Note: Descriptions are shown in the official language in which they were submitted.
The invention relates to copolymers of (I
unsaturated dicarboxylic acid esters and ~-olefins and
to the production and use thereof.
Federal Republic of Germany Offenlegungsschrift
(Published Patent Specification) 27 27 239 discloses olefin-
malefic acid copolymer derivatives which are built up from
olefins having an average of 2 - 24 carbon atoms and malefic
acid, and which are esterified with monovalent alcohols
having a chain length of 2 - 20 carbon atoms in a molar
ratio of 1 : 0.5 to 1 : 2 of malefic acid to alcohol The
olefin-maleic acid copolymer derivatives are produced by
copolymerizing malefic acid or malefic acid android with
(-olefins, followed by esterification to the half-ester
or to the divester. The olefin-maleic acid copolymer
derivatives described therein are particularly suitable
as lubricants for forming synthetic materials These
products are semi-solid to solid at room temperature. The
pour point is well above 0C.
In addition to this, high molecular copolymers of
oC-olefins and TV unsaturated dicarboxylic acid esters
have become known, for example as hair sprays (Austrian
Patent 254 327) and as agents for coating medications
(Austrian Patent 263 011). These are produced by Capella-
meriting ~-olefins and unstriated dicarboxylic acids
and acid androids, followed by esterification of the
copolymers, and are solid or wax-like at room temperature.
Federal Republic of Germany OffenlegungsschriEt
17 70 860 discloses a copolymer made of a C22-C28-1-
olefin and dibehenyl Malta obtained by polymerizing at
150C and described as a wax-like product. I-t was proposed
I
to add hydrocarbons to the product in order to lower the
solidification point and to increase fluidity as a whole.
It is stated in Federal Republic of Germany
Offenlegungsschrift 17 70 860 -that improvement in fluidity
can be obtained only with ester polymers in which the number
of carbon atoms in the alkyd portion is greeter
than 20.
Austrian Patent 479 746 describes fluidity
improvers or modifiers for wax-like hydrocarbon oils which reduce the
pour point thereof. Here again , long side chains for the
alcohol components of the dicarboxylic acid esters are
described as absolutely necessary. The consistency of the
products at room temperature is wax-like to solid. In this
case, therefore, the pour point is dental above 0C.
Japanese Printed Publication 55-157 687 describes
a copolymer consisting of an ~-olefin and a dialkylester of an
unstriated dicarboxylic acid as an additive for lubricants.
The unstriated dicarboxylic acids are, in
practice, malefic acids or fumaric acid. Mixtures thereof are
not described.
The alcohol component should comprise 1 to 18,
preferably 1 - 8 carbon atoms; it is highly preferable to use
methanol. The alcohols may be branched or unbranched. There
is no mention of a mixture.
The ~-olefins contain 4 to 60 carbon atoms, and the
copolymers made of ~-olefins having 4 to 18 carbon atoms are
fluid at room temperature. In the case of mixtures of ~-olefins
having 6 to 10 carbon atoms, the pour point is between 38
and 40C. In the case of mixtures of ~-olefins having 16-18
carbon atoms, it is between 6 and 7C and -17 and -18C,
depending upon the alcohol. The copolymer of ~olefins
having 12 - 14 carbon atoms has a pour point between 12 and 13 C.
- 2 -
I
(see Table l -test 2).
The fluid copolymers have excellent oil properties,
both undiluted and dissolved in mineral oil, either as
lubricants, as machine oil, as turbine oil or as an oil for
metal shaping (cf. bottom of page 7). The oil properties
and the resistance to abrasion increase as -the number of carbon
atoms in the alcohol component decreases. For this reason,
total preference was given -to methanol (page 4, paragraph 2),
in which case, -the pour point increases. It indeed increases
from between -17 and -18C to between 6 and 7C upon changing
over from octanol to methanol.
Lubricating oils having a low pour point and the
lowest possible change in viscosity, even without additives,
have been sough-t for some considerable time
Lubricating oils which have a low pour point even
without additives, and which undergo the smallest possible
change in viscosity over a wide range of temperatures, have
long been sough-t.
These demands are largely me-t by the polymers
according to the invention and, as such, they are already
outstanding lubricating oils.
- pa -
.:
In one preferred embodiment of the invent
lion, the copolymers are built up in such a way that the
unstriated dicarboxylic acid ester is an unswept-
rated dicarboxylic acid divester. Suitable -unsaturated
dicarboxylic acid esters include: esters of malefic acid,
fumaric acid, citraconic acid, mesa conic acid or itaconic
acid. however, preference is given to the esters of malefic
acid and Iumaric acid.
Copolymers in which the ~-olefin is unbranched
have lower pour points than those in which the ~-olefins
are branched. Thus the copolymers preferred according to
the invention are those in which the ~-olefin component is
unbranched. The mole ratio of ~-olefin to unstriated
dicarboxylic ester is preferably Owe : I
It was totally unexpected that the method act
cording to the invention would make it possible to build
up the fluid copolymers of the invention from an ~-olefin
having 10 - 16 C-atoms and a unstriated dicarboxylic
acid ester, the alcohol component of which is a straight
chain or branched chain moo alcohol having 3 - 10 C-atoms,
the said copolymers being fluid and improving the flow and
viscosity properties of mineral oils and lubricants to a
substantially greater extent than known high molecular
weight polymers made of very long chained ~-olefins and
unstriated dicarboxylic acid esters with long chained
alcohol components. The method according to the invention
is characterized in that an ~-olefin having 10 - 16 C-atoms
and a unstriated dicarboxylic-acid ester, the alcohol
component of which is a straight chain or branched chain
monoalcohol having 3 - 10 C-atorns, are copolymerized at a
-- 3 --
temperature from 140 to 210C, in the presence of a
peroxide catalyst, in an inert gas atmosphere.
It is particularly preferred to use us-
saturated dicarboxylic acid divesters, more particularly
malefic acid divesters or fumaric acid divesters.
The copolymers acquire particularly satisfactory
flow and viscosity properties if between 0.005 and 0.05
mole/mole of monomer is added to the peroxide catalyst.
The peroxide catalyst is preferably added in batches at
intervals. According to a preferred embodiment of the
invention, the addition of the catalyst is effected by
initially adding one third of the total amount thereof,
the remainder being added in - 12 batches Preferred
unstriated dicarboxylic esters are unstriated
dicarboxylic acid ductile esters and unstriated dip
carboxylic acid dihexyl-esters. The reaction temperature
is preferably between 160 and 200~C.
In order to achieve a molar ratio of ~-olefin to
unstriated dicarboxylic acid ester ox 0.5 : 4, the
monomers are used in a molar ratio of 0.5 : 7.
The copolymers according to the invention are
not used as lubricating oils merely because of their
viscosity characteristics, the ability to emulsify, and
their low pour point. They may also be used as additives
to adjust the viscosity characteristics and reduce the pour
point of mineral oils and lubricants. The cross-linked
polymers are particularly suitable as additives. The
cross-linking agents used may be all known bifunctional
cross-linking agents, for example divinylbenzene and bus-
acrylate, but preference is given to bis-maleates o-f dip
alcohols, bis-maleicimides, Delilah ethers, Delilah esters
- 4 -
Lo 8
and divinely esters. Mixtures of cross-linking agents may
also be used. Suitably between 0.05 and 0.2 mole/mole of
unstriated dicarboxylic acid ester is added to the
polymerization batch.
Cross-linked copolymers according to the invention
may be used directly as gear oils or to improve the viscosity
characteristics of lubricants.
Cross-linked copolymers according to the invention
fully meet the high demands made upon transformer oils, such
as resistance to aging, stability, low pour point, no
measurable release of gas, high dielectric strength, and
low dielectric loss factor. Furthermore, the low toxicity,
as compared with the chlorinated biphenyls normally used
as transformer oils and mixed with trichlorobenzolene in
order to reduce the viscosity, is a substantial advantage
of the copolymers of the invention when used as transformer
oils. They may, of course, be used quite generally as in-
sulfating oils, copolymers with very low pour points and
low viscosity being outstandingly suitable as switch oils.
As regards conventional measuring methods, reference is
made to Ullmanns Encyclopedic don technician Chemise,
Thea Edition, Volume 20, pages 607 et seq.
Another main use for the copolymers of the invent
lion is as lubricants for forming thermoplastic synthetic
materials.
The fluid condition at room temperature permits
very satisfactory mixing with other aids to processing.
More particularly, it is possible to procure, with the
copolymers according to the invention, stabilize lubricant
mixtures for PVC processing, for which other lubricants
cannot easily be used
I
The copolymers of the invention are emulsifiable
and provide stable emulsions. They may therefore be used,
in admixture with waxes and with the copolymers of Federal
Republic of Germany Offenlegungsschrift 27 27 239, in wax
polishing preparations for example for shoe polishes, floor
polishes, lubricants for metal processing, etc. In the
form of aqueous emulsion they may also be used as coolants
for machining and forming metal parts.
The invention is illustrated in greater detail
and by reference to particular and preferred embodiments
in the following examples.
Example 1.
1 Mole of malefic acid android, 3 moles of Allot*
C8 and 0.4 g of p-toluene-sulphonic acid are heated to the
boiling point ox the mixture and the reaction water (about
1 mole) is drawn off. After about 4.5 hours, the acid
number was still 0.44. The reaction mixture was cooled -to
100C, 1 ml of triethylamine was added, and stirring was
carried out at this temperature for about 30 min. The
excess Allot* and amine were distilled off by applying a
vacuum, 1 Mole of C12 ~-olefin was added to the reaction
product obtained. The mixture was heated to 160C and
10 batches of 0.005 moles of Detroit, bottle peroxide were
added at intervals of about 30 minutes. 30 Minutes after
the addition of the last batch of peroxide, vacuum is a
plied and the unpolymerized olefin is distilled off. The
last of the olefin was removed in a thin layer evaporator.
The olefin: ester ratio in the copolymer was
determined from the oxygen content of the elemental analysis.
The viscosity was measured with an bullied
*trade mark
-- 6 --
I
viscosimeter.
The molecular weight was determined with the aid
of gel permeation chromatography.
DIP pry En 6 was used to determine the pour point.
Method B of IS standard 29 09 was used to determine
the viscosity index
The monomer ratio is to be understood to mean the
molar ratio of the ~-olefin used to the unsaturated
dicarboxylic acid ester used.
The polymer ratio indicates the ratio of ~-olefin
to unsaturated dicarboxylic acid ester in the copolymer.
The copolymer obtained in this example had a pour
point of -39~, a molecular weight of 2500, and a viscosity
index of 168.
Exam
6 Moles of Colophon and 2 moles of dibutyl
Malta were placed in a reaction vessel previously flushed
with nitrogen, and were held under a nitrogen atmosphere.
The mixture was heated to 200C. The catalyst used was t
bottle hydroperoxide, 0.03 of a mole being added initially,
followed by 10 batches of 0.004 mole each. Upon completion
of the polymerization, excess olefin and dibu-tyl Malta
were distilled off in a vacuum at 0.01 mm Ho.
The results obtained with other olefins, and with
a molar ratio of olefin: dibutyl Malta of 1 : 1, are given
in the following Table.
I 3 3
I,
o
.,, o
O I I
Q l l l l l l I
I
X
Us
O I: I
U H ~11~d' LO Jo I
0 ~Ir-l.--1 I Irk I I
Jo
Jo
O O O O O O O O
U --l OWE O Owl )
a) n ED
One O I
I I I 0 0 0 0
o P:
Pi
m
En
o 1_1
o .. .. .. .. .. .. .. ..
J
.,1
O O ED
o
Us W
En I r l
-- 8 --
I
Example 3.
As in Example 1, malefic acid divesters were
polymerized with Colophon and Colophon in 2 molar
ratio of 1 1 and 1 : 3, under otherwise similar conditions.
The L exults appear in Table 2. By way of comparison, dim ethyl
Malta was also copolymerized with Colophon in a ratio
of 1 . 1 and 1 : 3 under -the same conditions. The results
show that this produces polymers with a pour point distinct-
lye above 0C. With a 1 : 1 ratio of Colophon, the pour
point is -4C, but the viscosity index is 69.
I
O I 0 Us 1 Lo O I Al O 1
Q, C_) I fry I I if) N I if) if) f`J I
O I
I
Al X
rq I fly I I` O if) it)
O fly If) d' N Us if) d' d' d' I if) fry O
I H
ray
OWE
O to O n O us O O O us rho fly foe O O O
fly Al O (I I O d' 1` I fox of) foe I
3 I I l I l I
a) o
rut Irk O f') ED Lo f') 0 0 co I 0 I in d'
I I) I l I O cry ID if) It fox 1
I I
O I r-l ~10 0 0 0 Jo 1 0 0 0 0 0 0
I o
O' if) I if) Jo l if) if) I
I
it I
fq
En r-l
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H O
O
to r-l
So
a do I foe do ED 0 0 Jo fly r-l r r-
I
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I Jo
0 I
I Al
O fly
I) r-l
I O O O O O O O O
O Jo r l I r-l r I r-l r-l r-l Al r--1 r-¦ r-¦ r-¦ I r-l I
O H
H X
rq fly I I I fly to fly fly fly I I fly N fly
En
-- 10 -
Example 4.
sing the procedure indicated in Example 1, octal
fumarates and octal Maltese, furthermore Huxley fumarates
and Huxley Maltese, were copolymerized with C10- and C12-
~-olefins. The results are given in Table 3.
- 11 -
~V~3~ to
O r; Lo I ) I I) 0
JO of) Al or) I Al d' I '`'
o
rl X
us a) I I errs r.
O i` d' ED I I) Lo Lo
m
.
I
I
o o o o o o o o
I) L') O Lo O O Lrl O O
~l)-rl Al I I O O ED I Lo')
I C) or r,~lr,~l I 1 r.
O I:
rod O I I I rho - O
00 I Dry) no
I rod O O O O
O
rye
O O
E rl
o Jo Jo Jo
I: pa
o
m
En
rod rod ED rod
rod
pa
I Jo a rod rrJ a) rod
E E ,1
I- Jo J
n
I
O U C)
O O O O O O O O
.,1
H to
r:q O
E I o o N I O O (I
O Jo I I , I I I ,-1 I I
to
O
m o
r:q I rye I I I I
to
- 12 -
~C~3~
Example 5.
36 Moles of Cluck -olefin were mixed with
2-ethylhexyl Malta it a reactor, flushed with nitrogen
and heated at 200~C. At 30 minute intervals, 11 batches,
each containing 0.08 mole of di-t-butyl peroxide, were
added. 30 Minutes after the last addition of peroxide,
the volatile products were distilled off with increasing
vacuum. Additional copolymers were produced by this
method, as shown in Table 4.
T A B L E 4
Monomer Polymer Molecular Pour
Test Jo Ester Ratio Reshoot Point C
-
4A2-Ethylhexyl 1 0.6 1500 -39
Malta
4Bdito 3 1.4 1450 -30
4CDibutylmaleate 1 0.78 1600 -29
4D2-Ethylhexyl- 1 0.7 1700 -29
fumarate
YE Dibutylfumarate 1 0.7 1700 -23
Example 6.
3 Moles of malefic acid android, 0.6 mole of
hexane Doyle and 480 ml. of Tulane are boiled for half
an hour under reflex. 9 Moles of buttonhole and 1.2 g. of
Tulane sulphonic acid are then added and the reaction
water is removed from the circuit. After water has ceased
to separate, 3 ml of triethylamine are added for neutral-
ration stirring is carried out for half an hour, and all
I
volatile elements are distilled off in a water jet vacuum
to a sup temperature of 160C. 3 Moles of Colophon
are then added, the reaction vessel is flushed with nitrogen,
is heated to 160C and 0.016 mole of dl-t-butyl peroxide,
10 batches in all, are added every 30 minutes. 30 Minutes
after the last addition, all volatile elements are distilled
off in the water jet vacuum. The resulting cross-linked
polymer has the following properties:
VI (Viscosity Index) = 179
Pour point = -12C
Example 7.
2 Moles of dibutyl fumarate, 2 moles of C14-C16
-~-olefin (average MY of the mixture = 205) and 0.2 mole
of divinylbenzene (50% in ethylvinylbenzene~are heated to
160C under nitrogen. 0.01 Mole of di-t-butyl peroxide is
added every 30 minutes, 10 batches in all. 30 Minutes after
the last addition, all volatile substances are distilled
off in the water jet vacuum. The remaining cross linked
polymer has the following properties:
VI = 211
Pour point = -2C
Example 8.
The suitability of the copolymers as lubricants
was also demonstrated in a continuous rolling test. To
this end, mixtures consisting of 100 parts by weight of
a PVC suspension, 1 part by weight of ductile tin Boyce-
ethylhexyl thioglycolate, 0.5 and 1 part by weight of the
copolymer and of a commercial lubricant, were produced.
The test was carried out under the following conditions:
Roll temperature 1~30C
rum 20
Every 10 minutes samples were taken and the test
was interrupted when the sample stuck to the roll or a
brown discoloration was observed. The results appear in
Table 5.
T A B L E 5
Furnace Test Transparency Time to Stick
Sample At 180C (min.) And Discolor
4C 130 8280 (did not adhere)
ED 130 75.6100 (did not adhere)
YE 130 79.290 (did not adhere)
I 110 65.090 (did not adhere)
A sample produced according to the above mentioned
formula was reduced to a sheet 0.4 mm in thickness by rolling
at 170C. The sample was placed in a furnace having rotating
compartments and held at 180C. Discoloration was monitored
every 10 minutes and compared with a corresponding sample of
commercial lubricant (ethyleneglycolester of montanic acid),
until the final discoloration was reached (furnace test).
A sheet 0.4 mm in thickness was produced as de-
scribed herein before, was cut, about 20 layers were placed
one on top of the other and were pressed to a thickness of
about 6 mm. Transparency was measured in a "Hunter lab D25"*
calorimeter.
Oven and transparency test values are also given
in Table 5.
Example 9.
The transparency of some of the copolymers was
measured with a commercial lubricant in use upon a plastic
*Trade Mark
- 15 -
cited suspension of PVC.
100 parts by weight of a suspension of PVC, 50
parts by weight of ductile phthalate, 1 part by weight of
dibutyl tin dimonomethyl Malta, and 1 part by weight of
a copolymer according -to the invention and of a commercial
lubricant, were mixed and made into sample sheets about
6 mm. in thickness, as described in Example 7.
The following values were obtained:
Test Piece Transparency %
PA 67.7
4B 54.4
I 41.5
Where the product was used as a lubricant for
forming synthetic materials, the following findings were
obtained from Examples 8 and 9:
In the furnace test, all of the tested copolymers
performed better than the commercial lubricants used by way
of comparison.
In the continuous rolling tests, the tested
copolymers performed as well as, or better than, the
commercial lubricants used by way o-f comparison.
As regards transparency, all of the tested polymers
are Ear better than the commercial lubricants used by way
of comparison.
.
- 16 -
