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WO1997035903A1 - Procede de modification chimique directe de (co)polyesters - Google Patents

Procede de modification chimique directe de (co)polyesters Download PDF

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Publication number
WO1997035903A1
WO1997035903A1 PCT/EP1997/001551 EP9701551W WO9735903A1 WO 1997035903 A1 WO1997035903 A1 WO 1997035903A1 EP 9701551 W EP9701551 W EP 9701551W WO 9735903 A1 WO9735903 A1 WO 9735903A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyester
compounds
polyesters
compound
phosphorus
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.)
Ceased
Application number
PCT/EP1997/001551
Other languages
German (de)
English (en)
Inventor
Werner Kägi
Werner Stibal
Stefan Deibert
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.)
Inventa AG fuer Forschung und Patentverwertung
Uhde Inventa Fischer AG
Original Assignee
EMS Inventa AG
Inventa AG fuer Forschung und Patentverwertung
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
Priority claimed from DE19711947A external-priority patent/DE19711947C2/de
Application filed by EMS Inventa AG, Inventa AG fuer Forschung und Patentverwertung filed Critical EMS Inventa AG
Publication of WO1997035903A1 publication Critical patent/WO1997035903A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/916—Dicarboxylic acids and dihydroxy compounds

Definitions

  • the invention relates to a new, simple method for the direct chemical modification of (co) polyesters and products, in particular fibers and filaments, produced from them inherently flame-retardant or otherwise modified (co) polyesters
  • polyesters especially PET (polyethylene terephthalate)
  • PET polyethylene terephthalate
  • PET polyethylene terephthalate
  • the concept was developed to carry out polymer modifications only after the final reactor in order to simultaneously produce different polymer quantities for the various uses from the main melt stream divided into a corresponding number of substreams
  • the latter concept is already used for physical modifications, ie the dispersion of inert solid additives (DE 40 39 857 C2).
  • DE 40 39 857 C2 One possibility of subsequently converting PET into CoPET by means of chemical modification was described in DE 44 29 524 A1.
  • Flame retardancy is a special variant of polyester modification. Flame retardants make the polyester flame-retardant. For some purposes (e.g. for public transport), legislation in certain countries even prescribes flame-retardant properties for textile materials. An overview of the current situation and future developments is provided by J. Troitzsch's article: Flame retardant polymers - current Status and future trends, Makromol. Chem., Macromol. Symp. 74 (1993) pp. 125-135. Among other things, it states that many effective flame retardants can no longer be used today or in the future for ecological or toxicological reasons. Phosphorus-containing retarders are not affected by such requirements. As mentioned in the publication, phosphorus has a flame-retardant effect in practically all forms, regardless of its oxidation state or the exact nature of the phosphorus compound.
  • Phosphorus-containing flame retardants have hitherto been distributed, in part as pure additives which do not react with the polymer, in the polymer matrix, as described, for example, in DE 44 12 969 C1 under Example 8 for a flame-retardant PET hollow fiber.
  • the disadvantage of a flame retardant that is only dispersed in the polyester is that repeated, extreme washing or
  • the flame retardant of such fibers is treated for cleaning is extracted again
  • Phosphorus compounds must therefore have functional groups that can be linked to the polymer
  • Such a compound is, for example, 2-methyl-2,5-dioxo-1-oxa-2-phospholane, often called phospholane for the sake of simplicity.
  • This compound is described in a product information from Hoechst from March 1979.
  • Polyesters modified with phospholane and fibers and game which can be produced therefrom have therefore already been described, but the process for chemical modification described above is cumbersome and therefore cost-intensive According to this prior art, the polycondensation reactor is "contaminated" with the relevant phosphorus compound during the chemical flame-resistant modification, which is associated with the aforementioned disadvantage of so-called “off-spec" transition quantities when converting to other polyester types
  • polymeric phosphorus-containing flame retardants have recently been developed which chemically contain a high proportion of phosphorus-containing subunits in a copolyester is bound, but this copolyester is in turn mixed as an additive, ie as a master batch, with the flame-retardant polyester to be finished, so that a blend is formed from which the end product can be produced
  • the polymeric flame retardant is produced by polycondensation from an aromatic dicarboxylic acid, an alkylene glycol and a phosphorus-containing monomer, which is a linear copolyester with a high bond in the macromolecule Phosphorus content gives carboxyphosphinic acids and the corresponding cyclic anhydrides, ie lactones, are described as suitable phosphorus-containing monomers, the cyclic compound preferably being a 5-membered ring.
  • a polycondensation reactor is therefore still required for the production of this special copolyester and is used by the user the flame-retardant polyester, for example polyethylene terephthalate or polybutylene terephthalate, is not chemically modified, but the polymeric flame retardant is simply mixed in in a certain proportion and then distributed (see Examples 7 to 9)
  • the flame-retardant polyester for example polyethylene terephthalate or polybutylene terephthalate
  • R with G chemical group, containing at least one heteroatom foreign to polyester, selected from the group P, N and S.
  • the polyester or the polyester melt in an application-related amount of up to 10 mol%, based on the repeating polyester units, optionally metered in together with further compounds, the polyester or the polyester melt and in a system which is closed against gas exchange and is at a higher pressure than the vapor pressure of the compounds used the polyester melt produced by melting or already present is mixed at at least 260 ° C., the group is reactively incorporated into or bound to the polyester, and after a total reaction and residence time of less than 30 minutes, the chemically modified polyester melt is further processed or discharged , granulated and subsequently processed
  • the formula (I) means that the chemical group G which carries the heteroatom forms a common ring with the reactive group R, ie the heteroatom is part of the ring.
  • the formula (II) means that the chemical group G, which carries the heteroatom, is substituted on a ring with the reactive bond R.
  • groups with heteroatoms could thus be elegantly incorporated into the (co) polyester chains (main chain ⁇ ) for the first time (if a compound of the formula (I) is used) or permanently bound to the polyester chains by chemical bonding (if a compound of the formula (II ) is used) so that inherently flame-retardant or otherwise modified (co) polyesters can be obtained therefrom. It is advantageous in the process according to the invention that the groups can be inserted or attached after the polyester has been produced and that the polycondensation system is not contaminated full flexibility and free choice to easily modify a base polyester
  • the heteroatoms contained in the chemical groups are P, N and S, and particularly preferably P phosphorus-containing groups, as described above, are particularly suitable for flame retardancy. Certain nitrogen-containing groups can also be used for the same purpose. Sulfuric acid group or its salt compound is particularly interesting for sulfur, because the polyester can be colored cationically by chemical modification with corresponding compounds. Conversely, polyester could be colored anionically by chemical modification with compounds of the formula (II) containing amino groups
  • polyesters are all thermoplastically processable polyesters, such as, for example, PET (polyethylene terephthalate), PBT (polybutylene terephthalate), PPT (polypropylene terephthalate), PEN (polyethylene naphthalate), their copolyesters or already in some way in the course of production Modified polyesters (eg with pentaerythnt for branching)
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PPT polypropylene terephthalate
  • PEN polyethylene naphthalate
  • polyester means both homo-polyester and copolyester.
  • PET is particularly preferred
  • Examples of compounds of the formula (I) are 3-methyl-3-oxo-3-phospha-
  • Examples of compounds of the formula (II) are 3- (9,10-dihydro-9-oxa-10-oxid-10-phosphaphenanthrene-10-yl) methyl-6-hydroxyhexaneurelactone, 2- (9th , 10-D ⁇ hydro-9-oxa-10-ox ⁇ d-10- phosphaphenanthren-10-yl) -methyl-bernste ⁇ nsaurea ⁇ hydr ⁇ d, dasNatr ⁇ umsalzdes 4-sulfophthalic anhydride or 3-Glyc ⁇ doxy-methoxy-phenylphosph ⁇ nox ⁇ d
  • the system which is sealed against gas exchange and is at a higher pressure than the vapor pressure of the compounds used, can be either
  • Extruder (if polyester granulate is assumed), as well as a simple pipe through which the polyester melt flows, which is provided with a metering opening and downstream with a mixing device. If more than one connection is used, the minimum system pressure depends on the connection the highest vapor pressure Dynamic mixers and preferably static mixers are used as mixers. The compounds which bring about the chemical modification are metered using suitable devices. In the case of a granulate melt extruder, the compounds in solid form (powder) can be added continuously to the granules entering the extruder In the case of the melt pipeline, the connections are advantageously melted separately and then pumped in liquid form continuously into the pipeline with the melt flow.
  • the polyester melt has already been dosed A temperature in the range from 5 " C above the melting point of the polyester to be modified to 310" C, but in any case at least 260 * C
  • An advantageous variant of the process according to the invention is to connect it directly to a continuous polycondensation end reactor and to modify a branched-off partial stream of the entire polyester melt in the manner according to the invention. In the latter variant, it is also possible under certain circumstances, instead of the pipe device, with liquid addition of the
  • connection in the side stream does not exceed a certain limit and the compound in contact with the melt in solid form is neither sublimed nor evaporated back from the dosing nozzle. Whether these conditions are fulfilled can be determined experimentally
  • the modified melt can be further processed into various products such as fibers, filaments, foils, injection molding, blow molding or extrusion articles.
  • PET is preferably modified with phosphorus-containing compounds and further processed into flame-retardant fibers and filaments. Suitable processing techniques are melting spins , Injection molding,
  • additives such as glass fibers, carbon fibers, mineral reinforcing agents and fillers, antistatic agents, stabilizers, dyes, etc. can be added to the chemically modified polyesters
  • additives which do not impair the spinnability can be used for melt spinning
  • FIG. 1 The reaction between PET and a compound A is shown in FIG. 1, the basic structure of which corresponds to formula (II) with a lactone bond (7-ring).
  • the exact name of compound A is 3- (9, 10-dihydro-9-oxa-10-oxide-10-phosphaphenanthren-10-yl) methyl-6-hydroxyhexanoic acid lactone.
  • DOP is the abbreviation for 9, 10-dihydro-9-oxa-10-phosphaphen-anthrene-10-oxid. This substance was called DOP (95 ) from the company Schill & Seilacher GmbH, Boblingen (Germany)
  • the 3-methylene-caprolactone can be prepared by a synthetic route which is described by M Mo ⁇ et al in J Org Chem (1983), 48 (22), 4058-67 (Patladium-catalyzed carbonylation A new synthesis of alpha-methyiene gamma -
  • delta-epsilon-lactams and lactones including bicyclic lactams of pyrrolizidine and indolizidme skeletons
  • Compound A for example, can be metered in powder form with a differential dosing weigher continuously to "textile grade" PET granules, which in the
  • Feed spigot of a spinning extruder is running
  • the dosing quantity should be selected so that the content of elemental phosphorus in the modified polyester or in the thread produced from it by melt spinning is approx. 0.6% by weight. This value can be the optimum between effort and effect regarding flame retardancy
  • FIG. 2 shows how a compound B, which corresponds in its basic structure to the formula (II) with a cyclic anhydride bond, reacts with a hydroxyl end group of PET.
  • the exact name of the compound B is 2- (9,10-dihydro-9 -oxa- 10-ox ⁇ d-10-phosphaphenanthren-10-yl) -methyl-bernste ⁇ nsaureanhydr ⁇ d B is the addition product of DOP and itaconic acid from which the water has been removed
  • This connection can thus be melted and metered into the polyester melt flow in a pipeline by means of a pump.
  • the temperature of the polyester melt is, for example, approx. 285'C and the pressure prevailing in the system, e.g. approx. 50 bar.
  • a static mixer built into the pipeline can be used for mixing
  • the resulting modified polyester can be spun directly from the melt into flame-retardant thread, whereby the same recommendations as for example 1 generally apply
  • Modified compound C which corresponds in its basic structure to formula (I) with lactone bond (4-ring).
  • the exact name of compound C is 3-methyl-3-oxo-3-phospha-3-hydroxypropauric acid lactone.
  • the phosphorus is converted into directly by transesterification the main chain of the polyester is incorporated.
  • the advantage of compound C is its high phosphorus content and the fact that, compared to the phospholane mentioned in the introduction to the description, no additional ethylene glycol is bound in the polyester chain.
  • FIG. 4 shows how a sulfonic acid group can be bonded to a polyester according to the invention so that it can be color-coated.
  • Compound D is the sodium salt of 4-sulfophthalic anhydride, that is to say a compound of the formula (II) with a cyclic anhydride bond.
  • Metering in to the polyester is possible in solid or liquid form.
  • the reaction mechanism corresponds to example 2. Because of the consumption of hydroxyl end groups, the degree of modification is also initially limited, but can be expanded by the method described in example 5 become
  • a monoepoxide compound is added to the polyester, for example styrene oxide (compound E), as shown in FIG. 5.
  • the monoepoxide compound preferably reacts with acid groups and thus converts COOH end groups into OH end groups
  • FIG. 5 shows by way of example how the new COOH end group additionally formed by modification with compound B (according to FIG. 2) is converted back into an OH end group using styrene oxide, both possible reaction products being shown
  • the styrene oxide can equally well react with an already existing COOH end group of the polyester (not shown) and in this way likewise increase the supply of OH end groups for the addition of the anhydride compound, which in the same direction increases the maximum possible Degree of modification and increased rate of modification is therefore particularly preferred for the gross reaction conversion, the simultaneous addition of the two compounds. If the anhydride and the monoepoxide compound are reacted in the same molar amounts, this also remains
  • FIG. 6 shows how a compound F, which corresponds in its basic structure to the formula (II) with epoxy bond, reacts with an acid end group of PET.
  • the exact name of the compound F is 3-glycidoxy-methoxy-phenylphosphine.
  • the compound F contains, as it were, the effect of an anhydride compound B combined with a monoepoxide.
  • FIG. 6 shows both possible reaction products. Because hydroxyl groups can also react with epoxy groups (not shown), there is also a degree of modification for a polyester Compound F has no upper limits comparable to compound B.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

L'invention concerne un procédé de modification chimique directe de (co)polyesters, selon lequel au moins un composé monomère, de formule générale (I) ou (II), où G est un groupe chimique renfermant au moins un hétéroatome étranger au polyester, choisi dans le groupe P, N et S; R est une liaison réactive du type lactone dans un cycle à 4, 7 ou 8 chaînons, ou un anhydride cyclique ou un époxyde, est ajouté au (co)polyester ou à la masse fondue de (co)polyester, en quantités dosées, suivant les besoins de l'application, jusqu'à 10 % mol, par rapport aux motifs récurrents de polyesters, éventuellement avec d'autres composés, et est mélangé à au moins 260 DEG C, dans un système fermé protégé contre les échanges gazeux, sous une pression supérieure à la tension de vapeur des composés ajoutés, avec la masse fondue de (co)polyesters, préparée par fusion ou déjà existante, le groupe étant incorporé chimiquement au (co)polyester ou lié à celui-ci et, après une durée totale de réaction et de séjour inférieure à 30 minutes, la masse fondue, chimiquement modifiée, de (co)polyester est transformée ou extraite, granulée puis encore transformée.
PCT/EP1997/001551 1996-03-26 1997-03-26 Procede de modification chimique directe de (co)polyesters Ceased WO1997035903A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE19611987.1 1996-03-26
DE19611987 1996-03-26
DE19711947.6 1997-03-25
DE19711947A DE19711947C2 (de) 1996-03-26 1997-03-25 Verfahren zur direkten chemischen Modifikation von (Co)polyestern

Publications (1)

Publication Number Publication Date
WO1997035903A1 true WO1997035903A1 (fr) 1997-10-02

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ID=26024158

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Application Number Title Priority Date Filing Date
PCT/EP1997/001551 Ceased WO1997035903A1 (fr) 1996-03-26 1997-03-26 Procede de modification chimique directe de (co)polyesters

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CN (1) CN1185792A (fr)
TR (1) TR199701437T1 (fr)
WO (1) WO1997035903A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4115350A (en) * 1977-07-27 1978-09-19 Allied Chemical Corporation Production of thermally stabilized polyester
DE2710034A1 (de) * 1977-03-08 1978-09-21 Inventa Ag Verfahren zur herstellung von hydrolysestabilen geformten gebilden aus polyestern
WO1995024445A2 (fr) * 1994-03-11 1995-09-14 Monsanto Company Compositions ignifuges contenant du polyester recycle

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2710034A1 (de) * 1977-03-08 1978-09-21 Inventa Ag Verfahren zur herstellung von hydrolysestabilen geformten gebilden aus polyestern
US4115350A (en) * 1977-07-27 1978-09-19 Allied Chemical Corporation Production of thermally stabilized polyester
WO1995024445A2 (fr) * 1994-03-11 1995-09-14 Monsanto Company Compositions ignifuges contenant du polyester recycle

Also Published As

Publication number Publication date
TR199701437T1 (xx) 1998-06-22
CN1185792A (zh) 1998-06-24

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