U.S. patent application number 13/703116 was filed with the patent office on 2013-06-06 for salt compositions and explosives using the same.
This patent application is currently assigned to THE LUBRIZOL CORPORATION. The applicant listed for this patent is Christopher J. Kolp, Barry Love, Antonio Mastrangelo, Thomas J. Wolak. Invention is credited to Christopher J. Kolp, Barry Love, Antonio Mastrangelo, Thomas J. Wolak.
Application Number | 20130139716 13/703116 |
Document ID | / |
Family ID | 45558807 |
Filed Date | 2013-06-06 |
United States Patent
Application |
20130139716 |
Kind Code |
A1 |
Wolak; Thomas J. ; et
al. |
June 6, 2013 |
SALT COMPOSITIONS AND EXPLOSIVES USING THE SAME
Abstract
This invention relates to novel salt compositions and to
explosive compositions comprising said salt compositions. The salt
compositions are useful as emulsifiers in the explosive
compositions. The explosive compositions are water-in-oil emulsion
explosives.
Inventors: |
Wolak; Thomas J.; (Mentor,
OH) ; Kolp; Christopher J.; (Mayfield Village,
OH) ; Mastrangelo; Antonio; (Carlton, GB) ;
Love; Barry; (Beverly, GB) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Wolak; Thomas J.
Kolp; Christopher J.
Mastrangelo; Antonio
Love; Barry |
Mentor
Mayfield Village
Carlton
Beverly |
OH
OH |
US
US
GB
GB |
|
|
Assignee: |
THE LUBRIZOL CORPORATION
Wickliffe
OH
|
Family ID: |
45558807 |
Appl. No.: |
13/703116 |
Filed: |
June 22, 2011 |
PCT Filed: |
June 22, 2011 |
PCT NO: |
PCT/US2011/041384 |
371 Date: |
February 26, 2013 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61358556 |
Jun 25, 2010 |
|
|
|
Current U.S.
Class: |
102/314 ;
149/108.8; 560/196 |
Current CPC
Class: |
B01F 17/0042 20130101;
C06B 47/145 20130101; F42B 3/00 20130101; C06B 23/009 20130101 |
Class at
Publication: |
102/314 ;
560/196; 149/108.8 |
International
Class: |
C06B 23/00 20060101
C06B023/00; F42B 3/00 20060101 F42B003/00 |
Claims
1. A composition comprising: (A) salt moieties derived from (A)(I)
at least one polycarboxylic acylating agent, said acylating agent
(A)(I) having at least one hydrocarbyl substituent having an
average of from about 20 to about 500 carbon atoms, and (A)(II) one
or more members selected from the group consisting of ammonia, at
least one amine, at least one alkali or alkaline earth metal, and
at least one alkali or alkaline earth metal compound; where two of
said moieties (A) are coupled together by (B) at least one compound
having at least two hydroxyls and at least one tertiary amino
group.
2. The composition of claim 1 wherein (A)(I) is derived from at
least one alpha-beta olefinically unsaturated carboxylic acid or
acid-producing compound, said acid or acid-producing compound
containing no less than 20 carbon atoms exclusive of the carboxyl
groups.
3. The composition of claim 1 wherein (A)(I) is represented by any
one or more of the following formulae: ##STR00010## wherein each
R.sup.1 in each formula is independently said hydrocarbyl
substituent of (A)(I) and wherein each R.sup.2 in each formula is
independently hydrogen or a methyl group.
4. The composition of claim 1 wherein said hydrocarbyl substituent
of (A)(I) is a poly(isobutylene) group.
5. The composition of claim 1 wherein component (B) comprises at
least one tertiary amine of the formula: ##STR00011## wherein each
a, b, and c is independently 0 or 1 so long as the total of a+b+c
is at least 2, and wherein each R.sup.3, R.sup.4 and R.sup.5 is
independently a hydrocarbon group containing from 1 to 50 carbon
atoms or an --(--R.sup.6--O--).sub.n-- group wherein R.sup.6 is a
alkenyl group containing from 1 to 6 carbon atoms, and n is an
integer from 1 to 50 or from 1 to 20.
6. The composition of claim 1 wherein component (B) comprises at
least one tertiary amine of the formula: ##STR00012## wherein each
R.sup.8 is independently a hydrocarbon group containing from 1 to
10 carbon atoms and where R.sup.9 is a hydrocarbon group containing
from 1 to 50 carbon atoms.
7. The composition of claim 1 wherein component (A)(II) comprises
at least one alkylene polyamine of the formula ##STR00013## wherein
n is a number of from 1 to about 10, each R.sup.7 is independently
a hydrogen atom or a hydrocarbyl group or a hydroxy-substituted
hydrocarbyl group having up to about 700 carbon atoms, and the
Alkylene group has from 1 to about 10 carbon atoms.
8. The composition of claim 1 wherein component (B) comprises:
3-(didodecylamino)propane-1,2-diol,
tallow-bis-(2-hydroxylethyl)amine, N-methyldiethanolamine,
N-ethyldiethanolamine, N-propyldiethanolamine
N-n-butyldiethanolamine N-tert-butyldiethanolamine
N-cyclohexyldiethanolamine N-2-ethylhexyldiethanolamine,
N-amyldiethanolamine, N-isobutyldiethanolamine,
N-sec-butyldiethanolamine, N-dodecyldiethanolamine,
N-hexadecyldiethanolamine, N-hydrogenated rapeseed
alkyldiethanolamine, N-hydrogenated tallowalkyldiethanolamine,
N-phenyldiethanolamine, N-m-tolyldiethanolamine,
bis(2-hydroxyethyl)octadecylamine,
bis(2-hydroxyethyl)cocoalkylamines, bis(2-hydroxyethyl)oleylamine,
bis(2-hydroxyethyl)soyaalkylamines,
bis(2-hydroxyethyl)tallowalkylamines, polyoxyethylene (5)
octadecylamine, polyoxyethylene (15) octadecylamine,
polyoxyethylene (5) cocoalkylamines, polyoxyethylene (15)
cocoalkylamines, polyoxyethylene (5) soyaalkylamines,
polyoxyethylene (15) soyaalkylamines, polyoxyethylene (5)
tallowalkylamines, polyoxyethylene (15) tallowalkylamines,
polyoxyethylene (20) tallowalkylamine,
3-(dimethylamino)-1,2-propanediol,
3-(diethylamino)-1,2-propanediol,
3-(dipropylamino)-1,2-propanediol,
3-(diisopropylamino)-1,2-propanediol,
3-(dioctadecylamino)-1,2-propanediol,
3-(dicocylalkylamino)-1,2-propanediol, or combinations thereof.
9. The composition of claim 1 wherein component (B) further
comprises at least one polyol.
10. The composition of claim 9 wherein the molar ratio of tertiary
amine to polyol in component (B) is from 1:0.5 to 10:1.
11. The composition of claim 1 further comprising diluent such that
the composition of claim 1 is present in the composition from about
10% to about 90% by weight, resulting in a concentrate
composition.
12. The composition of claim 1 further comprising an oxidizer phase
comprising at least one oxygen-supplying component with an organic
phase comprising at least one carbonaceous fuel, resulting in an
explosive composition.
13. An emulsion explosive composition comprising a discontinuous
oxidizer phase comprising at least one oxygen-supplying component,
a continuous organic phase comprising at least one carbonaceous
fuel, said carbonaceous fuel comprising at least one wax, and an
emulsifying amount of the composition of claim 1.
14. A cartridge comprising a cartridge casing containing either a
cap-sensitive or booster sensitive emulsion explosive, said
emulsion 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 the composition of claim 1.
15. The composition of claim 1 wherein said hydrocarbyl substituent
of (A)(I) is substantially free of hydrocarbon groups containing
less than 20 carbon atoms.
Description
FIELD OF THE INVENTION
[0001] This invention relates to novel salt compositions and to
explosive compositions comprising said salt compositions. The salt
compositions are useful as emulsifiers in the explosive
compositions. The explosive compositions are water-in-oil emulsion
explosives.
BACKGROUND OF THE INVENTION
[0002] Water-in-oil emulsion explosives typically comprise a
continuous organic phase and a discontinuous oxidizer phase
containing water and an oxygen-supplying source such as ammonium
nitrate, the oxidizer phase being dispersed throughout the
continuous organic phase. Examples of such water-in-oil emulsion
explosives are disclosed, inter alia, in U.S. Pat. Nos. 3,447,978;
3,765,964; 3,985,593; 4,008,110; 4,097,316; 4,104,092; 4,218,272;
4,259,977; 4,357,184; 4,371,408; 4,391,659; 4,404,050; 4,409,044;
4,448,619; 4,453,989; and 4,534,809; U.K. Patent Application GB
2,050,340A; and European Application No. 0,156,572 and
0,155,800.
[0003] One type of surfactant and/or emulsifier used in
conventional emulsion explosive comprises a salt of a mid molecular
weight (as defined below) hydrocarbyl-substituted carboxylic
acylating agent, i.e. polyisobutylene succinic anhydride (PIBSA),
and a salted low molecular weight hydrocarbyl-substituted
carboxylic acylating agent, i.e. a salted alkenyl succinic
anhydride. These two moieties are coupled together by reacting them
with a linking compound. Suitable linking compounds include
compounds comprising: (i) two or more primary amino groups, (ii)
two or more secondary amino groups, (iii) at least one primary
amino group and at least one secondary amino group, (iv) at least
two hydroxyl groups, (v) at least one primary or secondary amino
group and at least one hydroxyl group, or combinations thereof. See
U.S. Pat. No. 5,047,175 for additional background on these
materials.
[0004] These coupled surfactants are often combined with a high
molecular weight (as defined below) emulsifier, such as the
reaction product of a high molecular weight PIBSA and an
alkanolamine, such as dimethylethanolamine. The resulting mixture
is then used as the surfactant formulations in emulsion explosive
compositions. See U.S. Pat. No. 5,920,031 for additional background
on these materials.
[0005] While these blends perform well, the surfactant packages are
expensive and the requirement of blending the coupled surfactants
with the additional high molecular weight surfactants adds
complexity and expense to the compositions.
[0006] There is a need for a surfactant that can provide
performance at least equivalent to that provided by the packages
described above without the need to add one or more additional
surfactants to the package.
[0007] In addition, the reactions used to prepare the coupled
surfactants described above can be slow and difficult to drive to
completion. This results in waste and inefficiency as well as
additional cost. There is a need to develop reactions that produce
effective surfactants for emulsion explosive compositions that
proceeds to completion more quickly and without the need for
expensive process modification, such as adding an expensive
catalyst, increasing the reaction temperature and/or reaction time,
etc.
[0008] Another problem with conventional surfactant packages is
that the coupled surfactants described above have to be prepared
with a mixture of a mid molecular weight hydrocarbyl-substituted
carboxylic acylating agent, i.e. polyisobutylene succinic anhydride
(PIBSA), and a salted low molecular weight hydrocarbyl-substituted
carboxylic acylating agent, i.e. a salted alkenyl succinic
anhydride. This need for both mid and low molecular weight
acylating agents adds cost and complexity to the process. There is
also a need for surfactants that perform well without the use of an
additional high molecular weight surfactant while still providing
at least comparable if not improved performance.
[0009] Still another problem with emulsion explosives is their
stability, particularly during transportation. If a surfactant, and
the emulsion it provides, has poor handling properties, the
emulsion may crystallize during transportation and be unsuitable
for use. Some premium surfactant packages that perform well in all
other areas have issues in this area. There is a need for
surfactants that perform well and which provide emulsions that are
more robust and avoid problems that can arise during
transportation. Comparable performance, or even slightly worse
performance in some areas, would be sufficient if the handling
properties, particularly as it related to stability during storage
and transportation could be improved. There is a need for
surfactants, and the emulsion explosives they would provide, that
address these issues.
SUMMARY OF THE INVENTION
[0010] The present invention provides for a novel salt composition
comprising: (A) salt moieties derived from: (A)(I) at least one
polycarboxylic acylating agent having at least one hydrocarbyl
substituent having an average of from about 20 to about 500 carbon
atoms (for example at least one mid-molecular weight polycarboxylic
acylating agent having at least one hydrocarbyl substituent having
an average of from about 20 to about 500 carbon atoms); and (A)(II)
one or more members selected from the group consisting of ammonia,
at least one amine, at least one alkali or alkaline earth metal,
and at least one alkali or alkaline earth metal compound; where two
of the described moieties (A) are coupled together by (B) at least
one compound having at least two hydroxyls and at least one
tertiary amino group.
[0011] The polycarboxylic acylating agent of (A)(I) may be
represented by any one or more of the following formulae:
##STR00001##
wherein each R.sup.1 in each formula is independently said
hydrocarbyl substituent of (A)(I) and wherein each R.sup.2 in each
formula is independently hydrogen or a methyl group. In some
embodiments the hydrocarbyl substituent is a poly(isobutylene)
group.
[0012] The a compound having at least two hydroxyls and at least
one tertiary amino group, that is component (B), may be represented
by the formula:
##STR00002##
wherein each a, b, and c is independently 0 or 1 so long as the
total of a+b+c is at least 2, and wherein each R.sup.3, R.sup.4 and
R.sup.5 is independently a hydrocarbon group containing from 1 to
50 carbon atoms or an --(--R.sup.6--O--).sub.n-- group wherein
R.sup.6 is a alkenyl group containing from 1 to 6 carbon atoms, and
in some embodiments 2 carbon atoms, and n is an integer from 1 to
50 or from 1 to 20.
[0013] The (A)(II) may be represented by the formula:
##STR00003##
wherein n is a number of from 0 to about 10 or from 1 to 10, each
R.sup.7 is independently a hydrogen atom or a hydrocarbyl group or
a hydroxy-substituted hydrocarbyl group having up to about 700
carbon atoms, and the Alkylene group has from 1 to about 10 carbon
atoms.
[0014] The present invention also provides either a
booster-sensitive or cap-sensitive emulsion explosive comprising a
discontinuous oxidizer phase comprising at least one
oxygen-supplying component, a continuous organic phase comprising
at least one carbonaceous fuel. The carbonaceous fuel may include
at least one wax, and an emulsifying amount of the surfactant
compositions described herein.
[0015] The present invention further provides a cartridge casing
containing at least one cap-sensitive emulsion explosive or booster
sensitive explosive composition, said emulsion 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 the
surfactant compositions described herein.
[0016] The invention further provides surfactants, as described
herein, where component (A)(I) is substantially free, or even free
of, acylating agents containing fewer than 50, 40, 20 or even 15
carbon atoms in their hydrocarbyl groups.
DETAILED DESCRIPTION OF THE INVENTION
[0017] Various features and embodiments of the invention will be
described below by way of non-limiting illustration.
[0018] The terms "low molecular weight", "mid molecular weight",
and "high molecular weight" as used in this specification and in
the appended claims are intended to provide a relative description
when discussing the acylating agents used in the preparation of the
coupled surfactants described herein as well as the acylating
agents used in the preparation of the non-coupled surfactants
sometimes used in combination with some conventional coupled
surfactants. In some embodiments low molecular weight means less
than half the molecular weight of the mid molecular weight
materials and high molecular weight means at least twice the
molecular weight of the mid molecular weight materials. In some
embodiments low molecular weight means the material referred to
contains less than 50 carbon atoms, or less than 40, 20 or even 15
carbon atoms. In some embodiments mid molecular weight means the
material referred to contains less from 20 to 500 carbon atoms, or
from 30, 40 or even 50 up to 500, 250, 150, 120 or even 100 carbon
atoms. In some embodiments high molecular weight means the material
referred to contains at least 120 carbon atoms, or from 100, 120 or
140 up to 500, 400 or even 300 carbon atoms. The number of carbon
atoms listed above may be applied either as respective minimum or
maximum values for a materials that contains a mixture of
hydrocarbons of varying sizes, or as defining the range that the
average number of carbon atoms present in a mixture of hydrocarbons
of varying sizes fall in. In some embodiments low molecular weight
means the material referred to has a number average molecular
weight (Mn) of less than 700 or even less than 500, or from 100 or
120 to 700 or 500 or even 450. In some embodiments mid molecular
weight means the material referred has an Mn of 500 to 1600 or from
800 or 900 to 1500, 1300, or even 1200. In some embodiments high
molecular weight means the material referred to has an Mn of from
1300 to 5000, or from 1300, 1500 or even 1600 up to 5000, 3000, or
even 2000.
[0019] 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 compositions derived from such emulsions
wherein at temperatures below that at which the emulsion is formed
the discontinuous phase is solid or in the form of droplets of
super-cooled liquid. This term also covers compositions derived
from or formulated as such water-in-oil emulsions that are in the
form of gelatinous or semi-gelatinous compositions.
[0020] The term "hydrocarbyl" is used herein to include: (1)
hydrocarbyl groups, that is, aliphatic (e.g., alkyl or alkenyl),
alicyclic (e.g., cycloalkyl, cycloalkenyl), aromatic, aliphatic-
and alicyclicsubstituted aromatic groups and the like as well as
cyclic groups wherein the ring is completed through another portion
of the molecule (that is, any two indicated groups may together
form an alicyclic group); (2) substituted hydrocarbyl groups, that
is, those groups containing non-hydrocarbon groups which, in the
context of this invention, do not alter the predominantly
hydrocarbyl nature of the hydrocarbyl group; those skilled in the
art will be aware of such groups, examples of which include ether,
oxo, halo (e.g., chloro and fluoro), alkoxyl, mercapto,
alkylmercapto, nitro, nitroso, sulfoxy, etc.; (3) hetero groups,
that is, groups which, while having predominantly hydrocarbyl
character within the context of this invention, contain other than
carbon in a ring or chain otherwise composed of carbon atoms.
Suitable heteroatoms will be apparent to those of skill in the art
and include, for example, sulfur, oxygen, nitrogen and such
substituents as pyridyl, furanyl, thiophenyl, imidazolyl, etc.
[0021] In general, no more than about three non-hydrocarbon groups
or heteroatoms and preferably no more than one will be present for
each ten carbon atoms in a hydrocarbyl group. Typically, there will
be no such groups or heteroatoms in a hydrocarbyl group and it
will, therefore, be purely hydrocarbyl.
[0022] The hydrocarbyl groups in some embodiments are free from
acetylenic unsaturation; ethylenic unsaturation, when present will
generally be such that there is no more than one ethylenic linkage
present for every ten carbon to-carbon bonds.
[0023] The term "lower" as used herein in conjunction with terms
such as alkyl, alkenyl, alkoxy, and the like, may be intended to
describe such groups which contain a total of up to 30, 24 or even
16 or 8 or 7 carbon atoms.
[0024] The term "substantially free of" as used herein is intended
to mean less than a significant amount that would impact the nature
or character of the composition and/or compound being described.
The term may also mean the material referred to is present at less
than 10%, 5%, 2%, 1%, 0.5%, or even 0.1% by weight of the
composition and/or component being described. In still other
embodiments it may mean that less than 1,000 ppm, 500 ppm or even
100 ppm of the material in question is present. In other
embodiments the term may mean no more than the amount
unintentionally and/or unavoidably present due to the use of
industrial materials that may contain byproducts and/or
impurities.
Component (A)(I)
[0025] The carboxylic acylating agent of component (A)(I) may be
aliphatic or aromatic, polycarboxylic acids or acid-producing
compounds. Throughout this specification and in the appended
claims, the term "carboxylic acylating agent" is intended to
include carboxylic acids as well as acid-producing derivatives
thereof such as anhydrides, esters, acyl halides and mixtures
thereof, unless otherwise specifically stated.
[0026] The acylating agent (A)(I) may contain polar substituents
provided that the polar substituents are not present in portions
sufficiently large to alter significantly the hydrocarbon character
of the acylating agent. Typical suitable polar substituents include
halo, such as chloro and bromo, oxo, oxy, formyl, sulfenyl,
sulfinyl, thio, nitro, etc. Such polar substituents, if present,
preferably do not exceed about 10% by weight of the total weight of
the hydrocarbon portion of the acylating agent, exclusive of the
carboxyl groups.
[0027] The polycarboxylic acylating agents (A)(I) are well known in
the art and have been described in detail, for example, in the
following U.S., British and Canadian patents: U.S. Pat. Nos.
3,024,237; 3,087,936; 3,163,603; 3,172,892; 3,215,707; 3,219,666;
3,231,587; 3,245,910; 3,254,025; 3,271,310; 3,272,743; 3,272,746;
3,278,550; 3,288,714; 3,306,907; 3,307,928; 3,312,619; 3,341,542;
3,346,354; 3,367,943; 3,373,111; 3,374,174; 3,381,022; 3,394,179;
3,454,607; 3,346,354; 3,470,098; 3,630,902; 3,652,616; 3,755,169;
3,868,330; 3,912,764; 4,234,435; and 4,368,133; British Patents
944,136; 1,085,903; 1,162,436; and 1,440,219; and Canadian Patent
956,397. These patents are incorporated herein by reference.
[0028] As disclosed in the foregoing patents, there are several
processes for preparing these acylating agents (A)(I). Generally,
these processes involve the reaction of (1) an ethylenically
unsaturated carboxylic acid, acid halide, anhydride or ester
reactant with (2) an ethylenically unsaturated hydrocarbon
containing at least about 20 aliphatic carbon atoms or a
chlorinated hydrocarbon containing at least about 20 aliphatic
carbon atoms at a temperature within the range of about 100-300
degrees C. The chlorinated hydrocarbon or ethylenically unsaturated
hydrocarbon reactant preferably contains at least about 30 carbon
atoms, more preferably at least about 40 carbon atoms, more
preferably at least about 50 carbon atoms, and may contain polar
substituents, oil-solubilizing pendant groups, and be unsaturated
within the general limitations explained hereinabove.
[0029] When preparing the carboxylic acid acylating agent, the
carboxylic acid reactant usually corresponds to the formula
R.sub.o--(COOH).sub.n, where R.sub.o is characterized by the
presence of at least one ethylenically unsaturated carbon-to-carbon
covalent bond and n is an integer from 2 to 6, and in some
embodiments is 2. The acidic reactant can also be the corresponding
carboxylic acid halide, anhydride, ester, or other equivalent
acylating agent and mixtures of two or more of these. Ordinarily,
the total number of carbon atoms in the acidic reactant will not
exceed about 20, or about 10 or even about 6, exclusive of the
carboxyl-based groups. In some embodiments the acidic reactant will
have at least one ethylenic linkage in an alpha,
[0030] The ethylenically unsaturated hydrocarbon reactant and the
chlorinated hydrocarbon reactant used in the preparation of these
carboxylic acylating agents (A)(I) are in some embodiments of
mid-molecular weight, as defined above, substantially saturated
petroleum fractions and substantially saturated olefin polymers and
the corresponding chlorinated products. Polymers and chlorinated
polymers derived from mono-olefins having from 2 to about 30 carbon
atoms are preferred. Especially useful polymers are the polymers of
1-mono-olefins such as ethylene, propene, 1-butene, isobutene,
1-hexene, 1-octene, 2-methyl-1-heptene, 3-cyclohexyl-1-butene, and
2-methyl-5-propyl-1-hexene. Polymers of internal olefins, i.e.,
olefins in which the olefinic linkage is not at the terminal
position, likewise are useful. These are exemplified by 2-butene,
3-pentene, and 4-octene
[0031] Interpolymers of 1-mono-olefins such as illustrated above
with each other and with other interpolymerizable olefinic
substances such as aromatic olefins, cyclic olefins, and
polyolefins, are also useful sources of the ethylenically
unsaturated reactant. Such interpolymers include for example, those
prepared by polymerizing isobutene with styrene, isobutene with
butadiene, propene with isoprene, propene with isobutene, ethylene
with piperylene, isobutene with chloroprene, isobutene with
p-methyl-styrene, 1-hexene with 1,3-hexadiene, 1-octene with
1-hexene, 1-heptene with 1-pentene, 3-methyl1-butene with 1-octene,
3,3-dimethyl-1-pentene with 1-hexene, isobutene with styrene and
piperylene, etc.
[0032] For reasons of hydrocarbon solubility, the interpolymers
contemplated for use in preparing the acylating agents of this
invention are preferably substantially aliphatic and substantially
saturated, that is, they should contain at least about 80% and
preferably about 95%, on a weight basis, of units derived from
aliphatic mono-olefins. Preferably, they will contain no more than
about 5% olefinic linkages based on the total number of the
carbon-to-carbon covalent linkages present.
[0033] In one embodiment of the invention, the polymers and
chlorinated polymers are obtained by the polymerization of a
C.sub.4 refinery stream having a butene content of about 35% to
about 75% by weight and an isobutene content of about 30% to about
60% by weight in the presence of a Lewis acid catalyst such as
aluminum chloride or boron trifluoride. These polyisobutenes
preferably contain predominantly (that is, greater than about 80%
of the total repeat units) isobutene repeat units of the
configuration: --[--CH.sub.2--C(CH.sub.3).sub.2--]--.
[0034] The chlorinated hydrocarbons and ethylenically unsaturated
hydrocarbons used in the preparation of the carboxylic acylating
agents is some embodiments have up to about 500 carbon atoms per
molecule. Suitable acylating agents for use in component (A)(I)
include those containing hydrocarbyl groups of from about 20 to
about 500 carbon atoms, or from about 30, 40 or even 50 to about
500 carbon atoms.
[0035] The polycarboxylic acylating agents (A)(I) may also be
prepared by halogenating a hydrocarbon such as the above described
olefin polymers to produce a poly-halogenated product, converting
the poly-halogenated product to a polynitrile, and then hydrolyzing
the polynitrile. They may be prepared by oxidation of a polyhydric
alcohol with potassium permanganate, nitric acid, or a similar
oxidizing agent. Another method involves the reaction of an olefin
or a polar-substituted hydrocarbon such as a chloropolyisobutene
with an unsaturated polycarboxylic acid such as
2-pentene-1,3,5-tricarboxylic acid prepared by dehydration of
citric acid.
[0036] The polycarboxylic acid acylating agents (A)(I) can also be
obtained by reacting chlorinated polycarboxylic acids, anhydrides,
acyl halides, and the like with ethylenically unsaturated
hydrocarbons or ethylenically unsaturated substituted hydrocarbons
such as the polyolefins and substituted polyolefins described
hereinbefore in the manner described in U.S. Pat. No. 3,340,281,
this patent being incorporated herein by reference.
[0037] The polycarboxylic acid anhydrides (A)(I) can be obtained by
dehydrating the corresponding acids. Dehydration is readily
accomplished by heating the acid to a temperature above about
70.degree. C., preferably in the presence of a dehydration agent,
e.g., acetic anhydride. Cyclic anhydrides are usually obtained from
polycarboxylic acids having acid groups separated by no more than
three carbon atoms such as substituted succinic or glutaric acid,
whereas linear anhydrides are usually obtained from polycarboxylic
acids having the acid groups separated by four or more carbon
atoms.
[0038] The acid halides of the polycarboxylic acids can be prepared
by the reaction of the acids or their anhydrides with a
halogenating agent such as phosphorus tribromide, phosphorus
pentachloride, or thionyl chloride.
[0039] Hydrocarbyl-substituted succinic acids and the anhydride,
acid halide and ester derivatives thereof are particularly
preferred acylating agents (A)(I). These acylating agents may be
prepared by reacting maleic anhydride with an olefin or a
chlorinated hydrocarbon such as a chlorinated polyolefin. The
reaction involves merely heating the two reactants at a temperature
in the range of about 100 to 300 degrees C., or about 100 to 200
degrees C. The product from this reaction is a
hydrocarbyl-substituted succinic anhydride wherein the substituent
is derived from the olefin or chlorinated hydrocarbon. The product
may be hydrogenated to remove all or a portion of any ethylenically
unsaturated covalent linkages by standard hydrogenation procedures,
if desired. The hydrocarbyl-substituted succinic anhydrides may be
hydrolyzed by treatment with water or steam to the corresponding
acid and either the anhydride or the acid may be converted to the
corresponding acid halide or ester by reacting with a phosphorus
halide, phenol or alcohol. In some embodiments the hydrocarbyl
group of component (A)(I) contains from 20, 30, 40 or even 50
carbon atoms up to 500 carbon atoms. In some embodiments the
hydrocarbyl group is derived from polyisobutylene and has a number
average molecular weight of 800 to 1500, 800 to 1200, 900 to 1100
or even about 1000.
[0040] As provided above, the hydrocarbyl-substituted succinic
acids and anhydrides (A)(I) can be represented by formulas (I)
through (IV):
##STR00004##
wherein each R.sup.1 in each formula is independently said
hydrocarbyl substituent of (A)(I) and wherein each R.sup.2 in each
formula is independently hydrogen or a methyl group. In some
embodiments the hydrocarbyl substituent is a poly(isobutylene)
group. In some embodiments the succinic acids and anhydrides are in
the form of formulas (I) and (II) and in other embodiments the
succinic acids and anhydrides are in the form of formulas (III) and
(IV). In formulas (I), (II), (III) and/or (IV), each R.sup.1 in
each formula is independently said hydrocarbyl substituent of
(A)(I) and wherein each R.sup.2 in each formula is independently
hydrogen or a methyl group. In some embodiments the hydrocarbyl
substituent is a poly(isobutylene) group. Each R.sup.1 may
independently contain from 20, 30, 40 or even 50 carbon atoms up to
500, 400, or even 350 carbon atoms.
[0041] Component (A)(I) may also include disuccans, such as those
represented by the following formula:
##STR00005##
where R.sup.1 and R.sup.2 are defined as provided above for
formulas (I) to (IV).
[0042] In some embodiments the acylating agent (A)(I) is an
aliphatic polycarboxylic acid, or a dicarboxylic acid. However
(A)(I) may also be an aromatic polycarboxylic acid or
acid-producing compound. The aromatic acids are preferably
alkyl-substituted, dicarboxysubstituted benzene, naphthalene,
anthracene, phenanthrene or like aromatic hydrocarbons. The alkyl
groups may contain up to about 30 carbon atoms. The aromatic acid
may also contain other substituents such as halo, hydroxy, lower
alkoxy, etc.
Component (A)(II)
[0043] The amines useful as component (A)(II) in preparing the salt
compositions of the invention include ammonia, and primary amines,
secondary amines and hydroxyamines. Component (A)(II) may include
monoamines, polyamines, and/or mixtures thereof. Suitable amines
include primary, secondary, and/or tertiary; aliphatic,
cycloaliphatic and/or aromatic amines.
[0044] Useful primary and secondary amines include aliphatic
monoamines. Aliphatic monoamines include mono-aliphatic and
di-aliphatic-substituted amines wherein the aliphatic groups can be
saturated or unsaturated and straight or branched chain. Thus, they
are primary or secondary aliphatic amines. Such amines include, for
example, mono- and di-alkyl-substituted amines, mono- and
dialkenyl-substituted amines, and amines having one N-alkenyl
substituent and one N-alkyl substituent, and the like. The total
number of carbon atoms in these aliphatic monoamines preferably
does not exceed about 40 and usually does not exceed about 20
carbon atoms. Specific examples of such monoamines include
ethylamine, di-ethylamine, n-butylamine, di-n-butylamine,
allylamine, isobutylamine, cocoamine, stearylamine, laurylamine,
methyllaurylamine, oleylamine, N-methyl-octylamine, dodecylamine,
octadecylamine, and the like. Examples of
cycloaliphatic-substituted aliphatic amines, aromatic-substituted
aliphatic amines, and heterocyclic-substituted aliphatic amines,
include 2-(cyclohexyl)-ethylamine, benzylamine, phenylethylamine,
and 3-(furylpropyl)amine.
[0045] Suitable amines include cycloaliphatic monoamines which are
those monoamines wherein there is one cycloaliphatic substituent
attached directly to the amino nitrogen through a carbon atom in
the cyclic ring structure. Examples of cycloaliphatic monoamines
include cyclohexylamines, cyclopentylamines, cyclohexenylamines,
cyclopentenylamines, N-ethyl-cyclohexylamines, dicyclohexylamines,
and the like. Examples of aliphatic-substituted,
aromatic-substituted, and heterocyclic-substituted cycloaliphatic
monoamines include propyl-substituted cyclohexylamines,
phenyl-substituted cyclopentylamines and pyranyl-substituted
cyclohexylamine.
[0046] Suitable amines include aromatic monoamines which are those
monoamines wherein a carbon atom of the aromatic ring structure is
attached directly to the amino nitrogen. The aromatic ring will
usually be a mononuclear aromatic ring (i.e., one derived from
benzene) but can include fused aromatic rings, especially those
derived from naphthylene. Examples of aromatic monoamines include
aniline, di(paramethylphenyl)amine, naphthylamine, N-(n-butyl)
aniline, and the like. Examples of aliphatic-substituted,
cycloaliphatic-substituted, and heterocyclic-substituted aromatic
monoamines include para-ethoxyaniline, paradodecylamine,
cyclohexyl-substituted naphthylamine and thienylsubstituted
aniline.
[0047] Heterocyclic polyamines can also be used. As used herein,
the terminology "heterocyclic polyamine" is intended to describe
those heterocyclic amines containing at least two primary amino
groups, at least two secondary amino groups, or at least one of
each, and at least one nitrogen as a heteroatom in the heterocyclic
ring. As long as there is present in the heterocyclic polyamines at
least two primary amino groups, at least two secondary amino
groups, or at least one of each, the hetero-N atom in the ring can
be a tertiary amino nitrogen; that is, one that does not have
hydrogen attached directly to the ring nitrogen. The hetero-N atom
can be one of the secondary amino groups; that is, it can be a ring
nitrogen with hydrogen directly attached to it. Heterocyclic amines
can be saturated or unsaturated and can contain various
substituents such as nitro, alkoxy, alkyl mercapto, alkyl, alkenyl,
aryl, alkaryl, or aralkyl substituents. Generally, the total number
of carbon atoms in the substituents will not exceed about 20.
Heterocyclic amines can contain heteroatoms other than nitrogen,
especially oxygen and sulfur. Obviously they can contain more than
one nitrogen heteroatom. The 5- and 6-membered heterocyclic rings
are preferred.
[0048] Among the suitable heterocyclic polyamines are the
aziridines, azetidines, azolidines, tetra- and di-hydro pyridines,
pyrroles, indoles, piperadines, imidazoles, di- and
tetra-hydroimidazoles, piperazines, isoindoles, purines,
morpholines, thiomorpholines, N-aminoalkylmorpholines,
N-aminoalkylthiomorpholines, N-aminoalkylpiperazines,
N,N'-di-aminoalkylpiperazines, azepines, azocines, azonines,
azecines and tetra-, di- and perhydro-derivatives of each of the
above and mixtures of two or more of these heterocyclic amines.
Useful heterocyclic polyamines are the saturated 5- and 6-membered
heterocyclic polyamines containing only nitrogen, oxygen and/or
sulfur in the hetero ring, especially the piperidines, piperazines,
thiomorpholines, morpholines, pyrrolidines, and the like. Usually
the aminoalkyl substituents are substituted on a nitrogen atom
forming part of the hetero ring. Specific examples of such
heterocyclic amines include N-aminoethylpiperazine and
N,N'-diaminoethylpiperazine.
[0049] Hydrazine and substituted-hydrazines can also be used. The
substituents which may be present on the hydrazine include alkyl,
alkenyl, aryl, aralkyl, alkaryl, and the like. Usually, the
substituents are alkyl, especially lower alkyl, phenyl, and
substituted phenyl such as lower alkoxy-substituted phenyl or lower
alkyl-substituted phenyl. Specific examples of substituted
hydrazines are methylhydrazine, N,N-dimethylhydrazine,
N,N'-dimethylhydrazine, phenylhydrazine,
N-phenyl-N'-ethylhydrazine, N-(para-tolyl)-N'-(n-butyl)-hydrazine,
N-(para-nitrophenyl)-hydrazine,
N-(para-nitrophenyl)-N-methylhydrazine,
N,N'-di-(para-chlorophenol)-hydrazine,
N-phenyl-N'-cyclohexylhydrazine, and the like.
[0050] Another group of amines suitable for use in this invention
are branched polyalkylene polyamines. The branched polyalkylene
polyamines are polyalkylene polyamines wherein the branched group
is a side chain containing on the average at least one
nitrogen-bonded aminoalkylene group, (i.e.
NH.sub.2--R--[--N(H)--R--].sub.X--), per nine amino units present
on the main chain; for example, 1-4 of such branched chains per
nine units on the main chain, but preferably one side chain unit
per nine main chain units. Thus, these polyamines contain at least
three primary amino groups and at least one tertiary amino
group.
[0051] Useful polyoxyalkylene polyamines include the
polyoxyethylene and polyoxypropylene diamines and the
polyoxypropylene triamines having average molecular weights ranging
from about 200 to about 2000. The polyoxyalkylene polyamines are
commercially available from the Jefferson Chemical Company, Inc.
under the trade name "Jeffamine". U.S. Pat. Nos. 3,804,763 and
3,948,800 are incorporated herein by reference for their disclosure
of such polyoxyalkylene polyamines.
[0052] As noted above, useful polyamines alkylene polyamines
conforming to formula (VI):
##STR00006##
wherein n may be from 1 to 10 or even 7; each R and R' is
independently a hydrogen atom, a hydrocarbyl group or a
hydroxy-substituted hydrocarbyl group having up to about 700, 100,
50 or even 30 carbon atoms, with the proviso that at least one of R
and at least one of R' are hydrogen; and the "Alkylene" group has
from 1 up to 18, or even 4 carbon atoms, and in some embodiments
the Alkylene group is ethylene or propylene. Useful alkylene
polyamines are those wherein each R and each R' is hydrogen with
the ethylene polyamines, and mixtures of ethylene polyamines being
particularly preferred. Such alkylene polyamines include methylene
polyamines, ethylene polyamines, butylene polyamines, propylene
polyamines, pentylene polyamines, hexylene polyamines, heptylene
polyamines, etc. The higher homologs of such amines and related
aminoalkyl-substituted piperazines are also included.
[0053] Alkylene polyamines that are useful include ethylene
diamine, diethylene triamine, triethylene tetramine, tetraethylene
pentamine, pentaethylene hexamine, propylene diamine, trimethylene
diamine, hexamethylene diamine, octamethylene diamine,
di(heptamethylene)triamine, tripropylene tetramine, tetraethylene
pentamine, trimethylene diamine, pentaethylene hexamine,
di(trimethylene)triamine, N-(2-aminoethyl)piperazine,
1,4-bis(2-aminoethyl)piperazine, and the like. Higher homologs as
are obtained by condensing two or more of the above-illustrated
alkylene amines are useful as amines in this invention as are
mixtures of two or more of any of the afore-described
polyamines.
[0054] Ethylene polyamines, such as those mentioned above, are
described in detail under the heading "Diamines and Higher Amines,
Aliphatic" in The Encyclopedia of Chemical Technology, Third
Edition, Kirk-Othmer, Volume 7, pp. 580-602, a Wiley-Interscience
Publication, John Wiley and Sons, 1979, these pages being
incorporated herein by reference. Such compounds are prepared most
conveniently by the reaction of an alkylene chloride with ammonia
or by reaction of an ethylene imine with a ring-opening reagent
such as ammonia, etc. These reactions result in the production of
the somewhat complex mixtures of alkylene polyamines, including
cyclic condensation products such as piperazines.
[0055] Alkoxylated alkylene polyamines (e.g.,
N,N-(diethanol)-ethylene diamine) can be used. Such polyamines can
be made by reacting alkylene amines (e.g., ethylenediamine) with
one or more alkylene oxides (e.g., ethylene oxide, octadecene
oxide) of two to about 20 carbons. Similar alkylene oxide-alkanol
amine reaction products can also be used such as the products made
by reacting the afore-described primary, secondary or tertiary
alkanol amines with ethylene, propylene or higher epoxides in a 1:1
or 1:2 molar ratio. Reactant ratios and temperatures for carrying
out such reactions are known to those skilled in the art.
[0056] Specific examples of alkoxylated alkylene polyamines include
N-(2-hydroxyethyl)ethylene diamine,
N,Nbis(2-hydroxyethyl)-ethylene-diamine,
1-(2-hydroxyethyl)piperazine, mono(hydroxypropyl)-substituted
diethylene triamine, di(hydroxypropyl)-substituted tetraethylene
pentamine, N-(3-hydroxybutyl)-tetramethylene diamine, etc. Higher
homologs obtained by condensation of the above-illustrated hydroxy
alkylene polyamines through amino groups or through hydroxy groups
are likewise useful. Condensation through amino groups results in a
higher amine accompanied by removal of ammonia while condensation
through the hydroxy groups results in products containing ether
linkages accompanied by removal of water. Mixtures of two or more
of any of the aforesaid polyamines are also useful.
[0057] Suitable hydroxyamines include primary or secondary amines.
They can also be tertiary amines provided said tertiary amines also
contain at least two hydroxyl groups. These hydroxyamines contain
at least two >NH groups, at least two --NH2 groups, at least one
--OH group and at least one >NH or --NH.sub.2 group, or at least
two --OH groups. The terms "hydroxyamine" and "aminoalcohol"
describe the same class of compounds and, therefore, can be used
interchangeably.
[0058] The hydroxyamines can be primary or secondary alkanol amines
or mixtures thereof. Such amines can be represented, respectfully,
by the formulae: H.sub.2N--R'--OH and (H)(R)N--R'--OH wherein R is
a hydrocarbyl group of one to about eight carbon atoms or
hydroxyl-substituted hydrocarbyl group of two to about eight carbon
atoms and R' is a divalent hydrocarbyl group of about two to about
18 carbon atoms. The group --R'--OH in such formulae represents the
hydroxyl-substituted hydrocarbyl group. R' can be an acyclic,
alicyclic or aromatic group. Typically, R' is an acyclic straight
or branched alkylene group such as an ethylene, 1,2-propylene,
1,2-butylene, 1,2-octadecylene, etc. group. Typically, R is a lower
alkyl group of up to seven carbon atoms.
[0059] The hydroxyamines can also be ether N-(hydroxy-substituted
hydrocarbyl)amines. These are hydroxyl-substituted
poly(hydrocarbyloxy) analogs of the above-described primary and
secondary alkanol amines (these analogs also include
hydroxyl-substituted oxyalkylene analogs). Such
N-(hydroxyl-substituted hydrocarbyl)amines can be conveniently
prepared by reaction of epoxides with afore-described amines and
can be represented by the formulae: H.sub.2N--(R'O).sub.x--H and
(H)(R)N--(R'O).sub.x--H wherein x is a number from about 2 to about
15 and R and R' are as described above.
[0060] Polyamine analogs of these hydroxy amines, particularly
alkoxylated alkylene polyamines (e.g., N,N-(di-ethanol)-ethylene
diamine) can also be used. Such polyamines can be made by reacting
alkylene amines (e.g., ethylenediamine) with one or more alkylene
oxides (e.g., ethylene oxide, octadecene oxide) of two to about 20
carbons. Similar alkylene oxide-alkanol amine reaction products can
also be used such as the products made by reacting the
afore-described primary or secondary alkanol amines with ethylene,
propylene or higher epoxides in a 1:1 or 1:2 molar ratio. Reactant
ratios and temperatures for carrying out such reactions are known
to those skilled in the art.
[0061] Hydroxyalkyl alkylene polyamines having one or more
hydroxyalkyl substituents on the nitrogen atoms, are also useful.
Useful hydroxyalkyl-substituted alkylene polyamines include those
in which the hydroxyalkyl group is a lower hydroxyalkyl group,
i.e., having less than eight carbon atoms. Examples of such
hydroxy-alkyl-substituted polyamines include
N-(2-hydroxyethyl)ethylene diamine, N,N-bis(2-hydroxyethyl)ethylene
diamine, 1-(2-hydroxyethyl)-piperazine,
monohydroxypropyl-substituted diethylene triamine,
dihydroxypropylsubstituted tetraethylene pentamine,
N-(3-hydroxybutyl)tetramethylene diamine, etc. Higher homologs as
are obtained by condensation of the above-illustrated hydroxy
alkylene polyamines through amino groups or through hydroxy groups
are likewise useful. Condensation through amino groups results in a
higher amine accompanied by removal of ammonia and condensation
through the hydroxy groups results in products containing ether
linkages accompanied by removal of water.
[0062] Examples of the N-(hydroxyl-substituted hydrocarbyl)amines
include mono-, di-, and triethanol amine, diethylethanol amine,
di-(3-hydroxyl propyl)amine, N-(3-hydroxyl butyl)amine,
N-(4-hydroxyl butyl)amine, N,N-di-(2-hydroxyl propyl)amine,
N-(2-hydroxyl ethyl) morpholine and its thio analog, N-(2-hydroxyl
ethyl)cyclohexyl amine, N-3-hydroxyl cyclopentyl amine, o-, m- and
p-aminophenol, N-(hydroxyl ethyl)piperazine, N,N'-di(hydroxyl
ethyl)piperazine, and the like.
[0063] Further hydroxyamines are the hydroxy-substituted primary
amines described in U.S. Pat. No. 3,576,743 by the general formula:
R.sub.a--NH.sub.2 wherein R.sub.a is a monovalent organic group
containing at least one alcoholic hydroxy group. The total number
of carbon atoms in R.sub.a preferably does not exceed about 20.
Hydroxy-substituted aliphatic primary amines containing a total of
up to about 10 carbon atoms are useful. The polyhydroxy-substituted
alkanol primary amines wherein there is only one amino group
present (i.e., a primary amino group) having one alkyl substituent
containing up to about 10 carbon atoms and up to about 6 hydroxyl
groups are useful. These alkanol primary amines correspond to
R.sub.a--NH.sub.2 wherein R.sub.a is a mono or poly
hydroxy-substituted alkyl group. Specific examples of the
hydroxy-substituted primary amines include 2-amino-1-butanol,
2-amino-2-methyl-1-propanol, p-(beta-hydroxyethyl)-aniline,
2-amino-1-propanol, 3-amino-1-propanol,
2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol,
N-(beta-hydroxypropyl)-N'-(beta-aminoethyl)-piperazine,
tris-(hydroxymethyl)amino methane (also known as trismethylolamino
methane), 2-amino-1-butanol, ethanolamine,
beta-(beta-hydroxyethoxy)-ethyl amine, glucamine, glusoamine,
4-amino-3-hydroxy-3-methyl-1-buten (which can be prepared according
to procedures known in the art by reacting isopreneoxide with
ammonia), N-3-(aminopropyl)-4-(2-hydroxyethyl)-piperadine,
2-amino-6-methyl-6-heptanol, 5-amino-1-pentanol,
N-(beta-hydroxyethyl)-1,3-diamino propane,
1,3-diamino-2-hydroxypropane, N-(beta-hydroxy
ethoxyethyl)-ethylenediamine and the like. U.S. Pat. No. 3,576,743
is incorporated herein by reference.
[0064] In addition to ammonia, the primary amines, secondary amines
and hydroxyamines discussed above, the amines useful as components
(A)(II) also include tertiary mono- and polyamines. The tertiary
amines are analogous to the primary amines, secondary amines and
hydroxyamines discussed above with the exception that they can be
either monoamines or polyamines and the hydrogen atoms in the
H--N< or --NH2 groups are replaced by hydrocarbyl groups.
[0065] The tertiary amines can be aliphatic, cycloaliphatic,
aromatic or heterocyclic, including aliphatic-substituted aromatic,
aliphatic-substituted cycloaliphatic, aliphatic-substituted
heterocyclic, cycloaliphatic-substituted aliphatic, cycloaliphatic
substituted aromatic, cycloaliphatic-substituted heterocyclic,
aromatic-substituted aliphatic, aromatic-substituted
cycloaliphatic, aromatic-substituted heterocyclic,
heterocyclic-substituted aliphatic, heterocyclic-substituted
cycloaliphatic and heterocyclic-substituted aromatic amines. These
tertiary amines may be saturated or unsaturated. If unsaturated,
the amine is preferably free from acetylenic unsaturation. The
tertiary amines may also contain non-hydrocarbon substituents or
groups as long as these groups do not significantly interfere with
the reaction of component (B) with component (A). Such
non-hydrocarbon substituents or groups include lower alkoxy, lower
alkyl, mercapto, nitro, and interrupting groups such as --O-- and
--S-- (e.g., as in such groups as
--CH.sub.2CH.sub.2--X--CH.sub.2CH.sub.2-- where X is --O-- or
--S--).
[0066] The monoamines can be represented by the formula
(R.sup.1)(R.sup.2)(R.sup.3)N wherein R.sup.1, R.sup.2 and R.sup.3
are the same or different hydrocarbyl groups. In some embodiments
R.sup.1, R.sup.2 and R.sup.3 independently hydrocarbyl groups of
from 1 to about 20 carbon atoms.
[0067] Examples of useful tertiary amines include trimethyl amine,
triethyl amine, tripropyl amine, tributyl amine,
monomethyldiethylamine, monoethyldimethyl amine, dimethylpropyl
amine, dimethylbutyl amine, dimethylpentyl amine, dimethylhexyl
amine, dimethylheptyl amine, dimethyloctyl amine, dimethylnonyl
amine, dimethyldecyl amine, dimethylphenyl amine,
N,N-dioctyl-1-octanamine, N,N-didodecyl-1-dodecanamine tricoco
amine, trihydrogenated-tallow amine, N-methyl-dihydrogenated tallow
amine, N,N-dimethyl-1-dodecanamine, N,N-dimethyl-1-tetradecanamine,
N,N-dimethyl-1-hexadecanamine, N,N-dimethyl-1-octadecanamine,
N,N-dimethylcocoamine, N,N-dimethylsoyaamine,
N,N-dimethylhydrogenated tallow amine, etc.
[0068] Useful tertiary alkanol amines are represented by the
formula (R)(R)N--R.sup.1--OH wherein each R is independently a
hydrocarbyl group of one to about eight carbon atoms or
hydroxyl-substituted hydrocarbyl group of two to about eight carbon
atoms and R.sup.1 is a divalent hydrocarbyl group of about two to
about 18 carbon atoms. The group --R.sup.1--OH in such formula
represents the hydroxyl-substituted hydrocarbyl group. R' can be an
acyclic, alicyclic or aromatic group. Typically, R' is an acyclic
straight or branched alkylene group such as an ethylene,
1,2-propylene, 1,2-butylene, 1,2-octadecylene, etc. group. Where
two R groups are present in the same molecule they can be joined by
a direct carbon-to-carbon bond or through a heteroatom (e.g.,
oxygen, nitrogen or sulfur) to form a 5-, 6-, 7- or 8-membered ring
structure. Examples of such heterocyclic amines include N-(hydroxyl
lower alkyl)-morpholines, -thiomorpholines, -piperidines,
-oxazolidines, -thiazolidines and the like. Typically, however,
each R is a lower alkyl group of up to seven carbon atoms. The
hydroxyamines can also be an ether N-(hydroxy-substituted
hydrocarbyl)amine. These are hydroxyl-substituted
poly(hydrocarbyloxy) analogs of the above-described hydroxy amines
(these analogs also include hydroxyl-substituted oxyalkylene
analogs). Such N-(hydroxyl-substituted hydrocarbyl)amines can be
conveniently prepared by reaction of epoxides with afore-described
amines and can be represented by the formula:
(R)(R)N--(--R.sup.1O--).sub.x--H wherein x is a number from about 2
to about 15 and R and R.sup.1 are as described above.
[0069] The alkali and alkaline earth metals that are useful as
component (A)(II) can be any alkali or alkaline earth metal. The
alkali metals are preferred. Sodium and potassium are particularly
preferred. The alkali and alkaline earth metal compounds that are
useful include, for example, the oxides, hydroxides and carbonates.
Sodium hydroxide and potassium hydroxide are particularly
preferred.
Component B
[0070] Component (B) of the present invention is a compound having
at least two hydroxyls and at least one tertiary amino group. This
compound serves as the linking bridge between two of the component
(A) moieties described above. Compounds suitable for use as
component (B) can be described as di-hydroxy tertiary amines.
[0071] As noted above, in some embodiments component (B) includes
at least one tertiary amine of the formula:
##STR00007##
wherein each a, b, and c is independently 0 or 1 so long as the
total of a+b+c is at least 2, and wherein each R.sup.3, R.sup.4 and
R.sup.5 is independently a hydrocarbon group containing from 1 to
50 carbon atoms or an --(--R.sup.6--O--).sub.n-- group wherein
R.sup.6 is a alkenyl group containing from 1 to 6 carbon atoms, and
in some embodiments 2 carbon atoms, and n is an integer from 1 to
50 or from 1 to 20.
[0072] In other words, so long as the compound contains two hydroxy
groups, it may be suitable. In some embodiments R.sup.3, R.sup.4
and/or R.sup.5 in formula (V) are hydrocarbyl groups, or even
alkenyl groups. In such embodiments, each --OH shown in formula (V)
above may be attached anywhere along the hydrocarbyl or alkenyl
group and are not necessarily present at the end of the group. In
some embodiments the --OH groups are located at the end of the
hydrocarbyl or alkenyl chain that serves as the individual R group.
In some embodiments two --OH groups are attached to the same
hydrocarbyl or alkenyl group, which may be branched. For example,
the group --R.sub.1--(OH).sub.a, or any of the other groups, may
include --CH.sub.2--CH(OH)--CH.sub.2--OH. In other embodiments, the
group --R.sub.1--(OH).sub.a, or any of the other corresponding
groups, may include, for example, --CH.sub.2--CH.sub.2--OH.
[0073] In some embodiments component (B) includes at least one
tertiary amine of the formula:
##STR00008##
wherein each R.sup.8 is independently a hydrocarbon group
containing from 1 to 10 carbon atoms and where R.sup.9 is a
hydrocarbon group containing from 1 to 50 carbon atoms.
[0074] Suitable compounds include
3-(didodecylamino)propane-1,2-diol, N-methyldiethanolamine,
N-ethyldiethanolamine, N-propyldiethanolamine
N-n-butyldiethanolamine N-tert-butyldiethanolamine
N-cyclohexyldiethanolamine N-2-ethylhexyldiethanolamine,
N-amyldiethanolamine, N-isobutyldiethanolamine,
N-sec-butyldiethanolamine, N-dodecyldiethanolamine,
N-hexadecyldiethanolamine, N-hydrogenated rapeseed
alkyldiethanolamine, N-hydrogenated tallowalkyldiethanolamine,
N-phenyldiethanolamine, N-m-tolyldiethanolamine.
[0075] Suitable tertiary amines also include
Bis(2-hydroxyethyl)octadecylamine (also known as
N-octadecyldiethanolamine), Bis(2-hydroxyethyl)cocoalkylamines
(also known as N-cocoalkyldiethanolamine),
Bis(2-hydroxyethyl)oleylamine (also known as
N-oleyldiethanolamine), Bis(2-hydroxylethyl)soyaalkylamines (also
known as N-soyaalkyldiethanolamine),
Bis(2-hydroxyethyl)tallowalkylamines (also known as
N-tallowalkyldiethanolamine), which are all commercially available
from Akzo Nobel under Ethomeen.TM. trade names.
[0076] The materials above may be prepared by ethoxylating a
primary amine. Further ethoxylation is also possible. Such
materials, which are also suitable for use as component (B), may be
represented by the formula:
##STR00009##
wherein each n is independently an integer having the value of 1 to
50 or even 1 to 20 and R.sup.10 is a hydrocarbyl group containing
from 1 to 50 or even from 1 to 20 carbon atoms. In some
embodiments, both n's in formula (IX) have the same value.
[0077] Examples of such materials include Polyoxyethylene (5)
octadecylamine, Polyoxyethylene (15) octadecylamine,
Polyoxyethylene (5) cocoalkylamines, Polyoxyethylene (15)
cocoalkylamines, Polyoxyethylene (5) soyaalkylamines,
Polyoxyethylene (15) soyaalkylamines, Polyoxyethylene (5)
tallowalkylamines, Polyoxyethylene (15) tallowalkylamines,
Polyoxyethylene (20) tallowalkylamine, all of which are available
commercially from Akzo Nobel under Ethomeen.TM. trade names.
[0078] Suitable materials may also be made by reacting a
dialkylamine with either glycidol or chloroglycerin
(3-chloro-1,2-propandiol). Examples of these materials include
3-(dimethylamino)-1,2-propanediol,
3-(diethylamino)-1,2-propanediol,
3-(dipropylamino)-1,2-propanediol,
3-(diisopropylamino)-1,2-propanediol,
3-(dioctadecylamino)-1,2-propanediol,
3-(dicocylalkylamino)-1,2-propanediol.
[0079] Combinations of any of the materials described above may
also be used. In some embodiments component (B) includes
3-(didodecylamino)propane-1,2-diol,
tallow-bis-(2-hydroxylethyl)amine, N-methyldiethanolamine, or
combinations thereof, which may also be used in combination with
any of the materials described above.
[0080] In some embodiments component (B) may further comprise one
or more polyols, such as ethylene glycol. Such materials may also
serve as the linking compound. However, to obtain the benefits of
the present invention a substantial portion of component (B) must
be made up of one or more compounds having at least two hydroxyls
and at least one tertiary amino group, as described above.
[0081] In some embodiments, component (B), and even all of the
materials used to make the surfactant, are substantially free to
free of non-amine containing polyols (which may also be described
as nitrogen-free polyols). In other embodiments, component (B) may
be no more than 40%, 25%, 10% or even 5% by weight non-amine
containing polyols, thus allowing for some use of conventional
polyols as the linking compound yet still obtaining at least a
portion of the benefits of the present invention derived from the
use of compounds having at least two hydroxyls and at least one
tertiary amino group, as described above.
[0082] When the optional polyol is present useful materials include
those compounds of the general formula: R(OH).sub.m wherein R is a
monovalent or polyvalent organic group joined to the --OH groups
through carbon-to-oxygen bonds (that is, --COH wherein the carbon
is not part of a carbonyl group) and m is an integer of from 2 to
about 10, or from 2 to about 6. These alcohols can be aliphatic,
cycloaliphatic, aromatic, and heterocyclic, including
aliphatic-substituted cycloaliphatic alcohols,
aliphatic-substituted aromatic alcohols, aliphatic-substituted
heterocyclic alcohols, cycloaliphatic-substituted aliphatic
alcohols, cycloaliphatic-substituted heterocyclic alcohols,
heterocyclic-substituted aliphatic alcohols,
heterocyclic-substituted cycloaliphatic alcohols, and
heterocyclic-substituted aromatic alcohols. The polyhydric alcohols
corresponding to the formula R(OH).sub.m preferably contain not
more than about 40 carbon atoms, more preferably not more than
about 20 carbon atoms. The alcohols may contain non-hydrocarbon
substituents or groups which do not interfere with the reaction of
the alcohols with the hydrocarbyl-substituted carboxylic acids or
anhydrides of this invention. Such non-hydrocarbon substituents or
groups include lower alkoxy, lower alkyl, mercapto, nitro, and
interrupting groups such as --O-- and --S-- (e.g., as in such
groups as --CH.sub.2CH.sub.2--X--CH.sub.2CH.sub.2 where X is --O--
or --S--).
[0083] Specific hydrocarbyl groups include methyl, butyl, dodecyl,
tolyl, phenyl, naphthyl, dodecylphenyl, p-octylphenyl ethyl,
cyclohexyl, and the like. Carboxylic acids useful in preparing the
ester derivatives are mono- or polycarboxylic acids such as acetic
acid, valeric acid, lauric acid, stearic acid, succinic acid, and
alkyl or alkenyl-substituted succinic acids wherein the alkyl or
alkenyl group contains up to about 20 carbon atoms. Members of this
class of alcohols are commercially available from various sources;
e.g., PLURONICS, polyols available from Wyandotte Chemicals
Corporation; POLYGLYCOL 112-2, a liquid triol derived from
ethyleneoxide and propylene-oxide available from Dow Chemical Co.;
polyalkylene glycols and various derivatives thereof, both
available from Union Carbide Corporation. However, the alcohols
used must have an average of at least two free alcoholic hydroxyl
group per molecule of polyoxyalkylene alcohol. For purposes of
describing these polyoxyalkylene alcohols, an alcoholic hydroxyl
group is one attached to a carbon atom that does not form part of
an aromatic nucleus.
[0084] Alcohols useful in this invention also include alkylene
glycols and polyoxyalkylene alcohols such as polyoxyethylene
alcohols, polyoxypropylene alcohols, polyoxybutylene alcohols, and
the like. These polyoxyalkylene alcohols (sometimes called
polyglycols) can contain up to about 150 oxyalkylene groups, with
the alkylene group containing from about 2 to about 8 carbon atoms.
Such polyoxyalkylene alcohols are generally dihydric alcohols. That
is, each end of the molecule terminates with an OH group. In order
for such polyoxyalkylene alcohols to be useful, there must be at
least two OH groups.
[0085] The polyhydric alcohols useful in this invention include
polyhydroxy aromatic compounds. Polyhydric phenols and naphthols
are useful hydroxyaromatic compounds. These hydroxy-substituted
aromatic compounds may contain other substituents in addition to
the hydroxy substituents such as halo, alkyl, alkenyl, alkoxy,
alkylmercapto, nitro and the like. Usually, the hydroxy aromatic
compound will contain from 2 to about 4 hydroxy groups. The
aromatic hydroxy compounds are illustrated by the following
specific examples: resorcinol, catechol, p,p'-dihydroxy-biphenyl,
hydroquinone, pyrogallol, phloroglucinol, hexylresorcinol, orcinol,
etc.
[0086] The polyhydric alcohols preferably contain from 2 to about
10 hydroxy groups. They are illustrated, for example, by the
alkylene glycols and polyoxyalkylene glycols mentioned above such
as ethylene glycol, diethylene glycol, triethylene glycol,
tetraethylene glycol, dipropylene glycol, tripropylene glycol,
dibutylene glycol, tributylene glycol, and other alkylene glycols
and polyoxyalkylene glycols in which the alkylene groups contain
from 2 to about 8 carbon atoms.
[0087] Other useful polyhydric alcohols include glycerol,
monooleate of glycerol, monostearate of glycerol, monomethyl ether
of glycerol, pentaerythritol, n-butyl ester of 9,10-dihydroxy
stearic acid, methyl ester of 9,10-dihydroxy stearic acid,
1,2-butanediol, 2,3-hexanediol, 2,4-hexanediol, pinacol,
erythritol, arabitol, sorbitol, mannitol, 1,2-cyclohexanediol, and
xylene glycol. Carbohydrates such as sugars, starches, celluloses,
and so forth likewise can be used. The carbohydrates may be
exemplified by glucose, fructose, sucrose, rhamose, mannose,
glyceraldehyde, and galactose.
[0088] Polyhydric alcohols having at least 3 hydroxyl groups, some,
but not all of which have been esterified with an aliphatic
monocarboxylic acid having from about 8 to about 30 carbon atoms
such as octanoic acid, oleic acid, stearic acid, linoleic acid,
dodecanoic acid or tall oil acid are useful. Further specific
examples of such partially esterified polyhydric alcohols are the
monooleate of sorbitol, distearate of sorbitol, monooleate of
glycerol, monostearate of glycerol, di-dodecanoate of erythritol,
and the like.
[0089] Useful alcohols also include those polyhydric alcohols
containing up to about 12 carbon atoms, and especially those
containing from about 3 to about 10 or 6 carbon atoms. This class
of alcohols includes glycerol, erythritol, pentaerythritol,
dipentaerythritol, gluconic acid, mannitol, sorbitol,
glyceraldehyde, glucose, arabinose, 1,7-heptanediol,
2,4-heptanediol, 1,2,3-hexanetriol, 1,2,4-hexanetriol,
1,2,5-hexanetriol, 2,3,4-hexanetriol, 1,2,3-butanetriol,
1,2,4-butanetriol, quinic acid,
2,2,6,6-tetrakis-(hydroxymethyl)cyclohexanol, 1,10-decanediol,
digitalose,
2-hydroxy-methyl-2-methyl-1,3-propanediol-(trimethylolethane),
2-hydroxymethyl-2-ethyl-1,3-propanediol(trimethylopropane), and the
like. Aliphatic alcohols containing at least about 3 hydroxyl
groups and up to about 10 carbon atoms are useful.
[0090] In some embodiments, where component (B) contains a mixture
of (i) one or more compounds having at least two hydroxyls and at
least one tertiary amino group and (ii) one or more polyols or
polyhydric alcohols, the ratio of (i) to (ii), on a molar basis can
be from 1:0.5 to 10:1 or from 1:1 to 5:1, or from 2:1 to 3:1 or
even from 2.5:1 to 3:1 or even about 2.7:1. Not wishing to be bound
be theory, it is believed that having at least an equal mix, or
even at least some excess of compounds having at least two
hydroxyls and at least one tertiary amino group over nitrogen-free
polyols, is necessary to obtain the primary benefits of the
invention.
Formation of the Salt Compositions
[0091] The salt compositions of the invention can be prepared by
initially reacting the acylating agents (A)(I) with component (B)
to form an intermediate, and thereafter reacting said intermediate
with component (A)(II) to form the desired salt. An alternative,
though less efficient method of preparing these salt compositions
involves reacting components (A)(I) and (A)(II) with each other to
form the salt moieties, and then reacting the salt moieties with
component (B).
[0092] The ratio of reactants utilized in the preparation of the
inventive salt compositions may be varied. Generally, for each
equivalent of acylating agents (A)(I) at least about one-half
equivalent of component (B) is used. From about 0.1 to about 2
equivalents or more of component (A)(II) is used for each
equivalent of component (A)(I) respectively. The upper limit of
component (B) is about 1 equivalent, based on --OH groups, of
component (B) for each equivalent of component (A)(I), based on
carboxyl groups.
[0093] In some embodiments the reactants are used such that from
0.2 to 1.0 or even 0.4 to 0.6 equivalents of the component (B), and
from 0.2 to about 2.0, or from 0.2 to 1.0, or even from 0.4 to 0.6
equivalents of component (A)(II). are used for each equivalent of
component (A)(I).
[0094] The number of equivalents of the acylating agent (A)(I)
depends on the total number of carboxylic functions present in
each. In determining the number of equivalents for each of the
acylating agents present in (A)(I) those carboxyl functions which
are not capable of reacting as a carboxylic acid acylating agent
are excluded. In general, however, there is one equivalent of
acylating agent (A)(I) for each carboxy group in these acylating
agents. For example, there would be two equivalents in an anhydride
derived from the reaction of one mole of olefin polymer and one
mole of maleic anhydride. Conventional techniques are readily
available for determining the number of carboxyl functions (e.g.,
acid number, saponification number) and, thus, the number of
equivalents of each of the acylating agents in (A)(I) can be
readily determined by one skilled in the art.
[0095] The acylating agent (A)(I) can be reacted with component (B)
according to conventional ester- and/or amide-forming techniques.
This normally involves heating acylating agent (A)(I) with
component (B), optionally in the presence of a normally liquid,
substantially inert, organic liquid solvent/diluent. Temperatures
of at least about 30 degrees C. up to the decomposition temperature
of the reaction component and/or product having the lowest such
temperature can be used. This temperature is preferably in the
range of about 50 to about 130 degrees C., more preferably about 80
to about 100 degrees C. when the acylating agent (A)(I) is an
anhydride. On the other hand, when the acylating agent (A)(I) is an
acids, this temperature is preferably in the range of about 100 to
about 300 degrees C. with temperatures in the range of about 125 to
250 degrees C. often being employed.
[0096] The reactions between components (A)(I) and (A)(II) are
carried out under salt forming conditions using conventional
techniques. Typically, components (A)(I) and (A)(II) are mixed
together and heated to a temperature in the range of about 20
degrees C. up to the decomposition temperature of the reaction
component and/or product having the lowest such temperature about
20 to 130 degrees C., or about 40 to 110 degrees C.; optionally, in
the presence of a normally liquid, substantially inert organic
liquid solvent/diluent, until the desired product has formed.
[0097] The product of the reaction between components (A)(I) and
(A)(II) must contain at least some salt linkage to permit said
product to be effective as an emulsifier in accordance with the
invention. In some embodiments at least about 10%, at least about
30%, at least about 50%, or even at least about 70%, and
advantageously up to about 100% of component (A)(II) that reacts
with the acylating agents (A)(I), respectively, form a salt
linkage.
Explosive Compositions
[0098] The explosive compositions of the invention are water-in-oil
emulsions which, in one embodiment, are cap-sensitive water-in-oil
emulsion explosives and in another embodiment are booster-sensitive
water-in oil emulsion explosives. These emulsion explosives employ
the salt compositions of the invention as emulsifiers. The
explosive emulsions comprise 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 at least one of the salt compositions of the
invention.
[0099] The continuous organic phase may be present at a level of at
least about 2% by weight, or in the range of from about 2% to about
15% by weight, or from about 3.5% to about 8% by weight based on
the total weight of explosive emulsion. The discontinuous oxidizer
phase may be present at a level of at least about 85% by weight, or
in the range of from about 85% to about 98% by weight, or from
about 92% to about 96.5% by weight based on the total weight of
said explosive emulsion. The salt compositions of the invention may
be present at a level in the range of from about 4% to about 40% by
weight, or from about 12% to about 20% by weight based on the total
weight of the organic phase. An oxygen-supplying component may be
present at a level in the range of from about 70% to about 95% by
weight, or from about 85% to about 92% by weight, or from about 87%
to about 90% by weight based on the total weight of the oxidizer
phase. The water may be present at a level in the range of about 5%
to about 30% by weight, or from about 8% to about 15% by weight, or
from about 10% to about 13% by weight based on the weight of the
oxidizer phase.
[0100] The carbonaceous fuel that is useful in the explosive
emulsions of the invention can include most hydrocarbons, for
example, paraffinic, olefinic, naphthenic, aromatic, saturated or
unsaturated hydrocarbons, and is typically in the form of an oil or
a wax or a mixture thereof. In general, the carbonaceous fuel is a
water-immiscible, emulsifiable hydrocarbon that is either liquid or
liquefiable at a temperature of up to about 95.degree. C., and
preferably between about 40.degree. C. and about 75.degree. C. Oils
from a variety of sources, including natural and synthetic oils and
mixtures thereof can be used as the carbonaceous fuel.
[0101] Natural oils include animal oils and vegetable oils (e.g.,
castor oil, lard oil) as well as solvent refined or acid-refined
mineral oils of the paraffinic, naphthenic, or mixed
paraffin-naphthenic types. Oils derived from coal or shale are also
useful. Synthetic oils include hydrocarbon oils and
halo-substituted hydrocarbon oils such as polymerized and
interpolymerized olefins (e.g., polybutylenes, polypropylenes,
propylene-isobutylene copolymers, chlorinated polybutylenes, etc.);
alkyl benzenes (e.g., dodecylbenzenes, tetradecylbenzenes,
dinonylbenzenes, di-(2-ethylhexyl)benzenes, etc.); polyphenyls
(e.g., biphenyls, terphenyls, alkylated polyphenyls, etc.); and the
like.
[0102] Another suitable class of synthetic oils that can be used
comprises the esters of dicarboxylic acids (e.g., phthalic acid,
succinic acid, alkyl succinic acid, maleic acid, azelaic acid,
suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic
acid dimer, malonic acid, alkyl malonic acids, alkenyl malonic
acids, etc.) with a variety of alcohols (e.g., butyl alcohol, hexyl
alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol,
diethylene glycol monoether, propylene glycol, pentaerythritol,
etc.). Specific examples of these esters include dibutyl adipate,
di(2-ethylhexyl)-sebacate, di-n-hexyl fumarate, dioctyl sebacate,
diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl
phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic
acid dimer, the complex ester formed by reacting one mole of
sebacic acid with two moles of tetraethylene glycol and two moles
of 2-ethyl-hexanoic acid, and the like.
[0103] Esters useful as synthetic oils also include those made from
C5 to C12 monocarboxylic acids and polyols and polyol ethers such
as neopentyl glycol, trimethylol propane, pentaerythritol, dip
entaerythritol, tripentaerythritol, etc.
[0104] Silicon-based oils such as the polyalkyl-, polyaryl-,
polyalkoxy-, or polyaryloxy-siloxane oils and silicate oils
comprise another class of useful oils. These include
tetraethyl-silicate, tetraisopropylsilicate,
tetra-(2-ethylhexyl)-silicate, tetra-(4-methyl-hexyl)-silicate,
tetra(p-tert-butylphenyl)-silicate,
hexyl-(4-methyl-2-pentoxy)-di-siloxane, poly(methyl)siloxanes,
poly-(methylphenyl)-siloxanes, etc. Other useful synthetic oils
include liquid esters of phosphorus-containing acid (e.g.,
tricresyl phosphate, trioctyl phosphate, diethyl ester of decane
phosphonic acid, etc.), polymeric tetrahydrofurans, and the
like.
[0105] Unrefined, refined and rerefined oils (and mixtures of each
with each other) of the type disclosed hereinabove can be used.
Unrefined oils are those obtained directly from a natural or
synthetic source without further purification treatment. For
example, a shale oil obtained directly from a retorting operation,
a petroleum oil obtained directly from distillation or ester oil
obtained directly from an esterification process and used without
further treatment would be an unrefined oil. Refined oils are
similar to the unrefined oils except that they have been further
treated in one or more purification steps to improve one or more
properties. Many such purification techniques are known to those of
skill in the art such as solvent extraction, distillation, acid or
base extraction, filtration, percolation, etc. Rerefined oils are
obtained by processes similar to those used to obtain refined oils
applied to refined oils which have been already used in service.
Such rerefined oils are also known as reclaimed or reprocessed oils
and often are additionally processed by techniques directed toward
removal of spent additives and oil breakdown products.
[0106] Examples of useful oils include a white mineral oil
available from Witco Chemical Company under the trade designation
KAYDOL; a white mineral oil available from Shell under the trade
designation ONDINA; and a mineral oil available from Pennzoil under
the trade designation N-750-HT.
[0107] The carbonaceous fuel can be any wax having melting point of
at least about 25.degree. C., such as petrolatum wax,
microcrystalline wax, and paraffin wax, mineral waxes such as
ozocerite and montan wax, animal waxes such as spermacetic wax, and
insect waxes such as beeswax and Chinese wax. Useful waxes include
waxes identified by the trade designation MOBILWAX 57 which is
available from Mobil Oil Corporation; D02764 which is a blended wax
available from Astor Chemical Ltd.; and VYBAR which is available
from Petrolite Corporation. Preferred waxes are blends of
microcrystalline waxes and paraffin.
[0108] In one embodiment, the carbonaceous fuel includes a
combination of a wax and an oil. In this embodiment, the wax
content is at least about 25% and preferably ranges from about 25%
to about 90% by weight of the organic phase, and the oil content is
at least about 10% and preferably ranges from about 10% to about
75% by weight of the organic phase. These mixtures are particularly
suitable for use in cap-sensitive explosive emulsions.
[0109] While its presence is not necessary, the explosive emulsions
can also contain up to about 15% by weight of an auxiliary fuel,
such as aluminum, aluminum alloys, magnesium, and the like.
Particulate aluminum is a preferred auxiliary fuel.
[0110] The oxygen-supplying component is preferably at least one
inorganic oxidizer salt such as ammonium, alkali or alkaline earth
metal nitrate, chlorate or perchlorate. Examples include ammonium
nitrate, sodium nitrate, calcium nitrate, ammonium chlorate, sodium
perchlorate and ammonium perchlorate. Ammonium nitrate is
especially preferred. Mixtures of ammonium nitrate and sodium or
calcium nitrate are also preferred. In one embodiment, inorganic
oxidizer salt comprises principally ammonium nitrate, although up
to about 25% by weight of the oxidizer phase can comprise either
another inorganic nitrate (e.g., alkali or alkaline earth metal
nitrate) or an inorganic perchlorate (e.g., ammonium perchlorate or
an alkali or alkaline earth metal perchlorate) or a mixture
thereof.
[0111] In one embodiment of the invention, closed cell,
void-containing materials are used as sensitizing components. The
term "closed-cell, void-containing material" is used herein to mean
any particulate material which comprises closed cell, hollow
cavities. Each particle of the material can contain one or more
closed cells, and the cells can contain a gas, such as air, or can
be evacuated or partially evacuated. In one embodiment of the
invention, sufficient closed cell void containing material is used
to yield a density in the resulting emulsion of from about 0.8 to
about 1.35 g/cc, more preferably about 0.9 to about 1.3 g/cc, more
preferably about 1.1 to about 1.3 g/cc. In general, the emulsions
of the subject invention can contain up to about 15% by weight,
preferably from about 0.25% to about 15% by weight of the closed
cell void containing material. Preferred closed cell void
containing materials are discrete glass spheres having a particle
size within the range of about 10 to about 175 microns. In general,
the bulk density of such particles can be within the range of about
0.1 to about 0.4 g/cc. Useful glass microbubbles which can be used
are the microbubbles sold by 3M Company and which have a particle
size distribution in the range of from about 10 to about 160
microns and a nominal size in the range of about 60 to 70 microns,
and densities in the range of from about 0.1 to about 0.4 g/cc.;
these include microbubbles distributed under the trade designation
B15/250. Other useful glass microbubbles are sold under the trade
designation of ECCOSPHERES by Emerson & Cumming, Inc., and
generally have a particle size range from about 44 to about 175
microns and a bulk density of about 0.15 to about 0.4 g/cc. Other
suitable microbubbles include the inorganic microspheres sold under
the trade designation of Q-CEL by Philadelphia Quartz Company. The
closed cell void containing material can be made of inert or
reducing materials. For example, phenol-formaldehyde microbubbles
can be utilized within the scope of this invention. If the
phenol-formaldehyde microbubbles are utilized, the microbubbles
themselves are a fuel component for the explosive and their fuel
value should be taken into consideration when designing a
water-in-oil emulsion explosive composition. Another closed cell
void containing material which can be used within the scope of the
subject invention is the saran microspheres sold by Dow Chemical
Company. The saran microspheres have a diameter of about 30 microns
and a particle density of about 0.032 g/cc. Because of the low bulk
density of the saran microspheres, it is preferred that only from
about 0.25 to about 1% by weight thereof be used in the
water-in-oil emulsions of the subject invention.
[0112] Gas bubbles which are generated in-situ by adding to the
composition and distributing therein a gas generating material such
as, for example, an aqueous solution of sodium nitrite, can also be
used can be used to sensitize the explosive emulsions. Other
suitable sensitizing components which may be employed alone or in
addition to the foregoing include insoluble particulate solid
self-explosives such as, for example, grained or flaked TNT, DNT,
RDX and the like and water-soluble and/or hydrocarbon-soluble
organic sensitizers such as, for example, amine nitrates,
alkanolamine nitrates, hydroxyalkyl nitrates, and the like. The
explosive emulsions of the present invention may be formulated for
a wide range of applications. Any combination of sensitizing
components may be selected in order to provide an explosive
composition of virtually any desired density, weight-strength or
critical diameter. The quantity of solid self-explosive ingredients
and of water-soluble and/or hydrocarbon-soluble organic sensitizers
may comprise up to about 40% by weight of the total explosive
composition. The volume of the occluded gas component may comprise
up to about 50% of the volume of the total explosive
composition.
[0113] Optional additional materials may be incorporated in the
explosive emulsions of the invention in order to further improve
sensitivity, density, strength, rheology and cost of the final
explosive. Typical of materials found useful as optional additives
include, for example, particulate non-metal fuels such as sulfur,
gilsonite and the like, particulate inert materials such as sodium
chloride, barium sulphate and the like, water phase or hydrocarbon
phase thickeners such as guar gum, polyacrylamide, carboxymethyl or
ethyl cellulose, biopolymers, starches, elastomeric materials, and
the like, crosslinkers for the thickeners such as potassium
pyroantimonate and the like, buffers or pH controllers such as
sodium borate, zinc nitrate and the like, crystals habit modifiers
such as alkyl naphthalene sodium sulphonate and the like, liquid
phase extenders such as formamide, ethylene glycol and the like and
bulking agents and additives of common use in the explosives art.
The quantities of optional additional materials used may comprise
up to about 50% by weight of the total explosive emulsion.
[0114] One method for making the explosive emulsions of the
invention comprises the steps of (1) mixing water, inorganic
oxidizer salts (e.g., ammonium nitrate) and, in certain cases, some
of the supplemental water-soluble compounds, in a first premix, (2)
mixing the carbonaceous fuel, the emulsifying salt compositions of
the invention and any other optional oil-soluble compounds, in a
second premix and (3) adding the first premix to the second premix
in a suitable mixing apparatus, to form a water-in-oil emulsion.
The first premix is heated until all the salts are completely
dissolved and the solution may be filtered if needed in order to
remove any insoluble residue. The second premix is also heated to
liquefy the ingredients. Any type of apparatus capable of either
low or high shear mixing can be used to prepare these water-in-oil
emulsions. Closed cell void containing materials, gas-generating
materials, solid self-explosive ingredients such as particulate
TNT, solid fuels such as aluminum or sulfur, inert materials such
as barytes or sodium chloride, undissolved solid oxidizer salts and
other optional materials, if employed, are added to the emulsion
and simply blended until homogeneously dispersed throughout the
composition.
[0115] The water-in-oil explosive emulsions of the invention can
also be prepared by adding the second premix liquefied organic
solution phase to the first premix hot aqueous solution phase with
sufficient stirring to invert the phases. However, this method
usually requires substantially more energy to obtain the desired
dispersion than does the preferred reverse procedure.
Alternatively, these water-in-oil explosive emulsions are
particularly adaptable to preparation by a continuous mixing
process where the two separately prepared liquid phases are pumped
through a mixing device wherein they are combined and
emulsified.
[0116] The salt compositions of this invention can be added
directly to the inventive explosive emulsions. They can also be
diluted with a substantially inert, normally liquid organic diluent
such as mineral oil, naphtha, benzene, toluene or xylene, to form
an additive concentrate. These concentrates usually contain from
about 10% to about 90% by weight of the salt composition of this
invention and may contain, in addition, one or more other additives
known in the art or described hereinabove.
[0117] It is known that some of the materials described above may
interact in the final formulation, so that the components of the
final formulation may be different from those that are initially
added. The products formed thereby, including the products formed
upon employing the composition of the present invention in its
intended use, may not be susceptible of easy description.
Nevertheless, all such modifications and reaction products are
included within the scope of the present invention; the present
invention encompasses the composition prepared by admixing the
components described above.
EXAMPLES
[0118] The following examples illustrate the preparation of the
salt compositions of this invention. Unless otherwise indicated, in
the following examples and elsewhere in the specification and
claims, all parts and percentages are by weight, and all
temperatures are in degrees centigrade (C). While the examples are
provided to illustrate the present invention, they are not intended
to limit it.
Comparative Example 1
[0119] A surfactant is prepared by reacting, in a 3 liter reaction
flask under a nitrogen blanket, 1033 grams of mid-molecular weight
polyisobutylene succinic anhydride (PIBSA), which itself is derived
from 1000 number average molecular weight (Mn) polyisobutylene
(PIB) and 31 grams of ethylene glycol. The reaction is carried out
in diluent oil at a temperature of about 85 degrees C. The ethylene
glycol is added to the PIBSA over time and the reaction is given
three hours to complete. The reaction results in a diol coupled
diester with a calculated yield of 99%. 402 grams (on an actives
basis) of the resulting coupled diester is charged to a 1 liter
reaction flask and reacted with 44 grams of diethylethanolamine.
The reaction is carried out in diluent oil at a temperature of
about 45 to 50 degrees C. The amine is charged over time and the
reaction is given 2 hours to complete. The resulting surfactant is
a diol coupled salt with a calculated yield of 99% and a total acid
number (TAN) of 28.6 compared to a theory TAN of 31.7. This is a
comparative example.
Example 2
[0120] A surfactant is prepared by reacting, in a 5 liter reaction
flask under a nitrogen blanket, 2008 grams of the PIBSA described
in Example 1 above and 344 grams of
tallow-bis(2-hydroxyethyl)amine. The reaction is carried out in
diluent oil at a temperature of about 85 degrees C. The amine diol
is added to the PIBSA over time and the reaction is given three
hours to complete. The reaction results in a diol amine coupled
diester with a calculated yield of 100%. 402 grams (on an actives
basis) of the resulting coupled diester is charged to a 1 liter
reaction flask and reacted with 39 grams of diethylethanolamine.
The reaction is carried out in diluent oil at a temperature of
about 45 to 50 degrees C. The amine is charged over time and the
reaction is given 2 hours to complete. The resulting surfactant is
a diol amine coupled salt with a calculated yield of 100% and a TAN
of 28.3 compared to a theory TAN of 28.2.
Example 3
[0121] A surfactant is prepared by reacting, in a 1 liter reaction
flask under a nitrogen blanket, 450 grams of the PIBSA described in
Example 1 above and 26 grams of N-methyldiethanolamine. The
reaction is carried out in diluent oil at a temperature of about 92
degrees C. The amine diol is added to the PIBSA over time and the
reaction is given three hours to complete. The reaction results in
a diol amine coupled diester that immediately salted. 39 grams of
dimethylethanolamine is added to the salt from the first step. The
reaction is carried out in diluent oil at a temperature of about 45
to 50 degrees C. The amine is charged over time and the reaction is
given 2 hours to complete. The resulting surfactant is a diol amine
coupled salt with a calculated yield of 91% and a TAN of 33.3
compared to a theory TAN of 31.7.
Example 4
[0122] A surfactant is prepared by reacting, in a 2 liter reaction
flask under a nitrogen blanket, 900 grams of the PIBSA described in
Example 1 above and 112 grams of tallow-bis(2-hydroxylethyl)amine.
The reaction is carried out in diluent oil at a temperature of
about 85 to 90 degrees C. The amine diol is added to the PIBSA over
time and the reaction is given one hour and then 7.3 grams of
ethylene glycol is added over time, maintaining the reaction at a
temperature of about 85 to 90 degrees C. The reaction results in a
diol amine coupled diester that also include some diol coupling.
The product immediately salted. 102 grams of diethylethanolamine is
added to the salt from the first step. The reaction is carried out
in diluent oil at a temperature of about 45 to 50 degrees C. The
amine is charged over time and the reaction is given 2 hours to
complete. The resulting surfactant is a diol amine coupled salt
with a calculated yield of 94% and a TAN of 29.5 compared to a
theory TAN of 29.1.
Example 5
[0123] A surfactant is prepared by reacting, in a 1 liter reaction
flask, 335 grams (on an actives basis, that is oil and/or solvent
free) a coupled diester prepared according to the first part of
Example 2 above, with 16 grams of diethylethanolamine. The reaction
is carried out in diluent oil at a temperature of about 45 to 50
degrees C. The amine is charged over time and the reaction is given
2 hours to complete. The resulting surfactant is a diol amine
coupled salt with a calculated yield of 99% and a TAN of 34.4
compared to a theory TAN of 29.5, and was achieved with a reduced
amine charge relative to Example 2.
Example 6
[0124] A surfactant is prepared by reacting, in a 1 liter reaction
flask, 335 grams (on an actives basis) of the resulting coupled
diester prepared in the first step of Example 2 above, with 24
grams of diethylethanolamine. The reaction is carried out in
diluent oil at a temperature of about 45 to 50 degrees C. The amine
is charged over time and the reaction is given 2 hours to complete.
The resulting surfactant is a diol amine coupled salt with a
calculated yield of 99% and a TAN of 34.0 compared to a theory TAN
of 28.8, and was achieved with an intermediate amine charge
relative to Examples 2 and 5.
Emulsion Evaluations
[0125] Examples 1 to 6 are used to prepare emulsions with an
aqueous ammonium nitrate oxidizer phase and an organic fuel phase.
The same aqueous ammonium nitrate oxidizer phase is used in each of
the samples. The organic fuel phase is either 100N diluent oil or
diesel fuel, as marked. Emulsions are characterized by examination
under a microscope. The emulsions are then subjected to a series of
stress and stability tests, detailed below.
[0126] Two shear tests were employed. A low shear paint shaker test
is used, which simulates transportation of the emulsion explosive,
from the production site to the work site where it would be used.
For this test the emulsion explosive composition is placed in a
paint shaker for four hours. A high shear syringe test simulates
pumping the emulsion explosive, for example from a storage
container into a bore hole where it will be detonated. In this test
the emulsion is injected through a small orifice of a syringe under
pressure. Testing is conducted at 30 and 50 psi injection
pressure.
[0127] Two stability tests are employed. In the ambient storage
test in the emulsion is stored for 30 days at ambient temperature
and then evaluated. In the thermal cycling test the emulsion is
held at -30.degree. C. for six hours and then held at +50.degree.
C. for six hours. The emulsion is then evaluated after five and ten
of these cycles in this accelerated aging test.
[0128] Fresh (untested) and stressed/aged (tested) emulsions were
evaluated under a microscope, in order to evaluate each sample's
performance. The evaluation using the microscope includes measuring
the amount of ammonium nitrate crystallisation, with lower
crystallization being desired. The lower the % coverage (crystal
count) the more stable the emulsion. Generally, crystal counts
below 5% are classed as a good pass; borderline emulsions have
between 5 and 10% crystal count and fails have more than 10%
crystallisation. The results of this testing are summarized in the
tables below:
TABLE-US-00001 TABLE A Percent Crystallization in Diesel Fuel
Emulsions, Run 1.sup.5. After 50 After After 10 After 30 Fresh PSI
4 HR Cycle Day Sample Surfactant Emul- Syringe Shaker Thermal
Ambient ID ID sion Test Test Test Test A-1 Comp 1.sup.1 0.00 0.25
0.01 1.17 0.02 A-2 Comp 2.sup.2 0.06 0.11 0.05 0.54 0.02 A-3 Comp
3.sup.3 0.02 0.09 CRYST.sup.4 0.26 0.01 A-4 Example 3 0.05 0.15
0.05 0.37 0.04 .sup.1Comparative Surfactant 1 is a salt formed from
a high molecular weight hydrocarbyl substituted succinic anhydride
and a tertiary alkanolamine, and does not have a coupled structure.
.sup.2Comparative Surfactant 2 is an ethylene glycol coupled
surfactant prepared from a 1:1 mixture of mid molecular weight
hydrocarbyl substituted succinic anhydride and a low molecular
weight hydrocarbyl substituted succinic anhydride where the two
anhydrides are linked by ethylene glycol and the resulting compound
is salted with a tertiary alkanolamine. .sup.3Comparative
Surfactant 3 is premium surfactant package that mixes Comparative
Surfactants 1 and 2, making it more complex to produce and more
expensive. .sup.4This indicates the sample crystallized during the
test, which is a severe failure. .sup.5Each of the emulsions in
Table A has the same formulation but differ in the surfactant used.
Each emulsion uses the same aqueous phase and the same diesel fuel
in the same amounts, and each sample uses its specific surfactant
at a 0.8% by weight actives level.
TABLE-US-00002 TABLE B Percent Crystallization in Diesel Fuel
Emulsions, Run 2.sup.4. After 50 After After 10 After 30 Fresh PSI
4 HR Cycle Day Sample Surfactant Emul- Syringe Shaker Thermal
Ambient ID ID sion Test Test Test Test B-1 Comp 1.sup.1 0.02 0.03
0.01 0.31 0.01 B-2 Comp 2.sup.2 0.01 0.02 0.05 0.45 0.01 B-3
Example 1.sup.3 0.04 0.38 0.20 1.25 0.20 B-4 Example 2 0.03 0.02
0.06 0.77 0.02 .sup.1Comparative Surfactant 1 is the same as that
defined in Table A above. .sup.2Comparative Surfactant 2 is the
same as that defined in Table A above. .sup.3Example 1 is a
comparative example as it does not contain a tertiary amine diol
linkage. .sup.4Each of the emulsions in Table B has the same
formulation but differ in the surfactant used. Each emulsion uses
the same aqueous phase and the same diesel fuel in the same
amounts, and each sample uses its specific surfactant at a 0.8% by
weight actives level.
TABLE-US-00003 TABLE C Percent Crystallization in 100 N Oil
Emulsions, Run 3.sup.5. After 50 After After 10 After 30 Fresh PSI
4 HR Cycle Day Sample Surfactant Emul- Syringe Shaker Thermal
Ambient ID ID sion Test Test Test Test C-1 Comp 1.sup.1 0.03 87.96
0.07 0.1 0.01 C-2 Comp 2.sup.2 0.01 2.23 0.01 0.06 0.01 C-3 Comp
3.sup.3 0.01 24.61 15.56 0.02 0.01 C-4 Example 1.sup.4 0.09 25.73
0.06 0.38 0.13 C-5 Example 2 0.03 35.85 0.02 0.24 0.03
.sup.1Comparative Surfactant 1 is the same as that defined in Table
A above. .sup.2Comparative Surfactant 2 is the same as that defined
in Table A above. .sup.3Comparative Surfactant 3 is the same as
that defined in Table A above. .sup.4Example 1 is a comparative
example as it does not contain a tertiary amine diol linkage.
.sup.5Each of the emulsions in Table C has the same formulation but
differ in the surfactant used. Each emulsion uses the same aqueous
phase and the same 100 N oil in the same amounts, and each sample
uses its specific surfactant at a 0.8% by weight actives level.
TABLE-US-00004 TABLE D Percent Crystallization in 100 N Oil
Emulsions, Run 4.sup.3. After 50 After After 10 After 30 Fresh PSI
4 HR Cycle Day Sample Surfactant Emul- Syringe Shaker Thermal
Ambient ID ID sion Test Test Test Test D-1 Comp 3.sup.1 0.01 92.42
CRYST.sup.2 0.08 NOT TESTED D-2 Example 4 0.02 86.69 0.05 0.19 NOT
TESTED .sup.1Comparative Surfactant 3 is the same as that defined
in Table A above. .sup.2This indicates the sample crystallized
during the test, which is a severe failure. .sup.3Each of the
emulsions in Table D has the same formulation but differ in the
surfactant used. Each emulsion uses the same aqueous phase and the
same 100 N oil in the same amounts, and each sample uses its
specific surfactant at a 0.8% by weight actives level.
[0129] Two stability tests are employed. In the ambient storage
test in the emulsion is stored for 30 days at ambient temperature
and then evaluated. In the thermal cycling test the emulsion is
held at -30.degree. C. for six hours and then held at +50.degree.
C. for six hours. The emulsion is then evaluated after five and ten
of these cycles in this accelerated aging test.
[0130] The results show that the surfactants of the present
invention, and the emulsion made from the same, address one or more
of the problems described above. For example, the data shows that
the compositions of the present invention can provide at least
comparable performance in a less complex and less expensive
surfactant package. The data also shows that the compositions of
the present invention can provide improved stability performance,
specifically with regards to stability during transportation of the
emulsion, while maintaining sufficient performance in other
areas.
[0131] Each of the documents referred to above is incorporated
herein by reference. Except in the Examples, or where otherwise
explicitly indicated, all numerical quantities in this description
specifying amounts of materials, reaction conditions, molecular
weights, number of carbon atoms, and the like, are to be understood
as modified by the word "about." Unless otherwise indicated, all
percent values, ppm values and parts values are on a weight basis.
Unless otherwise indicated, each chemical or composition referred
to herein should be interpreted as being a commercial grade
material which may contain the isomers, by-products, derivatives,
and other such materials which are normally understood to be
present in the commercial grade. However, the amount of each
chemical component is presented exclusive of any solvent or diluent
oil, which may be customarily present in the commercial material,
unless otherwise indicated. It is to be understood that the upper
and lower amount, range, and ratio limits set forth herein may be
independently combined. Similarly, the ranges and amounts for each
element of the invention can be used together with ranges or
amounts for any of the other elements. As used herein, the
expression "consisting essentially of" permits the inclusion of
substances that do not materially affect the basic and novel
characteristics of the composition under consideration.
* * * * *