JPS5946938B2 - Method for producing quaternary hydroxyalkylammonium alkoxide and phenoxide - Google Patents

Description

[Detailed description of the invention] The present invention relates to a method for producing novel compounds.

More specifically, the present invention relates to a method for producing quaternary hydroxyalkylammonium alkoxides and phenoxides. Quaternary hydroxyalkylammonium hydroxides, such as dimethyl-bis[β-oxy-ethyl]-ammonium hydroxide also known as N,N-
Dimethyl-N,N-dihydroxyethylammonium hydroxide is available from Beilst
ein) Organic Chemistry
, Volume Ⅰ (Eng. 922), Volume 284.

Processes for the preparation of such quaternary ammonium hydroxides are also disclosed in the prior art and involve reacting an alkylene oxide with a tertiary amine in an aqueous medium having a pH of 8 to 9. Method for producing quaternary hydroxyalkyl tertiary heterocyclic ami7 base and the formula (by reacting alkylene oxide with diazabicyclooctane and water)
However, in the formula, R is hydrogen or an alkyl group having 1 to 10 carbon atoms.

) has also been disclosed.

In the prior art, reactions to make quaternary ammonium compounds use water as a coreactant (CO-Reactant), and water is usually present in excess.

These reactions are in contrast to the synthetic reactions that produce the compositions of the present invention, which are conducted in the absence of water or other solvents and use carbinol as a co-reactant. According to the present invention, the structural formula: where R and R1 are lower alkyl, R2 is hydroxy lower alkyl, R3 is hydrogen, R4 is hydrogen or lower alkyl, and R5 has 1 carbon atom. to 2 alkyl or enyl.

), a quaternary N,N-dilower alkyl-N-hydroxy lower alkyl-N-(2-hydroxy) lower alkylammonium alkoxide or phenoxide is provided.

The compounds of this invention are particularly useful in processes for making polyurethane and polyurethane-polyisocyanurate foams.

That is, this compound is used as a catalyst and combined with precursors consisting of a polyol, a polyisocyanate, a blowing agent and a foam stabilizer in a suitable mixing tube to form a foamed plastic in a manner well known in the art. The compounds of the present invention can also be used as epoxide polymerization catalysts, and can also be used in the production of polyols from diols or triols and alkylene oxides. It can also be used as a catalyst in the production of phenolic resins and other applications requiring basic catalysts. Quaternary hydroxyalkylammonium alkoxides and phenoxides are prepared by adding stoichiometric amounts of tertiary amines, alkylene oxides, and carbinols at controlled temperatures ranging from 0 to about 100°C, preferably from 100 to 40°C. Synthesized by reaction.

The tertiary amine, preferably used in excess in making the compounds of the present invention, has the formula where R, Rl and R2 are as defined above.

Specific examples of these tertiary amines include triethanolamine, methyldiemenolamine, ethyldiethanolamine, dimethylethanolamine, butyldiethanolamine, octadecyldiethanolamine, cyclohexyldiethanolamine, benzyldiethanolamine, benzylmethylethanolamine, diethylethanolamine, diethyldiethanolamine, Includes cyclohexynolamine, methyloctadecylethanolamine, and methyloctacenylethanolamine.

Alkylene oxide has the formula 1ν4 (However, in the formula, R3 and R are the same as V above.)

). Examples of alkylene oxides particularly suitable for the synthesis of the compounds of the invention include propylene oxide, ethylene oxide, 1,2-butylene oxide, 1,
Included are 2-benzene oxide, styrene oxide, diene alpha dioxide, such as butadiene epoxide, and mixtures thereof.

Carbinol has the formula R5OH (However, in the formula, R5 is the same as above f)).

selected from those with

Examples include methanol, benzyl alcohol, furfuryl alcohol, phenols, resorcinols, substituted phenols such as bisphenol A, etc., forming the methoxide, benzoxide, furfuryl oxide, phenoxide congeners of the compositions of the invention.

The synthetic reaction for producing the compound of the present invention is carried out using the following formula (in the above formula, R, Rl, R2, R3, R4 and R5
is as above.

) can be expressed as

The compounds of the present invention are preferably obtained by reaction with an excess of tertiary amine and contain tertiary amine in the range of about 30 to 50 mole percent.

Since the molecular weight of the quaternary hydroxyalkylammonium alkoxide or phenoxide is much greater than the molecular weight of the tertiary amine, it is
The weight percent of grade amine is less than 50, typically 1
It ranges from 0 to 40 weight percent. The following examples illustrate methods of making compounds of the invention and their use in polymerizations.

Examples 1 and 2 These examples illustrate the preparation of quaternary hydroxyalkylammonium alkoxide or phenoxide catalysts of the present invention.

A round bottom flask equipped with a stirrer, thermometer, reflux condenser, and funnel was charged with 1 mole of dimethylethanolamine (DMEA) and any % mole of carbinol listed in Table 1 below. 1/at such a rate that the reaction temperature does not exceed 50°C.
The mixture was stirred while adding 2 moles of propylene oxide. After the addition of propylene oxide was complete, the mixture was stirred for an additional 2 hours before the quaternary and tertiary amine content was analyzed by nuclear magnetic resonance (NMR) and titration analysis. Table 1 below shows the compounds obtained and their titration analysis. All of the products in Table 1 contained 50 mole percent unreacted DMEA. The NMR spectrum of the product in Table 1 showed two resonance signals for two different methyl groups. That is, one is at 2,2 ppm relative to tertiary N-methyl protons, and the other is at 3,3 ppm relative to quaternary N-methyl protons.
It was pm. Reference Example 3 This example illustrates the production of isocyanurate with the quaternary hydroxyalkylammonium methoxide compound of Example 1.

In an 8 oz (2279) glass shear, 15 parts toluene, 5 parts phenyl isocyanate, and 1 part compound of Example 1 were mixed. The reactants were mixed well and left at room temperature for 2 days. did.

The solid precipitate that formed during this time was filtered off and washed with a small amount of a solvent such as 50 volume percent acetone and 50 volume percent toluene. Then, the washed precipitate was heated to 60°C.
It was dried for 1 hour in a vacuum dryer. The table below shows the melting points of the triphenyl isocyanurate products produced and the % yield of theory of the products obtained. Control Example 1 The control example shown in the table below should be used as a basis for comparing isocyanurate products obtained with the compounds of the invention with products obtained using commercially available polyurethane catalysts.

This control experiment was performed using the same method used in Example 3. The melting points of the products obtained with the isocyanurate product control example catalyst and the compound of the present invention are described in the literature [B, D, Beitchm
an), Industrial and Engineering Chemistry, Product Research and Development (Industrial) DEng
neeringChemistryPrOductRe
Melting point 282A-2 for the triphenyl isocyanurate product reported in 1966, Vol. 5, pp. 35-41
It can compete with 84.9 nu.

Reference Example 4 Using the same method as shown in Example 3, 8 ounces (227 g
), 5 parts phenyl isocyanate, 15 parts toluene, and the catalyst of Example 2, namely N,N-dimethyl-N-
Hydroxyethyl-N,2-hydroxypropylammonium phenoxide 50 mol% and DMEA 50 mol%
0.4 parts were added.

When the reaction was stirred, it generated a significant exotherm and immediately formed a precipitate. The precipitate was filtered off, washed with toluene and dried in a vacuum oven at 50° C. for 1 hour. The resulting triphenyl isocyanurate product had a melting point of 284-285°C.
The infrared spectrum showed characteristic bands of isocyanate at 5.8μ and 7.06μ. Reference Examples 5 and 6 Rigid polyurethane foams were made using the compounds of the present invention.

Each sample of foam was made using a precursor material with the following composition. (1) SelectrO
fOam) 6406 (trademark) is a mixture of a polypropylene oxa 4-dopropanol derivative of sucrose and an alkylene oxide derivative of ethylenediamine having a molecular weight of about 800 (see U.S. Pat. No. 3,153,002);
Pittsburgh Plate Glass Co.
Manufactured by plateGlass CO, ).

(2) DC-193 surfactant is disclosed in U.S. Patent No. 2834
No. 748 and No. 3,917,480, manufactured by DOw-GO Corning Co., Ltd.
Manufactured by CO).

(3) Hylene TIC (trademark) is a technical grade toluene diisocyanate (TDI) manufactured by E,I,duPOntDe (NemOur
manufactured by sandCO).

The precursors and selected catalysts were subjected to standard hand mixing procedures used in rigid foam one-shot procedures. Measurements were taken on creaming time, gelling time, swelling time and non-sticking time. The table below shows the amount of compound used in each experiment and the time required to produce the rigid foam. The compositions of Examples 5 and 6 had a molar ratio of the respective quaternary compound to DMEA of 50:
50 or about 67 and 73% by weight respectively. Control Examples 2-3 The control examples shown in the table below should be used as a basis for comparing the polymerization results obtained with the compounds of the invention and the results of two commercially available standard catalysts. .

Control experiments used the same precursors and foam manufacturing methods as Examples 5-6. In addition to being highly active in the production of polyurethanes and polyurethane-polyisocyanurate foams, the compounds of the present invention are catalysts containing heterocyclic components such as those described in Erner, U.S. Pat. No. 3,010,963. Therefore, it is more easily compatible with the polyols used commercially today.

Other well-known polyurethane catalysts are added to the compounds of this invention to create a catalyst system that polymerizes the specific precursor into the desired type of foam.

The embodiments of the present application will be described below.

The method according to the claims, wherein the tertiary amine is dimethylethanolamine.

(c) The method according to item 1 above, wherein the alkylene oxide is propylene oxide.

3. The method according to item 2 above, wherein the carbinonol is methanol.

4. The method according to item 2 above, wherein the carbinol is phenol.

Claims (1)

[Claims] 1 Structural formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, R and R_1 are lower alkyl, and R_2
is hydroxylower alkyl, R_3 is hydrogen, R_4 is hydrogen or lower alkyl, and R_5 is alkyl having 1 to 2 carbon atoms or phenyl. ) in the method for producing a quaternary N,N-dilower alkyl-N-hydroxy lower alkyl-N-(2-hydroxy) lower alkylammonium alkoxide or phenoxide having the formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, R, R_1 and R_2 are as defined above.) A tertiary amine having the formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, , R_3 and R_4 are as defined above.) and a lower alkylene oxide having the formula: R_5
A method comprising reacting a carbinol with OH (wherein R_5 is as defined above) at from 0<0>C to about 100<0>C.