DE1595673A1 - Process for the production of polyaddition and / or polycondensation products with hexacyclic oxaspirane groups - Google Patents

Description

Processes for the production of polyaddition and / or polycondensation products with hexacyclic oxaspirane groups. High molecular weight compounds with the 2,4,8,10-tetraoxaspiro- (5,5) -undecane group are known. According to German Patent 1,151,813, 3,9-bis (1,1-dimethyl-2-hydroxy-ethyl) -2,4,8,10-t et raozaspiro and e can reacted with NCO pre-adducts, used as an intermediate for plastics, synthetic waxes and foams and as a stabilizer for polyvinyl chloride. The same tetroxaspiro compound is used in US Pat. No. 3,092,640 for the production of polyesters, polyurethanes and polycarbonates.

3,9-bis (carbathoxy) -2,4,8,10-tetroxaspiro- (5,5) -undecane is described in US Pat. No. 3,092,597 for reaction with glycol to form polyesters or, in particular, with polyethylene glycols to form water-soluble polyesters. Other tetroxaspiro-undecane-carboxylic acids such as, for example, 3,9-bis- (1,1-diethyl-3-carboxypropyl) -2,4,8,10-tetroxaspiro- (5,5) -undecane or 3,9-bis (2-carboxyethyl) -2,4,8,10-tetroxaspiro- (5,5) -undecane were used in US Pat. No. 3,161,619 for the preparation of polyamides.

The present invention relates to a process for the preparation of polyaddition and / or polycondensation products with recurring hexacyclic oxaspirane groups and is characterized in that compounds of the general formula and R '= H, alkyl of 1-4 carbon atoms; x = 1-3) are reacted in a manner known per se with the countercomponents complementary to the functional groups R.

Those in German Patent 1,151,813, US Patents 3,9-bis- (alkyl) -2,4,8,10-tetroxaspiro-undecane compounds mentioned 3 092 640 and 3 092 597 (Diols, dicarboxylic acids and diamines) lead to polyesters, polyurethanes and polycarbonates with relatively low softening points, low tendency to crystallize, lower Rigidity of the plastic products made therefrom, which z. B. from the intended Use of such products to make synthetic waxes and lubricants emerges. Further is the preparation of the 3,9-bis (alkyl) -2,4 ', 8,10-tetroxaspiro- (5,5) -undecane compounds from aliphatic hydroxyl or carboxy aldehydes or aldehyde derivatives and pentaerythritol uneconomical, since these intermediate products are technically very difficult to access.

In contrast to this, the method according to the invention is distinguished by has a number of advantages: The one using 3,9-bis (phenyl) or - (cyclohexyl) -2,4,8,10-tetroxaspiro- (5,5) -undecane compounds Polyaddition or polycondensation products manufactured are plastics (polyurethanes, Polyureas, polycarbonates, polyesters and polyamides) with high melting points, high crystallization tendency of the moldings made from the products stretching, high rigidity and high thermal stability.

The one used to make the the groups containing plastics compounds used according to the invention can be made from technically easily accessible intermediates, e.g. B. from appropriately substituted benzaldehydes or acetophenones and pentaerythritol, easily produce with high yields.

The following compounds may be mentioned by way of example: Diols: 3,9-bis- [4 '(2'- or -3') -hydroxyphenyl] -2,4,8,10-tetroxaspiro- (5,5) -undecane, 3,9-bis- [4'- (2'- or -3 ') - hydroxyphenylmethyl] -2,4,8,10-tetroxaspiro- (5,5) -undecane, 3,9-bis- [4' (2'- odr -3 ') -hydroxypenyläthyl] -2,4,8,10-tetroxaspiro- (5,5) -undecane, the Oxäthylierungs- or Oxpropylierungsprodukte the bisphenols mentioned, z. B. 3,9-3is- (4 'ß-hydroxy-ethoxyphenyl) -2,4,8,10-tetroxaspiro- (5,5) -undecane, 3,9-bis (4 'ß-hydroxypropoxyphenyl) -2,4,8,10-tetroxaspiro- (5,) - undecane, 3,9-bis- [4' - (2'- or -3 ') - hydroxycyclohexyl] -2,4,8,10-tetroxaspiro- (5,5) -undecane, 3,9-bis- [4 '(2' or -3 ') hydroxycyclohexylmethyl] -2,4,8,10-tetroxaspiro- (5,5) -undecane, 3,9-bis- (4'-ß-hydroxyethoxycyclohexyl) -2,4,8,10-tetroxaspiro- (5,5) undecane; Dicarboxylic acids or their esters of lower alcohols: 3,9-bis [4 '- (or-3') - carboxyphenyl] -2,4,8,10-tetroxaspiro- (5,5) -undecane, 3,9-bis- [4'- (or-3 ') - phenoxy-acetic acid] -2,4,8,10-tetroxaspiro- (5,) - undecane, 3,9-bis- [4'- (or -3 ') -phenoxypropionic acid] -2,4,8,10-tetroxaspiro- (5,5) -undecane, 3,9-bis- [4'- (or -3 ') -phenoxy-butyric acid] -2,4,8,10-tetroxaspiro- (5,5) -undecane, 3,9-bis- [4'- (or -3 ') -phenoxy-acetic acid-3,9-dimethyl] -2,4,8,10-tetroxaspiro- (5,5) -undecane, 3,9-bis- [4 '- (or -3') -carboxycyclohexyl] -2,4,8,10-tetroxaspiro- (5,5) -undecane, 3,9-bis- [4'- (or -3 ') - cyclohexylacetic acid] -2,4,8,10-tetroxaspiro- (5,5) -undecane, or the esters the aforementioned saunas with C1 to C4 alcohols.

Diamines: 3,9-bis- [4'- (or 3 ', or 2') - aminophenyl] -2,4,8,10-tetroxaspiro- (5,5) -undecane, 3,9-bis- [4'- (or 3 ') - aminophenyl-3,9-methyl] -2,4,8,10-tetrexaspiro- (5,5) -undecane, 3,9-bis [4 '- (or 3') - aminophenyl-3,9-ethyl] -2,4,8,10-tetroxaspiro- (5,5) -undecane, 3,9-bis- [4 '- (or 3') - aminocyclohexylmethyl) -2,4,8,10-tetroxaspiro- (5,5) -undecane, 3,9-bis- [4 '- (or 3') - aminocyclohexyl-3,9-ethyl] -2,4,8,10-tetroxaspiro- (5,5) -undecane.

The compounds of the general formulas are converted to polyurethanes, polyureas, polycarbonates, polyesters and polyamides by processes known per se with polyaddition or polycondensation.

The compounds known per se, which serve as the second component complementary functional groups corresponding to the functional groups R in the oxaspirons Have groups. So the diols (R = OH or -0-OH2-CHR'-OH) with diisocyanates, which can already be higher molecular and resinous pre-adducts to form polyurethanes realize. With polycarboxylic acids or their esters are obtained by esterification or Transesterification polyester. The corresponding polycarbonates are formed from the diols with phosgene.

Conversely, as above, one can use oxaspirans with carboxyl groups or their esters with polyols by esterification or transesterification, likewise polyester obtain. Polyureas are formed from the diamines (R = KE2) with diisocyanates, with bis-chlorocarbonic acid esters also polyurethanes, with polycarboxylic acid anhydrides Polyamides, the polyvalent acid chlorides also polyamides. Leave the diamines also react with epoxy resins.

Those complementary to the oxasptranediols, dicarboxylic acids and diamines Compounds that convert the oxaspiranes to polyurethanes, polyureas, polycarbonates, Complementing polyesters and polymaiden include: hexane diisocyanate, 1,6-, 2, and 2-6-toluene diisocyanate, 1,5-naphthylene diisocyanate, 4,4'-diphenylmetrane diisocyanate, 1,4-butanebischlorocarbonic acid ester, 1,6-hexanediolbischlorocarbonic acid ester, 1,4-phenylenebisoxethyl ether chlorocarbonic acid ester, Phosgene, diphenyl carbonate, ethylene glycol, butanediol, 1,6-hexanediol, hydroquinone, 1, 4-phenylenebisoyethylether, thiodiglycol, diglycol, N-methyldiethanolamine, 1,4-bis-hydroxycyclohexane, Bisoxethyl terphthalate, adipic acid, sebacic acid, succinic acid, tere- and Isophthalic acid, 2,7-naphthalenedicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid, 1,4-phenylenebisoxyacetic acid, pyromellitic dianhydride, etc.

Derivatives of these complementary compounds such as dicarboxylic acid chlorides, esters, phenyl carbamates, isocyanate releasers can be used.

It is also possible to have two oxaspirans that have complementary groups R have to implement with each other with polyaddition or polycondensation, z. B. 3,9-bis r4'-aminophenyl ~ 7-2,4,8,1O-t-etroxaspiro- (5, 5) -undecane can with the Acid chloride of 3,9 to # 4'-carboxyphenyl ~ 7-2,4,8,10-tetroxaspiro- (5,5) -undecane can be converted to polyamide according to Schotten-Baumann.

The implementation of the oxaspirans with the complementary compounds too Polyurethanes, polyureas, polycarbonates, polyesters and polyamides. he follows in the usual way in the melt, in solution or in an organic-aqueous, two-phase system in the manner of an interfacial condensation.

Oxaspirandiols are in solution, e.g. B. in toluene, chlorobenzene, dichlorobenzene reacted with diisocyanates at 100 to 1600 C or with one another in a solvent-free manner fused, for which reaction temperatures of 150 to 2200 C are required. Oxaspirandiamines can at 200 to +200 C in an interfacial condensation with bis-chlorocarbonic acid esters implemented in a two-phase system.

Oxaspirandiamines are with polyisocyanates, z. B. also NCO pre-adducts from higher molar polyhydroxyl compounds and excess diisocyanates, in z. B. Dimethylformamide solution bie 20 ° to +600 a implemented. The implementation can but also in dioxane, tetrahydrofuran, dimethylsulfonoxide, toluene, etc. take place.

Oxaspirandiols are condensed with diphenyl carbonate in the melt with elimination of phenol; Oxaspiran phenols can work in a two phase reaction system be reacted with phosgene in the presence of alkali (-10 ° to +200 C).

Oxaspirandiols or dicarboxylic acids are complementary with the Dicarboxylic acids or the diols after the addition of condensation catalysts, such as alkaline earth or heavy metal oxides, polycondensed. Of course, the Dioarboxylic acid meter be fed to the reaction.

Oxaspirandicarboxylic acids or diamines are complementary with the Diamines or dicarboxylic acids or their derivatives are polycondensed in the melt. the oxaspirandiamines can also be used with dianhydrides, such as pyromellitic dianhydride, in solution, e.g. B. Dimethylformamide are converted. The resulting polyamide carboxylic acids can then be deformed from the solution as a lacquer and on the surface of a transform painted object into polyimide at temperatures above 3000 C.

Depending on the choice of components, the reaction products can be made into injection molded bodies, Threads or foils or lacquer coatings are processed.

Example 1: 51.3 g of 3,9-bis (3'-aminophenyl) -2,4,8,10-tetroxaspiro- (5.5) undecane (pp. 234-2350C) are dissolved in 250 g of dimethylformamide.

At 25 ° C., a solution of 25.50 g of 1,6-hexane diisocyanate in 100 g of dioxane and 50 g of dimethylformamide is added dropwise in about 30 minutes with thorough stirring. n The polyurea with repeating units is isolated by precipitating the viscous solution in water.

The polymer melts at 240 - 248 0C and has a K value of 47.

The solution of the addition product can be cast into foils or after are spun into threads using the wet or dry spinning process.

Example 2: a) 51.3 g of 3,9- (3'-aminophenyl) -2,4,8,10-tetroxaspiro- <5.5) -undecane are dissolved in 250 g of dimethylformamide. At 2500, a solution of 38.0 g of 4'-diphenylmethane diisocyanate in 80 g of dioxane and 50 g of dimethylformamide is added dropwise with thorough stirring at 2500. The polyurea with recurring units is isolated by precipitating the viscous solution in water.

K = 51.0, m.p. 265-270 ° C. The .Polyurea solution can be e.g. pour glass supports into pilms, which after evaporation of the solvent (1 h / 1000C) result in crystal clear, hard foils (peeled from the base). am in an analogous manner is prepared from 51.3 g of 3,9-bis- (4'-aminophenyl-2,4,8,10-tetroxaspiro- (5,5) -undecane and 38.75 g of 4,4'-diphenylmethane diisocyanate produce the polyurea isomeric to a).

K = 52.5, m.p. 27 ° C. The polyurea can be obtained from the dimethylformamide solution deform into hard, scratch-resistant coatings.

The starting material 3,9-bis (4'-aminophenyl) -2,4,8,10-tetroxaspiro- (5,5) -undecane is made by hydrogenating the well-known dinitrospirane compound in dimethylformamide obtained with Raney nickel as a catalyst. Yield 94.5%, m.p. 17400. The diamine is made from 2 ml of dioxane and 5 ml of alcohol / g or from 3 ml of glycol monomethyl ether and 2 ml of water recrystallized.

C19H22N2O4 calc. O 66.65 H 6.48 N 8.18 0 18.69 (342.4) found. C 66.42 H 6.56 N 8.38 0 18.33 Example 3: 55.5 g of 3,9-bis (4'-aminophenyl-methyl) -2,4,8,10-tetroxaspiro- (5th , 5) -undecane are dissolved in 260 g of dimethylformamide. At 20-25 ° C., a solution of 37.75 g of 4,4'-diphenylmethane diisocyanate in 50 g of dioxane is added dropwise with thorough stirring in about 15 minutes. The viscous solution is cast into films. The films obtained after evaporation of the solvent melt at 270.degree.

To prepare the starting material, first 3,9-bis- (4'-nitro-phenyl-methyl), 2,4,8,10-tetroxaspiro- (5,5) -undecane in very high yield by reacting 333 g of 4-nitroacetophenone and 136 g of pentaerythritol obtained in 700 ml of toluene in the presence of 1.0 g of p-toluenesulfonic acid (seven hours Heating while distilling off the water of reaction).

Yield 98.5%, m.p. 243-245 ° C.

The dinitrospirane is made from 3 ml of glycol monomethyl ether acetate and 1.0 ml of dimethylformamide per gram recrystallized.

C21H22N2 ° 8 calc. C 58.61 H 5.15 N 6.51 10 29.74 (430.4) found. C 58.60 H 5.15 N 6.49 0 29.53 The starting material 3,9-bis (4'-aminophenyl-methyl) -2,4,8,10-tetroxaspiro- (5'5) '- undecane is made from the dinitro compound by catalytic hydrogenation in dimethylformamide manufactured. Yield 93.5%, m.p. 221-222 ° C.

The diaminospiran is made from 3.5 ml of dimethylformamide and 2.5 ml of alcohol / g recrystallized.

C21H26N204 calcd. C 68.10 H t, 08 N 7.56 0 17.28 (370.4) found. C 67.75 H 7.06 N 7.60 0 17.56 Example 4: 38.2 g of 3,9-bis (4'-amino-cyclohexyl-methyl) -2,4,8,10-tetroxaspiro- (5,5) -undecane are dissolved in 90 g of dimethylformamide. At 25 ° C., the solution of 25.0 g of 4,4'-diispcyanatodiphenylmethane in 70 g of dimethylformamide is added dropwise with stirring. A viscous solution of the polyurea with the following structural units is obtained The polyurea melts above 265 ° C. The K value, measured in a 1% solution in m-cresol, is 60.8. The dimethylformamide solution of the polyurea can be poured into films which, after the solvent has dried off, give clear, flexible sheets. The modulus of elasticity of such a film, which can be stretched in a ratio of 1: 1.3 in all directions, is 260 kg / mm2.

The starting material 3,9-bis (4'-aminocyclohexyl-methyl) -2,4,8,10-tetroxaspiro- (5,5) -undecane is obtained by hydrogenating 250 g of 3,9-bis (4'amino-phenylmethyl) -2,4,8,10-tetroxaspiro- (5,5) -undecane (see under Example 3) in 1.2 l of dioxane with 50 g of 5 of a ruthenium on aluminum oxide obtained at 110 - 130 ° C. The diamine is obtained as a light-colored resin in almost 90% strength Yield of 203 equivalent weight calculated 191.

Example 5: 200 g of a polyester made from adipic acid, hexanediol (1.6) and pentaglycol (molar ratio of hexanediol: pentaglycol = 65:35; reaction number 67.4 corresponding to a molecular weight of 1660) are mixed with 48.8 g of 4,4'-diisocyanatodiphenylmethane Heated to 1000C for 60 minutes. Determined after dissolving the melt in 200 g Dipxan the NCO content of the NCO was 1.29%.

One carries 100 g of this NCO pre-adduct solution with thorough stirring in a Solution of 6.50 g of 3,9-bis (4'-amino-cyclohexyl-methyl) -2,4,8,10-tetroxaspiro- (5,5) -undecane in 175 g of dimethylformamide. The highly viscous solution of the reaction product obtained can easily be cast into films which, after the solvent has evaporated (1st h / 110-130 ° C) result in elastic, removable films from the base, the films can be cut into elastic threads.

But it can also be the highly viscous solution in a known manner after Wet or dry spinning processes are deformed into elastic threads.

Properties of the film: Thickness (mm) Ö, 11 tear strength (kg / cm2) 363 Elongation (%) 510 RF break (kg / cm2) 2220 module 20% (kg / cm2) 18 Module 300% (kg / cm2) 74 Tear strength (Graves) (Kg / cm) 19 Micro hardness 60 Example 6: 200 g of the polyester from Example 5 are mixed with 57.0 g of 4,4'-diisocyanatodiphenylmethane as there implemented and dissolved in 100 g of dioxane. The NCO content is 1.95%.

150 g of this NCO pre-adduct solution are slowly poured into a Solution of 12.4 g of 3,9-bis- (3'-aminophenyl) -2,4,8,10-textroxa spiro- (5,5) -undecane stirred into 290 g of dimethylformamide. The viscous solution of the elastomer is like Cast into films in Example 5, these have a tear strength of 334 kg / cm2 and an elongation of 615%.

Example 7: a) To a solution of 102.6 g of 3,9-bis (4'-aminophenyl) -2,4,8,10-tetrozaso- (5,5) -undecane (For preparation, see Example 4 in 500 g of dimethylformamide and 70 g of triethylamine a solution of 61.2 g of isophthaloyl chloride in 200 g of dioxane is added dropwise at 15-20 ° C.

The reaction mixture is stirred into precipitation of the polyamide in water. The polyamide, washed several times with water, is dried, it sinters at 255 ° C, without melting in the usual sense.

The polyamide can be formed into threads or foils from dimethylformamide / lithium chloride (5% LiCl). b) If 102.6 g of 3, 9-bis- (3'-aminophenyl) -2,4,8,10-tetroxaspiro- (5,5) -undecane are used instead of the p-diamine, a polyamide is obtained which melts at 240 - 245 ° C.

Example 8: 19.1 g of 3,9-bis (4'-amino-cyclohexyl-methyl) -2,4,8,10-tetroxaspiro- (5,5) -undecane are dissolved in 80 g of pyridine. At 25-300 ° C., a solution of 10.5 g of isophthalic acid chloride in 20 g of dioxane is added dropwise and the reaction mixture is then heated on a water bath for 30 minutes. Stirring the reaction mixture into 500 ml of water gives the polyamide with recurring structural units failed. It melts at 245-25000.

Example 9: a) 64.80 g of 3,9-bis (4'-hydroxy-ethoxyphenyl) -2,4,8,10-tetroxaspiro- (5,5) -undecane are dissolved hot in 300 g of trichlorobenzene.

25.25 g of hexane (1,6) diisocyanate in 100 g of trichlorotenzene are added dropwise at 160.degree for ten minutes and then keeps the reaction mixture for 30 minutes 160 ° C. After cooling, the solvent is decanted from the polyurethane, this mechanically crushed and steam distilled from the rest adherent and trapped solvent freed.

M.p. 178-18300. b) If the hexane diisocyanate is replaced by 38.25 g of 4,4'-diisocyanatodiphenylmethane, a polyurethane with a melting point of 190 ° C. is obtained.

To prepare the starting material, 172 g of 3,9-bis (4'-hydroxyphenyl) -2,4,8,1 O-tetroxaspiro- (5,5) -undecane with 40 g caustic soda in 800 ml water at 5000 solved. In 30 minutes, it is added dropwise to the 50 ° C. solution of the spirane bis-phenol 90 g of ethylene chlorohydrin and then holds the reaction mixture for two hours at 75 ° C. After cooling, the precipitate is filtered off with suction and washed with water and dried. The dialcohol is made from 5.0 ml of glycol monomethyl ether acetate and 0.5 ml of dimethylformamide recrystallized. yield: 68%, mp: 215-217 ° C 023H2808 calc. C 63.88 H 6.53 0 29.59 (432.5) found. C 64.25 H 6.25 0 29.42 The 3,9-bis (4'-hydroxyphenyl) -2,4,8,10-tetroxaspiro- (5,5) -undecane in turn, is obtained by adding 136 g of pentaerythritol with 245 g of p-hydroxybenzaldehyde heated to boiling in 500 ml of toluene after the addition of 1.0 g of p-toluenesulfonic acid. That Water of reaction is distilled off azeotropically with toluene as an entrainer. After 8 hours the calculated amount of water (36 ml) is split off.

After cooling, the crude spirane bisphenol crystallizes in 82% strength Yield from. The dried crude product, washed with water, is made from 5.0 ml Ethyl acetate and 1.0 ml of dimethylformamide per; Gram recrystallized; -Fp. 258-26000.

C19H20O6 calcd. C 66.26 H 5.85 0 27.87 (344.4) found. C 66.05 H 5.94 0 27.83 Example 10: a) 25.92 g of 3,9-bis- (3'-hydroxyethoxyphenyl) -2,4,8,10-tetroxaspiro- (5,5) -undecane are used as in Example 9 in 80 g of trichlorobenzene at 190 ° C. with 15.50 g of 4,4'-diisocyanato-diphenyl-methane around (45 minutes / 190 ° C), a polyurethane of # 1 = 0.50 (1% in m-cresol) is obtained and mp. 180 ° C. b) 3,9-bis (3'-hydroxy-ethoxy-phenyl) -2,4,8-tetroxspiro- (5,5) -undecane is prepared according to the starting material in Example 9. yield 91%; M.p. 143-145 ° C. (from 3 ml of alcohol and 2 ml of water per gram).

C23H28O8 calc. 0 29.59 (432.5) found. 0 29.22 c) The 3,9-bis- (3'-hydroxyphenyl) -2,4,8-10-tetroxaspiro- (5,5) -undecane is also prepared analogously to the 4'-isomer as indicated in Example 9. Yield 84%; Mp. 24-248 ° C (from 3 ml of glycol monomethyl ether acetate and 2.5 ml Water per gram).

C19H20O6 calcd. C 66.26-H 5.85 (344.4) found. C 66.31 H 5.92 Example 11: a) 64.80 g of 3,9-bis- (4'-hydroxy-thoxyphenyl) -2,4,8,10-tetroxaspiro- (5,5) -undecane will. with 29.1 g of dimethyl terephthalate in the presence of 25 mg of lead oxide and 25 mg of antimony oxide polyesterified.

The polyester (melting point 2500C) is insoluble in dimethylformamide and m-cresol, but soluble in phenol / tetrachloroethane (6: 4).

Boispisl 12: 3,9-bis (4'-phenoxyacetic acid ethyl ester) -2,4,8,10-tetroxaspiro- (5,5) -undecane is esterified with ethylene glycol.

103.2 g of 3.9-bis (4'-phenoxyacetic acid ethyl ester) -2,4,8 10-totrosaspiro- (5,5) -undeoan are with 20 g of ethylene glycol in the presence of 30 mg of lead oxide and 5 mg of cobalt acetate in a condensation vessel equipped with a stirrer, thermometer and nitrogen inlet tube first transesterified at temperatures up to 2200 C and then with distilling off the excess ethylene glycol in vacuo (final vacuum 0.2 Torr0 polyesterified. The The softening point of the polyester is 210 to 2200 ° C., K value 51.0 in phenol tetrachloroethane (6: 4) as a 19% solution.

The starting material is obtained by reacting 82 g of + -formylphenoxyacetic acid ethyl ester with 26 g of pentaerythritol in 150 ml of toluene in the presence of 0.2 g of p-toluenesulfonic acid. The elimination of water is complete after 1 1/2 hours. Yield 84%; M.p. 94-95 ° C (from alcohol / toluene).

C27H32O10 calcd. C 62.78 H 6.24 0 30.97- (516.6) found. C 62.37 H 6.27 0.31.68 Example 13: a) 68.8 g of 3,9-bis- (4'-hydroxyphenyl) -2,4,8,10-tetroxaspiro- (5,5) undecan are dissolved with 16.0 g of caustic soda in 450 ml of water. After adding 150 ml of methylene chloride, 30 g of phosgene are passed in at 25 ° C. with vigorous stirring in about two hours. 1.0 g of triethylbenzylammonium chloride are then added and the mixture is stirred for a further two hours. a polycarbonate with the structural units is obtained from melting point 260 - 265 ° C. b) If the 3,9-bis (3'-hydroxyphenyl) -2,4,8,10-tetroxaspiro- (5'5) -undecane is used and the reaction is analogous to a), a polycarbonate of melting point is obtained 190-200 ° C. Example 14: In a solution of 34.2 g of 3,9-bis- (3'-aminophenyl) -2,4,8,10-tetroxasipro- (5,5) -undecane in 300 ml of anhydrous dimethyl acetamide 21.9 g of sublimed pyromellitic acid dianhydride are added within 30 minutes at 10-15 ° C.

The two components are allowed to react at room temperature and in this way a pale, viscous solution is obtained. The polyamide-carboxylic acid solution can be used for wire enamelling, with high-temperature, scratch-resistant coatings being obtained at baking temperatures of 400 ° C.

Example 15: As in Example 14, 74.0 g of 3,9-bis (4'-aminophenyl-methyl) -2,4,8,10-tetroxaspiro- (5,5) -undecane are obtained in 600 ml of dimethylacetamide with 43.6 g of sublimed pyromellitic anhydride to one viscous polyamide-polycarboxylic acid solution converted. This can be used to produce high temperature resistant Coatings are used.

Example 16: 38.2 g of 3,9-bis (4'-amino-cyclo-hexyl-methyl) -2,4,8,10-tetroxaspiro- (5,5) -undecane with 14.6 g of adipic acid in a nitrogen inlet tube and thermometer provided condensation vessel with a slow increase in temperature in six hours heated up to 260 5 C. A tough polyamide melt is obtained (from which threads to let go). Softening range 195 to 210 ° K = 58.0, (1% in m-cresol).

Example 17: 38.2 g of 3,9-bis (4'-amino-cyclo-hexyl-methyl) -2,4-8,10-tetroxaspiro- (5,5) -undecane and 51.6 g of 3,9-bis (4'-phenoxyacetic acid ethyl ester) -2,4,8,10-tetroxaspiro- (5,5) -undecane are slowly heated to 260 to 2700 C under the guidance of pure nitrogen. Alcohol elimination starts at around 140 to 1500 C.

The total duration of the condensation is about three hours. That Polymaid softens at 220 to 230 ° C, K = 52.2 (1% in m-cresol).

Claims (1)

Claim. Process for the preparation of polyaddition and polycondensation products with recurring hexacyclic oxaspirane groups, characterized in that compounds of the general formulas R '= H, alkyl having 1-4 carbon atoms; x = 1 - 3) are implemented in a manner known per se with the Gregan components complementary to functional groups R.