Water in oil emulsion explosive compositions comprises a discontinuous aqueous phase comprising at least one oxygen-supplying component, a continuous organic phase, an emulsifying amount of an emulsifier composition comprising: the reaction product of an amine (C) characterized by the presence within its structure of at least one H--N group and an intermediate formed in the reaction of (A) at least one olefinic compound containing at least one group of the formula ##STR1## and (B) at least one carboxylic reactant selected from the group consisting of compounds of the formula R.sup.3 C(O)(R.sup.4).sub.n C(O)OR.sup.5 (III) wherein each of R.sup.3 and R.sup.5 is independently H or a hydrocarbyl group, R.sup.4 is a divalent hydrocarbylene group, and n is 0 or 1, and reactive sources thereof and optionally, from about 0.5 to about 2 moles, per mole of (B), of (D) at least one aldehyde or ketone; and optionally a sensitizer.
U.S. Pat. No. 4,710,248 discloses an emulsion explosive composition comprising a discontinuous oxidizer-phase dispersed throughout a continuous fuel phase with a modifier comprising a hydrophilic moiety and a lipophilic moiety. The hydrophilic moiety comprises a carboxylic acid or a group capable of hydrolyzing to a carboxylic acid. The lipophilic moiety is a saturated or unsaturated hydrocarbon chain. The emulsion explosive composition pH is above 4.5.
U.S. Pat. Nos. 4,840,687 and 4,956,028 disclose explosive compositions comprising a discontinuous oxidizer phase comprising at least one oxygen-supplying component, a continuous organic phase comprising at least one water-immiscible organic liquid, and an emulsifying amount of at least one nitrogen-containing emulsifier derived from (A) at least one carboxylic acylating agent, (B) at least one polyamine, and (C) at least one acid or acid-producing compound capable of forming at least one salt with said polyamine. Examples of (A) include polyisobutenyl succinic acid or anhydride. Examples of (B) include the alkylene polyamines. Examples of (C) include the phosphorus acids (e.g., O,S-dialkylphosphorotrithioic acid). These explosive compositions can be water-in-oil emulsions or melt-in-oil emulsions.
U.S. Pat. No. 4,863,534 discloses an explosive composition comprising a discontinuous oxidizer phase comprising at least one oxygen-supplying component, a continuous organic phase comprising at least one carbonaceous fuel, and an emulsifying amount of (A) at least one salt composition derived from (A)(1) at least one high-molecular weight hydrocarbyl-substituted carboxylic acid or anhydride, or ester or amide derivative of said acid or anhydride, the hydrocarbyl substituent of (A)(1) having an average of from about 20 to about 500 carbon atoms, and (A)(2) ammonia, at least one amine, at least one alkali or alkaline earth metal compound; and (B) at least one salt composition derived from B)(1) at least one low-molecular weight hydrocarbyl-substituted carboxylic acid or anhydride, or ester or amide derivative of said acid or anhydride, the hydrocarbyl substituent of (B)(1) having an average of from about 8 to about 18 carbon atoms, and (B)(2) ammonia, at least one amine, at least one alkali or alkaline earth metal, and/or at least one alkali or alkaline earth metal compound.
U.S. Pat. No. 4,822,433 discloses an explosive emulsion composition comprising a discontinuous phase containing an oxygen-supplying component and an organic medium forming a continuous phase wherein the oxygen-supplying component and organic medium are capable of forming an emulsion which, in the absence of a supplementary adjuvant, exhibits an electrical conductivity measured at 60.degree. C., not exceeding 60,000 picomhos/meter. The reference indicates that the conductivity may be achieved by the inclusion of a modifier which also functions as an emulsifier. The modifier is comprised of a hydrophilic moiety and a lipophilic moiety. The lipophilic moiety can be derived from a poly[alk(en)yl] succinic anhydride. Poly(isobutylene) succinic anhydride having a number average molecular eight in the range of 400 to 5000 is specifically identified as being useful. The hydrophilic moiety is described as being polar in character, having a molecular weight not exceeding 450 and can be derived from polyols, amines, amides, alkanol amines and heterocyclics. Example 14 of this reference discloses the use of a 1:1 condensate of polyisobutenyl succinic anhydride (number average molecular weight=1200) and dimethylethanol amine as the modifier/emulsifier.
U.S. Pat. No. 4,919,178 discloses water in oil emulsion explosives in which the emulsifier is the reaction product of two components. The first component is the reaction product certain carboxylic acids or anhydrides, including substituted succinic acids and anhydrides with ammonia or an amine and an alkali metal or an alkaline earth metal. The second component is the salt of a phosphorous containing acid.
European Patent application EP 561,600 A discloses a water-in-oil emulsion explosive in which the emulsifier is the reaction product of a substituted succinic acylating agent, having at least 1.3 succinic groups per equivalent weight of substituents, with ammonia and/or an amine. The substituent is a polyalkene having an number average molecular weight of greater than 500 and preferably 1300-1500.
U.S. Pat. No. 4,919,179 discloses a water-in-oil emulsion explosive wherein the emulsifier is a particular type of ester of polyisobutenyl succinic anhydride.
U.S. Pat. No. 4,844,756 discloses a water-in-oil emulsion explosive wherein the emulsifier is a salt produced by reacting a hydrocarbyl substituted carboxylic acid or anhydride, including substituted succinic acids and anhydrides, with ammonia, an amine, and/or an alkali or alkaline earth metal.
U.S. Pat. No. 4,818,309 discloses a water-in-oil emulsion explosive wherein the emulsifier is a polyalkenyl succinic acid or derivative thereof. The succinic acid may be used in the form of an anhydride, an ester, an amide or an imide. A condensate with ethanolamine is preferred.
U.S. Pat. No. 4,708,753 discloses a water-in-oil emulsion suitable for use in explosive and functional fluids wherein the emulsifier is a reaction product of a hydrocarbyl substituted carboxylic acid, including a succinic acid, with all amine. The substituent contains 20-500 carbon atoms, and the aqueous phase contains a water soluble, oil insoluble functional additive.
European Patent EP 102,827 A discloses a water-in-oil emulsion composition useful as a well control fluid. The emulsifier is a polyamine derivative, especially an alkylene polyamine derivative, of a polyisobutenyl succinic anhydride or a borated or carboxylated derivative thereof.
U.S. Pat. No. 4,445,576 discloses a water-in-oil emulsion composition useful as a spacer fluid in well drilling. The emulsifier is an amine derivative, especially a polyamine derivative, of a polyalkenyl succinic anhydride.
U.S. Pat. No. 4,999,062 describes an emulsion explosive composition comprising a discontinuous phase comprising an oxygen-releasing salt, a continuous water-immiscible organic phase and an emulsifier component comprising a condensation product of a primary amine and a poly[alk(en)yl]succinic acid or anhydride and wherein the condensation product comprises at least 70% by weight succinimide product.
United States defensive publication T969,003 discloses water in oil emulsion fertilizer compositions prepared by dissolving an invert emulsifier in an oil such as kerosene. A liquid (aqueous) fertilizer is emulsified with the oil to form an invert emulsifier.
Patent application WO96/28436 describes gamma and delta lactones of formulae (I) and (II) ##STR2##
used as emulsifiers in explosive compositions comprising a continuous organic phase and a discontinuous aqueous phase containing an oxygen-supplying compound. In the formulae, R is hydrocarbyl, R* is hydrogen, methyl or another hydrocarbyl, and Q is an amide, ammonium salt or ester functionality.
Water-in-oil explosive emulsions are often blended with ammonium nitrate prills or ANFO, a composition produced by adding a liquid oil such as light oil and the like to porous ammonium nitrate prills for the purpose of increasing the explosive energy of such emulsions.
B. B. Snider and J. W. van Straten, J. Org. Chem., 44, 3567-3571 (1979) describe certain products prepared by the reaction of methyl glyoxylate with several butenes and cyclohexenes. K. Mikami and M. Shimizu, Chem. Rev., 92, 1021-1050 (1992) describe carbonyl-ene reactions, including glyoxylate-ene reactions. D. Savostianov (communicated by P. Pascal), C. R. Acad. Sc. Paris, 263, (605-7) (1966) relates to preparation of sonic .alpha.-hydroxylactones via the action of glyoxylic acid on olefins. M. Kerfanto et. al., C. R. Acad. Sc. Paris, 264, (232-5) (1967) relates to condensation reactions of .alpha.-.alpha.-di-(N-morpholino)-acetic acid and glyoxylic acid with olefins. B. B. Jarvis et al, Synthesis, 1079-82 (1990) relates to reactions of oxocarboxylic acids with olefins under acidic conditions to give .alpha.-hydroxy butyrolactones.
U.S. Pat. Nos. 5,696,060, 5,696,067 and 5,779,742 describe nitrogen containing derivatives of carboxylic acylating agents derived from the reaction product of an amine (C) characterized by the presence within its structure of at least one H--N group and an intermediate formed in the reaction of (A) at least one olefinic compound containing at least one group of the formula ##STR3##
and (B) at least one carboxylic reactant selected from the group consisting of compounds of the formula
R.sup.3 C(O)(R.sup.4).sub.n C(O)OR.sup.5 (IV)
wherein each of R.sup.3 and R.sup.5 is independently H or a hydrocarbyl group, R.sup.4 is a divalent hydrocarbylene group, and n is 0 or 1, and reactive sources thereof, in amounts ranging from 0.6 moles (B) per mole of (A) to 3 moles (B) per equivalent of (A). In an optional embodiment, the intermediate is prepared by including in the reaction from about 0.5 to about 2 moles, per mole of (B), of (D) at least one aldehyde or ketone. These are describe as useful as performance improving additives for lubricating oil composition.
SUMMARY OF THE INVENTION
This invention is directed to water-in-oil emulsions which are useful as explosives. These emulsions comprise a discontinuous aqueous phase comprising at least one oxygen-supplying component, a continuous organic phase comprising at least one carbonaceous fuel, and an emulsifying amount of an emulsifier composition comprising:
the reaction product of an amine (C) characterized by the presence within its structure of at least one H--N group and an intermediate formed in the reaction of
(A) at least one olefinic compound containing at least one group of the formula ##STR4##
and
(B) at least one carboxylic reactant selected from the group consisting of compounds of the formula
R.sup.3 C(O)(R.sup.4).sub.n C(O)OR.sup.5 (III)
wherein each of R.sup.3 and R.sup.5 is independently H or a hydrocarbyl group, R.sup.4 is a divalent hydrocarbylene group, and n is 0 or 1, and reactive sources thereof, in amounts ranging from 0.6 moles (B) per mole of (A) to 3 moles (B) per equivalent of (A). In an optional embodiment, the intermediate is prepared by including in the reaction from about 0.5 to about 2 moles, per mole of (B), of (D) at least one aldehyde or ketone.
In one embodiment, these emulsions are stably blended with ammonium nitrate prills that have been made using one or more crystal habit modifiers to control crystal growth and one or more surfactants to reduce caking.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The term "emulsion: as used in this specification and in the appended claims is intended to cover not only water in oil emulsions but also melt-in-oil emulsions. The water in oil emulsions have a discontinuous aqueous phase containing oxidizing materials suspended in a continuous oil phase. The melt-in-oil emulsions have a discontinuous oxidizer phase containing oxidizing salts which have a melting point low enough that they may be conveniently emulsified into the continuous oil phase. The oxidizing salts may contain some water of hydration and accordingly, an emulsion prepared without addition of water to form the discontinuous phase may actually contain some water. However, the presence of water in a melt-in-oil emulsion is not required and the discontinuous phase often comprises a low melting mixture of oxidizing salts. Although there is not a sharp line between water in oil and melt-in-oil emulsions, the term water in oil is used when the salts are dissolved in additional water to form the discontinuous phase and the term melt-in-oil is used when the oxidizing salts are liquefied without the addition of water to form the discontinuous phase.
As used herein, the terms "hydrocarbon" or "hydrocarbon based" means a group which is purely hydrocarbon, that is, a compound of hydrogen and carbon containing no hetero atoms. The term "hydrocarbyl" means that the group being described has predominantly hydrocarbon character within the context of this invention. Hydrocarbyl groups include groups that are purely hydrocarbon in nature, that is, they contain only carbon and hydrogen. They may also include groups containing non-hydrocarbon substituents or atoms which do not alter the predominantly hydrocarbon character of the group. Such substituents may include halo-, alkoxy-, nitro-, etc. These groups also may contain hetero atoms. Suitable hetero atoms will be apparent to those skilled in the art and include, for example, sulfur, nitrogen and oxygen. Therefore, while remaining predominantly hydrocarbon in character within the context of this invention, these groups may contain atoms other than carbon present in a chain or ring otherwise composed of carbon atoms. Thus, the term "hydrocarbyl" is broader than the terms "hydrocarbon" or "hydrocarbon based" since all hydrocarbon and hydrocarbon based groups are also hydrocarbyl groups while the hydrocarbyl groups containing hetero atoms are not hydrocarbon or hydrocarbon based groups.
In general, no more than about three non-hydrocarbon substituents or hetero atoms, and preferably no more than one, will be present for every 10 carbon atoms in the hydrocarbyl based groups. Most preferably, the groups are purely hydrocarbon in nature, that is they are essentially free of atoms other than carbon and hydrogen.
The Emulsifier Compositions
In one embodiment, the compositions of this invention employ an emulsifier comprising a compound of the formula ##STR5##
wherein A is a hydrocarbyl group or a hydroxy-substituted hydrocarbyl group. In one embodiment A is selected from groups of the formula ##STR6##
wherein z=0 or 1;
X is a divalent hydrocarbyl group selected from the group consisting of
C(R.sup.6)(C(R.sup.5)(R.sup.7)(R.sup.8)) when z=0, and
C(R.sup.7)(R.sup.8) when z=1; and
each of R.sup.5, R.sup.6, R.sup.7, and R.sup.8 is independently H or a hydrocarbon based group.
R.sup.5 is H or hydrocarbyl. When R.sup.5 is hydrocarbyl, it is usually an aliphatic group, often a group containing from 1 to 30 carbon atoms, often from 8 to 18 carbon atoms. In another embodiment, R.sup.5 is lower alkyl, wherein "lower alkyl" is defined hereinabove. Most often, R.sup.5 is H or lower alkyl.
When at least one of R.sup.6, R.sup.7 and R.sup.8 is a hydrocarbyl group, it preferably contains from 7 to 5,000 carbon atoms. More often, such hydrocarbon groups are aliphatic groups. In one embodiment R.sup.6 is an aliphatic group containing from 10 to 300 carbon atoms. In another embodiment, R.sup.6 contains from 30 to 100 carbon atoms and is derived from homopolymerized and interpolymerized C.sub.2-18 olefins.
In a further embodiment, at least one of R.sup.7 and R.sup.8 is an aliphatic group containing from 10 to 300 carbon atoms. Often, at least one of R.sup.7 and R.sup.8 contains from 30 to 100 carbon atoms and is derived from homopolymerized and interpolymerized C.sub.2-18 olefins. The polymerized olefins are frequently 1-olefins, preferably ethylene, propylene, butenes, isobutylene, and mixtures thereof. Polymerized olefins are often referred to herein as polyolefins.
In yet another embodiment at least one of R.sup.7 and R.sup.8 is an aliphatic group containing from 8 to 24 carbon atoms. In another embodiment at least one R.sup.7 and R.sup.8 is an aliphatic group containing 12 to 50 carbon atoms. Within this embodiment, most often one of R.sup.7 and R.sup.8 is H and the other is the aliphatic group.
Each of R.sup.1 and R.sup.2 is H or a hydrocarbon based group. In one particular embodiment, each of R.sup.1 and R.sup.2 is independently H or a lower alkyl group provided at least one is lower alkyl. In another embodiment, one of R.sup.1 and R.sup.2 is H and the other is lower alkyl. As used herein, the expression "lower alkyl" refers to alkyl groups containing from 1 to 7 carbon atoms. Examples include methyl, ethyl and the various isomers of propyl, butyl, pentyl, hexyl and heptyl. In one especially preferred embodiment, each of R.sup.1 and R.sup.2 is H.
R.sup.3 is H or hydrocarbyl. These hydrocarbyl groups are usually aliphatic, that is, alkyl or alkenyl, preferably alkyl, more preferably lower alkyl. Especially preferred is where R.sup.3 is H or methyl, most preferably, H.
R.sup.4 is a divalent hydrocarbylene group. This group may be aliphatic or aromatic, but is usually aliphatic. Often, R.sup.4 is an alkylene group containing from 1 to 3 carbon atoms. The `n` is 0 or 1; that is, in one embodiment R.sup.4 is present and in another embodiment, R.sup.4 is absent. More often, R.sup.4 is absent.
In one preferred embodiment, each of R.sup.1, R.sup.2 and R.sup.3 is independently hydrogen or a lower alkyl or alkenyl group. In one especially preferred embodiment, each of R.sup.1, R.sup.2 and R.sup.3 is hydrogen and each of y and n=0.
In another preferred embodiment, R.sup.6 is an aliphatic group containing from 8 to 150 carbon atoms, R.sup.5 is H, n is 0 and R.sup.3 is H.
The subscript `y` is an integer ranging from 1 to 200, more often from 1 to 50 and even more often from 1 to 20. Frequently y is 1.
Each of R.sup.9 and R.sup.10 is independently H, alkoxyhydrocarbyl, hydroxyhydrocarbyl, hydrocarbyl, aminohydrocarbyl, N-alkoxyalkyl- or hydroxyalkyl-substituted aminohydrocarbyl, or a group of the formula .paren open-st.Y.paren close-st..sub.a R.sup.11 --B, wherein each Y is a group of the formula ##STR7##
each R.sup.11 is a divalent hydrocarbyl group, R.sup.12 is as defined above for R.sup.9 and R.sup.10, and B is H, hydrocarbyl, amino, hydroxyhydrocarbyl, an amide group, an amide-containing group, an acylamino group, an imide group, or an imide-containing group, and a is 0 or a number ranging from 1 to 100 (in this case preferably no more than three R.sup.9, R.sup.10, and R.sup.12 contain amide groups, imide-containing groups, acylamino groups or amide-containing groups); or R.sup.9 and R.sup.10 taken together with the adjacent N constitute a nitrogen-containing heterocyclic group; or one of R.sup.9 and R.sup.10 taken together with the adjacent N constitute a N--N group.
These and other compositions which now have been found to be useful as emulsifiers in the compositions of the present invention are described in U.S. Pat. Nos. 5,696,060; 5,696,067; and 5,779,742. It should be understood that these references teach the materials and the use thereof in lubricating oil compositions. They do not teach or suggest the use of the materials as emulsifiers or in emulsions containing them.
The Method of Preparation of Emulsifier Compositions
The emulsifier compositions used in this invention are prepared by first reacting, optionally in the presence of an acidic catalyst selected from the group consisting of organic sulfonic acids, heteropolyacids, Lewis acids, and mineral acids,
(A) at least one olefinic compound containing at least one group of the formula ##STR8##
and
(B) at least one carboxylic reactant selected from the group consisting of at least one carboxylic reactant selected from the group consisting of compounds of the formula
R.sup.3 C(O)(R.sup.4).sub.n C(O)OR.sup.5 (III)
wherein each of R.sup.3 and R.sup.5 is independently H or a hydrocarbyl group, R.sup.4 is a divalent hydrocarbylene group, and n is 0 or 1, and reactive sources thereof in amounts ranging from 0.6 moles (B) per mole of (A) to 3 moles (B) per equivalent of (A), to form an intermediate. Subsequently, an amine (C) characterized by the presence within its structure of at least one H--N group is reacted with the intermediate produced in the reaction of A and B above, to form the emulsifier. In an optional embodiment, the intermediate is prepared by including in the reaction from about 0.5 to about 2 moles, per mole of (B), of (D) at least one aldehyde or ketone;
In the preparation of the intermediate, all of reactants (A) and (B), and optionally (D), may be present at the same time. However, it has been found that improvements in yield and purity of the product arising from the reaction of (A) and (B) are often attained when the carboxylic reactant (B) is added to the olefinic compound (A) either portionwise or continuously over an extended period of time, usually up to about 10 hours, more often from 1 hour up to about 6 hours, frequently from about 2 to about 4 hours.
The reaction of the olefin and carboxylic reactant is conducted, usually under an inert atmosphere such as N.sub.2, at temperatures ranging from ambient up to the lowest decomposition temperature of any of the reactants, usually from about 60.degree. C. to about 220.degree. C., more often from about 120.degree. C. to about 180.degree. C., preferably up to about 160.degree. C. The process employs from about 0.6 moles (B) per mole of (A) to 3 moles (B) per equivalent of (A), more often from about 1.8 moles (B) per mole of (A) to about 2.5 moles (B) per equivalent of (A), even more often from about 1.9 moles (B) per mole of (A) to about 2.1 moles (B) per equivalent of (A). The reaction may be conducted in the presence of an azeotroping solvent to remove H.sub.2 O from the reactants or H.sub.2 O formed during the reaction. Well known azeotroping solvents include toluene, xylene, cyclohexane, etc. Cyclohexane is the preferred azeotroping solvent.
Depending upon reaction conditions, the reaction of the carboxylic reactant (B) and the olefinic compound (A) yields a variety of products.
In one embodiment, described in U.S. Pat. No. 5,777,142 to Adams et al, wherein the ratio of reactants ranges from about 0.6 moles (B) per equivalent of (A), to about 1.5 moles (B) per equivalent of (A), a composition comprising a compound of the formula ##STR9##
wherein each of R.sup.1 and R.sup.2 is H or a hydrocarbon based group,
R.sup.3 is H or hydrocarbyl;
R.sup.4 is a divalent hydrocarbylene group;
n=0 or 1;
y is an integer ranging from 1 to about 200;
R.sup.5 is H or hydrocarbyl; and
X is a group of the formula ##STR10##
wherein each of R.sup.6, R.sup.7 and R.sup.8 is independently H or a hydrocarbon based group, provided that at least one of R.sup.1, R.sup.2, R.sup.6, R.sup.7 and R.sup.8 is a hydrocarbon based group containing at least 7 carbon atoms, is obtained
In another embodiment, described in European Patent Publication 759,443, carrying the reaction further provides a composition comprising a compound of the formula ##STR11##
each of R.sup.1 and R.sup.2 is H or a hydrocarbon based group,
R.sup.3 is H or hydrocarbyl;
R.sup.4 is a divalent hydrocarbylene group;
n=0 or 1;
y=0 or 1;
wherein X is a divalent hydrocarbyl group selected from the group consisting of ##STR12##
R.sup.5 is H or hydrocarbyl; and
each of R.sup.6, R.sup.7 and R.sup.8 is independently H or a hydrocarbon based group, provided that at least one of R.sup.1, R.sup.2, R.sup.6, R.sup.7 and R.sup.8 is a hydrocarbon based group containing at least 7 carbon atoms.
In yet another embodiment, described in U.S. Pat. No. 5,739,356, when the reactants are reacted in amounts ranging from more than 1.5 moles up to about 3 moles (B) per equivalent of (A), a composition comprising regioisomers selected from the group consisting of ##STR13##
wherein each R.sup.1 is H or a hydrocarbon based group,
each R.sup.3 is H or hydrocarbyl;
each R.sup.4 is a divalent hydrocarbylene group;
each n=0 or 1;
y=0 or 1;
wherein X is a divalent hydrocarbyl group selected from the group consisting of ##STR14##
each R.sup.5 is H or hydrocarbyl; and
each of R.sup.6, R.sup.7 and R.sup.8 is independently H or a hydrocarbon based group, and T is selected from the group consisting of --OH and R.sup.5.
As noted hereinabove, the emulsifier compositions used in the present invention may be prepared by an alternative method, described in U.S. Pat. No. 5,739,356 in which the reaction product of the olefin (A) and the carboxylic reactant (B) is further reacted with an aldehyde or ketone (D).
The Catalyst
The first step in preparing the emulsifier compositions used in this invention is optionally conducted in the presence of an acidic catalyst. Acid catalysts, such as organic sulfonic acids, for example, paratoluene sulfonic acid, methane sulfonic acid and sulfonated polymers such as those marketed under the tradename AMBERLYST.RTM. (Rohm & Haas), heteropolyacids, the complex acids of heavy metals (e.g., Mo, W, Sn, V, Zr, etc.) with phosphoric acids (e.g., phosphomolybdic acid), and mineral acids, for example, H.sub.2 SO.sub.4 and phosphoric acid, are useful. The amount of catalyst used is generally small, ranging from about 0.01 mole % to about 10 mole %, more often from about 0.1 mole % to about 2 mole %, based on moles of olefinic reactant.
(A) The Olefinic Compound
The olefinic compound employed as a reactant in the preparation of the emulsifier compositions used in this invention contains at least one group of the formula ##STR15##
and has the general formula
(R.sup.1)(R.sup.2)C.dbd.C(R.sup.6)(CH(R.sup.7)(R.sup.8)) (II)
wherein each of R.sup.1 and R.sup.2 is, independently, hydrogen or a hydrocarbyl group, preferably a hydrocarbon based, group. Each of R.sup.6, R.sup.7 and R.sup.8 is, independently, hydrogen or a hydrocarbyl, preferably a hydrocarbon based group; preferably at least one is a hydrocarbyl group containing at least 7 carbon atoms. These olefinic compounds are diverse in nature. In one preferred embodiment, R.sup.1 and R.sup.2 are both hydrogen, R.sup.7 is hydrogen, R.sup.8 is an aliphatic hydrocarbyl group, and R.sup.5 is a methyl group.
Virtually any compound containing an olefinic bond may be used provided it meets the general requirements set forth hereinabove for (II) [and does not contain any functional groups (e.g., primary or secondary amines) that would interfere with the carboxylic reactant (B)]. Useful olefinic compounds may be terminal olefins, i.e. olefins having a H.sub.2 C.dbd.C group, or internal olefins. Useful olefinic compounds may have more than one olefinic bond, i.e., they may be dienes, trienes, etc. Most often they are mono-olefinic. Examples include linear .alpha.-olefins, cis- or trans-disubstituted olefins, trisubstituted olefins and tetrasubstituted olefins.
When (A) is a monoolefinic, one mole of (A) contains one equivalent of C.dbd.C; when (A) is diolefinic, one mole of (A) contains 2 equivalents of C.dbd.C bonds; when (A) is triolefinic, one mole of (A) contains 3 equivalents of C.dbd.C bonds, and so forth.
Aromatic double bonds are not considered to be olefinic double bonds within the context of this invention.
As used herein, the expression "polyolefin" defines a polymer derived from olefins. The expression "polyolefinic" refers to a compound containing more than one C.dbd.C bond.
Among useful compounds are those that are purely hydrocarbon, i.e., those substantially free of non-hydrocarbon groups, or they may contain one or more non-hydrocarbon groups as discussed in greater detail herein.
In one embodiment, the olefinic compounds are substantially hydrocarbon, that is, each R group in (II) is H or contains essentially carbon and hydrogen. In one aspect within this embodiment, each of R.sup.1, R.sup.2, R.sup.7 and R.sup.8 is hydrogen and R.sup.6 is a hydrocarbyl group containing from 7 to about 5,000 carbon atoms, more often from about 12 up to about 200 carbon atoms, often from about 30, preferably from about 50, up to about 100 carbon atoms. In another aspect of this embodiment, each of R.sup.1 and R.sup.2 is hydrogen, R.sup.6 is H or a lower alkyl group, especially methyl, and the group (CH(R.sup.7)(R.sup.8)) is a hydrocarbyl group containing from 7 to about 5,000 carbon atoms, more typically from about 12 up to about 200 carbon atom, preferably from 30, often from about 50, up to about 100 carbon atoms.
As used here, and throughout the specification and claims, the expression "lower" with "alkyl", "alkenyl", etc. means groups having 7 or fewer carbon atoms, for example, methyl, ethyl and all isomers of propyl, butyl, pentyl, hexyl and heptyl, ethylene, butylene, etc.
In another embodiment, one or more of the R groups present in (II) is an organic radical which is not purely hydrocarbon. Such groups may contain or may be groups such as carboxylic acid, ester, and amide, cyano, hydroxy, thiol, tertiary amino, nitro, alkali metal mercapto and the like. Illustrative of olefinic compounds (II) containing such groups are methyl oleate, oleic acid, 2-dodecenedioic acid, octene diol, linoleic acid and esters thereof, and the like.
Preferably, the hydrocarbyl groups are aliphatic groups. In one preferred embodiment, when an R group is an aliphatic group containing a total of from about 30 to about 200 carbon atoms, the olefinic compound is derived from homopolymerized and interpolymerized C.sub.2-18 mono- and di-olefins, preferably 1-olefins. Examples of such olefins are ethylene, propylene, butene-1, isobutylene, butadiene, isoprene, 1-hexene, 1-octene, etc. In a preferred embodiment, the olefins contain from 2 to about 5 carbon atoms, preferably 3 or 4 carbon atoms. R groups can, however, be derived from other sources, such as monomeric high molecular weight alkenes (e.g. 1-tetracontene), aliphatic petroleum fractions, particularly paraffin waxes and cracked analogs thereof, white oils, synthetic alkenes such as those produced by the Ziegler-Natta process (e.g., poly-(ethylene) greases) and other sources known to those skilled in the art. Any unsaturation in the R groups may be reduced by hydrogenation according to procedures known in the art, provided at least one olefinic group remains as described for (II).
In one preferred embodiment, at least one R is derived from polybutene, that is, polymers of C.sub.4 olefins, including 1-butene, 2-butene and isobutylene. Those derived from isobutylene, i.e., polyisobutylenes, are especially preferred. In another preferred embodiment, R is derived from polypropylene. In another preferred embodiment, R is derived from ethylene-alpha olefin polymers, including ethylene-.alpha.-olefin-diene polymers, especially those wherein the diene is a non-conjugated diene. Representative of such polymers are the ethylene-propylene copolymers and ethylene-propylene-diene terpolymers marketed under the TRILENE.RTM. tradename by the Uniroyal Company. Molecular weights of such polymers may vary over a wide range, but especially preferred are those having number average molecular weights (M.sub.n) ranging from about 300 to about 20,000, preferably 700 to about 10,000, often from 900 to 2,500. In one preferred embodiment, the olefin is an ethylene-propylene-diene terpolymer having M.sub.n ranging from about 900 to about 8,000, often up to about 2,000. Such materials are included among the Trilene.RTM. polymers marketed by the Uniroyal Company, Middlebury, Conn., USA and Ortholeum.RTM. 2052 marketed by the DuPont Company. Also contemplated are polydiene polymers, those prepared by polymerizing dienes.
Ethylene-alpha olefin copolymers and ethylene-lower olefin-diene terpolymers are described in numerous patent documents, including European patent publication EP 279,863, Japanese patent publication 87-129,303 and the following United States patents:
3,598,738 4,357,250
4,026,809 4,658,078
4,032,700 4,668,834
4,137,185 4,937,299
4,156,061 5,324,800
4,320,019
each of which is incorporated herein by reference for relevant disclosures of these ethylene based polymers.
A preferred source of hydrocarbyl groups R are polybutenes obtained by polymerization of a C.sub.4 refinery stream having a butene content of 35 to 75 weight percent and isobutylene content of 15 to 60 weight percent in the presence of a Lewis acid catalyst such as aluminum trichloride or boron trifluoride. These polybutenes contain predominantly (greater than 80% of total repeating units) isobutylene repeating units of the configuration ##STR16##
These polybutenes are typically monoolefinic, that is they contain but one olefinic bond per molecule.
The olefinic compound may be a polyolefin comprising a mixture of isomers wherein from about 50 percent to about 65 percent are tri-substituted olefins wherein one substituent contains from 2 to about 500 carbon atoms, often from about 30 to about 200 carbon atoms, more often from about 50 to about 100 carbon atoms, usually aliphatic carbon atoms, and the other two substituents are lower alkyl.
When the olefin is a tri-substituted olefin, it frequently comprises a mixture of cis- and trans-1-lower alkyl, 1-(aliphatic hydrocarbyl containing from 30 to about 100 carbon atoms), 2-lower alkyl ethene and 1,1-di-lower alkyl, 2-(aliphatic hydrocarbyl containing from 30 to about 100 carbon atoms) ethene.
In one embodiment, the monoolefinic groups are predominantly vinylidene groups, i.e., groups of the formula ##STR17##
especially those of the formula ##STR18##
although the polybutenes may also comprise other olefinic configurations.
In one embodiment the polybutene is substantially monoolefinic, comprising at least about 30 mole %, preferably at least about 50 mole % vinylidene groups, more often at least about 70 mole % vinylidene groups. Such materials and methods for preparing them are described in U.S. Pat. Nos. 5,071,919; 5,137,978; 5,137,980; 5,286,823 and 5,408,018, and in published European patent application EP 646103-A1, each of which is expressly incorporated herein by reference. They are commercially available, for example under the tradenames ULTRAVIS.RTM. (BP Chemicals) and GLISSOPAL.RTM. (BASF).
In one embodiment, the olefinic compound is a polyolefin comprising a mixture of isomers, at least about 50% by weight of the mixture comprising isomers of the formula
H.sub.2 C.dbd.C(R.sup.6)(CH(R.sup.7)(R.sup.8))
wherein R.sup.6 is H or lower alkyl, preferably methyl.
As is apparent from the foregoing, olefins of a wide variety of type and of molecular weight are useful for preparing the compositions of this invention. Useful olefins are usually substantially hydrocarbon and have number average molecular weight ranging from about 100 to about 70,000, more often from about 200 to about 7,000, even more often from about 1,300 to about 5,000, frequently from about 400 to about 3,000. Particularly preferred is where the olefinic compound contains from about 30 to about 200 carbon atoms, more often from about 50 to about 100 carbon atoms. Lower olefins such as those containing from about 7 to about 30 carbon atoms, for example, octenes, octadecenes, mixed olefin, such as C.sub.8-28 linear olefins, are useful. Linear alpha-olefins containing from 7-100 carbon atoms, preferably from 8-50 carbons and often from 8 to about 28 carbon atoms are useful. In one typical embodiment, the olefinic compound contains from
Specific characterization of olefin reactants (A) used in the processes of this invention can be accomplished by using techniques known to those skilled in the art. These techniques include general qualitative analysis by infrared and determinations of average molecular weight, e.g., M.sub.n, number average molecular weight, and M.sub.w, weight average molecular weight, etc. employing vapor phase osmometry (VPO) and gel permeation chromatography (GPC). Structural details can be elucidated employing proton and carbon 13 (C.sup.13) nuclear magnetic resonance (NMR) techniques. NMR is useful for determining substitution characteristics about olefinic bonds, and provides some details regarding the nature of the substituents. More specific details regarding substituents about the olefinic bonds can be obtained by cleaving the substituents from the olefin by, for example, ozonolysis, then analyzing the cleaved products, also by NMR, GPC, VPO, and by infra-red analysis and other techniques known to the skilled person.
(B) The Carboxylic Reactant
The carboxylic reactant is at least one member selected from the group consisting of compounds of the formula
R.sup.3 C(O)(R.sup.4).sub.n C(O)OR.sup.5 (III)
wherein each of R.sup.3 and R.sup.5 is independently H or a hydrocarbyl group, preferably H or lower alkyl, R.sup.4 is a divalent hydrocarbylene group, and n is 0 or 1, and reactive sources thereof. Most preferably R.sup.3 is H and R.sup.5 are H and n=0.
Reactive sources include compounds of the formula ##STR19##
wherein each of R.sup.3 and R.sup.5 and each R.sup.9 is independently H or a hydrocarbyl group, R.sup.4 is a divalent hydrocarbylene group, and n is 0 or 1. These include acetals, ketals, hemiacetals and hemiketals of (III) and esters thereof. In one embodiment, both R.sup.9 are hydrocarbyl, preferably alkyl, more preferably, lower alkyl, groups. Highly preferred are the compounds wherein one of R.sup.9 is hydrocarbyl, preferably lower alkyl, and one is H: ##STR20##
wherein each of R.sup.3 and R.sup.5 is independently H or a hydrocarbyl group, especially wherein the hydrocarbyl group is lower alkyl. R.sup.4 is a divalent hydrocarbylene group, preferably lower alkylene, and n is 0 or 1, preferably 0. Especially preferred are the glyoxylate lower alkyl ester, lower alkyl hemiacetals. Cyclic trimers are useful.
The carboxylic reactant may be a compound of the formula ##STR21##
wherein each of R.sup.3 and R.sup.5 is independently H or alkyl. Such compounds may arise when the carboxylic acid or ester reactant is hydrated.
R.sup.3 is usually H or an aliphatic group, that is, alkyl or alkenyl, preferably alkyl, more preferably lower alkyl. Especially preferred is where R.sup.3 is H or methyl, most preferably, H.
R.sup.4 is a divalent hydrocarbylene group. This group may be aliphatic or aromatic, but is usually aliphatic. Often, R.sup.4 is an alkylene group containing from 1 to about 3 carbon atoms. The `n` is 0 or 1; that is, in one embodiment R.sup.4 is present and in another embodiment, R.sup.4 is absent. More often, R.sup.4 is absent.
When R.sup.5 is hydrocarbyl, it is usually an aliphatic group, often a group containing from 1 to about 30 carbon atoms, often from 8 to about 18 carbon atoms. In another embodiment, R.sup.5 is lower alkyl, wherein "lower alkyl" is defined hereinabove. Most often, R.sup.5 is H or lower alkyl, especially methyl, ethyl, propyl and butyl.
Examples of carboxylic reactants are glyoxylic acid, and other omega-oxoalkanoic acids, glyoxylic acid hydrate, keto alkanoic acids such as pyruvic acid, levulinic acid, ketovaleric acids, ketobutyric acids, esters thereof, preferably the lower alkyl esters, methyl glyoxylate methyl hemiacetal, 4-formylbenzoic acid, 4-formylphenoxyacetic acid, esters thereof, carboxy benzaldehyde, the hemiacetals and hemiketals of keto- or aldehydoalkanoic acids such as glyoxylic acid and keto alkanoic acids such as pyruvic acid, levulinic acid, ketovaleric acids, and ketobutyric acids, and the corresponding acetals and ketals, and numerous others. The skilled worker, having the disclosure before him, will readily recognize the appropriate carboxylic reactant (B) to employ to generate a given intermediate. Preferred carboxylic reactants are those that will lead to preferred products of this invention.
Preferred (B) reactants are lower alkyl glyoxylate, lower alkyl hemiacetals. In an especially preferred embodiment, R.sup.3 and one R.sup.9 are hydrogen and the other R.sup.9 and R.sup.5 are methyl. In this especially preferred embodiment, the reactant is represented by the structure ##STR22##
and is known as glyoxyno acid methyl ester methylhemiacetal. It is marketed by DSM Fine Chemicals.
(D) The Aldehyde or Ketone
The aldehyde or ketone reactant which may optionally be employed in the preparation of the emulsifier compositions used in this invention is a carbonyl compound other than a carboxy-substituted carbonyl compound. Accordingly, it is to be understood that it is not contemplated herein that reactant (D) includes any of the species defined hereinabove as reactant (B). Suitable compounds include those having the general formula RC(O)R', wherein R and R' are each, independently, H or a hydrocarbyl group as defined hereinabove. As noted in the description, hydrocarbyl groups may contain other groups or heteroatoms which do not interfere with the process and products of this invention. Preferably, reactant (D) contains from 1 to about 12 carbon atoms. Suitable aldehydes include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, pentanal, hexanal, heptaldehyde, octanal, benzaldehyde, and higher aldehydes. Other aldehydes, such as dialdehydes, especially glyoxal, are useful, although monoaldehydes are generally preferred.
The most preferred aldehyde is formaldehyde, which can be supplied as the aqueous solution often referred to as formalin, but is
