DE2240197A1 - PROCESS FOR THE PREPARATION OF EPOXIDES FROM COMPOUNDS OF THE LEUKAURIN TYPE - Google Patents

Description

Dr. Michael Hann August 11, 1972

Patent attorney H / W (481) 15,596-F

63 of which
Ludwigstrasse 67

The Dow Chemical Company, Midland, Michigan, USA

PROCESS FOR THE PRODUCTION OF EPOXIDS OF CONNECTIONS OF THE LEUKAURIN TYPE

Priority: USA / August 19, 1971 / Ser.No. 173.259

You already have di-, tri- and tetra (hydroxyphenyl) alkanes These reacted with compounds such as epichlorohydrin for the production of glycidyl ether Glycidyl ethers have also been used in efforts to produce resins with high temperature resistance hardened.

t ■ -

»The production of epoxides from tri- and tetra- (hydroxyphenyl) alkanes It has also been considered because the starting materials for this, such as leukaurine, are available.

Tris (4-hydroxyphenyl) methane, which is usually referred to as leukaurine, can be obtained by reduction Manufacture of Aurin with zinc dust and acetic acid. The leukaurine or its substituted

309811/1108

Derivatives can also be obtained by condensation of Phenols are produced with aromatic ketones or aldehydes. For example, tris (4-hydroxyphenyl) ethane can be used by reacting phenol and 4-II-hydroxyacetophenone obtain. Derivatives of these compounds with substituents on the phenyl rings derived from the phenol are obtained if one uses corresponding substituted phenols as starting materials.

Dearborn et al, see IEC 45 , no. 12, have made epoxides of bi-, tri-, and tetraphenols by a process in which the phenol, epichlorohydrin, and caustic alkali are mixed and heated, coupling and dehydrohalogenation occurring in a single step. As part of this ErJir.cng ■. ■; ..: v. : .- ^ represents that

that through this Vorzu.ren. . Leukaurine

epoxy has an epoxy foot .-. Lonai_-, acv, "2 and only> to products 1, the. .- ^ resistance not satisfied. Vov. In ^ aresse si "- ± this context nor the en. _eche.: the US-Pd-. if th 2 857 362 and 2,863,852.

In US Pat. No. 2,965,611, Schwarzer disclosed the epoxidation of tri- and tetra (hydroxyphenyl) alkanes, products being formed which have no more than 2 epoxyalkoxyphenyl groups on an alkylene carbonator. This epoxidation mechanism from Schwarzer is similar to that from Dearborn, with the exception that the mixture of phenol and epichlorohydrin was refluxed before the aqueous caustic alkali was added. Von Schwarzer was born. by this method but only an epoxide of a tetra. kis connection established.

SAD ORIGINAL

In GB-PS 875 811 Neumann has the preparation of the trisepoxy compound by a method similar to Schwarzer described, but using solid caustic alkali instead of aqueous caustic alkali.

The object of the present invention is an improved process for the preparation of epoxides of compounds of the leukaurin type.

According to the invention, this object is achieved by a process for the preparation of epoxides of compounds of the leukaurine type by reacting a leukaurine compound with an epihalohydrin by, in a first stage, a leukaurine compound with an epihalohydrin in the presence of a coupling catalyst """converts", with one hydroxyl equivalent cL.r Leu! rinverbindung gsweise abe at least 5 mol, ve -..-: the epihalohydrin used 10 moles, and "_ j reacting in a second stage by adding at least one equivalent of a strong base per Hydroxyläquivalent'zu leading end.

You get. ' - ..ei eir. J / poxy with a medium epoxy

function: iLz. from at least about 2.5 to about 5 or

of around at least 70% of the theory for the number of available hydroxyl groups of the triphenoIisehen compound used as starting material, wherein the one of these details is decisive, which is :, higher Corresponds to the degree of epoxidation. The product is c_, serdem

3 0 9 8 1 1/1 1 Q 8.

BATH ORIGINAL

224Ü197

primarily an epoxidation product and contains only small amounts of various resinous by-products, as can be seen from the evaluation of the epoxidation with about 23 to 81 for the reaction products after this Invention results. The epoxidation rating is defined as the ratio of the epoxy equivalent of the product divided by the mean epoxy functionality. For this evaluation, the epoxy equivalent weight is only derived from the e'poxy-substituted aromatic nucleus calculated. These Rating is therefore a measure of firstly the efficiency in converting the hydroxyl groups into Epoxy groups and, secondly, the avoidance of the formation of by-products. The conversion products in the process of this invention are liquids or solids that are viscous at room temperature and are very mobile masses at around 50 ° C.

The leukaurin compounds used as a starting material in the invention are phenolic compounds which generally correspond to the following formula

<0H) _m .

3 0 9 811 '1 10 ί'

In this formula, Q is hydrogen or an alkyl radical having: up to about 10 carbon atoms; every R is a Alkyl radical with up to about 12 carbon atoms, phenyl radical or a cycloalkyl radical with 3 to 6 carbon atoms; X is Cl, Br or N0 “; each m 'is independently 1 or 2; each ρ is independently of one another 0 to and each η is 0 to 6.

These pheno! Compounds of the leukaurin type are obtained in general, by using an aromatic aldehyde or an aromatic ketone, such as hydroxybenzaldehydes or hydroxyalkanolcetones with an excess, preferably with a very large excess of a substituted or unsubstituted phenol. the Mixing the starting materials is expedient stirred while warming, a strong acid such as H 2 SO, HCl or HBr being used as a catalyst. The reaction that occurs is exothermic and, after the evolution of heat has subsided, the reaction takes place brought to an end with warming. The product is isolated in the usual way.

The tri (polyhydroxyphenyl) alkane used for epoxidation can be substituted on the phenyl radicals derived from the phenol in any position, e.g. by substituents a like Cl, Br or NO. For the skilled person it is clear < that certain substituents, in particular the substituents directing in the meta position, the condensation of the Phenols with the aldehyde or the ketone to leukaurin-like

30981 1 / i108

Materials can prevent. For the production of such leukaurin compounds, condensation is used first carried out and the condensation product is then substituted. Examples of such substitutions are nitration and halogenation. On the other hand, it is desirable to make such substitutions before the To carry out epoxidation, as the oxirane rings are sensitive and could be opened upon substitution.

By using a substituted phenol or by Substitution of the three-ring compounds obtained by condensation can be compounds of the leukaurine type with produce a variety of different substituents on the phenyl rings without difficulty. As examples for substituted phenols that may be corked, the following are mentioned: o-Cyclohcxylphenyl, o-Cresoi, o-Hexylphenol, 2-Methylresorcin, 4-dodecylresorcinol, ρ-cresol, p-tert-butylphenol, o-phenylphenol, ra-Ciresoi and the like.

As Epihalohydr ^. is primarily used in the invention Epichlorohydrin used. However, other known epihaloaydrins can also be used with good success, such as Epibrorahydrin, 1-chloro-2,3-epoxy-2-: aethylpropane and the like.

In the case of the epoxidation of the leukaurine compounds, according to the invention, preference is given to a higher stage in the first stage Temperature than worked in the second stage. Particularly suitable reaction temperatures for the implementation in the

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first stage are from about 60 to about 150 ° C, preferably under reflux cooling at boiling temperature is being worked on. The reaction time in the first stage is generally at least about 30 minutes, preferably but about 1 hour.

Preferred reaction temperatures for the implementation in the second stage is about 35 to 70 ° C and the preferred reaction times are about 0.5 to 3 hours. It is advisable to stir during the reaction. The optimal reaction temperatures and reaction times can be based on this information for the individual Identify connections without difficulty.

Known coupling catalysts, such as organically substituted ammonium and phosphonium compounds, amines, salts and the like, are used as coupling catalysts in the first stage of the reaction. Examples of suitable coupling catalysts are benzyl _? Trimethyl] ammonium halides, especially the chloride; tert.amines, such as benzyldimethylamine, triethylamine, Ν, Ν, Ν ¹ , N ¹ -tetramethylethylenediamine and the like; N-methylraorpholine; Triphenylphosphonium halides, such as iodide, bromide or chloride; Triphenylethylphosphonium diethyl phosphate and corresponding ionic salts including phosphonates, acetates, nitrates and the like. The preferred coupling catalyst is benzyltrimethylammonium chloride (BTMAC).

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22A0197

After a sufficient time has elapsed for the epigroups to be coupled to the hydroxyl groups, the reaction mixture is cooled, preferably to the temperatures mentioned above. The dehydrohalogenation is then brought about in the second stage by adding a base, preferably a strong base, such as caustic alkali, for example NaOH, NaOH in saturated Na ₂ CO 2 solution, sodium aluminate or the like. A particularly suitable base is, for example, 3N NaOH, but also 30 to 50X NaOH, which _is expediently added to the solution with azeotropic removal of water. It is also possible to use 20% strength alcoholic KOH under reflux with good effect. In general, 3-n NaOH in saturated aqueous Na "CO" solution is used as the base.

In practicing the invention, it is preferred to add the appropriate phenolic leukaurin compound Leukaurin itself, an epihalohydrin, preferably epichlorohydrin and a coupling or condensation capacitor in a suitable reaction vessel, which is equipped with a Stirrer, thermometer and a reflux condenser is equipped. The reaction mixture is then heated to boiling under reflux for one hour. After that the mixture cooled to about 50 ° C, e.g. in a water bath, and while maintaining this temperature, aqueous sodium hydroxide solution is added to saturated aqueous Na CO 2 solution Stir added. At least one equivalent of alkali is used per hydroxyl equivalent of the leukaurine compound. A slight stoichiometric excess of alkali should preferably be used.

3 0 9 8 1 1/110 8

The lye is heated for about an hour. and stirring is added, then the resulting mixture is left

separate into an organic and aqueous phase and

discards the aqueous phase. The remaining organic phase

is heated again to 50 °, e.g. in a water bath, and while stirring, sodium hydroxide is again saturated aqueous sodium carbonate solution added.

The reaction mixture becomes about one more with stirring Held at 50 ° C. for an hour, the separated organic phase is washed again with water, which is obtained by adding acetic acid was slightly acidified, washed and then washed with water alone until the wash water is neutral reacts to pH paper. A little sodium chloride can be added to the washing water to reduce the inclination of the water to reduce the formation of an emulsion in the organic phase. After the lapping with water is finished, the organic .. material obtained is lowered under Pressure to remove traces of water and unreacted Epichlorohydrin distilled. The epoxide of the leukaurine compound is then obtained in a high degree of purity with a molecular weight and an epoxide equivalent weight which largely correspond to the theoretical values.

An epoxide preferably produced according to the invention is the tri (4- (2,3-epoxypropoxy) phcnyl) methane with an epoxy equivalence weight of about 153 to 160, an epoxy functionality of about 2.8 to 3.2 ( evaluation of Epoxidieruii _o seffizienz about 47 to 58) and a viscosity of about 8500 to 13,000 Cp at 50 ° C.

3 0 9 8 11/110 8

- ίο -

The epoxides of leukaurin compounds obtained in the invention correspond to the general formula

- OCH ₂ C - CH ₂

In the Q H or an alkyl radical with up to about 10 carbon atoms is; each R independently of one another is an alkyl radical with up to about 12 carbon atoms, a pheriyl radical or is cycloalkyl of 3 to about 6 carbon atoms; each Y independently of each other H or -CH_

is, each Z independently of one another is H or

each Y is Cl, Br, or NO_; each m independently of one another Is 0 to L; each ρ is independently 0 to 2 and η is 0 to 6.

The leukaurine epoxides produced according to the invention are valuable starting materials for the production of Resins with good temperature resistance are. They can be used alone or in a mixture with other epoxies cure the known curing catalysts.

30981 1/1 1Ό8

As examples of compounds that are mixed with the Epoxides prepared according to the invention can be used are monofunctional reactive ones • Called thinners, such as phenyl glycidyl ether, allyl glycidyl ether, butyl glycidyl ether, cyclohexene monoxide and the same; Alkylene oxides such as butylene oxide, propylene oxide, octylene oxide and the like. Also poly, functional epoxides are useful in a mixture with the epoxides according to the invention, with as examples therefor Epoxynovalake, liquid and solid Glye5.dylather of dihydroxy compounds, butadiene dioxide, diglycidyl ether, Cyclopentadiene dioxide ^ Vinylcyclohexendioxid Bis- (2,3-Epoxycyclopentyl) ether, Diglycidyl phthalate, diglycidyl aniline, trisepoxides from aminophenols and epihalohydrins and the like. Mixtures of several such additives can also be used. Further Mixtures of epoxy compounds that can be used are disclosed in U.S. Patent No. 2,935,488.

The polyepoxides produced by the process of the invention can be cured alone or in a mixture with other polyepoxides with the aid of known curing agents under known conditions. The following hardeners are particularly suitable: methylenedianiline. m-phenylenediamine and mixtures thereof; ο p-phenylenediamines; Benzidine; Diaminediphenyl sulfone; 2,6-diaminopyridine; Benzyldimethylamine; Tetramethylethylenediamine; N-methylmorpholine; Diethylenetriamine; Triethylenediamine; Tetramethylguanidine; Dicyandiamide; Dimethylethanolamine; Diethanolamine; Trialkylamines such as triethylamine, tripropylamine and tributylamine; 4-picoline and the like. Also suitable are BF "complexes _? like BF ^ -Mono-

ethylamine; Borates such as tricresyl borate; Anhydrides, like Nadi emethyl anhydride, hexahydrophthalic anhydride, Do-

309811/1108

docenylsuccinic anhydride, succinic anhydride, Maleic anhydride, glutaric anhydride, pyromellitic dianhydride, Trimellitic anhydride, tetrahydrophthalic anhydride, chlorendic acid anhydride, polysebacic acid polyanhydrides, polysulfides, Polymaleic anhydride, phthai acid anhydride, benzophenone-etracarboxylic acid dianhydride, Cyclopentanetetracarboxylic dianhydride and the like.

All of these hardening agents can be hardened with the leukaurine epoxides produced according to the invention within a wide temperature range depending on the desired properties of the hardened product and the hardening agent used. For example, with a very mild curing, 2 hours at 120 ° C. using aromatic amines; Cure tert-amines, BF »complexes, borates and the easily soluble or low-temperature melting anhydrides. For optimum properties, curing in a plurality of stages is adapted, such as 16 hours at 85 ⁰ C and 16 hours at 16O ° C or 16 hours at 85 C, 16 hours at 160 C and 4 hours at 230 C. As a rule, very short curing times are desirable and high heat distortion temperatures can be achieved by treating for 2 hours at 2? , Mixtures of maleic anhydride and pyromellitic anhydride, mixtures of hexahydrophthalic anhydride and trimellitic anhydride or pyromellitic anhydride and mixtures of phthalic anhydride and trimellitic anhydride or pyromellitic anhydride. You can also use other anhydrides, such as cyclopentanetetracarboxylic dianhydride or benzophenonetetracarboxylic dianhydride in a mixture with maleic

3 0 9 8 1 1/1 1 0 P.

Use acid phthalic or hexahydrophthalic anhydride. In addition, the anhydrides which melt at high temperatures can also be used alone if they have been incorporated into the resin so that complete dispersion has been achieved.

Because of their extraordinarily high dimensional stability temperature They are cured in the heat and because of their excellent resistance to high temperatures Resins made from the epoxy compounds prepared according to the invention are particularly useful in numerous fields Interest. '

The resins according to the invention are distinguished by an excellent combination of flexural strength and dimensional stability in warmth and heat resistance and also by other superior qualities. You let therefore in numerous areas where high demands are placed on the properties of the resins, use.

In the sector of epoxy resins reinforced with glass fibers, they are used for protective shields against high temperatures. ratuen and for conical noses and also for housings of rocket motors and combustion chambers. Other suitable Areas of use for the fiberglass laminates are other areas with high thermal stress, e.g. printed Circuits. As the new cured products have excellent resistance to Solvents and other chemicals distinguish them, they can also be used with good effect in reinforced with glass fibers Use pipes that are also higher at the same time

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Have heat resistance. Similar areas of application are Pressure balls and containers where good resistance against solvents, chemicals and / or heat is desired. Other areas of application are the production of hoods, chimneys and the like with large Resistance to acids, alkalis or solvents.

These new epoxies can also be used in building materials in combination with carbon fibers, boron fibers or glass fibers, for example in aircraft construction, where a
greater heat resistance of the building materials is required.

For use in the electrical field, go to Use of suitable hardeners to obtain hardened masses, which are characterized by a higher heat resistance and have a higher warning resistance than before available epoxy resins, whereby the new cured products also have low dielectric constants, high resistance, low electrical loss, and higher resistance to electrical Arcing and higher tracking resistance.

Coatings made from the epoxy compounds are distinguished greater resistance to chemicals, heat or solvents. This applies to both coatings, which were obtained without solvents as well as for coatings based on products modified with fatty acid esters, being these fatty acid esters of tungol, dehydrated Can derive castor oil or flaxseed oil.

The new epoxies are also an excellent basis for the recently developed F.poxy-acrylates and others Very chemically stable vinyl ester resins.

309811/1108

Another area of application in which the new polyepoxides are particularly well suited to set against high temperature resistant adhesive.

The invention will be further elucidated in the following examples explained.

example 1

In order to explain the production of the starting materials for the polyepoxides according to the invention, the production is described here of tris (4-hydroxyphen3'-l) methane, which is usually called Leukaurine is known, described.

In a three-necked flask equipped with a stirrer, thermometer and reflux condenser, 122 g p-hydroxybenzaldehyde (1 gram-mole) and 1410 g phenol (15 gram-mole), given. The flask is placed over a water bath with a

Temperature of 40 C arranged and its contents are vigorously stirred. Then anhydrous HCl is slowly bubbled through the mixture. An external reaction begins, but the water bath cools the reaction mixture to such an extent that a
is exceeded.

that a maximum temperature of about 44 C is not cool

After the exothermic reaction has subsided, continue to stir with anhydrous HCl for about 6 hours the reaction mixture kept on the water bath at 40 ° C. is bubbled through. At the end of this period, the Stand reaction mixture overnight at room temperature.

The resulting mixture is washed twice with water, then it is distilled in vacuo, taking most of the excess Phenol is removed. The remaining phenol 'will

309811/1108

driven off with steam. The distillation is then continued until all of the water is removed.

A dark pink crystalline mass forms, which only contains traces of resin. The product weighs 290 g, which corresponds to 99% of theory.

Under similar reaction conditions, other leukaurins « raw materials for polyepoxides manufactured. The following table shows the starting materials and the catalysts. The reaction conditions and the work-up of the product are essentially the same as those mentioned above Details match.

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No. starting material

Starting material catalyst

product

• A. Phenol

B. phenol

C. p-cresol

D. 2-t-butylphenol

E. Mixture of

4-octylene and 4-dodecyl-phenol

F. 4-n-hexylresorcinol "

G. 4-Cyclohexylresorcinol "

4-IIydroxyaceto- phenone

4-hydroxyoctano · phenone

p-hydroxybenzaldehyde

H. 4-Dodecylresorcinol

If

Il

dd

v / aterfr. HCl 1,1, l-Tris- (ph \ ^r droxy-

+ Thioglycolic acid phenyl) ethane

Glacial acetic acid +
H ₂ SO ₄

ZnCl,

anhydrous HCL + 1.1, l-C Thioglycolic acid phen} '!) Octane

2,2 ', 4-trihydro3cy-3,3' t-butyl triphenyl methane

ι Ι

4,4 ', 4 "-trihydroxy-3,3

-1 -but} '! tr iphen / lrccthan q

2.2 ', 4 "-Tr! Hydroxy (mixture I ^{c =>} of 5,5'-didodecyl-dioctyl - *» and S-octyl-S'-dodecyD-tri * phenyimethane

2,2 ', 4,4', 4 "-pentahydrpxy-5,5'-d i-n-hexy1-1r iphenylmethane

2,2 ', 4.4', 4 "-Pentahydroxy-5,5 ^f dicyclohexyltriphenylmethar.

2,2 ', 4,4', 4 "-pentahydroxy-5,5'-didodecyltripheitylraethane

22Αύι97

Example 2

This example concerns the production of dinitroleucaurine. Ilalogenated compounds can be replaced by analogous Process are produced.

30 g of leukaurine are dissolved in 700 ml of glacial acetic acid in a three-liter flask. 15 ml concentrated ENT " in 85 ml of glacial acetic acid then slowly added to the leukaurine at a temperature of about 24 ° C. Through the When an exothermic reaction occurs, the contents of the flask are heated to 28 ° C.

The reaction mixture is allowed to stand overnight and
then pour it into 1800 ml of H “0. The precipitate obtained
is filtered off and washed with water. The product,
which is a light yellow powder, weighs 35.5 g, corresponding to 90.5 / Ό of the theoretical yield of dinitroleucaurine. The nitrogen content found is 7.9%, compared to a theoretical value of 7.33%.

Example 3

The trisepoxide of leukaurine was made in the following manner
prepared: 290 g (3 equivalents) of leukaurine, 2780 g (30 mol) of epichlorohydrin and 2.9 g of a GOZigen solution of benzyltrimethylammonium chloride (1% of the trisphenol) are added to a flask equipped with a stirrer, thermometer and reflux condenser. The flask is stirring and
Return cooling to boiling temperature (119 ° C) for one
Heated hour. Then it is cooled and placed in a water bath

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of 50 ° C and there are 1000 ml of a 3-molar NaOII in saturated Na "CO" added, (1, equivalent of NaOH per equivalent of trisphenol). The mixture is kept at 50 ° C. for one hour while stirring. That consumed NaOH is separated and the epichlorohydrin solution is returned to the flask, in a 50% water bath

heated and treated again with 500 ml of a 3 molar NaOH in saturated Na_C0 "solution for one hour. The used NaOH solution is separated off again. The reaction mixture is then first diluted with aqueous acetic acid and then washed with water until it reacts neutrally. The water and the epichlorohydrin are distilled off under vacuum.

The resin obtained has a "color value of 10 according to the Gardner scale, an epoxy equivalent weight of 158 (theoretical 153), an average epoxide functionality of 3.1, a viscosity of 8800 centipoise at 50 ° C, ^theoretical: a molecular weight of 490 ( 463) and an epoxidation efficiency factor of 51.

Example 4

The trisepoxide of Example 3 was mixed with various curing agents, molded into test samples and hardened. The essential conditions and results are summarized in Table II.

30981 171108.

Table II , Harder Parts Hardening 16 h 150 ° C. Barcol Dimensional stability No. 16 h I8OO C. hardness age in 16 h 160 ° C. the warmth Hardener / conditions 16 h 232 ° C. 0 c 100 2 h 232 ° C. BF MAA Parts 2 h 232 ° C. 48 > 266 * 1. DATA resin - 263 2. MXDA 3.0 42 221 3. DADS 11.8 39 > 266 4th BF ₃ MAA 19.8 47 > 2 & 6 5. DADS 35.6 45 > 266 6th 3.0 35.6

* Upper limit of the equipment used (ASTM D648-56 for all tests)

BFJMÄA - boron trifluoride monoethylamine DATA - diethylenetriamine MXDA - meta-xylylenediamine DADS - diaminodiphenylsulfone

The same trisepoxide was also used with mixtures of curing agents cured, curing at 93 ° C for 2 hours and then at 232 ° C for 15 hours. The results are given in Table III.

811/110

224ΰι97

Table III

No. 1. Harder Part 2. Hardener
Harder/
100
Parts
resin Parts
Harder/
100
Parts
resin - Trimellitic anhydride Barcol
hardness Dimensional stability
age in
the warmth
⁰ C 7. NMA ' 92.0 DMP-30 • 2.0 Pyromellitic dianhydride 44 262 8. TMA 3.3 MA 38.6 49 > 266 9. TMA 0.86 MA 45.7 49 > 266. 10. TMA 8.0 MA 24.0 46 > 266 11. PMDA 1.3 MA / · ' 45.7, 50 > 266 12. PMDA 13.3 MA 24.0 ' 43 > 266 13. PMDA 5.3 MA 38.6 45 > 266 NMA Nadic methyl anhydride TMA PMDÄ DHP-30 - Tris (dimethylaminomethyl) phenol MA Maleic anhydride Example 5

In a manner similar to Example 4, polyepoxides were made made from a number of tri (hydroxyphenyl) alkanes, mixed with the stoichiometric amount of methylenedianil, Cured and tested at 100 ° C for 2 hours and at 180 ° C for 18 hours. Table IV summarizes these results given. There are the values for the calculated and the found epoxy equivalent weight (EÄG), the dimensional stability entered in the heat (FBW), the Barcol hardness, the flexural strength and the flexural modulus. The flexural strength and

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2240T97

the flexural modulus was determined according to ASTM D790-66. Tripheny! Methane is abbreviated to "TPM".

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Table IV

No. Polyepoxide from

EÄG EÄG. calc.

O
CD
OO

1. 4,4 ', 4 "-trihydroxy-2,2'-dimethyl-TPM,

2. 4,4 ', 4 "-T.rihydroxy-3,3'-dimethyl TPM

3. 2,2 ', 4 ^M trihydroxy-5,5'-dimethyl TPM

4. 4,4 ', 4 "trihydroxy-3,3' -diphenyl TPM

5. 4,4 ', 4 "-trihydroxy-3,3'-dicyclohexyl-

6. 2,2 ', 4,4', 4 "-pentahydroxy ~ TPM

7. 2,2 ', 4,4', "4" -pentahydroxy-5,5 'dicyclohexyl TPM

8.2 ', 4.4', 4 "-pentahydroxy-5,5'-di-n-

'' hexyl-TPM

9.2 ', 4,4', 4 "-pentahydroxy-5, 5 ^{i -dido-}

decyl TPM

10.4.4 ^! , 4 "-trihydroxy-l, l, l-triphenyl-

ethane

11. Pentachloro-tris (4-hydroxyphenyl) -

methane

162.7
162.7
162.7
204.1
208.2
120.9
154.1

154.5
210.5

159.0
208.0 *

FBW Barcol Flexural Strength ™ ⁰ C hardness kg / cm ²
(psi)

170 178 172 212 218 134 163

165 200

171 220

45
52
44
47
48
64
44

38
266 X6

260 45
212 43

221
233
228
201
208
266
266

modulus kg / cm2 (psi) ^; · '

790 (11300)

850 (12100)

1170 (16600)

1330 (19000)

1060 (15100)

470 C 6700)

470 (6700)

31200 (44ΊΌ00) .: 3.1.S00 (454000) 32900 (469000) 3/300 (530000) 28900 (413 000) 2SCOO (AlOOOO) 25400 (363000)

660 (9400) 2160Q (308000)

620 (8800) 1.6500 (235000)

580 (8200) 3 ⁰ IOO (457000)

650 (9200).-I.-... ™ ,.

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Example 6

Mixtures of the trisepoxide of leukaurine (TEL) and the diglycidyl ether of bisphenol A (DGÄBA), epoxy equivalent weight 172 to 176 and a hardening agent. The mixtures were molded into test samples and cured at 93 ° C for two hours and at 232 ° C for 15 hours. The measured results are shown in Table V. emerged.

Table V . Weight%
. DGÄBA Weight%
TEL Harder Parts hardener /
100 parts resin Dimensional stability
in the warmth ° C No, ,SO 20th 179 1. 50 50 MDA 28.3 210 2. 20th 80 264 3. 80 20th 193 4th 50 50 PMDA
MA 13.3
24.0 247 5. 20th 80 262 6 .. 80 20th 157 7th 50 50 PMDA
MA 13.3
24.0 226 8th·.

9. 20

80

265

MDA - methylenedianiline

PMDA - pyromellitic dianhydride

MA - maleic anhydride

With other epoxies according to this invention a similar increase in dimensional stability under heat is obtained mixing and hardening with the diglycidyl ether of bisphenol A.

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Example 7

Mixtures of the trisepoxide of leukaurine (TEL) and another epoxy resin identified in more detail in Table VI with one part methaphenylenediamine as hardener per 100 parts of the resin were prepared, molded and heated at 85 ° C. for 16 hours and at 160 ° C. for 16 hours hardened. The results obtained can be seen in Table VI. . . '

Table VI /

Ro.% By weight other. 'Weight% dimensionally stable - flexural strength TEL epoxy resin different in kg / cm ^ (psi)

Epoxy resin heat ° C

1. 100 ■ no 0 265 990 (14100) 2: - 75 A. 25th 204 1280 (18200) 3. 50 A. 50 198 1470 (21000) 4th 75 B. 25th 198 1120 (16000) 5. 50 B. 50 193 1510 (21500) 6th 0 B. 100 153 2290 (32600) 7th 75 C. 25th 197 "1070 (15200) 8th. 50 C. 50 ■ 182 1240 (17700)

A - vinyl cyclohexene diepoxide

B - Copolymer of ethylene glycol and mixed isomers of bis (2,3-epoxycyclopentyl) ether '"

C - resorcinol diglycidyl ether

3 0 9 8 11/110 8

- 26 - ' Example 8 (comparative experiments)

In order to clearly demonstrate the superiority of the epoxies made by the process of this invention, the following were made Tests carried out:

There were four samples of the glycidyl ether of leukaurine after manufactured and investigated the following four processes:

1. DEARBORN

In order to reproduce DEARBORN's in the above-mentioned article in I & EC as exactly as possible, the following working method was used:

583 g epichlorohydrin, 5 times the amount of leukaurine to be used, was placed in a two-liter, three-necked flask equipped with a stirrer and a thermometer. The contents of the flask were heated to 60 °. : 123 g of leukaurine, 1.262 equivalents (0.421 moles) were added in 505 ml of an aqueous 10% sodium hydroxide solution, a dark red solution was formed.

Into the heated epichlorohydrin solution was vigorously Stir the leukaurine solution in sodium hydroxide slowly added.

The exothermic reaction was expected to raise the temperature of the contents of the flask by about 10p to 70 ° or higher would, but no such exothermic reaction occurred. The contents of the flask were therefore heated up externally heated to 70 ° and stirring was continued with the addition of the solution of leukaurine in sodium hydroxide. By a very With little exothermic reaction, the temperature of the contents of the flask was increased to 74O.

309811/1108

The addition of the 628 g of the leukaurine solution in sodium hydroxide was finished in 5Q minutes. Then the heating was taking Stirring continued for an additional 90 minutes, with the intention of terminating the reaction.

The conversion of sodium hydroxide and epichlorohydrin resulted in sodium chloride. This salt solution was separated and the product obtained was treated with a dilute sodium chloride solution which has been mixed with a small amount of acetic acid. had been acidified, washed. The product obtained was then dried over anhydrous magnesium sulfate and dried under, distilled at low pressure to remove unreacted epichlorohydrin.

2. HEUMAJM -

Example 2 of GB-PS 875 811 was made using Reworked leukaurine as a phenolic starting material.

3. BLACKER

Example 3 of U.S. Patent 2,965,611 was made using Reworked leukaurine as a phenolic starting material.

4. INVENTION

Example 3 of this invention was followed up. ■

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22AÜ197

The four epoxies made from the same starting materials, however using four different epoxidation methods were then made with a stoichiometric Quantity (49.5 g / Oil Aq.) Methylenedianil in mixed, deformed into test specimens and cured for two hours at 100 ° C and then for 18 hours at 180 ° C.

The values for the essential properties of both the uncured and the cured resins are given in the table VII compiled;

Table VII

Epoxy EÄG EF BEE ³ ) FBW Biegefestig- bending module gef. ¹ ) found 2) ο c ⁴ ) speed

kg / cm ^ (psi) kg / cm ^ (psi)

Dearborn
Neumann 294
432 2.0
1.3 147
334 147
5) 610 (8700) 34600 (492000 Black
invention 218
156 2.1
3.1 104
50 193
266 850
840 (12100)
(12000) 35500
32300 (520000
(460000

1) Epoxy equivalent weight (theory = 153)

2) epoxy functionality (theory = 3.0)

3) Evaluation of the epoxidation efficiency (theory ^β 51)

4) Dimensional stability in heat

5) During the curing, the sample foamed so that no further tests were possible

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Example 9

In this example the influence of the change the concentration of the epoxides prepared according to the invention on mixtures with other epoxides. The following experiments are carried out for this purpose:

The ^{percentage of the trisepoxide of leukaiirin- (TEL) given in x} table VIII was mixed with the diglycidyl ether of dihydroxytriphenyl-1,1,1-ethane (DTPÄ) with the stoichiometric. Amount of metaphenylenediamine mixed and cured at 85 ° C for 16 hours and at 160 ° C also for 16 hours. The results are shown in Table VIII.

Table VIII -

No. Weight% Weight% Barcol- dimensional stability- flexural strength TEL DTPÄ hardness in kg / cm ² (psi)

Heat ⁰ C

1 95 5 47 263. 900 (12800) 2 90 10 '. 49 245 870 (12300) 3 85 15th 47 222 830 (11800) 4th 80 20th 47 210 ⁼ 910 (12900) 5 70 30th '45 201 950 (135Ö0) 6th 50 50 45 190 940 (13400)

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Example 10

Increasing the dimensional stability in the heat Addition of small amounts of the epoxides according to the process of the invention was illustrated by the following experiments.

The trisepoxide of leukaurine (TEL) was similar to Example 8 with different amounts of the Diglycidyl ethers of bisphenol Λ (DGÄPA) mixed. The curing agent used was stoichiometric amounts of methylenedianiline used and for curing, the specimens were heated to 100 ° C for 2 hours and 180 ° C for 18 hours. The results are given in Table IX.

Table IX . Weight% Weight% For No. TEL DGPBA ⁰ C 0 100 160 1 10 90 177 2 20th 80 198 3 50 50 219 4th 80 20th 331 5 * 90 10 339 6th

Dimensional stability in heat *

Determined by thermomechanical analysis according to the publication in Perkin-Elmer Industrial News 20 , No. 4 (1970), pages 6 to 7, with adaptation to the use of a DuPont Thermal Mechanical Analyzer Instrument using the same size sample with dimensions 7 .6 5.1 χ 0.76 mm (0.3 "0.2" χ 0.02 ").

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Claims (3)

Patent claims: Process for making epoxides of compounds of the leukaurine type by reacting a leukaurine compound with an epihalohydrin, characterized in that that in a first stage a leukaurine compound is reacted with an epihalohydrin in the presence of a coupling catalyst, with one hydroxyl equivalent of the leukaurin compound, at least 5 "moles of the epihalohydrin are used, and the reaction in a second Step after adding at least one equivalent of a base per hydroxyl equivalent of the leukaurin compound End leads. 2. The method according to claim 1, characterized in that the reaction in the first stage at one temperature from about 60 to about 150 ° G and in the second stage at a lower temperature than in the first Stage takes place. 3. The method according to claim 2, characterized in that the temperature in the second stage does not exceed 70 ° C. - ■ 309811/1108