DE2436359A1 - Process for the production of hardenable and heat hardenable synthetic resins containing nitrogen and boron - Google Patents

Description

Process for the production of curable and thermosetting synthetic resins containing nitrogen and boron.

Hoechst Aktiengesellschaft, Prankfurt / Main

The present invention relates to a method of making curable and thermosetting, nitrogen and Boron-containing synthetic resins by reacting phenolic compounds with boron compounds, nitrogen compounds and formaldehyde or formaldehyde-releasing compounds with heating.

In the German Auslegeschrift 1 816 211 is already a Process for the production of phenol-formaldehyde resins, which contain a chemically bound metal or metalloid, by condensation of a phenol with formaldehyde and Removal of the water formed and, if applicable, the hydrochloric acid formed and the solvent from the reaction mixture, known, which is characterized is that the metal or metalloid in the form of boric acid, phosphorus oxychloride, molybdenum trichloride, molybdenum, Titanium tetrachloride, tungsten hexachloride, zirconium oxychloride and manganese dichloride on the phenyl radical, which can carry halogen, alkyl or amino substituents before the reaction, is bound via covalent or ionic bonds before or after the condensation with the formaldehyde. When using a p-aminophenol condensed with boric acid

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Formaldehyde resin produces a resin which contains an amine residue and a borate ion in its molecule. Furthermore, in Example 1, the synthesis of a boron-phenol-formaldehyde resin is described there. The curing of this resin is readily catalyzed by hexamine and takes place at 150 to 16O ⁰ C instead of 20 minutes. However, in terms of the type of production and their composition, these known products cannot be compared with the products produced according to the invention. In addition, the annealing resistance of these known resins is not yet sufficient.

In the German Offenlegungsschrift 1 570 419 is a Process for the production of curable, thermosetting synthetic resins specified, which is characterized in that daft

one aryl borates of the general formula BO (OAr), wherein

χ y

y to «" ^ 1,5 and y <Cl to ^> - 0, initially in

dissolves fusible, formaldehyde-supplying substances, if necessary in the presence of solvents, and then, if necessary in stages, further reacted with formaldehyde or formaldehyde-supplying substances in the heat. Suitable catalysts for splitting the formaldehyde-supplying substances are, inter alia, hexamethylenetetramine, B ₂ O, individually or as a mixture. Instead of the formaldehyde-supplying substances, it is also possible to use low molecular weight polymethylol compounds of phenols, urea, melamine and similar substances. However, these resins which can be produced in this way cannot be compared with the products produced according to the invention. The known products also have a lower Hitzebzw. Resistance to annealing and hydrolysis.

In the German Offenlegungsschrift 1 570 415 is a Process for the production of curable, boron-containing synthetic resins described, which is characterized in that

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roan cyclic aryl borates of the general formula

Ar
0

0 ^ O

Ar-O -B B-O-Ar

- ^ - -S η

where η ^ l and Ar is an aryl radical, condensed in the heat with formaldehyde or formaldehyde-supplying substances, possibly step-white. As suitable catalysts for

Splitting of the formaldehyde-supplying substances are mentioned there, inter alia, hexamethylenetetramine, ^B ₂ ° 3 individually or in a mixture. Instead of the formaldehyde-supplying substances, it is also possible to use low molecular weight polymethylol compounds of phenols, urea, melamine and similar substances. However, these resins which can be produced in this way cannot be compared with the products produced according to the invention. The known products also have a lower resistance to heat, annealing and hydrolysis.

In the previously known processes in which phenol-formaldehyde resins, which contain boron and nitrogen chemically bound, are produced, there is a disadvantage in the presence of water in the end product, which promotes hydrolysis of the chemically bound boron and, moreover, the boron is not quantitatively incorporated.

Another disadvantage of the previously known nitrogen and boron-containing synthetic resins is that the starting board derivatives not chemically defined compounds are

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• I I> I 'ι · ·

len, so that from approach to approach there is no identically structured boron-containing synthetic resin can be obtained.

Furthermore, the previously known processes for the production of nitrogen * and boron-containing synthetic resins have the disadvantage that a temperature of about 100-110 ^° C. must not be exceeded during the condensation with formaldehyde and during the further condensation, since otherwise the desired conversion can no longer be controlled . As a result, the known boron-containing synthetic resins do not yet have sufficient resistance to annealing.

The object of the present invention is to provide a process for producing curable and thermosetting nitrogen- and boron-containing synthetic resins by reacting phenolic compounds with boron compounds, nitrogen compounds and formaldehyde or formaldehyde-releasing compounds with heating, with complete conversion of the nitrogen and boron compounds is achieved, so that even from batch to batch, anhydrous synthetic resins with a uniform structure are obtained which have a particularly pronounced resistance to annealing and are resistant to hydrolysis. In addition, the nitrogen- and boron-containing synthetic resins produced by the process according to the invention should have better solubility in organic solvents than the nitrogen- and boron-containing synthetic resins known hitherto. Thus, in the case of the nitrogen- and boron-containing synthetic resins produced according to the invention, it should be possible to use some of the aromatic hydrocarbons in solvents to produce clear synthetic resin solutions.

Resins with a pronounced resistance to annealing are those that pass a special test. In this test, 0.5 g of the ^{hardened at 20O 0} C in 24 hours (in Ab-

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Essence of curing agents or catalysts) and powdered resin subjected to thermal analysis. Here, the temperature is raised first under nitrogen to 600 ° C, and thereafter, in the presence of air up to 1000 ⁰ C at a rate of 10 ⁰ C per minute. After this treatment, the residue must have at least twice the weight of the incorporated boron oxide. This value can reach five times the weight of the boron oxide built into the synthetic resin.

The invention relates to a process for the production of curable and thermosetting, nitrogen- and boron-containing Synthetic resins by reacting phenolic compounds with Nitrogen compounds, boron compounds and formaldehyde or formaldehyde-releasing compounds under heating, characterized in that.

(a) Phenol alone or a mixture of phenol and alkyl phenols and / or cycloalkylphenols and / or alkenylphenols and / or cycloalkenylphenols which are in the o-position Η atoms and alkyl radicals with 1-30 carbon atoms and / or cycloalkyl radicals with 5-10 carbon atoms, which are monocyclic or bicyclic, and / or alkenyl radicals with 1-30 carbon atoms and / or cycloalkenyl radicals with 5-10 carbon atoms, which are also monocyclic or bicyclic, and / or aryl-substituted and / or aralkyl-substituted phenols with an aromatic ring in the substituent, wherein the phenol and / or the phenol derivative can also be halogen-substituted,

(b) basic nitrogen compounds,

(c) formaldehyde and / or paraform and / or trioxane,

(d) esterifiable boron compounds and

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(e) primary and / or secondary aliphatic saturated Monoalcohols with 2-5 carbon atoms gradually with removal of the water of reaction implemented and at the same time

(I) First, the components (a), (b) and (c) are reacted to form a nitrogen-containing Kpndensationsprodukt under complete installation of the components (b) and (c) 68 110 ⁰ C, the condition applies that the components ( a) and (c) are present in a molar ratio of 1: 0.5 to 0.8 and (b) to (cj in a molar ratio of 1: 1), the calculation basis for component Cb) being the equivalents of active hydrogen atoms contained therein, however a ratio (b) to (d) of 0.1 to 0.5 to 1 should be present and the calculation basis for (b) the nitrogen contained therein in moles and the calculation basis for (d) the boron contained therein in moles applies,

(II) the nitrogen-containing condensation product obtained is reacted in the presence of components (d) and (e) with azeotropic removal of the water of reaction at 120 150 ⁰ C, the condition that in the reaction the components (a) and (d) in a weight ratio of 100: 5 to 100: 20 and (d) is calculated as boron oxide and components (d) and (e) are also used in a molar ratio of 1: 1 to 1: 4,

or

(Ha) the nitrogen-containing condensation product obtained is freed from water by treatment in vacuo with heating and then ^{mixed with esters from components (d) and (e) and / or aliphatic boric acid esters (de 1} ), the ester. from components (d) and (e) or (de ^? ), as

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Boron oxide calculated, is present in a weight ratio of 100: 5 to 100: 20 to component (a) *

and the reaction batches obtained according to (II) or (Ha)

with '

(III) formaldehyde and / or paraform and / or trioxane are reacted as component (c) and the batch is kept at 95-100 ° C. until component (c) is incorporated (as formaldehyde) and then with removal of the volatile constituents reduced pressure at ^{110-150 0} C and the heating is stopped as soon as the synthetic resin obtained has reached a B-time at 160 ° C of about 30 seconds to 6 minutes.

The invention furthermore relates to the use of the boron-containing compounds produced by the process of the invention Synthetic resins as heat-resistant binders for molding compounds, hard papers and brake linings. .

^{The B-time or hardening time is based on the information from the test procedure 1} J described in the book "KUNSTSTOFF-PRAKTIKUM" · (Gaeteno D'Alelio, Carl Hanser-Verlag, Munich, 1952), p. 174, where 0 , 3 g of resin at the specified temperature in a well with a diameter of 2 cm and a maximum depth of 8 mm with a glass rod pulled out to the tip, stirred until it hardens and the time required for this is measured.

Suitable substituted phenols are those which have alkyl radicals with 1-30 carbon atoms, cycloalkyl radicals, as substituents with 5-10 carbon atoms, which are monocyclic or bicyclic

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are built, alkenyl radicals with 1-30 carbon atoms and / or Cycloalkenyl radicals with 5-10 carbon atoms, which are also monocyclic or bicyclic, contain. Halogen-substituted Phenols and aryl-substituted as well as aralkylated phenols with an aromatic ring in the substituent are also suitable.

Substituted phenols (a) must be selected so that they have 1, 2, 3 or 4 substituents on the phenol nucleus, but at least 1 phenol carbon atom that is reactive with formaldehyde must be present in the ring and the reaction rate of the substituted phenol against formaldehyde ¹ JO to The reaction rate of the unsubstituted phenol is 150 $ (compare LA Cohen and WM Jones; "JOURNAL OF THE AMERICAN CHEMICAL SOCIETY", vol. 85, 1963, p. 3 * 102). The reaction rate can also be determined by comparative measurement of the formaldehyde consumption as a function of the reaction time in alkali-containing, molar solutions of the phenols. The reaction rate is understood to mean the effective reaction rate measured in the heterogeneous medium.

However, those substituted phenols (a) which contain two carbon atoms which are reactive toward formaldehyde are preferred contained in the phenolic ring. Substituted phenols (a) with three reactive sites on the phenol ring can can be used individually or as a mixture.

The following can be used as substituted phenols (a) for the present process: m-cresol, 3,4-, 3,5-, 2,5-dimethyphenol, m-ethylphenol, m-propylphenol, m-n-butylphenol, p-tert-butylphenol, o- and / or p-n- and / or iso-propenylphenol, o- and / or p-allylphenol, o-phenylphenol, p-phenylphenol, m-phenylphenol, with particularly o-

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and / or p-ct- and / or -ß-Phenyläthy! phenol, individually or are preferred as a mixture; there are also o- and / or p-a- and / or -ß-phenylisopropylphenol, o- and / or p-a- and / or -ß-Methylphenyläthylphenol, also technical Alkylation products of olefins on phenols, their production e.g. in British patent specification 327,383 * Page 5, lines 25-3 * 1, as well as o- and / or p-aminophenols in the process of the invention useful as substituted phenols (a). Dihydroxydiphenylalkander.ivate are also substituted phenols (a) with the general formula

R ₂

where R. and Rp are identical or different and denote a hydrogen atom or an aliphatic radical with the general formula CH _{2n + 1} , where η has the values 1 to 5 and the condition applies that the substituent ^R 2 ~ V ~ ^R 1 in is arranged o- and / or p-position to the phenolic hydroxyl groups,
useful.

Of the last-mentioned substituted phenols (a) the following are preferably used: 1,1-di- (V-hydroxyphenyl) -2-methylpropane and bisphenol A.

Mixtures of at least one substituted phenol which contains one phenolic hydroxyl group per molecule, and phenol are used in proportions such that the average functionality of the sum of these phenolic compounds compared to formaldehyde is between 2.5 and 3.0.

509815 / Ί23 7

- ίο -

The basic nitrogen compounds (b) that can be used are, for example: ammonia, hydrazine, primary mono- and diamines, the condition that these are soluble in the reaction mixture or during the reaction become soluble. Suitable monoamines are, for example, methylamine, ethylamine, propylamine, aniline and tolidine.

Suitable diamines are, for example, di (p-aminophenyl) sulfide, Di-fc-aminophenyl) methane, ethylenediamine,

The following are preferred:

Methylamine, aniline, di- (p-aminophenyl) sulfide, di- (p-

aminopheny1) methane.

The products used as component (c), namely largely dehydrated formaldehyde, paraform or trioxane individually or mixtures thereof can also be used in the form of their hydrous technical products are used in the process of the present invention. The formaldehyde can be used in gaseous form or dissolved in a suitable organic solvent, e.g. dissolved in methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol and amyl alcohol, these alcohols as n- or as isomeric alcohols or as a mixture thereof. This formaldehyde-alcohol solution may be up to 10 wt. water contain, but anhydrous or low-water formaldehyde-alcohol solutions are preferred.

Formaldehyde and / or paraform and / or trioxane or mixtures made of formaldehyde, paraform and trioxane may and can be used as technical products Contains up to 10% by weight of water individually or in a mixture. The water contained in these components (c) is at the reaction is removed from the reaction mixture together with the water of reaction. In level I, watery ones are also allowed Formaldehyde solution can be used; expedient

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are 30 - ■ M wt .-% aqueous formaldehyde solutions.

The following can be used as esterifiable boron compounds (d): boric acid, boron oxide individually or as a mixture. Aliphatic boric acid esters (de ¹ ) whose alcohol radicals consist of primary and / or secondary saturated monoalcohol radicals with 1-5 carbon atoms can also be used, the further reaction having to be carried out according to the procedure in stages Ha and III. Boric acid and boron trioxide and trimethyl borate (de ¹ ) are preferably used individually or in a mixture.

As primary and / or secondary aliphatic saturated Mono alcohols are suitable: ethanol, n-propanol, isopropanol, n-butanol, 2-methylpropanol-1, butanol-2, n-pentanol, pentanol-2, pentanol-3, 3-methylbutanol-1, 2-methylbutanol-1,3-methylbutanol-2. To be favoured 2-methylpropanol-1 (isobutanol) and n-butanol are used.

The following can be used as a water entrainer: Benzene, toluene and xylene.

Preferred water entrainers are toluene and xylene used.

If the process according to the invention is carried out according to reaction II, care must be taken that components (d) and (e), which are reacted with one another in the presence of the product prepared in stage I and in the presence of an entrainer, are at least 90% by weight. - Eliminate% of the theoretical amount of water at the reaction temperature of ^{120-15O 0 C.} The components must be reacted with stirring. At the end of the reaction, the boron compound capable of esterification must be clearly dissolved in the reaction mixture when heated.

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The duration of this conversion is at least 8 hours, but not more than 30 hours. In the further implementation with further (c), the Components also reacted with stirring and kept at 95 C until the formaldehyde content was titrated a consumption of more than 90/6 of the added Formaldehyde or formaldehyde-releasing substance. This implementation decreases when using Phenol about 4 hours or longer, but not more than 20 hours, with the use of alkylphenol up to 10 hours or longer, but not longer than 2 * 1 hours, in claim.

Care must be taken that the paraformaldehyde and / or the trioxane used, if any, have gone into solution no later than 30 minutes after the reaction temperature has been reached, which is achieved by using these finely ground. However, 100 ⁰ C to be clear - after the completion of this part of the step reaction, the mixture is cloudy in the cold, to the heat at the 95th

The subsequent removal of the volatiles under reduced pressure to take place so rapidly that the solvent is more than 60 $ distilled off within an hour and the temperature in the tab 110 by vigorous heating - has reached 150 ⁰ C.

In the subsequent condensation period at 110 150 ⁰ C, which takes from 6 minutes to 30 seconds at 160 ° C, depending on the component (a) used and the temperature between * »to 10 hours until the B time is reached the remainder of the solvent is distilled off, with a total of at least 8556 of the total solvent used should be distilled off.

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In the final phase of the reaction, due to the high viscosity of the resin prepared according to the invention, very good mixing by stirring must be ensured, since otherwise local overheating can easily occur. Suitably the temperature is between 120 and IO I ^{1 0} C is held in this final stage.

In the particularly preferred embodiment of the method of the invention, the necessary removal of volatiles is carried out in such a way that the reaction mixture in the process stages II and Ha heated to 120 ⁰ G under atmospheric pressure and then by application of vacuum, the solvent is distilled off to give the The vacuum is set in such a way that the temperature in the batch does not fall below 115 ° C and does not exceed 130 ° C. The further work-up takes place as described above. -

In the process of the present invention, boron-containing synthetic resins with particular heat resistance, mechanical resistance and annealing resistance are obtained if phenol as component (a), ammonia as component (b), aqueous formaldehyde solution as component (c), paraformaldehyde in stage III and as a water entrainer Toluene, boric acid can be used as component (d) and isobutanol as component (e), the weight ratio of (a) to (d) - (d) being calculated as boron trioxide being 100: 12, the molar ratio (d) to (e ) 1: 1.2 and the molar ratio (a) to (c) 1: 1.6 and the molar ratio (b) to (d) - (d) as boron, (b) calculated as nitrogen - 0.2: 1, and in step I at a temperature up to 10O ⁰ C, then in stage II 8 hours at a temperature up to 150 ⁰ C, then in stage III with further component (c) 3 hours at 95 - held 100 ° C and finally heated to 130 ^° C. under reduced pressure (20-40 Torr),

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- 11 »-

until the end product has a B-time of 30 seconds to 2 minutes at 160 ° C.

Particularly good properties with regard to compressibility of by the process of the invention, resins are obtained when used in molding compounds for pressing temperatures between 90 - 100 reaches ⁰ C when obtained as a mixture of components (a) one mole Phenyläthylphenol (isomer mixture) and 3.5 moles of phenol ( , according to the method described in DT DOS 2 330 850) with 1.5 moles of boric acid as component (d), 2 moles of isobutanol or n-butanol as component (e), ammonia as component (b) and such an amount of formaldehyde solution and Paraformaldehyde is reacted as component (c) so that the molar ratio (a) to (c) 1: 1.2 to 1: 2 and the molar ratio (b) to (d) (d) calculated as boron, (b) as nitrogen - 1: 0.4, and the process of production is such that components (a), (b) and (c) ^{are reacted together in process stage I at 100 °} C. and then in stage II the mixture together with components (d) and (e) for 8 hours in the presence of 50 g of tolu ol as a water entraining agent at 100 - kept 150 ° C and in stage III in the presence of paraformaldehyde as the component (c) the mixture for 8 hours at 90 - held 100 ° C and thereafter removal of the volatiles under reduced pressure (20 - HO Torr ) at 120 ° C is heated for 5 minutes at 16O ° C up to a time-B.

Equally good results are obtained when trioxane is used as component (c).

Equally good results are also obtained if boron trioxide is used as component (<t).

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The best results are obtained if the latter reaction mixture is heated in stage III under normal pressure at 120 ⁰ C and after the application of the vacuum, the solvent distilled off wii'd, wherein the adjustment of the vacuum is controlled so that the temperature in the approach does not falls below 115 ° C, and is kept at this temperature, the mixture until it has a B time comprises at 16O ⁰ C for 5-6 minutes.

Special embodiments of the invention are thereby characterized in that as components (a), (b), (c), (d) and (e) or (de ') the compounds listed in Table I below are used and these compounds are used in the molar or weight ratios listed in Table I that optionally as an entrainer, the entrainers listed in the table are used and that according to the in the Table I indicated process stages and those mentioned there Implementation temperatures and reaction times is proceeded.

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Tabel

(first part)

cn ο co oo

Entrainer a b d or d ^T e Molar ratio d ·: b 0.37 ι.) toluene phenol ammonia Boric acid Isobutanol 1 0.37 ' 2.) toluene Phenol / phenyl
ethylphenol 7: 2 ammonia Boric acid Isobutanol 1 0.27 3.) toluene phenol ammonia Boric acid Isobutanol 1 0.49 4.) toluene phenol ammonia Boric acid Isobutanol 1 0.49 5.) toluene phenol ammonia Boric acid Isobutanol 1 0.25 6.) toluene phenol ammonia Boric acid Isobutanol 1 • 0.37 7.) 'Toluene phenol ammonia Boron oxide n-butanol 1 0.37 8th.) toluene m-cresol (42-
Weight £) phenyl
ethylphenol 7: 2 ammonia Boric acid Isobutanol 1 '0.5 9.) toluene phenol aniline Boric acid Isobutanol 1 0.37 10.) toluene phenol aniline Boric acid Isobutanol 1 ' 0.37 11.) toluene phenol Hydrazine
hydrate Boric acid Isobutanol 1 0.37 12.) toluene phenol Methylamine Boric acid Isobutanol 1 ■ 0.37 13.) toluene phenol Di- (p-ami-
nophenyl) -
sulfide Boric acid Isobutanol 1 . 0.37 14.) Xylene phenol ammonia Boric acid Amyl alcohol 1 . 0.37 15.) Xylene phenol ammonia Boric acid n-butanol 1 : 0.37 16.) - phenol ammonia Trimethyl
borate - 4 >

cn o co

Molar ratio
a: c 1.45 T a b e 1.13 lie I (second 12th Part) c (level III) 1 1.45 Molar ratio
d: e 1.13 Weight ratio
a: d 9.6 c (level I) Paraformaldehyde 1.) 1 · 1.45 1 1.13 100 8.7 44% strength by weight water
formaldehyde Il 2.) 1 . 1.45 . 1 1.8 100 : 20 »Τ It 3.) 1 1.52 1 1.13 100 12 ' dd dd 4.) 1 1.45 1 1.13 100 18th It dd 5 ·) 1.45 1 Iil3 100 12th dd 6.) 1 1.45 1 1.13 100 8.8 I! dd 7.) 1 ' 1.45 1 1.13 100 12th It dd 8th.) · . 1 1.45 1 1.13 100 • .12 H It 9.) 1 . 1.45 • 1.13 100 : 12 It H ' 10.) j_ 1.45 1.13. 100 . 12th " It 11.) ' 1 1.45 1 . 1.13 100 • ¹² dd Il 12.) 1 1.45 ,1 1.13 100 12th dd dd 13.) • ι 1> 45 ι 1.13 100 . 12th » Trioxane 14.) 1 : r, 45 ■ 1 1.13 100 • 12 It 40% by weight
butanolic
POrmaldehvdlösu 15.) 1 1 100 It Paraformaldehyde 16. ·) 1 100 dd

co cn to

Tabel

(third part)

cn ο co oo

cn

ro

reaction time reaction time reaction time Reaction temperatures in step II bw. Ila ■ in Stages- B-time _ Level I. Level II or Ila Stage III I. 12O-15O ° C 95-13O ⁰ C procedure at 160 ° C ι.) 1 hour 10 hours 8 hours 70-11O ⁰ C 120-15O ⁰ C 95-13O ⁰ C I, II, III ■ 1-4 min. 2.) 2 hours 10 hours 16 hours 70-11O ⁰ C 12O-15O ° C 95-13O ⁰ C I, II, III 4-6 min. 3.) 1 H. 10 hours 9 hours 70-11O ⁰ C 120-150 ° C 95-130 ° C I, II, III 1-4 min. 4.) 1 H. 10 hours 8 hours 70-11O ⁰ C 120-15O ⁰ C 95-13O ⁰ C I, II, III 1-4 min. 5.) 1 H. 10 hours 8 hours 70-11O ⁰ C 120-15O ⁰ C 95-13O ⁰ C I, II, III 1-4 min. 6.) 1 H. 10 hours 8 hours 70-11O ⁰ C 120-150 ° C 95-13O ⁰ C I, II, III 1-4 min.
* 7.) 1 H. 8 hours 8 hours 70-110 ⁰ C. 120-150 ⁰ C. 95-130 ° C i, 11, ni 1-4 min. 8th.) 1 H. 10 hours 7 hours 70-11O ⁰ C 120-15O ⁰ C 95-130 ⁰ C. I, II, III 4-6 min. 9.) 1 H. 10 hours 10 hours 70-11O ⁰ C 120-15O ⁰ C 95-130 ⁰ C. I, II, III 1-4 min. 10.) 1 H. 10 hours 9 hours' 70-11O ⁰ C 120-15O ⁰ C 95-13O ⁰ C I, II, III 1-4 min. 11.) 1 H. 10 hours 7 hours 70-11O ⁰ C 120-15O ⁰ C 95-13O ⁰ C I, II, III , 1-4 min. 12.) 1 H. 10 hours 9 hours 7Q-10 ⁰ C 12O-150 ° C 95-13O ⁰ C I, II, III 1-4 min. 13.) • 1 H. 12 hours 8 hours 70-11O ⁰ C 12O-150 ° C 95-13O ⁰ C I, II, IH 1-4 min. 14.) 1 H. 8 hours 8 hours 70-11O ⁰ C 12O-15O ° C 95-13O ⁰ C I, II, III 1-4 min. 15.) 1 H. 9 hours 8 hours 70-11O ⁰ C 90-10O ⁰ C 95-13O ⁰ C I, II, III 1-4 min. 16.) 1 H. - 10 hours - Ila, HI 1-4 min.

! -> ■ OO

N3

U)

U) cn

The boron-containing phenol-pprmaldehyde synthetic resins produced according to the invention are distinguished from the previous boron-containing phenol-formaldehyde resins in that they can also be dissolved in solvent mixtures which contain up to kO% aromatic solvents. They are also distinguished by the fact that they are extremely easy to grind and that they can be stored for a long time in the ground state.

When used as a binder in brake pads for the automotive, plug-in and. Engineering industry they have the advantage of good moldability of the pads, in part, when a mixture of 20 - * OK mole percent o-'and / or p-Phenyläthylphenol and 60 - 80 mole percent of phenol used even at temperatures below 100 ⁰ C.

The resins produced according to the invention are distinguished from other boron-containing phenol-formaldehyde resins also in that hard papers made from them have very good dielectric properties. The method according to the invention also enables production always more uniform resins. '

Furthermore, the boron-modified phenol-formaldehyde resins produced by this process are particularly heat-resistant even when substituted phenols are used and show when phenol is used alone and with a content of more than 105? Boron oxide after annealing in air at 1000 ⁰ C after 2 hours or a residue of more than 40 parts by weight 56th

The boron-containing synthetic resins produced by the process according to the invention have the following structural units:

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2A36359

R ₁ , R «, R .. are hydrogen and / or halogen and / or alkyl and / or cycloalkyl and / or alkenyl and / or cycloalkenyl and / or aryl and / or aralkyl,

Rjj alkyl, alkenyl, cycloalkyl, cycloalkenyl, Aryl, aralkyl, hydrogen,

η has values between 2 and 15

Example 1:

846 g of phenol as component (a), Jk g of 25% by weight aqueous ammonia as component (b) and 222 g of HH % by weight aqueous formaldehyde as component (c) are refluxed together for 90 minutes. Then 180 g of crystallized boric acid are added as component (d), 5 g of oxalic acid, 237 g of isobutanol as component (e) and 100 g of toluene as water entrainer, the mixture is heated to the boil and 375 ml of water are distilled off in a circuit. It is cooled to 80 ^° C., and 310 g of 95% strength by weight paraformaldehyde are added

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added and heated to 90 ⁰ C until the formaldehyde consumption is over $ 90 (about ¹ J hours). Then, the mixture under vacuum while distilling off the solvent is heated up to 130 ⁰ C and held until the B-time is hours at 16O ⁰ C min .: The obtained resin is reddish yellow in color, has a melting point of 65 ⁰ C by the capillary, and is characterized by high rate of cure without the addition of curing agents at temperatures from 18O ⁰ C aus.-

Preparation of a mixture of phenylethylphenol in 3.5 moles of phenol

423 g of phenol and 108 g of styrene and 20 g of crystalline oxalic acid are mixed and heated to 150-160 ° C. with stirring heated and held at this temperature for 4 hours. According to this, the content of free styrene is below 1 percent by weight dropped and there is a light-colored, oily Reaction product before. This mixture is used as component (a). ~

Example 2:

A mixture of 396 g of phenylethylphenols and 658 g of phenol, prepared according to the information in DT-DOS 2330850 as described above as component (a), 74 g of 25 wt. Aqueous ammonia as component (b) and 222 g of hk wt. -tigern aqueous formaldehyde as component (c) are kept at the boil for 90 minutes under reflux. It is then cooled to 8O ⁰ C, to I80 g of boric acid as component (d), 5 g of oxalic acid - was added 237 g of isobutanol as the component (e) and 100 g of toluene as a water entrainer, heated to boiling and -entwässert circulated to 390 ml of water are separated. It is then cooled to 8O ⁰ C, and 313 g of 95 wt .- $ strength Paraform- · aldehyde added. It is then heated to 95 ° C and

held at this temperature until the added paraformaldehyde is consumed in excess of $ 90, which takes about 9 hours. Then, in a vacuum, the solvent is distilled off until the temperature rose to 130 ⁰ C. The batch is held at this temperature up to a B time (160 ° C.) of 5 minutes. The resulting resin is characterized in that it can be pressed from molding compositions prepared at temperatures below 100 ⁰ C. The melting point of the resin is 75 ° C using the capillary method.

Example 3:.

Proceed as indicated in Example 1, only instead of of the 180 g of boric acid only 130 g of boric acid and instead of the 237 g of isobutanol only 171 g are used. The resulting Resin is characterized by particularly rapid hardening at 180 ° C.

Example 4:

8 ¹ g of phenol as component (a), 160 g of 25% by weight aqueous ammonia as component (b) and 222 g of 4% by weight aqueous formaldehyde as component (c) are refluxed for 90 min. held. Then 300 g of crystalline boric acid as component (d) and 626 g of isobutanol as component (e) and 100 g of toluene as water entrainer are added, the mixture is heated to boiling and 680 ml of water are distilled off in a circuit.

It is cooled to 80 ⁰ C, adding 310 g of 95 wt .- $ paraformaldehyde are added and heated to 90 ⁰ C until the formaldehyde consumption over 90 $ is (ca. ¹ I hours). Then, the mixture under vacuum while distilling off the solvent is heated up to 130 ⁰ C and held until the B-.Zeit at l60 ° C is 1 »minutes.

The resin obtained is reddish-yellow in color, has a temperature of 65 ° C according to the capillary method and is

50S815 / 1237

net is achieved through high curing speed without adding hardeners at temperatures from 180 ^° C.

Example 5: -

The procedure is as indicated in Example 2, but the addition of oxalic acid is dispensed with and in stage III, after the reaction with 313 g of 95% by weight paraformaldehyde (as already described in Example 2), the temperature after consumption is over 90% of the added paraformaldehyde increased to 120 ⁰ C and the solvent distilled off under vacuum, the vacuum being applied so that a temperature of 115 ° C is not exceeded. The batch is distilled until the reaction product has reached a B time of 6 minutes. The resulting resin is distinguished by excellent properties when it is processed into brake linings, in particular these brake linings have high coefficients of friction, a slight drop in the coefficient of friction over time and very little initial fading. In addition, the resin may be at a melting point of 75 ° C at temperatures below 100 ⁰ C pressed.

Example 6:

The procedure is as indicated in Example 1, but instead of 310 .g 95 wt. -% paraformaldehyde is now used, 330 g of 95% by weight paraformaldehyde, and the addition of oxalic acid is dispensed with. The resin obtained is reddish in color and has a melting point of 75 ^° C. with a B time of * 1 min.

Example 7:

The procedure is as indicated in Example 1, but instead of 180 g of crystalline boric acid, 270 g is now used crystalline boric acid used. Isobutanol is increased in the same ratio. The use of oxalic acid is

509815/1237

- 2k -

draws, and kkO ml of water are distilled off with recycling of the dehydrated solvent. The resulting resin is of a reddish color, has a melting point of 85 ⁰ C and characterized by high annealing strength.

Example 8:

The procedure is as indicated in Example 1, but the use of oxalic acid is dispensed with and stage III is followed in such a way that after the formaldehyde has been consumed in excess of 90% of the amount used, the batch is heated to 120.degree and then the solvent is distilled off in vacuo in such a way that by appropriate regulation of the Vacuum the temperature does not drop below 115 ° C. The resin obtained imparts on processing into brake linings these extraordinarily good coefficients of friction, low initial fading and very good constancy of the coefficients of friction over time.

Example 9:

The procedure is as indicated in Example 8, but instead of the 237 g of isobutanol, an equal amount of n-butanol is used as component (e) and an equivalent amount of boron trioxide is used instead of 270 g of crystalline boric acid. The resulting resin has a melting point of 85 ⁰ C.

Example 10:

The procedure is as indicated in Example 5, but instead of the 658 g of phenol, an equivalent amount of technical grade is used Cresol (with 42 wt. JC m-cresol) was used. That resulting resin is characterized by high curing speed.

Example 11:

The procedure is as indicated in Example 8, but instead of the Tk g of 25% by weight of 56% aqueous ammonia, 135 g

509815/1237

Aniline used. The resulting resin is brown in color Color and is characterized by particularly high heat resistance and glow resistance.

Example 12: -

846 g of phenol, 101 g of aniline and 222 g of 44 wt Oxalic acid and 180 g of boric acid are added, the mixture is heated to the boil and water is removed by azeotropic distillation, the water being separated off from the distillate and the dehydrated distillate being fed back into the reaction mixture until 320 ml of water have been split off. The temperature rises in the mixture to 150 ⁰ C. It is then cooled to 80 ° C and 310 g 95 parts by weight 5? Is paraformaldehyde was added and maintained at 95 ° C until the formaldehyde consumed. Then the solvent is distilled under vacuum until the temperature rose to 130 ⁰ C, and the batch held at this temperature to a B time of 4 minutes at 16O ° C.

The resin obtained is deep red, has a melting point of 90 ^° C. and is characterized by particularly good heat resistance.

Example 13:

The procedure is as indicated in Example 8, but instead of ammonia as component (b), half the molar amount of a 24 wt. -% aqueous hydrazine hydrate solution

admitted.

The resulting resin is deep red in color and has a sheen

a melting point of 90 ° C.

509815/1237

Example 14:

The procedure is as indicated in Example 8, except that instead of the ammonia, a molar amount of an iJO wt .- ^ igen is used aqueous methylamine solution added.

Das.resultierende resin is of red-yellow color and has a melting point of 7O ⁰ C.

Example 15:

The procedure is as indicated in Example 8, but instead of ammonia, half the molar amount of di- (p-amino-

phenyl) sulfide is used.

The resulting resin has a high melt viscosity and is characterized by improved resistance to annealing.

It has a melting point of 85 ⁰ C.

Example 16:

The procedure is as indicated in Example 8, but instead of the paraformaldehyde added in stage III, a mixture consisting of 50 mol% each of trioxane and paraformaldehyde in the same molar amount as the amount of paraformaldehyde used in Example 8 is used. The resulting resin is reddish yellow in color and has a melting point of 80 ⁰ C.

Example 17:

The procedure is as indicated in Example 8, but instead of the paraformaldehyde used in stage III an equal molar amount of a mixture consisting of

50 mol SS trioxane and 40% by weight butanolic alcohol each Paraformaldehyde solution, used.

The resulting resin is reddish-yellow in color,

is characterized by an increased hardening speed

and has a melting point of 82 ^° C.

509815/1237

Example 18:

The procedure is as indicated in Example 8, but instead of the paraformaldehyde used in process stage III an equal molar amount of a mixture, each consisting of 50 MoI-? Paraformaldehyde and 40% by weight

butanolic formaldehyde solution, used.

The resulting resin is reddish in color and shows

a melting point of 74 C.

Example 19 =.

846 g of phenol as component (a), 74 g of 25% strength by weight aqueous ammonia as component (b) and 220 g of 44% strength by weight aqueous formaldehyde as component (c) are refluxed together for 90 minutes. Then the water is distilled off under vacuum, is increased until the temperature in the mixture to 100 ⁰ C. At this temperature, trimethyl borate is added in an amount corresponding to 180 g of boric acid, cooled to below the boiling point, and 310 g of 95% by weight paraformaldehyde are added. 100 ⁰ C until the formaldehyde consumption over 90 MoI St is - mixture is heated to 95 (ca. 6 hrs.). Then proceed as in Example 8.

The resulting resin is reddish yellow in color and has a high melt viscosity and a melting point of 80 ⁰ C. ·. .

Example 20:

The procedure is as indicated in Example 8, but xylene is used as the water entrainer and isobutanol instead

an equal molar amount of amyl alcohol is used.

The resulting resin is reddish in color and has a white color

a melting point of 82 ^° C.

509815/1237

Example 21:

The procedure is as indicated in Example 20, but is

an equal molar amount of n-butanol was used instead of the amyl alcohol.

The resulting resin has a melting point of 75 ° C

In further training of this procedure it has now been found that the production of these nitrogen- and boron-containing synthetic resins through the use of inorganic or organic acids can be accelerated as esterification catalysts, the acids of the above mentioned species are useful if their pK is less than 2.5. These are inorganic or organic acids used in amounts of 0.1 to 1 percent by weight based on the weight of component (a) used.

Suitable catalysts for this purpose are, for example, sulfuric acid, hydrochloric acid, p-toluenesulfonic acid, Oxalic acid, formic acid.

Otherwise, the mode of operation is the same as in the main patent indicated used to carry out the procedure.

Example 22:

8 ^ 6 g of phenol as component (a), 7H g of 25% by weight aqueous ammonia as component (b) and 222 g of M% by weight aqueous formaldehyde as component (c) are refluxed together for 90 minutes. Then 180 g of crystallized boric acid are added as component (d), 1 ml of concentrated sulfuric acid, 237 g of isobutanol as component (e) and 100 g of toluene as a water entrainer, heated to the boil and 375 ml of water are distilled off in a circuit. It is cooled to 8O ⁰ C, add 310 g 95 parts by weight iigen paraformaldehyde are added and heated to 95 ° C until the Pormaldehydverbrauch # 90 is (about 4 hours).

509815/1237

Then the batch is in vacuo while distilling off the Solvent up to 130 ° C. heated and held until until the B-time at 1.60 ° C is 4 minutes. The received Resin is reddish-yellow in color, has a melting point of 65 ° C according to the capillary method and draws due to the high curing speed without the addition of hardeners at temperatures from 180 ° C.

Example 23: -

The procedure is as in Example 22 _; indicated, but instead of 1 ml of concentrated sulfuric acid, 5 g of concentrated formic acid are used.

Example 24: '

The procedure is as indicated in Example 22, except that instead of 1 ml of concentrated sulfuric acid, 5 g of crystalline acid are obtained p-Toluenesulfonic acid used. The resin obtained is reddish in color and has a a melting point of 70 ° C.

Example 25:

The procedure is as indicated in Example 23, however

5 ml of 36% strength by weight aqueous hydrochloric acid were used.

The resin obtained has a melting point of approx.

70 ° C.

yew 1 ν f «

Claims (1)

1. Process for producing curable and thermosetting synthetic resins containing nitrogen and boron by reaction of phenolic compounds with nitrogen compounds, boron compounds and formaldehyde or formaldehyde-releasing compounds Compounds under heating, characterized in that (a) Phenol alone or a mixture of phenol and alkyl phenols and / or cycloalkylphenols and / or alkenylphenols and / or cycloalkenylphenols, the have Η atoms in the o-position and alkyl radicals with 1-30 carbon atoms and / or cycloalkyl radicals with 5-10 C atoms that are monocyclic or bicyclic and / or alkenyl radicals with 1-30 C atoms and / or Cycloalkenylröste with 5-10 C-atoms, which also have a monocyclic or bicyclic structure are, have, and / or aryl-substituted and / or aralkyl-substituted phenols with an aromatic Ring in the substituent, the phenol and / or the phenol derivative also being halogen-substituted can, (b) basic nitrogen compounds, (c) formaldehyde and / or paraform and / or trioxane, (d) esterifiable boron compounds and (e) primary and / or secondary aliphatic saturated monoalcohols with 2-5 carbon atoms be implemented gradually with removal of the water of reaction and thereby (I) First, the components (a), (b) and (c) uiiijgesetst to a nitrogen-containing condensation product under complete installation of the components (b) and (c) at 68 IiO ⁰ G wer-öen _s wherein the condition is true, dal the Components Ca) and (e) in molar ratio - 31 - '■ - ■■'. l: O _s 5 to 0.8 and (b) to (c) are present in a molar ratio of 1: 1, the calculation basis for component (b) being the equivalents of active hydrogen atoms contained therein, however, a ratio (b) to (d) from O ₃ I to 0.5 to 1 and the calculation basis for (b) the nitrogen contained therein in moles and the calculation basis for (d) the boron contained therein in moles, (II) the resulting nitrogen-containing condensation product in the presence of the components (d) and (e) with azeotropic removal of the reaction water at 120 - is reacted 150 ⁰ C, wherein the condition is true, that in the implementation of the components (a) and (d) are present in a weight ratio of 100: 5 to 100: 20 and (d) is calculated as boron oxide and components (d) and (e) are also used in a molar ratio of 1: 1 to 1: U ~ , or (Ha) the nitrogen-containing condensation product obtained is freed from water by treatment in vacuo with heating and then ^{mixed with esters from components (d) and (e) and / or aliphatic boric acid esters (de 1} ), the ester from components (d ) and (e) or (de '), calculated as boron oxide, is present to component (a) in a weight ratio of 100: 5 to 100: 20, and the reaction batches obtained according to (II) or (Ha) 5 0 9 815/1237 with (III) formaldehyde and / or para form and / or trioxane as component (c) are reacted and the approach to the installation of the component (c) (as formaldehyde) at 95 - 100 is held ⁰ C, and thereafter removal of the volatiles under reduced pressure at 110-150 ⁰ C is heated and the heating is terminated as soon as the resin obtained has a B time has reached at 16O ° C from about 30 seconds to 6 minutes. Process according to claim 1, characterized in that phenol as component (a), ammonia as component (c), aqueous formaldehyde solution, in stage III paraformaldehyde and toluene as the water entrainer, boric acid as component (d) and as component (e) Isobutanol can be used, the weight ratio of (a) to (d) - (d) being calculated as boron trioxide - 100: 12, the molar ratio (d) to (e) 1: 1.2 and the molar ratio ( a) to (c) 1: 1.6 and the molar ratio (b) to (d) - (d) as boron, (b) calculated as nitrogen - 0.2: 1 and in stage I at a temperature of up to 100 ^° C., then in stage II for 8 hours at a temperature of up to 150 ^° C., then in stage III with further component (c) for 3 hours at 95-100 ^° C. and finally under reduced pressure (20-40 torr) is heated to 130 ⁰ C until the end product has a B time of 30 seconds to 2 minutes at 160 ° C. 3. The method according to claim 1, characterized in that the component mixture (a) is one mole of phenylethylphenol (Mixture of isomers) and 3.5 moles of phenol (obtained according to the process described in DT-DOS 2 330 850) 509815/1237 with 1.5 moles of boric acid as component (d), 2 moles of isobutanol or n-butanol as component (e), ammonia implemented as component (b) and such an amount of formaldehyde solution and paraformaldehyde as component (c) is that the molar ratio (a) to (c) 1: 1.2 to 1: 2 and the molar ratio (b) to (d) - (d) as boron, (b) calculated as nitrogen - is 1: 0.4, and the process of manufacture is such that components (a), (b) and (c) ^{are reacted together in process stage I at 100 °} C. and then in stage II the mixture together with components (d) and - "Ce) for 8 hours in the presence of 50 g of toluene as water entrainer at 100 ° - 150 ° C and in stage III in the presence of paraformaldehyde as a component (c) the mixture for 8 hours at 90 - (- 40 Torr 20) at 120 ⁰ C to a B-time is heated at l60 ° C for 5 minutes held 100 ⁰ C, and thereafter removal of the volatiles under reduced pressure. 4. The method according to claim 1, characterized in that as components (a), (b), (c), (d) and (e) or (de ¹ ) the compounds listed in Table I are used and these compounds are used in the molar or weight ratios listed in Table I, that the entrainers listed in the table are optionally used as entrainers and that the process steps indicated in Table I and the reaction temperatures and reaction times indicated there are used. , 5. The method according to claim 4, characterized in that in the third process stage the reaction mixture is ^{heated to 120 °} C. under normal pressure and the solvent is distilled off by applying a vacuum 509815/1237 is, the vacuum is set in such a way that the temperature is 115 ° C not below and 130 ° C not exceeds and at this temperature the resin up to a B-time at 160 C of 30 seconds to 6 minutes. is held. 6. The method according to claim 1, characterized in that in the third process stage, the reaction mixture is ^{heated to 120 0} C under normal pressure and the solvent is distilled off by applying a vacuum, the vacuum being set in such a way that the temperature is not 115 ° C does not exceed below and 130 ⁰ C and at this temperature the resin is to a B time at l60 ° C of 30 seconds to 6 minutes held.. 7. The method according to any one of claims 1 to 6, characterized characterized in that the products obtained contain the following structural purities: 509815/1237 ■ "< R ₁ , Rp, R- denote hydrogen and / or halogen and / or alkyl and / or cycloalkyl and / or alkenyl and / or cycloalkenyl and / or aryl, and / or aralkyl, R ^ alkyl, alkenyl, cycloalkyl, cycloalkenyl, Aryl, aralkyl, hydrogen, η has values between 2 and 15. 8. The method according to any one of claims 1 to 7, characterized characterized in that the reaction in the presence of an inorganic or organic acid whose pK is smaller than 2.5 is performed. 9. Use of the prepared according to any one of claims 1 to 8 Nitrogen and boron-containing synthetic resins as heat-resistant binders for molding compounds, hard papers and brake pads. 10. New curable and thermosetting, nitrogen and Boron-containing synthetic resins, produced according to one of the processes according to claims 1 to 8. 509815/1237 ORIGINAL INSPECTEO