DE2450539A1 - POLYAETHERESTERS CONTAINING HYDROXYL GROUPS AND THEIR USE FOR THE MANUFACTURE OF FLAME RESISTANT PLASTICS - Google Patents

Description

Bayer Aktiengesellschaft 2450539

Central area of patents, trademarks and licenses

509 Leverkusen, Bayerwerk GM / Bre

2 OCT 3. 1974

Polyether esters containing hydroxyl groups and their use for the production of flame-retardant plastics

Bis-ß-hydroxyalkyl ethers of halogenated bisphenols are known as hydroxy components for the production of flame-retardant plastics. These bisethers are solidly crystalline or glass-like resins. The esters of these ethers with dicarboxylic acids are also known and have already been used for the production of flame-resistant plastics. For example, Canadian patent 663 describes the preparation of an ester by esterifying bis-ßhydroxyäthyldibromobisphenol and 1,2-propylene glycol with a mixture of phthalic anhydride and maleic anhydride. This ester contains 25.2 % bromine and is a glass-hard resin at room temperature. For the production of polyurethane and polyisocyanurate plastics, however, it is advantageous that the starting components are liquid and have a low viscosity so that the foaming mixture can be poured.

As low-viscosity and well-tolerated components for production Polyurethane and polyisocyanurate plastics have long been used with advantage to contain free hydroxyl groups Polyethers such as polyethylene glycol or polypropylene glycol a. The hydroxyl-containing polyethers of bisphenols are also already known here. The German Offenlegungsschrift 2 232 540, however, it can be seen that polyethers of halogenated bisphenols could not be produced under the customary production conditions. The treatment of high-

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halogenated bisphenols with alkylene oxides, in particular of Tetrabromobisphenol, even when using an excess of alkylene oxide, only leads to the bisethers mentioned above Art.

It is obvious that these bis-ethers are contained in the low-viscosity polyalkylene glycols to solve this bisethers as halogen carriers the foaming approach for the production of flame-retardant Incorporate foams. However, the dissolving power of these bisethers in such hydroxyl compounds is very poor. The ether recrystallizes from solutions which contain the ethers in the required high concentrations a short time, or the solution solidifies to a solid crystal slurry that can no longer be poured. However, you can according to German Offenlegungsschrift 2 232 540 low-viscosity pourable polyether derivatives of halogenated bisphenols can be obtained. The procedure here is that first the hydroxyl-containing polyethers in a manner known per se are made of halogen-free bisphenols, which are then subsequently treated with elemental halogen, especially bromine, are halogenated. The polyethers obtained in this way have a pourable consistency and the foams produced with them, in particular polyisocyanurate foams show excellent fire behavior. However, they have the disadvantage that they become brittle on the surface tend and show poor adhesion to top layers. In addition, the procedure is designed according to the above-mentioned German Offenlegungsschrift in practice is complicated because the polyetherification and the Halogenation represent two completely different reactions, which each require special equipment and precautions therefore have to be carried out in two separate production plants. The high expenditure on equipment (use of corrosion-resistant Equipment, e.g. made of special steels, etc.) during halogenation requires it in the interest of the best possible reaction utilization to strive for the highest possible degree of halogenation. Accordingly, it is used to produce a halogen-containing one

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flame-retardant plastic or a preliminary product more efficient, starting from a highly halogenated starting material than the finished plastic or the intermediate product afterwards to halogenate to a correspondingly lower degree of halogenation.

It has now been found that the production of a low-viscosity, halogen and hydroxyl-containing starting material for the production of flame-resistant polyurethane and polyisocyanurate plastics can be achieved in a technically particularly simple manner, surprisingly, for example, the isocyanurate foams produced with this starting material 'no embrittlement and good adhesion show on top layers. (Compare example 9). According to the invention, one starts from the halobisphenol-bis-β-hydroxyalkyl ethers which can be prepared in the customary manner and esterifies them with a di- or polycarboxylic acid in the presence of an excess of a di- or polyalkylene glycol. Furthermore, it has been shown that it is not necessary to prepare the bisether separately and to isolate it in substance. Rather, to simplify the preparation of the products according to the invention, one can proceed by dissolving a nucleus-halogenated bisphenol in a di- or polyalkylene glycol, then alkoxylating the phenolated groups of the bisphenol by adding an alkylene oxide at elevated temperature and then alkoxylating the mixture of bisethers and polyalkylene glycol thus obtained esterified. The new polyether esters obtained in this way can contain 50 % or more of halogenated bisphenol bisether (in chemical bond). The products are of low viscosity and, depending on the amount of excess polyalkylene glycol used, have hydroxyl numbers in the range from approx. 100-300.

The invention relates to polyether esters containing hydroxyl groups with an acid number of 0-5, preferably 0-1 and a hydroxyl number between 100-300, preferably 150-250, obtained by esterification of

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a) Bishydroxyalkyl ethers of halogenated 2,2-diphenylolpropanes the general formula

Rr

η = 0,

worm

up to Rg = H, C ₁ -C ₄ -AlkVl, preferably H, CH, and up to Rj ₀ = H, C ^ -C / -alkyl, halogen, preferably H, Br, CH,.,

and where at least one of the radicals R 1 to R _{10 should be} a halogen atom, preferably a bromine atom, with

b) saturated and / or unsaturated aliphatic and / or aromatic polycarboxylic acids in the presence of

c) dialcohols of the following formula

X ₁ Χ,

h fr

HO

- C — C - + - A —- C —C —J -

\ j 4i

• X ₂ X ₄ Xy Xg

wherein
X ₁ to X ₍ η
A.

= H, C ₁ -C alkyl, preferably H, CH 1, = 1-10 and = 0, S

mean.

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The products according to the invention retain despite their high content. on high-melting bisphenol bisethers their liquid consistency even when stored at low temperatures. This is particularly surprising because, due to the high excess of hydroxyl during the esterification, it was to be expected that part of the bisether in the resulting ester mixture was present in unesterified or semi-esterified form, and therefore there was the possibility of the unesterified or semi-esterified constituents crystallizing out was.

The polyether esters according to the invention generally have a viscosity of 10-200 poise / 25 ° C., preferably of 20 - 100 poise / 25 ° C.

Bisphenols of the following structure are suitable as starting material for the polyether esters according to the invention:

R ₁ , R ₂ , R ₃ , R ₄ H, Cj-C ₄ -alkyl, preferably H, CH ,, C _? H,-,

RiRiRiRi halogen, preferably Cl, Br, where at least S-K ₁ , K ₂ , K ₃ , K _{4 at least 1 R = halogen #}

Tetrabromobisphenol of the formula is preferably used

Br ^ "3 Br

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used as starting material; Tetrachlorobisphenol or dibromobisphenol can also be used as starting substances for the production of the products claimed according to the invention.

These bisphenols can be alkoxylated directly in solutions with polyalkylene glycols according to the variant of the process described (and then esterified). The alkylene oxides mentioned below can be used here. As catalysts During the alkoxylation in the polyalkylene glycol solution, alkaline substances such as NaOH, KOH, Sodium methylate, sodium phenolate, potassium acetate, potassium carbonate etc. can be used. The alkoxylation can be carried out at temperatures of 80-180.degree. C., preferably 110-140.degree. C., in a manner known per se Way to be carried out.

As bisphenol-bis-ether, which are used as starting components for the Esterification can be used, the substances may be mentioned, which by reaction of the halogenated bisphenols with e.g. Ethylene oxide, 1,2-propylene oxide, epichlorohydrin, 1,2-butylene oxide or 3-hydroxymethyl-3-ethyloxetan can be obtained. the Alkoxylation for the preparation of the bisethers can, instead of the alkylene oxides, also be carried out with alkylene carbonates in a manner known per se Way to be carried out. Possible carbonates are: ethylene carbonate, 1,2-propylene carbonate, 1,2-butylene carbonate and Grlycerine carbonate.

Suitable acids for the esterification of the bisethers according to the invention are the aliphatic, cycloaliphatic and aromatic polycarboxylic acids, for example succinic acid, adipic acid, sebacic acid, diglycolic acid, thiodiglycolic acid, maleic acid, fumaric acid, citric acid, cyclohexanedicarboxylic acid, cyclohexanedicarboxylic acid, cyclohexanedicarboxylic acid, hydrohexanedicarboxylic acid, tetrahydomethyl-ethanoic acid, tetrahydomethyl-ethanoic acid, isotrahydomethyl-ethanoic acid, tetrahydomethyl-ethanoic acid, tetrahydomethyl-ethrophthalic acid, tetrahydomethyl-ethanoic acid, tetrahydrophthalic acid, adipic acid, for example succinic acid, adipic acid, and aromatic polycarboxylic acid -, terephthalic acids, tetrachlorophthalic acid, tetrabromophthalic acid, trimellitic acid. Instead of the free polycarboxylic acids, Le A 15 946 - 6 -

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the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols or mixtures thereof used to manufacture the polyester.

from the above-mentioned frll-gi F ^ rmpi inghesn. In question: dietylene glycol, polyethylene glycols of the formula

H- To-CH ₂ -CH ₂ J _n -OH (n = 3 - 10)

as well as thiodiglycol, bis-ß-hydroxyethyl sulfone and the next Polyethers and polythioethers described in more detail below, furthermore Dipropylene glycol, polypropylene glycol of the formula

H-

0-CH ₉ -CI-OH (n = 3 - 10)

In addition to the diols mentioned, up to 20 mol% of monoalkylene glycols such as ethylene glycol, 1,2-propylene glycol, 1,2-butylene glycol, neopentyl glycol, C-chlorohydrin can also be used in the esterification. The esterification is generally carried out at temperatures of 120-200 ^° C., preferably 140-170 ^° C., with the introduction of inert gases under normal pressure or in vacuo.

Esterification catalysts such as toluenesulfonic acid, black lead, Dibutyltin oxide, antimony trioxide, salts and alcoholates of titanium can be added. During the esterification you can Solvents can be used as azeotropic entrainers. However, the esterification takes place in the absence of solvent Given preference.

After the esterification, it remains despite the high excess of glycol often still a low acid number, which no longer disappears on further heating under esterification conditions.

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In cases where this residual acid numbers that are usually less than 10, interfere with the further processing of the ester may be, the acid value by treating the ester with alkylene oxides at temperatures of 100-130 ⁰ C are completely eliminated - 150 ⁰ C, preferably at 120th The abovementioned alkylene oxides can be used here.

The polyether esters according to the invention are valuable starting materials for the production of isocyanate-based plastics, in particular for the production of flame-retardant isocyanurate foams with excellent mechanical properties and high flame resistance.

As starting components to be used according to the invention for the manufacture " In addition to the polyether esters according to the invention, plastics also include aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates into consideration, such as those from ¥. Siefken in Justus Liebig's Annals of Chemistry, 562, pages 75 to 136, are described, for example ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutane-1,3-dlisocyanate, Cyclohexane-1,3- and 1,4-diisocyanate as well as any mixtures of these isomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (DAS 1 202 785, U.S. Patent 3,401,190), 2,4- and 2,6-hexahydrotolylene diisocyanate and any mixtures of these isomers, hexahydro-1,3- and / or -i, 4-phenylene diisocyanate, Perhydro-2,4'- and / or - ^ '- diphenylmethane diisocyanate, 1,3- and 1,4-phenylene diisocyanate, 2,4- and 2,6-tolylene diisocyanate and any mixtures of these isomers, diphenylmethane-2,4'- and / or ™ 4,4'-diisocyanate, naphthylene-1,5-dlisocyanate, Triphenylmethane-4,4 ', 4 "-triisocyanate, polyphenyl-polymethylene-polyisocyanate, as obtained by aniline-formaldehyde condensation and subsequent phosgenation and, for example, in British Patents 874,430

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and -848 671 are described, m- and p-Isocyanatophenylsulfonyl-isocyanate according to the American patent 3 454 606, perchlorinated aryl polyisocyanates, as described, for example, in German Auslegeschrift 1 157 601 (American Patent 3 277 138;) are, polyisocyanates containing carbodiimide groups, as described in German patent specification 1 092 007 (American patent specification 3 152 162) are described, diisocyanates, wi® them in the American U.S. Patent 3,492,330, polyisocyanates containing allophanate groups, such as those described in U.K. Patent specification 994 890, Belgian patent specification 761 626 and the published Dutch patent application 7 102 524- containing isocyanurate groups Polyisocyanates, such as those in American patent 3,001,973, in German patents 1 022 789, 1 222 067 and 1 027 394 as well as in the German Offenlegungsschriften 1 929 034 and 2 004 048 are, urethane-containing polyisocyanates, such as those in Belgian patent 752 261 or in the American Patent 3 394 164 are described, acylated urea groups containing polyisocyanates according to German Patent 1 230 778, polyisocyanates containing biuret groups, such as those in the German Patent 1 101 394 (American patents 3 124 605 and 3 201 372) and in British patent 889 050 are described, polyisocyanates prepared by telomerization reactions, such as those in the American U.S. Patent 3,654,106 containing ester groups Polyisocyanates such as those disclosed in British Patents 965,474 and 1,072,956, in the American patent 3,567,763 and in the German patent 1,231,688, reaction products are mentioned of the above isocyanates with acetals

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according to German Patent 1,072,385, polymeric fatty acid residues containing polyisocyanates according to US Pat. No. 3,455,883.

It is also possible to remove the isocyanate group-containing distillation residues obtained during the technical production of isocyanates, optionally dissolved in one or more of the aforementioned polyisocyanates, to be used. Furthermore it is possible to use any mixtures of the aforementioned polyisocyanates.

As a rule, the technically easily accessible polyisocyanates, e.g. 2,4- and 2,6-tolylene diisocyanate, are particularly preferred and any mixtures of these isomers ("TDI"), polyphenyl-polymethylene-polyisocyanates, such as those produced by aniline-formaldehyde condensation and subsequent phosgenation are produced ("raw MDI") and carbodiimide groups, urethane groups, Allophanate groups, isocyanurate groups, urea groups or polyisocyanates containing biuret groups ("modified polyisocyanates").

According to the invention, water and / or volatile organic substances are also used as blowing agents. Examples of organic blowing agents are acetone, ethyl acetate, halogen-substituted alkanes such as methylene chloride, chloroform, ethylidene chloride, vinylidene chloride, monofluorotrichloromethane, chlorodifluoromethane, dichlorodifluoromethane, and also butane, hexane, heptane or diethyl ether. A propellant effect can also be achieved by adding compounds which decompose at temperatures above room temperature with the elimination of gases, for example nitrogen, for example azo compounds such as azoisobutyronitrile. Further examples of propellants and details of the use of propellants can be found in the Kunststoff-Handbuch, Volume VII, edited by Vieweg and Höchtlen, Carl-Hanser-Verlag, Munich 1966, e.g. on pages 108 and 109, 453 to 455 and 507 to 510 described.
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The catalysts used in the polymerization reactions are compounds which are already at room temperature initiate a polymerization reaction of the NCO group. Such compounds are for example in the French Patent specification 1,441,565, Belgian patents 723 153 and 723 152 and German patent 1,112,285.

Such catalysts are especially mononuclear or polynuclear Mannich bases from condensable phenols, oxo compounds and optionally substituted by alkyl, aryl or aralkyl radicals secondary amines, especially those in which formaldehyde is used as the oxo compounds and dimethylamine is used as the secondary amine have been. In general, according to IR spectroscopic analyzes, depending on the conditions, in particular are formed in the foams Depending on the reaction temperature reached, more or less high proportions of carbodiimide structures.

Other suitable catalysts are the alkali or alkaline earth salts of carboxylic acids and phenols. The amount of polymerization catalyst is essentially determined by the type (and, if applicable the basicity) of the catalyst is determined; you can between 0.1 and 100 wt .-%, preferably between 0.3 and 25 wt .-% of catalyst component, based on the isocyanate component, insert.

According to the invention, the usual catalysts are suitable for the polyurethane reaction, for example tertiary amines such as triethylamine, tributylamine, N-methyl-morpholine, N-ethyl-morpholine, N-cocomorpholine, N, N, N ¹ , N'-tetramethyl-ethylenediamine , 1,4-diazabicyclo- (2,2,2) -octane, N-methyl-N'-dimethylaminoethyl-piperazine, N, N-dimethylbenzylamine, bis- (N, N-di-ethylaminoethyl) adipate, N- , N-diethylbenzylamine, pentamethyl-diethylenetriamine, N, N-dimethylcyclohexylamine, N, N, N ', N'-tetramethyl-1,3-butanediamine, Ν, Ν-dimethyl-ß-phenylethylamine, 1,2-dimethylimidazole, 2 -Methylimidazole.

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Hydrogen atoms active towards isocyanate groups tertiary amines are e.g. triethanolamine, triisopropanolamine, N-methyl-diethanolamine, N-ethyl-diethanolamine, N, N-dimethylethanolamine, and their reaction products with alkylene oxides, such as propylene oxide and / or ethylene oxide.

Silaamines with carbon-silicon bonds are also used as catalysts, as described, for example, in German patent specification 1 229 290, in question, e.g. 2,2,4-trimethyl-2-silamorpholine, 1,3-diethylaminomethyl-tetramethyl-disiloxane.

According to the invention, organic metal compounds, in particular organic tin compounds, can be used as catalysts.

Tin (II) salts are preferably used as organic tin compounds of carboxylic acids such as tin (II) acetate, tin (II) octoate, Tin (II) ethylhexoate, and tin (II) laurate and the dialkyltin salts of carboxylic acids, such as dibutyltin diacetate, dibutyltin dilaurate, Dibutyltin maleate or dioctyltin diacetate into consideration.

Further representatives of catalysts to be used according to the invention and details about the mode of operation of the catalysts are in the Kunststoff-Handbuch, Volume VII, published by Vieweg and Höchtlen, Carl-Hanser-Verlag, Munich 1966, e.g. on pages 96 to 102.

These catalysts are generally used according to the invention in an amount between about 0.001 and 10% by weight, based on the total used new polyether ester and compounds mentioned below with at least two opposite isocyanates reactive hydrogen atoms with a molecular weight of 62 to 10,000 are used.

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Surface-active additives can also be used according to the invention (Emulsifiers and foam stabilizers) can also be used. The sodium salts of castor oil sulfonates, for example, are used as emulsifiers or of fatty acids or salts of fatty acids with amines such as oleic acid diethylamine or stearic acid diethanolamine. Also alkali or ammonium salts of sulfonic acids such as dodecylbenzenesulfonic acid or dinaphthylmethanedisulfonic acid or of fatty acids such as ricinoleic acid or of polymeric fatty acids can also be used as surface-active additives will.

Water-soluble polyether siloxanes are primarily used as foam stabilizers in question. These connections are in general constructed so that a copolymer of ethylene oxide and propylene oxide is linked to a polydimethylsiloxane residue. Such foam stabilizers are, for example, in the American Patent Nos. 2,834,748, 2,917,480 and 3,629,308.

According to the invention, reaction retarders, e.g. acidic substances such as hydrochloric acid or organic acid halides, can also be used. furthermore cell regulators of the type known per se such as paraffins or fatty alcohols or dimethylpolysiloxanes as well Pigments or dyes and flame retardants of the type known per se, e.g. tris-chloroethylphophate or ammonium phosphate and polyphosphate, also stabilizers against aging and weathering influences, plasticizers and fungistatic and Bacteriostatic substances, fillers such as barium sulfate, diatomite, soot or whiting chalk can also be used.

Further examples of optionally also to be used according to the invention surface-active additives and foam stabilizers as well as cell regulators, reaction retarders, stabilizers, flame-retardant substances, plasticizers, dyes and fillers as well as fungistatic and bacteriostatic substances as well as details about use and mode of action

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these additives are published in the Kunststoff-Handbuch, Volume VE by Vieweg and Höchtlen, Carl-Hanser-Verlag, Munich 1966, e.g. on pages 103 to 113.

According to the invention, to be used if necessary for the production of plastics Starting components are also compounds with at least two isocyanate-reactive hydrogen atoms of a molecular weight of 400 10,000 as a rule. This includes amino groups and thiol groups or compounds containing carboxyl groups, preferably polyhydroxyl compounds, in particular two to eight hydroxyl groups comprising compounds, especially those of molecular weight 800 to 10,000, preferably 1,000 to 6,000, e.g. at least two, usually 2 to 8, but preferably 2 to 4, hydroxyl-containing polyesters, polyethers, polythioethers, Polyacetals, polycarbonates, polyester amides, such as those used for the production of homogeneous and cellular polyurethanes are known per se.

The possible polyesters containing hydroxyl groups are, for example, reaction products of polyvalent, preferably dihydric and optionally additionally trihydric alcohols with polybasic, preferably dibasic »carboxylic acids. Instead of the free polycarboxylic acids, the corresponding polycarboxylic acid anhydrides or corresponding Polycarboxylic acid esters of lower alcohols or mixtures thereof can be used to produce the polyesters. the Polycarboxylic acids can be aliphatic cycloaliphatic? ·, be aromatic and / or heterocyclic in nature and optionally, e.g. by halogen atoms, substituted and / or unsaturated. Examples include: succinic acid, Adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, trimellitic acid, phthalic anhydride, Tetrahydrophthalic anhydridef hexahydrophthalic anhydride, Tetrachlorophthalic anhydride, endo-

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methylene tetrahydrophthalic anhydride, glutaric anhydride, maleic acid, maleic anhydride, fumaric acid, dimeric and trimeric fatty acids such as oleic acid, optionally mixed with monomeric fatty acids, dimethyl terephthalate, bis-glycol terephthalate. Examples of polyhydric alcohols include ethylene glycol, propylene glycol (1,2) and - (1,3), butylene glycol (1,4) and - (2,3), hexanediol (1,6), octanediol (1, 8), neopentyl glycol, cyclohexanedimethanol (1,4-bis-hydr oxymethylcyclohexane), 2-methyl-1,3-propanediol,

Glycerine, trimethylolpropane, herantriol- (1, 2, 6), butanetriol- (1,2,4), Trimethylolethane, pentaerythritol, quinite, mannitol and sorbitol, methyl glycoside, also diethylene glycol, Triethylene glycol, tetraethylene glycol, polyethylene glycol] ^ Dipropylene glycol, polypropylene glycols, dibutylene glycol and Polybutylene glycols in question. The polyesters can be proportionate have terminal carboxyl groups. Also polyesters from lactones, e.g. E-caprolactone or hydroxycarboxylic acids, e.g. cj-hydroxycaproic acid can be used.

The polyethers which can be used according to the invention, at least two, usually two to eight, preferably two to three, hydroxyl groups are those of the type known per se and are obtained, for example, by polymerizing epoxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin with themselves, for example in the presence of BF ,, or by Anlgerung of these epoxides, optionally as mixtures or successively, to starting components containing reactive hydrogen atoms such as alcohols or amines, for example water, ethylene glycol, propylene glycol- (1,3) or - ( 1,2), trimethylolpropane, 4,4'-dihydroxydiphenylpropane »aniline, ammonia, ethanolamine, ethylenediamine. Sucrose polyethers, as described, for example, in German Auslegeschriften 1,176,358 and 1,064,938, are also suitable according to the invention. In many cases, those polyethers are preferred which predominantly (up to 90 % by weight, based on all OH groups present in the polyether) have primary OH groups. Also through vinyl poly

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merisate modified polyethers, such as those produced by the polymerization of styrene or acrylonitrile in the presence of polyethers (American patents 3,383,351 " 3,304,273, 3,523,093, 3,110,695, German patent specification 1,152,536) are also suitable, as are OH groups comprising polybutadienes.

Among the polythioethers are in particular the condensation products of thiodiglycol with themselves and / or with others Glycols, dicarboxylic acids, formaldehyde, aminocarboxylic acids or amino alcohols are listed. Depending on the co-components acts the products are polythio mixed ethers, polythio ether esters, Polythioether ester amides.

Suitable polyacetals are, for example, the compounds which can be prepared from glycols such as diethylene glycol, triethylene glycol, 4,4 ^l -dioxethoxydiphenyldimethylmethane, hexanediol and formaldehyde. Polyacetals suitable according to the invention can also be prepared by polymerizing cyclic acetals.

Polycarbonates containing hydroxyl groups are those of known type into consideration, for example by reacting diols such as propanediol (1,3), butanediol (1,4) and / or hexanediol (1,6), diethylene glycol, triethylene glycol, tetraethylene glycol with diaryl carbonates, for example diphenyl carbonate or Phosgene, can be produced.

The polyesteramides and polyamides include, for example, the predominantly linear condensate obtained from polyvalent saturated and unsaturated carboxylic acids or their anhydrides and polyvalent saturated and unsaturated amino alcohols, diamines, polyamines and their mixtures.

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BAD ORfGiNAL

Polyhydroxy compounds already containing urethane or urea groups and optionally modified natural polyols, such as castor oil, carbohydrates, starch, are also usable. Addition products of alkylene oxides with phenol-formaldehyde resins or with urea-formaldehyde resins can also be used according to the invention.

Representatives of this to be used according to the invention Compounds are, for example, in High Polymers, Vol. XVI, "Polyurethanes, Chemistry and Technology", written by Saunders-Frisch, Interscience Publishers, New York, London, Volume I, 1962, pages 32 - 42 and pages 44 - 54 and Volume II, 1964, pages 5-6 and 198 - 199, as well as in the Kunststoff-Handbuch, Volume VII, Vieweg-Höchtlen, Carl-Hanser-Verlag, Munich, 1966, e.g. on pages 45 to 71.

Compounds with at least two isocyanate-reactive hydrogen atoms and having a molecular weight of 32-400 can also be used as the foundation for starting components that may be used. In this case too, this is understood to mean hydroxyl groups and / or amino groups and / or thiol groups and / or carboxyl groups, preferably compounds containing hydroxyl groups and / or amino groups , which serve as chain extenders or crosslinking agents. These compounds generally have 2 to 8 isocyanate-reactive hydrogen atoms, preferably 2 or reactive hydrogen atoms. Examples of such compounds include: ethylene glycol, propylene glycol (1,2) and - (1,3), butylene glycol (i, 4) and - (2,3), pentanediol (1,5), hexanediol (1,6), octanediol- (1,8), neopentyl glycol, 1, A-bis-hydroxymethyl-cyclohexane, 2-methyl-1,3-propane diol, glycerine, trimethylolpropane, hexanetriol- <1,2,6 ), Trimethylolethane, pentaerythritol, quinitol, mannitol and sorbitol,

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/ r

Diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycols with a molecular weight of up to 400, dipropylene glycol, polypropylene glycols with a molecular weight of up to 400, dibutylene glycol, polybutylene glycols with a molecular weight of up to 400, 4,4'-dihydroxydiphenylpropane, di-hydroxymethyl-hydroquinone, Ethanolamine, diethanolamine, triethanolamine, 3-aminopropanol, ethylenediamine, 1,3-diaminopropane, 1-mercapto-3-aminopropane, 4-hydroxy- or -amino-phthalic acid, succinic acid, adipic acid, hydrazine, Ν, Ν'-dimethylhydrazine, 4,4'-diamino-diphenylmethane.

The reaction components are according to the invention by the one-step process known per se, the prepolymer process or the Brought semi-prepolymer processes to implementation, often using mechanical equipment, e.g. those that are in U.S. Patent 2,764,565. Details of processing devices that can also be considered according to the invention are given in the Kunststoff-Handbuch, Volume VI, published by Vieweg and Höchtlen, Carl-Hanser-Verlag, Munich 1966, e.g. on pages 121 to 205.

An IR spectroscopic examination of the obtained according to the invention produced foams shows high proportions of isocyanurate rings in addition to small amounts of carbodiimide groups, if the polyisocyanate is polymerized became.

The foams obtained according to the invention can be used, for example, as Insulating material in the construction industry or for the technical sector or as construction material as well as in the furniture industry Find use.

The ether esters obtained according to the invention can also be used as starting material for the production of cellular or homogeneous Polyurethane plastics are used, which in turn are used for e.g. coatings, insulation or paintwork can be used.

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Comparative experiments

1. Attempts at dissolving with tetrabromobisphenol bis-hydroxyethyl ether.

a) 50 parts by weight of the ether were dissolved in 50 parts by weight of triethylene glycol by heating. The bromine content of the solution is approx. 25 %. The hydroxyl number of the solution is 464. On cooling to room temperature, the solution solidifies to form a stiff crystal slurry.

b) 50 parts by weight of the ether mentioned were dissolved in 50 parts by weight of polyethylene glycol (molecular weight 400). With a bromine content of about 25% of the hydroxyl value of the mixture is 218. On cooling to 20 ⁰ C, the solution solidifies crystalline.

c) 50 parts by weight of the abovementioned ether are dissolved in 50 parts by weight of an ester containing hydroxyl groups. The ester was prepared by condensing 2 moles of adipic acid with 3 moles of triethylene glycol. With a bromine content of approx. 25 % , the hydroxyl number of the solution is 175. On cooling to room temperature, the solution, which is clear in the heat, solidifies in crystalline form.

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example 1

to

1150 parts by weight bis-ß-hydroxyäthyltetrabromobisphenol, 750 parts by weight

eth ylen
Parts Tr ^ Iykol and 403 parts by weight of adipic acid are heated together with 2 parts by weight of titanium tetrabutoxide with stirring and introduction of nitrogen in a standard esterification apparatus for 19 hours at 170 ⁰ C. After a condensation time of 15 hours, the acid number falls to a value of 3.5 mg KOH / g and then stops falling. The reaction mixture is cooled to 120-125 ° C. and brought to an acid number of zero within 6 hours by passing in ethylene oxide. To remove dissolved, unreacted ethylene oxide, the reaction mixture is then for another hour at 80 - 100 ⁰ C stirred in vacuo.

2180 parts by weight of a brownish oil are obtained. The tetrabromobisphenol bisether content of the product is thus approx. 52 %.

The product shows the following analytical data:

Viscosity: 66 p / 25 ° C OH number: 195 Bromine content: 25.3-4

The product retains its liquid consistency even when stored at 0-10 ^{° C.}

Example 2

äth ylen-Tr-T = V

ä 1150 parts by weight, 750 parts by weight of glycol Tetrabrombisphenolbisäther, 520 parts by weight of adipic acid, 18.5 parts by weight of maleic anhydride, and 2 parts by weight of titanium tetrabutoxide as described in Example 1, heated 24 hours on 170 ⁰ C. . The acid number of the esterification product is then 4. The product is brought to an acid number of 0 ^{at 130 ° C. by treatment with ethylene oxide.}

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• rl

2310 parts by weight of a burnt viscous oil are obtained, which shows the following key figures:

Viscosity: 140 p / 25 ° C Bromine content: 24.0 - 24.1 % OH number: 150 - 151

The product remains liquid after cooling. Example 3

1150 parts by weight of tetrabromobisphenol bisether, 750 parts by weight of Tr2> ^ "glycol, 420 parts by weight of tetrahydrophthalic acid and 2 parts by weight of titanium tetrabutoxide are heated in the manner described for 24 hours at 170 ° C, the acid number up to 4 The reaction product is ^{cooled to 125 °} C. Ethylene oxide is then passed in for several hours, the acid number falling to 0. To remove the unreacted ethylene oxide, the esterification mixture is heated in vacuo for 1 hour at 120 ° C. The ester ceases brownish colored oil that does not show any signs of crystallization even when standing at low temperatures for a long time.

Viscosity: 200 p / 25 ° C Bromine content: 25.2 - 4 % OH number: 203

Example 4

230 parts by weight Tetrabrombisphenolbisäther, 75 parts by weight of triethylene glycol, 100 parts by weight of polyethylene glycol (MW 400), 73 parts by weight of adipic acid and 2.1 part by weight of titanium tetrabutoxide are at 160 - 167 ⁰ C heated 21 hours as described above. The acid number of the resulting ester is 2.3. The reaction mixture is stirred at 118 - 122 ⁰ C treated with ethylene oxide, wherein the acid value disappears.

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470 parts by weight of a dark brown resin are obtained, which shows the following key figures:

Viscosity: 140 p / 25 ° C
Bromine content: 24.8 - 25 %
OH number: 151 - 153

Example 5

1896 parts by weight of tetrabromobisphenol bisather, 1125 parts by weight Diethylene glycol and 1023 parts by weight of adipic acid are under Passing in nitrogen, heated to 160 ° C. for 33 hours. The acid number of the esterification product is then 5.4. the Reaction mass is treated with ethylene oxide at 130 ° C until no more acid number can be detected.

3440 parts by weight of a brownish, viscous oil are obtained, which shows the following key figures:

Viscosity: 70 p / 25 ° C
Bromine content: 23.0 - 23.2 % OH number: 186 - 188.

Example 6

990 parts by weight of tetrabromobisphenol are used in 750 parts by weight Triethylene glycol with the addition of

2 parts by weight of dissolved sodium phenolate and heated with stirring to 125 ⁰ C. Then, within 7 1/2 hours 190 parts by weight of ethylene oxide at a temperature between 125 - 130 ⁰ C initiated. After completion of the Äthylenoxidzugabe vacuum is applied and the reaction mixture for one hour under stirring to 125 - maintained 13O ⁰ C to remove unreacted ethylene oxide to remove. The reaction mixture solidifies to a crystalline mass on cooling. Then, at normal pressure and a temperature of 110 ° C., 403 parts by weight of adipic acid and 2 parts by weight

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Si

Titanium tetrabutoxide added. While introducing nitrogen, the reaction mixture is heated in one hour to 16O ⁰ C and stirred for 4 hours at this temperature. 57 parts by weight of HpO distill off. A vacuum is then applied and heating is continued for a further three hours at a pressure of 16-18 torr, a further 20 parts by weight of water being split off. A light yellow colored viscous oil is obtained, which shows the following key figures:

Viscosity: 52 p / 25 ° C

Bromine content: 26.0 %

OH number: 197 - 203

Acid number: 1.2.

Example 7

A mixture of 66.7 parts by weight of the polyether ester Example 2, 33.3 parts by weight of a propoxylated ethylenediamine with an OH number of 650, 1 part by weight of a commercially available foam stabilizer, 1 part by weight of triethylamine and 25 parts by weight of trichlorofluoromethane is intensively stirred for 5 seconds with 100 parts by weight of a crude 4,4'-diphenylmethane diisocyanate. The setting time is 15 seconds. A hard polyurethane foam is obtained which is "normally flammable" according to DIN 4102 and has a bulk density of 30 kg / m ^, while foams are the same Type, however, without the addition of the polyether esters according to the invention prove to be "easily flammable".

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Example 8

A mixture of 30 parts by weight of the polyether ester from Example 4, 10 parts by weight of trichloroisopropyl phosphate, 3 parts by weight of the amino polyether from Example 7, 1 part by weight of glycerol, 1 part by weight of the stabilizer from Example 7, 1 »5 parts by weight a 25 ^ solution of potassium acetate in diethylene glycol and 22 parts by weight of trichlorofluoromethane is made on a foaming machine of the type HK 500 from Hennecke / Birlinghoven 100 parts by weight of an isocyanate group-containing prepolymer, which is composed of 95 parts by weight of the isocyanate from Example 7 and 5 parts by weight of a polypropylene glycol having the OH number is prepared. The reaction mixture is 15 seconds in a Form with a base area of 1 χ 1 m entered. The foam rises approx. 50 cm and sets after 40 seconds.

The foam, which predominantly contains polyisocyanurate groups, has a bulk density of 35 kg / m 2. and is heavy according to DIN 4102 " flammable ". The foam block is made in sheets and raw half-shells etc., which are used as insulating materials in building construction or for the insulation of pipelines.

Example 9

Example 8 is used; the amount of catalyst (potassium acetate solution) however, it is increased to 2.0 parts by weight; in addition, 0.5 part by weight of tris (dimethylaminomethyl) phenol is added. This formulation is processed on a double conveyor belt system from Hennecke / Birlinghoven, Siegkreis. Polyethylene-coated aluminum foils are used as cover layers. The foam shows good adhesion to the Top layer. The panels are used in the roofing of buildings. If in this recipe the invention Polyether ester with a bisphenol-A polyether brominated in accordance with Offenlegungsschrift 2 232 540 (with the same bromine content) replaced, the foam does not adhere to the top layers because the foam is brittle on the surface.

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Claims (1)

1. Polyether ester containing hydroxyl groups with an acid number of '0-5, preferably 0-1, and a hydroxyl number between -300, preferably 150-250, obtained by esterification a) Bishydroxyalkyl ethers of halogenated 2,2-diphenylolpropanes the general formula ^0H ) ₂ where η = 0.1 R ^ to Rg = H, C ^ -C ^ -alkyl, preferably H, CH ,, C ₂ H, - and Ry to R ₁₀ = H, Cj-C ^ -alkyl, halogen, preferably H, Br, CH, mean and where at least one of the radicals R ₇ -R _{10 should be} a halogen atom, preferably a bromine atom b) saturated and / or unsaturated aliphatic and / or aromatic polycarboxylic acids in the presence of c) dialcohols of the following formula: HO-C-C-hA-C-C H-OH wherein X ₁ to X ₈ = H, Cj-C ^ -alkyl, preferably H, CH ,, η = 1-10, - A = 0, S. mean. Le A 15 946 - 25 - 609818/1062 Polyether esters containing hydroxyl groups according to Claim 1, obtained by esterification of the bis-ß-hydroxyalkyl halobisphenol ethers with polycarboxylic acids in the presence of dialcohols, optionally in the presence of esterification catalysts, by heating to Ti
wise 140 to 170 ⁰ C. by heating to temperatures of 120 to 200 ⁰ C, preferably 3. Hydroxyl group-containing polyether ester as claimed in claim 1, obtained by a solution of a nuclear halogenated bisphenol in a dialcohol much of alkylene oxides, preferably ethylene oxide or propylene oxide, in the presence of the known alkoxylation catalysts at temperatures of 80 - 180 ^0C, preferably 110 - 14O ° C is added, are etherified until substantially all of the phenolic hydroxyl groups and that the mixture thus obtained kernhalogeniertem Bisphenoläther and polyalkylene glycols with polycarboxylic acids, optionally in the presence of esterification catalysts, by heating at temperatures from 120 to 200 ⁰ C, preferably 140-170 ° C, optionally is esterified with the introduction of inert gases and / or reduced pressure. 4. Hydroxyl-containing polyether esters according to claims 1-3 with a bromine content of 20-30 %, obtained by esterifying 1 mole of tetrabromobisphenol-bis-ß-hydroxyethyl ether with 2-2.5 moles of adipic acid in the presence of 3.0-3.5 moles Diethylene glycol. 5. Polyether esters containing hydroxyl groups according to claims 1-3 with a bromine content of 20-30%, obtained by esterification of 1 mole of tetrabromobisphenol-bis-ß-hydroxyethyl ether with 1.25-2.0 moles of adipic acid in the presence of 2.5-3.0 moles of triethylene glycol. Le A 15 946 - 26 - 60981 8/1 062 6. Use of the hydroxyl-containing polyether esters according to Claims 1-5 for the production of plastics by reaction with polyisocyanates. 7. Use of the hydroxyl-containing polyether esters according to claims 1-5 and 6 for the production of isocyanurate plastics, preferably foams. Le A 15 946 - 27 - 609818/1062