of carboxyl end groups contained in the starting polyester, the amounts of mono- and / or biscarbodiimides and of polycarbodiimides are selected so that the resulting polyester is 30 to 200 ppm, preferably 30 to 150 ppm, in particular 30 to 100 Contains ppm of mono- and / or biscarbodiimides and at least 0.02% by weight of polycarbodiimides and the content of free monocarbodiimide is not 33 ppm. This mixture of polyester and carbodiimides can be spun in a known manner to form threads and monofilaments or staple fibers and processed further.
Gemäß der vorliegenden Erfindung ist es vorteilhaft, Polyester als Spinnmaterial einzusetzen, die bereits aufgrund ihrer Herstellung nur eine geringe Menge von Carboxylendgruppen aufweisen. Dies kann beispielsweise durch Einsatz des sogenannten Feststoffkondensationsverfahrens erfolgen. Es wurde gefunden, daß einzusetzende Polyester weniger als 20, vorzugsweise sogar weniger als 10 mVal Carboxylendgruppen pro kg aufweisen sollten. In diesen Werten ist bereits der Zuwachs durch das Aufschmelzen mit berücksichtigt worden.According to the present invention, it is advantageous Use polyester as spinning material, which already due to their production only a small amount of Have carboxyl end groups. For example by using the so-called Solid condensation process take place. It was found that polyesters to be used are less than 20, preferably even less than 10 meq carboxyl end groups should have per kg. In these values is already the Increase due to melting has also been taken into account.
Polyester und Carbodiimide sind bei hohen Temperaturen nicht beliebig lange zu lagern. Bereits weiter oben wurde darauf hingewiesen, daß beim Aufschmelzen von Polyestern zusätzliche Carboxylendgruppen entstehen. Auch die eingesetzten Carbodiimide können sich bei den hohen Temperaturen der Polyesterschmelzen zersetzen. Es ist daher wünschenswert, die Kontakt- bzw. Reaktionszeit der Carbodiimidzusätze mit den geschmolzenen Polyestern möglichst zu begrenzen. Bei Einsatz von Schmelzextrudern ist es möglich, diese Verweilszeit im geschmolzenen Zustand auf weniger als 5, vorzugsweise weniger als 3 Minuten herabzusetzen. Eine Begrenzung der Aufschmelzzeit im Extruder ist nur dadurch gegeben, daß für eine einwandfreie Reaktion zwischen Carbodiimid und Polyester-Carboxylendgruppen eine ausreichende Durchmischung der Reaktanten erfolgen muß. Dies kann durch entsprechende Ausgestaltung der Extruder oder beispielsweise durch Einsatz von statischen Mischern erfolgen.Polyesters and carbodiimides are not at high temperatures to store for any length of time. It was already mentioned above noted that when melting polyesters additional Carboxyl end groups arise. Even the ones used Carbodiimides can at high temperatures Decompose polyester melts. It is therefore desirable that Contact or reaction time of the carbodiimide additives with the to limit molten polyesters as much as possible. When in use of melt extruders, it is possible to spend this time in the molten state to less than 5, preferably less less than 3 minutes. A limitation of Melting time in the extruder is only given by the fact that for a perfect reaction between carbodiimide and polyester carboxyl end groups sufficient mixing of the Reactants must take place. This can be done by appropriate Design of the extruder or, for example, by use by static mixers.
Im Prinzip sind für den Einsatz gemäß der vorliegenden Erfindung alle fadenbildenden Polyester geeignet, d.h. aliphatisch/aromatische Polyester wie z.B. Polyäthylenterephthalate oder Polybutylenterephthalate, aber auch vollständig aromatische und beispielsweise halogenierte Polyester sind in gleicher Weise einsetzbar. Bausteine von fadenbildenden Polyestern sind vorzugsweise Diole und Dicarbonsäuren, bzw. entsprechend aufgebaute Oxycarbonsäuren. Hauptsäurebestandteil der Polyester ist die Terephthalsäure, als geeignet sind natürlich auch andere vorzugsweise para- oder trans-ständige Verbindungen wie z.B. 2,6-Naphthalindicarbonsäure aber auch p-Hydroxybenzoesäure zu nennen. Typische geeignete zweiwertige Alkohole wären beispielsweise Ethylenglykol, Propandiol, 1,4-Butandiol aber auch Hydrochinon usw. Bevorzugte aliphatische Diole haben zwei bis vier C-Atome. Besonders bevorzugt ist Ethylenglykol. Längerkettige Diole können aber in Anteilen bis zu ca. 20 Mol-%, vorzugsweise weniger als 10 Mol-% zur Modifizierung der Eigenschaften eingesetzt werden.In principle, are for use according to the present Invention suitable for all thread-forming polyesters, i.e. aliphatic / aromatic polyesters such as e.g. Polyethylene terephthalate or polybutylene terephthalate, but also completely aromatic and for example Halogenated polyesters can be used in the same way. Building blocks of thread-forming polyesters are preferred Diols and dicarboxylic acids, or correspondingly constructed Oxycarboxylic acids. The main acid component of the polyester is Terephthalic acid, of course others are also suitable preferably para- or trans-permanent connections such as e.g. 2,6-naphthalenedicarboxylic acid but also p-hydroxybenzoic acid call. Typical suitable dihydric alcohols would be for example ethylene glycol, propanediol, 1,4-butanediol also hydroquinone, etc. Preferred aliphatic diols have two up to four carbon atoms. Ethylene glycol is particularly preferred. Longer-chain diols can, however, be used in proportions of up to approx. 20 mol%, preferably less than 10 mol% for modification of the properties are used.
Für besondere technische Aufgaben haben sich jedoch besonders hochmolekulare Polymerisate aus reinem Polyäthylenterephthalat und deren Copolymerisate mit geringen Zusätzen an Comonomeren bewährt, sofern die Temperaturbelastung den Eigenschaften von Polyäthylenterephthalat überhaupt gerecht wird. Andernfalls ist auf geeignete bekannte vollaromatische Polyester auszuweichen.For special technical tasks, however, have become special high molecular weight polymers made from pure polyethylene terephthalate and their copolymers with low additions of comonomers proven, provided that the temperature load the properties of polyethylene terephthalate at all. Otherwise is known to be suitable fully aromatic polyester to dodge.
Besonders bevorzugt sind demzufolge erfindungsgemäße Polyesterfasern und -filamente, die überwiegend oder vollständig aus Polyäthylenterephthalat bestehen und insbesondere solche, die ein Molekulargewicht entsprechend einer Intrinsic-Viskosität (Grenzviskosität) von mindestens 0,64, vorzugsweise mindestens 0,70 [dl/g] aufweisen. Die Intrinsic-Viskositäten werden in Dichloressigsäure bei 25°C bestimmt. Die Stabilisierung der erfindungsgemäßen Filamente bzw. Fasern wird durch Zugabe einer Kombination von einem Mono- und/oder Biscarbodiimid auf der einen Seite und einem polymeren Carbodiimid auf der anderen Seite erreicht. Bevorzugt ist der Einsatz von Monocarbodiimiden, da sie sich insbesondere durch eine hohe Reaktionsgeschwindigkeit bei der Umsetzung mit den Carboxylendgruppen des Polyesters auszeichnen. Sie können jedoch, falls gewünscht, teilweise oder vollständig durch entsprechende Mengen an Biscarbodiimiden ersetzt werden, um die bei diesen Verbindungen schon bemerkbare geringere Flüchtigkeit auszunutzen. In diesem Fall ist jedoch dafür Sorge zu tragen, daß die Kontaktzeit ausreichend lang gewählt wird, um auch bei Einsatz von Biscarbodiimiden beim Mischen und Einschmelzen im Schmelzextruder eine ausreichende Reaktion sicherzustellen.Accordingly, particular preference is given to the invention Polyester fibers and filaments, the predominant or consist entirely of polyethylene terephthalate and especially those that have a molecular weight an intrinsic viscosity (intrinsic viscosity) of at least 0.64, preferably at least 0.70 [dl / g]. The Intrinsic viscosities are in dichloroacetic acid at 25 ° C certainly. The stabilization of the filaments according to the invention or fibers by adding a combination of one Mono- and / or biscarbodiimide on one side and one polymeric carbodiimide achieved on the other hand. The use of monocarbodiimides is preferred since they are especially by a high reaction rate the reaction with the carboxyl end groups of the polyester award. However, you can, if desired, partially or completely by appropriate amounts Biscarbodiimides are replaced by those in these compounds to use already noticeable lower volatility. In In this case, however, care must be taken to ensure that the Contact time is chosen to be long enough, even at Use of biscarbodiimides in mixing and melting ensure a sufficient reaction in the melt extruder.
Die in den Polyestern nach der Polykondensation noch verbliebenen Carboxylgruppen sollen gemäß dem erfindungsgemäßen Verfahren überwiegend durch Reaktion mit einem Mono- bzw.Those in the polyesters after the polycondensation remaining carboxyl groups should according to the invention Process mainly by reaction with a mono- or
Biscarbodiimid verschlossen werden. Ein geringerer Anteil der Carboxylendgruppen wird unter diesen erfindungsgemäßen Bedingungen auch mit Carbodiimidgruppen des zusätzlich eingesetzten Polycarbodiimids reagieren.Biscarbodiimide be closed. A lower proportion the carboxyl end groups is among these according to the invention Conditions also with carbodiimide groups in addition used polycarbodiimide react.
Die erfindungsgemäßen Polyesterfasern und Filamente enthalten daher anstelle der Carboxylendgruppen im wesentlichen deren Reaktionsprodukte mit den eingesetzten Carbodiimiden. Mono- bzw. Bis-Carbodiimide, die nur, wenn überhaupt, in sehr geringem Maße in freier Form in den Fasern und Filamenten vorkommen dürfen, sind die bekannten, Aryl-, Alkyl- und Cycloalkyl-Carbodiimide. Bei den Diarylcarbodiimiden, die bevorzugt eingesetzt werden, können die Arylkerne unsubstituiert sein. Vorzugsweise werden jedoch in 2- oder 2,6-Stellung substituierte und damit sterisch gehinderte aromatische Carbodiimide eingesetzt. Bereits in der DE-AS 1 494 009 wird eine Vielzahl von Monocarbodiimiden mit sterischer Behinderung der Carbodiimidgruppe aufgezählt. Besonders geeignet sind beispielsweise von den Monocarbodiimiden das N,N'-(Di-o-tolyl)-carbodiimid und das N,N'-(2,6,2',6'-Tetraisopropyl)-diphenyl-carbodiimid. Biscarbodiimide, die gemäß der Erfindung geeignet sind, werden beispielsweise in der DE-OS 20 20 330 beschrieben.The polyester fibers and filaments of the invention therefore contain instead of the carboxyl end groups in essentially their reaction products with those used Carbodiimides. Mono- or bis-carbodiimides, which only if at all, to a very small extent in free form in the Fibers and filaments may occur are the known, Aryl, alkyl and cycloalkyl carbodiimides. Both Diarylcarbodiimides, which are preferably used, the aryl nuclei may be unsubstituted. Preferably however, are substituted in the 2- or 2,6-position and thus sterically hindered aromatic carbodiimides used. Already in DE-AS 1 494 009 Variety of monocarbodiimides with steric disabilities the carbodiimide group listed. Are particularly suitable for example, of the monocarbodiimides, the N, N '- (di-o-tolyl) carbodiimide and the N, N '- (2,6,2', 6'-tetraisopropyl) diphenyl carbodiimide. Biscarbodiimide, which according to the Invention are suitable, for example, in DE-OS 20 20 330.
Als Polycarbodiimide sind erfindungsgemäß Verbindungen geeignet, bei denen die Carbodiimideinheiten über ein- oder zweifach substituierter Arylkerne miteinander verbunden sind, wobei als Arylkerne Phenylen, Naphthylen, Diphenylen und der vom Diphenylmethan abgeleitete zweiwertige Rest in Betracht kommen und die Substituenten nach Art und Substitutionsort den Substituenten der im Arylkern substituierten Mono-Diarylcarbodiimiden entsprechen.According to the invention, compounds are polycarbodiimides suitable in which the carbodiimide units on or doubly substituted aryl nuclei linked together are, as aryl nuclei phenylene, naphthylene, diphenylene and the divalent radical derived from diphenylmethane in Come into consideration and the substituents according to type and The place of substitution is the substituent in the aryl nucleus correspond to substituted mono-diarylcarbodiimides.
Ein besonders bevorzugtes Polycarbodiimid ist das
handelsübliche aromatische Polycarbodiimid, das in
o-Stellung zu den Carbodiimidgruppen, d.h. in 2,6- oder
2,4,6-Stellung am Benzolkern mit Isopropylgruppen
substituiert ist.
Die in den erfindungsgemäßen Polyesterfilamenten frei oder
gebunden enthaltenen Polycarbodiimide haben vorzugsweise
ein mittleres Molekulargewicht von 2000 bis 15 000,
insbesondere jedoch von 5000 bis 10 000. Wie bereits oben
ausgeführt, reagieren diese Polycarbodiimide mit deutlich
geringerer Geschwindigkeit mit den Carboxylendgruppen.
Wenn es zu einer solchen Reaktion kommt, wird vorzugsweise
zunächst nur eine Gruppe des Carbodiimids reagieren. Die
weiteren im polymeren Carbodiimid vorhandenen Gruppen führen
jedoch zu der gewünschten Depotwirkung und sind die Ursache
für die wesentlich verbesserte Stabilität der erhaltenen
Fasern und Filamente. Für diese gewünschte thermische und
insbesondere hydrolytische Beständigkeit der geformten
Polyestermassen ist es daher entscheidend, daß die in ihnen
vorhandenen polymeren Carbodiimide noch nicht völlig umgesetzt
wurden, sondern noch freie Carbodiimidgruppen zum Abfangen
weiterer Carboxylendgruppen aufweisen.A particularly preferred polycarbodiimide is the commercially available aromatic polycarbodiimide, which is substituted with isopropyl groups in the o-position to the carbodiimide groups, ie in the 2,6- or 2,4,6-position on the benzene nucleus.
The polycarbodiimides contained free or bound in the polyester filaments according to the invention preferably have an average molecular weight of from 2000 to 15,000, but in particular from 5,000 to 10,000. As already stated above, these polycarbodiimides react with the carboxyl end groups at a significantly lower rate. If such a reaction occurs, preferably only one group of the carbodiimide will initially react. However, the other groups present in the polymeric carbodiimide lead to the desired depot effect and are the cause of the substantially improved stability of the fibers and filaments obtained. For this desired thermal and, in particular, hydrolytic resistance of the molded polyester compositions, it is therefore crucial that the polymeric carbodiimides present in them have not yet been completely reacted, but instead have free carbodiimide groups for trapping further carboxyl end groups.
Die erzeugten erfindungsgemäßen Polyesterfasern und Filamente können übliche Zusätze wie z.B. Titandioxyd als Mattierungsmittel bzw. Zusätze beispielsweise für Verbesserung der Anfärbbarkeit oder zur Verminderung von elektrostatischen Aufladungen enthalten. In gleicher Weise sind natürlich auch Zusätze oder Comonomere geeignet, die die Brennbarkeit der erzeugten Fasern und Filamente in bekannter Weise herabsetzen können. The polyester fibers and filaments produced according to the invention usual additives such as Titanium dioxide as Matting agents or additives for example for Improve the dyeability or to reduce electrostatic charges included. In the same way additions or comonomers are of course also suitable the flammability of the fibers and filaments produced can reduce in a known manner.
Es können auch z.B. Buntpigmente, Ruß oder lösliche Farbstoffe in der Polyesterschmelze eingearbeitet werden oder bereits enthalten sein. Durch Zumischen anderer Polymerer, wie z.B. Polyolefinen, Polyestern, Polyamiden oder Polytetrafluorethylenen ist es möglich, gegebenenfalls ganz neue textil-technische Effekte zu erzielen. Auch der Zusatz vernetzend wirkender Substanzen und ähnlicher Zusätze kann für ausgewählte Anwendungsgebiete Vorteile bringen.For example, Colored pigments, soot or soluble Dyes are incorporated into the polyester melt or already included. By adding others Polymers, e.g. Polyolefins, polyesters, polyamides or polytetrafluoroethylene it is possible, if necessary to achieve completely new textile-technical effects. Also the Addition of cross-linking substances and similar additives can bring advantages for selected areas of application.
Wie bereits oben ausgeführt ist zur Herstellung der erfindungsgemäßen Polyesterfasern und -filamente ein Vermischen und Aufschmelzen erforderlich. Vorzugsweise kann dieses Aufschmelzen im Schmelzextruder direkt vor dem eigentlichen Spinnvorgang erfolgen. Der Zusatz der Carbodiimide kann durch Beimischen zu den Polyesterchips, Imprägnieren des Polyestermaterials vor dem Extruder mit geeigneten Lösungen der Carbodiimide, aber auch durch Panieren oder ähnlichem erfolgen. Eine weitere Art des Zusatzes ist insbesondere für die Zudosierung der polymeren Carbodiimide, die Herstellung von Stammansätzen in Polyester (Masterbatches). Mit diesen Konzentraten kann das zu behandelnde Polyestermaterial direkt vor dem Extruder oder, bei Verwendung beispielsweise eines Doppelschneckenextruders, auch im Extruder vermischt werden. Falls das zu verspinnende Polyestermaterial nicht in Chipsform vorliegt, sondern beispielsweise laufend als Schmelze angeliefert wird, müssen entsprechende Dosiervorrichtungen für das Carbodiimid gegebenenfalls in aufgeschmolzener Form, vorgesehen werden.As already stated above for the production of the polyester fibers and filaments according to the invention Mixing and melting required. Preferably can this melting in the melt extruder directly before actual spinning process take place. The addition of the Carbodiimide can be added to the polyester chips, Impregnate the polyester material before the extruder suitable solutions of the carbodiimides, but also by Breading or the like. Another type of Additive is especially for the metering of the polymer Carbodiimide, the production of master batches in Polyester (masterbatches). With these concentrates it can Polyester material to be treated directly in front of the extruder or, when using for example one Twin screw extruder, also mixed in the extruder will. If the polyester material to be spun is not is in chip form, but for example continuously as Corresponding melt must be delivered Metering devices for the carbodiimide optionally in melted form, can be provided.
Wie bereits oben ausgeführt, richtet sich die Menge der im Einzelfall zuzusetzenden Menge von Mono-und/oder Biscarbodiimiden nach dem Carboxylendgruppengehalt des Ausgangspolyesters unter Berücksichtigung der voraussichtlich bei dem Aufschmelzvorgang noch entstehenden zusätzlichen Carboxylendgruppen. Hierbei ist darauf zu achten, daß nicht Verluste durch ein vorzeitiges Verdampfen der eingesetzten Mono- bzw. Biscarbodiimide auftreten. Eine bevorzugte Zugabeform für das Polycarbodiimid stellt die Zugabe von Stammansätzen dar, die einen höheren Prozentsatz, z.B. 15 %, an Polycarbodiimid in einem üblichen polymeren Polyestergranulat enthalten.As already explained above, the amount of the Amount of mono and / or to be added in individual cases Biscarbodiimides according to the carboxyl end group content of the starting polyester taking into account the probable at the Melting process still occurring additional Carboxyl end groups. Here is to ensure that there is no loss due to premature Evaporation of the mono- or biscarbodiimides used occur. A preferred form of addition for the Polycarbodiimide represents the addition of base batches, which have a higher percentage, e.g. 15% Polycarbodiimide in a conventional polymer Contain polyester granulate.
Besonders hingewiesen werden soll noch einmal auf die Gefahr von Nebenreaktionen, die bei der thermischen Belastung durch den gemeinsamen Schmelzvorgang sowohl für den Polyester als auch für die eingesetzten Carbodiimide bestehen. Aus diesem Grunde sollte die Verweilzeit der Carbodiimide in der Schmelze vorzugsweise weniger als 5 min, insbesondere weniger als 3 min betragen. Unter diesen Umständen reagieren bei guter Durchmischung die eingesetzten Mengen an Mono- bzw. Biscarbodiimid weitgehend quantitativ, d.h. sie sind anschließend nicht mehr in freier Form in den ausgepreßten Fäden nachweisbar. Darüberhinaus reagiert zu einem, wenn auch deutlich geringeren Prozentsatz, bereits ein Teil der Carbodiimidgruppen der eingesetzten Polycarbodiimide, die jedoch vor allen Dingen die Depotfunktion übernehmen. Durch diese Maßnahme ist es erstmals möglich geworden, Polyesterfasern und -filamente zu erzeugen, die wirksam und über einen sehr langen Zeitraum gegen thermischen und insbesondere gegen hydrolytischen Abbau geschützt sind, obwohl sie geringere Mengen an freien Mono-und/oder Biscarbodiimiden un deren Spalt- und Folgeprodukten enthalten als vergleichbar gute bekannte Produkte, wobei die geringen Mengen dieser Substanzen durch Abluft- und Abwasserreinigungsmaßnahmen soweit entfernt werden können, daß sie nicht zur Belästigung oder Schädigung der Umwelt führen. Durch die Anwesenheit von polymeren Carbodiimiden wird erreicht, daß die gewünschte Langzeitstabilisierung der so behandelten Polyestermaterialien gewährleistet ist. Es ist überraschend, daß diese Funktion durch die Polycarbodiimide zuverlässig erfolgt, obwohl Stabilisierungsversuche unter alleinigem Einsatz dieser Verbindungen nicht zu der geforderten Stabilisierung geführt haben.Particular attention should be drawn to the Danger of side reactions in the thermal Burden of the common melting process for both the polyester as well as for the carbodiimides used consist. For this reason, the dwell time of the Carbodiimides in the melt, preferably less than 5 min, in particular be less than 3 minutes. Under these Circumstances react well with thorough mixing Quantities of mono- or biscarbodiimide largely quantitative, i.e. they are then no longer in free form in the squeezed threads detectable. It also responds to a percentage, albeit a significantly lower one some of the carbodiimide groups used Polycarbodiimides, which primarily function as a depot take over. This measure makes it possible for the first time become to produce polyester fibers and filaments that effective and against a very long period of time thermal and especially against hydrolytic degradation are protected, although they have smaller amounts of free Mono- and / or biscarbodiimides and their cleavage and Subsequent products contain known as comparably good Products, the small amounts of these substances through exhaust air and wastewater treatment measures so far can be removed that they are not for nuisance or Cause damage to the environment. Through the The presence of polymeric carbodiimides ensures that the desired long-term stabilization of the treated in this way Polyester materials is guaranteed. It’s surprising that this function is reliable due to the polycarbodiimides takes place, although attempts to stabilize under sole Use of these connections not to the required Have led to stabilization.
Durch Einsatz von polymeren Carbodiimiden für die Langzeitstabilisierung ergibt sich neben der geringeren thermischen Zersetzbarkeit und geringeren Flüchtigkeit dieser Verbindungen auch eine wesentlich größere Sicherheit in toxikologischer Hinsicht. Dies gilt insbesondere für alle die Polymermoleküle von Polycarbodiimiden, die bereits wenigstens mit einer Carbodiimidgruppe über eine Carboxylendgruppe des Polyesters mit dem Polyestermaterial chemisch verbunden wurden.By using polymeric carbodiimides for the Long-term stabilization results in addition to the lower thermal decomposability and lower volatility of these Connections also have a much greater security in toxicological. This applies in particular to everyone the polymer molecules of polycarbodiimides that already at least one carbodiimide group via one Carboxyl end group of the polyester with the polyester material were chemically linked.
Die folgenden Beispiele sollen zur Erläuterung der Erfindung dienen. Bei allen Beispielen wurde ein getrocknetes, feststoffkondensiertes Polyestergranulat mit einem mittleren Carboxylendgruppengehalt von 5 mVal/kg Polymerisat eingesetzt. Als monomeres Carbodiimid diente N,N'-2,2',6,6'-Tetraisopropyldiphenyl-carbodiimid. Das in den nachfolgend beschriebenen Versuchen eingesetzte polymere Carbodiimid war ein aromatisches Polycarbodiimid, das jeweils in o-Stellung, d.h. in 2,6- oder 2,4,6-Stellung, mit Isopropylgruppen substituierte Benzolkerne aufwies. Es wurde nicht im reinen Zustand, sondern als Masterbatch (15 % Polycarbodiimid in Polyethylenterephthalat) eingesetzt (Handelsprodukt ®Stabaxol KE 7646 der Rhein-Chemie, Rheinhausen, Deutschland). The following examples are intended to illustrate the invention to serve. In all examples, a dried, solid-condensed polyester granulate with a medium Carboxyl end group content of 5 meq / kg polymer used. N, N'-2,2 ', 6,6'-tetraisopropyldiphenylcarbodiimide was used as the monomeric carbodiimide. That described in the below Experimental polymeric carbodiimide was an aromatic Polycarbodiimide, each in the o-position, i.e. in 2,6- or 2,4,6-position, substituted with isopropyl groups Had benzene cores. It wasn’t in the pure state, but as a masterbatch (15% polycarbodiimide in Polyethylene terephthalate) used (commercial product ®Stabaxol KE 7646 from Rhein-Chemie, Rheinhausen, Germany).
Das Vermischen des Carbodiimides mit dem Masterbatch und dem Polymermaterial erfolgte in Behältern durch mechanisches Schütteln und Rühren. Anschließend wurde diese Mischung einem Einschneckenextruder der Fa. Reifenhäuser, Deutschland, Typ S 45 A vorgelegt. Die einzelnen Extruderzonen wiesen Temperaturen von 282 bis 293°C auf, der Extruder wurde mit einem Austrag von 500 g Schmelze/min gefahren unter Verwendung von üblichen Spinndüsen für Monofilamente. Verweilzeit der Mischungen im geschmolzenen Zustand 2,5 min. Die frisch ausgesponnenen Monofilamente wurden nach einer kurzen Luftstrecke in einem Wasserbad abgeschreckt und anschließend kontinuierlich zweistufig verstreckt. Das Verstreckungsverhältnis lag bei allen Versuchen bei 1:4,3. Die Temperatur bei der Verstreckung in der ersten Stufe betrug 80°C und in der zweiten Stufe 90°C, die Laufgeschwindigkeit der Spinnfäden nach Verlassen des Abschreckbades betrug 32 m/min. Im Anschluß wurde eine Thermofixierung in einem Fixierkanal bei einer Temperatur von 275°C durchgeführt.Sämtliche ausgesponnene Monofilamente wiesen einen Enddurchmesser von 0,4 mm auf. Als Stabilitätstest wurde die feinheitsbezogene Höchstzugkraft (= Reißfestigkeit) an den erhaltenen Monofilamenten einmal direkt nach der Erzeugung und ein zweites Mal nach Lagerung der Monofile bei 135°C in einer Wasserdampfatmosphäre nach 80 Stunden geprüft. Danach wurde erneut die Reißfestigkeit bestimmt und der Quotient aus Restreißfestigkeit und ursprünglicher Reißfestigkeit errechnet. Er ist ein Maß für die erreichte Stabilisierungswirkung der Zusätze.Mixing the carbodiimide with the masterbatch and The polymer material was done in containers by mechanical Shake and stir. Then this mixture a single-screw extruder from Reifenhäuser, Germany, Type S 45 A submitted. The individual extruder zones showed Temperatures from 282 to 293 ° C, the extruder was with a discharge of 500 g of melt / min of common spinnerets for monofilaments. Dwell time of Mixtures in the molten state 2.5 min. The fresh spun monofilaments were removed after a short Air gap quenched in a water bath and then stretched continuously in two stages. The The draw ratio was 1: 4.3 in all tests. The temperature in the first stage stretching was 80 ° C and in the second stage 90 ° C, the Running speed of the spinning threads after leaving the Quench bath was 32 m / min. Subsequently, one Heat setting in a fixing channel at one temperature of 275 ° C. All spun monofilaments had a final diameter of 0.4 mm. As Stability test was the fineness-related maximum tensile strength (= Tensile strength) on the monofilaments obtained once immediately after generation and a second time after storage the monofilament at 135 ° C in a water vapor atmosphere Checked for 80 hours. After that, the tensile strength again determined and the quotient of residual tensile strength and original tensile strength calculated. It is a measure of the stabilizing effect of the additives.
In diesem Beispiel wurden Monofile ohne jeglichen Zusatz ausgesponnen. Die erhaltenen Proben wiesen natürlich kein freies Monocarbodiimid auf, der Carboxylendgruppengehalt betrug 6,4 mVal/kg Polymer. In der nachfolgenden Tabelle sind die Versuchsbedingungen und die erhaltenen Ergebnisse zusammengefaßt worden. In this example, monofilaments were made without any addition spun out. The samples obtained naturally showed no free monocarbodiimide, the carboxyl end group content was 6.4 meq / kg polymer. In the table below are the test conditions and the results obtained have been summarized.
Auch dieses Beispiel wurde zum Vergleich ausgefertigt. Unter den gleichen Bedingungen wie in Beispiel 1 wurde wiederum ein Monofil hergestellt, wobei jedoch 0,6 Gew.-% des N,N'-(2,6,2',6'-Tetraisopropyl-diphenyl)-carbodiimid allein als Verschlußmittel für die Carboxylgruppen eingesetzt wurde. Die Menge von 0,6 Gew.-% entspricht einen Wert von 16,6 mVal/kg, es wurde also mit einem Überschuß von 10,2 mVal/kg Polymer gearbeitet. Unter diesen Bedingungen wird ein Polyestermonofil erhalten, das eine sehr gute Stabilität gegenüber thermisch hydrolytischen Angriff zeigt. Nachteilig ist jedoch der Gehalt an freiem Monocarbodiimid in Höhe von 222 ppm in den fertigen Produkten.This example was also made out for comparison. Under the same conditions as in Example 1 were again used produced a monofilament, but with 0.6 wt .-% of N, N '- (2,6,2', 6'-tetraisopropyl-diphenyl) carbodiimide used solely as a closing agent for the carboxyl groups has been. The amount of 0.6% by weight corresponds to a value of 16.6 mVal / kg, so it was with an excess of 10.2 mVal / kg polymer worked. Under these conditions get a polyester monofilament that has very good stability against thermal hydrolytic attack. Disadvantageous however, the free monocarbodiimide content is 222 ppm in the finished products.
Auch hier wurde zu Vergleichszwecken das Beispiel 1 wiederholt. Diesmal wurde jedoch eine Menge von 0,876 Gew.-% des oben beschriebenen Polycarbodiimids zugesetzt und zwar in Form eines 15 %igen Masterbatches. Dieser Versuch wurde durchgeführt, um noch einmal die Angaben der Vorliteratur zu überprüfen, nach denen selbst bei einem merklichen Überschuß von Polycarbodiimid, vermutlich aufgrund der geringen Reaktionsfähigkeit, eine gegenüber dem Stand der Technik herabgesetzte thermische und hydrolytische Beständigkeit zu beobachten ist. Dieses Beispiel zeigt deutlich, daß dies tatsächlich der Fall ist. Interessant ist, daß diese gewählte Menge an Polycarbodiimid bereits zu einer merklichen Vernetzung des Polyesters zu führen scheint, wie aus dem deutlichen Anstieg der Intrinsic-Viskositäts-Werte abgeleitet werden kann. Im allgemeinen ist eine derartige Vernetzung bei fadenbildenden Polymeren nur innerhalb enger Grenzen zulässig, wenn sie streng reproduzierbar erfolgt und keine Spinnschwierigkeiten oder Schwierigkeiten bei der Verstreckung der daraus hergestellten Fäden zu erwarten sind. Example 1 was also used here for comparison purposes repeated. However, this time an amount of 0.876% by weight of the polycarbodiimide described above in the form of a 15% masterbatch. This attempt was made carried out once again the information in the previous literature check after which even with a noticeable excess of polycarbodiimide, probably due to the low Responsiveness, one over the prior art reduced thermal and hydrolytic resistance can be observed. This example clearly shows that this is actually the case. It is interesting that this is chosen Amount of polycarbodiimide already at a noticeable Crosslinking of the polyester seems to result, as from the significant increase in intrinsic viscosity values can be. Generally, such networking is with thread-forming polymers only within narrow limits permissible if it is strictly reproducible and none Difficulty in spinning or difficulty in drawing the threads made from it are to be expected.
Das Verfahren gemäß Beispiel 1 bzw. Beispiel 2 wurde wiederholt, wobei jetzt jedoch Mengen an Monocarbodiimid zugesetzt wurden, die sich aus dem stöchiometrisch berechneten Wert bzw. einem 20 %igen Überschuß an Monocarbodiimid ergeben. Auch die hier erhaltenen Ergebnisse sind in der folgenden Tabelle aufgeführt. In einem Lauf 4a wurde genau die stöchiometrisch benötigte Menge an Monocarbodiimid zugegeben, während in einem Lauf 4b ein Überschuß von 1,3 mVal/kg an Monocarbodiimid eingesetzt wurde. Wie in der Tabelle gezeigt, entsprechen die gefundenen relativen Restfestigkeiten nach einer Behandlung bei 135°C in Wasserdampfatmosphäre nach einer Zeit von 80 Stunden nicht dem Stand der Technik. Ein Überschuß von ca. 20 %, wie er beispielsweise auch bereits den Zahlenangaben der DE-AS 24 58 701 entnommen werden kann, führt ebenfalls noch nicht zu den hohen hydrolytischen Beständigkeiten, wie sie gemäß dem Stand der Technik beispielsweise gemäß Beispiel 2 erreicht werden können. Das bedeutet jedoch, daß gemäß dem Stand der Technik nur mit einem erheblichen Überschuß an Monocarbodiimid eine besonders gute relative Restfestigkeit nach thermisch-hydrolytischer Belastung erzielt werden konnte. Das ist zwangsläufig mit einem großen Gehalt an freiem Monocarbodiimid verbunden.The procedure according to Example 1 or Example 2 was repeated, but now amounts of monocarbodiimide were added, resulting from the stoichiometric calculated value or a 20% excess Monocarbodiimide result. Even those preserved here Results are shown in the table below. In a run 4a was exactly the stoichiometrically required Amount of monocarbodiimide added while in one run 4b an excess of 1.3 meq / kg of monocarbodiimide was used. As shown in the table the relative residual strengths found after a Treatment at 135 ° C in a steam atmosphere after a Time of 80 hours not state of the art. An excess of approx. 20%, such as the one already Figures from DE-AS 24 58 701 can be taken leads also not yet to the high hydrolytic Resistance as it is according to the state of the art can be achieved for example according to Example 2. However, this means that according to the prior art only with a significant excess of monocarbodiimide is a particular good relative residual strength after thermal hydrolytic Load could be achieved. That is inevitable with a large content of free monocarbodiimide.
Beispiel 1 wurde wiederholt, diesmal jedoch
erfindungsgemäß neben Monocarbodiimid auch ein
Polycarbodiimid eingesetzt.
Bei diesem Versuch wurden 0.4 Gew.% Monocarbodiimid und
0.32 Gew% Polycarbodiimid, bezogen auf Polyester
zugegeben. Example 1 was repeated, but this time, in addition to monocarbodiimide, a polycarbodiimide was also used according to the invention.
In this experiment, 0.4% by weight of monocarbodiimide and 0.32% by weight of polycarbodiimide, based on polyester, were added.
Wie aus der Tabelle zu ersehen ist, hält sich der Gehalt des so hergestellten Polyesters an freiem Monocarbodiimid innerhalb der oben angegebenen Grenzen. Die thermischhydrolytische Stabilität des Materials liegt sogar noch geringfügig über der der besten bisher bekannten Kompositionen.As can be seen from the table, the salary persists of the polyester thus produced on free monocarbodiimide within the limits given above. The thermal hydrolytic The stability of the material is still there slightly above that of the best known so far Compositions.
Das so hergestellte Monofilament war zur Herstellung von Papiermaschinensieben hervorragend geeignet.The monofilament thus produced was used to manufacture Paper machine screens are ideally suited.
Die experimentellen Ergebnisse und die
Reaktionsbedingungen sind in der folgenden Tabelle
zusammengestellt. In Spalte 2 sind die Mengen des
zugesetzten Monocarbodiimids, in Spalte 3 die des
Polycarbodiimids in Gew%, bezogen auf den Polyester,
angegeben.
Weitere Spalten zeigen die Meßwerte der erhaltenen
Monofilamente, die jeweils einen Durchmesser von 0,40 mm
aufwiesen. Zunächst wird die Menge an Carboxylendgruppen
in mVal/kg angegeben, danach die Menge an freiem
Monocarbodiimid in ppm (Gewichtswerte). Die Bestimmung des
Gehaltes an freiem Carbodiimid erfolgte durch Extraktion und
gaschromatographische Analyse, ähnlich wie in der
JP-AS 1-15604-89 beschrieben. Es folgen weitere Spalten, in
denen die relative Restfestigkeit und die Intrinsic-Viskosität
der einzelnen Fadenproben angegeben werden.
The experimental results and the reaction conditions are summarized in the following table. Column 2 shows the amounts of monocarbodiimide added, column 3 those of polycarbodiimide in% by weight, based on the polyester.
Further columns show the measured values of the monofilaments obtained, each of which had a diameter of 0.40 mm. First the amount of carboxyl end groups is given in mVal / kg, then the amount of free monocarbodiimide in ppm (weight values). The free carbodiimide content was determined by extraction and gas chromatographic analysis, similar to that described in JP-AS 1-15604-89. Further columns follow in which the relative residual strength and the intrinsic viscosity of the individual thread samples are given.
Claims (16)
- Polyester fibers and filaments which, following reaction with carbodiimides, have capped carboxyl end groups, characterized in thatthe capping of the carboxyl end groups has been predominantly effected by reaction with mono- and/or biscarbodiimides which are present in the fibers and filaments in an amount of from 30 to 200 ppm, based on the weight of the polyester,the free carboxyl end group content is less than 3 meq/kg of polyester, the fibers and filaments additionally containing at least 0.02 percent by weight of at least one free polycarbodiimide or of a reaction product containing still reactive carbodiimide groups and the free monocarbodiimide content is not 33 ppm.
- The fibers and filaments of claim 1, characterized in that the free mono- and/or biscarbodiimide content is from 30 to 150 ppm, preferably from 30 to 100 ppm, based on the weight of the polyester.
- The fibers and filaments of claim 1 or 2, characterized in that the free carboxyl end group content is less than 2, preferably less than 1.5, meq/kg of polyester.
- The fibers and filaments of at least one of the preceding claims, characterized in that they contain at least one free polycarbodiimide or a reaction product containing still reactive carbodiimide groups in an amount of from 0.05 to 0.6, preferably from 0.1 to 0.5, percent by weight.
- The fibers and filaments of at least one of the preceding claims, characterized in that the fiber-forming polyester has an average molecular weight corresponding to an intrinsic viscosity of at least 0.64 [dl/g] measured in dichloroacetic acid at 25°C.
- The fibers and filaments of at least one of the preceding claims, characterized in that the polycarbodiimide(s) used has or have an average molecular weight between about 2000 to 15,000, preferably 5000 to 10,000.
- A process for preparing carbodiimide-stabilized polyester fibers and filaments, characterized in that it comprises adding to the polyester prior to spinning an amount of not more than 0.5% by weight of a mono- and/or biscarbodiimide and also at least 0.05% by weight, based on polyester, of at least one polycarbodiimide and then conventionally spinning into filaments, the amounts of mono- and/or biscarbodiimides and of polycarbodiimides being chosen in such a way that the resulting polyester contains from 30 to 200 ppm, preferably from 30 to 150 ppm, in particular from 30 to 100 ppm, of mono- and/or biscarbodiimides and at least 0.02% by weight of polycarbodiimides and the free monocarbodiimide content is not 33 ppm.
- The process of claim 7, characterized in that the polyester to be spun has a carboxyl end group content of 20 meq/kg or less after spinning without carbodiimide addition.
- The process of at least one of claims 7 and 8, characterized in that the contact time between molten polyester and carbodiimide additions is less than 5, preferably less than 3, minutes.
- The process of at least one of claims 7 to 9, characterized in that the polyester to be processed has an average molecular weight corresponding to an intrinsic viscosity of at least 0.64 [dl/g] measured in dichloroacetic acid at 25°C.
- The process of at least one of claims 7 to 10, characterized in that the polycarbodiimide is added to the polyester to be processed as a concentrate (masterbatch) in a polymer, preferably in polyester.
- The process of at least one of claims 7 to 11, characterized in that the carbodiimides are added immediately prior to spinning of the polyester at a point upstream of or in the extruder.
- The process of at least one of claims 7 to 12, characterized in that the monocarbodiimide used is N, N'-2,6,2',6'-tetraisopropyldiphenylcarbodiimide.
- The process of at least one of claims 7 to 13, characterized in that the polycarbodiimide used is an aromatic polycarbodiimide which is isopropylsubstituted on the benzene nucleus in the o-position relative to the carbodiimide groups, i.e. in the 2,6- or 2,4,6-position.
- Filaments as claimed in at least one of claims 1 to 6, characterized in that they are monofilaments having a round or profiled cross-section with a - if necessary equivalent - diameter of from 0.1 to 2.0 mm.
- The use of the filaments of any one of claims 1 to 6 and 15 for producing papermaker's machine wirecloths.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4108278 | 1991-03-14 | ||
DE4108278 | 1991-03-14 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0503421A1 EP0503421A1 (en) | 1992-09-16 |
EP0503421B1 true EP0503421B1 (en) | 1998-01-07 |
Family
ID=6427284
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP92103536A Expired - Lifetime EP0503421B1 (en) | 1991-03-14 | 1992-03-02 | Polyester fibres modified with carbodiimides and process for their preparation |
Country Status (14)
Country | Link |
---|---|
US (1) | US5885709A (en) |
EP (1) | EP0503421B1 (en) |
JP (1) | JP3228977B2 (en) |
KR (1) | KR100209864B1 (en) |
AT (1) | ATE161903T1 (en) |
BR (1) | BR9200867A (en) |
CA (1) | CA2063023A1 (en) |
DE (1) | DE59209093D1 (en) |
ES (1) | ES2113384T3 (en) |
FI (1) | FI104568B (en) |
IE (1) | IE920829A1 (en) |
MX (1) | MX9201124A (en) |
RU (1) | RU2094550C1 (en) |
TW (1) | TW212820B (en) |
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-
1991
- 1991-11-28 JP JP31474991A patent/JP3228977B2/en not_active Expired - Fee Related
-
1992
- 1992-02-01 TW TW081100834A patent/TW212820B/zh active
- 1992-03-02 EP EP92103536A patent/EP0503421B1/en not_active Expired - Lifetime
- 1992-03-02 ES ES92103536T patent/ES2113384T3/en not_active Expired - Lifetime
- 1992-03-02 DE DE59209093T patent/DE59209093D1/en not_active Expired - Fee Related
- 1992-03-02 AT AT92103536T patent/ATE161903T1/en not_active IP Right Cessation
- 1992-03-12 FI FI921068A patent/FI104568B/en active
- 1992-03-12 KR KR1019920004037A patent/KR100209864B1/en not_active IP Right Cessation
- 1992-03-13 CA CA002063023A patent/CA2063023A1/en not_active Abandoned
- 1992-03-13 MX MX9201124A patent/MX9201124A/en not_active IP Right Cessation
- 1992-03-13 RU SU925011051A patent/RU2094550C1/en active
- 1992-03-13 IE IE082992A patent/IE920829A1/en unknown
- 1992-03-13 BR BR9200867-4A patent/BR9200867A/en not_active IP Right Cessation
-
1996
- 1996-10-25 US US08/735,317 patent/US5885709A/en not_active Expired - Fee Related
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1767572A1 (en) | 2005-09-21 | 2007-03-28 | Raschig GmbH | Formulations comprising stabilizers against hydrolysis |
EP2933285A1 (en) | 2014-04-15 | 2015-10-21 | Raschig GmbH | Hydrolysis stabiliser formulations |
Also Published As
Publication number | Publication date |
---|---|
US5885709A (en) | 1999-03-23 |
TW212820B (en) | 1993-09-11 |
JPH04289221A (en) | 1992-10-14 |
KR920018261A (en) | 1992-10-21 |
FI921068A (en) | 1992-09-15 |
ES2113384T3 (en) | 1998-05-01 |
ATE161903T1 (en) | 1998-01-15 |
IE920829A1 (en) | 1992-09-23 |
JP3228977B2 (en) | 2001-11-12 |
BR9200867A (en) | 1992-11-17 |
KR100209864B1 (en) | 1999-07-15 |
FI921068A0 (en) | 1992-03-12 |
CA2063023A1 (en) | 1992-09-15 |
RU2094550C1 (en) | 1997-10-27 |
FI104568B (en) | 2000-02-29 |
EP0503421A1 (en) | 1992-09-16 |
MX9201124A (en) | 1992-10-30 |
DE59209093D1 (en) | 1998-02-12 |
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