WO2007042387A1 - Procede pour produire des nanocomposites polyester - Google Patents

Procede pour produire des nanocomposites polyester Download PDF

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Publication number
WO2007042387A1
WO2007042387A1 PCT/EP2006/066654 EP2006066654W WO2007042387A1 WO 2007042387 A1 WO2007042387 A1 WO 2007042387A1 EP 2006066654 W EP2006066654 W EP 2006066654W WO 2007042387 A1 WO2007042387 A1 WO 2007042387A1
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Prior art keywords
melt
polyester
acid
organophilic
polycondensation
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PCT/EP2006/066654
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German (de)
English (en)
Inventor
Angelo SCHÜTZ
Klaus Rucho
Jens Henkel
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Epc Anlagenbau Rudisleben Gmbh
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Publication of WO2007042387A1 publication Critical patent/WO2007042387A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
    • B01F25/50—Circulation mixers, e.g. wherein at least part of the mixture is discharged from and reintroduced into a receptacle
    • B01F25/51—Circulation mixers, e.g. wherein at least part of the mixture is discharged from and reintroduced into a receptacle in which the mixture is circulated through a set of tubes, e.g. with gradual introduction of a component into the circulating flow
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • B01J19/1806—Stationary reactors having moving elements inside resulting in a turbulent flow of the reactants, such as in centrifugal-type reactors, or having a high Reynolds-number
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • B01J19/1887—Stationary reactors having moving elements inside forming a thin film
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • B01J19/20—Stationary reactors having moving elements inside in the form of helices, e.g. screw reactors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/26—Nozzle-type reactors, i.e. the distribution of the initial reactants within the reactor is effected by their introduction or injection through nozzles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
    • B01J3/006—Processes utilising sub-atmospheric pressure; Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
    • B01F25/60—Pump mixers, i.e. mixing within a pump
    • B01F25/62—Pump mixers, i.e. mixing within a pump of the gear type
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00002—Chemical plants
    • B01J2219/00004—Scale aspects
    • B01J2219/00006—Large-scale industrial plants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00002—Chemical plants
    • B01J2219/00027—Process aspects
    • B01J2219/00031—Semi-batch or fed-batch processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00761—Details of the reactor
    • B01J2219/00763—Baffles
    • B01J2219/00779—Baffles attached to the stirring means
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

  • the present invention relates to a process for the preparation of polyester anocomposites according to the preamble of patent claim 1.
  • Polyester (homo-PET, co-PET) is a favorable thermoplastic material which, due to its range of properties in the area of technical applications, has also been used for packaging materials (food packaging films, beverage containers, cosmetics etc.). Polyester as such are therefore not only the raw material for the textile industry, but are also processed in considerable quantities into technical films, but above all to packaging materials (Containers, foodstuffs, beverage bottles, etc.).
  • the shape and color of the PET bottle are unlimited: various individual designs are available.
  • the new container not only supports the launch of new varieties, such as beer-based beverages, but also draws consumer attention to traditional beers.
  • FIG. 1 illustrates which important functions a PET bottle to be modified for beer bottlings (also applies to flavor-sensitive juices, etc.) must fulfill in particular.
  • nylon-MXD6 / nanosilicate inner layer acts as the actual high-barrier layer, whereby the additional incorporation of small amounts of organoclay into N-MXD6, according to Nanocor (Technical Paper, Nanocor Inc.), leads to CO 2 permeation over the pure Reduced N- MXD6 interlayer to 50% and correspondingly reduced the O ⁇ permeation to 25%.
  • Nylon MXD6 itself is already a higher-priced matrix polymer.
  • Polymer nanocomposites are used, inter alia, for polyamide 6 as matrix (obtained via melt compounding of nylon 6 base polymer or in-situ polymer).
  • Caprolactam to polyamide nanocomposites have long been known and are already commercially available from some companies (Bayer AG, Honeywell, UBE Industries, RTP).
  • Nanohistate silicates in the case of the thermoplastic matrix polyamide 6 have proven to be very successful in obtaining commercial polyamide nanocomposite packaging materials (in particular food packaging films) both via melt compounding processes and above all via the in situ polymerization process (Honeywell: Aegis TM NC (XA-2908 Type), UBE Industries, Bayer AG: Durethan® KU2-2601), are mainly the technical and technological problems for polyester especially for in situ polymerization with Nanotiksilikaten (thermal decomposition of Nano Mrssilikate, foaming in the Reactors, considerable vacuum disturbances, insufficient polymer viscosities, insufficient dispersing quality) have not yet been solved.
  • the improvements in gas barrier properties achieved with them are only to be assessed as low compared to expectations.
  • the gas barrier and the optical transparency of polymer nanocomposites can not be significantly improved.
  • the melt viscosity of polyester increases sharply, as is the case with slow-running batch reactors or disc-ring finisher reactors, which leads inter alia to melt viscosity ranges> 30,000 poise and, associated therewith, to reduced polycondensation rate due to delayed EG-condensate diffusion the melt.
  • Solid phase condensation stage to higher molecular weight PET nanocomposites (0.7 .... 1.0 dl / g) are condensed in the solid phase with accelerated solid phase condensation times to higher viscosity polyester.
  • the best oxygen barrier values are for with Ethoquad 18/25 from Akzo Chemie America (octadecyl [polyoxyethylene (15)] ammonium chloride) - also referred to as Ethomeen 18/25) modified Montmorri- lonite with 5.0 cm3 / 100 microns x 24 xm 2 x bar for about 12 wt.% addition amount of Ethoquad and 18/25 organoclay with 9.7 cm3 / 100 microns x 24 xm 2 x bar for about 7 wt.% of Ethoquad 18 / 25- MMT in the PET matrix (in-situ incorporation) attained.
  • Eastman also used a variant of the self-modification of Na-MMT with aminododecanoic acid in some examples in the in situ modification of PET (this corresponds to the commercially available
  • 11 wt% - type Nanocor Inc. in order in the respective sheets has an oxygen barrier of about 30-34 cm3 / 100 .mu.m 24 xm 2 x bar with appropriate addition amount of the organoclays of respectively the third.
  • a process for the preparation of polymer clay nanocomposites, including PET is claimed, which refers only to a batch mixing of the mixture of modified nanosheet silicates with the polymer matrix or a melt compounding process in the extruder.
  • the claimed mixture of at least two differently organophilic modified nanohelics in the process engineering process of a transesterification reaction of DMT or esterification of PTA and subsequent melt condensation reaction described.
  • the covalent bonding of the layered silicate particles to the polymers should lead to an increase in the stability of the reinforcing effect compared to an ionic bond.
  • free carboxyl or anhydride groups for covalent bonds to a polymer matrix should also be present.
  • polyesterimidimidhydrides mentioned in this description are liquid-crystalline compounds which, even in the range of low added amounts of 1% by weight, exhibit a considerable mechanical property enhancement (modulus of elasticity, strength) of melt blends with nylon 6 or Polyester, since they already have a very high inherent performance of modulus and strength.
  • a commercially available bentonite which has been organophilicized by the manufacturer with dimethylstearylbenzylammonium ions was used as the organophilic layered silicate for the actual postmodification with polyesterimide anhydride.
  • the dimethylstearylbenzylammonium ion has a quaternary structure and is thus not very stable thermally and decomposes very easily even at temperatures above 230 ° C. This decomposition behavior at temperatures above 230 ° C. will certainly be retained even when the OH surface groups are present the phyllosilicate platelets are subsequently modified with polyester anhydride groups. For this reason, such with
  • Polyesterimidanhydridruppen subsequently modified organophilic phyllosilicates based on quaternary ammonium salts hardly for a Polymersmeltzekondensation in the high temperature range from 275 to 290 0 C suitable to obtain in this way polyester nano-composite with exfoliated Nano Mrssilikaten, since a thermal decomposition orga-ophilic Nano-layer silicates not only with a re-aggregation of originally organophilic, intercalated phyllosilicates to montmorillonite is accompanied, but also significantly affected by the large number of liquid and gaseous decomposition products, in particular the melt polycondensate of polyester or even prevented.
  • biodegradable copolyesters based on aromatic dicarbonyl monomers DMT or terephthalic acid, sodium 5-sulphoisophthalate and 1,2,4-benzenetricarboxylic anhydride, aliphatic dicarboxylic acids such as aipic acid, ethylene glycol and 1,4-benzene Butanediol mainly for the use of short-lived food-disposable packaging for fast-food foods described which u. a.
  • Schichtsil ikate can be added.
  • a large part of the mixture or the entire mixture is subjected to a filtration step (b ') in order to retain particles or agglomerates which are greater than 1000 nm, in particular greater than 500 nm.
  • a third stage (c) the initiation of the polymerization of the monomer (s) and / or the prepolymer (s) then takes place in the presence of the phyllosilicates
  • the polymerization of a majority of the polymerisable monomers and / or prepolymers present in the mixture then takes place for a third period of time at a third temperature or in a third temperature range.
  • an already at least partially exfoliated present phyllosilicate is used, wherein the phyllosilicate on receiving the stage 3 (c), the initiation of the polymerization of the monomer (s) / The prepolymer comprises, already in substantially exfoliated form.
  • the agitation during process stages 1 and 2 is detected by shearing, stirring, shaking, vibrating and / or the application of ultrasound.
  • the agitation should achieve a submicroscopic shear.
  • the duration of the agitation, the respective temperature and the intensity of the agitation in the respective stages of agitation are intended to cause a large part of the layer silicates to be defolated or dispersed in the monomer and / or the prepolymer.
  • the second period of agitation in process stage 2 is maintained at 12, preferably up to 18 hours stirring time.
  • the process temperatures in the process steps at least 20 0 C below the softening temperature and / or-melting, temperature of the polymeric composite or below the sum of 100 0 C and softening temperature of the polymeric composite material.
  • cyclic polyester oligomers allow the intercalation and exfoliation of sheet silicates much better than the actually widespread linear polyester oligomers (linear polyester oligomers by progressive condensation of bis-hydroxyethylene terephthalate).
  • linear polyester oligomers by progressive condensation of bis-hydroxyethylene terephthalate.
  • cyclic polyester oligomers are very low viscous polyester oligomers sationsre force under a Ringö Stammlymeri- with the aid of titanium tin-organic catalysts in only a very short time (a few minutes) at low process temperatures (about 20 - 30 0 C below the melting point of the respective polyester matrix) can anionically polymerize to polyester anocomposites.
  • the macrocyclic polyester oligomers simply cause better intercalation of the organophilic sheet silicates incorporated therein and the subsequent exfoliation of these sheet silicate intercalates is much better promoted during ring-opening polymerization than is the case in the polycondensation reaction of linear polyester oligomers to polyesters with glycol elimination.
  • the solution described in the following uses the promising in-situ incorporation of a thermally stable organophilic nanosheet silicate based on sodium montmorillonite, modified with the hydrochloride of aminododecanoic acid, in the form of a commercial nanosheet silicate type in a polyester matrix, in particular a PET matrix.
  • the invention further described in the following permanent high shear dispersion of the organophilic phyllosilicate by using a separate product cycle in the esterification of terephthalic acid and ethylene glycol and in the polycondensation of Veresteruns, from the previous esterification with the involvement scherintensiver gear pumps serves the intercalation and exfoliation of the claimed theromostable organophilic Schhicht - to favor silicate types in the polyester matrix, especially in the PET matrix, to the highest possible degree.
  • the special use of a static mixing element in the product circulation line of the PET melt condensation stage in particular after obtaining a sufficiently high melt viscosity of the polyester anocomposites, causes an additional melt shear dispersion via the multiplicity of mixing elements arranged in this mixing element.
  • the additional use of a melt distributor nozzle with multiple rotating distributor ring at the melt circulation inlet of the polycondensation reactor is utilized, whereby the circulating polyester melt stream is subjected to the principle of effective thin-film evaporation.
  • the polycondensation time of the polyester anocomposites, in particular PET nanocomposites, obtained with the thermally stable nanosheet silicates according to the invention can be reduced to approximately the same level as that obtained comparatively for phyllosilicate-free polyesters.
  • thermostable PET nanoclay composites by in-situ melt-phase condensation and subsequent SSP as alternative thermostable organophilic nanosheet silicates, special quaternary honey salts (dodecyltriphenylphosphonium bromides or 10- [3,5-bis (methoxycarbonyl) phenoxy] decyltri- phenylphosphonium bromides), which however can not have any commercial exploitation prospects since these phosphonium compounds are toxicologically very important since phosphine compounds are formed in the thermal decomposition of quaternary phosphonium salts according to the reaction scheme according to FIG.
  • the inventive method relates in particular to a special technology for in situ polycondensation of innovative nanocomposite structural materials of polyethylene terephthalate (homo-PET or Co-PET) as matrix polymers and a specially organophilically modified, higher temperature resistant Nano Mrssilikat nanodisperse amplification kung or barrier and UV enhancing additive components.
  • homo-PET or Co-PET polyethylene terephthalate
  • the process according to the invention teaches the permanent intensive shearing of the higher temperature-stable organophilic phyllosilicate used both in a pressureless or pressurized esterification stage of 100-85 mole% terephthalic acid and 0-15 mole% isophthalic acid with ethylene glycol and in a melt polycondensation stage Achieving a vacuum ⁇ ⁇ 5 mbar with circulatory mode of operation of the respective product streams with a 3 to 10-fold product circulation rate during the respective process stage times via toothed teeth radpumpen.
  • a static mixing element is also used in the product cycle of the melt polycondensation stage, which, in particular when obtaining melt viscosities with an IV> 0.5 dl / g, causes intense melt pressure shear during the passage of this static mixing element.
  • Both the intensive shearing on the gear pump circuits in the esterification and in the polycondensation stage and, moreover, the intensive melt pressure shear in the polycondensation stage bring about a surprisingly high degree of intercalation or exfoliation of the introduced thermally stable organophilic phyllosilicate type the PET esterification product, but especially in the polycondensed PET nanocomposite, which was evident by a high transparency of the obtained Polyesternanocomposite according to the embodiments.
  • the technology of the present invention aims to improve the transesterification or esterification (esterification pressures up to 5 bar) and the polycondensation process both by incorporating a higher temperature resistant organophilic nanoclay (I24TL) with a special formulation adaptation to the specifics of the technological process conditions (Vacuum 0.3 - 3 mbar, polycondensation temperatures of 275 ...
  • polyester nanocomposites in particular based on polyethylene terephthalate nanocomposites (PET-NC), via the in-situ polymerization route of bis-hydroxyethylene terephthalate obtained after the DMT transesterification or PTA reaction.
  • PET-NC polyethylene terephthalate nanocomposites
  • a new embodiment of the technology for obtaining nanocomposite materials based on co-polyester the established DMT transesterification or TPA pressure-esterification process and subsequent polycondensation of the intermediate bis-hydroxyethylene terephthalate to polyester by in-situ incorporation of already commercially available organophiles already approved for food contact in polyamide nanocomposite packaging materials exfoliable montmorillonite type (I24TL) with high thermal stability and excellent polymer compatibility to the co-polyester.
  • PET co-polyester
  • I24TL exfoliable montmorillonite type
  • a maximum formation of the delaminated nanostructures of I24TL (exfoliation) during the technological process of in-situ polymerization by steps according to the invention in the process stages of esterification and melt polycondensation should significantly impair the gas barrier and UV absorption behavior of the resulting PET-NCs. be flown and controlled.
  • FIG. 17 shows a scheme of a product circulation procedure of a plant operated semi-continuously for the production of polyester, both in the pressure esterification reactor and in the polycondensation reactor, via corresponding gear pumps heated with heat transfer oil.
  • a paste preparation container 1 a mixture of terephthalic acid (PTA), isophthalic acid (IPA), ethylene glycol (EG) and a 1-15 percent, preferably 5-10 percent I24TL ethylene glycol suspension (which is mixed with a friction ball mill) pre-grinding in the preceding separate process stage and has been stoichiometrically balanced with KOH) and a catalyst (antimony III acetate) while stirring with a paddle stirrer as a viscous paste.
  • PTA terephthalic acid
  • IPA isophthalic acid
  • EG ethylene glycol
  • a 1-15 percent, preferably 5-10 percent I24TL ethylene glycol suspension which is mixed with a friction ball mill pre-grinding in the preceding separate process stage and has been stoichiometrically balanced with KOH) and a catalyst (antimony III acetate) while stirring with a paddle stirrer as a viscous paste.
  • this paste mixture passes via an eccentric screw pump 2 into the esterification reactor 3 with rectification column and installed fast rotating propeller stirrer, where it constantly circulates until the end of the pressure esterification reaction is circulated through a gear pump 4 while the 3 - 10 times, preferably 5 - 6 times, the amount of esterification formed during the esterification time of 100 - 200 minutes depending on the set esterification pressure in the gear pump circulation is moved.
  • the I24TL nanosheet silicate Due to the gear pump 4 in the pressure esterification reactor, the I24TL nanosheet silicate, which is already slightly precentered by ethylene glycol in the attritor, is constantly subjected to intensive shear, whereby a very high degree of intercalation with partly beginning exfoliation of the phyllosilicate used can be achieved towards the end of the esterification at a degree of esterification> 95% , Obviously by a significant decrease in the turbidity of the esterification product in comparison to a Druckverest mecanicsfahrweise without the claimed circulation method via the gear pump.
  • Polyesternanocompositemmelz is deformed via a melt discharge nozzle in a cold water tub to strands, which are then cut by means of strand pelletizer 10 to granules and a silo tank 11 collected.
  • exfoliated I24TL nanosheet silicate platelets thus introduced into the polyester matrix on the way of the in-situ melt condensation, which on account of their stoichiometric balance with KOH do not form a covalent bond with the polyester matrix, cause the formation according to the invention of a defined microcrystalline and nanocrystallite structure during the crystallization from the amorphous state, which in turn has an advantageous effect on the accelerated diffusion behavior of ethylene glycol in the solid-phase condensation of the polyester according to the invention in SSP plants and thus shortened SSP residence times, since from the crystallized Polyesternanocompositematerial with lower crystallite large compared to layer silicate-free polyester material larger Kristal I itab distren the free ethylene glycol formed by post-condensation from the SSP granules can be removed by vacuum or hot nitrogen easier.
  • the shear thinning behavior of the obtained polyester anocomposite melt was determined in accordance with the present invention, the steepness of the increase in the melt viscosity curve in said low shear range representing a measure of the exfoliation quality.
  • was found to be sufficient to achieve good to very good exfoliation of the I24TL nanosheet silicate platelets in the polyester matrix (see FIG. 6, Example 2).
  • n.sub.1 -0.7 I a shear thinning coefficient n.sub.1 -0.7 I indicated good to very good exfoliation.
  • WAXS wide-angle X-ray diffraction
  • a newly formed X-ray reflex peak in the 2-theta range 6-7 degrees also has re-aggregated Nano Mrssilikatplättchen towards montmorillonite lattice structure, which is due to thermal decomposition of organophilic Nano Mrssili- katen the case.
  • Pure sodium montmorillonite (Na-MMT) has an X-ray reflectance peak at 2Theta of about 8 degrees, depending on the residual moisture content of water.
  • the invention relates to the production and application of a single-grade PET nanocomposite having an excellent barrier effect, which is suitable, in particular, for use as a bottle raw material, without the use of a second matrix polymer.
  • a material designed according to the present invention enables multiple material or chemical recycling while retaining the originally obtained mechanical and barrier properties with acceptable technical properties. see effort. Montmorillonite as a natural phyllosilicate has no toxic properties even after organophilization with aminododecanoic acid, so that even higher levels of incorporation into the polyester matrix should be harmless, which is prescribed by law, especially in the food-grade range for film and bottle packaging according to FDA regulation and consumer goods regulation.
  • the invention relates to a process for obtaining polyester types (homo-PET and Co-PET) having improved manufacturing and service properties, which contain, in particular, higher temperature-resistant organophilic nanosheet silicates in the range of 0.01 to 20 wt.%.
  • a commercially available, thermally very stable organophilic nanosheet silicate type is the process of producing HOMO polyester or co-polyester as an additive in amounts of 0.01-20 wt.%, Preferably 0.5-10 wt.%, during the in situ polymerization of bis-hydroxyethylene terephthalate monomer (BHET) to obtain polyesters of the present invention having a high exfoliation rate of the used Nano Mrssilikatplättchen used in the polyester matrix.
  • the nanosheet silicate type used is, for example, a nanomer I24TL based on sodium montmorillonite which is commercially available from Nanocor Inc.
  • the I24TL monomer and also KOH, or NaOH or hexamethylenediamine are either already added to a paste mixture comprising aromatic dicarboxylic acid, preferably terephthalic acid (PTA). and isophthalic acid (IPA) and a dialkylene glycol, preferably ethylene glycol, and then esterified without pressure or under pressure up to 5 bar to diglycol cerephthalate, or in another variant of the invention already in present, melted co-BHET esterification product ( Bis-hydroxyethylene-co-terephthalate) is metered in by the DMT process or by the TPA direct esterification process, and then in a second process stage the actual polycondensation of the di-glycol terephthalate or diglycol co-modified with I24Tl phyllosilicate. Terephthalates performed.
  • PTA terephthalic acid
  • IPA isophthalic acid
  • a dialkylene glycol preferably ethylene glycol
  • nanosheet silicate additive and KOH, or NaOH in the melt of BHET or BHET / Co monomer in the temperature range of 170-240 ° C takes place either as a solid or in the case of hexamethylenediamine a ls g loly aqueous solution, or preferably in the form of an ethylene glycol suspension consisting of nanomer I24TL and KOH (or NaOH or hexamethylenediamine), which had previously been prepared via a corresponding dispersion stage (dispersion with urea rack and wet ball mill).
  • This particular oil suspension according to the invention is preferably already present during the homogenization of a paste mixture consisting of aromatic dicarboxylic acids (preferably terephthalic acid and isophthalic acid), glycols (preferably ethylene glycol, diethylene glycol and cyclohexane-imethanol) and a polycondensation catalyst (preferably antimony triacetate) is added and subsequently subjected to an esterification to give di-glycol terephthalate or diglycol-co-terephthalate.
  • aromatic dicarboxylic acids preferably terephthalic acid and isophthalic acid
  • glycols preferably ethylene glycol, diethylene glycol and cyclohexane-imethanol
  • a polycondensation catalyst preferably antimony triacetate
  • FIG. 13 provides a corresponding graphical overview of the oxygen barrier values obtained in Examples 2 and 3 in comparison with an additive-free polyester film and a polyester film filled only with 3 wt% sodium montmorillonite.
  • the need for a stoichiometric balancing of the excess of carboxyl end groups (COOH) introduced by the aminododecanoic acid of the I24TL nanomer - and the associated reduction in the pH in the polyester melt - plays a very important role, for which purpose according to the present invention the additional simultaneous addition of KOH, or NaOH or Hexamethylendia- min heard.
  • COOH carboxyl end groups
  • PET-NC precursor materials were used for a subsequent SSP reaction .
  • organophilic nanosheet silicates with quaternary ammonium salts based on long-chain alkyl groups C14... C18
  • Process temperatures in the in-situ polycondensation process for PET led to a thermal decomposition of the organophilic Nano Mrssilikate due to the above HOFFMANN degradation reaction.
  • the thermal decomposition of the nanosheet silicate used Upon application of the vacuum to carry out the polycondensation reaction, the thermal decomposition of the nanosheet silicate used increasingly increased with increasing polycondensation temperature.
  • the released gaseous decomposition products therefore caused only a vacuum of at most 20 mbar at a product temperature of 280 0 C and 50 mbar at 285 - 288 0 C towards the end of the polycondensation.
  • a strong brown low molecular weight Homo-Polyesternanocomposit was obtained with an IV of only 0.40 dl / g. Due to the low polymer viscosity, no APET cast film was produced.
  • Comparative Example 3 The procedure of Comparative Example 3 was repeated except that the addition amount of the thermally stable in a vacuum drying cabinet at 2 mbar and 100 0 C dried organophilic nano-layer silicate I24TL on 31 g (3 wt.% Based on the polyester) was increased. Excess ethylene glycol a product temperature of 265 0 C was in the subsequent transesterification with stirring until reaching distilled off and the thus continued transesterification reaction proceeded again without foaming of the melt. When applying the vacuum program, there were no problems, so that a final vacuum of 2 mbar at a product temperature of 286 0 C was easily achieved.
  • the granulated polyester chips were sufficiently dried and used to cast an APET reference film 100 ⁇ m thick on a laboratory film casting machine from Göttfert.
  • the thus-obtained reference film has a high UV transmittance of 90% in the wavelength region of 350 nm.
  • the granulated polyester chips were sufficiently dried and poured therefrom an APET film of thickness 100 .mu.m on a laboratory film casting of Göttfert.
  • the oxygen-Barrierertest with the gas permeation measurement instrument of Brugger gave an O 2 permeability value of 38.4 cm3 / 100 microns x 24 h x bar.
  • the obtained polyester film still has a very high UV transmittance value of 90% in the wavelength range of 350 nm comparable to that of the reference film of Comparative Example 5. Only at a wavelength of ⁇ 325 nm does a strong reduction in UV transmission begin.
  • Comparative Example 4 The procedure of Comparative Example 4 was repeated in that immediately after addition of the addition amount of 31 g (3 wt.% Based on polyester) of dried in a vacuum oven at 2 mbar and 100 0 C thermally stable organophilic Nanotiksilikates I24TL Nanocor Inc. on reaching 190 0 C product temperature now 3 g (0, 17 mol) of hexamethylenediamine in the form of an aqueous 70% solution were additionally added. Excess ethylene glycol was expelled until reaching a product temperature of 265 ° C. The distilled EG contained no hexamethylenediamine (indicator test and Smell test).
  • Embodiment 2 is a diagrammatic representation of Embodiment 1:
  • the granulated polyester chips were sufficiently dried and cast thereon a 100 ⁇ m thick APET film on a laboratory film caster.
  • the oxygen-Barrierertest with the gas permeation measuring gave an O 2 permeability value of 23 cm3 / 100 microns x 24 h x bar.
  • the obtained film furthermore has a greatly reduced UV transmission in the wavelength range of 350 nm with 30% residual transmission compared with 90% of a comparable polyester reference film without nanosheet silicate (Comparative Example 5).
  • the granulated polyester chips were sufficiently dried and poured therefrom an APET film of thickness 100 .mu.m on a laboratory film casting of Göttfert.
  • the oxygen-Barrierertest with the gas permeation measuring Brugger gave an O 2 permeability value of 10 cm3 / 100 x 24 microns hx bar.
  • the obtained film furthermore has a markedly reduced UV transmission in the wavelength range of 350 nm with 15% residual transmission compared to 90% of a comparable polyester reference film without nanosheet silicate (Comparative Example 5).
  • the granulated polyester chips were sufficiently dried and poured therefrom an APET film of thickness 100 .mu.m on a laboratory film casting of Göttfert.
  • the oxygen-Barrierertest with the gas Permeation Brugger gave an O 2 permeability value of 20 cm3 / 100 microns x 24 h x bar.
  • the film obtained therefrom furthermore exhibited a markedly reduced UV transmission in the wavelength range of 350 nm with 30% residual transmission compared to 90% of a comparable polyester reference film without nanosheet silicate (see FIG. 15 for comparative example 5).
  • Solid phase condensation experiments at temperatures of 225 0 C and 230 0 C in a vacuum oven at a pressure of 1 mbar resulted in a shortening of the SSP residence time by a factor of 2 to obtain an intrinsic viscosity of 0.92 dl / g.
  • Embodiment 5 is a diagrammatic representation of Embodiment 5:
  • the homogeneous paste was pumped into the preheated at 220 ° C 280 liter esterification reactor with attached rectification and started by increasing the jacket temperature according to a temperature ramp Druckverungsre hope the paste at a Reaktorinnend jerk of 4 bar to diglycol co-terephthalate.
  • both the initial paste mixture, and esterification product increasingly formed during this time were intensively sheared through a heated gear pump in the circulation in the esterification stage and 8 times the amount of the esterification product in the reactor via this circulation line back into the Promoted esterification reactor.
  • the degree of esterification of this experimental setting was determined to be 98% by way of the amount of water eliminated and the number of carboxyl groups determined from an esterification sample.
  • Sampling after the end of the esterification a sampling valve showed an almost transparent, slightly yellowish esterification product.
  • This esterification product was pressed after the esterification reaction at a product temperature of 260 0 C by means of the gear pump in a 200-liter polycondensation reactor, which was equipped with a helical stirrer, which initially rotated at 40 rev / min.
  • the gear-melt-feed and melt-discharge pump was put in operation, first the low-viscosity diglycol-co-terephthalate and later the higher-viscosity PET melt in the circuit via a static mixing unit and a distributor nozzle / distributor ring back into the Polycondensation reactor moved.
  • a static mixing unit and a distributor nozzle / distributor ring back into the Polycondensation reactor moved.
  • an intensive shear dispersion of the I24TL phyllosilicate was achieved.
  • the speed was decreased from 40 U / min to 10 U / min.
  • the polycondensation reaction was terminated after 165 minutes.
  • the melt pressure in the circulation line was 50 bar at the end of the polycondensation.
  • the PET nanocomposite melt was then removed by means of the same geared melt pump under vacuum through a 20-hole nozzle plate in a cooled granulation bath and added to it Formed strands, which were then cut with a strand granulator to 2.5 x 3.5 mm long granules.
  • the intrinsic viscosity of this co-PET Nanocmposite experimental setting was determined to be 0.71 dl / g, the COOH Endgrupeniere to 31 ⁇ equv / g and had the melting point to 245 0 C.
  • the obtained PET NC granules completely transparent and had a yellowish-brownish color.
  • Cast films were prepared from the sample material having a 3 wt% I24TL nanohistate silicate content.
  • Figure 18 shows a TEM image of such an unstretched cast film, which indicates that a significant portion of the I24TL nanosheet silicates are very well exfoliated (clearly visible as isolated sheet silicate platelets) or a residual intercalate structure (tac-to-platelet stacks ) is present.
  • the oxygen barrier test with the gas Permeation Brugger gave an O 2 permeability value of 19 cm3 / 100 microns x 24 h x bar.
  • Embodiment 6 is a diagrammatic representation of Embodiment 6
  • Example 5 The same formulation and experimental parameters as used in Example 5 were used, except that during the esterification reaction as well as during the polycondensation reaction, the respective product circuits were out of operation via the respective gear pumps, and thus above all in the polycondensation so that the permanent melt conveyance via the static mixer unit as well as via the melt distribution nozzle / melt distributor ring was also not in operation.
  • the intrinsic viscosity T his co-PET Nanocmposite experimental setting was determined to be 0.70 dl / g, the COOH end group ⁇ equv / g to 51 and melting point about 241 0 C.
  • the obtained PET NC granules were slightly turbid, and had a yellowish brown color.
  • Casting films were again produced from the sample material having an I24Tl nanosheet silicate content of 3 wt%.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Polymers & Plastics (AREA)
  • Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

L'invention concerne un procédé pour produire des nanocomposites polyester en vue d'un traitement ultérieur pour produire des films d'emballage correspondants ou des récipients d'emballage. Selon l'invention, entre 0,01 et 20 % en poids d'un silicate nanocouches organophile et stable thermiquement et des quantités équimolaires correspondantes d'agents supplémentaires de base sont d'abord estérifiés, sous forme solide ou comme suspensions contenant de l'éthylène-glycogène dispersés, avec des acides dicarboxyliques aromatiques monomères et des glycols aliphatiques monomères dans un réacteur d'estérification sans pression ou à une pression jusqu'à 5 bar, lors de l'introduction d'une sollicitation intensive et permanente dans le déroulement du circuit par une pompe à roue dentée jusqu'à un degré d'estérification supérieur à 95 %, en silicate-diglycol-co-téréphtalate en couches à degré élevé et intercalées. Puis ils sont transformés dans un réacteur à polycondensation soumis à une pression sous vide dans un circuit continu du mélange polyester présentant une sollicitation intensive et permanente au moyen d'une pompe à roue dentée et d'un élément de matière fondue, ainsi que lors de l'utilisation d'un dispositif d'évaporation en couches minces accéléré par des ions se présentant sous la forme d'une buse de répartition de la matière fondue, en association avec des anneaux de répartition de matière fondue rotatifs dans une réaction de polycondensation in situ à phase de fonte, en nanocomposites co-polyester transparents, à viscosité élevée présentant un degré d'exfoliation élevé de la couche de silicate stable thermiquement ainsi obtenue.
PCT/EP2006/066654 2005-10-10 2006-09-22 Procede pour produire des nanocomposites polyester WO2007042387A1 (fr)

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DE102005048769A DE102005048769A1 (de) 2005-10-10 2005-10-10 Verfahren zur Herstellung von Polyester mit verbesserten Herstellungs- und Gebrauchseigenschaften zur Anwendung in der Verpackungsmittelindustrie
DE102005048769.6 2005-10-10

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DE102009010597A1 (de) * 2008-07-12 2010-01-14 Epc Industrial Engineering Gmbh Verfahren zur Herstellung von Polyester, insbesondere linearer Polyester, für Textilgarne und Textilfasern sowie für Flaschen und Anlage zur Durchführung des Verfahrens
CN103469326A (zh) * 2013-09-22 2013-12-25 徐州斯尔克纤维科技股份有限公司 一种大直径高粘涤纶单丝的制作方法

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DE102007037422A1 (de) * 2007-08-08 2009-02-19 Perma-Tec Gmbh & Co. Kg Schmierstoffspender

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US5707439A (en) * 1995-04-03 1998-01-13 General Electric Company Layered minerals and compositions comprising the same
WO1998029499A1 (fr) * 1996-12-31 1998-07-09 Eastman Chemical Company Compositions de polyester a indice logarithmique de viscosite eleve contenant des particules en plaquettes
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DE10128356A1 (de) * 2000-06-14 2003-01-02 Thueringisches Inst Textil Verfahren zur Herstellung nanoverstärkter, thermoplastischer Polymerer
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DE3806548A1 (de) * 1987-03-04 1988-09-15 Toyoda Chuo Kenkyusho Kk Verbundmaterial und verfahren zu dessen herstellung
US5707439A (en) * 1995-04-03 1998-01-13 General Electric Company Layered minerals and compositions comprising the same
WO1998029499A1 (fr) * 1996-12-31 1998-07-09 Eastman Chemical Company Compositions de polyester a indice logarithmique de viscosite eleve contenant des particules en plaquettes
DE19905503A1 (de) * 1999-02-10 2000-08-17 Basf Ag Thermoplastische Nanocomposites
CA2548450A1 (fr) * 2003-12-12 2005-06-23 Kaneka Corporation Composition de resine polyester et objet moule

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102009010597A1 (de) * 2008-07-12 2010-01-14 Epc Industrial Engineering Gmbh Verfahren zur Herstellung von Polyester, insbesondere linearer Polyester, für Textilgarne und Textilfasern sowie für Flaschen und Anlage zur Durchführung des Verfahrens
CN103469326A (zh) * 2013-09-22 2013-12-25 徐州斯尔克纤维科技股份有限公司 一种大直径高粘涤纶单丝的制作方法

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