JPH0322860B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to monotertiary alkyl derivatives of toluenediamine. Alkylated diamines have been known for a considerable time and are used in the production of polyurethane elastomers. These diamines are typically used in that form as chain extenders for polyurethanes, ie, to create short chain urea linkages to strengthen elastomers. As is known, this alkyl group changes the reactivity of the amine and therefore gives the composition unique processing properties for producing polyurethane elastomers. A second use of these alkylated diamine products is found in the production of diisocyanates which are also suitable for the synthesis of polyurethane elastomers. They can also be used as plasticizers or as intermediates in the production of pesticides and alkyd resin modifiers. Two types of synthetic methods have been used to produce alkylated aromatic amines, such as alkylated toluene diamines. One of the earliest methods used for the production of alkylated aromatic diamines involved the Friedel-Crafts alkylation of aromatic hydrocarbons, followed by dinitration of the alkylated aromatic hydrocarbons and then the amines of the nitro groups. Reduction to radicals was used. This diamine could be converted to a diisocyanate by reaction with phosgene. Another method of making alkylated aromatic amines involved nitration of an aromatic hydrocarbon, followed by reduction to an amine and alkylation of the amine. Representative patents describing various alkyl aromatic diamines and their derivatives are: US Pat. No. 2,963,504 discloses 2,6-diisocyanate-4-tert-butyltoluene compositions made from 2,6-diamino-4-tert-butyltoluene derivatives. No synthesis method is given. However, from the disclosed isomeric structure, the product was prepared by alkylating toluene and dinitration of the alkylated product, followed by reduction of the nitro group to the amine. Rec.Tray.Pays- Bas . 2-Amino- by nitration and subsequent reduction of tert-butyltoluene
A method for making 3,5-di-tert-butyltoluene and 2,6-diamino-3,5-di-tert-butyltoluene is shown. US Pat. No. 2,706,735 discloses 5-tert-butyl isophthalonitrile. This derivative was prepared by reacting 5-tert-butyl isophthalic acid with ammonia over activated alumina at elevated temperatures. US Pat. No. 3,991,023 discloses aromatic ester amine derivatives of benzoic acid and their alkylated derivatives. US Pat. No. 4,365,051 discloses alkyl aromatic amine benzonitriles and alkyl aromatic amine benzoates as chain extenders for the production of polyurethanes. US Pat. No. 3,794,621 discloses aromatic amine esters as chain extenders for polyurethanes. In all the above aromatic amines, the alkyl group is the same whether the other organic group is a methyl group, as in the case of toluene, or an ester or nitrile group, as in the case of aromatic esters or aromatic nitriles. It is in the para position to the organic group. It is noted that these products are suitable for use in isocyanate and polyurethane production. As opposed to being in the para position to the amine,
A number of aromatic amines having an alkyl group ortho to the amine have also been used for the production of polyurethane resins. In some cases, these amines were either monoalkyl or dialkyl derivatives of amines in which the alkyl group has 2 to 3 carbon atoms. This method recognizes that these alkyl groups dramatically alter the reactivity of the aromatic amine. For example, o-alkylated diethyltoluenediamine is desirable for use in a urethane molding process called RIM (reaction injection molding). U.S. Pat. Nos. 3,428,610 and 4,218,543 disclose the use of alkylated toluenediamines in the production of polyurethane resins,
The latter patent specification shows its use in a RIM manufacturing process. The alkylated diamine has 1-
Methyl-3,5-diethylphenylene-2,4-
Diamines and 1,3,5-trimethylphenylene-2,4-diamines are included. Diethyl toluenediamine derivatives are diethyl TDA or
It is called DETDA and is probably the most widely used alkylated derivative of toluenediamine for RIM production. Although there are many patent specifications disclosing a wide variety of alkylated aromatic amines, only a few of these amines have been synthesized. Some examples of alkylated aromatic amines can be found in the following patent specifications: U.S. Pat. No. 2,762,845 discloses 2,6-diethylaniline, isopropylaniline, ethyltoluidine and diethyl-m-toluidine. British Patent No. 846226 describes o- and p-
Both tert-butylanilines are disclosed,
U.S. Pat. No. 3,275,690 describes isopropylaniline and diisopropylaniline, monotertiary
Butylaniline and di-tert-butylaniline, ethylaniline and dimethyldiethylaniline are disclosed. West German Patent No. 1051271 discloses monoisopropylaniline, diisopropylaniline and triisopropylaniline, and U.S. Pat. No. 3,222,401 discloses cycloalkyl derivatives of aniline, such as o-cyclooctylaniline, o-( Dimethylcyclohexyl)aniline and p-(dimethylcyclohexyl)aniline and o-methylcyclopentylaniline and p-methylcyclopentylaniline are disclosed. U.S. Pat. No. 4,440,952 describes 1-methyl-
The synthesis of 2,4-diamino-5-isopropylbenzene and 1-methyl-2,6-diamino-3-isopropylbenzene and the use of the 2,6-isomer as a chain extender for polyurethane formulations are demonstrated. There is. European Patent No. 0 069 286 discloses various alkyl-substituted phenylene diamines as chain extenders for the production of polyurethanes by reaction injection molding. Some of these compositions suggested to be suitable for such use include 1,3-dimethyl-5-tert-butyl-2,6-diaminobenzene, 2-methyl-4,6-di-tert-butyl -1,3
-diaminobenzene, 1,3-dimethyl-5-tertiary amyl-2,4-diaminobenzene. European Patent No. 0107108 discloses the synthesis of C _1-4 alkylated vic-toluenediamines and their use as extenders for the production of polyurethane-polymer elastomers. The examples show ethylated vic-toluenediamine. U.S. Pat. No. 2,737,536 discloses the production of various tertiary hydrocarbons by reacting aromatic hydrocarbons with paraffinic hydrocarbons having tertiary carbon atoms in their structure in the presence of an olefinic hydrocarbon and an acidic alkylation catalyst. The production of alkyl-substituted aromatic hydrocarbons is disclosed. Mono- and polyhydroxybenzenes, mono- and polyaminobenzenes, hydroxyaromatic acids, aminophenols and many others are paraffins such as methylbutane, methylpentane and dimethylpentane and methylcyclopentane and cyclo It was suggested that it could be alkylated with alkanes. Suitable catalysts for alkylation include acids such as hydrochloric acid. Although a variety of alkylated aromatic diamine derivatives have been synthesized, such as diethyl TDA,
Such amines still present some problems to manufacturers in terms of flexibility, handling and formulation. For example, the reactivity of diethyl TDA is too great to facilitate the production of large molded parts by the RIM process, such as in the production of various types of automobile grilles. They are also too reactive for the production of cast elastomers. A second problem associated with alkylated aromatic diamines is that they are suspected carcinogens, which poses problems for their handling. This problem is similar to the case of aromatic amines with halogen atoms incorporated into the aromatic amine composition to retard the activity of the amine in that such techniques were unable to alter the mutagenic properties of the amine. Similar. The present invention relates to monotertiary alkyltoluenediamines and derivatives having a well-defined isomeric structure. In contrast to compositions according to the prior art, this tertiary alkyl group is ortho to the amine group and the alkyl group contains a tertiary carbon atom. These are the following formulas

【formula】

【formula】

[Formula] [In the formula, R ₁ , R ₂ and R ₃ are C _1-3 alkyl groups, or R ₂ and R ₃ are combined
C forming a _5-6 membered ring]. There are several advantages associated with the distinctly isomeric compounds of the present invention. One point is that mono-tertiary alkylated-2,6-toluenediamine is diethyl
It has a slower reactivity than TDA, thus making the isomer mixture more acceptable for RIM urethane production in a variety of large automotive parts. Another advantage is that the 2,6-isomer can be used in cast elastomers. Third, the mono-tert-butyltoluenediamine isomer showed no mutagenic activity in the Ames test. Fourth, monotertiary alkyltoluenediamine derivatives when used as chain extenders impart very good mechanical properties to the resulting polyurethane elastomers. Fifth, mono-tertiary alkylated toluene diamines can be converted to isocyanates to impart unique properties to polyurethane resins and sixth, about 80% of the 2,4-isomer and 20
% of the 2,6-isomer, these isomers when blended form a liquid mixture that is liquid at room temperature and is well suited for processing formulations. FIG. 1 is a plot of rheology data for mono-tert-butyltoluenediamine and prior art DETDA expressed as a function of time. FIG. 2 is a plot of prior art and test rheology data for tertiary butyltoluenediamine expressed as a function of time. FIG. 3 is a plot of rheological data for an alkylated 2,6-toluenediamine chain extender expressed as a function of time. FIG. 4 is a plot of rheological data for alkylated 2,4-toluenediamine expressed as a function of time. FIG. 5 is a plot of rheology data for tertiary alkylated 2,6-toluenediamine and non-tertiary alkylated 2,6-toluenediamine expressed as a function of time. As mentioned above, the compound of the present invention has the following formula:

【formula】

【formula】

[Formula] [In the formula, R ₁ , R ₂ and R ₃ are C _1-3 alkyl groups, or R ₂ and R ₃ together are C _5-6
form a member ring]. The main difference between the toluenediamine described herein and that according to the prior art is that the toluenediamine of the present invention is a monoalkyl-substituted toluenediamine derivative containing a tertiary alkyl group in the ortho position to one amino group. and the alkyl group contains a tertiary carbon atom, such as a tertiary butyl group. As shown, these toluenediamines are 2,4-diamino, 2,6-diamino or 2,3 or 3,4-vic toluenediamine derivatives. The methyl group is present in the 1 position. The compounds of the present invention are synthesized by alkylation of toluenediamine compounds as opposed to the technique of alkylating aromatic hydrocarbons, such as toluene, followed by amination via nitration. It is because the alkylation is carried out on toluenediamine that a monoalkyl group having a tertiary carbon atom is obtained in the position ortho to the amino group in the aromatic composition. If the alkylation is carried out first on aromatic hydrocarbons as opposed to toluene diamines, the alkyl group is introduced in the para position to the methyl group (meta to the amine). However, at least 2
Only in the case of European Patent No. 69286, where alkyl (methyl) groups are present, it is possible to obtain compositions with an alkyl group in the position ortho to the amino group. On the other hand, the alkyl group in toluenediamine is ortho oriented, so the monoalkyl group is ortho to the amino group. Although much of the prior art for the production of alkylated aromatic diamines uses homogeneous catalyst systems, such as aluminum-based catalysts, such techniques
-Methyl-5-tertiary alkylphenylene-2,4
-diamine or 1-methyl-3-tertiary alkylphenylene-2,6-diamine production. Perhaps many homogeneous catalyst systems do not have sufficient acidity or reactivity to allow the introduction of tertiary alkyl groups on the aromatic ring. The present technique uses heterogeneous catalyst systems to carry out the alkylation of aromatic amines, examples of which include silica-alumina, montmorillonite, crystalline molecular sieves, and zeolites. I can do it. Among these, crystalline zeolite and crystalline molecular sieve have the desired acidity and monotertiary
It appears to offer advantages in that it can provide selective production of alkyltoluenediamine products. Crystalline zeolites are well known and are basically alumino-silicates in which the molar ratio of silica to alumina is very high, for example 3:1 or more. Such zeolites can be substituted with various cations to alter their acidity and thus their activity with respect to achieving alkylation of toluenediamine. These cations can also change the effective pore size of zeolites and thus their catalytic activity. Two common types of zeolites are X zeolite and Y zeolite, with Y zeolite characteristically having a higher silica content. Typically, Y zeolites have a silica to alumina molar ratio of about 3:1. × zeolites and Y zeolites are common examples of zeolites suitable for the practice of this invention, but others may include, for example, the hawkiasite, offretite, chabazite, KL omega, and ZSM series. Y zeolite or haujasite is preferred because the silica to alumina ratio and pore arrangement are well suited for the production of many mono-tertiary alkyltoluenediamine products. This is particularly true for the reaction of isobutylene with toluenediamine to produce mono-tert-butyltoluenediamine. As noted, the acidity of zeolites can be adjusted by substituting various cations for the sodium atoms in synthetic or natural zeolites. Examples of preferred cations suitable for the catalyst system include, for example, rare earth metals such as lanthanum, cerium, praseodymium and various transition metals and hydrogen. Zeolites exchanged with basic metals make the resulting zeolite slightly acidic, but fairly inert. Alkali metals particularly reduce the reactivity of exchanged zeolites.
For this purpose, weakly acidic zeolites, i.e. hydrogen,
Those with rare earth metal exchange or those with a high silica to alumina ratio are preferred. Zeolite pore size affects the reactivity and type of product produced. They can be made either larger or smaller by various known means. For example, it is known that pore size can be reduced by chemical adjustment, such as boron and phosphorus oxide addition or coke formation. Thus, it is possible to synthesize products with large molecular sizes in many zeolite systems from the unchanged zeolite by increasing the effective pore size of the zeolite. The primary method of increasing pore size is by removing alumina from the catalyst structure. Some of the main techniques for alumina removal include hydrothermal treatment (steaming) and acid cleaning. That is, a zeolite that may have insufficient pore size to admit molecules for reaction can be expanded to have an effective pore size to accommodate the entrance of such molecules. Alternatively, the effective pore size of the zeolite may be increased by the introduction of large metal cations if the pore size is too large, e.g., significant amounts of di-tertiary alkylated toluenediamine product are produced. can be reduced. However, the preferred method is to select zeolites with smaller effective pore sizes to limit the synthesis of products with larger molecular sizes. Mono-tertiary alkyltoluene diamines are produced by reacting olefins with toluene diamines in the presence of the aforementioned acidic acid catalysts. Third
Examples of olefins for producing toluenediamine derivatives having carbon atoms include isobutylene, isoamylene, 2-ethyl-1-pentene,
Mention may be made of 2-ethyl-2-pentene, 2-methyl-1-pentene, 2-methyl-2-pentene, isooctene and 1-methylcyclohexhine. The relationship between the branch and the olefin must be such that the tertiary carbon is available for alkylation. Thus R ₁ , R ₂ and R ₃ can have 1 to 3 carbon atoms, or R ₂ and R ₃ together can form a 5- to 6-membered ring. 2,4-toluenediamine to 2,6-toluenediamine and 2,3 to 3,4-vic-
Ring alkylation of toluenediamine is carried out by reacting toluenediamine with an olefin or olefin precursor (eg, a tertiary alkanol). When olefins are produced from olefin precursors, such as alcohols, such olefins are believed to be produced in the reaction system by dehydration of the alcohol. Water, typically one by-product from such reactions, tends to deactivate the catalyst system and temperature adjustments may be required. Typically, when the 1,1-disubstituted olefin is used for the alkylation reaction, the temperature is about
100-250℃, preferably 160-200℃ and the pressure is about 15-2000psig, preferably 100-200℃
It is 1000 psig. Variations in pressure and temperature within the above ranges are commonly used to optimize selectivity and conversion to the desired product. The molar ratio of olefin to toluene diamine used in this reaction is about 1 to 10:1, and the reaction time is generally about 2
~48 hours. When using a fixed bed catalytic reactor, the feed to the reactor expressed as LHSV is approximately
0.05 to 6 hours ^-1 . Alkylated amines can be used in formulations such as 2,
The 4- and 2,6-isomers may be used on their own as a mixture, or these isomers may be used in combination with other aromatic and alkylated diamines. 2, which is about 65-80% 2,4-isomer, 20-35% 2,6-isomer and optionally 0-5% vic-isomer by weight;
Mixtures of 4- and 2,6-isomers are attractive for a number of reasons. One reason is that commercially available toluenediamine feedstocks typically contain about 80% 2,4-isomer and 20% after vic-toluenediamine separation.
% of the 2,6-isomer. The commercial route to another toluenediamine is about 65%
yielding an isomer ratio of 2,4-isomer and 35% 2,6-isomer. Mixtures can be alkylated in the same manner as individual isomers. A second reason is that isomer mixtures of 65 to 80% by weight of 2,4-isomers and 20 to 35% of 2,6-isomers are advantageous for RIM production. It is believed that a small amount of the 2,6-isomer extends the reaction time sufficiently to allow the molding of larger and more complex or intricate parts than if only the 2,4-isomer were used. This is because it makes you Additionally, the 80/20 mixture described above is a liquid that provides greater flexibility in handling urethane formulations. Examples are provided below to illustrate embodiments of the present invention for synthesizing alkylated aromatic amines and the properties of these alkylated amines in the production of polyurethane resins. Example 1 Synthesis of 3-t-butyl-2,6-toluenediamine This synthesis of ortho-t-butyltoluenediamine (hereinafter abbreviated as t-butyl TDA) was carried out in a 1-gallon tank equipped with a mechanical stirrer. A pressurized stainless steel reactor was used. The reactor was charged with 150 g of a powdered commercially available silica-alumina catalyst containing 13% alumina and 1500 g (12.24 moles) of 2,6-toluenediamine. The autoclave was sealed and purged with nitrogen. A residual nitrogen blanket was left in the autoclave and the pressure was 16 psig. The contents of the reactor were heated to 200° C. with constant stirring. Then, isobutylene is fed into the reactor and heated to 870% over 30 minutes.
g or 15.5 moles and the initial reaction force is 970 psig.
It became. This gave a molar ratio of isobutylene to toluenediamine of 1.26:1. The reaction mixture was kept at a temperature of 200° C. for about 4.5 hours with constant stirring. After 45 hours, the contents of the reactor were cooled to approximately 150°C and
Stirring was stopped. The reactor was opened and the contents were discharged from the reactor. The catalyst was removed from the reaction mixture by filtration. The reaction product was analyzed by gas chromatography, and the following analysis results were obtained. Mol% 2,6-toluenediamine 43.34 2-(t-butylamino)-6-aminotoluene
3.30 3-t-butyl-2,6-toluenediamine
42.36 3,5-di-t-butyl-2,6-toluenediamine 8.6 2-(t-butylamino)-5-t-butyl-6
-Aminotoluene 1.82 Both mono- and di-tert-butyltoluenediamine products were being produced. Example 2 Synthesis of 5-t-butyl-2,4-toluenediamine A 300 c.c. Hastalloy C pressure reactor equipped with a mechanical stirrer was used for the production of t-butyltoluenediamine. Approximately 100 g (0.819 mol) of 2,4-toluenediamine is charged to the reactor, and 5 g of 36% aqueous hydrochloric acid are added at the same time. The reactor was sealed and purged with nitrogen gas. A nitrogen blanket of 33 psig was applied. The contents of the reactor were then heated to 180° C. with continuous stirring. Isobutylene was fed into the reactor and 53.4 g (0.96 mole) was added over 15 minutes. Upon addition of isobutylene, the pressure within the reactor increased to 766 psig. Then the reaction mixture,
It was kept at 180°C for 24 hours with constant stirring. The pressure was then reduced to 524 psig. Contents at 160℃
and stirring was stopped. The reaction vessel was then opened and the reaction products were analyzed. Its composition is as follows. Mol% 2,4-toluenediamine 50.70 2-(t-butylamino)-4-aminotoluene
1.84 2-amino-4-(t-butylamino)toluene 12.71 5-t-butyl-2,4-toluenediamine
26.71 2,4-di(t-butylamino)toluene 1.31 2-(t-butylamino)-5-t-butyl-4
-Aminotoluene 5.28 2-Amino-5-t-butyl-4-(t-butylamino)toluene 1.45 Example 3 The procedure of Example 1 was followed, using 15 g of powdered montmorillonite clay instead of the silica-alumina catalyst and T-butyltoluenediamine was prepared using 150 g (1.23 moles) of the 2,4-toluenediamine isomer as opposed to the 2,6-toluenediamine isomer. The reaction contents were purged with nitrogen as in Example 1 and the contents were heated to 180 °C with stirring.
heated to ℃. Then add about 278 g to the reaction mixture.
(4.95 mol) of isobutylene was added over 20 minutes.
Initial reaction pressure increases to 1210 psig and the contents to 180 psig
It was maintained at ℃ for 23 hours. At this point, heat the contents to 150℃.
and the reactor was opened. The catalyst was then recovered by heating. The reaction product was analyzed and contained the following: Mol% 2,4-toluenediamine 57.82 2-(t-butylamino)-4-aminotoluene
5.49 2-amino-4-(t-butylamino)toluene 18.27 5-t-butyl-2,4-toluenediamine
16.85 2,4-di(t-butylamino)toluene 0.42 2-(t-butylamino)-5-t-butyl-4
-Aminotoluene 0.47 2-Amino-5-t-butyl-4-(t-butylamino)toluene 0.27 Example 4 2,4- and 2,6-isomers of toluenediamine on H-Y zeolite of
Alkylation of an 80:20 mixture with isobutylene 15.0 g of H-Y zeolite (powder), 120.0 g (0.98 mol) of 2,4 in a 1000 c.c. Hastalloy C pressure reactor equipped with a mechanical stirrer. −
Toluenediamine and 30.0 g (0.25 moles) of 2,6-toluenediamine were charged. The reactor was sealed and purged with nitrogen gas to obtain a 217 psig nitrogen gas blanket. While stirring the contents
Heated to 180°C. Next, isobutylene (280g,
4.98 mol) was added over 15 minutes. An initial reaction pressure of 1271 psig was obtained. The reaction mixture was stirred at constant speed.
It was held at 180°C for 18 hours and then cooled to 150°C. At this point, stirring was stopped and the residual pressure was released. After removing the catalyst by heating, a product mixture was obtained with the following composition: Mol% 2,4-toluenediamine 19.09 2,6-toluenediamine 6.30 2-(t-butylamino)-4-aminotoluene
2.03 2-amino-4-(t-butylamino)toluene 8.11 5-t-butyl-2,4-toluenediamine
48.79 3-t-butyl-2,6-toluenediamine
12.73 2-(t-butylamino)-5-t-butyl-4
-Aminotoluene 1.60 2-Amino-5-t-butyl-4-(t-butylamino)toluene 0.55 2-(t-butylamino)-5-(t-butyl)-
6-Aminotoluene Trace 3,5-di-t-butyl-2,6-toluenediamine 0.81 These results indicate that H-Y zeolite was extremely effective in producing mono-tert-butyltoluenediamine. . Although a small amount of N-butylated toluenediamine was produced, this product is suitable for recycling and conversion to ring alkylated products. However, only a small percentage, for example about 3%,
-butyltoluenediamine products (including ring alkylation and N-alkylation) were produced,
Conversion was approximately 70%. Example 5 Preparation of 5-tert-butyl-2,4-toluenediamine In a 1000 c.c. Hastalloy C pressure reactor equipped with a mechanical stirrer was added 15.0 g of powdered H-Y zeolite and 150.0 g (1.23 mol). of 2,4-toluenediamine was charged. The reactor was sealed and purged with nitrogen gas to obtain a residual 225 psig nitrogen gas blanket. The reactor contents were heated to 180°C while stirring at 500 rpm.
heated to. Next, isobutylene (279.0g,
4.98 mol) was added over 2 hours to obtain a reactor pressure of 1225 psig. This is 4.05 moles isobutylene to 1
The molar ratio of mol toluenediamine was given. The reaction mixture was held at 180° C. for 16 hours with constant stirring. Cool the contents to 150°C and stop stirring,
The residual pressure was released. The catalyst was removed by thermal aging to give the following product mixture. Mol% 2,4-toluenediamine 15.59 2-(t-butylamino)-4-aminotoluene
1.66 2-amino-4-(t-butylamino)toluene 8.02 5-t-butyl-2,4-toluenediamine
71.60 2,4-di(t-butylamino)toluene 0.20 2-(t-butylamino)-5-t-butyl-4
-Aminotoluene 1.38 2-amino-5-t-butyl-4-(t-butylamino)toluene 0.55 Example 6 Production of 3-t-butyl-2,6-toluenediamine 15.0 g of powdered H-Y type zeolite catalyst,
140.0 g (1.15 moles) of 2,6-toluenediamine was charged to a 1000 c.c. Hastalloy pressure reactor with a mechanical stirrer as in Example 2. The reactor was sealed and purged with nitrogen gas to a pressure of 200 spig of residual nitrogen blanket at room temperature.
The contents were heated to 180°C with stirring. When isobutylene (267 g, 4.76 mol) is added to this reaction mixture over 20 minutes, the initial reaction pressure is
It became 1100spig. This had a molar ratio of isobutylene:toluenediamine of 4.1:1. The reaction mixture was kept at 180° C. for 39 hours under constant stirring. The reaction product was isolated by the procedure described in Example 1. The product had the following composition: Mol% 2,6-toluenediamine 30.48 2-(t-butylamino)-6-aminotoluene
9.79 3-tert-butyl-2,6-toluenediamine
56.13 2-(t-butylamino)-5-t-butyl-6
-aminotoluene 1.19 3,5-di-tert-butyl-2,6-toluenediamine 1.28 The results regarding conversion and selectivity were similar to those obtained for the conversion of the 2,4-isomer in Example 5. . Lower amounts of di-tert-butylated product could be produced at slightly lower conversions. The conversion was greater than 70% and the selectivity to the di-t-butyl isomer was less than 4%. Example 7 A series of alkylated products were prepared under various conditions and using various catalyst systems and according to the general procedure outlined in Examples 1-6. These reactions A-L are listed in Table 1. For convenience, the term alkyl has been used to describe the specific alkylation products shown in the product description section of the table.

【table】

[Table] *Analysis was done on samples without olefin.

[Table] *Analysis was done on samples without olefin.

【table】

Table: Example 8 A series of polyurethane-urea elastomers were prepared using various chain extenders and evaluated in a pot-life test system relative to each other to determine the reactivity of the chain extenders in standard urethane formulations. .
Polyurethane-urea elastomers were tested using prepolymers of poly(1,4-oxytetramethylene) glycol end-capped with 2,4-toluene diisocyanate with an NCO content of approximately 5-7%. It was prepared by reacting with chain extenders aromatic diamines and diols. The nominal stoichiometric ratio of isocyanate:diamine chain extender:diol is 2:1:
It is 1. Commercially, the prepolymer is sold by the EIdupont de Nemours Company under the trade name ADIPRENE L-167, and is also available as poly(ε-caprolactone).
The diol is manufactured by Interox
Chemicals Limited) to CAPA 200
It is sold under the following display. Potlife's test system consists of a constant temperature (50°C) heated test chamber capable of holding 7 grams of test sample and equipped with a vertical through-bore piston. This piston moves up and down inside the test sample over time. (The increase in temperature due to exothermic reactions is discounted.) The force required to move the piston inside the polymer sample is measured by an arbitrary unit of measure. Display the interconnectedness of this force as a function of time. This carpot life interaction of the urethane system during curing is then related to the known force-viscosity interaction for urethane-urea systems. Table 2 shows numerical values of the experimental model coefficients, expressed as 10 logarithms of viscosity, as a function of time and triadic force for several chain extenders. The coefficients are given as: log(viscosity) = I + A (time) + B (time) ² + C (time) ³ The first force ("A") coefficient is a "quasi" reaction rate constant that assesses the initial reactivity. “Quasi” rate constant
Smaller values for (A) are longer. and shows desirable pot lives. The value of T-5000 is
It is the time when the reaction product has a relative viscosity of 5000 units. Although this value is arbitrary,
This value is suitable for use in determining the performance of test materials in RIM or cast elastomer processes. For relatively small and simple injection molded parts, T-5000 may be used for about 2.5 minutes, but for larger or more complex molded parts, T-5000 can be used for more than 5 minutes, e.g. 10 to 40 minutes. It would take 5000 hours. Figures 1 and 2 illustrate the results obtained for the test substance t-butyltoluenediamine. These figures are in comparison to other aromatic diamine chain extenders, an 80/20 mixture of tBTDA and di-t-butyltoluenediamine products.
-t-butyltoluenediamine isomer and 2,
Figure 2 shows the relative potency of 6-t-butyltoluenediamine isomers. Figure 1 shows that the pot life line (curve 1) for the 80/20 commercial mixture of 3,5-diethyl-2,4-toluenediamine/3,5-diethyl-2,6-toluenediamine is similar to that for t-butylated toluenediamine. Contrasted with the obtained linearity. 5
2,4-TDA monoalkylated with isobutylene only at the − position (5tB24TDA) (curve 2)
shows reactivity comparable to twice the ethylated TAD mixture. However, mono-t-butylated 2,6-TDA (curve 4) has a lower “A” (term)
(DETDA is 8092 and 5tB24TDA is,
7697, whereas 06721) and T
-5000 values (17.8 minutes versus 2.2 and 2.2 minutes, respectively) indicate a much longer pot life. The position of the substituent on the reacting amine center determines the relative magnitude of the steric reduction. 8 of 5tB24TDA and 3tB26TDA, which are supercooled liquids with a melting point of 38℃
Once the 0/20 mixture (curve 3) crystallizes,
Almost 50% greater than the 80/20 mixture of DETDA,
That is, it has a T-5000 of 3.2 minutes versus 2.2 minutes. This gives greater latitude in RIM processing of large or fine molded parts using tBTDA. FIG. 2 explains the equilibrium between the steric retardation effect and the electron donating effect. Activation by the alkyl group substituent only occurs if the t-butyl group is not in the ortho position to the reacting amine substituent, as in the case for 4-t-butyl-2,6-toluenediamine (curve 5). exists. Thus, a possible chain extender produced by nitration/reduction of pt-butyltoluene is simply 0.5 min T-
5000, has an A-factor of 3.87 and reacts very quickly. 3,5-di-tert-butyl-2, in our polyurethane/urea preparation when 2,6-TDA is alkylated with isobutylene at two ortho positions instead of one. The reactivity of 6-toluenediamine (curve 7) increases rather than decreases with respect to the mono-ot-butylated product. T-5000 is mono-substituted 2,6-TDA at 17.8
min to 11.3 min for the disubstituted product. The steric hindrance blocking around the less reactive amino groups is similar in each case. (−
The NH ₂ group is the −CH ₃ group and the nearest −C
(surrounded by _three CH ₃ ) groups). however,
In the case of 35DtB26TDA, the second −C(CH ₃ ) ₃
The alkylating group provides the extra electron donation that promotes the reaction. This electron activation is t
-Butyl-2,4-diaminobenzene (T-5000
= 10.7 minutes Curve 8) was converted to 5-t-butyl-2,4-diaminometaxylene (5tB24DAmX curve 6) (T
-5000=2.6 minutes). In the case of this substituted xylene, the steric retardation noted for 3-t-butyl-2,6-TDA is due to the amino-reactive activation provided by the addition of the second two methyl ring substituents. It will be canceled out. Figures 3 and 4 graph the data in Table 3.
The figure further explains these ring position substitution effects. In the case of 2,6-toluenediamine, the greater steric bulk of the isopropyl group relative to the ethyl group increases the pot life from 1.13 to 1.63 minutes (curves 9 and 10). Also, a decrease in reactivity is seen when 2,6-TDA is substituted with one alkyl group instead of two, as in the case of 3tB26TDA. 3-isopropyl-2,6-
TDA (curve 11) has a pot life of 2.47 minutes,
Or 3,5-diisopropyl-2,6-
It shows a value about 50% higher than in the case of TDA (curve 10). However, the t-butyl group is much more effective on a percentage basis than the isopropyl group in amine deactivation. Figure 4 details the effect on the 4-amine position with the t-butyl group compared to the orthoalkyl substituent. In curve 14, 5-isopropyltoluenediamine can be considered as the base case for comparison with 3,5-diisopropyl-TDA (curve 16), and in curve 16, the 3-position substituent is less reactive than the 4-position amine. greatly increases the suppression of Therefore, 3,5-diethyl-2,4-TDA (curve
15) is slightly more reactive than the diisopropyl isomer. On the other hand, t at a single 5-position substituent
-butylation, in which the groups are simultaneously 3- and 5-
It can be seen that the deceleration is lower than that of di-substitution at the − position.
3,5-di-t-butyl-2,4-toluenediamine has not been synthesized. This seems to be because the three-dimensional suppression is too large. FIG. 5 illustrates the principles of third carbon generalization in producing the desired chain extender reaction rate. TDA
3-Cyclopentenyl-2,6-TDA (T-5000
= 3.5 min, (curve 18)) is much slower for t-alkyl-substituted 3-methylcyclopentyl-2,6-TDA obtained from the reaction of methylcyclopentene with 2,6-TDA. (T-5000
= 12.2 minutes (curve 20)). Obviously, 2-methyl-1
The steric agglomeration of t-amyl-2,6-toluenediamine (curve 21), produced by reacting either with -butene or 2-methyl-2-butene, is due to the elimination of cyclopentane ring suppression. This still makes the reaction slower. Also illustrating the general idea that t-alkyl groups substantially retard the rate is 5-t
-butyl-3,4-TDA (T=5000=7.2 min, (curve 19)), which is a sufficiently slow reaction rate for elastomer production.

[Table] Example 9 Potlife T-5000 value was 10 minutes or more o
A cast elastomer was prepared from -t-butylated 2,6-toluenediamine. These chain extenders,
MOCA, chlorotoluenediamine, and t-butyl-2,4-benzenediamine were combined with Adiprene-167 using a series of molded test specimens using conventional hand mix techniques. were prepared, their physical properties tested and compared in the table below. More specifically, a conventional toluene diisocyanate end-capped polytetramethylene glycol was degassed under partial vacuum at 90-100°C. The bubbling process was stopped, the prepolymer was weighed and mixed vigorously with the appropriate amount of molten aromatic amine chain extender to obtain the isocyanate index reported in the table. The resulting mixture was poured into an aluminum mold whose 150 x 150 x 1.9 mm cavity was suitably pretreated with a mold release agent. Under pressure from a 30 ton hydraulic press
After curing for 2 hours at 100°C, the specimens were removed from the mold and placed in an air oven at 100°C.
Cure for 22 hours followed by post-curing for 7 days at ambient temperature conditions. 23+/- of samples prior to analytical testing.
At a temperature of -2℃ and a relative temperature of 50+/-5%
I left it for 40 hours. Physical properties were measured according to ASTM method. Hardness (ASTM D2240) and tensile strength (ASTM D1708) measurements are each an average of five measurements, and tear resistance (ASTM D624, dle C) values are an average of three measurements. Table 3 shows the physical properties measured according to the ASTM method for tensile modulus, tensile strength at break, elongation at break, tear resistance, and durometer hardness. More specifically, the tensile strength at a given elongation and breakage is
Tear resistance as per ASTM D1708
D624 (Die C) and durometer hardness are
Measured by ASTM D2240.

[Table] Example 10 Utilization of RIM elastomers Reaction injection molded elastomers were manufactured using the SA 8-20 experimental machine (LIM Kunststoff Technology) suitable for binary mixture processes.
Technologie Gmlh, Kiltsee, Austria). 10 to 30 for component “A” (methylene diphenyl diisocyanate, MDI) and component “B” (polyol, chain extender and catalyst)
cc/min metering pump with variable speed (50-250rpm)
Driven by a motor at the same time on a chain gear which is moved according to the mixture. Any desired mixing ratio can be achieved by means of a variable speed gear. Components A and B are each directed to the mixing chamber by controlled compressed air operated valves. A high speed motor, which can be continuously adjusted from 10000 to 18000 rpm by means of a frequency converter, mixes these components. The pump block and mixing head are movable and propelled automatically by compressed air toward the stationary mold.
A substitutable "O" ring provides a seal between the mixing head and the mold. A series of polyurethane-urea elastomers were prepared from the reaction of commercially prepared liquid methylene diphenyl diisocyanate (MDI) with appropriate molecular weight (1000-3000 equivalents) triols supplemented with aromatic diamines. Table 4 shows the 80/20 isomer mixture of 3,5-diethyl-2,4-toluenediamine/3,5-diethyl-2,6-toluenediamine and the 80/20 5-tert-butyl-2,4 -Toluenediamine/3-tert-butyl-2,6-toluenediamine is reacted with various triols using the same isocyanate, Isonate 181 from Upjohn. For all elastomers,
An attempt was made to maintain an isocyanate index of 1.05, and a mechanical check for unmixed and unreacted A and B components was carried out through the SA 8-20 type sampling port set up for this purpose. Steam temperature was set by controlling the circulation of temperature-controlled water through double-walled A and B reservoirs, and mixing block temperature was achieved by electric resistance heaters. The mold was subjected to isothermal conditions throughout the injection molding operation prior to being placed on the jig through which the mixing head was guided. 200×200×2mm and 200×200× in aluminum mold with each size 26×27×4cm
Each 3 mm cavity was treated with mold release agent before each injection molding. After the injection was completed, while the mold was still open and not loaded, the mixing rotor was cleaned in the reaction system with dioctyl phthalate, flushed with nitrogen, and prepared for the next injection shot. The specimens were cured for 12 hours at 60°C, the mold release agent removed and 2 mm thick specimens placed under appropriate conditions for hardness, tensile and tear testing.
Furthermore, the yield tensile is reported for crosslinked RIM elastomers based on the shape characteristics of InStron stress-strain curves. In addition, bending modulus and maximum stress (ASTM D1708) (5 1″×
Sag (measured on each of the 3" pieces) and thermal stability values (ASTM
D3769) is also shown in the table. Table 4 shows that the tBTDA RIM elastomer has better extensibility (lower stress at the same strain) and higher maximum elongation, but has lower thermal stability than the DETDA RIM elastomer. The contribution of physical properties based on each t-butylated toluenediamine isomer is shown in Table 5. The 0.95 and 1.05 data shown for isocyanate are 3-tert-butyl-
2,6-Toluenediamine is 5-t-butyl-
more thermally unstable than 2,4-toluenediamine,
This indicates that it appears to be contributing more significantly. Also, the tensile strength and maximum % elongation are reduced. This is thought to be due to the fact that 3tB26TDA has poor symmetry between the two isomers.

【table】

【table】

【table】

[Table] Example 11 A series of chain extenders were used in Salmonella 5 in the absence (-) or presence (-) of metabolic activation.
Two strains were used to test in the Ames mutagen assay. Table 6 shows the results of various test compounds, including various known aromatic diamine chain extenders, against these five Salmonella strains. Data represent the amount of test compound in micrograms per test plate that gave a positive (+) mutagenicity result. According to Pharmakon Research International, the Ames Test Data Evaluation Criteria, shown in Table 6, clearly state that ``The majority of tests for Salmonella/granuloma assays have clearly positive results. +) or clearly negative (-). A positive result is described as a reproducible increase in the number of histidine-independent colonies with respect to the dose. This administration Dose-response relationships often require small adjustments to the initial dose in replicate tests; the historical control is within one standard deviation of the historical mean and the test chemical is equal to three times the vehicle control value or A test chemical is considered positive if it produces a greater maximum increase; a negative result is defined as the absence of a reproducible increase in the number of histidine-independent colonies.''

[Table] Aminotoluene

Similar to the evaluations obtained with prior art chain extenders, Table 6 above shows that chlorotoluenediamine and diethyltoluenediamine are Ames positive. Both isomers of mono-tBTDA are Ames negative and therefore offer process advantages to urethane manufacturers. 3,5-di-t-butyl-2,6-diaminotoluene was shown to be Ames positive even though some of the bacteria were unaffected. Because of the low values reported, it appears that the data may be erroneous. Therefore, this data may not actually reflect the inherent properties of 3,5-t-butyl-2,6-diaminotoluene. Ames test data for other t-alkyl-substituted toluenediamines indicate that only one t-alkyl group is present and that the reactivity of t-alkyl-substituted toluenediamine in polyurethane is higher than mono-t-butyl-toluenediamine. It should have a negative Ames value given the close similarity.

[Brief explanation of drawings]

Figure 1 is a plot of rheology data for mono-tert-butyltoluenediamine and prior art DETDA expressed as a function of time;
Figure 3 is a plot of rheological data for prior art and test tertiary-butyltoluenediamine expressed as a function of time; Figure 4 is a plot of rheology data for alkylated 2,4-toluenediamine as a function of time, and Figure 5 is a plot of rheology data for alkylated 2,4-toluenediamine as a function of time. 2 is a plot of rheology data for 2,6-toluenediamine and non-tertiary alkylated 2,6-toluenediamine.

Claims (1)

[Claims] 1 formula [In the formula, R ₁ , R ₂ and R ₃ are C _1-3 alkyl groups, or R ₂ and R ₃ are taken together]
Toluenediamine with an alkyl substituent having one tertiary carbon atom, forming a C _5-6 membered ring. 2. The toluenediamine according to claim 1, which is 2,6-diamino-3-tert-butyltoluene. 3. The toluenediamine according to claim 1, wherein R ₁ is an ethyl group, R ₂ is a methyl group or an ethyl group, and R ₃ is a methyl group. 4. Toluenediamine according to claim 1, wherein R ₁ is a methyl group and R ₂ and R ₃ together form a ring having 5 to 6 carbon atoms. 5 R ₁ is an ethyl group, R ₂ is an ethyl group,
Claim 1 in which R ₃ is a methyl group
Toluenediamine as described in Section. 6. The toluenediamine according to claim 1, wherein R ₂ and R ₃ are taken together to form a 6-membered carbon ring. 7. The toluenediamine according to claim ₁ , wherein R 1 is a methyl group, and R ₂ and R ₃ are a methyl group or an ethyl group. 8. The toluenediamine according to claim 1, wherein R ₂ and R ₃ are taken together to form a 5-membered carbon ring.