DD160063A1 - PREPARATION METHODS FOR ISOCYANOIC ACID AND OXAZOLIDONE RINGS CONTAINING CROSSLINKED POLYMERS - Google Patents

Abstract

The invention relates to a process for the preparation of isocyanuric and oxazolidone rings containing crosslinked polymers which have a high thermal stability and flame resistance and can be used except in the usual plastic application areas as construction materials and electrical insulating materials in electrical engineering. The processing of reaction resin compositions consisting of polyisocyanates, polyepoxides, tertiary amines and optionally additives and having a very high reactivity at room temperature, according to the usual technologies under shaping and warming is possible by adding organic electron acceptors to inhibit the reaction at low temperatures which are stable under processing and application conditions and do not affect the electrical properties of the polymers. Thereby, a use of the reaction resin compositions based on polyisocyanate and polyepoxide in the casting technology for the production of castings, Impraegnierung of fabrics for prepreg and laminate production, as Traenkharz in electrical engineering, as adhesive resin, etc. is possible, with the resulting products throughout electrical engineering can be used especially where high demands are placed on the thermostability.

Description

iiers O e Liuns: sverf e U reindeer 1 j. π ρ 3 o cyan ti 2 acid- unci Czaa 1 idonrinere V-. tha t en < vernet te Pol 3e

field of use

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the processing under molding and subsequent;

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of zonstru- lation advertising oils and electrical insulating materials with high stability and flannie- tigkeit and can be preferred in the Slektrctechnik s Inga sets.

Characteristic of the known technical solution

: ' i '"?, - ¹ ^ 't ~ \ i i' * ->" _ | - '! "^ v <I', - '(,'.". J "-" ,, - ' ~ ] C * ~ "Ώ O ΓΛ O '.. i ^" J ¹ ^ ¹ Υ * ΐ *! ~ "'""**" Ί -; ** / "" l ^; Va O 1Γ * ΤΤ "· ζΛ 7 ":

of polyisocyanates with polyepoxides ^ polyosasoiidones

Thermal stability and the presence of halogen ions due to the use of "quaternary ammonium halides as catalysts are not suitable for use as thermostable electrical insulating materials.

According to DD-PS 125 746 -erden by using epoxy / isocyanate ratios - ^ - 1 polyisocyanurate polyoxa

22792

zolidone e'rhalten, although possess a sufficient thermal stability, but which are also due to the catalyst system used, consisting of quaternary ammonium salts, metal or Ainmoniumhalogeniden and tertiary amines, also not suitable for use as Elektroisolier- materials.

According to US-PS 3 ^ 9 ^ 888 is known similar polymers of isocyanurate or Uretdionringe and free isocyanate group-QgQ containing ^ ^ ^ ^ ^ "^ ⁷ ' ¹ ^^^^ to ^ - ^ e ^T : 7i ^ r * di ^a τ-ιΊι ßw ^ made the Isocyanuratringe -in liquid Polyeposiaen,?; Erden "as catalysts tertiary amines added. At the same time, however, the addition of mineral, carboxylic or sulfonic acids or acid chlorides is necessary in order to stop the reaction. The resulting ions in the polymer have a negative effect on the electrical properties, so that these polymers can be used as electrical insulating materials also is not möslich, According to DE-OS 2,359,386 it is also known, polyisocyanates and polyepoxides for making Isocyanurat--! TTiri Π r ji. 7, r \ 1 * i ei π η '^ i ^ Ti C ο. η ή- ^: - ~ ο 1 ταηιΐρ'Π "πΊ ιπτιρτόπ a-? y τ; ι q a-ρ γ? : = η η

if tertiary amines are used as accelerators. Although this achieves sufficient electrical properties

!.Long! The fact that the 3eaktionsharsmassen prepared according to DS-CS 2359336 have too short Geuesclau at room temperature and moderately elevated temperatures, so that they are not suitable for the usual techniques for the production of electrical insulation materials.

Aim of the invention

The invention is based on the object of polyisocyanates u. Poiyecosiden cross-linked polymers with high thermal stability produce. The Yorteil compared to the known solutions is that the resulting polymers are very gvf3 suitable for use as electrical insulators and in an economical manner according to the usual in the production of insulating materials her-- '-. let ask ..

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Essence of the invention

The stated object is achieved by allowing, in the technical reaction resin processing necessary intermediate temperatures stable at room temperature and practical side use consisting of polyisocyanates, PolyeOcxiden and tertiary amines Reaktionsharsniässen by stable organic substances are added which have electron-accepting Eigenschai th *

The depositors working with halide-containing catalysts and catalysis, for the production of?

the presence of halogen ions in the polymer

njf-Q? i ~ '\ O ht - ^' S * ""'%' *? t ^ ⁵ XSC ^ ^ ^ * '^'"^ ^ 2 ^ proff P ^: ^" ^ ^ ^ ^ ^? 5 ττ ~ '. t Tiig-r- ^ g ?! kö ^ ^r "'s"G'Pupd"^ptziic' ^^ ^^ eei st is the VeT ^ e '"' - making catalysts based on tertiary Anine because the polymer thus produced good electrical Sisensc ^ Aften äufv / e * 'se "^» The ErrOic ^ sü. However, additions described at the temperature of stable conditions and practical periods of use lead to completely insufficient electrical properties of the polymers due to cleavage in acid or halogen ions.

The only 7-series ?? ^Endl: polyisocyanate Poiyeposid-Eeaktionsharzmassen manufactured ng of tertiary amines as catalysts already show at room temperature so high reactivity, üa8 too short for eiο Gießverarbeitung industrial scale too short Gebraachszeiten of casting resin in which Laminather ^ "RECOVERY Use times of the impregnation system and an unstable Zv? I3chenzustand in the Prepregstadiam result Sine lowering of the Zatalysatorgehaites of the reaction

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tion resin mixture does not lead to the goal, because at the same time an intensification of the heat treatment (increasing the curing temperature or extension of the curing times) is necessary, which is disadvantageous economic

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no longer occurs.

It has been found that the said disadvantages can be avoided and the stated goal is achieved if, as room-temperature inhibiting substances, stable organic substances with electron-accepting properties are used. As is known, organic substances have .sit, special structures, eg. 3. C-C double bonds in conjunction with Cl-ations, CI7 or FITRO groups, etc. Electron-accepting properties. For the intended use all electron acceptors in the carrier, the donors electron-acceptor-acceptor complex (3DA. ~ Complexes). but can not react with the polyepoxides or polyisocyanates themselves.

Very good action is possessed by z, 3,1,1,2,2-tetracyanoethylene, 7,7,8,8-tetracyanoquinodimethane, 2.3j516-tetrachlorobenzoquinone-C1,4), 2,3j5j6-tetraarombenzoquinone (1> 4), 2,3,5,6-tetraiodobenzoquinone - (1,4), 2,3-dichloro-5,6-dicyanobenzoc-ammonone (1,4), 1,2-ditnitrobenzene and isomers, etc.

The indicated substances are only examples and do not limit the scope of the substances suitable according to the invention.

The Slektronenakseptoren be the components polyisocyanate and Polyepo ^ id bzvi, the mixture of both components in amounts of at least 0.05§in accordance with the reactivity of this mixture and on the active ingredient

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the selected Jilektronenakzeptors in quantities of

Komponentenj added. The polyisocyanate / polyepozide mixture is prepared so that the tsocyanate / spoxide ratio is 11.

As polyisocyanate, all compounds are referred to

Tic, aromatic or mixed G-circular structure Z7ie ± and more isocyanate groups, examples being: 2,4-ToluylendiisocyaB'at and isomers, diphenylmethane-4,4'-diisocyanate, its isomers and. polynuclear homologues containing mixtures, for example Polymethylenpolyphenylisocyanat, Hezamethylen-

The above isocyanates, the free isocyanate groups

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oligoarous compounds aromatic-aliphatic or

As examples, be mentioned biglycidyl ethers of 4,4-Dihydrc:;: ydiphenyl-2 ₃ 2-oropan and mixtures with corresponding Cligoseren, diu, polyglycidyl ether of di-, polyphenols including Hovolaken, of di- and. Polycarboxylic acids, of yinyl cyclic iron u, a. cycloaliphatic compounds,

As catalysts for the formation of the crosslinked polymers of the abovementioned components serve tertiary amines. Suitable are trialkylamines. Triethylenediamine, morpholine, imidazole, triasin derivatives; Particularly suitable are compounds with Dirnethylaminomethylsubstituenten on benzene ring, which may also contain hydroxyl groups.

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The Haktionsharzmasse may optionally 'still additives are added, which act as fillers, such as quartz powder, and reduce the shrinkage in the subsequent curing process or improve the thermal conductivity of the Fomistoffes or have special effects when using the molding material, such as. 3, alumina trihydrate, which improves the Eriechstromfestigkeit of the molding material,

Especially auch.bei the application of such additives occurs depending on the added amount, a strong increase in the viscosity of Gießharznasse ', which leads in conjunction with short periods of use to great processing difficulties. By erfindungsgenäße method, these difficulties can be completely overcome by the use se of the Gießharzinasse be extended in the desired manner by appropriate addition of electron receptors. The addition of electron acceptors also makes it possible to increase the processing temperature, so that the reduction in viscosity caused thereby permits easier processing and, in particular, also permits evacuation necessary for achieving a bubble-free casting resin composition.

Other suitable additives are selected polyols which, given a suitable molecular size and structure, act as internal plasticizers and substantially improve the flexibility of the molding material and the mechanical properties dependent thereon. Since the incorporation reaction. these polyols already at room temperature hzvi. at low elevated temperature, especially in the presence of tertiary amines is going on, the application of the method according to the invention is of great importance to avoid a premature Viskcsitätsanstieges, Likewise, in the impregnation of paper, mica paper ^ Glasseidengeweben or-fleece, etc.

mixed mixtures "consisting of polyisocyanates, polyepoxides, tertiary amines and optionally of organic solvents added to slektronenakzeptoren" Thus, the impregnation systems remain stable, ie the viscosity, which is decisive for the applied amount, remains during the technologically required Time constant, "that is not the pail without the addition of the electron acceptors,

üach your casting, impregnating, soaking us ^ is further worked in herlcöninilicher manner "3o GUB pieces are cured by heating to temperatures of-1ÖG to 250 ⁰ G, preferably 15O to 180 C. pre-

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In addition to the known good properties, high thermal stability, high flammability, good mechanical properties even at elevated temperatures, the products obtained have excellent electrical properties up to higher temperatures, so that they are used excellently as construction materials and as electrical insulating materials. can earth,

Ausführungsbeisoiel Example 1:

100 parts by mass of diphenylmethane-4,4'-diisocyanate are melted and mixed with 50 parts by weight of a Dian-Zipoxid-resin with an epoxide equivalent of 200 to a very low viscosity liquid at 35 ° C of 35 sPa · s. If, at this temperature, 0.15 part by weight of di-ethylbenzyiamine is added as an accelerator, a viscosity of 1.5 Pa-s is reached after 0.5 hours, so that processing by casting or impregnation is possible

2 2 7 9 2 0 7

etc.-not; more is possible. If an amount of 0.15 parts by weight of 2, 3, 5, 6-letrachlorobenzoquinone Ci, 4) is dissolved in the reaction resin composition before the accelerator addition, the service life of the mixture is 6 to 7 hours at 35 ^° C.

The mixture with the addition of the Slektronenakseptors is poured into molds, which are heated for 2 h at 110 ^u C and 16 h at 180 G. The specimens are slightly darker in color than those of a mixture without the addition of a slektronenakzeptors, but have the same mechanical and electrical properties and the pale good Thenaostabilität on.

 100 parts by weight of polymethylsilphenyl isocanate are mixed with 50% by weight of Dian-Spozidhars (spocid equivalent

^ 200) and by adding 15 parts by weight of ethyl acetate. adjusted to a required viscosity for impregnation purposes. As an inhibitor is a l'close of 0.20 parts by weight of 2,3, 5,6 ^j Te trot rombenzochinon- (1.4) was added, advantageously dissolved in sigsäureethylester 'Eb, compartment of the addition of 0.20 parts by mass may dimethylbenzylamine the solution for the preparation of prepregs for Laininatherstellung be used without a deterioration of the ability to use by gelation occurs within a few days. Without the additive according to the invention, the solution became useless after a few hours. With the above mixture are glass silk fabric with a

p

iilächeiinaasse of about 16GI g / m ~ impregnated and dried at 80 to 10C ⁰ O ,. The prepregs obtained are stacked in the desired Ali number one above the other and pressed at 160 ⁰ C for 1 h. By post-curing at 180 ^° C., the electrical properties can be improved a little. The dielectric loss factor of this

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9

Laminate reads up to i'einperaturen of 18O ⁰ C at 7?

Example 3 » .

, The mixture mentioned in Example 1 is added with stirring 225 parts by weight of fine Quarzmenl --wobei to improve the degassing to 50 ⁰ C can be heated without it comes to gel before pouring, as it would be without the use of the addition of tetrachlorobenzoquinone Case is. After curing as in Example 1, there are J'onnstoffe the heat resistance class H with a Wänaefο nabeständigkeit after

Martens of 2S0 '^ 0 and a bending strength of ο ^w

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Example 4:

100 parts by weight of folymethylene polyphenyl isocyanate with 45 parts by weight of an epoxidized novolak of epoxide equivalent 175 ^ nd with 35 parts by weight of a based on glycerol Prooylenoxid and ethylene oxide

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produced. Polyol with an OH number of 35 ^ g KOH / g stirred. After addition of 0.7 part by weight of dimetnylbenzylamine and 2,3,5) 0-Tetrachlorbenzochinon- (1.4) is poured as in Example 1 in molds and cured. The Wärnieforsibeständigkeit by Martens et is ~ a 200 ⁰ C, the impact strength is 25 N / mm.

Claims (2)

22792 Srf indimgsansOruch 1. Production process for isocyanuric acid and oxazolidone rings-containing crosslinked polyners with _i higher   ihermostability and suitability as electrical insulants, such as extending the processability technological life by delaying reaction in the processing temperature range when reacting polyisocyanates and polyepoxides in an equivalent ratio> 1, in the presence of tertiary amines using conventional curing resin processing technologies niche slektronenakzeptoren in amounts of at least 0.05 % , 2. Production process for isocyanuric and Oxazc- lidonringe containing crosslinked polymers, characterized by the fact that the processing in the presence of! Fillers, z. As quartz, slate, Aluminiumtriosidtrihydrat occurs. 3a Production process for Isocyanuric acid and oxazolidone rings containing crosslinked polymers according to item 1 or 2, characterized in that the processing is carried out with the addition of polyols.