DE2420774A1 - QUARTERLY HYDROXY ALKYLAMMONIUM ALKYLATES AND PHENOLATES AND METHODS FOR THEIR PRODUCTION - Google Patents

Description

The invention relates to quaternary hydroxyalkylammomium alkylates and phenates and a process for their production.

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Quaternary Hydroxyalkylammoniumalkylate and phenolates receives · man stoichiometric amounts, by reacting a tertiary amine, an alkylene oxide and a carbinol at controlled temperatures ranging from 0 to about 100 ⁰ C, preferably 10 to MO ⁰ C.

The preferred for the preparation of the compounds according to the invention Tertiary amines used in excess correspond to the following general formula

RR ₁ -N

R ₂
in which R, R ₁ and Rp have the meanings given above.

Examples of tertiary amines include triethanolamine, methyldiethanolamine, ethyldiethanolamine, dimethylethanolamine, Butyl diethanolamine, octadecyl diethanolamine, cyclohexyldiäfchanolamine, Benzyl diethanolamine, benzylmethylethanolamine, diethylethanolamine, Diethylcyclohexanolamine, methyloctadecylethanolamine and methyloctadecenylethanolamine.

The alkylene oxides correspond to the following general formula

R, -C CH

in which R, and Rj have the meanings given above.

Examples of such alkylene oxides which are used for the synthesis of Compounds according to the invention are particularly suitable are propylene oxide, ethylene oxide, 1,2-butylene oxide, 1,2-pentene oxide, Styrene oxide, the dioxides of dienes, for example butadiene epoxide and mixtures thereof.

The carbinols are made under the following general formula

409885/136 5

R ₅ OH

in which R _{5 has} the meanings given above, corresponding compounds are selected.

Exemplary representatives of this group are methanol, benzyl alcohol, furfuryl alcohol, phenol ₉ resorcinol, substituted phenols, for example bis-phenol A, and the like and lead to the methylate, benzylate, furfurylate and phenolate homologues of the compounds according to the invention.

The synthesis reaction to be carried out to form the compound according to the invention can be described by the following equation will

R ₄ - N + R, - C-

SXr \ it I

CH

R _C OH ρ

^R ? 3

LN-CH ₉ -C-OH

Ii 2 ι

Rn R Ii

in the R,
own.

OR,

and R, - the meanings given above

The compounds of the invention, preferably by a Reaction formed in which an excess amount of the tertiary amine is used, contain about 30 to 50 Μοί-Ϊ of this tertiary amine. Since the molecular weight of the quaternary Hydroxyalkylammonium alkylate or phenolate is substantially greater than that of the tertiary amine, the content of the tertiary amine Amines, expressed in weight units based on the weight of the Total compound, below 50 and is usually in one Range from about 10 to MO weight-J.

409885/1365

-C-

The following examples illustrate the preparation of the inventive Compounds and their use in polymerization.

Examples 1 and 2

These examples illustrate the preparation of one according to the invention quaternary hydroxyalkylammonium alkoxide and one according to the invention hydroxyalkyl quaternary ammonium phenolate.

A round-bottom flask equipped with a stirrer, a thermometer, a reflux condenser and a dropping funnel is charged with one mole of dimethylethanolamine and half a mole of one of the carbinols given in Table I below. The mixture is stirred during the addition of half a mole of propylene oxide, which is supplied at such a rate that the reaction temperature does not exceed 50 ⁰ C. After the end of the propylene oxide addition, the mixture is stirred for a further 2 hours before it is analyzed by nuclear magnetic resonance (NMR) and titrimetrically for the content of quaternary amines and tertiary amines. The compounds formed and their titrimetric analysis values are given in Table I below. Each of the products listed in Table 1 below contains 50 Μοί-Ϊ unreacted dimethylethanolamine. The NMR spectra of the products given in Table I show two resonance signals for the two different methyl groups, the signal corresponding to the protons of the tertiary N-methyl group at 2.2 ppm and that of the protons of the quaternary N-methyl groups. Group corresponding signal occurs at 3.3 ppm.

409885/13 6 5

Table I. Quaternary hydroxy alky lammoniunethyl lat or phenolate Respondents

product

Examples

ο co oo

Tertiary anin

Dimethylethanolamine

Carbinol

Methanol

Dimethyl phenol ethynolamine

Alkylene oxide

Propylene oxide

Propylene oxide

N, N-dimethyl-N-hydroxyethyl-N, 2 _: hydroxypropylammonium methylate

N, N-dimethyl-N-hydroxyethyl-N, 2-hydroxypropyl-ammonium phenolate

Titrimetric analysis mEq / g quart. mEq / g tert.

2.52

2.81

4.95

3.30

Example 3

This example illustrates the formation of an isocyanurate using the hydroxyalkyl quaternary ammonium methylate compound (Composition) of Example 1. In glass jars (237 ml (eight ounce)) 15 parts of toluene, 15 parts of phenyl isocyanate and 1 part of the compound (composition) from Example 1 are mixed mixes the reactants thoroughly and lets them stand for 2 days at room temperature. The one during this period The solid precipitate formed is filtered off and treated with a small amount of 50 volume Ϊ acetone and 50 volume Ϊ toluene containing solvent mixture washed. The washed precipitate is then placed in a vacuum oven at 60 ° C for one hour dried. In the following Table II are the melting point of the resulting triphenyl isocyanurate product and the percentage Yield of the product, based on the theoretically achievable amount, indicated.

Comparative example 1

The values given in Table II below permit one Comparison of the isocyanurate product obtained with the product according to the invention with the product obtained with a commercially available one PοIyurethane catalyst receives. In this comparative experiment, the same procedure is used as in Example 3 is described.

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Table II

Isocyanurate formation

catalyst

Isocyanurate product . ⁰ C yield %

° comparison

Example 3

2,4,6-tri (dimethylaminomethyl) phenol (DMP-30, manufactured by Röhm & Haas Co.)

N.N-Dimethyl-N-hydroxyethyl-N, 2-hydroxypropylammonium methylate in 50 Μοί-Ϊ dimethylethanolamine 287-288

287-288

The melting points mentioned with the comparative catalyst and The product obtained with the composition according to the invention is similar to that in the literature (B.D.Beitchman, Industrial and Engineering Chemistry Product Research and Development, Vol.V, pp. 35 to 41 (1966)) given melting point of 282 to 284.9 of the obtained Triphenyl isocyanurate product comparable.

Example 4

Using the procedures described in Example 3, a 237 ml (eight ounce) flask is charged with 5 parts of phenyl isocyanate, 15 parts of toluene, and 0.4 parts of the catalyst of Example 2, i.e. 50 mol. Ν, Ν-dimethyl-N-hydroxyethyl- -N, 2-hydroxypropylammonium phenolate and 50 Μοί-ί dimethylethanolamine. The reactants are stirred and lead to an instantaneous precipitation with considerable exothermic release of heat. The precipitate is filtered off, washed with toluene and dried ^{in a vacuum oven at 50 ° C. for one hour.} The melting point of the resulting triphenyl isocyanurate product is 284 to 285 ° C. The infrared spectrum shows the characteristic isoeyanate bands at 5.8 and 7.06 u.

Examples 5-6

Using the compounds or compositions according to the invention rigid polyurethane foams are produced. The foam samples are prepared using one of the following ingredients containing precursors:

Amount (g)

Component A ¹ (Selectrofoam 6406) 109

Surface active silicone ² (DC-193) 1.5

Trichloromonofluoromethane 47

di Tt
Technical tolylene isocyanate ^ (Hylene TIC) 105

1. Component A (Selectrofoam 6406) is a mixture of a polypropylene oxide propanol derivative of sucrose and an alkylene oxide derivative of ethylene diamine with a molecular weight of

409885/1365

about 800 (see US Pat. No. 3,153,002) and is supplied by Pittsburgh Plate Glass Co. manufactured.

2. The silicone surfactant (DC-193) contains polysiloxane Palyoxyalkylen-Bloekraisehpolymerisate, such as the 2 ^ 83 748 and 3917 ¹ JSO described in the UEs Patents, and is manufactured by the Dow-Corning Co..

3. This ethylene diisocyanate sold under the name Hylene TIC technical quality is guaranteed by E.I. du Pont DeNemours and Co. manufactured.

The precursor and selected catalysts are subjected to a standard hand mix process for one-shofc production of a rigid foam. During the manufacture of the stirring time (cream time), the gel time to be _9, the rise time and the time elapsed until obtaining a non-adhesive product were determined. The following Table III gives the amounts of the compounds used in the runs and the times achieved in forming the rigid foams. The compositions of Examples 5 and 8 have a molar ratio of the quaternary compound to diethylethanolamine of 50-50 or contain about 67 or 73 weight units.

Comparative Examples 2-3

The comparative values given in Table II below serve as a comparison between those with the invention Compositions and those with two commercially available standard catalysts results obtained in the polymerization. The same precursors are used in the comparative approaches ttJid seam formation method applied as in Examples 5 to 6 described.

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Table III

Quaternary hydroxy alky lainmoniuimne thy lat or phenolate as polyurethane catalysts

catalyst Results, seconds

■ τ »Comparative example 2A

oo Comparative Example 2B cn

^. Comparative - »Example 3A

C ₀ comparative

example 3B Example 5A Example 5B Example 6A

Triethylenediamine (DABCO R-8020)

Triethylenediamine (DABCO R-8020)

Dimethylethanolamine

Dimethylethanolamine

N, N-dimethyl-N-hydroxyäthy1-N, 2-hydroxypropylammoniummethylat

N, N-Dimethy1-N-hydroxyäthy1-N, 2-hydroxypropylammoniummethylat

N, N-dimethyl-N-hydroxyethyl-N, 2-hydroxypropylammonium phenolate

meq / g
quart. meq / g
tert. lot Stir
Time gel
Time Climb
Time Time to receive
one non-sticky
Product - - 0.8 15th 45 115 100 - - 1.0 13th 40 110 73 - - 0.8 20th 58 195 170 - 1.0 17th 47 165 140 4 95 ' 2.52 0.8 22nd 53 265 245

4.95 2.52 1.0 17 42 220

3.30 2.81 0.8 15 37 170

195

150

Portion Table III

Quaternary hydroxyalkylammonium methylate or phenolate as polyurethane catalysts

catalyst Results _s seconds

meq / g meq / g amount * stir gel rise time to obtain
quart, tert. time time time of a non-sticky product

CO CT)

Example 6B

Ν, Ν-Dimethyl-N-hydroxyethyl-N, 2-hydroxypropylammonium phenolate

32

150

Parts of the catalyst per 100 parts of polyol

In addition to the fact that the compounds of the invention or compositions are very effective for the production of polyurethane foams and polyurethane-polyisocyanurate foams, are they for certain of the ones currently in commercial use Polyols are more compatible than the catalysts containing a heterocyclic radical, such as those described in US Pat. No. 3,010,963.

Other well-known polyurethane catalysts can also be incorporated into the compounds or compositions according to the invention be, whereby one obtains a catalyst system that for the polymerization of certain precursors to the desired Foam type is particularly well adapted.

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Claims (8)

Claims 1. Hydroxyalkyl quaternary aramonium alkylates and common formula - CH ₂ - C - OH
R. 0R _c in the R, R ₁ and Rp independently of one another are alkyl groups or hydroxyalkyl groups with 1 to 4 carbon atoms, aryl groups or aralkyl groups with 6 to 10 carbon atoms or optionally substituted cycloalkyl groups with 3 to 10 carbon atoms, R, and Rh independently of one another are hydrogen atoms, alkyl groups with 1 to 12 carbon atoms or aryl groups or aralkyl groups with 6 to 18 carbon atoms and Rc is an alkyl group with 1 to 2 carbon atoms or an aryl group or an aralkyl group with 6 to 10 carbon atoms
mean. 2. N.N-Dimethyl-N-hydroxyethyl-N ^ -hydroxypropylammonium methylate. 3. Ν, Ν-dimethyl-N-hydroxyethyl-N, 2-hydroxypropylammonium phenolate. 4. Process for the preparation of the compounds according to claim 1, characterized in that one is a tertiary amine of the general formula -N ι 409885/1365 in the R, R. and R _{2 have} the meanings given in claim 1, in the absence of a solvent with an alkylene oxide of the general formula R, - C CH ₀ in the FL · and Ru have the meanings given in claim l and a carbinol of the general formula R ₅ OH in the R _{5 has} the meanings given in claim 1, at a temperature in the range from 0 to about 100 ⁰ C. 5. The method according to claim 4, characterized in that the tertiary amine is dimethylethanolamine used. 6. The method according to claim 5, characterized in that that propylene oxide is used as the alkylene oxide. 7. The method according to claim 6, characterized in that that methanol is used as the carbinol. 8. The method according to claim 6, characterized in that that phenol is used as the carbinol. 409885/1365