DE1816241A1 - Metal- or metalloid-containing phenol-formaldehyde resins and processes for their preparation - Google Patents

Description

DR. MÜLLER-BORi DIPL-ΙΝΘ. GRALFS 1 β 1 fit g /

DIPL.-PHYS. DR. MANITZ DIPL.-CHEM. DR. DEUFEL. '8 I -D Z 4 |

PATENT LAWYERS

Dec 20, 1968

Lo / pö - N 1000

HOED-AYIATIOU SOCIETE NATIONALE BS COUSTRUGTIOUS 'AEEONAUTIQUES

12 "bis, Avenue Bosquet, Paris 7th, France.

Metal- or metalloid-containing phenol-formaldehyde resins and methods of making them

Priority France of December 20, 1967 PV 133.200

The invention relates to metal- or metalloid-containing phenol-formaldehyde resins and to methods their manufacture.

One already knows phenol forma, ldehyde resins of the type "Resol", which metal oxides, for example oxides of zirconium, tungsten, manganese, molybdenum, or metalloid oxides, for example those of phosphorus or boron in the form of additives.

These additives serve in particular to give the resins better heat resistance, however they generally lead to the formation of an oxide deposit and thus to a non-homogeneous one Dimensions"

BATH ORIGINAL

09830/1343

The invention therefore relates to phenol-formaldehyde resins which in particular the fire resistance is increased.

The phenol-formaldehyde resins according to the invention are particularly notable for the fact that they are supercovalent or ionic bonds have metal or metalloid chemically bonded to their molecule.

Further characteristics are:

- The phenyl radical can also have other substituents have, for example, alkyl radicals, halogens or amino groups;

- the metalloids are phosphorus or boron;

- the metals are zirconium, tungsten, manganese or molybdenum;

- the resins are soluble in common solvents and their solutions have a color depending from the bound metal or metalloid ion.

The process for the production of resins according to the invention is essentially characterized in that the Metal or the metalloid is bound via the phenyl radical before or after the condensation with the formaldehyde, and that the water formed and any hydrochloric acid formed are removed from the reaction medium In the case of condensation after binding the metal or metalloid, formaldehyde becomes monomeric or polymeric anhydride Form or used in aqueous solution "

If the resins of the invention are exposed to high temperatures, they will degrade much more slowly than Ordinary resins, because initially the inorganic element they contain is attacked by the oxygen,

90 9830/13 A3

then part of this element with the carbon of the resin reacts to form carbides, which are known for their refractory properties. These carbides are formed much more easily than in the case of ordinary resins which contain admixed metal oxides, because the latter must first be reduced in order to react with the carbon.

In the case of composite materials, for example of the resin-glass fabric type, the inorganic element reacts in the same way with the silicon dioxide present and forms refractory SiIiodverbindungen which withstand very high temperatures above 2200 C; Boron also reacts with silicon dioxide in the presence of carbon as a reducing agent and forms borosilicide _9, which is known for its refractory properties. Tungsten reacts with the carbon and produces tungsten carbide, the most refractory of all known carbides.

When using a p-amino-phenol-formaldehyde resin condensed with boric acid, a resin is obtained which contains an amine function (-KHp) and a boronate ion (B ₂ Oz) in its molecule, which means that favorable conditions are given to at high temperatures, above 2500 ⁰ C to get a product "in situ" which comes close to boron nitride.

The following examples are intended to explain the invention in more detail. but without restricting them »

Example 1 :

Synthesis of boron-phenol-formaldehyde resin

1. Allow a stoichiometric amount of phenol with boric acid in the presence of a water vapor extraction agent, wel-

90 9-830 / 1343

ekes consists of xylene at a ^{temperature gradually rising from 130 0} to 150 0, react. The reaction is carried out in a three-necked flask which allows mechanical stirring, the attachment of a descending condenser and that of a thermometer.

The reaction time is 3 hours. That with the reaction Any water formed between the boric acid and the phenol is recovered by condensation, as is almost all of it Starting xylene.

This reaction, the yield of which reaches the theoretical yield of 100 % , gives triphenyl borate with elimination of 3 molecules of water.

The triphenyl borate is then cooled and thoroughly Suspending in dry xylene converted into a liquid, crystalline mass.

This is then added with stirring and descending Cooling trioxymethylene in small proportions (the amounts used are, for example, 3 x 0.83 g-mol trioxymethylene, d. H. 25 g to 94 g Hienol).

The removal of the water from the condensation is effected by a stream of dry nitrogen.

The reaction is extremely exothermic and starts from 70 ⁰ O onwards. The temperature may rise to 110 ⁰ O, but should not exceed this value.

909830/1 343

- 5 -
The reaction is completed in approximately 60 minutes,

After -complete removal of the water and removal the oily fractions give an alcohol-soluble, light yellow, pale green resin with a melting point of 85 ° CV

In alcoholic solution, the resin provides a slight, initial deposition of boric acid, then it stabilizes.

The percentage of boron in the stabilized resin is "19.5 %, which corresponds to one molecule of boric acid on '' ■■ wood molecules of phenol or 2 molecules of boric acid on 1 molecule of lexacyclic resin.

The hardening of the resin is easily catalyzed by hexamine and takes place at 150 ° C - 160 ° C in 20 minutes,

Into a three corn flask equipped with a mechanical stirrer, a distillate condenser and a thermometer from. 6 liters of XnIialt are added to 1000 g of phenol and 200 g of boric acid and 1 100 cm xylene, the flask should be in a device are heated, which can be quickly cooled from the outside.

From 1J) 5 ° C, the xylene comes to a boil and carries the water out of condensation with itself .. You catch a mixture from xylene and water. The volume of water shows the extent of condensation.

The boric acid gradually disappears and after about 120 minutes the reaction mixture becomes almost transparent.

BAO 909830/1343

The amount of trapped water from the Eondeneation shows at 190 cm, the end of the reaction to the humidity xylene is recovered almost entirely, d "a. 1400 cn '+ 2-3 / ό entrained phenol.

With the addition of 1000 cm "'of dry xylene, it is allowed to ice The tripiienyl borate obtained cool and gives in small Divide with stirring 268 g of trioxymethylene under supervision of the temperature rise

-Once the temperature exceeds 75 C, untertriebt iuon temporarily adding the frioxymethylens, IiLjL; rt-a- ~ ier ~ n and the condensation reaction calms down by means of an additional temperature. As soon as all of the trioxymetivylene has been added and the temperature has stabilized, the process is heated for 60 minutes, during which the xylene is distilled off under nitrogen; A sampling of the resin indicates the end of the fire. Kan evalcuiert removed and about 10 ° / o xylene, moisture and oily components, Kan receives a Hasse of 1550 g of a light yellow, pale green, transparent, soluble in alcohol and in ijiwesenheit of 5- / 3 hexamine curable resin,

Example 2

Synthesis of p-aminophenol-boroformaldeliydiiarz: 3 hols of p-aminophenol (3 × 109 g) are condensed with 1 hol Boric acid (61.8 g) in the presence of xylene as a steam extractant; distill throughout India X7 / I0I and condensation water off, one in water is obtained soluble, crystalline hasse of tri-p-amino phenyl borate of an intense blue color.

This tri-p-aminophenyl borate is then

BAO 909830/1343

moving 70 ° above in the presence of a quantity of formaldehyde which ■ O _f 8; 3 moles per kol p-aminophenol corresponding to condensed "ivlan observed an immediate dissolution in formaldehyde, followed by a slow condensation in the presence ■ an acidic catalyst during about 3 hours, Ivian removes moisture, xylene and oily parts; a solid resin of red color is obtained.

Example 3

Synthesis of phosphoryl-phenol-formaldehyde resin The phosphorous resin is formed by binding a phosphoryl radical on 10 molecules of the "pheno-L-ii'ormaldehyde resin already shown. The procedure is the following: ■

In dry dioxane, 1 mole of hexacyclic phenol - Formaldehyde resin, i.e. approximately 633 grams, dissolved. Afterward 0.1 mol of phosphorus oxychloride POGl- is added at room temperature with stirring.

The mixture is carefully stirred and a dry one A stream of nitrogen was passed through to remove the hydrogen chloride gas formed from this condensation.

After passing the nitrogen through for three hours and heating to about 6O ⁰ G, a phosphoryl derivative is formed. The dioxane is removed by evacuation.

A clear, pale yellow, in Iko-Jioi is then obtained soluble resin containing phosphorus. This llarz owns good thermal stability in an oxidizing medium. In a reducing medium, the phosphorus evaporates in the form of Phosphorus with its own characteristic odor.

BATH ORIGINAL

9 09830/1 3 A3

9 3 I * -

- 8 - ■

2. 64.8 g of hexacyclic phenol-formaldehyde hair of the "novolak" type are dissolved in 165% pure and dry dioxane. _{To this, 1 g of POOl x} dissolved in 10 curd of dioxane is added dropwise with stirring. While passing through dry nitrogen, the mixture is heated to 60 ° for a further 2 h.

As soon as no more hydrogen chloride is evolved, the dioxane is distilled off in vacuo. A pale light yellow is obtained Alcohol-soluble resin with good thermal stability and a yield of 100% * on phenol and phosphorus.

Example 4- Synthesis of molybdenum phenol formaldehyde resin

This resin can be made by two different methods;

On the basis of molybdenum chloride MopClg »wtlchee was obtained by the action of aqua regia on metallic pieces of Holybdenum (molybdenum waste) .Mim allows molybdenum chloride to react. In a walser-free environment, dark green * colybdenum phenolate and ammonium halide are found, so that sublimation is removed

In a dry, xylene-free solution, this Holybden- ph # nol * t von # rÜn «r FÜrbuig is allowed to react with Trioaytt« thyleii without catalytic ingredients

ATTF dt · «· Type uaa Vei" e "rhält man" in Hars with "iner inten- nitm V4ötett" a ifirlning what "ittiptoiion · in alcohol without forming sound and is soluble without deposits.

OQ Il 30 / UiI

* ι f

Since the extraction of molybdenum chloride is expensive and difficult is, the molybdenum-phenol-formaldehyde resin starting from commercially available, relatively cheap molybdic acid Η £ ΜοΟ ^ be won.

The way of representation is even simpler and faster and results in an in terms of homogeneity and percentage Proportion of molybdenum higher quality resin than that previous. ;

162 g (1 mol) of commercially available, dry molybdic acid are allowed to react with 15ΟΟ g (16 mol) of phenol, which corresponds to 18 % metallic molybdenum in the resin.

One observes a progressive increase of clear green color to dark green at 60 ⁰ G under stirring and descending distillation. After a condensation time of 2 hours, 1 kg of aqueous, 40% strength formaldehyde solution (400 g) is added, which corresponds to 0.85 mol of formaldehyde per 1 mol of phenol used. The temperature is increased to 90 ° after 2.20 cm ^{5 of} concentration Sulfuric acid has been added as a catalyst for the condensation reaction. The reaction starts at 90 ^° C. and after a condensation of 90 minutes a deep green colored resin / "" is obtained. ^;

- "-" - ■■ I

Removing water and oily components in a vacuum and maintaining 17ΟΟ g. deep green resin mass, which is soluble in alcohol with an intense violet color «.

Example 5

Synthesis of titanium-phenol-formaldehyde resin

This intensely red colored Härjs behaves like a real

909830/1343

I »» suffered

J t 4 »I * · * t |

dye (fixation on fabric fibers during impregnation) »It has good thermal stability» Its manufacture comprises 2 levels:

4.2 mol (596 g) of dry phenol are placed in a reaction vessel of 2 liters, which is then ^{melted at 50 °} C. A stream of dry nitrogen is passed through it and 191 g of fuming titanium tetrachloride are added dropwise, without stirring, using a bromination pear »

With a violent reaction, when this drop falls, hydrogen chloride is formed with violent release, which is carried along by the nitrogen stream and in washing bottles is collected, after all the titanium tetrachloride has been added, the mixture is heated under reflux. The hydrogen chloride gas is completely expelled from the mixture.

In the vessel, 420 g of intensely red, crystallized Titanphenolat (tetraphenyltitanate) are left with a melting point of 130 ⁰ C.

In flasks containing 220 g of titanium phenolate (0.5 mole) are added 30 g of trioxymethylene, i.e. a ratio of 2 moles Formaldehyde to 1 mole of titanate. The condensation is carried out for 2 hours without a catalyst, and an almost solid resin is obtained, which after removal of oily parts in a vacuum completely solid, thermoplastic, but insoluble in alcohol and acetone with an intense red color is soluble in dimethylformamide. The Har * hardens in the presence of 10% hexamine.

The weight determination showed 10% ionically bound titanium metal in the macromolecule of the resins with an approximate molecular weight from 50D.

BATH 909830/1343

t It f Iff

Example 6

Synthesis of tungsten-phenol-formaldehyde resin

Tungsten hexachloride (WGIg) is mixed with aramonium phenolate (Melting point 275 0) in stoichiometric amount «

The color changes from sieve violet to green. It finds a release of NH, Gl, which sublimates and takes place deposits in the colder parts of the cooler. Man distributes the HH.C1 as far as possible, then the product is diluted with dioxane. Phenol is added in small portions of trioxane with stirring. This forms Like the resin, and the water formed in this reaction is carried away with a dry nitrogen stream.

After a reaction time of 90 minutes, the solvent is driven off and the by-products and the rest of the moisture are distilled off in vacuo.

A pale green hair which is soluble in alcohol is obtained *

After leaving a few layers to stand for a long time, the solution separates a slight residue of a tfοIfran compound | Hol'-VCl ₆ (213 g) gives 3 g of inorganic yerbine-210 Hta it 700 Phl h itl

manure. 210 g wwHtaA with 700 g phenol according to Tieraonatlgsa Leaving it to stand reacted and it was found that ta Resin remained stable.

Example 7

Synthesis of zirconium-phenol-lOraaldehyde-HarB

For this process, freshly prepared un & hydrated zirconyl chloride (ZrOCIg.8HgO) in alcoholic solution. For this one gives an alcoholic one indifferently

30/1343 ^'BAD

Solution of phenol. Brown diphenyl zirconate is likely to form, which then after evaporation of the solvent and neutralization of the remaining Hydrochloric acid with trioxymethylene dissolved in dioxane was allowed to react.

A condensation takes place in a homogeneous mixture, whereby the resin formed is soluble in this mixture.

The dioxane is removed by distillation in vacuo, as are the other reaction products, such as the phenol-formaldehyde condensation resulting water and oily by-products. The resin obtained has a rose-like appearance Color, Bs is soluble in alcohol.

2. 322 g of freshly made ZrOölg.eHgO are measured in 700 cm 'absolute Dissolved alcohol. For this purpose 188 g are also used

3
Pure phenol dissolved in 200 cm of alcohol is added.

The two compounds are allowed to react for 3 hours while the alcohol is refluxed. You remove the alcohol by distillation and leaves the mass obtained with 1000 g

with
Phenol react without solvent and »stir.

100% dry dioxane is added and the mixture is neutralized the mixture up to a pH of 5 »A 0.83 mol of trioxane per 94 g of phenol is added in small portions Add amount of trioxane.

The mixture is condensed for 90 minutes in a dioxane solution under reflux this solvent. The solvent and the water formed during the reaction are removed in vacuo, •. then the distillation is carried out under a stronger vacuum, . continued to further purify the resin.

909830/1343 BAD

kl k *

1 BI 6241

-13-

Obtained 1.3QO g of clear, yellowish pink, soluble in alcohol, "resin, which is curable in the presence of 9 $ Hex & minutes at 15O ⁰ G in 10 min..

Example 8 ν

Synthesis of manganese-phenol-formaldehyde resin

1. This resin is made from manganese chloride hydrate (MnClg.SHgO) of molecular weight 162.

This is left with ammonium phenolate in terms of the .f | two Ghloratpme of equimolecular amount react. It educates anunonium chloride and a manganese phenolate ■ similar, bluish product. One determines the reaction of the mixture, a pH of 5.6 is for the continuation of the ! Reaction in a slightly acidic medium is advantageous. One adds Phenol until a molar ratio of manganese / Phenol = 0.125 added.

As soon as the manganese phenolate has spread evenly, are given in. Aqueous suspension of irioxymethylene in a Add amount that is 0.83 moles of formaldehyde to 1 mole of phenol

is equivalent to. . ^

The temperature is increased until an expthermal is triggered Reaction, let condensation follow *! 3 h continued. After separating off the water and the alcohol-soluble components a black lipstick resin *

Ija's resin forms stable alcoholic solutions of deep brown barbel without depositing solid inorganic stumps.

2. 300 g of pure Phenpl are melted with the addition of ypn

■ '' - ^■■;!

BATH ORIGINAL

Q Q 9 8 3 Q / 1 3 A 3

~ 14 ~

0.125 g-atom of manganese in the form of manganese chloride (MnCIo i.e., 65.3 S * The hydrogen chloride produced in this reaction acid is made by adding 13.8 g of N3L in Neutralized in the form of a 34% solution.

One observes a complete dissolution and a continuous "border change of the coloring to deep blue after four hours of reaction in the heat (9O ⁰ C).

The mixture is left to stand for 12 h without neutralization *

'. permit. Is added 80 g of formaldehyde in 40% strength by weight solution added and heated to 7O ⁰ C,

After cooling and condensation for three hours, one isolates; products liquid by distillation and 265 g in alcohol soluble, deep brown resin that does not form inorganic deposits over time,

The invention described with reference to the examples is limited Of course, this does not apply to them, and in particular it can be done without compromising the framework indicated let certain changes be made.

W ! - patent claims-

9 Q 9 8 3 Q / 1 3 A 3

Claims (1)

(Ct «· * r ι - 15 - Claims 1, process for the production of curable and heat-resistant phenol-formaldehyde resins, which skin a chemically bound metal or metalloid, by condensation of a phenol with formaldehyde and removal of the water formed and the hydrochloric acid and the solvent formed from the reaction mixture, thereby geke η η ζ eich η et _s that the metal or metalloid used in the form of an oxide, an acid or a salt is bound to the plienyl radical before or after the condensation with the formaldehyde « 2. The method according to claim 1 _f, characterized in that the bonded metal is molybdenum, titanium, tungsten or zirconium, and the bonded metalloid is boron or phosphorus. 5. The method according to claim 1 _9, characterized in that the phenyl radical ialogen «, alkyl or amino substituents can carry before the reaction. 4-. Method according to claim 1, characterized in that the phenyl radical in the form of phenol or ammonium phenolate in üie .Reaktion is introduced. 5 «The method according to claim 1, characterized in that the formaldehyde in aqueous solution, or in the case of condensation after binding of the metal or metalloid preferably in anhydride, monomeric or polymeric Shape is used. 9098.30 / 1343 were obtained by a method according to claims 1 to 5, and contain a chemically bonded metal or metalloid, characterized in that the metal or Metalloid is bound via covalent or ionic bonds that the resins in the usual solvents with the formation of a color dependent on the bound element, and that the resins too at high temperatures lead permanent connections. 7. Resins according to claim 6, characterized in that they are made of boron phenol, boron-p-aminophenol, phosphorylphenol, molybdenum phenol, Titanium phenol, tungsten phenol, zirconium phenol, Manganese phenol formaldehyde resins exist. 9 0 9 8 3 0/1343