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Description  |
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FIELD OF THE INVENTION
This invention relates to phosphorus compositions and more particularly to
phosphorus-containing compositions and their use as synthetic lubricants
and as lubricants in liquid compositions containing liquid
fluorine-containing hydrocarbons.
BACKGROUND OF THE INVENTION
Chlorofluorocarbons, generally referred to in the industry as CFCs, have
been widely used in refrigeration systems. The use of CFCs has been
diminishing in recent years because of demands from environmentalists for
the reduction if not complete ban of the use of CFCs because of the
detrimental effect of CFCs on the atmosphere's ozone layer. Examples of
CFCs include CFC-11 which is chlorotrifluoromethane, CFC-12 which is
dichlorodifluoromethane, and CFC-113 which is
1,2,2-trifluoro-1,1,2-trichloroethane. Finding a safe replacement of CFC
refrigerants has been a problem which has been difficult to solve. Several
replacement candidates have been suggested as alternatives to the fully
halogenated hydrocarbons. Examples of safe alternatives include
halogenated hydrocarbons containing at least one hydrogen atom such as
HCFC-22 which is difluorochloromethane, HCFC-123 which is
1,1-dichloro-2,2,2-trifluoroethane, HFC-134a which is
1,1,1,2-tetrafluoroethane, and HCFC-141b which is
1,1-dichloro-1-fluoroethane.
The ozone depletion potential of these proposed substitutes is
significantly less than the ozone depletion potential of the previously
used CFCs. Ozone depletion potential is a relative measure of a capability
of a material to destroy the ozone layer in the atmosphere. HCFC-22 and
HFC-134a generally are recommended as being candidates in refrigerant
applications, and HFC-134a is particularly attractive because its ozone
depletion potential has been reported as being zero.
The problem with using these alternative materials is that the alternative
materials have different solubility characteristics than the CFCs used in
refrigerants presently. For example, mineral lubricating oil is
incompatible (i.e., insoluble). Such incompatibility results in
unacceptable compressor life in compressor-type refrigeration equipment
including refrigerators and air-conditioners including auto, home and
industrial air-conditioners. The problem is particularly evident in auto
air-conditioning systems since the compressors are not separately
lubricated, and the mixture of refrigerant and lubricant circulates
throughout the entire system.
In order to perform as a satisfactory refrigeration liquid, the mixture of
refrigerant and lubricant must be compatible and stable over a wide
temperature range such as from about 0.degree. C. and above 80.degree. C.
It is generally desirable for the lubricants to be soluble in the
refrigerant at concentrations of about 5 to 15% over a temperature range
of from -40.degree. C. to 80.degree. C. These temperatures generally
correspond to the working temperatures of an automobile air-conditioning
compressor. In addition to thermal stability, the refrigeration liquids
must have acceptable viscosity characteristics which are retained even at
high temperatures, and the refrigeration liquid should not have a
detrimental effect on materials used as seals in the compressors.
U.S. Pat. No. 4,428,854, issued to Enjo et al, relates to an absorption
refrigerant composition comprising 1,1,1,2-tetrafluoroethane and organic
solvent capable of dissolving the ethane. Triethylphosphorotriamide,
hexamethylphosphorictriamide, triethylenephosphate, triethylphosphate and
like phosphate-type solvents are disclosed as phosphoro organic solvents
capable of dissolving the ethane.
U.S. Pat. No. 4,431,557, issued to Shimizu et al, relates to a fluid
composition comprising a fluorocarbon refrigerant, a hydrocarbon oil and
an alkylene oxide additive. The fluid may contain additional additives
such as load-carrying compounds such as phosphorus acid esters, phosphoric
acid esters, thiophosphoric acid esters, organic sulfur compounds or
organic halide compounds, etc.
U.S. Pat. No. 4,454,052, issued to Shoji et al, relates to stabilized
absorption composition comprising (A) a halogenated hydrocarbon
refrigerant, (B) a liquid absorbant of a polyethylene glycol methyl ether,
and (C) at least one stabilizer selected from phosphite esters, epoxy
compounds and organo tin compounds.
U.S. Pat. No. 4,755,316, issued to Magid et al, relates to lubricants for
refrigeration systems using tetrafluoroethane. The fluids employ certain
polyoxyalkylene glycols as lubricating oils. Magid et al discloses
additives which may be used to enhance performance in Table D. Among the
additives listed are phosphates, thiophosphates, and phosphites.
Reactions of trialkyl phosphites with various alpha,beta-unsaturated acids,
esters, ketones, aldehydes, amides and nitriles in protonating solvents
has been described in literature. For example, see Tetrahedron, 1966, Vol.
22, pages 2561-2573. Reactions of dialkyl phosphites with activated
olefins such as those mentioned above by a free radical mechanism also
have been described in the literature such as, for example, in Methoden
der Organische Chemie, Vol. 12/1, pages 463-490, Houben-Weyl.
Phosphorus-containing compositions prepared by the above processes are
useful in a variety of applications. For example, they are useful as
fire-retardant additives.
SUMMARY OF THE INVENTION
This invention relates to a composition comprising:
(A) a major amount of a fluorine-containing hydrocarbon containing one or
two carbon atoms; and
(B) a minor amount of a phosphorus-containing composition comprising at
least one compound characterized by the following formula;
##STR2##
wherein R.sub.1 and R.sub.2 are each independently hydrocarbyl groups or
hydrocarbyloxyalkylene groups and R.sub.1 and R.sub.2 taken together have
a total of 2 to about 24 carbon atoms excluding any oxyalkylene carbon
atoms;
a is 0 or 1;
b is 1 or 2;
c is 1, 2 or 3;
d is 0, 1 or 2, provided that c+d=3;
if b is 1, Z is selected from the group consisting of --R.sub.5,
--XR.sub.5, --N(H)R.sub.5, --N(R.sub.5).sub.2, --C(X)R.sub.5, --CN,
--S(O)R.sub.5, --S(O).sub.2 R.sub.5, --S(O).sub.2 N(R.sub.3)(R.sub.4) and
##STR3##
if b is 2, Z is --N(R.sub.5)--, X is oxygen or sulfur;
Y is a hydrocarbylene group having 1 to about 20 carbon atoms;
R.sub.5 is a hydrocarbyl group having 1 to about 18 carbon atoms;
R.sub.3 and R.sub.4 are each independently hydrogen; or a hydrocarbyl group
having 1 to about 24 carbon atoms; or R.sub.3 and R.sub.4 taken together
form a heterocyclic ring.
The present invention provides compositions which are useful as
refrigeration liquids in refrigerators and air-conditioners including
auto, home and industrial air-conditioners. The invention provides
phosphorus-containing compositions which are compatible with
fluorine-containing hydrocarbons used in refrigerators and
air-conditioners. The phosphorus-containing compositions act as a
lubricant for air-conditioners.
DETAILED DESCRIPTION OF THE INVENTION
In the specification and claims, unless the context indicates otherwise,
the use of the term alkyl-group is meant to encompass all isomeric
arrangements of the group, such as primary, secondary, and tertiary, as
well as iso- and neo-arrangements of the group.
In the specification and claims, the use of the term alkylene or
hydrocarbylene is meant to encompass divalent hydrocarbon or hydrocarbyl
groups. For instance, propylene is a divalent hydrocarbon group having 3
carbon atoms.
Throughout this specification and claims, all parts and percentages are by
weight, temperatures are in degrees Celsius, and pressures are at or near
atmospheric unless otherwise clearly indicated.
The term "hydrocarbyl" includes hydrocarbon, as well as substantially
hydrocarbon, groups. Substantially hydrocarbon describes groups which
contain non-hydrocarbon substituents which do not alter the predominantly
hydrocarbon nature of the group. Non-hydrocarbon substituents include halo
(especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto,
nitro, nitroso, sulfoxy, etc., groups. The hydrocarbyl group may also have
a heteroatom, such as sulfur, oxygen, or nitrogen, in a ring or chain. In
general, no more than about 2, preferably no more than one,
non-hydrocarbon substituent will be present for every ten carbon atoms in
the hydrocarbyl group. Typically, there will be no such non-hydrocarbon
substituents in the hydrocarbyl group. Therefore, the hydrocarbyl group is
purely hydrocarbon.
The term "lower" as used herein in conjunction with terms such as
hydrocarbyl, alkyl, alkenyl, alkoxy, and the like, is intended to describe
such groups which contain a total of up to 7 carbon atoms.
(A) Fluorine-Containing Hydrocarbon.
The fluorine-containing hydrocarbon present in the liquid compositions
contain at least one C--H bond as well as C--F bonds. In addition to these
two essential types of bonds, the hydrocarbon also may contain other
carbon-halogen bonds such as C--Cl bonds. Because the liquid compositions
of the present invention are primarily intended for use as refrigerants,
the fluorine-containing hydrocarbon preferably contains one or two carbon
atoms, and more preferably two carbon atoms.
As noted above, the fluorine-containing hydrocarbons useful in the liquid
compositions of the present invention may contain other halogens such as
chlorine. However, in one preferred embodiment, the hydrocarbon contains
only carbon, hydrogen and fluorine. These compounds containing only
carbon, hydrogen and fluorine are referred to herein as fluorohydrocarbons
(hydrofluorocarbons or HFCs). The hydrocarbons containing chlorine as well
as fluorine and hydrogen are referred to as chlorofluorohydrocarbons
(hydrochlorofluorocarbons or HCFCs). The fluorine-containing hydrocarbons
useful in the composition of the present invention are to be distinguished
from the fully halogenated hydrocarbons which have been and are being used
as propellants, refrigerants and blowing agents such as CFC-11, CFC-12 and
CFC-113 which have been described in the background.
Specific examples of the fluorine-containing hydrocarbons useful in the
liquid compositions of the present invention, and their reported ozone
depletion potentials are shown in the following Table I.
TABLE I
______________________________________
Compound
Designation Formula ODP*
______________________________________
HCFC-22 CHClF.sub.2
0.05
HCFC-123 CHCl.sub.2 CF.sub.3
<0.05
HCFC-141b CH.sub.3 CCl.sub.2 F
<0.05
HFC-134a CH.sub.2 FCF.sub.3
0
______________________________________
*Ozone depletion potential as reported in Process Engineering, pp. 33-34,
July, 1988.
Examples of other fluorine-containing hydrocarbons which may be useful in
the liquid compositions of the present invention include trifluoromethane,
1,1,1-trifluoroethane, 1,1-difluoroethane, and 1,1,2,2-tetrafluoroethane.
In general, fluorine-containing hydrocarbons which are useful as
refrigerants are fluoromethanes and fluoroethanes boiling at a relatively
low temperature at atmospheric pressure, e.g., below 30.degree. C. The
useful fluorocarbon refrigerants serve to transfer heat in a refrigeration
system by evaporating and absorbing heat at a low temperature and
pressure, e.g., at ambient temperature and atmospheric pressure, and by
releasing heat on condensing at a higher temperature and pressure.
The liquid compositions of the present invention contain a major amount of
the fluorine-containing hydrocarbon. More generally, the liquid
compositions will comprise greater than about 50% up to about 99% by
weight of the fluorine-containing hydrocarbon. In another embodiment, the
liquid compositions contain from about 70% to about 99% by weight of the
fluorine-containing hydrocarbon.
B. Phosphorus-Containing Compositions
In addition to the fluorine-contraining hydrocarbon, the compositions of
the present invention comprises
(B) a minor amount of a phosphorus-containing composition comprising at
least one compound characterized by the following formula
##STR4##
wherein R.sub.1 and R.sub.2 are each independently hydrocarbyl groups or
hydrocarbyloxyalkylene groups and R.sub.1 and R.sub.2 taken together have
2 to about 24 carbon atoms excluding any oxyalkylene carbon atoms;
a is 0 or 1;
b is 1 or 2;
c is 1, 2 or 3;
d is 0, 1 or 2, provided that c+d=3;
if b is 1, Z is selected from the group consisting of --R.sub.5,
--XR.sub.5, --N(H)R.sub.5, --N(R.sub.5).sub.2, --C(X)R.sub.5, --CN,
--S(O)R.sub.5, --S(O).sub.2 R.sub.5, --S(O).sub.2 N(R.sub.3)(R.sub.4) and
##STR5##
if b is 2, Z is --N(R.sub.5)--, X is oxygen or sulfur;
Y is a hydrocarbylene group having 1 to about 20 carbon atoms;
R.sub.5 is a hydrocarbyl group having 1 to about 18 carbon atoms;
R.sub.3 and R.sub.4 are each independently hydrogen; or a hydrocarbyl group
having a total of 2 to about 24 carbon atoms; or R.sub.3 and R.sub.4 taken
together form a heterocyclic ring.
The phosphorus-containing compositions characterized by the above formulae
are preferably free of acetylenic and aromatic unsaturation. Compounds
which contain such unsaturation generally are insoluble in the
fluorine-containing hydrocarbons and in particular, in
1,1,1,2-tetrafluoroethane. The soluble lubricants of this invention also
are preferably free of olefinic unsaturation except that some olefinic
unsaturation may be present so long as the lubricant is soluble.
In formula (1), R.sub.1 and R.sub.2 are each independently hydrocarbyl
groups or hydrocarbyloxyalkylene groups where R.sub.1 and R.sub.2 taken
together have a total of 2 to about 24 carbon atoms excluding any
oxyalkylene carbon atoms.
For purposes of this invention the total number of aliphatic carbon atoms
of R.sub.1 and R.sub.2 must have from 2 to about 24 carbon atoms,
preferably from 2 to about 18, more preferably from 2 to about 16. The
total number of aliphatic carbon atoms is the total of all carbon atoms
present in the hydrocarbyl group or hydrocarbyloxyalkylene group minus the
number, if any, of carbon atoms in the oxyalkylene portion of the
hydrocarbyloxyalkylene group. Generally the total number of aliphatic
carbon atoms will be the total number of alkyl carbon atoms, i.e., the sum
of the carbon atoms of any alkyl group plus the carbon atoms of any
hydrocarbyl portion of the hydrocarbyloxyalkylene group.
Preferably, when R.sub.1 or R.sub.2 is a hydrocarbyl group, R.sub.1 and
R.sub.2 each independently have 1 to about 8 carbon atoms. Most
preferably, R.sub.1 and R.sub.2 are each independently an alkyl having 1
to about 8 carbon atoms, preferably having from 1 to about 6 carbon atoms.
In another embodiment, R.sub.1 and R.sub.2 are selected from the group
consisting of straight alkyl groups having from 1 to about 4 carbon atoms
and branched alkyl groups having from 1 to about 8 carbon atoms. R.sub.1
and R.sub.2 may both be straight alkyl groups or branched alkyl groups.
Also encompassed by the present invention is where R.sub.1 is a branched
alkyl group and R.sub.2 is a straight chain alkyl group. R.sub.1 and
R.sub.2 are selected from the group consisting of methyl, ethyl, propyl,
butyl, pentyl, hexyl, heptyl and octyl groups.
When R.sub.1 or R.sub.2 is a hydrocarbyloxyalkylene group, preferably
R.sub.1 and R.sub.2 are a hydrocarbyloxyalkylene group having from 1 to
about 20 oxyalkylene groups and from 1 to about 18 carbon atoms in the
hydrocarbyl group. Preferably R.sub.1 or R.sub.2 is an alkyloxyalkylene
group. In one embodiment, the hydrocarbyloxyalkylene group preferably has
one oxyalkylene group, more preferably an oxyethylene or an oxypropylene
group and from 1 to about 12 carbon atoms in the hydrocarbyl group, more
preferably 1 to about 6, more preferably 1 to about 4. Examples of R.sub.1
or R.sub.2 groups include methoxyethyl, methoxypropyl, ethoxyethyl,
ethoxypropyl, propoxyethyl, propoxypropyl, butoxyethyl and butoxypropyl.
In another embodiment, R.sub.1 or R.sub.2 is a hydrocarbyloxyalkylene which
is a hydrocarbyl terminated polyoxyalkylene. Preferably, R.sub.1 or
R.sub.2 is a hydrocarbyl terminated polyoxyalkylene group having from 2 to
about 30 oxyalkylene groups, more preferably about 2 to about 20, more
preferably about 3 to about 15, more preferably about 3 to about 10. The
alkylene portion of the group preferably has from 1 to about 8 carbon
atoms, more preferably about 2 to about 4, more preferably 2 or 3. The
alkylene portion is preferably ethylene, propylene or mixtures thereof.
The hydrocarbyl portion of the hydrocarbyl terminated polyoxyalkylene is
defined the same as when R.sub.1 or R.sub.2 is a hydrocarbyl group above.
When R.sub.1 or R.sub.2 is a hydrocarbyl terminated polyoxyalkylene group,
R.sub.1 or R.sub.2 may be derived from a hydrocarbyl terminated
polyoxyalkylene glycol. The hydrocarbyl terminated polyoxyalkylene glycols
are produced generally by treating an aliphatic alcohol with an excess of
an alkylene oxide such as ethylene oxide or propylene oxide. For example,
from about 6 to about 40 moles of ethylene oxide or propylene oxide may be
condensed with the aliphatic alcohol. Preferably, the hydrocarbyl
terminated polyoxyalkylene is an alkyl terminated polyoxyalkylene. A
variety of alkyl terminated polyoxyalkylenes are known in the art, and
many are available commercially.
The alkyl terminated polyoxyalkylene glycols useful in the present
invention are available commercially under such trade names as
"TRITON.RTM." from Rohm & Haas Company, "Carbowax.RTM." and
"TERGITOL.RTM." from Union Carbide, "ALFONIC.RTM." from Conoco Chemicals
Company, and "NEODOL.RTM." from Shell Chemical Company. The TRITON.RTM.
materials are identified generally as polyethoxylated alcohols or phenols.
The TERGITOLS.RTM. are identified as polyethylene glycol ethers of primary
or secondary alcohols; the ALFONIC.RTM. materials are identified as
ethoxylated linear alcohols which may be represented by the general
structural formula
CH.sub.3 (CH.sub.2).sub.d CH.sub.2 (OCH.sub.2 CH.sub.2).sub.e OH
wherein d varies between 4 and 16 and e is a number between about 3 and 11.
Specific examples of ALFONIC.RTM. ethoxylates characterized by the above
formula include ALFONIC.RTM. 1012-60 wherein d is about 8 to 10 and e is
an average of about 5 to 6; ALFONIC.RTM. 1214-70 wherein d is about 10-12
and e is an average of about 10 to about 11; ALFONIC.RTM. 1412-60 wherein
d is from 10-12 and e is an average of about 7; and ALFONIC.RTM. 1218-70
wherein d is about 10-16 and e is an average of about 10 to about 11.
The Carbowax.RTM. methoxy polyethylene glycols are linear ethoxylated
polymer of methanol. Examples of these materials include Carbowax.RTM.
methoxy polyethylene glycol 350, 550 and 750, wherein the numerical value
approximates molecular weight.
The NEODOL.RTM. ethoxylates are ethoxylated alcohols wherein the alcohols
are a mixture of alcohols containing from 12 to about 15 carbon atoms, and
the alcohols are partially branched chain primary alcohols. The
ethoxylates are obtained by reacting the alcohols with an excess of
ethylene oxide such as from about 3 to about 12 or more moles of ethylene
oxide per mole of alcohol. For example, NEODOL.RTM. ethoxylate 23-6.5 is a
partially branched chain alcoholate of 12 to 13 carbon atoms with an
average of about 6 to about 7 ethoxy units.
In formula (1) and formula (2), Y is a hydrocarbylene group having 1 to
about 20 carbon atoms, preferably 1 to about 12 carbon atoms. More
preferably, Y is an alkylene group. Most preferably, Y is selected from a
group consisting of methylene, ethylene, propylene and butylene.
In formula (1), a is 0 or 1. Preferably, a is 0 when Z is --R.sub.5. Also
preferably a is 1 when Z is selected from the group consisting of:
--XR.sub.5, --N(H)R.sub.5, --N(R.sub.5).sub.2, --N(R.sub.5)--,
--C(X)R.sub.5, --CN, --S(O)R.sub.5, --S(O).sub.2 R.sub.5, --S(O).sub.2
N(R.sub.3)(R.sub.4) and
##STR6##
When b=1, Z is --R.sub.5, --XR.sub.5, --N(R.sub.5).sub.2, --C(X)R.sub.5,
--CN, --S(O)R.sub.5, --S(O).sub.2 R.sub.5, --S(O).sub.2 N(R.sub.3)
(R.sub.4) or
##STR7##
When b=2, Z is --N(R.sub.5)--.
In a preferred embodiment, b=1 and Z is selected from the group consisting
of --R.sub.5 ; --S(O).sub.2 N(R.sub.4); --S(O).sub.2 R.sub.5 and
##STR8##
In a more preferred embodiment, b=1 and Z is selected from the group
consisting of --R.sub.5 and
##STR9##
In formula (1) and formula (2), R.sub.5 is a hydrocarbyl group having 1 to
about 18 carbon atoms, preferably, from 1 to about 14. More preferably,
R.sub.5 is an alkyl group. R.sub.5 may be selected from the group
consisting of methyl, ethyl, propyl, butyl, pentyl, octyl, dodecyl and
octadecyl. R.sub.5 is preferably dodecyl.
In another embodiment of the present invention R.sub.1, R.sub.2 and R.sub.5
taken together contain a total of 3 to about 26 aliphatic carbon atoms,
preferably, 3 to about 22, more preferably 3 to about 20, and more
preferably 3 to about 16. The total number of aliphatic carbon atoms is
calculated and discussed above.
In formula (2), R.sub.3 and R.sub.4 are each independently selected from
the group consisting of hydrogen; and a hydrocarbyl group having 1 to
about 24 carbon atoms. R.sub.3 and R.sub.4 taken together may form a
heterocyclic ring. Preferably R.sub.3 and R.sub.4 are alkyl groups having
from 1 to about 8 carbon atoms. In a preferred embodiment R.sub.3 and
R.sub.4 are selected from the group consisting of branched alkyl groups
having from 1 to about 8 carbon atoms and straight chain alkyl groups
having from 1 to about 4 carbon atoms. R.sub.3 and R.sub.4 are selected
from the group consisting of methyl, ethyl, propyl, and butyl.
R.sub.3 and R.sub.4 may join to form a heterocyclic ring with a nitrogen
atom. The heterocyclic ring may contain more than one heteroatom. For
instance, R.sub.3 and R.sub.4 may combine to form heterocyclic rings
selected from the group consisting of imidazoline, a oxazoline, a
pyridine, and a morpholine. Preferably, R.sub.3 and R.sub.4 join together
to form a morpholine. The morpholine may be substituted.
In formula (2), c is 1, 2 or 3. Also d is 0, 1 or 2. It is provided that
c+d must equal 3 to fulfill the valence requirements of the phosphorus
atom. Preferably c is 1 and d is 2.
In formula (2), X is oxygen or sulfur. Preferably, X is oxygen.
The materials described by formula (1) above may be prepared by the
reaction of a phosphite with an olefin or a vinyl or allyl containing
compound selected from the group consisting of an ether, a sulfone, a
ketone, a sulfoxide, a nitrile or an aldehyde.
Vinyl or allyl compounds useful in the present invention include but are
not limited to methyl vinyl ether, ethyl vinyl ether, methyl vinyl ketone,
ethyl vinyl ketone, acrylonitrile, vinyl sulfoxide, vinyl sulfone, allyl
butyl ether, allyl amine, allyl cyanide and allyl ethyl ether.
Olefin compounds useful in the above identified reaction include olefins
having from 2 to about 24 carbon atoms, preferably 6 to about 18 carbon
atoms, and most preferably about 8 to about 18 carbon atoms. These
olefinic compounds may be alkylene tetramers of ethylene, propylene and
butylene. For instance, an oligomeric olefin of propylene (tetrapropylene)
is useful in the present invention. Other useful olefins include octene,
dodecene, hexene and the like.
The phosphites may be reacted with the olefins or vinyl or allyl compounds
under free radical conditions. Any free radical initiator is useful
provided the initiator has a half life sufficient to cause addition of the
phosphite. The conditions and free radical initiators are known in the
art. Examples of free radical initiators useful in the present invention
include di-tertiary-butyl peroxide, benzoyl peroxide and other initiators.
The reaction is conducted at a temperature from about 75.degree. C. to
about 175.degree. C., with about 100.degree. C. to about 150.degree. C.
being preferred. The reaction usually is accomplished in about 0.5 to
about 12 hours, with about 4 to 6 hours being preferred. Reactions of
phosphites with alpha, beta unsaturated systems is disclosed in
Tetrahedron, 1966, Vol. 22, pages 2561-2573 and Methoden der Organische
Chemie, Vol. 12/1, pages 463-490, Houben-Weyl, those disclosures are
hereby incorporated by reference.
Compounds encompassed under formula (1), when Z is R.sub.5 and a is 0 may
also be prepared by the reaction of a phosphite with an alkyl halide. The
reaction occurs between about 50.degree. C. and about 200.degree. C., with
about 75.degree. C. to about 150.degree. C. being preferred. It is
preferred that the alkyl halide be a primary alkyl halide. The alkyl
groups useful in the above-identified reaction are selected from the group
consisting of ethyl, propyl, butyl, hexyl, octyl, and dodecyl. Dodecyl and
octyl are preferred. Preferred alkyl halides are chloroalkyl halides and
bromoalkyl halides.
Another method to make compounds encompassed by formula (1) is by the
reaction of a phosphite with an aldehyde or ketone and the vinyl or allyl
compound. The reaction occurs between about 75.degree. C. and about
200.degree. C. with about 75.degree. C. to about 150.degree. C. being
preferred. Although the reaction may occur without catalyst, it may be
beneficial to use a basic catalyst, such as sodium hydroxide. Useful
aldehydes include aldehydes having from 1 to about 12 carbon atoms,
preferably 1 to about 6 carbon atoms, or aldehyde synthons. Aldehyde
synthons are materials that although not being an aldehyde, react as an
aldehyde. A well known aldehyde synthon is paraformaldehyde, which is
preferred. Preferred aldehydes are paraformaldehyde, formaldehyde,
ethanal, and propanal, with paraformaldehyde and formaldehyde preferred.
Materials defined by formula (2) may be prepared by the reaction of a
phosphorus oxychloride with an amine. The reaction occurs between about
50.degree. C. and about 200.degree. C., with about 75.degree. C. to about
150.degree. C. preferred. The amines that are useful in the present
reaction are primary or secondary amines and contain 2 to about 24 carbon
atoms. Preferably, the amines contain 1 to about 18 carbon atoms,
preferably 14 or fewer carbon atoms. Examples of these amines include but
are not limited to propyl amine, butyl amine, hexyl amine, octyl amine and
dodecyl amine.
The following examples describe phosphorus-containing compositions useful
in the present invention.
EXAMPLE 1
In a suitable vessel, 723 parts (4.25 moles) of polypropylene tetramer with
725 parts (5.25 moles) of diethylhydrogen phosphite are mixed and then
heated to 130.degree. C. Then 50 grams of di-t-butylperoxide are added in
5 gram increments over 8 hours. The reaction is stripped at 100.degree. C.
and 30 millimeters of mercury. The residue (major portion) is the product.
EXAMPLE 2
In a suitable vessel, 388 parts (2 moles) of dibutylphosphite and 236 parts
(2 moles) of 3-sulfolene are mixed and then heated to 100.degree. C. One
part of sodium hydroxide and 60 parts (2 moles) of paraformaldehyde are
added to the mixture which is maintained at 100.degree. C. for 3 hours.
The reaction is vacuum stripped to 150.degree. C. and 30 millimeters of
mercury. The residue (major amount) is the product.
Liquid Compositions
The liquid compositions of the present invention comprise a major amount of
a fluorine-containing hydrocarbon and a minor amount of at least one
soluble phosphorus-containing composition of the types described above.
"Major amount" is meant to include an amount equal to or greater than 50%
by weight such as 50.5%, 70%, 99%, etc. The term "minor amount" includes
amounts less than 50% by weight such as 1%, 5%, 20%, 30% and up to 49.9%.
Generally, the fluorine-containing hydrocarbon makes the balance of the
liquid compositions, i.e., is present in the amount to provide 100% of the
liquid composition. For instance, if the phosphorus-containing composition
is present at 5% by weight, then the fluorine-containing hydrocarbon would
be present in an amount to provide 100% by weight of a liquid composition
or, in this case, 95% by weight. In one embodiment, the liquid
compositions of the present invention will comprise from about 70 to about
99% of the fluorine-containing hydrocarbon (A) and from about 0.1% to
about 30%, preferably from about 0.5% to about 25%, more preferably from
about 1% to about 22% by weight of the phosphorus-containing compositions
(B). In another embodiment, the phosphorus-containing compositions (B) may
be used as a lubricant or a component of a lubricant formulation. (B) is
present, as a lubricant, in an amount from about 9% to about 30%,
preferably about 9% to about 25%, more preferably about 10% to about 20%
by weight of the liquid compositions. Lubricants for stationary compressor
system should have a kinematic viscosity at 100.degree. C. of at least 3
centistokes (cSt), preferably about 3 cSt to about 2000 cSt, more
preferably from about 3 to about 20. For mobile air-conditioning systems,
the lubricant should have a viscosity greater than about 10 cSt,
preferably from about 10 to about 2000, more preferably from about 10 to
50.
In another embodiment, the phosphorus-containing compositions (B) are
present as additives in a lubricant formulation. When (B) is an additive,
it is present in an amount from about 0.1% to about 8%, preferably about
0.5% to about 6%, more preferably from 0.75% to about 5% by weight, i.e.,
fluorine-containing hydrocarbon plus lubricant. Preferably the lubricant
formulation contains a polyoxyalkene glycol (C-1) or a carboxylic ester
(C-2 or C-3) about 25% by weight of the liquid composition, more
preferrably from about 10 to about 20%.
(C) Polyoxyalkylene Glycol or Carboxylic Ester
The polyoxyalkylene glycol (C-1) or carboxylic ester (C-2 & C-3) is present
in an amount up to where the total amount of phosphorus-containing
composition plus the amount of polyoxyalkylene glycol or carboxylic ester
is in a "minor amount" up to about 49.9% by weight. Preferably the
polyoxyalkylene | | |
