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Patent 1070664 Summary

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(12) Patent: (11) CA 1070664
(21) Application Number: 232727
(54) English Title: VISCOSITY INDEX ADDITIVES FOR LUBRICATING OILS
(54) French Title: ADDITIFS AMELIORANTS L'INDICE DE VISCOSITE D'HUILES DE GRAISSAGE
Status: Expired
Bibliographic Data
(52) Canadian Patent Classification (CPC):
  • 253/114
(51) International Patent Classification (IPC):
  • C10M 157/00 (2006.01)
(72) Inventors :
  • SMITH, MARVIN F. (JR.) (Not Available)
  • SZYKOWSKI, JOHN P. (Not Available)
(73) Owners :
  • EXXON RESEARCH AND ENGINEERING COMPANY (United States of America)
(71) Applicants :
(74) Agent: NA
(74) Associate agent: NA
(45) Issued: 1980-01-29
(22) Filed Date:
Availability of licence: N/A
(25) Language of filing: English

Patent Cooperation Treaty (PCT): No

(30) Application Priority Data: None

Abstracts

English Abstract


U.S. 506,360


ABSTRACT OF THE DISCLOSURE
A lowered viscosity at low temperatures is obtained in a
lubricant comprising a major proportion of a lubricating oil and a minor
proportion of at least two viscosity index improvement additives,
said additives comprising an ethylene copolymer type additive including
nitrogen derivatives thereof and an ester base polymer type additive
having oxygen, and optionally also having nitrogen functionality.
Lower viscosities at low temperatures have been obtained with the
synergistic mixture than when either type additive is used alone.



Claims

Note: Claims are shown in the official language in which they were submitted.


THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A lubricating oil composition which is fluid at -40°F,
comprising a major proportion of a mineral lubricating oil and a viscosity
index-improving amount in the range of 0.3 to 8 wt. % of a synergistic mix-
ture with regard to low temperature viscosity, of an oil-soluble ethylene
copolymer V.I. improver and an oil-soluble ester base copolymer V.I. improver;
wherein said ethylene copolymer has a weight average
molecular weight of about 10,000 to 800,000 an Mw/Mn ratio of less than about
10 and a degree of crystallinity of up to about 25 wt. %, said ethylene
copolymer comprising 30 to 80 mole % ethylene, 10 to 70 mole % propylene
and about 0 to 10 mole % of C4 to C28 olefin;
wherein said ester base copolymer has a number average
molecular weight of about 50,000 to 500,000 and is a polymer comprising
at least 80 wt. % of C8 to C20 alkyl ester of acrylic acid, methacrylic
acid or maleic acid;
wherein, the amount of said ethylene copolymer is in
the range of 0.1 to 2 wt. %; and
wherein, the amount of said ester base copolymer is
in the range of 0.2 to 6.0 wt. %, and furthermore is 1.0 to 9.0 times
the weight amount of said ethylene copolymer.
2. A lubricating composition according to claim 1,
wherein said ethylene copolymer consists of ethylene and propylene
moieties.
3. A lubricating composition according to claim 1,
wherein said ethylene copolymer is in the form of its oxidized and aminated
derivative having in the range of about 0.03 to 5 wt. % nitrogen, which
has been prepared by oxidizing a lubricating oil solution of a copolymer
ethylene and propylene at a temperature of 80°C to 300°C and for a time
sufficient to impart to said solution a combined oxygen content of 0.01
to 10.0 wt. % oxygen, based on the weight of said oil solution, and


then aminating said oxidized oil solution with a polyethylene amine of
the formula:

Image

wherein s is 2 and t is 2 to 6.
4. A composition according to claims 1 or 3 wherein
said ester base copolymer consists essentially of alkyl methacrylate
moieties.
5. A composition according to claims 1 or 3 wherein
said ester base copolymer is a polymer comprising alkyl ester of maleic
acid and styrene.
6. A composition according to claims 1 or 3 wherein
the amount of said ethylene copolymer is about 0.36 wt. % and said ester
base copolymer is a polyalkylmethacrylate present in the amount of
about 2.0 wt. %.
7. A composition according to claims 1 or 3 wherein
the amount of said ethylene copolymer is about 0.36 wt. %, and said
ester base copolymer is a polymer comprising alkyl ester of maleic acid
and styrene, said ester base copolymer being present in the amount of
about 1.8 wt. %.
8. The composition of claims 1 or 3 wherein said
ethylene copolymer comprises about 75 mole percent ethylene and about 25
mole percent propylene with a weight average molecular weight of about 80,000.
9. The composition according to claims 1 or 3 wherein
said lubricating oil is an automatic transmission fluid.

31

Description

Note: Descriptions are shown in the official language in which they were submitted.


~070664
1 This invention relates to polymers useful as vis-
2 cosity index improvers for lubricants. More particularly,
3 it is concerned with the complementary effect which is ob-
4 tained when an oil-soluble ester base polymeric additive
iæ used in combination with a second polymeric additive
6 which is essentially hydrocarbon or its aminated-oxidized
7 derivative. The complementary effect is exhibited by the
8 significantly lower viscosity at low temperatures possessed
9 by lubricants containing this combination over that shown
by either type of additive when used alone.
11 The use of polymers as viscosity index (indicated
l2 hereafter as V.I.) improvem~nt additives in lubricating
13 oils is old in the art. Polymers compri~ing C8~Cl8 alcohol
14 esters of acrylic or methacrylic acid and derivatives there-
of having a number average molecular weight in the range of
l6 50,000 to 500,000 are widely used for this purpose. More
17 recently, Ziegler-Natta copolymers of ethylene and higher
18 alpha olefins, particularly propylene, and terpolymers of
19 ethylene, a higher alpha olefin and a non~conjugated di~
olefin, in a molecular weight range of lO,000 to 200,000 have
21 become known as V I. improvers.
22 In general, these ethylene copolymers prepared by
23 Ziegler-Natta type synthesis are less expensive because of
24 low raw material cost, and are frequently more effective on
a cost-potèncy basis than the aforesaid acrylate ester type
26 of V.I. improver.
27 When free of diluents, the ethylene copolymers have
28 a consistency ranging from heavy viscous syrups in the low-
29 er molecular weight ranges to elastomeric solids in the
higher molecular weight ranges and are accordingly usually
31 marketed as oil concentrates. Since the polyolefins are
32 essentially hydrocarbon in structure they are compatible

~070664
1 with para~finic or naphthenic oils at concentrations normally
2 used in multiple grade oils and do not separate from solu~
3 tion at low temperatures.
4 Also proposed as VoI~ improvers are nitrogen~con-
s taining derivatives of the~e copolymers obtain~ed by the oxi-
6 dation of these ethylene copolymers which oxidized deriva~
7 tives are thereafter reacted with amines to produce nitro-
8 gen-containing derivatives.
9 Polyalkylacrylates vary in their solubility in
hydrocarbons and the pour point which they impart to an oil
11 depends on the carbon chain length of the alkyl radicalD
l2 In the C8 to C12 range where the solidification temperature
13 of the polymers is low, the usual high oxygen content of
14 from 12.5 to 16.2 wt. % limits the solubility of the polymer
in hydrocarbons due to its high polarity, and it is best
l6 used in synthetic ester lubricantsO In the C~4 to~C20
17 range, the solidification temperature rises rapidly and at
8 the upper carbon number range which has the maximum solu
19 bility in petroleum lubricants, the products resemble paraf~
fin wax.
21 ~espite considerable studies on the s~bject, no
22 accurate method is available for predicting the VoI~ change
23 or the compatibility of polymers having diverse structures
24 when mixed in a common solvent such as mineral lubricating
oil.
26 There is considerable prior art on both the ethyl~
27 ene copolymer type of VoIo improver and the ester base
28 polymer type of V I.improver. Many of the recent patents
29 on the ethylene copolymer VoI~ improver made by copolymer-
izing ethylene with higher olefins, usually propylene, have
31 generalized disclosures that the polymer can be used in
32 conjunction with other additives, including in some cases
~ 3 ~

~070664
1 other V.I improvers, for example, see U~S Patents
2 3,509,056; 3,389,087; 3,326,804; 3,513,095, 3,598,738S and
3 3,790,480.
4 More pertinent i8 U.S. Patent 3,691,078 which
teaches an ethylene copolymer as a V.I improver in lubri-
6 cating oil, e.g. crankcase oils and automatic transmission
7 fluids (ArF) together with Ool to 10 wt. % of certain pour
8 point depressants, such as the reaction product of chlor~
9 inated wax and naphthalene; polyalkylmethacrylates; co~
polymers of alkylaminoalkylmethacrylate and alkylmethacry~
11 late; and polyalkylacrylates. lt appears that the commer~
l2 cial practice as exmplified therein is to use only the min-
13 imum amount of the polyalkylacrylate VoIo improver as the
14 pour point depressant to be used together with the ethylene
copolymer to achieve the desired pour point In this regard,
l6 such a poly~lkylacrylate V.I. improver as Acryloid 732 is
17 commercially available as a 35~40 weight percent active con~
18 oentrate in a paraffinic diluent and is generally used as
19 æuch in up to 1.2 weight percent (about 0O4~005 weight %
active polyalkyl methacrylate), to achieve a finished oil
21 pour point of o20 to -40Fo
22 U.S Patent 3,697,429 discloses ethylene copolymer
23 V.I improvers of the type included herein together with up
24 to 2% of a pour point depressant o~ 1,000 to 50,000 molecular
weight which pour point depressant is usually characterized
26 by C6_1g straight chain groups, including polymers and co~
27 polymers of n-alkyl methacrylates, n~alkyl acrylates and co-
28 polymers of alkyl fumarate and vinyl acetate.
29 It is understood by one skilled in the art that
lubricating oil additives are blended into base mineral oil
31 stock as A composition consisting of the active compound in }
32 ~ mineral oil diluent.

4 -
~r,lde h~arK

1070664

1 It has now been discovered that when an ester base
2 type V.I. improver characterized by the presence of oxygen
3 and optionally nitrogen functionality (as distinguished
4 from the other in which such functionality is absent) is
combined with a second VoI~ improver which i8 essentially
6 hydrocarbon in nature, iOeO, an ethylene~higher olefin co-
7 polymer or its oxidized and aminated ("polyaminox") deriva-
8 tive, the combination imparts to the lubricating oil a lower
9 pour point and a lower viscosity at low temperatures than
when either additive i8 used alone at the same concentrations
11 a8 the blend.
l2 The V.I. improver additive combinations of the
13 invention tiffers from the aforesaid UOSo 3,691,078 and
14 3,697,429 in that this invention call~ for higher ratios of
ester base copolymer YoIo improver to ethylene copolymer
16 VoIo improver than that taught in either of the referenced
17 patentsO The weight ratio of ester base copolymer VoI ~m~
18 prover to ethylene copolymer VoIo improver ranges from about
19 0.8 to about 99; and optimally about 105 to about 4 (as used
herein "ethylené copolymer" includes the "polyaminox" deriv~
21 atives)c
22 Ethylene copolymers have been wide~y taught and
23 used as V.I. improvers in the lubricating oil industryO
24 These ethylene copolymers m~y be prepared by the polymeriza~
tion of ethylene with a C3 to Clg, eOgO, C3 to C8 alpha~
26 olefin, preferably propylene, and optionally one or more co~
27 polymerizable additional monomers
28 The alpha olefins may be linear or branched, lf
29 the branching occurs three or more carbon atoms from the
double bondO While a ~ingle alpha olefin ~s preferable,
31 mixtures of C3 to Cl8 olefins may be employed. Suitable
32 examples include propylene, l~butene, l~pentene, l~hexene,

~ 5 c:~

1070664

1 l-heptene, l-octene, l~nonene, l~decene, 4~methyl-l~pentene,
2 4-methyl~l-hexene, 5~methylol~hexene, 4,4~dimethyl-l~pentene,
3 4-methyl-l~heptene, 5-methyl~l~heptene, 6~methylol-heptene,
4 4,4-dimethyl-1-hexene, 5,6,5-trimethyl-l~heptene and mixtures
thereof.
6 Ethylene~propylene copolymers are preferred for
7 the purposes of this invention. It is also possible to use
8 a third monomer to form a terpolymer, a fourth monomer to
9 form a tetrapolymer and frequently it is desirable to use a
mixture of numerous mono~ and/or diolefins to prepare the
11 ethylene copolymer V~Io improver (see U S. Patents 3,5~2,180;
l2 3,551,336; 3,598,738; 3,691,078; 3,697,429; and 3,790,480).
13 The third monomer type may be one or more C5 to C~8 dioleins.
4 These dio~ arealso ~e~rably ~nearbut may be branched if the
branching occurs three or more carbon atoms from the double
bond. The amount of the third monomer contained in the
17 polymer may range from 0 to about 10 mole percent9 e~g.,
18 0.1 to 5~0 mole percent.
19 The diolefins which are useful as third monomer
for copolymerization with ethylene and propylene include
21 the bicyclic, alicyclic or aliphatic nonconjugated diole
22 fins containing about 5~28 carbon atoms, preferably about 6
23 12 carbon atoms. Suitable monomers include 1,5~cycloocta~
24 diene, 1,4hexadiene, dicyclopentadiene, 5~methylene~2~nor-
bornene, 5vinyl~2-norbornene, 1,5=cyclododecadiene, 2,4~
26 dimethyl2,7-octadiene, 3(2~methylcl~propenyl) cyclopentene,
27 1,5-octadecadiene, 5-ethylidene~2-norbornene, 1,4~pentadiene;
28 1,5-hexadiene; 1,6~heptadiene; 1,17octadecadiene; 5-(5'
29 hexenyl)~2~norbornene; 2,5~norbornadiene; etc.
The copolymers may be prepared by polymeriæing a
31 mixture of the monomer components containing the following
32 components by weight, based upon 100 parts by weight of
~ 6 -


.
. . , . , .. :
.. . .

1070664

1 solvent employeds
2 TABLE I
3 ~ onent ~33~ 133~ L~5~ Typical
4 Ethylene 0.1~10~0 1.0~600 3 0~4 7
Higher alpha~olefin 0.1~20 0 1 0~15 0 2 8~4 9
6 Diolefin 0.0~200 0 0~1.0
7 Hydrogen 1X1O~7~1X1O~2 lx10~6~x6x10-3 2.35xlO 4~
6x10S
8 The monomer mixture may be polymeri~ed to form
9 the desired polymer in the presence of a catalytic amount of
a catalyst composition containing as catalyst, a compound of
11 a transition metal and, as cocatalyst, an organom~tal com~
2 pound such as titanium tetrachloride, vanadium oxychloride
3 or vanadium tetrachloride, and diethyl aluminum chloride,
14 tri-isobutyl aluminum or ethylaluminum sesquichloride, re~
spectively.
l6 The preferred catalyst composition includes 0.00001
l7 to 0.0001 mole, e~gO 0 00005 mole, of transition metal
18 halide catalyst and 0000007~0000~ mole of organoaluminum
l9 cocatalyst per 100 parts of solvent employedO
The nonreactive reaction medium may be an aromatic
21 hydrocarbon such as toluene, a saturated aliphatic hydro~
22 carbon such as heptane, pentane, or hexane, or a chloro~
23 hydrocarbon such as tetrachloroethylene, etcO
24 All steps in this reaction should preferably be
carried out in the absence of oxygen9 moisture, carbon di~
26 oxide or other harmful materialsO Preferably, all reac~
27 tants and catalyst are pure and dry and blanketed with
28 inert gas, such as nitrogen or methane~
29 During polymerization, the reaction mixtures are
agitated and maintained at temperatures of ~40Co to 100C.,
31 e.g., -10C. to 70C~, preferably about 30C and pressures
32 of 0-1000 psig,, preferably 0~300 psigo, e g 60 psig , dur-

107~)664

1 ing a period of 1~300 minutes, preferably 3~60 minutes, e g
2 15 minutes.
3 At the end of this period, the reaction mixture
~ is worked up to separate product copolymer.
In the preferred embodiments, the ethylene con-
6 tent of the copolymer is controlled by varying the mole
7 ratio of ethylene to`propylene.
8 Ethylene/alpha olefin especially ethylene/propyl-
9 ene copolymers useful in the present invention and produced
by the aforesaid method will usua~y have characteristics
11 summarized in the following tableo
12 TABL~
13 PropertY ~ es~ Preferred R~r~e
14 Ethylene, mol % 30~80 40~70
Alpha-Olefin, mol ~h 10~70 25~60
l6 Third Monomer, mol % 0~10 0~5
17 Degree of crystallinity, 0~25 3-15
18 wt. percent as determined
19 by the method of Ver Strate
and Wilchinsky- Journal of
21 Polymer Science, VolO9, p
22 127 (1971).
23 ~ X 10-3 10~200 20~140
~24 hn X 10 3 5~100 10~70
hw X 10-3 10-800 10-400
26 Mw/Mn 10 or below 6 or below
27 While the ethylene copolymers may be made by di~
28 rect synthesis in the desired weight average molecular
29 weight range of 10,000 to 800,000 and are desired molecu~
lar weight spread, the lower molecular weight polymers may
~1 also be made by physically degrading a higher molecula~
.. ..
3~ weight polymer as by extruding the polymer under high shear
33 and/or temperature.

. ,,



,

, . , ~
~ . . .
.
: . :

lot7~66

1 POLYOLEFIN A CONCENTRATE
2 Thi8 iB a VoI~ improver concentrate of 93 weight
3 'percent mineral oil, and 7 weight percent of an ethylene
4 copolymer of the following compo~itiono
POLYOLEFIN A
6 Ethylene mol % 75
7 Propylene'mol % 25
8 Third Monomer mol % O
9 Cryst~llinity, wt. ~ 3
~n X 10-3 40
RW X 10~3 ~0
l2 Mw ~ 2
13 A typical laboratory ~ynthe~s of this ethylene
1~ copolymer is as followso Predried ethylene and propylene
were fed continuously as gases through calibrated roto-
l6 meters at 20Co to a glass reactor provided with an ex-
17 ternal cooling Jacket, mixer, and inlet lines for monomers,
18 solvent, principal catalyst, cocatalyst and hydrogen, and
19 an overflow line'to a'quench tank. Under steady~state
operating conditions the volume in the reactor was 700 ml.
21 Temperature of the reaction mixture was maintained at the
22 desired level by prechilling the reactor feeds and by cir-
23 culating chilled water through the jacket upon demand of a
24 sensitive temperature controller.
Hydrogen addition was measured by means of a cali-
26 brated rotometer. Solvent and catalyst feeds were accurate-
27 ly metered by means of feed pump~
28 Individual solutions of principal catalyst and
29 cocatalyst were prepared by diluting 0,75 millimoles VOC13
and 15 millimoles of Et3A12C13 to 360 ml~ with n~heptane,
31 which had been dried and freed of impurities by percolation
32 through columns filled with Linde 5A molecuLar sieves and

c~ g ..

`` 10~0664
1 aotivated silica gel. Similarly purified heptane was used as
2 solvent. Feeds to the reactor are shown in Table III below:
3 TABLE III
4 Reactor Feeds:
Heptane Solvent 500 ml/min.
6 Ethylene 1.38 li~ers/min.
7 Propylene 5.47 liters/min.
8 VOC13 solution 7.25 ml/min.
9 Et3A12C13solution 7.25 ml/min.
Hydrogen 112.0 ml/min.
11 Reaction Temperature - 55C.
12 POLYOLEFIN B CONCENTRATE
13 This is a V.I. improver concentrate of 92 wt. %
14 mineral lubricating oil and 8 wt- ~/O ethylene copolymer of
the following composition:
16 POLYOLEFIN B
17 Ethylene mol % S4
18 Propylene mol V/o 46
19 Third Monomer mol ~/O - 0
20 Crystallinity, wt. % 0 ;
21 Mn X 10-3 60
22 Mw X 10 3 120
23 Mw/Mn 2
2~ A typical laboratory synthesis of this copolymer
may be carried out in the same general manner as used to pre-
26 pare Polyolefin A, but varying the ethylene and propylene -
27 feeds. Both Polyolefin A and B are conventional V.I.
28 improvers.
29 "Polyaminox" Derivatives of the Ethylene Copolymers and
- Terpolymers
31 The above-described ethylene copolymers are oxi-
32 dized and thereafter reacted w~th amines to produce the
33 "polyaminox" derivatives (the aminated oxidized derivatives
34 of the ethylene copolymer type additive ea~lier discussed).

- 10 -

-- . .

1070664

a~idation of hydroc~rbon polymers is well-kna~m.
2 Reaction of ~xidized ethylene copolymer with
3 nltrogen-containing compounds, guch ag amines, is also well
4 kno~, e.g. 8ee U.S. Patents 3~076~791 snd 3~785~980~
S Oxidation of hydrocarbon polymers prior to the
6 amine reaction can be carried out by numerous processes in-
7 cluding hydroperoxidation of ethylene-propylene copolymers
8 (U~S~ 3~785~980) and mechanical degradation while heating
9 i~ air (U.S. 3~769~216)o
~10 P rtcularly useful herein are ethylene copolymers
1 oxidizet in mineral oil and subsequently reacted with amines
l2 as describet in Serial No~ C~. 223~8C~ 9PR~ 7J ~
13 In this process, a wide variety of mineral lubricating oils
14 ~y be used as solvent for the polymer-oil solutions to be
oxidized. The oils ~y range in viscosity from about 5 to
l6 1000 SUS @100F., most preferably 80 to 200 SUS @100F.
17 They m~y be straight-run distillates in the lu~ricant range,
18 e.g., boiling above 600Fo~ or m~y have been further refined.
19 Also suit-ble are ~ynthetic hydrocarbon oils in the lubri
cant range m~de by polymerization, oligomerlzation, alkyl~
21 ation of aromatics with olefins ant the like Preferred
22 are oils h~ving a sulfur content of less than 0 25 weight
23 percent, a nitrogen content of less th~n 25 mlcrograms per
24 ml., and an aromatic content of le~s than 30 weight percent.
O~cidation of the copolymers and terpolymers dis-
26 801vet in the oil is conveniently carried out ln a stirred
27 reactor with air, or air prediluted with an inert ga~ such
28 as nitrogen or carbon dio~cide 80 as to minimi~e explosion
29 hazards. The air, or diluted air, m~y be introduced into
the oil-polymer solution in a finely divided state at a
3t~ t~mperab~re in the r~nge of about 80.Co to 300C., prefer-
3~ ably 100C. to 230C. with rapid agitation of the reactor
- 11 -

.

1070G64

1 contents.
2 In general9 in the range of 0.5 to 90, e.g., 4
3 to 60 weight percent of the oil~polymer solution will be
4 polymer. Usually, ~bout 20 to 60 weight percent of the
solution will be polymer when the polymer is of low molecu-
6 lar weight, e.g~, with a number average molecular weight
7 (Mn) less than 20,000. For polymers with Rn equal to or
8 greater than 20,000, the preferred concentrations are in
9 the rarKe of 4 to 20 weight percent polymer, based on the
total weight of the oil-polymer solution
11 Qxidation of the oil-polymer ~olution is con~
l2 ducted for 8 time sufficient to impart to the solution a
13 combined oxygen content of about 0~01 tO 10.0, e.g., 0.1 to
14 8, preferably Ool to S~0 weight percent, depending on the
composition of the oil, the polymer and the concentration
l6 of polymer in solution
17 As used herein, such terms a~ "oxidi~ed", or "oxi
18 dized oil polymer solution" etc. indicate~ that air or oxy~ ~
19 gen containing gas i8 used for the oxidation, and precludes ~-
the use of other oxidative reagents such a~ ozone.
21 Useful amine compounds for condensation with the
22 oxidized polymeroil solutions to form the l'polyaminox" pro
23 ducts of thls invention include am~nes of about 2 to 60,
24 e.g., 3 to 20, total carbon atoms and about 1 to 12, e.g.,
1 to 6 nitrogen atom~ in the molecule, which amine~ may be
26 hydrocarbyl amines or may include other groups, e.g., 1 to
27 4 hydroxyl groups, alkoxy groups, amide groups, imidaæoline
28 groups and the likeO
29 Preferred amine~ are aliphatic, saturated amines,
and include those of the general formulae~
31 R~N~R" and R-N-(CH2 )3~N (CH2)s~]tN~R
32 R' Rl Rl R'
12 -

. , ~ : ': ' ,' . ,'

10 70 6 6 4

1 wherein R, R' and R" are independently selected from th~
2 group consisting of hydrogen; Cl to C12 straight or brar.ched
3 chain alkyl radicals; Cl to C12 alkoxy substituted C2 to
4 C6 alkylene radical~; C2 to C12 hydroxy or amino alkylene
5 ~ radicals; and Cl to C12 alkylamino ~ubstituted C2 to C6
6 alkylene radicals; s i~ 2 to 6, preferably 2 to 4; and t
7 i8 0 to 10, preferably 2 to 6.
8 Examples of suitable amine compounds represented
9 by the above include: n~octyl amine; n~dodecyl amine; di-
(2-ethylhexl) amine, 1,3~diaminoethane; 1,3~diaminopropane;
11 1,4-diaminobutane; 1,6~diaminohexane; diethylene triamine;
l2 triethylene tetramine; tetraethylene pentaamine; 1,2~ ~
13 propylene diamine; diD(1,2Qpropylene) triamine; di (1,3
14 propylene) triamine; N,N-dimethyl 1,3~diaminopropane; N,N~
di-(2Qaminoethyl) ethylene diamine, N,N~di~(2hydroxyethyl)-
l6 1,3propylene d~mine, 3dodecyl oxy propylamine; N-dodecyl-
17 1,3-propane dlamine; diethanol amine; morpholine,o trishydroxy
18 methyl aminomethane (THAM), diisopropanol amine, etc.
19 Still other useful amine compounds include~ ali-
cyclic d~amines such as 1,4-dir(aminomethyl) cyclohexane and
21 heterocyclic nitrogen compounds such as imidazolines and N-
22 aminoalkyl piperazines of the general formulaO
23 CH2 - CH2
24 NH2-(CH2)p o ~ N-G
\ CH2 ~ CH ~
26 wherein G is independently selected from the group consist
27 ing of hydrogen and~ aminoalkylene radicals of from 1 to
28 3 carbon atoms; and p is an integer of from l to 4. Ex-
29 ampIes include 2~pentadecyl imidazoline, N~(2~aminoethyl)
piperazine; N~(3~aminopropyl) piperazine; and N,N'~di(2-
31 aminoethyl) pipera~ine.
32 Other alkylene amino compounds that can be used

- 13 -

. ~, .. , .. .. , . , ... . ..... .. .. . . . . .. . .. . ... .. . ~ .. . . . ... . .. . . . . .
.....

107~664


1 include dialkylamino alkyl amine such as dimethylamino ethyl
2 amine, dimethylamino propyl amine, methylpropylamino amyl
3 amine, etc. These may be characterized by the formula:
4 R2
H2N - Rl ~ N
6 R3
7 wherein Rl is an alkylene radical, e.g., an ethylene~ propy-
8 lene, or butylene radical, and R2 and R3 are Cl to C5 alkyl
9 radicals.
Commercial mixtures of amine compounds may advan-
11 tageou~ly be used for t~é preparation of the "polyaminox"
12 composition~ of this invention. For example, one process
13 for preparing alkylene amines involves the reaction of an
14 alkylene dihalide (such as ethylene dichloride or propylene
dichloride) with ammonia, which results ln a complex mix-
16 ture of alkylene amines wherein pairs of nitrogens are
17 ~oined by alkylene groups, forming such compounds as di-
18 ethylene triamine, triethylene tetra-amine, tetraethyIene
19 penta-amine and isomeric piperazines. Low cost poly(ethy-
lene amines) compounds having a composition approximating
21 tetraethylene penta-amine are available commercially under
22 the trade names Polyamine H, Polyamine 400, (PA-400) and
23 Polyamine 500 (PA-500). Similar mater~als may be made by
24 the polymerization of aziridine, 2-methylaziridine and aze-
tidine.
26 The re important alkylene polyamine or aliphatic
27 polyamine compound used in this invention can be broadly
28 characterized as an alkylene amino compound containing from
2 to 12 nitrogen atoms where pairs of nitrogen atoms are
~ ~oined by alkylene groups of from 2 to 4 carbon atoms.
31 Reaction of thè amine compound with the polymer
32 ~olution takes place readily at a temperature in the range

A~e~ - 14 -

- :' : , -

,

10~70664

1 of abou~ 40C. to 300C., preferably at a temperature in
2 the range of 100C. to 200C. Accordingly, after the
3 oxidation of the oil~polymer solution has reached the
4 deslred level, the required amount of amine compound,
usually in the range of about 0.1 to 4.0 wt.~ based on
6 the weight of the polymer, may be added with mixing and
7 the reaction mixture maintained at the required temperature
8 while removing any water that forms. The time for com-
9 pletion of the reaction of the amine compound with the
oxidized oil-polymer solution is in the order of about
1 15 minutes to about 50 hours depending on temperature,
l2 degree of mixing and reactivity of the amine compound.
13 m e final aminated product will usually contain in the
!4 range of about 0.03 to 5, e.g. Ool to 3.0 wto~ nitrogen,
based on the total weight of the aminated polymer.
16 POLYOLEFIN C CONCENTRATE
17 This V.I. ~mprover ccnsist~ cf about 92 wt.~
18 mineral oil and 8 wt.~ of the "polyaminox" derivative of
19 the oxidized in oil mixture of 1528 grams of an ethylene/
propylene copolymer (about 75 mole percent ethylene)
21 having a ~ of about 130,000 and 1528 grams cf an ethylene/
22 propylene copolymer (about 56 mole percent ethylene)
23 having a ~ of about 195,000. Each copolymer was indivi-
24 dually dispersed in mineral oil and oxidized by passing
air through the mixture at elevated temperatures. The
26 copolymer of about 75 mole percent ethylene was oxidized
27 at 340F. for 11-1/4 hours. The copolymer of about 56
28 mole percent ethylene was oxidized at 340F. for 21
29 hours. Each showed infrared (rR) absorptions a~ 1720 cm~
ln a 5 mm cell of 0.208 and 0.244, respectively. To this
31 mixture of oxidized ethylene-propylene copolymers having
32 a Mw of about 90,000 9 4.6 grams of diethylene triamine

- 15 -

1070664

1 was added at between 25C~ and 100Co after nitrogen
2 sparging. The t~mperature was raised to and kept at
3 about 160C. for 2-2/3 hours under an inert atmosphere of
4 nitrogen and thereafter cooled to 120Co whereupon it was
bottled. Thi9 "polyaminox" concentrate showed a nitrogen
6 content of 0.046 wtc~/oo
7 e Ester Base PolYmers
8 Usually these V.I. improving, oil-soluble ester
9 base polymers will have number average molecular weights
in the range of 20,000 to 1~0009000D preferably 50,000 to
11 500,000 and most preferably, 50,000 to 200~000O These
12 ester base polymers are derived essentially, e.g., 80
13 wt.% or more of the total polymer, from C8 to C20,
14 preferably Cl2 to Clg, alkyl esters of a C3 to Cg,
preferably C3 to C5 monoethylenically unsaturated mono-
l6 or dicarboxylic acidO VoI~ polymers of this ester base
17 type are well-known in the art and are usualLy made by
18 free radical initiation, eOgO, using a peroxide~ in a
19 solvent.
Such esters frcm w~ich the poly~er is essen-
21 tially derived include alky1 acryldte~ alkyl methacrylate,
22 dialkyl fumarate, and dialkyl itaconateO
23 The most common of these VoIo improvers are
24 polymers of acrylic esters represented by the formula
R
26 CH2 = C - COOR~ ~-
27 wherein R represents hydrogen or methyl and R' represents
28 an oil solubilizing group, especially an alkyl group of
29 8 to 24 carbon atoms. The alkyl group may be essentially
straight chain and preferably contains 12 to 18 carbon
3l atoms altbough methyl and ethyl branchlng can be tolerated.
32 Representative polyacrylic and pol~methacrylic esters that

16 ~


.
',

lOqO664

1 promote oil solubility comprise octyl, decyl, isodecyl,
2 dodecyl, isododecyl) myristyl, cetyl, s~earyl, eicosyl
3 and tetracosyl polyacrylates and polymethacrylates~ The
4 term "acrylic ester" in this invention includes both
acrylates and methacryla~es~ Mixtures of both alkyl
6 acrylates and alkyl methacrylates may be used.
7 Lower alkyl acrylic esters having alkyl groups
8 smaller than 8 carbon atoms and derived from acrylic or
e~cr~l~c
9 moth~ayo~ e acid may be used in combination with the
previously mentioned higher acrylic esters. The presence
11 of small alkyl groups in the copolymers may help improve
l2 such properties as the viscosity index. Typical lower
13 acrylic esters are methyl~ ethyl 9 propyl, butyl, amyl,
14 and hexyl acrylates and methacrylates. These lower alkyl
acrylic esters may be employed in amounts ranging from 0
16 to 25 mole /O~ based on the total ester ccntent.
17 In addition to the aforementioned acrylic
18 esters, there may be used to form the backbone9 in minor
19 amounts, one or more other free radical polymerizable
monoethylenically un~aturated compounds, particularly
21 monovinylidene compounds, i.e. 9 those having one CH2=C
22 group in its structure, such a~ vinyl esters; e.g.
23 vinyl acetate, styrene and alkyl styrenes 9 vinyl alkyl
24 ethers, e.g. vinyl butyl ether, vinyl dodecyl ether and
vinyl octadec~l ether.
26 In addition, nitrogen~contain~ng monomers can
27 be copolymerized with the foregoing monomers9 said
28 nitrogen-containing monomers include ~hose represented by
29 the formulao
R - C = C - H
31 Rl R2
32 wherein Rl and R2 can ~e hydrogen and/or alkyl radicals

,
- 17 ~

1070664
1 and R is a 5- or 6 membered heterocyclic nitrogen-
2 containing ring and which con~ains one or more sub~ti- -
3 tuent hydrocarbon gr~ups~ ln ~he above ~or~ula9 the
4 vinyl radical csn be attached to the nitrogen or to a
carbon atom in the radical Ro Examples of such vinyl
6 dcrivatives include 2~vinylpyrid~ne9 4~vinylpyridine,
7 2-~ethyl-5~vinylpyrid~ne, 2~ethyl~5-vinylpyridine, 4-
8 methyl-5-vinylpyridine, N~vinylp~rroLidone 9 4~vinyl
9 pyrrolidone and the like.
0 Other monomers that can be included are the
11 unsaturated amides such as ~hose of the formula:
l2 / Rl
13 CH2 - C
14 \ CoNHR3
wherein Rl is hydrogen or me~hyl9 and R3 is hydrogen or
16 an alkyl radical having up to about 24 carbon atoms.
17 Such amides are obtained by reacting acrylic acid or a
18 low molecular weight acrylic ester with an amine such as
19 butylamine, hexylamfne, tetrapropylene 9 amine 9 cetylamine
and tertiary~alkyl primary am~nes. The tertiary-alkyl
21 primary amines referred ~o ccnfonm to the characterizing
22 structure
23 C
24 ~ C - C 8
C
26 wherein a tertiary cArbon atom9 ~Oe., one devoid of
27 hydrogen atoms is bonded to a pr~mary amino rad~cal~
28 i.e., -NH2. Such tertiary alkyl pr~mary am~nes should
29 contain at least about 6 and generally not more than about
24 carbon atoms in the tertiaryalkyl substituent. In
31 most instances, the ter~iary~alkyl substi~uen~ will
32 contain from about lO to abcut 24 carbon atoms. Specific

-`~
1070664

1 examples of tertiary~alkyl primary amines useful for
2 the purposes of this invention include ter~iary-octyl
3 primary amine, tertiary~decyl primary amine and tertiary~
4 hexadecyl primary amine, tertiary-eicosyl primary amine
and tertiary-triacontyl primary amine. It is not necessary
6 to use a single tertiary alkyl primary amine; in fact, it
7 is generally more convenient to use a commercial mixture
8 of æuch amines wherein the ter~i~ry-alkyl substituent con-
9 tains from about 10 to about 24 carbon atoms. A typical
mixture of such commercial tertiary-alkyl primary amines,
11 for example, consists of tertiar~-alkyl primary amines
l2 containing from about 12 to about 14 carbon atoms, said
13 mixture averaging about 12 carbon atom~ per amine molecule.
1~ Still other monomers that can be included are
amides and mixed amides-esters of the vinyl monocarboxylic
l6 and dicarboxylic acids mentioned previously. These
17 monomers and the earlier discussed lower alkylacrylic
18 esters, monovinylidene compounds, nitrogen containing
19 monomers and unsaturated amides may individually or
collectively employed in total amounts ranging from 0 to
21 25 mole percent, based on ~he totaL ester content.
22 The following specific ester base polymers
23 were used in the examples of the invent~onO
24 POL ~SIrlllA~ CONCENTRATE
This was a V~Il improver concentra~e of 63 wt.~/o
26 oil and 37 wt.% of an ester base copolymer consisting of
27 a major proportion of about 95 mole % of C10 to C20 alkyl
28 methacrylate monomer with alcohols containing an average
29 carbon number of 14.5 and a minor proportion (about 0.5
mole %) of an amino~methacrylate copolymerized with the
31 aid of a free radical catalyst. The copolymer has a
32 nitrogen content o 0.2 wt.% and a number average

- 19 -

1070664

1 molecular weight in the range of 50,000 to 100,000.
2 POLYESTER B CONCENTRATE
.
3 This was a commercial V.I. improver concentrate
4 (sold as Acryloid 953 by Rohm and Haas) of 62 Wt~% oil
8 and 38 wt.~ of ester base copolymer consisting of a major
6 proportion of C10 to C18 alkyl (average number of carbons
7 is 12-15 range) methacrylate monomers and a minor propor-
8 tion of a nitrogen-containing monomer which copolymer
9 upon chemical analysis contains about 0.2 wt.% nitrogen
lo with a number average molecular weight between 509000 and
1 1 100, 000 .
l2 POLYESTER C CONCENTRATE
13 This was a commercial V.I. improver additive
14 concentrate of about 66 wt.% oil and about 34 wt.% of a
terpolymer sold as LZ 3702 by Lubrizol Corporation.
l6 This additive consists of styrene, dialkyl maleate and
17 a minor proportion of a nitrogencontainlng monomer which
18 terpolymer upon chemical analysis contains about 0.15%
19 nitrogen with a number average molecular weight between
50,000 and 100,000.
21 POLYESTER ~ CONCENTRATE
22 This was a commercially available concentrate
23 of 60 wt.% oil and 40 wt.% polyalkyl methacrylate sold
24 as Acryloid 732 by Rohm and Haas Chemical Co.
The molecular weights for the polyester
26 concentrates are all set forth as number average ~n)
27 which are calculated through the technique of membrane
28 osmometry using a 3-Stabin Dohrmann Semi-Automatic
29 Recording Osmometer with toluene as a solvent and
measured at about 35C.
31 The polymer blends of the invention are broadly
32 from about O.8 to 99, preferably 1.0 to 9.O and optimally
Trade /nO.~ IC - 20

~070664

l 1.5 to 4 parts by weight of the ester base copolymer per
2 part by weight of ~he ethylene copolymer and/or its "poly-
3 aminox" derivative.
4 The polymer mixtures of this invention can be in-
corporated in lubricating oil compositions, e.g., automotive
6 crankcase oils, in concentrations within the range of about
7 0.1 to about 2 weight percent ethylene copolymer and/or
8 "polyaminox" derivative (on an active basis) based on the
9 weight of the total compositions, whereas for the ester base
copolymer concentrations within the range of 0.2 to 6 weight
11 percent is appropria~eO
12 The overall concentration of the mixture in the
C 13 lubricating oil composition would be from abou~ wt. %
14 to about 8 wt. % of the total composi~ionO
In the above lubricating oil9 other conventional
16 additives may also be present, including dyes, pour point
17 depressants, antiwear agents9 e~g. tr~cresyl phosphate, zinc
18 dialkyl dith~ophosphates ~f 3 ~o 8 carbon a~oms, antioxi-
19 dants such as phenyl alpha-naphthylamine, tertn octylphenol
sulfide, bisphenols such as 4,4l~methylene bis (2,6-di-tert.
21 butyl phenol), as well as ashless dispersants or detergents,
22 such as polyisobutenyl succinimides~ pen~aerythritol esters
23 of polyisobutenyl succinic anhydride, etc.
24 EXAMPLES
The following mineral lubrica~ing oils were used
26 for compounding the lubricants which were then tested for
27 viscosity as shown in the following tablesO
28 Solvent Neutral S-70 A solvent extracted9 hydrofined oil
29 having a viscosity at 210F. of 36.5 SUS; viscosity at 100F.
of 74 SUS; viscosity index of 78; and a pour point of -20F.
31 Solvent Neutral H-75 A solvent extracted, hydrofined oil
32 having a viscosity at 210F. of 36.8 SUS, viscosity at 100F.
~ 21 ~


. ~ . . . . .

i07~664

1 of 72 SUS; viscosity index of 108; and a pour point of 0F.
2 Solvent Neutral H-100 A solvent extract oil having a vis- :
3 cosity at 210F. of 40.5 SUS, viscosity a~ 100F. of 110
4 SUS; viscosity index of 106 and a pour point of 0F.
Solvent Neutral H-150 A solvent extracted oil having a vis-
~ 2/o
6 c08ity at ~ F. of 155 SUS~ viscosity at 100F. of 44.0
7 SUS; viscosity index of 107; and a pour point of 0F.
8 Solvent Neutral H-llO A blend of eight volume parts of Sol-
9 vent Neutral H-100 with two volume parts of Solvent Neutral
H-150. All viscosity measurements are by ASTM Method D-445.
11 A series of experiments was run in which blends of
12 the various polyolefin and ester based polymers were made in
13 the oils listed above by addition of a polymer concentrate
14 of each to the oil with stirring and heating at about 140- :
150F. until solution was complete. The Brookfield viscosi-
16 ties of the blends in centipoises were then determined at
17 -40F. The results obtained are given in Table IV.




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1 Comparison of the results obtained in Experiment
2 11 with 2 and 6; 12 with 4 and 8; 13 and 13-A with 4, 4-A
3 and 10; 14 and 14-A with 4, 4-A and 6; 19 with 16 and 18;
4 26-27-A with 19-25, shows the complementary effect obtainet
with the combination of a polymeric polyolefin and polyester
6 atditive compared to either used alone.
7 Extending these data, experiments were run in which
8 blends of Polyester Polymer A and Polyolefin A were made at
9 various concentrations in Solvent Neutral Oil S-70 and the
viscosities of the blends determined at several temperatures.
11 In order to approximate the properties of a finished auto-
12 matic transmission fluid a detergent-inhibitor package was
13 added to each blend to provide 2 wt. % of the detergent-
14 inhibitor compounds. The detergent-inhibitor combination
comprised a mixture of a polyisobutenyl succinic anhydride-
,
16 tetraethylene pentamine contensation product; a phosphosul-
17 iurizet terpene; a zinc dialkyl-dithiophosphate; an ethoxy-
18 latet alkyl phenol, an aryl naphthylamines; ant a silicone
19 antifoamant. The results obtained are shown in Table V.

~ :

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- 25 -

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107V664



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- 26 -

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1~7~3664
1 The data in Tables IV and V indicate.that the poly-
2 olefins possess greater thickening power than the polyfunc-
3 tional VI improvers when measured at the same concentration
4 and that mixtures of the polyolefins and polyfunctional com-
pounds containing from 2 to 6570 of the polyolefin, based on
6 the total polymer in the blend, show lower viscosities at
7 low temperatures than equivalent concentrations of either
8 V.I. improver.
9 A further advantage in the use.of mixtures aside
from the lower cost of the polyolefins compared to the poly~
11 functional compounds is the lower pour point and improved
12 fluitity of blcnd at lower temperatures. The improved flui-
13 dity results in better lubricant dispensibility from a con-
14 tainer which has remained at low tempera~ures for a period
of tlme. Table VI gives the results of a number of blends
16 illustrating these properties.




- 27 -

.

.

'1~70664


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. .

1070664
1 Lower viscosities at low temperatures are impor-
2 tant for lubricants such as automotive transmission fluid,
3 automotive engine oils and multigrade gear oils since such
4 fluids must meet certain maximum levels at specifiet temper-
ature8 tailored to each lubricant type and grade. Lubricant
6 formulations strive for certain minimum viscosities at high
7 temperature and the aforementioned max~ viscosities at
8 low temperature to yield the desired viscometric performance.
9 mis invention provides a means for meeting such require-
ments economically; particularly for operation temperatures
11 ranging from -60F. to +15F.
12 Such useful automatic transmission fluid is repre-
13 sented by the following formulation (all or a part of the
14 additives can be present):
15 Additive t~Pe Compound Amount %
16 Diluent/base oil Mineral Oil 94.2 (or
17 (100 neutral) balance)
18 Viscosity Index Polyolefin A 0.25
19 improvers Polyester A 0.75
20 Corrosion Inhibitor phosphosulfurized 0.3
21 terpene
22 Oxidation Inhibitor phenyl alpha 0.3
23 naphthylamine
24 Friction Modifier calcium olea~e 0.4
25 Seal swellant dihexyl ph~halate 2.0
26 Dispersant polyisobu~enyl 1.5
27 succinimide
28 Antiwear agent zinc dialkyl dithio 0.3
29 phosphate
30 Anti-foamant polydimethyl siloxane 0.002
31 All percentages are in volume percent except for the anti-
32 foamant and viscosity index improvers, which are given as
33 weight percent.




,' , ' . . . ...

Representative Drawing

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Administrative Status

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Administrative Status

Title Date
Forecasted Issue Date 1980-01-29
(45) Issued 1980-01-29
Expired 1997-01-29

Abandonment History

There is no abandonment history.

Owners on Record

Note: Records showing the ownership history in alphabetical order.

Current Owners on Record
EXXON RESEARCH AND ENGINEERING COMPANY
Past Owners on Record
None
Past Owners that do not appear in the "Owners on Record" listing will appear in other documentation within the application.
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Document
Description 
Date
(yyyy-mm-dd) 
Number of pages   Size of Image (KB) 
Drawings 1994-03-25 1 6
Claims 1994-03-25 2 70
Abstract 1994-03-25 1 13
Cover Page 1994-03-25 1 16
Description 1994-03-25 28 1,140