Note: Descriptions are shown in the official language in which they were submitted.
1 This invention relates to nitrogen~containing
2 polymerîc adducts and to ~ubricatlng oil composi~ions con-
3 taining said adducts as multifunctional additives,
4 especially ~hose adducts derived from copolymers which have
a substantially saturated hydrocarbon backbone-chain with
6 side-chain unsaturation and unsatura~edg polar, nitrogen-
7 containing organic reactants~
8 The literature abounds with discussions of multi-
9 functional viscosity index (V.I.) improvers containing
nitrogen to enhance their dispersant activity~ Included
11 therein are polymeric nitrile-containing subs~ances as
12 lubricating oil additives with de~ergent-dispersant and
13 ot~er properties.
14 The incorpora~ion of any ni~rlle moiety in said
V.I.-improving polymeric substances according to the prior
16 art was generally by conventional means including copolymer-
17 ization of one or more olefins with a nitrile containing
18 monomer (U~S. Patent 3,445,387), ree radical gxafting as
19 by hydroperoxida~ion of an ethylene copolymer directly
with a polar vinylidene monomer~ such as acrylonitrile (see
21 U.S. Patent 3J 404,09l), and reacting a nitrile~containing
22 compound with a reactive copolymer such as is obtained from
23 a ~ree radical grafting of maleic anhydride to polyiso-
24 butylene (see U.S, Patent 3g448J049~
2s These processes which utilize ~ree radical~,
26 either generated by shearing stresses during masticatlon
27 or by hea~ing organic compounds, such as peroxldes~ to
28 prepare a polymeric adduct have certain disadvantages~
~ including irreversible crossllnking o~ the copolymer and
homopolymerization of monomeric components. One o~ su~h
31 disadvantages ls shown in U.S. Patent No. 3,236J917 which
32 discloses adducts prepared by heating a mixture of ethylene/
, ~7
~ ~9 ~
1 propylene ~opolymer and maleic anhydride in the presence
2 of an organic peroxide which ini~iates the addition
3 reactlon by the generation of free radicals. UnfortunatelyJ
4 among other reactions generated therein, a molecule of
s maleic anhydride grafts into two copolymer chains thereby
6 irreversibly crosslinking the copolymer and markedly
7 decreasing its solubility in oil. One approach to
8 overcoming this disadvantage is shown in U.S. Patent
9 3,3789492 which teaches lubricating oil compositions w~lch
comprise a major proportion o a lubricating oil and a
11 minor, but V.I. improving proportion of a reaction product
12 of an unsaturated hydrocarbon polymeric compound, e.g.
13 polybutadiene, with an unsaturated, polar~ nitxogen-
14 containing organic compound, e.g. acrylonitrila, which is
grafted onto said polymeric co~pound by a free radical
16 initiated reaction.
17 Another approach to preparing an oil-soluble
18 nitrogeneous ashless dispersant involves reacting a
19 polyolefin with acrylonitrile and chlorine or bromine at
elevated temperatures9 followed by reacting the product with
21 enough aliphatic amine to replace the halogen at~ms and
22 thereafter with maleic anhydride and finally with an
23 aliphatic amine or polyamine (se~ U.S. Patent 3,9l4,203~.
24 It has now been found that multifunctional V I.
improvers of enhanced dispersancy can be obtained by
26 thermally incorporating a C3~C2~ ethylenically unsatura~ed
27 nitrogen-contalning reactant onto a carbon~to-carbon double
28 bond which is pendant ~rom a substantially saturated
~ hydrocarbon polymer backbone by a thermal ("ene") addi~ion.
The ene reaction~ as report~d in the li~erature,
31 has ~een defined as the indirec~ substituting addi~ion o~
32 ~ compound with a double bond (enophile) to an olefin with
l an allylic hydrogen (ene) and involves allylic shift of
2 one double bond, tr~nsfer of ~he allylic hydrogen to the
3 enophile and bonding between the ~wo unsaturated termini.
4 (See Hofman, "The Ene Reaction", Angew. Chemie,Interna-
tional Edition,Vol. 8~ 556~578 (1969)).
6 The ene adducts are readily distinguished from
7 other functionalized adducts, such as epoxide functionalized
8 adducts reported in UOS. Patent 3~84~,010, since ene
9 adducts maintain a site of ole~inic unsatura~ion and are
characterized by an olefîn to olefin i.e. car~on to carbon
11 bond ~ormation.
12 In their broadest form, this novel class of
13 products of the invention can be characterized as ene
14 adducts of a C3-C24 ethylenically unsaturated nitrogen-
containing reactant and a copolymer of ethyleneJ at least
16 one C3-C50 alpha-monoolefin and a~ least one C5 C24 non~
17 conjuga~ed diene, said adduct containing from about 0.005
18 to about 7% by weight nitrogen and having a number average
19 molecular weight (Mn) of from abo~t 1,000 to abou~ 500~000.
Preferably, the adducts contain about 0.005 to about 0.8
2l wt.% nitrogen, more pre~erably 0.02 to 0.5 wto% nitrogen.
22 The molecular weLght (Mn)is preferably ~rom about 1,000 to
23 10,000 or dispersant appli~ations and from about lO,000 to
24 200,000 for V.I. improver-dispersan~ applications. The
2s adducts of ~he invention are 9ui~ed fox lubrlcating oil
26 applications when they posse 8 su~icien~ oil-solubility,
27 i.e. at least about 10 wt.% at 20C. based on the total
28 weight o the lubrlcating oil composition; howe~er, when
29 oil~nsolubleJ these adducts o~ the i~vention have
application as oil-resistant rubbers ln seals and gaske~s,
31 such as or a~tomobile sutomatic transmissions,
32 The lubricati~g oil compositions of ~his
~ ~ 9 ~ ~ ~
1 invention comprise a major proportion of a lubricating oil
2 and a minor, but V.I.-lmproving proportion of said adducts.
3 Copolymers of ethylene, at least one C3 to C50
4 alpha-monoolefin, and at leas~ one non~conju~atad diene
prepared by means o~ Ziegler-Natta catalysis are well
6 known. These copolymers have a subs~an~ially saturated
7 hydrocarbon backbone chain which cau~es ~he copolymer to
8 be relatively inert to ozone attack and oxidative
9 degradation and side chain unsaturation available for
adduct formation by means of the ene addition.
11 Propylene is normal~y selected as the C3-C50
12 alpha-monoolefin in preparing such copolymers because of
13 its availability and for reasons of economics. Other
14 alpha-monoolefins, such as l-butene, l~pentene, l-hexene,
l-decene, l-dodecene, and l hexade~ene, can be selected
16 in place of or in addition to propylene in preparing such
17 copolymars. The term ~PDM as used herein refers to the
18 copolymers of ethylene, propylene, and at l~ast one
19 non-conjugated diene useful for this invention; sald
diene is usualIy a Cs-C24~ preferably C6-Cl4, diene.
21 An especially preferred class of EPDM is that in
22 which the non-conjuga~ed d~ene is monoreactive. Monoreac-
23 tive non-conjugated dienes have one double bond which
24 readily en~ers the copolymerization reaction with the
ethylene and ~he C3-Cso alpha-monoole~in, and a second
26 double bond w~ich does not, to any appreciable extent, i.e.
27 less than about 20 percent, enter the copolymerization
28 reaction. Copolymers of ~his clas~ have maximum pendant
group unsaturation for a given diene contentJ which
~ unsa~uration is a~ailable for adduct formation.
31 Monoreactive non-conjugat0d dienes which can be
32 selected for preparing the pre~erred clas~ of oil-soluble
1 EPDM copolymers include linear aliphatic dienes of at
2 least six carbon atoms which have one terminal double bond
3 and one internal double bond~ e.g. 1,4-hexadlene, and
4 cyclic dienes wherein one or both of the carbon-to-carbon
double bonds are part of a carbocyclic ring, e.g. 5-
6 ethylidene-2-norbornene.
7 Other suitable non-conjugated dienes include
8 straight chain acyclic dienes such as 1,5~heptadlene,
9 1,6-octadlene; branched chain acyclic dienes such as
5 methyl-1~ 4-hexadiene3 single ring alicyclic dienes such
11 as lJ4-cyclohexadiene~ multi-single ring alicyclic dienes
12 and multi~ring alicyclic fused and bridged ring dienes
13 such as dicyclopentadiene~ 5-methylene-2-norbornene,
14 5-methylene-6-methyl-2-norbornene, 5-methylene-6J6
dimethyl-2-norbornene~ 5-propenyl-2-norborneneJ 5-(3-cyclo-
16 pentenyl)-2-norbornene and 5-cyclohexylidene-2-norbornene.
17 The copolymers which are to be reac~ed with the
18 ethylenically unsaturated nitrogen-containing reactant,
19 e.g~ the nitrile monomers3 to form the ene adducts,
~ comprise about 30 to 85 mole % ethylene; about 15 to 70
21 mole % o the C3-Cso, e-g- C3 to ~189 optimally C3 ~o
22 Cg, alpha-monoolefin, and about 0.5 to 20 mole % of the
23 diene. Preerred are pol~mers consisting of ethylene,
24 said higher alpha-olein and said diene containing
40 ~o 70 mol % ethylene and 2 to 15 mol % dienes, ~he
26 remainder being propylene. On a welght basis usually at
27 least 2 or 3 w~.% o~ the polymer will be the non-conjugated
28 diene. Mixtures of monoolefins and/or mixtures of non-
~ conjugated dienes can be used.
In general, the catalyst compositions used to
31 prepare these copolymers comprise a pri~c~pal cataly~t
32 cons~sting of a transition metal compound from Groups IVb,
~U~4~
1 Vb and VIb of the Periodic Table of the Elements,
2 particularly compounds o~ titanium and vanadium, e.g.
3 VOCl3, and organometallic reducing compounds from
4 Groups IIa, IIb and IIIa, particularly organo-aluminum
ompounds~ e-g- (C2~s)3 A12C13. which are designa~ed as
cocatalysts. Examples of suitable ca~alysts and preferred
7 reaction conditions are shown in U.S, Patent 3,551,336.
8 The copolymers may have molecular weights (Mn)
9 of about 1,000 to 500,000; preferably 10,000 to 200,000;
and usually abou~ 20,000 to 100,000. In general~ polymers
11 having a narrow range of mole ular weight, as determined
12 by the ratio o~ weight average molecular weight (Mw) to
13 number average molecular weight (Mn) are preferred.
14 Polymers having a MW/Mh of less than 10, pre~erably less
lS than 7, and most pre~erably 4 or less are most desirable.
16 Polymers in this range may be obtained by a choice of
17 s~nthesis conditions, such as choice of principal catalyst
8 and ~ocatalyst com~ination~ addition of hydrogen during
19 the synthesis, or post synthesis treatment~ such as
extrusion at elevated temperatures and under high shear
21 through small orifices. While these copolymers are
22 essentially amorphous in character by superficial
23 inspection, they may contain up to 25 pereent by weight of
24 crystalline segments as determined by X-ray or dlf~eren-
tial scanning calor-lmetry.
26 Broadly, ~he e~hylenically unsaturated nitrogen-
27 con~aining reac~an~s contemplat0d by ~he present invention
28 generally consist o carbon, hydrogen and nitrogen and
29 may al50 contain oxygen. These nitrogen-containing
reactants may also contain substituent groups suc~ as
31 keto, hydroxylJ ether, mercapto~ sulfide, sulfoxide,
32 sulfonyl~ etc. Generally, these nitrogen-containing
~g8~
1 reactants will contain about 3 ~o 24 carbon a~ms and
2 must contain an electron withdrawing group in such
3 proximity to ~he unsaturation whereby the olefinic bond
4 is activated by at least one electron-attracting group.
S The terms "electron-withdrawing" and "electron-attracting"
6 are used as synonyms herein.
7 Thus, in its broadest fonm, the ethylenically
8 unsaturated nitrogen-containing reactant may be selected
9 from a broad group of tetra-substituted ole~ins. Thus,
the reactant can be represented by the ge~eral formula:
11 ~ ~l \ / R ~
12 ( / C = C \ ) Nx
13 ~ R2 R4 ~
14 wherein Rl~ R2~ R3 and R4 are independently selected from
one or more electron~attracting groupsJ N represents a
16 nitrogen moiety and x ranges from l to 50. Thus, the
17 only restriction placed upon said groups is that the final
18 reactant contains at least one nitrogen atom. In this
19 manner, the ethylenically unsaturated nitrogen-containîng
reactant may be represented by the above general formula
21 where R13 R2, R3 and R4 are independen~ly selected from
22 ~he groups consisting of hydrogen and Cl to C30 straight
23 and branched chain alkyl, arylalkyl, cycloalkyl, alkenyl,
24 arylalkenyl and cycloalkenyl moieties and/or one or more
reactive group~ of the class consisting of alkyl
26 unsaturation, cyano, carboxyl~ epoxide, thiol3 carbonyl,
27 isocyanate, thionyl, amido, hydroxyJ iminoJ acylhalide,
28 halo, lactamo~ lactono, dicarboxylic acid anhydride,
29 thioIic anhydride, thionic anhydride~ dithionlc anhydride~
disubstituted amino, trisubstituted amino, ureido, isourea
31 and dicarboxylamic acid anhydride or oneohalf o~ cyclic
32 dicarboxylic acid an~ydrides a in malelc anhydride or
9 ~
1 one-hal of cyclic thionic anhydride or one-half of
2 cyclic dithionic anhydride or one-hal of cyclic dicar-
3 boxylic amic acid anhydride or one-half of cyclic N
4 Cl-lg hydrocarbyl imides suçh as N-dodecylmaleimide and
pyrrolidine.
6 The term "NX", as used in ~he above formula, is
7 designed to indicate that the nitrogen-containing group
8 or moiety is present in one or more of the "R" groups and/or
9 several nitrogen-containing groups may be present in the
same "R" group; however, there must be at least one N-
11 containing moiety in the reactant with a preferred range
12 of X of 1 to 10, more preferably 1 to S. Thus, in acrylo-
13 nitrile, Rl~ R2 and R3 are hydrogen atoms while X~l;
14 that is, R4 is a "CN" group. Examples of these groups
include alpha-chloroacrylonitrile; N,N-dibutyl acrylamide;
16 acrylamide; N-t-octyl acrylamide; thioacrylamide; N-n-
17 octylacrylamide; N~acryloyl-morphiline, thioacrylamide;
18 ammonium acrylate; vinylidene cyanide; N,N-dimethylamino
19 ethyl methacrylate; t-dodecylaminoethyl acrylate;
N-octyl maleimide; N-vinyl-S-methyl-2-pyrrolidone;
21 pyrrolidinyloctyl vinyl sul~ide; N-vinylethyleneurea;
22 N-vinyl-1,2-propyleneurea; N-vinylcarbazole; butanamido-
23 decyl vinyl ether; ace~amidooctadecyl vinyl ether;
24 ureidoethyl vinyl ether; and 2-vinyl-5-methylpyridine; and
tetracyanoethylene.
26 One preerred type of nitrogen-containing
27 reactants, i.e. unsaturated~ polar, nitrogen-con~aining
28 enophiles~ to which the present invention is directed,
~ has the ormula
H R' O R"
"
31 RC - C - C - X - tCH2~n ~ N \
3? R " '
84~L
1 wherein X is oxygen~ or an NR group, n is a whole number
2 from 1 to 5~ preferably 2 to 5, R and R' are either
3 ~ydrogen or a Cl to C4 ~lkyl group~ R" and R " ' are each
4 Cl to C12, preferably Cl to C4, hydrocarbyl groups, e.g.
alkyl groups. The various R groups may be the same or
6 different.
7 Specific examples of compounds which may be
8 employed as the preferred nitrogen-con~aining enophlles
9 include dimethylaminoethyl methacrylate, diethylamino~
propyl methacrylamide~ di(isobutyl) aminoe~hyl methacryla~e,
11 methylisobutyl-aminopropyl acrylate, 4-vinyl pyridineJ
12 ethylene imine, N-vinyl pyrrolidone etc. Mixtures of
13 various nitrogen-containing enophiles may be used. Another
14 preferred type of nitrogen-containing enophiles, i e.
unsaturated, polar, ni~rogen-containing organic compounds,
16 to w~ich the present invention is particularly directed
17 are nitriles having the formula:
18 X X
19 R-CH=C-CN or CH2=CH-CH-CN
wherein ~ is a hydrogen atom or a lower alkyl, e.g~,
2~ methyl, ethyl, and the like, X is a hydrogen atomJ a
22 halogen atom, a cyano or a lower alkyl group9 e.g. methyl,
23 ethyl, propyl, butyl and the like~ Examples of nitrile
24 monomers which are contemplated by the aforedescribed
~tructure include, acrylonitrileg methàcrylonitrile, alpha-
26 bromoacrylonitrile~ alpha-chloroacryloni~rile, vinylidene
27 cyanide, allyl cyanide, and the like.
28 The thermal ene addition o the ethylenically
29 unsaturated nitrogen-containing reacbant to the saturated
ethylene backbone copolymer having pendant group carbon-to-
31 carbon unsaturation i8 theorized to occur by the ~ollowing
32 reaction (using a copolymer o~ ethylene, propylene and
- 10 -
1 5-ethylidene-2-norbornene and acrylonitrile as the
2 thermal ene reactants) equation:
3 Polymer
4 Backb ne ~ CH3
~ ~ H hea~
H2C=C-CN - :~
~ 0 ~R3
13 A molecule of acrylonitrile adds to the polymer
14 at the site of pendant group unsaturation and involves
allylic shift of one double bond, transfer of the allylic
16 hydrogen to the acrylonitrile and thus bonding between the
17 two unsaturated groups. It is understood that the exocyclic
18 olefinJ i.e. of the 5-ethylidine-2-norbornene, can only
19 shi~t away from the bridgehead to the C5 C6 position. A
shift of the double bond toward the bridgehead, i.e.
21 C~-Cs, is for~idden by Bredt's rule.
22 Ene adducts of this invention can be prepared by
23 any process which intimately mixes the nitrogen-containing
24 reactant or reactants with the copolymer and concurrently
or subsequently heats the mixture to a temperature where
26 thermal ene addition occurs without appreciable generatlon
27 o~ free radicals. Reaction temperatures will generally be
28 at least 100G. to obtain addu~t formation at acceptable
29 rates and less than about 250C. to avoid any signiflcant
copolymer breakdown and/or homopolymerization o the
- 11
~3
l ethylenically unsaturated nitrogen-containing reactant~
2 Although preferred temperature ranges will vary with the
3 particular copolymer and reactant and can readily be
4 determined by one skilled in the art; optimally, it ranges
from about 150C. to about 225C. J e.g. about 170C.
6 Mixing of the reactant and copolymer can ~e by blending
7 together nea~ or with a solvent in an internal mixer or
8 extruder. Preferably the blending and subsequent "ene"
9 reaction is carried out in a hydrocarbon solvent at
elevated temperatures~
ll Thus in the preferred process, the ethylene
12 backbone copol~mer is dissolved in a hot solvent such as
13 benzene, heptane, cyclohexane, optimally, mineral oil, and
14 the reactant e.g~ acrylonitrile, is introduced into the
solu~ion. The solution is heated at from about 150C. to
16 225C. for several hours in the substantial absence of air
17 or oxygen and, preferably under a blanket of inert gas,
18 e~g.~ nitrogen. Modest elevated pre~sures o~ the inert
l~ gas can be used to maintain the reactant in solution.
Should a solvent other than mineral oil be usedg diluent
21 oil maybe added and the light solvent and unreacted
22 ethylenically unsaturated ni~rogen containing reactant
23 are then removed. The remaining residue is a solution of
24 ene adduct in diluent oil, particularly useful as an
additive package for lubricating oils.
26 For said reactants which readily homopol~merize
27 under free radical conditions~ the ~ollowing method may be
28 utiliæed in order to moderate ~he generation oE ~ree
~ radicals:
Dissol~e said copol~mer, said reactant and up to
31 about 1 wt.% (based on weight of said reactant) o a free
32 radical scavenger (inhibitor such as hydroquinone to
- 12 -
1 eliminate homopolymerization of said reactant~ in a hot
2 solvent, such as mineral oîl, heptaneJ benzene, or cyclo~
3 hexane; andJ heat to reac~ion temperaturesJ e g. from
4 about 150C. to 225C. for several hours in the substan-
tial absence of oxygen (flushed several times with nitrogen
6 prior to starting ~he reaction) and under a blanket o~
7 modestly pressurized inert gas, such as nitrogen. If the
8 solvent is not oil, then diluent oil may be added and the
9 light solvent and unreacted nitrile monomer can be readily
removed. The reamining residue is a mixture of ene adduct
11 of the ethylene copolymer and said reac~ant in diluent oil.
12 The proportions in which the above-described
13 nitrogen-containing reactants are to be used may range
14 widely according to the abilîty of said ethylene copolymer
and said nitrogen-containing reactant to react with each
16 other, but normally should range from about 0~1 to 400,
17 preferably about 10 to about 200 parts by weight of said
18 nitrogen-containing reactant to 100 parts by weight of said
19 ethylene backbone copolymer.
It is generally desired to form oil-soluble
21 adducts containing about 0O005 to 0 6%~ and preferably
22 about 0.02 to 0.50% by weight nitrogen (all of said % by
23 weight nitrogen values in this speci~ication determined by
24 the Kjeldahl method). Adducts containing such quantities
of nitrogen have sufficient dispersancy sites for additive
26 applications, to enhance lubricatlng oil performance. To
27 achieve a desired degree o adduct ormation within a
28 reasonable tlme~ high concentrations of reactants (usually
29 a substantial excess of nitrogen-containing reactant) are
helpful~ One will generally select an ethylene copolymer
31 having about thrice the amount of pendant group unsatura-
32 tion as ls stoichiometrically tbased on nitrogen equivalent)
- 13 -
~ 8 ~
1 required for the desired amount of ni~rogen incorporation.
2 SimilarlyJ about two to ive times as much nitrogen-
3 containing reactant (based on equivalent nitrogen) is
4 added as is desired in the oil-soluble adduct. ConverSiQn
of about 20 to 50% of the nitrogen containing reactant
6 will result in copolymer adduct having the desired composi-
7 tion. For example, if one desires to obtain an adduct
8 derived rom an ethylene/propylène/5-ethylidene-2-
9 norbornene copolymer having 0.15 wt.~/o nitrogen content,
he could conveniently mi~ said copolymer having 0.08 moles
11 pendant group unsaturation per kilogram of copolymer with
12 0.2 moles of acrylonitrile as s~id reactant and heat the
13 mixture for a time sufficient to convert 25% of the
14 nitrile reactant thereby obtaining the desired product~
If desired, two or more different ethylene backbone co-
lb polymers and/or two or more different types of nitrogen-
17 containing reactants can be reacted.
18 Ene adducts of the invention broadly will con-
19 tain from 0.005% to about 7% by weight nitrog0n. As the
nitrogen content increases above about 0O6 wt.%, the ene
21 adduct becomes increasingly less soluble in hydrocarbons
22 such as mineral oil w~ereby the adducts utility as a
23 hydrocarbon resistant material is increasedO ~urther, the
24 ene adduct undergoes reduced elasticity as the nitrogen
content increases above about 1 wt~/o~
26 These ene adducts which include polar groups,
27 such as imides, amides, esters, anhydrides, epoxides,
28 nitriles (preferred), etc.~ ma~ also be hydrolyzed to
29 produce novel polymeric compositions which can be used
per se as a dispersant and/or V.I. improver or which can
31 be used as an intermediate ~or the preparation of other
32 novel polymers are particularly useful as multifunctlonal
1 34~
1 V.I. improvers for mineral oil lubricantsO When used ~s
2 intermediates, these hydrolyzed ene adducts of the
3 invention can be tailored ~o provide varying functional
4 groups requisite for a given application. For example,
as in the case of an adduct produced with acrylonitrile,
6 the resultant ene adduct can be readily hydrolyzed to
7 provide sites for reaction with alkylene polyamines to
8 provide enhanced lube oil dispersancy.
9 The hydrolysis of these ene adducts of the
lo invention is readily carried out under alkaline (base
11 hydrolysis) or acidic (acid hydrolysis) condit~ons.
12 Suitable bases include alkali metal and alkaline ear~h
13 metal bases such as sodium hydroxide, potassium hydro~ide,
14 calcium hydroxideS barium hydroxide and the like. Suitable
acids are mineral acids such as sulfuric acid~ nitric acid,
16 hydrochloric acid and the like~ Both the base and acid
hydrolysis can be carried out at a temperature ranging
18 ~rom about 0CO to about 225C., prefcrably from about 20C.
19 to about 125 C. The hydrolysls is usefully carried out
at relatively mild conditionsg i-0O only a catalytic amount
21 of the hydrolyzing agent is employed.
22 The corresponding carboxyl ~ontaining adducts
23 either in their original solution or aft2r isolation and
24 redissolving in suitable hydrocarbon solvents o the ~ype
mentioned are contacted with approximately equimolar
26 amounts of nucleophilic reagents to convert the carboxyl
27 derivatives into the new nucleophilic derivatives.
28 Examples of suitable ~unctional nucleophilic
reagent~ include water, Cl to Cl3 alcohols, Cl to Cl8
pre~erably C2 to Cl2 monobasic acids, Cl to Cl8 amines,
31 C2 ~o Cl8 amidesg phenol, thiophenol, alkyl phenols or
32 thiophenol wi~h l to 4 alkyl groups of l to 12 carbons
- 15 -
~g~
1 each, Cl to Cl~ alkyl mercaptans, dialkylaminophenolsJ
2 N3N-dialkylamlnoarylene diamines, alkyl imidazolines~ aryl
3 ether alcohols, alkyl ether alkylene amines and the like.
4 Further descriptions of preferred ~orms of some
of these functional agents follow:
6 The Cl to C13 alcohols can be branched or
7 unbranched saturated, alipha~icJ àromatic, primary,
8 secondary~ or tertiary alcohols, preferably monohydric
9 alcohols, but including other alcohols. Particularly
lo preferred are polyhydric alcohols of 2 tv 6 hydroxy groups
11 as well as amino alcoholsO Examples include methanol,
12 isopropanol3 C8 Oxo alcohol, lauryl alcohol, benzyl
13 alcohol, ethylene glycol, monododecyl ether o triethylene
14 glycolJ glycerol, pentaerythritolJ glucose, dipentaery-
thritol, sorbitol, Cellosolve~ Carbitol~ diethanolamine,
16 etc.
17 The Cl to C18, preferably C2 to C12 monobasic
18 acids, can be branched or unbranched9 saturated, aliphatic,
19 monocarboxylic acids, preferably the saturated fatty acids
such as acetic acid, butyric acid, caproic acid, lauric
21 acid, etc.
22 T~e Cl to C18 amines can be branched or unbranched
23 saturatedJ aliphatic, primary or secondary amines, contain~
24 ing 1 to 8 nitrogens, preferably mono- or dlamines, such as
ethylamine~ butylamine, sec. butylamine, diethylamine, etc.,
26 but ineluding higher polyamines such as alkylene poly-
27 amines/ wherein pairs of nitrogen atoms are joined by
28 alkylene groups of 2 to 4 carbon atoms. ThusJ polyæmines
~ of the formula:
NH2(cH2)n-[NH(~2)n]m-~H2
31 are lncluded where n is 2 to 4 and m is 0 to 6. Examples
32 of such polyamines ~nclude tetraethylene pentamine,
- 16 -
1 tripropylene tetramine, N-aminoalkyl piperazines, e.g.,
2 M-(2-aminoethyl) piperazine, N~N'-di(2-aminoethyl)
3 piperazine~ etc. Particularly preferred are the C4 to Cl3
4 N,N-dialkylamino alkylene diamines such as N,N-dimethyl-l,3-
propylene-diamine, etc Also, preferred is tetrae~hylene
6 pentamlne, as well as corresponding commercial mixtures
B 7 suc~ as "Polyamine HJ ~I and "Polyamine 500~"
8 The alkyl phenols or thiophenols are those with
9 l to 4 alkyl groups, preferably averaging l to 2 alkyl
groups, wherein the alkyl groups each contain l to l2
11 carbon atoms which can be straight chain or branched chain12 such as cresol, n-octyl phenol, di-n-octyl phenol,
13 monoisobutyl thiophenol~ etc.
14 The above-discussed reactions with the hydrolyzed
adduct can be carried by procedures well known in the art.
16 For the preferred amine functionalization the amination of
17 the carboxylate groups is usefully carried out in a
18 solution by reaction with the hydroly2ed ene adduct
19 dissolved in a solvent such as mineral oil. The formation
of the amide dispersants in high yield can be effected by
21 adding from about O.l to l, preerably about 0.7 to l~ molar
22 proportions of alkylene polyamine per molar proportion o~
23 carboxylate groups per kilogram of the hydrolyzed adduct to
24 said solution and heating the mixture at 140C. to 165C.
untll the appropriate amount of water o~ reaction is
26 evolved.
27 In some applications, it is useful to modify
28 the aminated hydrolyzed ene adduct dispersant by su~sequent
~ boration as generally taugh~ in U.S. Paten~s 3,087~936 and
3,254,025. This is readily accomplished by treating said
31 aminated ene adduct with a ~oron compound selected from
32 the class consi~ting of boron oxide, boron halides, boron
17 -
1 acids and esters of boron acids in an am~unt to provide
2 from abou~ 0.3 ~o 0.9 wt.% boron, based on the total
3 weight of said borated, aminatedg hydrolyzed ene adduct.
4 The nitrile ene adduct can also be converted to
the corresponding imine or amine or mixtures of both through
6 reductive procedures well known to one skilled in the art.
7 Although the preferred method of reduction may be accom-
8 plished with hydrogenation catalysts such as copper,
g rhodium, palladium or nickel at elevated temperatures and
pressures, li~hium aluminum hydride, sodium borohydride,
11 may also be used. Another suitable method of converting
12 said nitrile to an amine is ~hrough the use of Grignard
13 reagents.
14 It is understood that the placement of a nitrile
such as described above onto said chain now provides a
16 site for further reactions such as chlorination, bromina-
17 tion~ alkylation, or the like. Once halogenated, this
18 position may be reacted with various nucleophiles as
19 described above to produce a new type of ~unctionality.
For example, the haloger~ may be displaced with an amine9
21 to provide additional functionality.
22 Generallyg the number average molecular weights
23 of the final polymeric adduc~s of ~he present invention,
24 employed as lubricant additives, will be in the ran~se of
about lO00 to about 50a,000 and pre~erably will be in the
26 ran~e of about l0,000 to 200,000. However, it will be
27 understood that higher or lower molecular weight products
28 may l:~e prepared, if desired. All molecular we:Lght values
-29 se~ forth in this specification are number average molecular
welghts ~n) as determined by vapor phase osmometry (VPl))
31 and membrane osmometry.
32 When the adduct additives of the present invention
1 are employed in lubricating oils3 they are preferably added
2 in proportions o~ about 0.01 to about 20.0% or more~ prefer-
3 ably about 0.1 to 10.0%, and more preferably about O.S to S.0
4 percent by weight. The proportions giving the best results
will vary somewha~ according to the nature of the adduct ad-
ditive, the nature of the lubricating oil base stock to which
7 it is added and the specific purpose which the lubricant is
8 to serve in a given case. For commercial purposes9 it is
9 convenient to prepare concentrated oil solutions in which the
lo amount of adduct additive in the composition ranges from 10
11 to about 49% by weight~ and to transport and store them in
12 such form. In preparlng a lubricating oil composition for
13 use as a crankcase lubricant the adduct additive concentrate
14 is merely blended with the base oil in the required amount.
The products of the present invention may be
16 employed not only in ordinary hydrocarbon lubricating oils
17 but also in the "heavy duty" type of lubricating oils which
8 have been compounded wlth such detergent ~ype additives as
19 metal soaps, metal petroleum sulfonates, metal phenates,
metal alcoholates and metal alkyl phenol sulfides.
21 The lubricating oil base stocks used in the
22 compositions of this invention may be straight mineral
23 lubricating oils or distillates derived ~rom paraffinic,
24 naphthenic, asphaltic, or mixed base crudes~ or, i desired~
2s various blended oils may be employed as well as residuals,
26 particularly those ~rom which asphaltic consti~uents have
27 been careully removed. Hydrogenated oils~ white oils, or
28 shale oil may be employed as well as synthetic oils
29 prepared, or example~ by the polymerizatlon o~ olefins or
by the reaction of oxides of carbon with hydrogen or
31 by the hydrogenation of coal or its products or one may
32 use es~ers of mono-ordibasic acids, es~ers o glycols) or
- 19 -
~ ~ 9 ~ ~ ~
l complex esters~ etc. Mixtures of any of the above or
2 wi~ mineral, animal or vegetable oils in any proportions
3 may al~o be usedO
4 E~AMPLE 1
6.75 grams o~ an ethylene copolymer consisting
6 of about 50 wt.% (63 mol %) e~hyleneg 41 wt,% (34 mol %)
7 propylene and 9 wt.% (3 mol %) of 5-ethylidene-2-nor-
8 bornene having a Mn of about 60,000, was dissolved in 83.25
9 grams of Solvent-150 Neutral (S150N) mineral oil was placed
in a 500 ml. reaction vessel suppor~ed on an electrio
ll heater so that the temperature of the reactants could be
12 controlled. 2.7 grams (0O05 moles) of acrylonitrile
13 was introduced into the reaction vessel ater which the
14 vessel was flushed with nitrogen and subjeoted to a
nitrogen pressure of about two inches of mercury which
l6 elevated pressure was maintained during the entire reaction
17 period. The reaction was carried out by heating the
18 ingredients with agitation at a temperature o~ about 150C.
19 for about 6 hours. T~e reaction vessel was thereafter
cooled to room temperature and the adduct product was
21 freed of other ma~erials by dialysis against a semiper-
22 meable rubber membrane overnight with boiling he~ane. The
23 dialyzed residue was ~hen dried for about 12 hours in a
24 vacuum o~en maintained a~ about 60C. and 120 ~m Hg
pressure whereby 4.15 gram~ of product adcluct w~s obta-lned
26 which contained 0.074 weight /O nitrogen.
27 EXAMPLE 2
28 The procedure of Example 1 was followed with
~ the following variations:
The ethylene copol~mer contains about 50 wt~/o
31 (61 mol %) ethylene~ ~5 wt.% (37 mol /O) propylene and
32 5 wt.% (2 mol %) 5-ethylidene-2-norbornene with a Mn o
- 20 -
1 about 45,000; 5 gxams of said polymer was dissolved in
2 60 grams of said mineral oil; 1 gram (0.006 moles~ of
3 N,N-dimethylamino ethyl methacrylate replaced the
4 acrylonitrile; and the reaction was carried out at a
temperature ranging from 190 to 210C~ ~or 7 hours;
6 3.0 grams of an adduct product ~ontaining 0.03 wt.%
7 nitrogen was obtained.
8 EXAMPLE 3
9 The process of Exa~ple 1 was followed however
the ingredients and conditions was varied in the following
ll manner:
12 The ethylene copolymer contained about 50 wt.a/o
13 (60 mol %) ethyleneg 46 wt~% (38 mol %) propylene and
14 4 wt.% (2 mol %) 1,4~hexadiene wit~ a Mn of about 50,000.
(This ethylene copolymer iæ available as Nordel 1320 from
16 E.I. duPont de Nemours & Co.) 2.25 gram~ of said polymer
17 was dissolved in 67.75 grams of Solvent 150 N mineral oil;
18 the amount of acrylonitrile was 20 grams ~10 grams added
19 after 5 hours); the reaction conditions were 150 to 160G~
for 12 hours; and the product yield was 2.1 grams of the
21 adduct product containing 0.20 wt.% nitrogen.
22 EXAMPLE 4
23 In this example the general procedure of Example 1
24 was ~ollowedJ however, the polymerization vessel was
replaced with a 3-liter rocker bomb lnto which 200 grams
26 of the ethylene copol~mer o~ Exa~ple 1, 2200 ml of heptane,
27 25 grams (0.47 moles) of acrylonitrlle and 2 grams of
28 hydroquinone were introduced and the vessel sealed. The
atmosphere in the vessel was replaced wi~h ni~rogen and
then pressuxized with nitrvgen to about 500 psi at room
31 temperature. The bomb was rocked at a temperature from
32 about 171 to 179Co for 19 hours. The product was
- 21 -
separated by precipitation from me~hanol and yielded 105
2 grams of recovered adduct conkaining about 0.084 wt.~/o
3 nitrogenO
4 EXAMPLE 5
The 3-liter rocker bomb described above was used
6 in t~is example. 200 grams of the ethylene copolymer of
7 Example 2, 2200 ml o heptane~ 11 grams tO.21 moles~ of
8 acrylonitrile and 1 gram of hydroquinone were introduced
9 and the bomb sealed. The contained air was replaced with
nitrogen and then the reactor was pressurized with nitrogen
ll to about 500 psi at room temperature. The bomb was seal~d
l2 and rocked at a ~emperature o 150 for 10 hours then 200
l3 for 2 hours. The reactor was next cooled, 200 ~c of
l4 sample taken) then 100 grams (1.88 moles) of additional
acrylonitrile added, and the above procedure repeated at
16 a temperature o 150 or 12 hours. The reactor was cooled
17 and the pro &ct recov~red by precipitation from me~hanol
18 to yield 143 g. of adduct which contained 00092 wt~%
19 nitrogen.
~X~ _ 9
21 The following examples are all set forth in
22 tabular form in Table I.
.
- 22 -
. - . .. , . :
., . -: - , .~ . ,
O H -1 O
O O O 0 ~0
_
C`J O0~ 5
~1 ~ ~ ~1 ~ O
~ ~ ~ ~ ~ I ~
~7 O ~ O
o I~ C~l O
. ~ ~ .
O O O O ~O
u~
q~
.~ 4_~
.~ a~ oo 00 00 g ~
~1
r 9 c
~ ~ . o r~
c) .,~ ~ ~ ~ ~ ~ o
¢ ~ :~
- , ~.,
~0 æ~ o ,~ ~
a
oP
~ ~ o ~ ~ ~
~, ~ o
C~
~ o I :~
;~
E~ 4
O O
23
.
1 EXAMPLE 10
__
2 200 grams of the copolymer of Example 2 (reac~ed
3 as a 10 wt.% solution in hexane) was processed similar to
4 the procedure of Example 5 with the following variations:
the pressure was 400 psi; the bomb rocked at 170C. for
6 15 hours; the reactor contents were filtered prior to
7 precipitation; and, the resulting yield of product after
8 drying ~n a ~acuum oven was 130.7 grams of an ene adduct
9 which con~ained 0.075 wt.% nitrogen~
EXAMPLE 11
.
ll (A) The following illustrates hydrolysis of an
12 ene add~ct. Into a dry flaskg under a nitrogen atmosphere
l3 was carefully placed a sample of the ene adduct of Example
14 10 (5 g. of adduct) in toluene ~100 ml) and refluxed wlth
3 g. potassium hydroxide dissolved in 15 cc distilled water.
16 The refluxing took place at 90~94C ~or 6.0 hours. The
17 solution was cooled to amblent tempera~ure and the hydrolyzed
18 copolymer recovered by precipi~ation from methanol (2 liter).
19 The resulting copolymer was washed with me~hanol (500 ml)
then dried in a vacuum oven at 100C for about 15 hours~
21 after which 4.05 g o copolymer was recovered. The nitrogen
22 level of the resulting copolymer was 0.03 wt.%.
23 ~B) The following illustra~es amînation of a
24 hydrolyzed ene adduct. 2 g. of the copolymer o Example
2S ll(A3 above was dissolved in toluene (100 ml3 ~hen care-
26 ully re1uxed (110C) under a ni~rogen atmosphere with a
27 solution of 0.5 g diethylene triamine for 5 hrs. The
28 ~olu~ion was cooled to ambient temperature and ~he amina~ed
29 copolymer recovered by precipita~ion from me~hanol ~o yield
1.9 g of product (95% yield). The nitrogen level o the
31 resulting product wa~ 0~09 wt~%.
- 2~ -
~ ~9 ~ 8
1 EXAMPLE 12
2 In thîs example the ef~icacy o~ the adducts of
3 this invention, particularly with regard to their unusual
4 dispersancy properties in lubricating oil applications, is
illustrated by comparison with a commercially available
B 6 multifunctional V.I. impro~er, sold as Lz 3702 by Lubrizol
7 Corporation of Cleveland, Ohio7 in a Sludge Inhibition
8 Bench Test (hereinafter designated SIB). The SIB test has
9 been found, after a large numbPr of evaluations~ to be an
excellent test for assessing the dispersing power o
11 lubricating oil dispersant additives.
12 The mediu~ chosen ~or the SIB test was a used
13 crankcase mineral lubricating oil compositlon having an
14 original viscosity of about 325 SUS at 38C~ that had been
used in a taxicab that was driven generally for short trips
16 only, thereby causlng a buildup of a high concen~ration of
17 sludge precursors. The oil t~at was usPd contained only a
18 refined base mineral lubrlca~ing oil, a viscosi~y index
19 improver, a pour point depressan~ and æinc dialkyldlthio-
phosphate antiwear additive. The oil contained no sludge
21 dispersant. A quantity of such used oil was acquired by
22 draining and refilling the taxicab crankcase at l000 2000
23 mile intervals.
24 The Sludge Inhibition Bench Tes~ is conduc~ed in
the following manner. The aforesaid used crankcase oil~
26 which is milky brown in color~ is ~reed of sludge by
27 c~ntriuging for l hour at about 39,000 gravitles (gs.~.
28 The resulting clear bright red supernatan~ oil is then
~ decanted from the insolublP sludge particles ~hereby
separated out. However, the supernatant oil still contains
31 oil-soluble sludge precursors which on heating under the
32 conditions employed by this test will tend to form additional
/t ~a f,/rD ~Y~ 4 - 25
, - -.~ ' ' .
4~
l oil-insoluble deposits of sludge. The sludge inhibiting
2 properties of the additives being tested are dstermined by
3 adding to portions of the supernatant used oil, a small
4 amount, such as 0.5, 1 or 2 weight percent~ on an active
ingredient basis, of the particular additive being tested.
6 Ten grams of each blend being tested is placed in a stain-
7 less steel centrifuge tube and is heated at 280F. for
8 16 hours in the presence of air. Following the heating~ the
9 tube containing t~e oil being tested is cooled and then
centrifuged for 30 minutes at about 399 000 gs. Any
11 deposits of new sludge that form in this step are
2 separated from the oil by decanting ~he supernatant oil and
then carefully washing the sludge deposits wlth 25 ml. of
pentane to remove all remaining oil ~rom the sludge. Then
the weight of the new solid sludge that has been formed in
16 the test, in milligrams, is determined by drying the
17 residue and weighing it. The results are reported as %
18 of sludge dispersed by comparison wlth a blank not
19 containing any additional additive. The less new sludge
formed, the larger the value of percent sludge dispersant,
21 and the more effective is the additive as a sludge
22 dispersant. In other words, if the additive is effective,
23 it will hold at least a portlon of the new sludge that forms
24 on heating and oxidation~ stably suspended in ~he oil 50
it does not precipitate down d~ring ~he centrifuging. Using
26 the above~desoribed testJ the dispersant action o~ the
27 several adducts prepared in accordance with this invention
28 were compared with the dispersing power of a dialyzed
~ product obtained rom dialysis of a commercial dispersan~
previously referred to as Lz 3702. Sufficient dialyzed
31 residue which analyzed about 0.~ wt.% nitrogen, was
32 dissolved in S-l~ON mineral oil ~o provide a 10% active
- 26 -
~ 9~
1 ingredient concen~rateO The dialyzed residue and adduct
2 products of the inven~ion were approprlately diluted in
3 mineral oil ~o furnish the 0.0125~ 0.025, 0.05 and .1 wt.%
4 of added additive test samples~ The test results are
S given in Table II.
6 ~
7 Concn. gms.
8 polymer/10 gms. % sludge
9 E a~ple Poly~ r of Used Oil dispersed
12-A Example 1 .1 96
ll .05 88.4
1~ .025 37.5
13 12-B Example 2 .1 82
1~ .05 53
12-C Example 3 .1 52~5
16 .Q5 37.6
17 12-D Example 4 ~1 79 r 9
18 05 49-3
19 12-~ Example 5 .1 91~S
.0~ 80l1
21 .025 62.0
22 .0125 36~7
23 12-F Example 6 ~1 96
24 .05 73
12-G Example 7 .1 79,3
26 .05 72.4
27 12-H Example 8 .1 95.0
2~ .05 g0.3
29 .~25 32.0
12-I Example 9 .1 82.7
31 ~05 71.6
32 12-J Lz 3702 .1 88.7
33 .Q5 73~3
34 .025 30.5
.0125 4.8
36 12-K Example 11 0.1 78
37 0~05 79
38 The e~e adducts o ~xamples 1~11 are derlved
39 from copolymers which have viscosity index improving
properties for lubricating oils. The data of Table II
41 thereore shows that the multifunctional V.I., ene adducts
- 27 -
l and ene adduct derivatives o~ the invention possess
2 superior dispersancy to a commercially available multi-
3 functional V.I, additive. The superior dispersancy is
4 obtained at a much lower nitrogen content, e.g. the
nitrogen of Example 1 is 0.074 wt.% whereas that of
6 Lz 3702 is 0.4 wt.%. It is also apparent from Table II
7 that an adduct prepared from a polymer containing a cyclic
8 nonconjugated diene is superior in dispersancy to one
9 obtained from a polymer containing a linear nonconjugated
diene (compare Example 12-A with Example 12-G).
1 1 ~:~
12 The nitrogen-containing adduct of the ethylene
13 copolymer prepared in Example 9 was tested as a viscosity
B 14 index improver in ENJ 102~ a blended mineral lubeloil
containin~ O.S wt.% of a polymeric pour depressant. The
6 blend was of two para~finic, solvent refined neutral oils,
17 one of which had a viscosi~y o about 150 SUS at 100F.
18 and constituted 25.75 weight percent of the blend; and,
19 the other had a viscosity of about 300 SUS at 100F~ and
constituted 73.75 weight percent of the blend. ~he
21 comparative resul~s of the adduct-modified ENJ 102
22 (Example 13-A) and the ENJ 102 (Example 13-B) are
23 summarized in Table III
24 TABLE III
K.V. (Cs) Vis. (P) Pour Pt. % sonic
26 Example @99C. ~-18C. _ _ breakdown
27 13-A 12.21 23.5 -37 29
23 13-B 6.26 19.2 37 0
The data of Table III shows that an adduct of this
invention has V.I. improYing charact~ristics while exhibiting
31 no d0trimental loss in pour point depression and suitable
32 shear stab~lity as reprssented by sonlc breakdown.
~ ~J~ 8 -
