U.S. patent application number 15/246624 was filed with the patent office on 2017-01-26 for emulsifier components and methods of using the same.
The applicant listed for this patent is The Lubrizol Corporation. Invention is credited to Frank L. Kroto, Thomas P. Oleksiak, Derek T. Phillips, Brett Wessler, Christopher H. Wise.
Application Number | 20170022443 15/246624 |
Document ID | / |
Family ID | 52484557 |
Filed Date | 2017-01-26 |
United States Patent
Application |
20170022443 |
Kind Code |
A1 |
Oleksiak; Thomas P. ; et
al. |
January 26, 2017 |
EMULSIFIER COMPONENTS AND METHODS OF USING THE SAME
Abstract
This invention relates to an additive comprising a functional
group derived from a first hydrocarbyl-substituted acylating agent
and a functional group derived from a second
hydrocarbyl-substituted acylating agent, where the functional
groups are coupled by a functional group derived from an alkylene
glycol. The invention also relates to an emulsifier component
prepared by a process that utilizes the described additive and
converts it to an emulsifier component by reacting it with a
neutralizing component. The invention also relates to a process of
making the described emulsifier component, and a method of
customizing an emulsifier component in a composition by using the
described additive and the described process for converting it to
the described emulsifier component.
Inventors: |
Oleksiak; Thomas P.;
(Twinsburg, OH) ; Phillips; Derek T.; (Willoughby
Hills, OH) ; Wise; Christopher H.; (Painesville
Township, OH) ; Wessler; Brett; (Wickliffe, OH)
; Kroto; Frank L.; (Concord Township, OH) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
The Lubrizol Corporation |
Wickliffe |
OH |
US |
|
|
Family ID: |
52484557 |
Appl. No.: |
15/246624 |
Filed: |
January 28, 2015 |
PCT Filed: |
January 28, 2015 |
PCT NO: |
PCT/US2015/013177 |
371 Date: |
August 25, 2016 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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61948071 |
Mar 5, 2014 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C10N 2020/04 20130101;
C10N 2030/24 20200501; B01F 17/0028 20130101; C10M 2203/1006
20130101; C10M 2207/127 20130101; C10M 2207/129 20130101; C10M
129/42 20130101; C10M 2215/042 20130101; C10M 159/12 20130101; C10M
2215/04 20130101; C10N 2040/20 20130101; C10N 2030/12 20130101 |
International
Class: |
C10M 159/12 20060101
C10M159/12 |
Claims
1. An additive comprising (i) a functional group derived from a
first hydrocarbyl-substituted acylating agent and (ii) a functional
group derived from a second hydrocarbyl-substituted acylating
agent, where the functional groups (i) and (ii) are coupled by a
functional group derived from an alkylene glycol; wherein the first
hydrocarbyl-substituted acylating agent comprises a hydrocarbyl
substituent group containing at least about 20 carbon atoms; and
wherein the second hydrocarbyl-substituted acylating agent
comprises a hydrocarbyl substituent group containing less than
about 20 carbon atoms.
2. The additive of claim 1 wherein the first
hydrocarbyl-substituted acylating agent comprises the reaction
product of a long chain hydrocarbon with a monounsaturated
carboxylic acid; wherein said long chain hydrocarbon has a number
average molecular weight greater than about 400.
3. The additive of claim 1 or claim 2 wherein the first
hydrocarbyl-substituted acylating agent comprises polyisobutylene
succinic anhydride, the polyisobutylene group having a number
average molecular weight greater than about 400.
4. The additive of any one of claims 1 through 3 wherein the second
hydrocarbyl-substituted acylating agent comprises the reaction
product of a long chain hydrocarbon with a monounsaturated
carboxylic acid; wherein said long chain hydrocarbon has a number
average molecular weight less than about 280.
5. The additive of any one of claims 1 through 4 wherein the second
hydrocarbyl-substituted acylating agent comprises hexadecenyl
succinic anhydride.
6. The additive of any one of claims 1 through 5 wherein the
alkylene glycol comprises a glycol having the general formula HO
(CH(R)).sub.x--O .sub.m--H where each R is independently H or an
alkyl group of 1 to 6 carbon atoms, each x is independently an
integer from 2 to about 10, and m is an integer from 1 to about
10.
7. The additive of any one of claims 1 through 6 wherein the
alkylene glycol is a linear alkylene glycol.
8. The additive of any one of claims 1 through 7 wherein the
alkylene glycol comprises a poly(ethylene glycol), a
poly(1,3-propylene glycol) or a copolymer of ethylene glycol and
1,3-propylene glycol.
9. The additive of any one of claims 1 through 8 wherein the
alkylene glycol comprises a glycol having the general formula
HO--(CH.sub.2).sub.x--OH wherein x is an integer from 2 to about
10.
10. The additive of claim 9 wherein the alkylene glycol comprises
ethylene glycol.
11. The additive of any one of claims 1 through 7 wherein the first
hydrocarbyl-substituted acylating agent comprises polyisobutylene
succinic anhydride, the polyisobutylene group having a number
average molecular weight greater than about 750; wherein the second
hydrocarbyl-substituted acylating agent comprises hexadecenyl
succinic anhydride; and wherein the alkylene glycol comprises
ethylene glycol.
12. The additive of any of claims 1 through 11 which is reacted
with a neutralizing component comprising an amine.
13. A process of making an emulsifier component comprising the
steps of: I. reacting a first hydrocarbyl-substituted acylating
agent, a second hydrocarbyl-substituted acylating agent, and an
alkylene glycol; wherein the first hydrocarbyl-substituted
acylating agent comprises a hydrocarbyl substituent group
containing at least about 20 carbon atoms; and wherein the second
hydrocarbyl-substituted acylating agent comprises a hydrocarbyl
substituent group containing less than about 20 carbon atoms;
resulting in an intermediate comprising (i) a functional group
derived from said first hydrocarbyl-substituted acylating agent and
(ii) a functional group derived from said second
hydrocarbyl-substituted acylating agent, where the functional
groups (i) and (ii) are coupled by a functional group derived from
said alkylene glycol; II. providing said intermediate for use as an
emulsifier component precursor; and thereafter III. converting said
intermediate to an emulsifier component by reacting said
intermediate with a neutralizing component.
14. The process of claim 13 wherein the first
hydrocarbyl-substituted acylating agent comprises the reaction
product of a long chain hydrocarbon with a monounsaturated
carboxylic acid; wherein said long chain hydrocarbon has a number
average molecular weight greater than about 400; and wherein the
second hydrocarbyl-substituted acylating agent comprises the
reaction product of a long chain hydrocarbon with a monounsaturated
carboxylic acid; wherein said long chain hydrocarbon has a number
average molecular weight less than about 280; wherein the alkylene
glycol comprises a glycol having of the general formula HO
(C(R)).sub.x--O .sub.m--H wherein each R is independently H or an
alkyl group of 1 to 6 carbon atoms, each x is independently an
integer from 2 to about 10 and m is an integer from 1 to about
10.
15. The process of claim 13 or claim 14 wherein the alkylene glycol
comprises a poly(ethylene glycol), a poly(1,3-propylene glycol) or
a copolymer of ethylene glycol and 1,3-propylene glycol.
16. The process of claim 13 or claim 14 wherein the alkylene glycol
comprises a glycol having the general formula
HO--(CH.sub.2).sub.x--OH wherein x is an integer from 2 to about
10.
17. The process of claim 14 wherein the first
hydrocarbyl-substituted acylating agent comprises polyisobutylene
succinic anhydride having a number average molecular weight greater
than about 750; wherein the second hydrocarbyl-substituted
acylating agent comprises hexadecenyl succinic anhydride; and
wherein the alkylene glycol comprises ethylene glycol.
18. The process of any one of claims 13 through 17 wherein the
neutralizing component comprises an amine.
19. A method of customizing an emulsifier component in a
composition, said method comprising the steps of: I. reacting a
first hydrocarbyl-substituted acylating agent, a second
hydrocarbyl-substituted acylating agent, and an alkylene glycol;
wherein the first hydrocarbyl-substituted acylating agent comprises
a hydrocarbyl substituent group containing at least about 20 carbon
atoms; and wherein the second hydrocarbyl-substituted acylating
agent comprises a hydrocarbyl substituent group containing less
than about 20 carbon atoms; resulting in an intermediate comprising
(i) a functional group derived from said first
hydrocarbyl-substituted acylating agent and (ii) a functional group
derived from said second hydrocarbyl-substituted acylating agent,
where the functional groups (i) and (ii) are coupled by a
functional group derived from said alkylene glycol; II. providing
said intermediate for use as an emulsifier component precursor; and
thereafter III. converting said intermediate to an emulsifier
component by reacting said intermediate with a neutralizing
component; resulting in a customized emulsifier component.
20. The method of claim 19 wherein the first
hydrocarbyl-substituted acylating agent comprises the reaction
product of a long chain hydrocarbon with a monounsaturated
carboxylic acid; wherein said long chain hydrocarbon has a number
average molecular weight greater than about 400; and wherein the
second hydrocarbyl-substituted acylating agent comprises the
reaction product of a long chain hydrocarbon with a monounsaturated
carboxylic acid; wherein said long chain hydrocarbon has a number
average molecular weight less than about 280; wherein the alkylene
glycol comprises a glycol having of the general formula
HO--(CH.sub.2).sub.x--OH wherein x is an integer from 2 to about
10.
21. The method of claim 19 or claim 20 wherein the neutralizing
component comprises an amine.
22. An emulsifier component prepared by a process comprising the
steps of: I. reacting a first hydrocarbyl-substituted acylating
agent, a second hydrocarbyl-substituted acylating agent, and an
alkylene glycol; wherein the first hydrocarbyl-substituted
acylating agent comprises a hydrocarbyl substituent group
containing at least about 20 carbon atoms; and wherein the second
hydrocarbyl-substituted acylating agent comprises a hydrocarbyl
substituent group containing less than about 20 carbon atoms;
resulting in an intermediate comprising (i) a functional group
derived from said first hydrocarbyl-substituted acylating agent and
(ii) a functional group derived from said second
hydrocarbyl-substituted acylating agent, where the functional
groups (i) and (ii) are coupled by a functional group derived from
said alkylene glycol; II. providing said intermediate for use as an
emulsifier component precursor; and thereafter III. converting said
intermediate to an emulsifier component by reacting said
intermediate with a neutralizing component.
23. The emulsifier component of claim 22 where said neutralizing
component comprises an amine.
Description
[0001] This invention relates to an additive comprising a
functional group derived from a first hydrocarbyl-substituted
acylating agent and a functional group derived from a second
hydrocarbyl-substituted acylating agent, where the functional
groups are coupled by a functional group derived from an alkylene
glycol, and in certain embodiments a linear alkylene glycol. The
invention also relates to an emulsifier component prepared by a
process that utilizes the described additive and converts it to an
emulsifier component by reacting it with a neutralizing component.
The invention also relates to a process of making the described
emulsifier component, and a method of customizing an emulsifier
component in a composition by using the described additive and the
described process for converting it to the described emulsifier
component.
BACKGROUND OF THE INVENTION
[0002] Hydrocarbyl-substituted carboxylic acylating agents having
at least about 30 aliphatic carbon atoms in the substituent are
known as additives in normally liquid fuels and lubricants.
Examples of such acylating agents include the
polyisobutenyl-substituted succinic acids and anhydrides. The use
of such carboxylic acylating agents as additives in normally liquid
fuels and lubricants is disclosed in U.S. Pat. Nos. 3,288,714 and
3,346,354.
[0003] These acylating agents are also useful as intermediates for
preparing additives for use in normally liquid fuels and lubricants
as described in U.S. Pat. Nos. 2,892,786; 3,087,936; 3,163,603;
3,172,892; 3,189,544; 3,215,707; 3,219,666; 3,231,587; 3,235,503;
3,272,746; 3,306,907; 3,306,908; 3,331,776; 3,341,542; 3,346,354;
3,374,174; 3,379,515; 3,381,022; 3,413,104; 3,450,715; 3,454,607;
3,455,728; 3,476,686; 3,513,095; 3,523,768; 3,630,904; 3,632,511;
3,697,428; 3,755,169; 3,804,763; 3,836,470; 3,862,981; 3,936,480;
3,948,909; 3,950,341; 4,234,435; and 4,471,091; and French Patent
2,223,415.
[0004] U.S. Pat. No. 3,216,936 describes nitrogen-containing
dispersants for use in lubricants which are obtained by the
reaction of an alkylene amine with an acidic mixture consisting of
a hydrocarbon-substituted succinic acid having at least about 50
aliphatic carbon atoms in the hydrocarbon substituent and an
aliphatic monocarboxylic acid. The aliphatic monocarboxylic acids
are described as including saturated and unsaturated acids such as
acetic acid, dodecanoic acid, oleic acid, naphthenic acid, formic
acid, etc. Acids having 12 or more aliphatic carbon atoms,
particularly stearic acid and oleic acid, are described as being
especially useful.
[0005] U.S. Pat. Nos. 3,639,242 and 3,708,522 describe compositions
prepared by post-treating mono- and polycarboxylic acid esters with
mono- or polycarboxylic acid acylating agents. The compositions
thus obtained are reported to be useful as dispersants in
lubricants and fuels.
[0006] U.S. Pat. No. 4,642,330 discloses dispersant salt
compositions made by reacting phosphorus-free carboxylic
solubilizers with sulfonic acid-free organic acids or mineral
acids. The carboxylic solubilizer is the reaction product of a
polycarboxylic acid acylating agent having at least one
hydrocarbon-based substituent of at least 8 to 500 carbon atoms
with at least one poly(alkyleneamine). The reference indicates that
these dispersant salt compositions have good thermal stability when
mixed with a surfactant or a hydrophilic organic solvent, and that
they can be used with aqueous solutions to disperse various fillers
including carbon black and to solubilize various fluids.
[0007] Nitrogen-containing, phosphorus-free carboxylic solubilizers
useful in water based functional fluids are disclosed in U.S. Pat.
Nos. 4,329,249; 4,368,133; 4,435,297; 4,447,348; and 4,448,703.
These solubilizers are made by reacting (I) at least one carboxylic
acid acylating agent having at least one hydrocarbyl substituent of
from about 12 to about 500 carbon atoms with (II) at least one (a)
N-(hydroxyl-substituted hydrocarbyl) amine, (b)
hydroxyl-substituted poly(hydrocarbyloxy) analog of said amine (a),
or (c) mixtures of (a) and (b). These patents indicate that
preferred acylating agents include the substituted succinic acids
or anhydrides, such as polyisobutenyl-substituted succinic
anhydride, and that the amines that are useful include the primary,
secondary and tertiary alkanol amines, such as diethylethanolamine
and mixtures of diethylethanolamine and ethanolamine. These
solubilizers are useful in dispersing oil-soluble, water-insoluble
functional additives in water-based functional fluids.
[0008] U.S. Pat. No. 5,047,175 discloses salt compositions
comprising: (A) at least one salt moiety derived from (A)(I) at
least one high-molecular weight 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) ammonia, at least one amine, at least one alkali
or alkaline earth metal, and/or at least one alkali or alkaline
earth metal compound; (B) at least one salt moiety derived from
(B)(I) at least one low-molecular weight polycarboxylic acylating
agent, said acylating agent (B)(I) optionally having at least one
hydrocarbyl substituent having an average of up to about 18 carbon
atoms, and (B)(II) ammonia, at least one amine, at least one alkali
or alkaline earth metal, and/or at least one alkali or alkaline
earth metal compound; said components (A) and (B) being coupled
together by (C) at least one compound having (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 or (v) at least one
primary or secondary amino group and at least one hydroxyl group.
These salt compositions are useful as emulsifiers in water-in-oil
explosive emulsions, particularly cap-sensitive explosive
emulsions.
[0009] U.S. Pat. No. 4,828,633 discloses emulsion explosives based
upon the emulsifier of U.S. Pat. No. 5,047,175.
[0010] U.S. Pat. No. 5,422,024 provides for aqueous oil-in-water
emulsion functional fluids comprising water, an oil and an
emulsifying quantity of a salt composition comprising: (A) at least
one salt moiety derived from (A)(I) at least one high-molecular
weight polycarboxylic acylating agent, said acylating agent (A)(I)
having at least one hydrocarbyl substituent having an average of
from about 20 to about 200 carbon atoms, and (A)(II) ammonia, at
least one amine, at least one alkali or alkaline earth metal,
and/or at least one alkali or alkaline earth metal compound; (B) at
least one salt moiety derived from (B)(I) at least one
low-molecular weight polycarboxylic acylating agent, said acylating
agent (B)(I) optionally having at least one hydrocarbyl substituent
having an average of average of up to about 18 carbon atoms, and
(B)(II) ammonia, at least one amine, at least one alkali or
alkaline earth metal, and/or at least one alkali or alkaline earth
metal compound; said components (A) and (B) being coupled together
by (C) least one compound having (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 or (v) at least one primary or secondary
amino group at least one hydroxyl group.
[0011] These materials described above have proven to be useful
emulsifiers however there is continued need for emulsifiers with
improved performance, as well as emulsifier systems that are more
easily customized for specific applications. There is a need to
allow the fluid users and/or manufacturers the ability to easily
adjust and/or adapt the emulsifier they are using based on the
specific fluid and/or end use they are dealing with. Thus there is
a continued need for better performing and/or more customizable
emulsifiers which can be customized by the fluid users and/or
manufacturers.
SUMMARY OF THE INVENTION
[0012] The disclosed technology provides an additive comprising (i)
a functional group derived from a first hydrocarbyl-substituted
acylating agent and (ii) a functional group derived from a second
hydrocarbyl-substituted acylating agent, where the functional
groups (i) and (ii) are coupled by a functional group derived from
an alkylene glycol such as a linear alkylene glycol; wherein the
first hydrocarbyl-substituted acylating agent comprises a
hydrocarbyl substituent group containing at least 20 carbon atoms;
and wherein the second hydrocarbyl-substituted acylating agent
comprises a hydrocarbyl substituent group containing less than 20
carbon atoms.
[0013] The invention further provides the described additive where
the first hydrocarbyl-substituted acylating agent comprises the
reaction product of a long chain hydrocarbon with a monounsaturated
carboxylic acid; wherein said long chain hydrocarbon has a number
average molecular weight greater than 400. In some embodiments,
long chain hydrocarbon has a number average molecular weight
greater than 450, at least 500, at least 750, or even at least 800.
(A "monounsaturated carboxylic acid" refers to a carboxylic acid
that contains one ethylenic unsaturation, that is, not counting the
carbonyl double bond.)
[0014] The invention further provides the described additive where
the first hydrocarbyl-substituted acylating agent comprises
polyisobutylene succinic anhydride having a number average
molecular weight greater than 400. In some embodiments, the
polyisobutylene succinic anhydride has a polyisobutylene group with
a number average molecular weight greater than 450, at least 500,
at least 750, or even at least 800.
[0015] The invention further provides the described additive
wherein the second hydrocarbyl-substituted acylating agent
comprises the reaction product of a long chain hydrocarbon with a
monounsaturated carboxylic acid; wherein said long chain
hydrocarbon has a number average molecular weight less than 400 or
less than 280 or less than 250. In some embodiments, long chain
hydrocarbon has a number average molecular weight from 100 to 400,
or from 200 to 400, or from 200 to 280, or from 200 to 250, or from
300 to 400, or even from 300 to 350, or even about 322.
[0016] The invention further provides the described additive
wherein the second hydrocarbyl-substituted acylating agent
comprises hexadecenyl succinic anhydride.
[0017] The invention further provides the described additive
wherein the alkylene glycol comprises a glycol having of the
general formula HO (C(R)).sub.x--O .sub.m--H wherein each R is
independently H or an alkyl group of 1 to 6 carbon atoms each x is
independently an integer from 2 to 10 and m is an integer from 1 to
10. That is, some or all of the R groups may be H and the remainder
(if any) of the R groups may be said alkyl groups. In certain
embodiments disclosed herein, one or more of the R groups may be
methyl groups. In certain embodiments throughout this document, the
number of carbon atoms in the glycol of the foregoing structure
will be less than 400, or less than 200, or less than 100, or 2 to
50, or 2 to 10, or 2 or 3.
[0018] In some embodiments, the alkylene glycol is a linear
alkylene glycol, and in some embodiments it comprises ethylene
glycol.
[0019] The invention further provides the described additive
wherein the first hydrocarbyl-substituted acylating agent comprises
polyisobutylene succinic anhydride having a number average
molecular weight greater than 750; wherein the second
hydrocarbyl-substituted acylating agent comprises hexadecenyl
succinic anhydride; and wherein the alkylene glycol comprises
ethylene glycol.
[0020] The invention further provides an emulsifier component
prepared by a process comprising the steps of: Step (I) reacting a
first hydrocarbyl-substituted acylating agent, a second
hydrocarbyl-substituted acylating agent, and an (optionally linear)
alkylene glycol; wherein the first hydrocarbyl-substituted
acylating agent comprises a hydrocarbyl substituent group
containing at least 20 carbon atoms; and wherein the second
hydrocarbyl-substituted acylating agent comprises a hydrocarbyl
substituent group containing less than 20 carbon atoms; resulting
in an additive comprising (i) a functional group derived from said
first hydrocarbyl-substituted acylating agent and (ii) a functional
group derived from said second hydrocarbyl-substituted acylating
agent, where the functional groups (i) and (ii) are coupled by a
functional group derived from said alkylene glycol; Step (II)
providing said additive for use as an emulsifier component
precursor; and Step (III) converting said additive to an emulsifier
component by reacting said additive with a neutralizing component.
Any of the additives described herein may be prepared and used as
described by this process.
[0021] The invention further provides the emulsifier component
described above where said neutralizing component comprises an
alkali or alkaline earth-metal base or an amine. Suitable amines
include NaOH, KOH, monoethanolamine, diethanolamine,
triethanolamine, methyl diethanolamine, dimethylethanolamine,
butylethanolamine, butyl diethanolamine, octyl diethanolamine,
cyclohexyl diethanolamine, monoisopropanolamine, diispropanolamine,
triispropanolamine, diglycolamine, 1-amino-2-methyl-1-propanol,
3-amino-4-octanol, dicylcohexylamine, octylamine, and any
combinations thereof.
[0022] The invention further provides a process of making an
emulsifier component comprising the steps of: Step (I) reacting a
first hydrocarbyl-substituted acylating agent, a second
hydrocarbyl-substituted acylating agent, and an (optionally linear)
alkylene glycol; wherein the first hydrocarbyl-substituted
acylating agent comprises a hydrocarbyl substituent group
containing at least 20 carbon atoms; and wherein the second
hydrocarbyl-substituted acylating agent comprises a hydrocarbyl
substituent group containing less than 20 carbon atoms; resulting
in an intermediate (which may also be referred to throughout this
document as an additive) comprising (i) a functional group derived
from said first hydrocarbyl-substituted acylating agent and (ii) a
functional group derived from said second hydrocarbyl-substituted
acylating agent, where the functional groups (i) and (ii) are
coupled by a functional group derived from said alkylene glycol;
Step (II) providing said additive for use as an emulsifier
component precursor; and, typically thereafter, Step (III)
converting said intermediate (or additive) to an emulsifier
component by reacting said intermediate (additive) with a
neutralizing component. Any of the additives described herein may
be prepared and used as described by this process.
[0023] The invention further provides the describe process wherein
the first hydrocarbyl-substituted acylating agent comprises the
reaction product of a long chain hydrocarbon with a monounsaturated
carboxylic acid; wherein said long chain hydrocarbon has a number
average molecular weight greater than 400; and wherein the second
hydrocarbyl-substituted acylating agent comprises the reaction
product of a long chain hydrocarbon with a monounsaturated
carboxylic acid; wherein said long chain hydrocarbon has a number
average molecular weight less than 400 or less than 280; wherein
the (optionally linear) alkylene glycol comprises a glycol having
of the general formula HO (C(R)).sub.x--O .sub.m--H wherein each R
is independently H or an alkyl group of 1 to 6 carbon atoms, each x
is independently an integer from 2 to 10 and m is an integer from 1
to 10.
[0024] The invention further provides the describe process wherein
the first hydrocarbyl-substituted acylating agent comprises
polyisobutylene succinic anhydride having a number average
molecular weight greater than 750; wherein the second
hydrocarbyl-substituted acylating agent comprises hexadecenyl
succinic anhydride; and wherein the alkylene glycol comprises
ethylene glycol.
[0025] The invention further provides a method of customizing an
emulsifier component in a composition said method comprising the
steps of: Step (I) preparing an additive by reacting a first
hydrocarbyl-substituted acylating agent, a second
hydrocarbyl-substituted acylating agent, and an (optionally linear)
alkylene glycol; wherein the first hydrocarbyl-substituted
acylating agent comprises a hydrocarbyl substituent group
containing at least 20 carbon atoms; and wherein the second
hydrocarbyl-substituted acylating agent comprises a hydrocarbyl
substituent group containing less than 20 carbon atoms; resulting
in an additive comprising (i) a functional group derived from said
first hydrocarbyl-substituted acylating agent and (ii) a functional
group derived from said second hydrocarbyl-substituted acylating
agent, where the functional groups (i) and (ii) are coupled by a
functional group derived from said alkylene glycol; Step (II)
supplying said additive into a composition that requires an
emulsifier component; and, typically thereafter, Step (III)
converting said additive, in said composition, to an emulsifier
component by reacting said additive with a neutralizing component;
resulting in a customized emulsifier component. Any of the
additives described herein may be prepared and used as described by
this method.
[0026] The invention further provides the described method wherein
the first hydrocarbyl-substituted acylating agent comprises the
reaction product of a long chain hydrocarbon with a monounsaturated
carboxylic acid; wherein said long chain hydrocarbon has a number
average molecular weight greater than 400; and wherein the second
hydrocarbyl-substituted acylating agent comprises the reaction
product of a long chain hydrocarbon with a monounsaturated
carboxylic acid; wherein said long chain hydrocarbon has a number
average molecular weight less than 400 or less than 280; and
wherein the alkylene glycol comprises a glycol having of the
general formula HO (CH.sub.2).sub.x--O .sub.m--H wherein each R is
independently H or an alkyl group of 1 to 6 carbon atoms each x is
independently an integer from 2 to 10 and m is an integer from 1 to
10.
DETAILED DESCRIPTION OF THE INVENTION
[0027] Various preferred features and embodiments will be described
below by way of non-limiting illustration.
[0028] It has been found that using the described additive provides
a benefit to emulsifier users, by allowing the user to optimize the
Hydrophilic-Lipophilic Balance (HLB), buffering system and
corrosion inhibition system of the additive resulting in an
emulsifier customized for use in the specific metalworking product
and/or application relevant to the user. This approach involves the
use of an additive that has never been used as an emulsifier
itself, which may then be further modified by emulsifier users to
achieve the specific emulsifier performance they desire.
The Additive
[0029] The disclosed technology provides an additive comprising (i)
a functional group derived from a first hydrocarbyl-substituted
acylating agent and (ii) a functional group derived from a second
hydrocarbyl-substituted acylating agent, where the functional
groups (i) and (ii) are coupled by a functional group derived from
an alkylene glycol which may be either a branched or a linear
alkylene glycol; wherein the first hydrocarbyl-substituted
acylating agent comprises a hydrocarbyl substituent group
containing at least 20 carbon atoms; and wherein the second
hydrocarbyl-substituted acylating agent comprises a hydrocarbyl
substituent group containing less than 20 carbon atoms.
[0030] The first hydrocarbyl-substituted acylating agent and the
second hydrocarbyl-substituted acylating agent, from which the
functional groups (i) and (ii) are derived, may also be described
as carboxylic acylating agents and may be aliphatic or aromatic,
polycarboxylic acids or acid-producing compounds. As used herein,
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.
[0031] The acylating agents 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.
[0032] Examples of low molecular weight polycarboxylic acids,
(i.e., the second hydrocarbyl-substituted acylating agent which
comprises a hydrocarbyl substituent group containing less than 20
carbon atoms), include dicarboxylic acids and derivatives such as
maleic acid, maleic anhydride, chloromaleic anhydride, malonic
acid, succinic acid, succinic anhydride, glutaric acid, glutaric
anhydride, adipic acid, pimelic acid, azelaic acid, sebacic acid,
glutaconic acid, citraconic acid, itaconic acid, allyl succinic
acid, cetyl malonic acid, tetrapropylene-substituted succinic
anhydride, etc. Lower alkyl esters of these acids can also be
used.
[0033] In some embodiments, both the first hydrocarbyl-substituted
acylating agent and the second hydrocarbyl-substituted acylating
agents are hydrocarbyl substituted succinic acids and
anhydrides.
[0034] The hydrocarbyl succinic acylating agents 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.
[0035] The high-molecular weight polycarboxylic acylating agents
(i.e. the first hydrocarbyl-substituted acylating agent which
comprises a hydrocarbyl substituent group containing at least 20
carbon atoms), are well known in the art and have been described in
detail, for example, in U.S. Pat. Nos. 3,215,707; 3,231,587;
3,288,714; 3,346,354; 3,912,764; 4,110,349; and 4,234,435; and
British Patent 1,492,337. These patents are incorporated herein by
reference.
[0036] The hydrocarbyl groups of the first and second
hydrocarbyl-substituted acylating agents are not overly limited so
long as they meet the requirements described herein. Especially
useful hydrocarbyl groups comprising 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 medial 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. 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. 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-methyl-1-butene
with 1-octene, 3,3-dimethyl- l -pentene with 1-hexene, isobutene
with styrene and piperylene, etc.
[0037] 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.
[0038] In one embodiment of the invention, the polymers are
obtained by the polymerization of a C4 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. These polyisobutenes
preferably contain predominantly (that is, greater than about 80%
of the total repeat units) isobutene repeat units of the
configuration --CH.sub.2C(CH.sub.3).sub.2--. The hydrocarbons and
ethylenically unsaturated hydrocarbons used in the preparation of
the higher molecular weight succinic acylating agents may have up
to about 200 carbon atoms per molecule. Some acylating agents are
those containing hydrocarbyl groups of from about 20 to about 150,
or from 30 to about 120, or from about 50 to about 80 carbon atoms.
The hydrocarbyl-substituted succinic acids and the anhydride may
prepared by reacting maleic anhydride with a high molecular weight
olefin. 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 or ester.
[0039] The hydrocarbyl group of the first hydrocarbyl-substituted
acylating agent may contain from about 20 to about 200 carbon
atoms, from about 30 to about 150 carbon atoms, from about 50 to
about 200 carbon atoms, or even from about 70 to about 80 carbon
atoms.
[0040] The second hydrocarbyl-substituted acylating agent, which
may also be referred to as the low molecular weight succinic
acylating agents can be prepared in essentially the same manner as
the high molecular weight materials. In some embodiments, its
hydrocarbyl group is an aliphatic or alicyclic hydrocarbyl group
with less than about 10% of its carbon-to-carbon bonds being
unsaturated. Its hydrocarbyl can be derived from olefins of from 2
to about 18 carbon atoms with alpha-olefins being particularly
useful. Examples of such olefins include ethylene, propylene,
1-butene, isobutene, 1-pentene, 2-methyl-1-butene,
3-methyl-1-butene, 1-hexene, 1-heptene, 1-octene, styrene,
1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene,
1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene,
1-octadecene.
[0041] Commercially available alpha olefin fractions such as C12-18
alpha-olefins, C12-16 alpha-olefins, C14-14 16 alpha-olefins,
C14-18 alpha-olefins, and C16-18 alpha-olefins, are particularly
useful. These commercial alpha-olefin fractions also usually
include minor amounts of alpha-olefins outside the given ranges. As
is the case for the high molecular weight materials, the
unsaturated material or optionally chlorinated analog is reacted
with maleic acid or maleic anhydride. The production of such
substituted succinic acids and their derivatives is well known to
those of skill in the art and need not be discussed in detail
herein.
[0042] In some embodiments, the first hydrocarbyl-substituted
acylating agent comprises the reaction product of a long chain
hydrocarbon with a monounsaturated carboxylic acid; wherein said
long chain hydrocarbon has a number average molecular weight
greater than 400. In some embodiments, long chain hydrocarbon has a
number average molecular weight greater than 450, at least 500, at
least 750, or even at least 800. In some embodiments, the first
hydrocarbyl-substituted acylating agent comprises polyisobutylene
succinic anhydride having a number average molecular weight greater
than 400. In some embodiments, the polyisobutylene succinic
anhydride has a number average molecular weight greater than 450,
at least 500, at least 750, or even at least 800.
[0043] In some embodiments, the second hydrocarbyl-substituted
acylating agent comprises the reaction product of a long chain
hydrocarbon with a monounsaturated carboxylic acid; wherein said
long chain hydrocarbon has a number average molecular weight less
than 400 or less than 280. In some embodiments, long chain
hydrocarbon has a number average molecular weight from 100 to 400,
or from 200 to 400, or from 300 to 400, or even from 300 to 350, or
even about 322, or 100 to less than 280. In some embodiments, the
second hydrocarbyl-substituted acylating agent comprises
hexadecenyl succinic anhydride.
[0044] The functional groups (i) and (ii) described above are
coupled by a functional group derived from an alkylene glycol. This
third functional group acts as a bridge between the low and the
high molecular weight functional groups derived from the acylating
agents described above. The low and high molecular weight agents
may be mixed together, and are reacted with the bridging molecule.
The reaction is such that the predominant species in the reaction
mixture is the product in which the alkylene glycol acts as a
bridge between a first hydrocarbyl-substituted acylating agent and
a second hydrocarbyl-substituted acylating agent. However, there
may be some formation of molecules in which two low molecular
weight succinic agents are linked as well as formation of species
in which two high molecular weight succinic agents are linked. In
some embodiments low and high molecular weight agents may be
reacted sequentially with the alkylene glycol. In this case, the
species comprising a first hydrocarbyl-substituted acylating agent
and a second hydrocarbyl-substituted acylating agent molecule
linked by an alkylene glycol greatly predominates over the other
species.
[0045] In general, any compound having (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, or (v) at least one
primary or secondary amino group and at least one hydroxyl group
may be used as a linking group. However, in the present invention,
it has been found that using an alkylene glycol, such as, in some
embodiments, a linear alkylene glycol, provides the best results,
i.e. the most customizable additive.
[0046] The alkylene glycols useful in the invention may also be
referred to generally as polyols, and includes those compounds of
the general formula: R.sup.1(OH).sub.m wherein R.sup.1 is a
divalent organic group joined to the --H groups through
carbon-to-oxygen bonds (that is, --COH wherein the carbon is not
part of a carbonyl group) and m is 2. These alcohols are be
aliphatic and in some embodiments contain not more than about 40,
or not more than about 20 carbon atoms.
[0047] Alcohols useful in this invention include alkylene glycols
with the alkylene group containing from about 2 to 10 or 2 to 8
carbon atoms. They may also include polyoxyalkylene glycol, that
is, materials represented by HO (C(R)).sub.x--O .sub.m--H where
each R is independently H or an alkyl group of 1 to 6 carbon atoms
each x is independently an integer from 2 to about 10 and m is an
integer greater than 1, that is, 2 to 10. They are illustrated, for
example, 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. Polyoxyalkylene glycols which are
copolymers of different alkylene oxide units may also be used, such
as copolymers of ethylene glycol and propylene glycols such as 1,2-
or 1,3-propylene glycol. They may be referred to as alkylene
glycols as an alternative to the nomenclature "polyalkylene
glycol"--both such materials may be used. Such materials may also
be referred to as oligomers, since the number of repeat units will
typically not exceed 10. In one embodiment the linear alkylene
glycol comprises a poly(ethylene glycol), a poly(1,3-propylene
glycol) or a copolymer of ethylene glycol and 1,3-propylene
glycol.
[0048] In some embodiments, one or more linking compounds is used
in combination with linear alkylene glycols described herein. Such
additional linker may include any compound having (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, or (v) at least one
primary or secondary amino group and at least one hydroxyl group
may be used as a linking group. In other embodiments, the linking
compounds contains the alkylene glycols described herein, and is
essentially free of, or even completely free of, any other linking
compounds.
[0049] In some embodiments, the described additive wherein the
alkylene glycol comprises a glycol having of the general formula
HO(CH.sub.2).sub.xOH wherein x is an integer from 2 to 10. In some
embodiments, the alkylene glycol comprises ethylene glycol.
[0050] The invention further provides the described additive
wherein the first hydrocarbyl-substituted acylating agent comprises
polyisobutylene succinic anhydride having a number average
molecular weight greater than 750; wherein the second
hydrocarbyl-substituted acylating agent comprises hexadecenyl
succinic anhydride; and wherein the alkylene glycol comprises
ethylene glycol.
[0051] In some embodiments, the first hydrocarbyl-substituted
acylating agent comprises the reaction product of a long chain
hydrocarbon with a monounsaturated carboxylic acid; wherein said
long chain hydrocarbon has a number average molecular weight
greater than 400; and the second hydrocarbyl-substituted acylating
agent comprises the reaction product of a long chain hydrocarbon
with a monounsaturated carboxylic acid; wherein said long chain
hydrocarbon has a number average molecular weight less than 400 or
less than 280; and the alkylene glycol comprises a glycol having of
the general formula HO (C(R)).sub.x--O .sub.m--H where each R is
independently H or an alkyl group of 1 to 6 carbon atoms each x is
independently an integer from 2 to about 10 and m is an integer
from 1 to about 10.
[0052] In some embodiments, the first hydrocarbyl-substituted
acylating agent comprises polyisobutylene succinic anhydride having
a number average molecular weight greater than 750; the second
hydrocarbyl-substituted acylating agent comprises hexadecenyl
succinic anhydride; and the alkylene glycol comprises ethylene
glycol.
The Emulsifier Component
[0053] The invention further provides an emulsifier component
prepared by a process that allows for the customization of the
emulsifier. The emulsifier component is prepared by: Step (I)
reacting a first hydrocarbyl-substituted acylating agent, a second
hydrocarbyl-substituted acylating agent, and an (optionally linear)
alkylene glycol; wherein the first hydrocarbyl-substituted
acylating agent comprises a hydrocarbyl substituent group
containing at least 20 carbon atoms; and wherein the second
hydrocarbyl-substituted acylating agent comprises a hydrocarbyl
substituent group containing less than 20 carbon atoms; resulting
in an additive comprising (i) a functional group derived from said
first hydrocarbyl-substituted acylating agent and (ii) a functional
group derived from said second hydrocarbyl-substituted acylating
agent, where the functional groups (i) and (ii) are coupled by a
functional group derived from said alkylene glycol; then Step (II)
providing said additive for use as an emulsifier component
precursor; and (typically thereafter) Step (III) converting said
additive to an emulsifier component by reacting said additive with
a neutralizing component. The emulsifier component described herein
may be prepared using any of the additives described herein, where
the additive is the emulsifier component precursor that is then
converted into the emulsifier component.
[0054] In Step (II), by providing said additive for use as an
emulsifier component precursor, it is meant that the emulsifier
component precursor (which may also be referred to as the additive)
is handled like a conventional emulsifier component would be.
However, in the case of the emulsifier component precursor, it is
converted into the specific emulsifier component of a downstream
party's choice, for example, a finished fluid blender and/or user,
who follows Step (III) and convert the additive to an emulsifier
component by reacting said additive with a neutralizing
component.
[0055] In some embodiments, providing said additive for use as an
emulsifier component precursor involves using, storing,
transporting, selling, blending, and/or otherwise handing the
additive before it is converted into the emulsifier component. In
some embodiments, the emulsifier component precursor is transported
and/or stored after the additive is formed, but before the additive
is converted to the emulsifier component.
[0056] The neutralizing components used to form the emulsifier
components described above are not overly limited. Typically, the
resulting emulsifier component is in the form of a salt. The
emulsifier components may be formed from mixtures of one or more
neutralizing components. In some embodiments, a single kind of
neutralizing component is used. In other embodiments, a mixture of
two or more neutralizing components are used.
[0057] The metals useful as neutralizing components include the
alkali and alkaline earth-metals that may be found in metal bases.
The amines useful as neutralizing components in preparing the salt
compositions of the invention include ammonia, and the primary
amines, secondary amines and hydroxyamines. In addition to ammonia,
the primary amines, secondary amines and hydroxyamines, the amines
useful as neutralizing components also include primary and
secondary monoamines, and tertiary mono- and polyamines. Useful
primary and secondary monoamines include aliphatic, cycloaliphatic
and aromatic monoamines. The tertiary amines are analogous to the
primary amines, secondary amines and hydroxyamines with the
exception that they can be either monoamines or polyamines and the
hydrogen atoms in the H--N< or --NH.sub.2 groups are replaced by
hydrocarbyl groups.
[0058] Useful polyamines include are characterized by the presence
within their structure of at least two --NH.sub.2 groups, at least
two >NH groups, or at least one --NH.sub.2 group and at least
one >NH group. These polyamines 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
amines may be saturated or unsaturated. If unsaturated, the amine
is preferably free from acetylenic unsaturation. These amines may
also contain non-hydrocarbon substituents or groups as long as
these groups do not significantly interfere with the reaction. Such
non-hydrocarbon substituents or groups include lower alkoxy, lower
alkyl, mercapto, nitro, and interrupting groups such as --O-- and
--S--. The polyamines include aliphatic, cycloaliphatic and
aromatic polyamines analogous to the aliphatic, cycloaliphatic and
aromatic monoamines described below except for the presence within
their structure of at least one additional >NH or --NH.sub.2
group.
[0059] 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
di-alkenyl-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.
[0060] Cycloaliphatic monoamines 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,
[0061] 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.
[0062] Aromatic monoamines include 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 naphthalene.
Examples of aromatic monoamines include aniline,
di(para-methylphenyl) 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 thienyl-substituted
aniline.
[0063] 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.
[0064] Among the suitable heterocyclic polyamines are the
aziridines, azetidines, azolidines, tetra- and di-hydro pyridines,
pyrroles, indoles, piperidines, imidazoles, di- and
tetrahydroimidazoles, 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.
[0065] 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, phenyl-hydrazine,
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.
[0066] 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 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.
These amines may be expressed by the formula:
NH.sub.2--(R--NH).sub.x N(R)((R--NH).sub.z--R--NH.sub.2)].sub.y
wherein R is an alkylene group such as ethylene, propylene,
butylene and other homologs (both straight chained and branched),
etc., but preferably ethylene; and x, y and z are integers; x is in
the range of from about 4 to about 24 or more, preferably from
about 6 to about 18; y is in the range of from 1 to about 6 or
more, preferably from 1 to about 3; and z is in the range of from
zero to about 6, preferably from zero to about 1. The x and y units
may be sequential, alternative, orderly or randomly distributed. A
useful class of such polyamines includes those of the formula:
NH.sub.2 (R--N(H)).sub.5--N(R)(R--NH.sub.2)--(R--N(H)).sub.2
.sub.n--H wherein n is an integer in the range of from 1 to about
20 or more, preferably in the range of from 1 to about 3, and R is
preferably ethylene, but may be propylene, butylene, etc. (straight
chained or branched). U.S. Pat. Nos. 3,200,106 and 3,259,578 are
incorporated herein by reference for their disclosures relative to
said polyamines.
[0067] Suitable polyamines also include polyoxyalkylene polyamines,
e.g., polyoxyalkylene diamines and polyoxyalkylene triamines,
having average molecular weights ranging from about 200 to about
4000, preferably from about 400 to 2000. Examples of these
polyoxyalkylene polyamines include those amines represented by the
formula: NH.sub.2-Alkylene-(O-Alkylene).sub.m-NH.sub.2 wherein m
has a value of from about 3 to about 70, preferably from about 10
to about 35. R-[-Alkylene-(O-Alkylene).sub.n-NH.sub.2].sub.3-6
wherein n is a number in the range of from 1 to about 40, with the
proviso that the sum of all of the n's is from about 3 to about 70
and generally from about 6 to about 35, and R is a polyvalent
saturated hydrocarbyl group of up to about 10 carbon atoms having a
valence of from about 3 to about 6. The alkylene groups may be
straight or branched chains and contain from 1 to about 7 carbon
atoms, and usually from 1 to about 4 carbon atoms. The various
alkylene groups present within the above formulae may be the same
or different.
[0068] 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 Texaco 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.
[0069] Useful polyamines are the alkylene polyamines, including the
polyalkylene polyamines, as described in more detail hereafter. The
alkylene polyamines include those conforming to the formula:
(R)(R)N-(Alkylene-N(R)).sub.n--R' wherein n is from 1 to about 10,
preferably from 1 to about 7; each R and R' is independently a
hydrogen atom, a hydrocarbyl group or a hydroxy-substituted
hydrocarbyl group having up to about 700 carbon atoms, preferably
up to about 100 carbon atoms, more preferably up to about 50 carbon
atoms, more preferably up to about 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 about 1 to about 18 carbon atoms,
preferably from 1 to about 4 carbon atoms, with the preferred
Alkylene being 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.
[0070] Alkylene polyamines that are useful include ethylene
diamine, diethylene triamine, triethylene tetramine, tetraethylene
pentamine, pentaethylene hexamine, propylene diamine, trimethylene
diamine, hexamethylene diamine, decamethylene 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
aforedescribed polyamines.
[0071] 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.
[0072] Alkoxylated alkylene polyamines (e.g.,
N,N-1(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 aforedescribed 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.
[0073] Specific examples of alkoxylated alkylene polyamines include
N-(2-hydroxyethyl) ethylene diamine,
N,N-bis(2-hydroxyethyl)-ethylene-diamine, 1-(2-hydroxyethyl)
piperazine, mono(hydroxypropyl)-substituted diethylene triamine,
di(hydroxypropyl)-substituted tetraethylene pentamine,
N-(3-hydroxybutyl)-tetra-methylene 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.
[0074] Useful hydroxyamines can be 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 --NH.sub.2 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.
[0075] The hydroxyamines can be primary or secondary alkanol amines
or mixtures thereof. Such amines can be represented, respectfully,
by the formulae: (H)(R)N--R'--OH wherein R is a hydrocarbyl group
of one to about eight carbon atoms or hydroxylsubstituted
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. The primary or secondary
alkanol amines may contain slightly larger R and R' groups, and may
contain up to about 40 carbon atoms.
[0076] 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 aforedescribed amines and can
be represented by the formulae: H.sub.2N--R'--OH and
(H)(R)N--R'--OH wherein x is a number from about 2 to about 15 and
R and R' are as described above.
[0077] Polyamine analogs of these hydroxy amines, particularly
alkoxylated alkylene polyamines (e.g., N,N-(diethanol)-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
aforedescribed 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.
[0078] Specific examples of alkoxylated alkylene polyamines include
N-(2-hydroxyethyl) ethylene diamine, N,N-bis(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 hydroxyalkylene
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 mono- or polyamines are also useful.
[0079] 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.
[0080] Further, hydroxyamines are the hydroxy-substituted primary
amines described in U.S. Pat. No. 3,576,743 by the general formula
R.sup.a--NH.sub.2 wherein R.sup.a is a monovalent organic group
containing at least one alcoholic hydroxy group. The total number
of carbon atoms in R.sup.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.sup.a--NH.sub.2 wherein R.sup.a is a mono- or
polyhydroxy-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-amino ethyl)-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-butene (which can be prepared
according to procedures known in the art by reacting isoprene-oxide
with ammonia), N-3-(aminopropyl)-4-(2-hydroxyethyl)piperidine,
2-amino-6-methyl-6-heptanol, 5-amino-1-pentanol,
N-(beta-hydroxyethyl)1,3diamino propane,
1,3-diamino-2-hydroxypropane, N-(beta-hydroxyethoxyethyl)ethylene
diamine, trismethylolaminomethane and the like. U.S. Pat. No.
3,576,743 is incorporated herein by reference.
[0081] 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
hydroxyalkyl-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 hydroxygroups results in products
containing ether linkages accompanied by removal of water.
[0082] Useful tertiary amines include 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. 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] The monoamines can be represented by the formula
N(R.sup.1)(R.sup.2)(R.sup.3) wherein R.sup.1, R.sup.2, and R.sup.3
are the same or different hydrocarbyl groups. Preferably, R.sup.1,
R.sup.2, and R.sup.3 are independently hydrocarbyl groups of from 1
to about 20 carbon atoms.
[0084] 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-di-dodecyl-1-dodecanamine tricoco
amine, trihydrogenated tallow amine, N-methyldihydrogenated 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.
[0085] Useful tertiary alkanol amines are represented by the
formula (R)(R)N--R'--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' is a divalent hydrocarbyl group of about two to about
18 carbon atoms. The group --R'--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 the amines
described above and can be represented by the formula:
(R)(R)N--(R'--O).sub.xH wherein x is a number from about 2 to about
15 and R and R' are as described above.
[0086] Useful polyamines include the alkylene polyamines discussed
above as well as alkylene polyamines with only one or no hydrogens
attached to the nitrogen atoms. Thus, the alkylene polyamines
useful as neutralizing components include those conforming to the
formula: (R)(R)N--(R'--O).sub.x--H wherein x is from 1 to about 10,
from 1 to about 7; each R is independently a hydrogen atom, a
hydrocarbyl group or a hydroxy-substituted hydrocarbyl group having
up to about 700 carbon atoms, preferably up to about 100 carbon
atoms, more preferably up to about 50 carbon atoms, more preferably
up to about 30 carbon atoms; and the "Alkylene" group has from
about 1 to about 18 carbon atoms, preferably from 1 to about 4
carbon atoms, with the preferred Alkylene being ethylene or
propylene.
[0087] The alkali and alkaline earth metals that are useful as
neutralizing components 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.
[0088] The invention further provides a process of making the
described emulsifier component. The process comprises the steps of:
Step (I) reacting a first hydrocarbyl-substituted acylating agent,
a second hydrocarbyl-substituted acylating agent, and an
(optionally linear) alkylene glycol; wherein the first
hydrocarbyl-substituted acylating agent comprises a hydrocarbyl
substituent group containing at least 20 carbon atoms; and wherein
the second hydrocarbyl-substituted acylating agent comprises a
hydrocarbyl substituent group containing less than 20 carbon atoms;
resulting in an additive comprising (i) a functional group derived
from said first hydrocarbyl-substituted acylating agent and (ii) a
functional group derived from said second hydrocarbyl-substituted
acylating agent, where the functional groups (i) and (ii) are
coupled by a functional group derived from said alkylene glycol;
Step (II) providing said additive for use as an emulsifier
component precursor; Step (III) converting said additive to an
emulsifier component by reacting said additive with a neutralizing
component. Any of the emulsifier components described above may be
prepared by this process.
[0089] In some embodiments, the process may be described as
initially reacting the first hydrocarbyl-substituted acylating
agent and the second hydrocarbyl-substituted acylating agent the
alkylene glycol to form an additive, and thereafter providing the
additive, as described above, to an end use who may then use the
additive to form the emulsifier component of his/her choosing by
reacting said intermediate with the neutralizing component to form
the desired salt.
[0090] The ratio of reactants utilized in the preparation of either
the additive (and/or the emulsifier component precursor) emulsifier
component may be varied over a wide range. Generally, for each
equivalent of each of the acylating agents, at least about one
equivalent of alkylene glycol is used. From about 0.1 to about 2
equivalents or more of neutralizing component are used for each
equivalent of components acylating agents, respectively. The upper
limit of alkylene glycol is about 2 equivalents of alkylene glycol
for each equivalent of acylating agents. Generally the ratio of
equivalents of acylating agents is about 0.5 to about 2, with about
1:1 being preferred. Preferred amounts of the reactants are about 2
equivalents of the alkylene glycol and from about 0.1 to about 2
equivalents of each of neutralizing component for each equivalent
of each acylating agent.
[0091] The number of equivalents of the acylating agents depends on
the total number of carboxylic functions present in each. In
determining the number of equivalents for each of the acylating
agents, 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 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 can be readily determined by one skilled in the
art.
[0092] An equivalent weight of a polyamine is the molecular weight
of the polyamine divided by the total number of nitrogens present
in the molecule where tertiary amino groups are counted. Thus,
ethylene diamine has an equivalent weight equal to one-half of its
molecular weight; diethylene triamine has an equivalent weight
equal to one-third its molecular weight. The equivalent weight of a
commercially available mixture of polyalkylene polyamine can be
determined by dividing the atomic weight of nitrogen (14) by the %
N contained in the polyamine; thus, a polyamine mixture having a %
N of 34 would have an equivalent weight of 41.2. An equivalent
weight of ammonia or a monoamine is its molecular weight.
[0093] An equivalent weight of polyhydric alcohol is its molecular
weight divided by the total number of hydroxyl groups present in
the molecule. Thus, an equivalent weight of ethylene glycol is
one-half its molecular weight.
[0094] An equivalent weight of a hydroxyamine would be its
molecular weight divided by the total number of nitrogen groups
present in the molecule. Thus, dimethylethanolamine would have an
equivalent weight equal to its molecular weight; ethanolamine would
also have an equivalent weight equal to its molecular weight.
[0095] An equivalent weight of an alkali or alkaline earth metal is
its molecular weight. An equivalent weight of an alkali or alkaline
earth metal compound is its molecular weight divided by the number
of alkali or alkaline earth metal atoms present in the
molecule.
[0096] The acylating agents can be reacted with the alkylene glycol
according to conventional ester and/or amide forming techniques.
This normally involves heating acylating agents with the alkylene
glycol optionally in the presence of a normally liquid,
substantially inert, organic liquid solvent/diluent.
[0097] The reactions between the additive and the neutralizing
component are carried out under salt forming conditions using
conventional techniques. Typically, the components are mixed
together and heated to a temperature in the range of about
20.degree. C. up to the decomposition temperature of the reaction
component and/or product having the lowest such temperature,
optionally, in the presence of a normally liquid, substantially
inert organic liquid solvent/diluent, until the desired product has
formed.
[0098] The invention further provides a method and/or use of the
additive described above as part of a process of customizing an
emulsifier component in a composition. This method and/or use
includes the steps of: Step (I) preparing an additive by reacting a
first hydrocarbyl-substituted acylating agent, a second
hydrocarbyl-substituted acylating agent, and an (optionally linear)
alkylene glycol; wherein the first hydrocarbyl-substituted
acylating agent comprises a hydrocarbyl substituent group
containing at least 20 carbon atoms; and wherein the second
hydrocarbyl-substituted acylating agent comprises a hydrocarbyl
substituent group containing less than 20 carbon atoms; resulting
in an additive comprising (i) a functional group derived from said
first hydrocarbyl-substituted acylating agent and (ii) a functional
group derived from said second hydrocarbyl-substituted acylating
agent, where the functional groups (i) and (ii) are coupled by a
functional group derived from said alkylene glycol; Step (II)
supplying said additive into a composition that requires an
emulsifier component; Step (III) converting said additive, in said
composition, to an emulsifier component by reacting said additive
with a neutralizing component; resulting in a customized emulsifier
component.
Functional Fluid Composition
[0099] The emulsion components described herein may be used to make
functional compositions such as oil-in-water emulsions which
comprise a continuous water phase, a discontinuous organic phase,
the emulsifying composition, and additives related to the function
to be performed by the functional fluid. The discontinuous organic
phase is preferably present at a level of at least about 1% by
weight, more preferably in the range of from about 1% to about 50%
by weight, more preferably in the range of from about 1% to about
20% by weight based on the total weight of emulsion. The continuous
water phase is preferably present at a level of about 99% by
weight, more preferably at a level in the range of from about 50%
to about 99% by weight, more preferably from about 80% to about 99%
by weight based on the total weight of said emulsion. The salt
compositions of the invention are preferably present at a level in
the range of from about 1% to about 100% by weight, more preferably
from about 20% to about 80% by weight based on the total weight of
the organic phase. When the emulsifier is 100% of the organic
phase, the emulsifier is acting to form an emulsion of itself in
the water phase, and the organic phase is the emulsifier.
[0100] The oil can include most liquid hydrocarbons, for example,
paraffinic, olefinic, naphthenic, aromatic, saturated or
unsaturated hydrocarbons. In general, the oil is a
water-immiscible, emulsifiable hydrocarbon that is either liquid at
room temperature. Oils from a variety of sources, including natural
and synthetic oils and mixtures thereof may be used.
[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; alkyl
benzenes, e.g., dodecylbenzenes, tetradecylbenzenes,
dinonylbenzenes, di-(2-ethylhexyl) benzenes, 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-ethylhexanoic acid, and the like.
[0103] Esters useful as synthetic oils also include those made from
C.sub.5 to C.sub.12 monocarboxylic acids and polyols and polyol
ethers such as neopentyl glycol, trimethylol propane,
pentaerythritol, dipentaerythritol, 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-methylhexyl)-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] Optional additional materials may be incorporated in the
composition of the present invention. Typical finished compositions
may include lubricity agents, anti-wear agents, dispersants,
corrosion inhibitors, other surfactants, and the like. The
emulsions of the present invention are shelf stable, which means
they exhibit shelf stability of at least six months and typically
one year or more.
[0108] A preferred method for making the emulsions of the invention
comprises the steps of (1) mixing the emulsifier with the oil
phase, (2) mixing the additives with the oil phase, (3) stirring
the oil phase with the water phase to form a oil-in-water emulsion.
Mixing of the oil with the appropriate additives may be conducted
in any suitable mixing apparatus. Any type of apparatus capable of
either low or high shear mixing may be used to mix the oil and
water phases to prepare these oil-in-water emulsions.
[0109] The amount of each chemical component described is presented
exclusive of any solvent or diluent oil, which may be customarily
present in the commercial material, that is, on an active chemical
basis, unless otherwise indicated. However, 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.
[0110] As used herein, the term "hydrocarbyl substituent" or
"hydrocarbyl group" is used in its ordinary sense, which is
well-known to those skilled in the art. Specifically, it refers to
a group having a carbon atom directly attached to the remainder of
the molecule and having predominantly hydrocarbon character.
Examples of hydrocarbyl groups include: [0111] hydrocarbon
substituents, that is, aliphatic (e.g., alkyl or alkenyl),
alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, and
aromatic-, aliphatic-, and alicyclic-substituted aromatic
substituents, as well as cyclic substituents wherein the ring is
completed through another portion of the molecule (e.g., two
substituents together form a ring); [0112] substituted hydrocarbon
substituents, that is, substituents containing non-hydrocarbon
groups which, in the context of this invention, do not alter the
predominantly hydrocarbon nature of the substituent (e.g., halo
(especially chloro and fluoro), hydroxy, alkoxy, mercapto,
alkylmercapto, nitro, nitroso, and sulfoxy); [0113] hetero
substituents, that is, substituents which, while having a
predominantly hydrocarbon character, in the context of this
invention, contain other than carbon in a ring or chain otherwise
composed of carbon atoms and encompass substituents as pyridyl,
furyl, thienyl and imidazolyl. Heteroatoms include sulfur, oxygen,
and nitrogen. In general, no more than two, or no more than one,
non-hydrocarbon substituent will be present for every ten carbon
atoms in the hydrocarbyl group; alternatively, there may be no
non-hydrocarbon substituents in the hydrocarbyl group.
[0114] 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. For instance, metal ions (of, e.g., a detergent) can migrate
to other acidic or anionic sites of other molecules. 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.
[0115] The invention may be better understood with reference to the
following non-limiting examples.
EXAMPLES
[0116] Several examples are prepared to demonstrate the
invention.
Comparative Example 1
[0117] A preformed salt emulsifier component is prepared in a
reaction vessel by adding 33.33 pbw of 1000 Mn highly reacted
polyisobutylene succinic anhydride, 28.41 pbw of hexadecenyl
succinic anhydride, and 23.15 pbw ISO 22 mineral oil. The mixture
is heated to 99.degree. C. under a nitrogen purge. Then 3.87 pbw of
ethylene glycol is slowly added to the reaction vessel and the
resulting mixture is held at about 99.degree. C. for 4 hours. The
reaction mixture is cooled to 68.degree. C. before adding 11.24 pbw
dimethylethanolamine. The following reaction is held below
93.degree. C. The amine salted product is then cooled to ambient
temperature.
Inventive Example 2
[0118] An unsalted ester acid emulsifier component is prepared in
the lab. In a reaction vessel, 40.45 parts by weight (pbw) of 1000
number average molecular weight (Mn) highly reacted polyisobutylene
succinic anhydride, 34.83 pbw of hexadecenyl succinic anhydride,
and 20.00 pbw ISO 22 mineral oil are mixed and heated to
135.degree. C. under a nitrogen purge. Then 4.72 pbw of ethylene
glycol is slowly added to the reaction vessel and the resulting
mixture is held at about 135.degree. C. for 4 hours. The resulting
unsalted product is then cooled to ambient temperature and
collected.
[0119] Using the additives of Comparative Example 1 and Inventive
Example 2, a set of additive packages (Examples A-1 to G-1) are
prepared and then used to prepare emulsion samples (Examples A-2 to
G-2) to evaluate the emulsion performance of the additives. The
formulations of the additive packages tested are summarized in the
table below, where all values are weight percent unless otherwise
noted. The additional additives used in each example are identical
and include a low HLB emulsifier, a fatty acid salt, a corrosion
inhibitor, and a biocide.
TABLE-US-00001 TABLE 1 Additive Packages: Inv Inv Inv Comp Inv Inv
Inv Ex A-1 Ex B-1 Ex C-1 Ex D-1 Ex E-1 Ex F-1 Ex G-1 Comparative Ex
1 0 0 0 8.0 0 0 0 (DMEA) Inventive Ex 2 7.30 6.47 7.00 0 4.56 4.04
4.37 Amine MEA TEA DMEA 0 MEA TEA DMEA (Type & wt %) 0.70 1.53
1.00 0.44 0.96 0.63 Additional Additives 15.5 15.5 15.5 16.0 16.05
16.05 16.05 ISO 22 Paraffinic oil Balance Balance Balance Balance
Balance Balance Balance
[0120] All of the additive packages described in table above are
prepared by blending the ingredients in the order listed and
heating the mixtures to 50.degree. C. with moderate stirring for
about one hour.
[0121] Each additive package is then used to prepare an emulsion.
Each emulsion sample is prepared by adding water so that the
concentration of the additive package is the same in each emulsion
sample (5% by weight). Each emulsion sample is shaken vigorously
shaken in a graduated cylinder and then allowed to stand for 24
hours before being rating for stability, by measuring the amount,
or percent, of oil visible in the sample, and the amount, or
percent, of cream visible in the sample. The less oil and cream
visible, the more stable the emulsion, and so the more effective
the additive package, and so the emulsifier additive. A formulation
is considered acceptable for use if it has 0% or a trace of oil and
no more than 0.5% cream after 24 hours.
[0122] An industry foam test was also conducted on some of the
emulsion samples. In this test, 200 ml of the emulsion example is
placed in a Sunbeam cake mixer and sheared at high speed for 300
seconds. Then the time, in seconds, for the foam to collapse after
the mixer is turned off is recorded, and this time is reported as
the foam break and/or collapse time. The shorter the time it takes
for the foam to collapse, the better the result, but a result of 60
seconds or less is generally considered acceptable.
[0123] The results of the testing are summarized in the table
below.
TABLE-US-00002 TABLE 2 Results Inv Inv Inv Comp Inv Inv Inv Ex A-2
Ex B-2 Ex C-2 Ex D-2 Ex E-2 Ex F-2 Ex G-2 Emulsifier Inv Ex 2 Inv
Ex 2 Inv Ex 2 Comp Inv Ex 2 Inv Ex 2 Inv Ex 2 Used in and and and
Ex 1 and and and Additive MEA TEA DMEA (DMEA) MEA TEA DMEA Package
Concentration 0.4 wt % 0.4 wt % 0.4 wt % 0.4 wt % 0.25 wt % 0.25 wt
% 0.25 wt % of Emulsifier in Emulsion Stability 0/0 O/Trace O/Trace
O/Trace O/Trace O/Trace O/Trace % oil/% cream PASS PASS PASS PASS
PASS PASS PASS 114 ppm water Stability O/Trace O/Trace O/Trace
0/0.5 O/Trace O/Trace O/Trace % oil/% cream PASS PASS PASS FAIL
PASS PASS PASS 600 ppm water Foam Break 132 sec 7 sec 9 sec <5
sec 9 sec <5 sec <5 sec 114 ppm water
[0124] The results above show the additives of the present
invention provide acceptable stability and emulsifier performance
while also providing the adding flexibility of allowing in-situ
salt formation.
[0125] Each of the documents referred to above is incorporated
herein by reference, including any prior applications, whether or
not specifically listed above, from which priority is claimed. The
mention of any document is not an admission that such document
qualifies as prior art or constitutes the general knowledge of the
skilled person in any jurisdiction. 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." 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.
[0126] As used herein, the transitional term "comprising," which is
synonymous with "including," "containing," or "characterized by,"
is inclusive or open-ended and does not exclude additional,
un-recited elements or method steps. However, in each recitation of
"comprising" herein, it is intended that the term also encompass,
as alternative embodiments, the phrases "consisting essentially of"
and "consisting of," where "consisting of" excludes any element or
step not specified and "consisting essentially of" permits the
inclusion of additional un-recited elements or steps that do not
materially affect the basic and novel characteristics of the
composition or method under consideration.
[0127] While certain representative embodiments and details have
been shown for the purpose of illustrating the subject invention,
it will be apparent to those skilled in this art that various
changes and modifications can be made therein without departing
from the scope of the subject invention. In this regard, the scope
of the invention is to be limited only by the following claims.
* * * * *