CS145891A2 - Curable resin for difficult-to-ignite and/or high-temperatures resistant plastics,method of such plastics production and their application - Google Patents

Description

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Hardenable resins for flame retardant and / or flame resistant plastics, a method of making such plastics and their use

Technical field

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable resin for high flammability and / or high temperature resistant plastics as described in claims 1 to 14, to a process for making such plastics as described in claims 15 to 17, as well as to the use of the plastics produced as described above. in claims 18 to 22, as electro-isolating agents, for support structures and as adhesives for bonding metals and polyamide films.

Background Art

Compounds containing 1-oxa-3-aza-tetraline groups and their prepolymers (hereinafter referred to as "oxazene resins") are for example known from the published applications CH-A5 Nos. 574 978, 579 113 and 606 169 · Z EP- No. 356,379 is a known curable resin (hardenable for high flammability and high temperature resistant plastics) which consists at least in part of a mixture (a) of a resin component comprising at least one xxxxxxxix thermosetting compound containing l-oxa-3. and / or consists of a flame retardant which is immiscible with the resin component and / or contains, in addition, optionally, at least one curable epoxy compound.

Although the hardening of this resin makes it possible to produce a highly flammable and high temperature product, its properties are still insufficient for many applications. The mechanical / electrical properties of the additive (s) are deteriorating. from

SUMMARY OF THE INVENTION It is therefore an object of the present invention to improve the flammability properties of oxazene resins without impairing their other properties. The above object has been solved by the present invention by producing a resin for flame retardant and / or high temperature resistant plastics. The resin is comprised of a composition consisting of a component comprising at least one compound containing a 1-oxa-3-aza-tetra-lineage which is thermally curable; (b) a component which comprises at least a first hardenable halogenated epoxide resin; (c) optionally a component which consists of at least one hardenable non-halogenated epoxy resin; and optionally

.......... J / d / epoxy resin hardeners.

Compounds of component (a) containing 1-oxa-3-aza-tetraline groups are obtained, for example, from phenol-reaction and formaldehyde and amine, e.g.

wherein R represents, for example, a hydrogen atom, a halogenalkyl group or an alkoxy group means an aliphatic or aromatic moiety.

These compounds can also be obtained by other methods leading to the same types of compounds.

Unlike other known condensation reactions of phenols, amines and formaldehyde, phenolic hydroxyl groups are consumed in this reaction. From the analytical determination of these groups in the reaction mixture, the amount of synthesized 1-oxa-3-aza-tetralin groups can thus be determined by the sublericum A. Pre-polymers of 1-oxa-3-aza-tetralin compounds can also be used. Since the 1-oxa-3-aza-tetraline moieties react with the polymerization, these prepolymers may contain fewer 1-oxa-3-aza-tetra-lineage groups. It is also critical that the intermediate-formed or hypothetical / monomeric reaction product comprises 1-oxa-3-aza-tetralin groups. This is easily deductible from the functionality of the experts. The 1-oxa-3-aza-trimethyl compound or a prepolymer thereof useful in the present invention is formed, for example, when the molar ratio within the boundary defined in the present invention is CR-A5 No. 606 169.

The starting or base materials for the 1-oxa-3-aza-tetraline compounds are phenol or its derivatives, as well as amines and formaldehyde. Preferably, the 1-oxa-3-aza-tetraline group-containing compounds are those which are formally derived from phenol and amine, of which one is more than monofunctional. Examples of suitable phenols are as follows:

Monovalent phenols, such as phenol alone, m-cresol and p-cresol, m-ethylphenol and p-ethylphenol, m-isopropylphenol, and p-isopropylphenol, m-isopropyloxyphenol, and p-isoooyloxyphenol, m-chlorophenol, and p-chlorophenol and beta-naphthol. In this case, para- and meta-substituted venols are preferred because no reactive sites are blocked. Further preferred are phenols which are not substituted by alkyl or alkoxy groups.

Divalent phenols such as 4,4-dihydroxy-diphenyl-methane, 3,3-dihydroxy-diphenylmethane, 2,2-bis- (4-hydroxyphenyl) -propane, 4,4-dihydroxy-stilbene, hydroxhinone, pyrocatechin and resorcin. Low condensed phenol formaldehyde novolac resins, optionally also in admixture with phenol. Examples of particularly suitable amines are as follows:

Aniline, Phenylenedismin, Benzidine, Diaminodiophenylmethane, 2,2-bis (aminophenyl) -3EK + kaxpropane, cyclohexylsmin, ethylenediamine and propylenediamine, especially p-phenylenediamine and 4,4-diamino diphenyl methane. Aromatic amines are preferred.

Particularly suitable are the 1-oxa-3-aza-tetralinoA4 compounds which are derived from novolak and aromatic amine, preferably from novolac with a polymerization degree of about 2a aniline, or from phenol and aromatic diamine.

The second component (b) comprises or consists essentially of: one or more glycidyl ethers of halogenated phenols, in particular polyhydric phenols, one or more glycidyl ethers of condensation products of halogenated phenols with aldehydes or ketones, or one or more glycidyl ethers of halogenated moons .

Particularly suitable is the glycidyl ether of the halogenated bisphenol A and the halogenated bisphenol P, especially tetrabromobisphenol A or tetrabromobisphenol as well as the glycidyl ether of the pumped novolak.

As the halogenated epoxy resin in the component (b), a pumped epoxy resin is preferred.

Said epoxy resins are known and commercially available. They have already been designed for the production of flame-retardant plastics. However, these have the following disadvantages: - they exhibit deep glass transition temperatures; - due to their high content of bromine xs in their burning, a considerable amount of highly toxic carbonyl dibromide is formed; - they are expensive.

Products available on the market, suitable as component (b) are, for example, the following epoxy resin resins:

Product # 1 / Trade Name "D.E.R. 511-A-SO ", PaThe Dow Chemical Company /

Bisphenol A-type brominated epoxy resin in aceto-new solution epoxy equivalent weight ^ 445-520 viscosity / 25 ° C / 1000-4000 mPa.s non volatile solvent color Gardner color, maximum bromine content ^ / flash point / TOC / 80-1 % by weight acetone 5 19 - 21 wt.

63 ° C

Product No. 2 / Trade Name "D.B.R.511-BK 80", PaThe Dow Chemical Company /

Brominated ketone epoxy resin type bisphenol A solution in methyl epoxy equivalent weight viscosity / 25 ° C / non-volatile solvent solvent color Gardner, maximum bromine content ^ / flash point / TOC / 4-45 - 522 1000-4000 mpa.s 80 ^ 1% w / w . methyl thylke t o n / - 19 - 21% wt.

High: 52 ° C

Product No. 3 / Trade Name "D.B.R. 512-A-80" PaThe Dow Chemical Company /

Brominated epoxy resin of bisphenol A types in acetoxy solution epoxy equivalent weight 480-460 viscosity / 25 ° C / 700-200 mPa s nonvolatile 80-1 wt. solvent color by gardner, maximum 1 / bromine content / flash point /T.O.C./ acetone 5

21 - 22.5 wt%

Product No. 4 / Trade Name "D.E.R. 512-EK 75" PaThe Dow Chemical Company /

Bisphenol A-type brominated epoxy resin in methyl ketone solution epoxy equivalent weight1 / viscosity / 25 ° C / non-volatile solvent

Gardner color, maximum bromine1 / Z flash point /T.O.C./ 480 - 560 500 - 1500 mPa.s75-1% by weight methyl ethyl ketone 3

21 - 22.5 wt% <- 2 ° C

Product No. 5 / Trade Name "D.E.R. 512-EK 80" PaThe Dow Chemical Company /

Brominated epoxy resin type B in the methyl ethyl ketone solution epoxy equivalent weight1 / 480 - 560 viscosity / 25 ° C / 1000 - 3500 mPa.s nonvolatile 80- 1 1 weight solvent methylethylketone color according to Gardner, max 5

bromine content 21 - 22.5 wt. flash point /T.O.C./ 52 ° C

Product δ, 6 / Trade Name "D.E.R. 521-A 80" PaThe Dow Chemical Company /

Brominated epoxy resin of bisphenol A type in acetoic solution

1 / epoxy equivalent weight 430 - 475 viscosity / 25 ° C / 1000 - 4500 mPa.s nonvolatile 80 80% 1% solvent acetone color according to Cardner, maximum bromine content 19 - 22% wt. flash point /T.O.C./ 63 ° C

Product # 7 / Trade Name "D.E.R. 542" Pa The DowChemical Company /

Bisphenol A type brominated epoxy resin

epoxy equivalent weight · * · / 305 - 355 Durrana softening point 50.5 - 62.5 ° C bromine content 44 - 49% weight flash point /T.O.C./ 199 ° C 10 -

Product # 8 / Trade Name ”D.S.R. 566-A 80 ”Pa DowChemical Company

Bisphenol A-type brominated epoxy resin in aceto-new solution epoxy equivalent weight ^ / 410 - 450

viscosity / 25 ° C / 800 - 4000 mPa.s no volatile fraction 80 ^ 1% by weight solvent acetone color by Gardner, maximum bromine content 5 18 - 20% by weight flash point temperature /T.O.C./ <2 ° C

Product # 9 / Trade Name ”QUATRSX 6410” Pa The DowChemical Company /

Bisphenol A epoxy equivalent weight epoxy epoxy resin 450 450

softening point 80 ° C viscosity / 150 ° C / 0.0180 nr.s "1 hydrolyzable chloride <150 ppm volatile content <^ 0.25% by weight bromine content 47-51% wt. glass transition temperature phenolic hardening 175 ° C 1 / based on solids content 11 -

Suitably, the halogen content is less than 3 gram equivalents, in particular less than 2 gram equivalents, per kilogram of the total weight of the component. Accordingly, in the case of resins in which the component (b) is a bulk epoxy resin, it is suitably less than 24% by weight, in particular less than 16% by weight, based on the total weight of the resin. Separately with less than 7.5, 2.5 or 1% by weight, flame retardant plastics are obtained. Suitably, the amount of component (b) is less than 50% by weight, in particular less than 30% by weight, based on the total weight of resin / component (a) + component (b). The seale resistive resins also obtain less than 5% by weight or even less than 2% by weight, based on the total weight of the resin, at a component content (b) of less than 15% by weight.

The fact that the advantages described below can be achieved by already small amounts of the component (b), especially the pumped epoxy resin, is highly surprising to those skilled in the art.

In addition to the considerably improved thermal properties combined with very good electrical properties, which are still discussed in detail below, it is a particular advantage that only a few toxic substances are produced during combustion and that only a low cost component must be used / b /.

The composition of the present invention may further comprise a component (c) which contains or consists of at least one curable non-halogenated epoxy resin. Suitably, the amount of this component is less than the amount of component (b), preferably less than half of the component (b).

Particularly suitable as such epoxy resins are monofunctional or multifunctional epoxy compounds, thermoset, catalytically or with curing compounds.

The composition of the present invention may contain, as a component / d / hardener for epoxy resins. Particularly preferred are multivalent salts, polycarboxylic acids and their anhydrides, dicyandiamide and novolaks.

Suitable epoxy compounds and curing agents are described, for example, in U.S. Pat

Sidney H. Goodman, Handbook of Thermoset Plastics, Noyespublikations, Park Ridge, NJ; W.G. Potter, Epoxide Besins, Ilife Books, London;

Henry Lee and Kris Keville, Handbook of Spoxy Hesins, McGraw-Hill Bock Company, New York / San Prancisco / Torcnto / London.

Heat curing of the curable resins at temperatures above 100 ° C, in particular from 140 ° C to 220 ° C, produces hardly flammable plastics, stable at high temperatures and heat resistant. Surprisingly, the cured plastics can be substantially improved by the additional heat treatment with respect to their properties. Thus, for example, the transition temperature is increased by 24 hours at 220 ° C to over 280 ° C. Suitably, the cured plastics are subjected to this additional heat treatment at temperatures ranging from 180 to <50 ° C, preferably from 200 to 230 ° C. The tempering time depends on the temperature. The following guideline values may serve as gripping points, but these times may be arbitrarily extended without damaging the plastics.

Curing - 13 - 4 hours at 2 hours at ISO ° C or200 ° C;

Tempering for 24 hours at 220 ° G.

These times may also be combined as desired. For example, the following temperature cycle can be operated: 30 min / 200 ° C + 30 min / 220 ° C + 30 min / 230 ° C + + 30 min / 250 ° C.

The properties of the plastics produced in this way can be adjusted with the aid of conventional additives for certain uses. Of particular note are the following: reinforcing fibers, such as glass fibers, quartz fibers, carbon fibers, mineral fibers and synthetic fibers, in conventional forms such as short fibers, staple fibers, yarns, fabrics or mats; plasticizers, in particular phosphorus compounds, carbon black or graphite; - dyes; hollow microspheres; 14 - metal powder; catalysts and flame retardants, in particular the following groups of substances or substances: aluminum hydroxide; hydrated calcium carbonate; magnesium hydroxide; elemental red phosphorus; inorganic salts of phosphorous oxygen acids, organic salts of phosphorous oxygen acids, polyphosphates; boric acid, salts of boric acid.

Suitable methods for processing are those known for thermosetting phenol formaldehyde resins or SP resins, such as hot prepreg, sheet holding compound, or molding, casting, fiber winding or vacuum impregnation.

Plastics obtainable by curing or curing and subsequent tempering of the resins of the present invention in a non-hardened or hardened form which are difficult to fire and resistant to high temperatures are suitable for use in particular: as electrical insulating agents, in particular distribution boards; for supporting structures, especially in aircraft construction; wherever high temperature resistant or flame retardant resins are to be used; 15 - as adhesives: EXAMPLES 4- Starting Materials In the following examples, the following starting materials are used:

Component / a / A / l / Oxazene resin 1

The reaction product of phenol with aniline and formaldehyde in a molar ratio of 1: 1: 2 structural formula

/ A / 2 / Oxazene resin 2

The reaction product of 1 mole / 2 eq / novolak, obtained by the reaction of 2 moles of phenols and 1 mole of formaldehyde, with 2 moles of aniline and 4 moles of formaldehyde per product of medium composition 16 -

/ A / 3 / Oxazene Resin 3

Reaction product of 4,4'-diamino-diphenylmethane. with phenol and formaldehyde at a molar ratio of 1: 2: 4 structural formula

0 17 -

Component (b) / B / l / Brominated epoxy resin 1 "DEM 542" by The Dow Chemical Company (product No. 7), with a bromine content of solids of 44 to 49% w / w / 3 / Brominated epoxy resin 2 "Quatrex 6410" by The Dow Chemical Company (product No. 3), the bromine content of the solid is 47 to 51% by weight.

Reinforcing agent / V / Glass fabric ”Type 90085” Fy Interglas-Textil GmbH2 Density: 108 g / m Fiber Density / cm: 24 x 24 Epoxy Silane Finish. 2. Production of samples

The components listed in Table 1 below are vacuum-mixed at a temperature between 100 and 130 ° C. Samples are then taken for thermoanalysis. The residue is placed between two Teflon-coated glass plates with or without glass fabric and cured in a hot-air oven at a temperature of 200 ° C for 2 hours. 18-3. Fire Resistance Test

The flame resistance test is performed as described below. UL-regulation 94 (vertical test), abbreviated as UL 94 "(see Jirgen Troitzsch, Brandverhalten von Kunststoffen, 1982 Mtinchen / Wien ISBN 3-446-13391-7, 396-399). The results are summarized in Table 1 below. the fact that the UL-94-V0 class is already achieved by adding 10% by weight when 20% by weight of the epoxy resin is added.

Mechanical properties and glass transition temperature (also called " glass temperature ") are determined by or without tempering using DOS / Differential Scanning Calorimetry (DMA) " Differential Mechanical Analysis " and TMA / " Thermo Mechanical Analysis ". The results are summarized in Table 2.

To a large extent, it was surprisingly possible to increase the glass transition temperature with a substantially reduced reduction of the ulu-module at this temperature (see, for example, sample 4, cf. Xb71-G). - 19 -> 5 «5 β Ν Ν

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Claims (10)

A hardenable resin for flame retardant and / or high temperature resistant plastics, characterized in that it consists of a mixture comprising a Ca) component which consists of at least one thermosetting compound containing 1-oxa-3 aza-tetraline groups; (b) a component consisting of at least one curable halogenated epoxide resin; optionally Cd) a component which consists of a sesscon of one curable non-halogenated epoxy resin; and optionally a hardener for epoxy resins. curing: the lines: c) the mtraline compound of component (a) nolic compound, forcaldehyde and and that the 1-oxa-3-aza- te is removed from the phe. A curable resin according to claim 1 or 2, characterized in that the 1-oxa-3-aza-terrazine compound of component Ca) is formally derived from a phenolic compound and an amine, one of which is a compound. more than monofunctional. 4. A curable resin as claimed in any one of claims 1 to 3 wherein the 1-oxa-3-aza-tetraline compound of component (a) is derived from no-call. The hardening resinous component of claim 4, wherein the 1-oxa-3-azae (b) is derived from the polymerization stage 1, p to 3. a traline-matt-hardening resin characterized in that the compound of component (a) of the amine is compounded. 1 to p, that 1-oxa-j-aza-te is derived from arc- 7. The curable in y denoting (b) consists of one-genated phenols. A resin according to any one of claims 1 to 6, wherein the second component or a plurality of glycidyl ethers of the halogenation of the hardening resin of claim 1, wherein the second component of one or more glycidyl ether derivatives halogenated phenols with aldehydes or ketones, A curable resin as claimed in any one of claims 1 to 8, wherein the second component (bX consists of at least one curable, hollowed epoxy resin *). Resin according to claims 1 to 9, characterized in that the content of halogen is less than 3 gram equivalents, in particular less than 2 gram equivalents, per kilogram of the total weight of the components present. The curable resin according to claims 1 to 10, characterized in that the amount of the component (b) is greater than 30 components (a) and (b) of the immotional, in particular of the lower weight based on the total weight of the 12 markers (c). A lesser amount of resin according to claims 1 to 11, which is a quantity of component (b). 13. A composition according to claim 1, wherein the component comprises polyvalent amines, polyvalent carboxylic acids or their anhydrides, dicyandiamide or novolac. 14. In claiming that (d) is less than the resin of claim 13, wherein the amount of component 1.2 of the equivalent total amount of components (a) and (b) and - what - 15. A process for the production of flame-retardant and / or high temperature plastic materials, characterized in that the resin according to one or more of claims 1 to 14 is hardened or hardened in a non-reinforced or hardened form and subsequently thermoformed. The method of claim 1b, wherein the resin is cured at a temperature above 100 ° C. The method of claim 1? The suction filter is tempered at an ISO temperature of up to 7L of resin 10. The use of plastics, or some of the claimed materials. 19. The use of plastics, either or a number of demanding structures. produced by the process according to one to 17 as electro-isolating processes according to the method of one of claims 5 to 17 as materials for the use of plastics produced by the process according to one or more of claims 17, in order to control the metal requirement. Pi. Use according to claim GG for bonding polyimide films.