Liquid compositions useful as release agents or cooling lubricants containing 1-chloro-2,2,2-trifluoroethyl difluoromethyl ether and an agent having a lubricant and/or release action and optionally further conventional additives for release agents or cooling lubricants, the use of such compositions as release agents or cooling lubricants, and a process for preparing such compositions.

BACKGROUND OF THE INVENTION 
The present invention relates to the use of 1-chloro-2,2,2-trifluoroethyl 
difluoromethyl ether as a constituent of liquid compositions which are 
useful as release agents and cooling lubricants; to the use of these 
compositions as release agents and/or cooling lubricants; and to a process 
for their preparation. 
In many industrial operations it is necessary to use auxiliaries by means 
of which the affinity between different materials, for example work piece 
and tool or molded article and mold, can be kept as low as possible. This 
is generally achieved, depending on the operation, by the use of release 
agents or cooling lubricants. Thus, release agents are needed in processes 
for preparing and processing plastics, foams, building materials, rubber 
articles, tires, metals, glasses, ceramic products and the like. Such 
process include production steps such as casting, molding, pressing and 
the like. As used herein, the term "release agents" refers to agents which 
form solid or liquid films which reduce the adhesion forces between two 
adjacent surfaces, that is to say which prevent adjacent surfaces from 
sticking together and thus are effective as release agents, peel agents or 
lubricants. Release agents may be solutions or dispersions of agents which 
exhibit a release action. 
The cutting, separating or abrasive machining of metals, that is to say 
metal machining operations such as, for example, drilling, cutting, 
punching, milling, turning and grinding, are usually carried out in the 
presence of cooling lubricants. In addition to cooling and lubricating, 
these lubricants also serve to prevent welding between work piece and 
tool. Excessively rapid wear of the tools is additionally prevented. 
According to K. Schardt, Kunststoffe, Vol. 72, P. 461-62 (1982) it is known 
to use silicones, metal soaps, waxes, fatty oils, synthetic polymers and 
inorganic substances as release agents. Solvents disclosed as useful in 
release agent compositions include liquid aliphatic hydrocarbons, 
halogenated hydrocarbons and water. 
German Published Patent Application No. DE 3,335,870 describes the 
preparation of special wax derivatives having a lubricant and/or release 
action which can be included together with solvents in release agents or 
cooling lubricants. Suitable solvents include the 
chlorofluorohydrocarbons: trichloromonofluoromethane, 
1,1,2-trichloro-1,2,2-trifluoroethane, 1,1,2,2-tetrachlorodifluoroethane, 
tetrachloromonofluoroethane and trichlorodifluoroethane. 
Despite much past effort at developing useful release agents and cooling 
lubricants, there remains a need for improved release agents and improved 
cooling lubricants. 
SUMMARY OF THE INVENTION 
It is the object of the present invention to provide improved compositions 
for use as release agents or cooling lubricants. 
Another object of the invention is to provide compositions for use as 
release agents or cooling lubricants with better environmental 
acceptability. 
It is also an object of the invention to provide a method of preventing a 
shaped article from adhering to a forming tool against which it is shaped. 
A further object of the invention is to provide a method of machining a 
metal article in which overheating of the metal article and excessive wear 
of a tool used to machine the article are prevented. 
It is also an object of the invention to provide a process for preparing 
improved release agent and lubricant compositions. 
These and other objects of the invention are achieved by providing liquid 
composition useful as a release agent or coolant lubricant comprising 
1-chloro-2,2,2-trifluoroethyl difluoromethyl ether and at least one agent 
having a lubricant or release action. 
In accordance with a further aspect of the invention, the objects are 
achieved by providing a method of a process for forming a shaped article 
comprising the steps of forming the article to a desired shape against a 
forming tool, and thereafter separating the formed article from the 
forming tool, wherein the forming tool is coated with an effective release 
promoting amount of a liquid composition comprising 
1-chloro-2,2,2-trifluoroethyl difluoromethyl ether and at least one agent 
having a release action. 
In accordance with yet another aspect of the invention, the objects are 
achieved by providing a process for forming a metal article comprising the 
step of machining a piece of metal with a tool, wherein an effective 
cooling and lubricating amount of a liquid composition comprising 
1-chloro-2,2,2-trifluoroethyl difluoromethyl ether and at least one agent 
having a lubricant action is introduced between said piece of metal and 
said tool. 
The objects of the invention are also achieved by providing a process 
comprising incorporating into 1-chloro-2,2,2-trifluoroethyl difluoromethyl 
ether an effective lubricating or release promoting amount of at least one 
agent having a lubricant or a release action.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS 
Liquid compositions which are suitable as release agents and cooling 
lubricants have now been found which contain 1-chloro-2,2,2-trifluoroethyl 
difluoromethyl ether and an agent having a lubricant and/or release action 
and optionally one or more conventional additives for release agents and 
cooling lubricants selected from the group consisting of 
evaporation-control agents, solubilizers, corrosion inhibitors and 
stabilizers. 
In one advantageous embodiment, the liquid compositions useful as release 
agents and cooling lubricants contain at least 15% by weight of 
1-chloro-2,2,2-trifluoroethyl difluoromethyl ether. For example, they may 
contain amounts in the range from 15 to 99.9% by weight. In addition, they 
contain from 0.1 to 80% by weight, preferably 0.1 to 40% by weight, of at 
least one agent having a lubricant and/or release action, and optionally 
up to 80% by weight of solubilizers and/or evaporation-control agents. 
As the agent having a lubricant and/or release action the compositions 
according to the invention may contain one or more substances selected 
from the group consisting of waxes and wax derivatives and/or an agent 
having a release action selected from the group consisting of paraffins, 
silicones, metal soaps, fats, oils, polymers and inorganic powders. As 
used herein, the term "waxes and wax derivatives" is intended to include 
both naturally occurring waxes of animal or vegetable origin and also 
synthetic waxes and wax derivatives. Among the naturally occurring waxes, 
it is preferred to use those which have a softening point of at least 
40.degree. C. 
In one preferred embodiment of the invention, the compositions according to 
the invention contain waxes and/or wax derivatives selected from the group 
consisting of the esters of long-chain carboxylic acids and monoalcohols 
having a total of 34 to 50 carbon atoms and derivatives thereof obtained 
by sulfochlorination or sulfidization, by hydrogenation, or by treatment 
with hydrogen fluoride. Esters which have an iodine value of less than 95 
are preferred. Esters having an iodine value in the range from 75 to 95 
are particularly preferred. Mixtures of such fatty acid esters have 
already been described in the literature and are commercially available. 
For example, wax derivatives which have been obtained by sulfochlorination, 
sulfidization hydrogenation or hydrogen fluoride treatment of unsaturated 
long-chain esters of carboxylic acids with monoalcohols having a total of 
34 to 50 carbon atoms are suitable. The sulfochlorinated and sulfidized 
esters are available as commercial products. 
It is also possible to use the wax derivatives which have been obtained in 
the form of partially saturated or completely saturated derivatives by 
hydrogenation of unsaturated long-chain esters of carboxylic acids with 
monoalcohols having a total of 34 to 50 carbon atoms. As used herein, the 
term "partially saturated derivatives" refers to derivatives which have an 
iodine value less than that of the educt used for the hydrogenation. For 
example, esters which have iodine values of less than about 40 can be used 
as partially saturated to saturated derivatives. Both the partially 
saturated and the saturated esters are commercially available. 
It is also possible to use wax derivatives which have been obtained by 
hydrogen fluoride treatment of unsaturated long-chain esters of carboxylic 
acids with monoalcohols having a total of 34 to 50 carbon atoms. The 
derivatives obtained by hydrogen fluoride treatment include, for example, 
the fluorine-containing, waxy compositions disclosed in Published German 
Patent Application No. DE 3,335,870, the fluorine contents of which are 
variable over a wide range. For example, the fluorine content of these 
adducts of hydrogen fluoride with unsaturated long-chain esters may range 
from 0.1 to 4.3% by weight. 
A completely different type of derivative obtainable by hydrogen fluoride 
treatment of these long-chain unsaturated esters, are oily products 
(referred to hereinafter as sesquimers) which have a molecular weight 1.1 
to 1.9 times that of the starting wax and which also have an unreacted wax 
content of less than 1% by weight. These wax derivatives contain very 
little, if any, bonded fluorine. As a rule, the fluorine content is less 
than 0.1% by weight, and the iodine value is in the range from 5 to 20. 
Other waxes which can be used for the purposes of the present invention 
include paraffin waxes or synthetic polymers such as, for example, 
optionally oxidized polyethylene waxes. Thus, for example, an oxidized 
polyethylene wax which has an average molecular weight of 3,700 to 4,500 
(determined by viscometry) is suitable. 
The compositions according to the invention may also contain silicones as 
release agents. Silicones in the form of oils, fats or resins may be used, 
either as such, or in the form of silicone emulsions or silicone pastes 
which contain a consistency-control agent such as highly disperse silica 
incorporated in the silicone oil. Silicone fats usually contain metal 
soaps as consistency-control agents. The silicone products used in the 
present invention are commercially available products. The silicone oil 
used can be, for example, a silicone oil which has a broad viscosity range 
in the range from 100 to 60,000 mm.sup.2 /s, in particular a viscosity in 
the range from 10,000 to 30,000 mm.sup.2 /s, and especially a viscosity in 
the range from 15,000 to 25,000 mm.sup.2 /s. 
Other suitable agents having a release action include metal soaps, for 
example fatty acid salts of the metals magnesium, calcium, zinc, aluminium 
or lead. For example, metal salts of stearic acid may be used. In such a 
case, it is preferred to use magnesium stearate. 
As further agents having a release action the compositions according to the 
invention can also contain inorganic powders, preferably graphite, talc or 
mica. 
Other conventional agents which have release properties, such as oils, for 
example mineral oils and ester oils, also may be used in the compositions 
according to the invention. Further suitable agents having a release 
action include polymers, for example polymer alcohols, such as, for 
example, polyethylene glycol, polyamides, polyolefins or 
polytetrafluoroethylene waxes. 
In a preferred embodiment of the invention, the compositions according to 
the invention contain conventional solubilizers and/or evaporation-control 
agents for release agents or cooling lubricants. Suitable solubilizers or 
evaporation control agents may be selected from the group consisting of 
liquid aliphatic hydrocarbons which have boiling points of up to 
200.degree. C. lower alcohols having 1 to 5 carbon atoms, lower ketones 
and lower carboxylic acid esters. The solubilizers generally serve to 
improve the dissolution of the agents having a release and/or lubricant 
action used in the compositions, in particular to improve the dissolution 
of the saturated, partially saturated and/or sulfochlorinated or 
sulfidized derivatives, and/or derivatives obtained by hydrogen fluoride 
treatment, of esters of long-chain carboxylic acids and monoalcohols 
having a total of 34 to 50 carbon atoms. The purpose of 
evaporation-control agents is generally to prevent the compositions 
evaporating too rapidly during use, for example as cooling lubricants. 
The solubilizers and/or evaporation-control agents preferably used in the 
liquid compositions according to the invention, which are suitable as 
release agents and cooling lubricants, are liquid aliphatic hydrocarbons 
which have boiling points of up to 200.degree. C., lower aliphatic 
alcohols or lower carboxylic acid esters which are able to form an 
azeotrope or azeotrope-like mixtures with 1-chloro-2,2,2-trifluoroethyl 
difluoromethyl ether. Examples of suitable solubilizers and/or 
evaporation-control agents include lower alcohols, for example methanol, 
ethanol, n-propanol and isopropanol; lower carboxylic acid esters, such 
as, for example, methyl acetate; liquid aliphatic hydrocarbons, for 
example petroleum fractions which have boiling points of up to 200.degree. 
C., e.g. heptane or petroleum fractions which have a boiling range of 
100.degree. to 140.degree. C. Of course, other known solubilizers and/or 
evaporation-control agents can also be used. 
Advantageously, the compositions according to the invention contain the 
solubilizers and/or evaporation-control agents in an amount of 1 to 80% by 
weight, preferably 1 to 40% by weight. 
In further embodiments of the compositions according to the invention, it 
can be advantageous to add known stabilizers and/or corrosion inhibitors 
in an amount of up to 1% by weight. The compositions according to the 
invention which are suitable as release agents and cooling lubricants can 
therefore contain commercially available corrosion inhibitors for metals, 
such as, for example, magnesium, aluminium, titanium, brass, bronze or 
steel. Corrosion inhibitors of this type are usually compositions which 
contain organic compounds containing hetero atoms such as sulfur or, in 
particular, nitrogen. For example, individual compounds or mixtures of 
benzothiazoles, for example mercaptobenzothiazole; benzimidazoles, for 
example 2-phenylbenzimidazole; triazoles, for example benzotriazoles and 
tolyltriazoles; oxazolines, for example alkyl- and/or 
hydroxyalkyl-substituted oxazolines; amides and amines, for example 
tertiary amines, have proved suitable. Corrosion inhibitors based on 
oxazoline have proved particularly advantageous. 
In addition, conventional stabilizers or consistency-controlling additives 
can optionally be added to the compositions according to the invention. 
The concentrations of the agents having a lubricant and/or release action 
in the compositions according to the invention may vary depending on the 
intended use. Thus, compositions useful as cooling lubricants may contain 
from 0.1 to 25% by weight, preferably 0.5 to 5% by weight of the 
above-mentioned waxes and/or wax derivatives as agents having a lubricant 
action. In one advantageous variant which is particularly suitable as a 
cooling lubricant, the above-mentioned solubilizers and/or 
evaporation-control agents are present in an amount of from 1 to 40% by 
weight, preferably 1 to 15% by weight. 
Compositions useful as release agents preferably contain from 0.1 to 35% by 
weight of an agent having a release action. Compositions useful as release 
agents also may contain conventional solubilizers in amounts of up to 80% 
by weight. Preferred release agent compositions comprise as solubilizers, 
from 10 to 80% by weight of petroleum fractions which boil within the 
range from 100.degree. to 140.degree. C. 
The compositions according to the invention may be either solutions or 
dispersions. As used herein, the term "dispersions" refers to both 
emulsions and suspensions. 
The invention also relates to a process for preparing compositions 
according to the invention, which process comprises incorporating one or 
more agents having a lubricant and/or release action and optionally 
further conventional release agent or cooling lubricant additives selected 
from the group consisting of evaporation-control agents, solubilizers, 
corrosion inhibitors and stabilizers, into 1-chloro-2,2,2-trifluoroethyl 
difluoromethyl ether. 
In addition the invention also includes the use of the compositions as 
cooling lubricants or as release agents, for example in the preparation of 
plastics or foams or in other fields of use. 
The cooling lubricant compositions according to the invention can be used 
in all known methods of machining metals. Thus, the compositions according 
to the invention can be applied in either liquid or aerosol form during 
metal machining, for example. In addition, the compositions according to 
the invention can be applied both externally, that is to say supplied to 
the tool from the outside, or internally, that is to say through suitable 
feeds provided in the tool itself. Internal application is used, for 
example, when carrying out deep drilling or in the case of internal 
grinding. The compositions according to the invention can also generally 
be used as cooling lubricants for abrasive treatment of hard surfaces. 
Use of the compositions according to the invention in processes for 
cutting, separating or abrasive machining of metals results in a 
distinctly lower energy consumption compared with the use of prior art 
cooling lubricants, especially in the case of cutting, separating or 
abrasive treatment of metals such as magnesium, aluminium, titanium, 
brass, bronze or steel. This result is particularly clearly evident when 
more compact metal parts are, for example, to be drilled, milled or cut. 
In addition, when the compositions according to the invention are used as 
cooling lubricants in metal machining processes, good removal of the 
slivers is ensured and built-up edges are prevented. The compositions 
according to the invention have very advantageous frictional wear values, 
which is an indication of their very good cooling and lubricant 
properties. 
The compositions according to the invention can also be used as release 
agents, for example in metal or plastic processing. The compositions 
according to the invention advantageously lower the adhesion between tool 
and work piece or mold and molding, which may be formed of metal or 
plastic material, for example of polyesters, silicone polymers or 
polyurethanes. The compositions according to the invention are 
particularly suitable as release agents in the production of shaped 
plastic articles, particularly foamed articles. By using compositions 
according to the invention as release agents, surface problems can be 
avoided between tool and work piece, for example in injection molding of 
plastics. The compositions according to the invention can be successfully 
used as release agents in foaming of polyurethane, with little or no 
impairment of foam formation. In this context, one advantage of the 
release agents according to the invention is that they can be highly 
energy-saving in use. As is known, in the production of foams the solvent 
must first be evaporated after coating the mold with the release agent. 
Much less heating of the mold is required to evaporate the solvent from 
the composition according to the invention than from conventional prior 
art compositions. The release agents according to the invention are also a 
valuable production aid facilitating mold release when molding plastics. 
Additional advantages of the compositions according to the invention 
become evident during long-term mold use, for example in that the molds 
need less frequent cleaning between operations. The release agents 
according to the invention can be used in conventional manner, for example 
in the form of liquids, pastes or sprayable release agents which can be 
applied, for example, using commercial spray equipment, aerosol cans or 
automatic spray systems. 
The compositions according to the invention containing 
1-chloro-2,2,2-trifluoroethyl difluoromethyl ether as a diluent or solvent 
have good adhesion-lowering properties, are highly chemically inert, and 
have a good spreading power and high yield. In addition, the high 
1-chloro-2,2,2-trifluoroethyl difluoromethyl ether content in the 
compositions according to the invention has the effect of substantially 
raising the flash point, so that in some cases the composition virtually 
no longer has a flash point. The compositions according to the invention 
are particularly simple to prepare due to the very good dispersing and 
emulsifying power of 1-chloro-2,2,2-trifluoroethyl difluoromethyl ether. 
The following examples are intended to illustrate the invention in further 
detail without restricting its scope. 
EXAMPLE 1 
A composition according to the invention was prepared by mixing together 5% 
by weight of HF-wax adduct, 21.0% by weight 1-chloro-2,2,2-trifluoroethyl 
difluoromethyl ether, and 74.0% by weight of a petroleum fraction having a 
boiling range of 100.degree. to 140.degree. C. As used herein, the term 
"HF-wax adduct" refers to a wax derivative obtained by hydrogen fluoride 
treatment of unsaturated long-chain esters of carboxylic acids with 
monoalcohols having a total of 34 to 50 carbon atoms, whereby hydrogen 
fluoride is added to the double bonds of the educt. The HF-wax adduct used 
in this example was prepared according to Example 1 of German Published 
Application No. DE 3,335,870. The composition according to the invention 
was obtained as a dispersion. 
EXAMPLES 2 TO 11 
Further examples of compositions according to the invention, which likewise 
possess outstanding release agent properties, were prepared analogously to 
Example 1 and are shown in the following table in which proportions of the 
components are listed in % by weight. 
__________________________________________________________________________ 
Composition Example No. 
Constituents 2 3 4 5 6 7 8 9 10 11 
__________________________________________________________________________ 
1-chloro-2,2,2-trifluoroethyl 
95.0 
95.0 
22.0 
19.0 
50.0 
20.0 
80.0 
20.0 
75.0 
20.0 
difluoromethyl ether 
Sesquimer* 5.0 
Wax Ester (iodine # 90-80) 
5.0 
Wax Ester (iodine # 40-20) 
4.0 
Wax Ester (iodine # 20-0) 
5.0 
Silicone Oil (20,000 mm.sup.2 /s) 
35.0 
Paraffin (m.p. 56-58.degree. C.) 
6.0 
Oxidized Polyethylene Wax 6.0 
4.0 
10.0 
(m.p. 89-99.degree. C.) 
Polyethylene Wax 7.0 
(m.p. 89-108.degree. C.) 
Magnesium Stearate 1.0 
Petroleum Fraction 74.0 
76.0 
15.0 
74.0 
14.0 
76.0 
14.0 
73.0 
(b.p. 100-140.degree. C.) 
Nature of Composition** 
D D S D S D D D D D 
__________________________________________________________________________ 
*Material from Example 2 of DE 3,335,870 
**S = Clear Solution; D = Dispersion 
EXAMPLES 12 TO 26 
The further examples 12 to 26 of compositions according to the invention 
which possess good lubricant properties and are suitable as cooling 
lubricants for cutting, separating and abrasive metal machining and are 
shown in the following table, were prepared analogously to Example 1. The 
components are given in % by weight. 
__________________________________________________________________________ 
Composition Example No. 
Constituents 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 
__________________________________________________________________________ 
1-Chloro-2,2,2-trifluoroethyl 
95.0 
95.9 
93.2 
92.8 
64.2 
97.0 
95.9 
94.7 
94.3 
63.7 
94.2 
94.5 
92.6 
63.0 
93.5 
difluoromethyl ether 
Sesquimer (iodine # 14) 3.0 
1.5 
1.5 
1.5 
1.0 3.0 
1.5 
Wax Ester (iodine # 90-80) 
5.0 
1.5 3.0 
3.0 
0.5 3.0 
1.5 1.5 
Isopropanol 2.6 2.6 2.6 
Ethanol 3.8 3.8 3.8 
Methanol 4.2 4.2 4.2 
Methyl Acetate 35.3 35.3 35.3 
n-Heptane 5.0 
Corrosion Inhibitor 0.2 
0.2 
0.2 
0.2 
composed of Oxazoline 
Nature of Composition 
D S S S S D D D D D S S D D S 
__________________________________________________________________________ 
*Material from Example 2 of DE 3,335,870 
**S = Clear Solution; D = Dispersion 
EXAMPLE 27 
In order to assess the release agent properties of compositions according 
to the invention, the inside surfaces of a mold used for producing foamed 
plastics were smeared with a thin layer of a composition according to the 
invention. The mold consisted of a polyethylene base plate, steel side 
walls and an aluminium cover plate. A conventional reaction mixture for 
producing polyurethane foams was poured into this mold, which had been 
treated with a composition according to the invention, and polymerized in 
a known manner to produce a polyurethane foam. The effectiveness of the 
composition according to the invention as a release agent was then 
assessed by how completely and how easily the resulting polyurethane foam 
could be released from the mold after the polymerization. 
The following criteria were used as a basis for the assessment: 
a) poor release action: foam adheres to inside surface of mold; 
b) good release action: foam easily separated from inside surfaces of mold; 
c) excellent release action: no detectable adhesion between inside surfaces 
of mold and foam. 
Seven polyurethane foam articles were produced in succession in a mold 
initially treated with the composition according to the invention, but 
without any intervening treatment of the mold with the composition of the 
invention between the successive molding operations. The following table 
shows the assessment of a composition according to the invention with 
respect to its suitability as a release agent. The composition of Example 
No. 8 was used in the tests. 
______________________________________ 
Number of Foam 
Molding Operations 
Release Agent Effect 
______________________________________ 
1 Excellent 
2 Excellent 
3 Excellent 
4 Excellent 
5 Excellent 
6 Good 
7 Poor 
______________________________________ 
The above results show that the composition according to the invention 
which was used in the test has an excellent release action for five 
successive foaming operations. This corresponds to approximately 70% of 
all tests carried out with this composition. A good or excellent release 
action was obtained for approximately 85% of all tests carried out with 
this composition. 
Similarly excellent results were achieved using the release agent 
composition of Example 1 according to the invention and the release agent 
compositions defined by Examples 2 through 7 and 9 through 11. 
The foregoing description and examples have been set forth merely to 
illustrate the invention and are not intended to be limiting. Since 
modifications of the described embodiments incorporating the spirit and 
substance of the invention may occur to persons skilled in the art, the 
invention should be construed broadly to include all variations falling 
within the scope of the appended claims and equivalents thereof.