WO2017148795A1 - Isophthalic acid dichloride for increasing the storage stability of xylylene diisocyanate - Google Patents

Isophthalic acid dichloride for increasing the storage stability of xylylene diisocyanate Download PDF

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WO2017148795A1
WO2017148795A1 PCT/EP2017/054201 EP2017054201W WO2017148795A1 WO 2017148795 A1 WO2017148795 A1 WO 2017148795A1 EP 2017054201 W EP2017054201 W EP 2017054201W WO 2017148795 A1 WO2017148795 A1 WO 2017148795A1
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xdi
isophthalic acid
xylylene diisocyanate
ipdc
storage stability
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PCT/EP2017/054201
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German (de)
French (fr)
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Mathias Matner
Christoph Eggert
Josef Sanders
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Covestro Deutschland Ag
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C263/00—Preparation of derivatives of isocyanic acid
    • C07C263/18—Separation; Purification; Stabilisation; Use of additives

Definitions

  • the present invention relates to the use of isophthalic acid dichloride for increasing the storage stability of xylylene diisocyanate and to compositions comprising xylylene diisocyanate and isophthalic acid dichloride.
  • Xylylene diisocyanate is an industrially important special diisocyanate, which stands by the combination of an aromatic ring with the two aliphatically bound isocyanate groups in its reactivity and its properties between the aromatic and the aliphatic diisocyanates. It is characterized by a high refractive index, similar to the aromatic diisocyanates, as well as, similar to the aliphatic diisocyanates, a low yellowing tendency in the fully reacted state (for example as polyurethane).
  • XDI in particular m-xylylene diisocyanate (m-XDI)
  • m-XDI m-xylylene diisocyanate
  • Pure XDI is not shelf-stable for more than a few weeks. Sometimes cloudiness and discoloration are observed after only a few days.
  • plastics e.g. Polyurethanes, ve used, also have the plastics produced therefrom discoloration and / or turbidity. This is undesirable both in packaging adhesives and in particular in optical components. Therefore, there is a considerable need for agents and processes that increase the storage stability of XDI.
  • 5,302,749 is represented by various phenol derivatives which could show stabilization by their weak acid character and by reaction with the XDI and formation of urethane species. Among these more than 10 potential stabilizers, only phenol shows a positive effect. Furthermore, in US Pat. No. 5,302,749, strong and weak acids were tested for their stabilizing effect. In the examined spectrum no acid was found, which showed a sufficient stabilizing effect. Efforts to stabilize the XDI by adding benzoyl chloride as acid generator (indirect acidification) were also unsuccessful. All these results indicate that the suitability of a compound as a stabilizer for XDI can not be reliably predicted based on known data. In particular, there are no identifiable structural Effect relationship. From this situation, it was surprising that only the isophthalic acid dichloride proved to be a suitable stabilizer for XDI among all compounds tested.
  • the object of the present invention was to identify substances which increase the storage stability of XDI without adversely affecting its performance properties. This object is achieved by the embodiments defined in the patent claims and in this specification.
  • the present invention relates to the use of isophthalic acid dichloride (IPDC) to increase the storage stability of xylylene diisocyanate.
  • IPDC isophthalic acid dichloride
  • isophthalic acid dichloride is meant a compound of formula (I)
  • xylylene diisocyanate is meant a compound of formula (II), (III) or (IV)
  • XDI is available by phosgenation of xylylenediamine. This phosgenation can take place in the liquid phase or in the gas phase.
  • IPDC is used to increase the storage stability of XDI which has been phosgenated in the gas phase.
  • the storage stability of m-XDI produced in the gas phase is increased by IPDC.
  • the term "storage stability” refers to the change in the properties of XDI during storage, particularly relevant properties are (i) color and (ii) clarity and (iii) performance properties
  • a key performance characteristic is the pot life of mixtures of XDI and The color and clarity of the XDI monomer are directly reflected in the appearance of the film or body produced, and too high a reactivity of the XDI - and thus a too short pot life - results in the reaction with polyols or polythiols a strong exotherm, which can lead to the occurrence of streaks and bubbles especially in transparent solids.
  • XDI should be as colorless and transparent as possible.
  • XDI without the addition of stabilizers shows a clear turbidity and a clear discoloration after only 1 week, while other typical properties such as the NCO content or the viscosity still have no measurable change.
  • Shelf-stable XDI shows after storage preferably a turbidity of a maximum of 1 NTU and a color index of 20 Hazen maximum.
  • the color number is preferably determined according to DIN EN ISO 11664-4 (from 01.06.2012).
  • the turbidity is preferably measured according to DIN EN ISO 7027 (from 01.04.2000).
  • shelf-stable XDI the above parameters are maintained within the limits defined above during storage of preferably at least 6 months, more preferably at least 3 months, and most preferably at least 8 weeks.
  • Storage at 23 ° C. under exclusion of air preferably takes place in a vessel which on the inside consists of one or more materials which do not react with isophthalic acid or isophthalic acid chloride.
  • preferred Materials that meet these requirements are metals, in particular aluminum or stainless steel, plastics, in particular polyethylene or polypropylene, glass and ceramic.
  • the vessel must insulate against the ingress of water vapor. Again, the aforementioned materials are suitable, provided that they are used with a sufficient wall thickness.
  • the storage takes place in an aluminum bottle.
  • a "receptacle consisting on the inside of one or more materials which do not react with isophthalic acid or isophthalic acid chloride” is a receptacle the inside walls of which are coated with or consisting of a corresponding material or a mixture of corresponding materials, so that the material contained therein XDI and the IPDC come into contact only with the corresponding surfaces and it is also preferred to ensure that water vapor can not penetrate into the closed vessel
  • the parts of the vessel that are not in contact with the XDI and XDI during storage of the XDI IPDC can be made of any materials, including those parts of the vessel that only come into contact with XDI and / or IPDC when they are filled or emptied.
  • ppm IPDC Preferably, between 100 and 1000 ppm IPDC, more preferably between 100 ppm and 500 ppm IPDC is added to the XDI.
  • the final concentration of IPDC is at least 100 ppm. More preferably, it is between 100 and 1000 pp, and most preferably between 100 and 500 ppm.
  • the present invention relates to a method for increasing the storage stability of XDI comprising the step of adding isophthalic acid dichloride (IPDC) to xylylene diisocyanate (XDI).
  • IPDC isophthalic acid dichloride
  • XDI xylylene diisocyanate
  • the present invention relates to a composition containing xylylene diisocyanate (XDI) and isophthalic acid dichloride (IPDC).
  • XDI xylylene diisocyanate
  • IPDC isophthalic acid dichloride
  • IPDC Preferably, between 100 ppm and 1000 ppm IPDC, more preferably between 100 and 500 ppm IPDC is added to the XDI.
  • the content of XDI is preferably 95% by weight, more preferably 97% by weight, and most preferably 98% by weight.
  • the final concentration of IPDC in the composition of the invention is preferably at least 100 ppm, more preferably between 100 and 1000 ppm, most preferably 100 to 500 ppm.
  • the various stabilizers were purchased from Sigma-Aldrich as a technical product and mixed at room temperature with XDI and stirred until they were completely dissolved.
  • the various XDI samples were filled in internally painted aluminum bottles and stored for several weeks / months at room temperature (23 ° C).
  • the NCO contents were determined titrimetrically in accordance with DIN EN ISO 11909 (from 01.05.2007).
  • the turbidity was measured with a 2100 AN IS Turbidimeter from Hach Lange in accordance with DIN EN ISO 7027 (from 01.04.2000).
  • the color number was determined with the aid of a LICO 690 from Hach Lange according to method DIN-EN-ISO 11664-4 (from 01.06.2012).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Paints Or Removers (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The present invention relates to the use of isophthalic acid dichloride for increasing the storage stability of xylylene diisocyanate and to compositions containing xylylene diisocyanate and isophthalic acid dichloride.

Description

Isophthalsäuredichlorid zur Erhöhung der Lagerstabilität von Xylylendiisocyanat  Isophthalic acid dichloride for increasing the storage stability of xylylene diisocyanate
Die vorliegende Erfindung betrifft die Verwendung von Isophthalsäuredichlorid für die Erhöhung der Lagerstabilität von Xylylendiisocyanat sowie Zusammensetzungen enthaltend Xylylendiisocyanat und Isophthalsäuredichlorid. The present invention relates to the use of isophthalic acid dichloride for increasing the storage stability of xylylene diisocyanate and to compositions comprising xylylene diisocyanate and isophthalic acid dichloride.
Xylylendiisocyanat ist ein industriell wichtiges Spezialdiisocyanat, das durch die Kombination eines aromatischen Ringes mit den beiden aliphatisch gebu ndenen Isocyanatgruppen in seiner Reaktivität und seinen Eigenschaften zwischen den aromatischen und den aliphatischen Diisocyanaten steht. Es zeichnet sich durch einen hohen Brechungsindex, ähnlich den aromatischen Diisocyanaten, sowie, ähnlich den aliphatischen Diisocyanaten, eine geringe Vergilbungsneigung im ausreagierten Zustand (z.B. als Polyurethan) aus. Dadurch hat XDI, insbesondere m-Xylylendiisocyanat (m-XDI), Verwendungen in vielen Bereichen gefunden, beispielsweise als Härter in Verpackungsklebstoffen oder bei der Herstellung von optischen Bauteilen wie z.B. Linsen. Xylylene diisocyanate is an industrially important special diisocyanate, which stands by the combination of an aromatic ring with the two aliphatically bound isocyanate groups in its reactivity and its properties between the aromatic and the aliphatic diisocyanates. It is characterized by a high refractive index, similar to the aromatic diisocyanates, as well as, similar to the aliphatic diisocyanates, a low yellowing tendency in the fully reacted state (for example as polyurethane). As a result, XDI, in particular m-xylylene diisocyanate (m-XDI), has found uses in many fields, for example, as curing agents in packaging adhesives or in the manufacture of optical components, e.g. Lenses.
Reines XDI ist nicht länger als wenige Wochen lagerstabil. Teilweise werden schon nach wenigen Tagen Trübungen und Verfärbungen beobachtet. Wird getrübtes und/oder verfärbtes XDI für als Rohstoff für die Herstellung von Kunststoffen, z.B. Polyurethanen, ve rwendet, weisen auch die daraus hergestellten Kunststoffe Verfärbungen und/oder Trübungen auf. Dies ist sowohl bei Verpackungsklebstoffen als auch insbesondere bei optischen Bauteilen unerwünscht. Deswegen besteht ein erheblicher Bedarf nach M itteln und Verfahren, die die Lagerstabilität von XDI erhöhen. Pure XDI is not shelf-stable for more than a few weeks. Sometimes cloudiness and discoloration are observed after only a few days. When cloudy and / or discolored XDI is used as a raw material for the production of plastics, e.g. Polyurethanes, ve used, also have the plastics produced therefrom discoloration and / or turbidity. This is undesirable both in packaging adhesives and in particular in optical components. Therefore, there is a considerable need for agents and processes that increase the storage stability of XDI.
Es sind zahlreiche Substanzen bekannt, mit denen sich Isocyanate stabilisieren lassen. Beispiele sind phenolische Stabilisatoren wie z.B. Pyrogallol, Catechol, Guaiacol, Eugenol oder Pentachlorphenol (US Patent 5,194,559). Jedoch ist die Stabilisierung von XDI - insbesondere in einer Qualität, die für optische Anwendungen geeignet ist - nicht trivial und auch nicht mit der Stabilisierung der Standard isocyanate vergleichbar. Eine sehr umfangreiche Untersuchung bezüglich der Stabilisierung von XDI wurde in US 5,302,749 beschrieben. Dort werden viele verschiedene Klassen von potentiellen Stabilisatoren in Bezug auf ihre Stabilisierungswirkung bei XDI untersucht. Den größten Anteil in US 5,302,749 stellen verschiedene Phenolderivate, die durch ihren schwachen Säurecharakter und durch Reaktion mit dem XDI und Bildung von Urethanspezies eine Stabilisierung zeigen könnten. Unter diesen mehr als 10 potentiellen Stabilisatoren zeigt nur Phenol eine positive Wirkung. Weiterhin wurden in US 5,302,749 starke und schwache Säuren auf ihre stabilisierende Wirkung hin untersucht. In dem untersuchten Spektrum fand sich keine Säure, die eine ausreichende stabilisierende Wirkung zeigte. Ebenfalls erfolglos waren die Bemühungen durch Zugabe von Benzoylchlorid als Säurebildner (indirekte Ansäuerung) das XDI zu stabilisieren. All diese Ergebnisse zeigen, dass die Eignung einer Verbindung als Stabilisator für XDI auf Grundlage bekannter Daten nicht zuverlässig vorhergesagt werden kann. Insbesondere gibt es keine erkennbare Struktur- Wirkungs-Beziehung. Von dieser Situation ausgehend war es überraschend, dass sich unter allen getesteten Verbindungen nur das Isophthalsäuredichlorid als geeigneter Stabilisator für XDI erwies. There are numerous known substances with which isocyanates can be stabilized. Examples are phenolic stabilizers such as pyrogallol, catechol, guaiacol, eugenol or pentachlorophenol (US Patent 5,194,559). However, the stabilization of XDI - especially in a quality that is suitable for optical applications - is not trivial and also not comparable to the stabilization of standard isocyanates. A very extensive study on the stabilization of XDI has been described in US 5,302,749. There, many different classes of potential stabilizers are being investigated for their stabilizing effect on XDI. The largest proportion in US Pat. No. 5,302,749 is represented by various phenol derivatives which could show stabilization by their weak acid character and by reaction with the XDI and formation of urethane species. Among these more than 10 potential stabilizers, only phenol shows a positive effect. Furthermore, in US Pat. No. 5,302,749, strong and weak acids were tested for their stabilizing effect. In the examined spectrum no acid was found, which showed a sufficient stabilizing effect. Efforts to stabilize the XDI by adding benzoyl chloride as acid generator (indirect acidification) were also unsuccessful. All these results indicate that the suitability of a compound as a stabilizer for XDI can not be reliably predicted based on known data. In particular, there are no identifiable structural Effect relationship. From this situation, it was surprising that only the isophthalic acid dichloride proved to be a suitable stabilizer for XDI among all compounds tested.
Ausgehend von den Substanzen, die zur Stabilisierung anderer Isocyanate geeignet sind, lag der vorliegenden Erfindung die Aufgabe zugrunde, Substanzen zu identifizieren, die die Lagerstabilität von XDI erhöhen, ohne dessen anwendungstechnische Eigenschaften zu beeinträchtigen. Diese Aufgabe wird durch die in den Patentansprüchen und in dieser Beschreibung definierten Ausführungsformen gelöst. Based on the substances which are suitable for the stabilization of other isocyanates, the object of the present invention was to identify substances which increase the storage stability of XDI without adversely affecting its performance properties. This object is achieved by the embodiments defined in the patent claims and in this specification.
In einer Ausführungsform betrifft die vorliegende Erfindung die Verwendung von Isophthalsäuredichlorid (IPDC) zur Erhöhung der Lagerstabilität von Xylylendiisocyanat. In one embodiment, the present invention relates to the use of isophthalic acid dichloride (IPDC) to increase the storage stability of xylylene diisocyanate.
Unter„Isophthalsäuredichlorid" wird eine Verbindung nach Formel (I) verstanden By "isophthalic acid dichloride" is meant a compound of formula (I)
Figure imgf000003_0001
Figure imgf000003_0001
Unter„Xylylendiisocyanat" wird eine Verbindung nach Formel (II), (III) oder (IV) verstanden By "xylylene diisocyanate" is meant a compound of formula (II), (III) or (IV)
Figure imgf000003_0002
Figure imgf000003_0002
(Ii) (Iii) (IV) (Ii) (iii) (iv)
Besonders bevorzugt bezeichnet „XDI" wie in der vorliegenden Anmeldung verwendet m- Xylylendiisocyanat gemäß Formel (III). Particularly preferred "XDI" as used in the present application m-xylylene diisocyanate according to formula (III).
XDI ist durch Phosgenierung von Xylylendiamin erhältlich. Diese Phosgenierung kann in der Flüssigphase oder in der Gasphase erfolgen. XDI is available by phosgenation of xylylenediamine. This phosgenation can take place in the liquid phase or in the gas phase.
Die Herstellung von XDI in der Flüssigphase wird in EP 0 384 463 Bl beschrieben. Dabei wird 1,3- Xylylendiamin-Hydrochlorid in einer ersten Reaktionsstufe bei oder unterhalb 30 °C in einem Ester als Lösungsmittel hergestellt und die Phosgenierung des Amin-Hydrochlorids in einem zweiten Reaktionsschritt bei 120-170 °C durchgeführt. Weitere Optimierungen der Flüssigphasen- phosgenierung werden bspw. in der US 5,523,467 oder der EP 1 908 749 AI beschrieben. The preparation of XDI in the liquid phase is described in EP 0 384 463 B1. In this case, 1,3-xylylenediamine hydrochloride is prepared in a first reaction stage at or below 30 ° C in an ester as solvent and the phosgenation of the amine hydrochloride in a second Reaction step carried out at 120-170 ° C. Further optimizations of the liquid-phase phosgenation are described, for example, in US Pat. No. 5,523,467 or EP 1 908 749 A1.
Die Hersteilung von XDI in der Gasphase wird in WO 2015/155365 beschrieben. Dabei wird das entsprechende Diamin (XDA) bei einem Druck von < 1.000 mbar abs. verdampft, wobei die mittlere Verweilzeit im Verdampferkreislauf 5 bis 90 Minuten beträgt, die Temperatur im Umpumpkreislauf der Verdampfung bei 40 bis 190"C liegt. Anschließend werden die um weitere 10-100°K über die Verdampfungstemperatur des XDA unter dem gegebenen Druck erhitzten XDA-Brüden nach bekannten Verfahren der Gasphasen phosgenierung mit Phosgen umsetzt. Bei diesem Verfahren neigt, trotz der drastischen Reaktionsbedingungen, das hochempfindliche XDA nicht zur Bildung von Nebenprodukten wie z.B. Ammoniak u nd nichtflüchtigen Xylylenpolyaminen. The production of XDI in the gas phase is described in WO 2015/155365. The corresponding diamine (XDA) at a pressure of <1,000 mbar abs. the average residence time in the evaporator circuit is 5 to 90 minutes, the temperature in the pumped circulation circuit of the evaporation is 40 to 190 ° C. Subsequently, the XDA heated by a further 10-100 ° K above the vaporization temperature of the XDA under the given pressure is evaporated. In this process, despite the drastic reaction conditions, the highly sensitive XDA does not tend to form byproducts such as ammonia and nonvolatile xylylene polyamines.
Besonders bevorzugt wird IPDC verwendet, um die Lagerstabilität von XDI, das in der Gasphase phosgeniert wurde, zu erhöhen. Ganz besonders bevorzugt wird die Lagerstabilität von in der Gasphase hergestelltem m-XDI durch IPDC erhöht. More preferably, IPDC is used to increase the storage stability of XDI which has been phosgenated in the gas phase. With very particular preference, the storage stability of m-XDI produced in the gas phase is increased by IPDC.
Der Begriff „Lagerstabilität" bezeichnet die Veränderung der Eigenschaften von XDI während der Lagerung. Besonders relevante Eigenschaften sind (i) Farbe und (ii) Klarheit und (iii) anwendungstechnische Eigenschaften. Eine wesentliche anwendungstechnische Eigenschaft ist die Topfzeit von M ischungen von XDI und gegenüber Isocyanatgruppen reaktiver Verbindungen, insbesondere Polyolen oder Polythiolen. Farbe und Klarheit des XDI Monomers spiegeln sich direkt im Erscheinungsbild des hergestellten Films oder Körper wider. Eine zu hohe Reaktivität des XDIs - und damit eine zu kurze Topfzeit - führen bei der Reaktion mit Polyolen oder Polythiolen zu einer starken Exothermie, die insbesondere bei transparenten Volumenkörpern zum Auftreten von Schlieren und Blasen führen kann. The term "storage stability" refers to the change in the properties of XDI during storage, particularly relevant properties are (i) color and (ii) clarity and (iii) performance properties A key performance characteristic is the pot life of mixtures of XDI and The color and clarity of the XDI monomer are directly reflected in the appearance of the film or body produced, and too high a reactivity of the XDI - and thus a too short pot life - results in the reaction with polyols or polythiols a strong exotherm, which can lead to the occurrence of streaks and bubbles especially in transparent solids.
Wie oben bereits dargelegt, sollte XDI möglichst farblos und transparent sein. XDI ohne Zusatz von Stabilisatoren zeigt bereits nach 1 Woche eine deutliche Trübung und eine deutliche Verfärbung, während andere typische Eigenschaften wie der NCO-Gehalt oder die Viskosität noch keine messbare Veränderung aufweisen. Lagerstabiles XDI zeigt nach der Lagerung bevorzugt eine Trübung von maximal 1 NTU und eine Farbzahl von maximal 20 Hazen. Die Farbzahl wird vorzugsweise nach DIN- EN-ISO 11664-4 (vom 01.06.2012) bestimmt. Die Trübung wird vorzugsweise nach DIN EN ISO 7027 (vom 01.04.2000) gemessen. As stated above, XDI should be as colorless and transparent as possible. XDI without the addition of stabilizers shows a clear turbidity and a clear discoloration after only 1 week, while other typical properties such as the NCO content or the viscosity still have no measurable change. Shelf-stable XDI shows after storage preferably a turbidity of a maximum of 1 NTU and a color index of 20 Hazen maximum. The color number is preferably determined according to DIN EN ISO 11664-4 (from 01.06.2012). The turbidity is preferably measured according to DIN EN ISO 7027 (from 01.04.2000).
Bei lagerstabilem XDI halten sich die oben genannten Parameter während einer Lagerung von bevorzugt wenigstens 6 Monaten, stärker bevorzugt wenigstens 3 Monaten und am stärksten bevorzugt wenigstens 8 Wochen in den oben definierten Grenzen. Bevorzugt erfolgt die Lagerung bei 23°C unter Luftabschluss in einem Gefäß, das auf der Innenseite aus einem oder mehreren Werkstoffen besteht, die nicht mit Isophthalsäure oder Isophthalsäurechlorid reagieren. Bevorzugte Werkstoffe, die diese Anforderungen erfüllen, sind Metalle, insbesondere Aluminium oder Edelstahl, Kunststoffe, insbesondere Polyethylen oder Polypropylen, Glas und Keramik. Weiterhin muss das Gefäß gegen das Eindringen von Wasserdampf isolieren. Auch hierfür sind die vorgenannten Werkstoffe geeignet, sofern sie mit einer hinreichenden Wandstärke verwendet werden. Ganz besonders bevorzugt erfolgt die Lagerung in einer Aluminiumflasche. In shelf-stable XDI, the above parameters are maintained within the limits defined above during storage of preferably at least 6 months, more preferably at least 3 months, and most preferably at least 8 weeks. Storage at 23 ° C. under exclusion of air preferably takes place in a vessel which on the inside consists of one or more materials which do not react with isophthalic acid or isophthalic acid chloride. preferred Materials that meet these requirements are metals, in particular aluminum or stainless steel, plastics, in particular polyethylene or polypropylene, glass and ceramic. Furthermore, the vessel must insulate against the ingress of water vapor. Again, the aforementioned materials are suitable, provided that they are used with a sufficient wall thickness. Most preferably, the storage takes place in an aluminum bottle.
Ein „Gefäß, das auf der I nnenseite aus einem oder mehreren Werkstoffen besteht, die nicht mit Isophthalsäure oder Isophthalsäurechlorid reagieren" ist ein Gefäß, dessen Innenwände mit einem entsprechenden Werkstoff oder einem Gemisch entsprechender Werkstoffe beschichtet sind oder daraus bestehen, so dass das darin enthaltene XDI und das IPDC nur mit den entsprechenden Oberflächen in Kontakt kommt. Weiterhin ist es bevorzugt, dass sichergestellt ist, dass Wasserdampf nicht in das geschlossene Gefäß eindringen kann. Die Teile des Gefäßes, die während der Lagerung des XDI nicht in Kontakt mit dem XDI und dem IPDC stehen, können aus beliebigen Materialien gefertigt sein. Dies gilt auch für jene Teiles des Gefäßes, die nur beim Befüllen oder Entleeren mit XDI und/oder IPDC in Kontakt kommen. A "receptacle consisting on the inside of one or more materials which do not react with isophthalic acid or isophthalic acid chloride" is a receptacle the inside walls of which are coated with or consisting of a corresponding material or a mixture of corresponding materials, so that the material contained therein XDI and the IPDC come into contact only with the corresponding surfaces and it is also preferred to ensure that water vapor can not penetrate into the closed vessel The parts of the vessel that are not in contact with the XDI and XDI during storage of the XDI IPDC can be made of any materials, including those parts of the vessel that only come into contact with XDI and / or IPDC when they are filled or emptied.
Bevorzugt werden zwischen 100 und 1000 ppm IPDC, stärker bevorzugt zwischen 100 ppm und 500 ppm IPDC zum XDI zugegeben. Preferably, between 100 and 1000 ppm IPDC, more preferably between 100 ppm and 500 ppm IPDC is added to the XDI.
In einer besonders bevorzugten Ausführungsform beträgt die Endkonzentration von IPDC wenigstens 100 ppm. Stärker bevorzugt liegt sie zwischen 100 und 1000 pp und am stärksten bevorzugt zwischen 100 und 500 ppm. In a particularly preferred embodiment, the final concentration of IPDC is at least 100 ppm. More preferably, it is between 100 and 1000 pp, and most preferably between 100 and 500 ppm.
In einer weiteren Ausführungsform betrifft die vorliegende Erfindung ein Verfahren zur Erhöhung der Lagerstabilität von XDI enthaltend den Schritt der Zugabe von Isophthalsäuredichlorid (IPDC) zu Xylylendiisocyanat (XDI). In a further embodiment, the present invention relates to a method for increasing the storage stability of XDI comprising the step of adding isophthalic acid dichloride (IPDC) to xylylene diisocyanate (XDI).
Alle weiter oben in dieser Anmeldung gegebenen Definitionen sind auch auf diese Ausführungsform anwendbar. All definitions given earlier in this application are also applicable to this embodiment.
In einer weiteren Ausführungsform betrifft die vorl iegende Erfindung eine Zusammensetzung enthaltend Xylylendiisocyanat (XDI) und Isophthalsäuredichlorid (IPDC). In another embodiment, the present invention relates to a composition containing xylylene diisocyanate (XDI) and isophthalic acid dichloride (IPDC).
Alle weiter oben in dieser Anmeldung gegebenen Definitionen sind auch auf diese Ausführungsform anwendbar. All definitions given earlier in this application are also applicable to this embodiment.
Bevorzugt werden zwischen 100 ppm und 1000 ppm IPDC, stärker bevorzugt zwischen 100 und 500 ppm IPDC zum XDI zugegeben. Der Gehalt an XDI beträgt bevorzugt 95 Gew.-%, stärker bevorzugt 97 Gew.-% und am stärksten bevorzugt 98 Gew.-%. Die Endkonzentration von IPDC in der erfindungsgemäßen Zusammensetzung beträgt vorzugsweise wenigstens 100 ppm, stärker bevorzugt zwischen 100 und 1000 ppm, am stärksten bevorzugt 100 bis 500 ppm. Preferably, between 100 ppm and 1000 ppm IPDC, more preferably between 100 and 500 ppm IPDC is added to the XDI. The content of XDI is preferably 95% by weight, more preferably 97% by weight, and most preferably 98% by weight. The final concentration of IPDC in the composition of the invention is preferably at least 100 ppm, more preferably between 100 and 1000 ppm, most preferably 100 to 500 ppm.
Die folgenden Beispiele dienen dazu, die Erfindung zu illustrieren. Sie sollen den Umfang der Patentansprüche nicht beschränken. The following examples serve to illustrate the invention. They are not intended to limit the scope of the claims.
Beispiele Examples
Alle Prozentangaben beziehen sich, soweit nichts Anderslautendes vermerkt, auf das Gewicht. All percentages are by weight unless otherwise stated.
Die verschiedenen Stabilisatoren wurden bei Sigma-Aldrich als technische Ware bezogen und bei Raumtemperatur mit XDI vermischt und so lange gerührt, bis sie vollständig gelöst waren . The various stabilizers were purchased from Sigma-Aldrich as a technical product and mixed at room temperature with XDI and stirred until they were completely dissolved.
Für die Lagerung wurden die verschiedenen XDI Muster in innenlackierte Aluminiumflaschen gefüllt und für mehrere Wochen/Monate bei Raumtemperatur (23°C) aufbewahrt. For storage, the various XDI samples were filled in internally painted aluminum bottles and stored for several weeks / months at room temperature (23 ° C).
Die Bestimmung der NCO-Gehalte erfolgte titrimetrisch nach DIN EN ISO 11909 (vom 01.05.2007). The NCO contents were determined titrimetrically in accordance with DIN EN ISO 11909 (from 01.05.2007).
Die Messung der Trübung erfolgte mit einem 2100 AN IS Turbidimeter der Firma Hach Lange nach DIN EN ISO 7027 (vom 01.04.2000). The turbidity was measured with a 2100 AN IS Turbidimeter from Hach Lange in accordance with DIN EN ISO 7027 (from 01.04.2000).
Die Farbzahl wurde mit Hilfe eines LICO 690 der Firma Hach Lange nach Methode DIN-EN-ISO 11664- 4 (vom 01.06.2012) bestimmt. The color number was determined with the aid of a LICO 690 from Hach Lange according to method DIN-EN-ISO 11664-4 (from 01.06.2012).
Als Grenzwerte für die Trübung und Farbzahl, unterhalb derer das XDI ohne Einschränkung verwendbar ist, wurden folgende Werte gewählt: As threshold values for the turbidity and color number, below which the XDI can be used without restriction, the following values were selected:
Trübung: 1 < NTU Farbzahl : 20 < Hazen Haze: 1 <NTU Color Number: 20 <Hazen
Figure imgf000007_0001
Phenol + p- Toluolsulfon-
Figure imgf000007_0001
Phenol + p-toluenesulfone
Vergleich 4 500 0,3 126 - - säureamid + Comparison 4 500 0.3 126 - - acid amide +
lonol  ionol
XDI-T P  XDI-T P
Vergleich 5 500 11 n.m. - - Addukt  Comparison 5 500 11 n.m. - adduct
Triphenyl- triphenyl-
Vergleich 6 500 1,4 18 - - phosphit Comparison 6 500 1,4 18 - - phosphite
Isophthal- isophthalic
Erfindungsgemäß According to the invention
säure- 100 0,3 8 0,4 10 acid 100 0.3 8 0.4 10
1 1
dichlorid  dichloride
Isophthal- isophthalic
Erfindungsgemäß According to the invention
säure- 300 0,3 10 0,5 10 2  Acid 300 0.3 10 0.5 10 2
dichlorid  dichloride
Isophthal- isophthalic
Erfindungsgemäß According to the invention
säure- 500 0,3 9 0,3 9 Acid 500 0.3 9 0.3 9
3 3
dichlorid  dichloride
n.m. = nicht messbar aufgrund der starken Trübung  n.m. = not measurable due to the strong turbidity

Claims

Patentansprüche claims
Zusammensetzung enthaltend Xylyiendiisocyanat (XDI) und Isophthalsäuredichlorid (IPDC). Composition containing xylylene diisocyanate (XDI) and isophthalic acid dichloride (IPDC).
Die Zusammensetzung nach Anspruch 1, wobei mindestens 100 ppm IPDC zum XDI zugegeben werden. The composition of claim 1, wherein at least 100 ppm IPDC is added to the XDI.
Die Zusammensetzung nach Anspruch 2, wobei zwischen 100 und 1000 ppm IPDC zum XDI zugegeben werden. The composition of claim 2, wherein between 100 and 1000 ppm of IPDC is added to the XDI.
Die Zusammensetzung nach einem der Ansprüche 1 bis 3, wobei der Gehalt an XDI wenigstens 95 Gew.-% beträgt. The composition of any of claims 1 to 3, wherein the content of XDI is at least 95% by weight.
Die Zusammensetzung nach einem der Ansprüche 1 bis 4, wobei XDI m-XDI ist. The composition of any one of claims 1 to 4 wherein XDI is m -XDI.
Verwendung von IPDC zur Stabilisierung von XDI. Use of IPDC to stabilize XDI.
Verfahren zur Erhöhung der Lagerstabilität von XDI enthaltend den Schritt der Zugabe von IPDC zu XDC. A method for increasing the storage stability of XDI comprising the step of adding IPDC to XDC.
PCT/EP2017/054201 2016-02-29 2017-02-23 Isophthalic acid dichloride for increasing the storage stability of xylylene diisocyanate WO2017148795A1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3404053A1 (en) * 2017-05-17 2018-11-21 SKC Co., Ltd. Xylylene diisocyanate composition with improved stability and reactivity and optical lens using the same

Citations (6)

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Publication number Priority date Publication date Assignee Title
US5194559A (en) 1991-03-25 1993-03-16 Mitsui Toatsu Chemicals, Inc. Optical urethane resins and plastic lenses comprising the same
US5302749A (en) 1991-03-19 1994-04-12 Mitsui Toatsu Chemicals, Incorporated Stabilizing method of isocyanate compounds and isocyanate compositions stabilized thereby
EP0384463B1 (en) 1989-02-23 1994-08-10 MITSUI TOATSU CHEMICALS, Inc. Preparation process of xylylene diisocyanate
US5523467A (en) 1994-03-22 1996-06-04 Mitsui Toatsu Chemicals, Inc. Process for the preparation of aliphatic polyisocyanates
EP1908749A1 (en) 2005-07-22 2008-04-09 Mitsui Chemicals, Inc. Process for production of isocyanate, isocyanate produced by the process, and use of the isocyanate
WO2015155365A2 (en) 2014-04-11 2015-10-15 Bayer Materialscience Ag Method for producing xylylene diisocyanates in the gaseous phase

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0384463B1 (en) 1989-02-23 1994-08-10 MITSUI TOATSU CHEMICALS, Inc. Preparation process of xylylene diisocyanate
US5302749A (en) 1991-03-19 1994-04-12 Mitsui Toatsu Chemicals, Incorporated Stabilizing method of isocyanate compounds and isocyanate compositions stabilized thereby
US5194559A (en) 1991-03-25 1993-03-16 Mitsui Toatsu Chemicals, Inc. Optical urethane resins and plastic lenses comprising the same
US5523467A (en) 1994-03-22 1996-06-04 Mitsui Toatsu Chemicals, Inc. Process for the preparation of aliphatic polyisocyanates
EP1908749A1 (en) 2005-07-22 2008-04-09 Mitsui Chemicals, Inc. Process for production of isocyanate, isocyanate produced by the process, and use of the isocyanate
WO2015155365A2 (en) 2014-04-11 2015-10-15 Bayer Materialscience Ag Method for producing xylylene diisocyanates in the gaseous phase

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3404053A1 (en) * 2017-05-17 2018-11-21 SKC Co., Ltd. Xylylene diisocyanate composition with improved stability and reactivity and optical lens using the same
US10723696B2 (en) 2017-05-17 2020-07-28 Skc Co., Ltd. Xylylene diisocyanate composition with improved stability and reactivity and optical lens using the same

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