阅读说明：本技术 制备具有抗降解剂和抗疲劳功效的化合物和混合物的方法 (Process for preparing compounds and mixtures having antidegradants and antifatigue effects ) 是由 M.A.布恩 D.L.小菲尔兹 F.伊纳茨-胡佛 于 2018-05-17 设计创作，主要内容包括：本发明公开了制备式I的抗降解剂化合物的方法,其中使式IV的对苯二胺与式II的二醇反应以获得包含抗降解剂化合物的混合物。<Image he="103" wi="345" file="592238DEST_PATH_IMAGE001.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image><Image he="55" wi="207" file="236846DEST_PATH_IMAGE002.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image><Image he="103" wi="214" file="693235DEST_PATH_IMAGE003.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(Disclosed is a process for preparing an antidegradant compound of formula I wherein a p-phenylenediamine of formula IV is reacted with a diol of formula II to obtain a mixture comprising the antidegradant compound.)

1. A method of making an antidegradant compound, the method comprising:

reacting p-phenylenediamine with a diol to thereby obtain a mixture comprising an antidegradant compound;

wherein the p-phenylenediamine corresponds to formula IV:

wherein each X is independently selected from the group consisting of alkyl, aryl, alkaryl groups and hydrogen;

the diol corresponds to formula II:

wherein each R is independently selected from (i) a substituted or unsubstituted alkyl group having C =0 to 12 (inclusive), (ii) a substituted or unsubstituted aryl group, and (iii) a substituted and unsubstituted alkaryl group; and

wherein R is¹And R³Each independently selected from alkyl, aryl, alkaryl groups and hydrogen,

the antidegradant compound is according to formula I:

wherein each R is independently selected from (i) a substituted or unsubstituted alkyl group having C =0 to 12 (inclusive), (ii) a substituted or unsubstituted aryl group, and (iii) a substituted and unsubstituted alkaryl group;

wherein each X is independently selected from the group consisting of alkyl, aryl, alkaryl groups and hydrogen;

wherein R is¹And R³Each independently selected from alkyl, aryl, alkaryl groups and hydrogen; and is

Wherein R is¹And R³Optionally bridged by polymethylene groups to form cycloalkyl groups;

wherein when C =0 in R, R¹And R³The same; and is

Wherein when C = 1 in R, R¹And R³Each is hydrogen.

2. The process of claim 1, wherein the step of reacting the p-phenylenediamine with the diol is conducted in the presence of a metal catalyst.

3. The method of claim 2, wherein the metal catalyst comprises one or more of homogeneous and heterogeneous metal catalysts.

4. The method of claim 2, wherein the metal catalyst comprises a catalyst based on ruthenium, iridium, platinum, palladium, tin, iron, Al₂O₃And TiO₂Ligand function of one or more ofA homogeneous catalyst or a solid supported heterogeneous catalyst.

5. The method of claim 1, wherein the para-phenylenediamine comprises 4-amino-para-phenylenediamine.

6. The method of claim 1, wherein the diol comprises one or more of ethylene glycol, propylene glycol, butylene glycol, or 1, 8-octanediol.

7. The method of claim 1, wherein the antidegradant compound comprises N, N' - (octane-1, 8-diyl) bis (N-phenyl-benzene-1, 4-diamine).

8. The method of claim 1, wherein the antidegradant compound comprises N, N' - (ethane-1, 2-diyl) bis (N-phenyl-benzene-1, 4-diamine).

9. The method of claim 1, wherein the antidegradant compound comprises N, N' - (1, 4-phenylenebis (ethane-1, 1-diyl)) bis (N-phenyl-1, 4-diamine).

10. The method of claim 1, wherein the antidegradant compound comprises N, N' - (1, 3-phenylenebis (ethane-1, 1-diyl)) bis (N-phenyl-1, 4-diamine).

11. The method of claim 1, wherein the antidegradant compound comprises (N, N ', N ') -N, N ' - (1, 4-phenylenebis (ethan-1-yl-1-ylidene)) bis (N-phenylphenyl-1, 4-diamine).

12. The method of claim 1, wherein the antidegradant compound comprises (N, N ', N ') -N, N ' - (1, 3-phenylenebis (ethan-1-yl-1-ylidene)) bis (N-phenylphenyl-1, 4-diamine).

Technical Field

The present invention relates generally to a process for preparing compounds and mixtures having antidegradants and antifatigue efficacy useful as additives to vulcanized rubber articles, vulcanizable elastomeric formulations, lubricants, fuels, fuel additives and other compositions requiring such efficacy or in compositions that may themselves be used as compositions to impart such efficacy.

Background

Many materials, such as plastics, elastomers, lubricants, cosmetics, and petroleum products (e.g., hydraulic fluids, oils, fuels, and oil/fuel additives for automotive and aerospace applications) are susceptible to degradation upon prolonged exposure to light, heat, oxygen, ozone, repeated mechanical action, and the like. Thus, compounds and compositions that exhibit efficacy as antidegradants are well known in the art. For example, U.S. patent No. 8,987,515 discloses aromatic polyamines that can be used to inhibit oxidative degradation, particularly in lubricant compositions. U.S. patent application publication No. 2014/0316163 discloses antioxidant macromolecules purportedly having improved solubility in many commercially available oils and lubricants.

Antidegradants that can be used to make articles formed from elastomers, plastics, etc., require very specific combinations of qualities that can be difficult to achieve. While antidegradants must have a significant commercially acceptable efficacy, they must also exhibit this efficacy over long periods of time associated with the use of the article, particularly at the exposed surfaces of the article where degradation by environmental factors such as light, oxygen and ozone occurs primarily. Just as it is important to protect surface exposed components, the efficacy of protecting the embedded components of the composite material from oxidative aging and repeated mechanical action is also of critical importance. Antidegradants must achieve these effects without negatively impacting the efficacy or desirable characteristics of other additives in the final article. Furthermore, antidegradants that provide or improve mechanical fatigue life after an article has been put into service, aged by oxidative aging, or aged by exposure to ozone are highly appreciated, as these antidegradants will inherently improve the useful mechanical service life of the article. Thus, elastomeric articles that undergo repeated mechanical bending, stretching, or compression during use would greatly benefit from this discovery.

Articles, particularly tires, formed from general purpose elastomers such as natural rubber are particularly susceptible to degradation by oxygen and ozone. As discussed in U.S. patent No. 2,905,654, the effect of oxygen degradation on rubber is different from the effect of ozone degradation on rubber; however, both of these effects can be detrimental to tire performance, appearance, and life expectancy. Fatigue and crack growth are also of particular concern, particularly for steel belt edge regions and tire sidewalls that are subject to significant stresses and tensile forces when bent, whether inflated, partially inflated, and over the life of the tire. U.S. patent No. 8,833,417 describes an antioxidant system which is said to increase long term resistance to fatigue and crack growth compared to known antioxidants as discussed immediately below.

Materials having efficacy as antidegradants are well known in the art for tire applications and are commercially available. For example, N, N' -disubstituted-p-phenylenediamines (e.g., Santoflex, tradename, available from Eastman Chemical Company)^®Those sold) are generally favored by many tire manufacturers for this purpose. EP patent application publication No. EP 3147321 a1 discloses a rubber composition, a tire, an amine compound and an anti-aging agent, and particularly a rubber composition purportedly suitable for tread rubber or sidewall rubber of a tire. As government regulations, market demands, and consumer expectations drive the rubber industry toward lighter weight tires to improve fuel efficiency and conserve natural resource feedstocks, there remains a continuing need for improved antidegradants, and methods of making the same, that exhibit (i) multiple efficacy against fatigue, crack growth, and various degradation mechanisms; (ii) increased efficacy, especially at lower concentrations; and (iii) a longer efficacy period when compared to current commercial materials.

Disclosure of Invention

In a first aspect, the present invention relates to compounds represented by formula I:

wherein each R is independently selected from (i) a substituted or unsubstituted alkyl group having C =0 to 12 (inclusive); (ii) substituted or unsubstituted aryl; and (iii) substituted and unsubstituted alkaryl groups; or wherein R is selected from substituted or unsubstituted alkyl having C =0 to 3 (inclusive);

wherein X¹、X²、X³And X⁴Each independently selected from alkyl, aryl, alkaryl groups and hydrogen; or wherein X¹、X²、X³And X⁴Each independently hydrogen or methyl;

wherein R is¹、R²、R³And R⁴Each independently selected from alkyl, aryl, alkaryl groups and hydrogen; or wherein R is¹、R²、R³And R⁴Each independently selected from butyl, propyl, ethyl, methyl or hydrogen; and wherein R¹And R²With R³And R⁴One of which may optionally be bridged by a polymethylene group;

wherein when C =0 in R, the group R is combined¹R²With a combination radical R³R⁴The same; and is

Wherein when C = 1 in R, R¹、R²、R³And R⁴Each is hydrogen.

In a second aspect, the present invention relates to compositions comprising a compound represented by formula I as shown above, and methods of making the same. In a further aspect, the present invention relates to antidegradant compositions and mixtures comprising the antidegradant compounds of the present invention.

In a further aspect, the present invention relates to antidegradant compositions comprising the compounds of the invention.

In another aspect, the present invention relates to lubricant compositions comprising the compounds of the present invention.

In yet another aspect, the present invention relates to vulcanizable elastomer formulations comprising the compounds of the present invention.

In yet another aspect, the present invention relates to a vulcanized elastomeric rubber article having at least one component formed from the vulcanizable elastomeric formulation of the present invention.

In another aspect, the present invention relates to a process for preparing antidegradant compounds, corresponding to formula I as shown above and as further described herein, as well as mixtures containing them. In this aspect, a p-phenylenediamine is reacted with a diol to obtain a mixture comprising an antidegradant compound; wherein the p-phenylenediamine corresponds to formula IV:

wherein each X is independently selected from the group consisting of alkyl, aryl, alkaryl groups and hydrogen; or wherein each X is independently hydrogen or methyl;

the diol corresponds to formula II:

wherein each R is independently selected from: (a) (i) a substituted or unsubstituted alkyl group having C =0 to 12 (inclusive); (ii) substituted or unsubstituted aryl; and (iii) substituted and unsubstituted alkaryl groups; or (b) a substituted or unsubstituted alkyl having C =0 to 3 (inclusive); and is

Wherein R is¹And R³Each independently selected from: (a) alkyl, aryl, alkaryl groups and hydrogen; or (b) butyl, propyl, ethyl, methyl or hydrogen; and wherein R¹And R³Optionally bridged by polymethylene groups to form cycloalkyl groups;

the antidegradant compound is according to formula I:

wherein each R is independently selected from: (a) (i) a substituted or unsubstituted alkyl group having C =0 to 12 (inclusive); (ii) substituted or unsubstituted aryl; and (iii) substituted and unsubstituted alkaryl groups; or (b) a substituted or unsubstituted alkyl having C =0 to 3 (inclusive);

wherein each X is independently selected from the group consisting of alkyl, aryl, alkaryl groups and hydrogen; or wherein each X is independently hydrogen or methyl;

wherein R is¹And R³Each independently selected from alkyl, aryl, alkaryl groups and hydrogen; or wherein R is¹And R³Each independently selected from butyl, propyl, ethyl, methyl or hydrogen; and wherein R¹And R³Optionally bridged by polymethylene groups;

wherein when C =0 in R, R¹And R³The same; and is

Wherein when C = 1 in R, R¹And R³Each is hydrogen.

The compounds of the present invention have surprisingly shown efficacy as antidegradants and antifatigue agents and are therefore particularly useful for imparting resistance to crack growth, degradation, and many manifestations thereof in a variety of applications. When used as a component in vulcanizable elastomer formulations forming vulcanized rubber articles, and more particularly in vehicle tires and components thereof, the compounds of the present invention have shown a particularly desirable and surprising combined efficacy against oxidative degradation, ozonated degradation, and resistance against fatigue and crack growth, which is superior to the combinations heretofore achieved by prior art materials. Further advantages and areas of applicability will become apparent from the description provided herein. It should be understood that the description and specific examples are intended for purposes of illustration only and are not intended to limit the spirit and scope of the present disclosure.

Detailed Description

As used herein, the following terms or phrases are defined as follows:

an "antidegradant" refers to a material that inhibits degradation (caused by, for example, heat, light, oxidation, and/or ozonation) or its manifestation of a composition, formulation, or article to which it is added or applied.

By "anti-fatigue agent" is meant a material that, after being applied in place for a period of time (whereby the composition, formulation or article is subjected to thermal, oxidative, ozone and mechanical degradation forces), improves the flex fatigue resistance of the composition, formulation or article to which it is added or applied.

"antioxidant" refers to a material that inhibits oxidative degradation of a composition, formulation or article to which it is added or applied.

By "antiozonant" is meant a material that inhibits ozone exposure degradation of a composition, formulation or article to which it is added or applied.

"elastomer" means any polymer that can be stretched to at least twice its original length under low stress after vulcanization (or crosslinking) and at room temperature, and will recover under force to about its original length upon immediate release of the stress, including but not limited to rubber.

"vulcanizable elastomer formulation" means a composition that comprises an elastomer and is capable of being vulcanized when subjected to vulcanization conditions.

In a first aspect, the present invention relates to a compound represented by the formula:

wherein each R is independently selected from (i) a substituted or unsubstituted alkyl group having C =0 to 12 (inclusive); (ii) substituted or unsubstituted aryl; and (iii) substituted and unsubstituted alkaryl groups;

wherein X¹、X²、X³And X⁴Each independently selected from alkyl, aryl, alkaryl groups and hydrogen; wherein R is¹、R²、R³And R⁴Each independently selected fromAlkyl, aryl, alkylaryl groups and hydrogen, and R¹And R²With R³And R⁴One of which may optionally be bridged by a polymethylene group; wherein when C =0 in R, the group R is combined¹R²With a combination radical R³R⁴The same; and, wherein when C = 1 in R, R¹、R²、R³And R⁴Each is hydrogen.

In certain embodiments according to formula I, R may be selected from substituted or unsubstituted alkyl groups of C =0 to 3 (inclusive). R may thus be such that C =0, C = 1, C = 2, or C = 3. In embodiments, C may be equal to 0 to 3 carbons, or 1 to 2 carbons, or 1 to 3 carbons, inclusive.

Thus, when R is absent such that C =0, then the carbon atoms depicted on both sides of the R group are directly bonded to each other to form an ethylene group. Alternatively, R may be a single carbon where C = 1, i.e. R may be a methylene group, such that a propylene group is bonded to each adjacent nitrogen atom. R may also represent an alkyl group having two carbon atoms, wherein C = 2, i.e. an ethylene group, such that a butylene group is bonded to each adjacent nitrogen atom. In yet another embodiment, R may be such that C may be equal to 3, i.e., a propylene group, such that a pentylene group is bonded to each adjacent nitrogen atom, or may be branched such that adjacent carbons are bonded to the carbon adjacent to the R group depicted, while the third carbon is bonded to only one of the two carbons bonded to those adjacent to the R group, i.e., an isopropylene group.

For the R group, we note that when C =0 in R, the group R is combined¹R²With a combination radical R³R⁴The same is true. Furthermore, we note that when C = 1 in R, then R¹、R²、R³And R⁴Each is hydrogen.

We also note that, according to certain aspects of formula I, X¹、X²、X³And X⁴May each independently be hydrogen or methyl. Those skilled in the art will understand that when X is¹、X²、X³And X⁴The nitrogen molecule to which it is bonded, each being hydrogen, is thus a secondary amine, known to be desirable in certain known or proposed mechanisms of antioxidant action. Alternatively, certain advantages may be realized when the compounds of the present invention are methylated compounds (forming methylated derivatives as shown in example 14), such as improved cure characteristics and fatigue resistance properties.

According to certain embodiments of formula I, R¹、R²、R³And R⁴Each independently selected from butyl, propyl, ethyl, methyl or hydrogen. Thus, in various embodiments, R¹、R²、R³And R⁴May be all hydrogen, or may be all methyl, or may be all ethyl, propyl or butyl, or may be a mixture of any of these. For example, R¹And R²One of which may be methyl and the other hydrogen, and R³And R⁴One of which may be methyl and the other hydrogen.

In an alternative embodiment according to formula I, R¹And R²With R³And R⁴One of which may be optionally bridged by a polymethylene group to form a cycloalkyl group. Thus, in various embodiments, the compounds of the present invention may comprise a substituted or unsubstituted cycloalkyl group, such as cyclobutane, cyclopropane, or cyclohexane, or cycloheptane, or cyclooctane, wherein R is¹、R²、R³And R⁴Two of which may contain a methylene group attached to a cycloalkyl group, or may each constitute the carbon of the cyclic alkyl group itself. Non-limiting cycloalkyl groups that may be present in the compounds of formula II include cyclohexane and cyclohexanedimethanol. Diols useful in forming such compounds containing a cyclic alkyl group thus also include, but are not limited to, cyclohexanediol, cyclohexanedimethanol. Similarly, dicarbonyl compounds useful for obtaining such compounds include cyclohexanedione and cyclohexanedialdehyde.

Non-limiting examples of compounds of the present invention include N, N' - (ethane-1, 2-diyl) bis (N-phenyl-benzene-1, 4-diamine); n, N' - (butane-2, 3-diyl) bis (N-phenyl-1, 4-diamine); n, N' - (octane-1, 8-diyl) bis (N-phenyl-benzene-1, 4-diamine); n, N' - (1, 4-phenylenebis (methylene)) bis (N-phenyl-1, 4-diamine); n, N' - (1, 3-phenylenebis (methylene)) bis (N-phenyl-1, 4-diamine); n, N '- (1, 4-phenylenebis (ethane-1, 1-diyl)) bis (N-phenylphenyl-1, 4-diamine) and N, N' - (1, 3-phenylenebis (ethane-1, 1-diyl)) bis (N-phenylphenyl-1, 4-diamine). These are represented schematically as follows, each with reference to a respective written embodiment(s) of the manufacturing method described below:

preferred examples of compounds according to formula I of the present invention include N, N '- (ethane-1, 2-diyl) bis (N-phenyl-1, 4-diamine) and N, N' - (butane-2, 3-diyl) bis (N-phenyl-1, 4-diamine) as depicted above.

In another aspect, the present invention relates to a process for preparing antidegradant compounds, corresponding to formula I as shown above and as further described herein, and mixtures containing them. In this aspect, a p-phenylenediamine is reacted with a diol to obtain a mixture comprising an antidegradant compound, wherein the p-phenylenediamine corresponds to formula IV:

wherein each X is independently selected from the group consisting of alkyl, aryl, alkaryl groups and hydrogen; or wherein X is hydrogen or methyl;

the diol corresponds to formula II:

wherein each R is independently selected from: (a) (i) a substituted or unsubstituted alkyl group having C =0 to 12 (inclusive); (ii) substituted or unsubstituted aryl; and (iii) substituted and unsubstituted alkaryl groups; or (b) a substituted or unsubstituted alkyl having C =0 to 3 (inclusive); and is

Wherein R is¹And R³Each independently selected from: (a) alkyl, aryl, alkaryl groups and hydrogen; or (b) butyl, propyl, ethyl, methyl or hydrogen; and wherein R¹And R³Optionally bridged by polymethylene groups to form cycloalkyl groups;

the antidegradant compound is according to formula I:

wherein each R is independently selected from: (a) (i) a substituted or unsubstituted alkyl group having C =0 to 12 (inclusive); (ii) substituted or unsubstituted aryl; and (iii) substituted and unsubstituted alkaryl groups; or (b) a substituted or unsubstituted alkyl having C =0 to 3 (inclusive);

wherein each X is independently selected from the group consisting of alkyl, aryl, alkaryl groups and hydrogen; or wherein each X is hydrogen or methyl;

wherein R is¹And R³Each independently selected from alkyl, aryl, alkaryl groups and hydrogen; or wherein R is¹And R³Each is selected from butyl, propyl, ethyl, methyl or hydrogen; and wherein R¹And R³Optionally bridged by polymethylene groups;

wherein, when C =0 in R, R¹And R³Are the same as, and

wherein, when C = 1 in R, R¹And R³Is hydrogen.

The present invention therefore relates to a process for the preparation of a compound according to formula I according to the following reaction scheme:

wherein each R is independently selected from (i) a substituted or unsubstituted alkyl group having C =0 to 12 (inclusive); (ii) substituted or unsubstituted aryl; and (iii) substituted and unsubstituted alkaryl groups; or wherein each R is independently selected from substituted or unsubstituted alkyl having C =0 to 3 (inclusive);

wherein each X is independently selected from the group consisting of alkyl, aryl, alkaryl groups and hydrogen; or wherein each X is hydrogen or methyl; r¹And R³Each independently selected from alkyl, aryl, alkaryl groups and hydrogen; or wherein R is¹And R³Each independently selected from butyl, propyl, ethyl, methyl or hydrogen; and wherein R¹And R³Optionally bridged by polymethylene groups;

wherein when C =0 in R, R¹And R³Are identical to each other

Wherein when C = 1 in R, R¹And R³Each is hydrogen.

Suitable p-phenylenediamines corresponding to formula IV useful in accordance with the present invention include those wherein each X is independently selected from the group consisting of alkyl, aryl, alkaryl groups and hydrogen; particularly those in which X is independently hydrogen or methyl, and particularly 4-amino-p-phenylenediamine.

Suitable diols corresponding to formula II useful according to the present invention include those wherein each R is independently selected from alkyl groups having C =0 to 12 (inclusive) or 0 to 3 (inclusive); substituted or unsubstituted aryl; and substituted and unsubstituted alkaryl groups. Suitable diols also include those wherein R¹And R³Each independently selected from alkyl, aryl, alkaryl groups and hydrogen; or butyl, propyl, ethyl, methyl or hydrogen, and wherein R¹And R³Those bridged by polymethylene groups. Thus, specific diols suitable for use according to the present invention include ethylene glycol, propylene glycol, butylene glycol, 1, 8-octanediol, and the like.

According to the present invention, a p-phenylenediamine corresponding to formula IV is reacted with a diol corresponding to formula II to obtain the desired antidegradant compound represented by formula I. This reaction can be described as reductive amination by hydrogen (borne hydrogen reduction), which can be accomplished by contacting p-phenylenediamine and a diol in the presence of a homogeneous or heterogeneous metal catalyst. The reaction may be carried out in the presence or absence of a solvent. Examples of useful solvents include, but are not limited to, cyclohexane, toluene, xylene, mesitylene, ethylene glycol, t-butyl methyl ether, and tetrahydrofuran. These solvents may be used alone or in combination as a mixture.

The amount of solvent used, if any, may be based on the amount of diol such that the weight% of solvent is from about 1% to about 75%, or from 25% to 40%, relative to the weight of diol present.

Examples of useful metal catalysts include those based on ruthenium, iridium, platinum, palladium, tin, iron, Al₂O₃And TiO₂The ligand-functionalized homogeneous catalyst or solid-supported heterogeneous catalyst of (a). The amount of catalyst used can be based on the amount of diol of formula II such that the wt% of catalyst is from about 0.005 wt% to about 10 wt% of active catalyst, based on the weight of diol present, excluding water content. The temperature of the reaction may be, for example, 50 ℃ up to 300 ℃.

Each of the above parameters can affect reaction kinetics, conversion, and selectivity. It is therefore preferred to select the reaction conditions such that the time required for completion is from 0.5 hours to 12 hours, most preferably from 1 to 3 hours.

Thus, the compounds of the present invention can be prepared from polyol starting materials by a hydrogen self-transfer procedure using homogeneous or heterogeneous catalysts (for a general description of the mechanism, see for example Guillena et al,Chem. Rev.2010,110, 1611). The compounds of interest can also be prepared from polycarbonyl starting materials using heterogeneous transition metal catalysts in the presence of hydrogen.

Precursors of the compounds of the present invention, the compounds of the present invention and their methods of preparation are illustrated by the following examples, which are not intended to limit the spirit or scope of the invention in any way.