COPOLYMERS OF .alpha.-OLEFIN AND ALKYLENE CARBOXYLIC ACIDS

COPOLYMERES D'ACIDES .alpha.-OLEFINE ET D'ALKYLENE CARBOXYLIQUES

English Abstract

ABSTRACT OF THE DISCLOSURE
A method for viscosifying control of an
organic liquid which comprises adding a sufficient of a
copolymer to such organic liquid to increase the
viscosifying of such organic liquid, said copolymer
having the formula:
<IMG>
wherein R1 is an alkyl group having 1 to 25 carbon
atoms, R2 is an alkylene group having 3 to 17 carbon
atoms, z is a hydrogen a mixture of hydrogen and an
alkyl group having 1 to 25 carbon atoms, x is 95.0 to
99.95 mole % and y is .05 to 5.0 mole %, and addi-
tionally this copolymer can be complexed with an amine
containing polymer, wherein the complex functions as
viscosification agent.

Claims

- 38 -
THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS
FOLLOWS:
1. A copolymer which has the formula:
<IMG>
wherein R1 is an alkyl group having about 1 to 25 carbon
atoms, R2 is an alkylene group having 1 to 17 carbon
atoms, z is a mixture of hydrogen and an alkyl group
having 1 to 25 carbon atoms, x is 95.0 to 99.95 mole %
and y is .05 to 5.0 mole %, wherein H comprises 55 to 95
mole % of z.
2. A method for viscosifying control of an
organic liquid which comprises adding a sufficient of a
copolymer to such organic liquid to increase the
viscosifying of such organic liquid, said copolymer
having the formula:
<IMG>

- 39 -
wherein R1 is an alkyl group having 1 to 25 carbon
atoms, R2 is an alkylene group having 3 to 17 carbon
atoms, z is a mixture of hydrogen and an alkyl group
having 1 to 25 carbon atoms, x is 95.0 to 99.95 mole %
and y is .05 to 5.0 mole %, wherein H comprises 1 to
45 wt.% of z.
3. A copolymer which has the formula:
<IMG>
wherein R1 is an alkyl group having 1 to 25 carbon
atoms, R2 is an alkyl group having 3 to 17 carbon
atoms, x is 95.0 to 99.95 mole % and y is .05 to 5.0
mole %.
4. A method of viscosifying an organic liquid
which comprises adding a sufficient quantity of a
copolymer to said organic liquid to increase the
viscosity of said organic liquid, said copolymer having
the formula:

- 40 -
<IMG>
wherein R1 is an alkyl group having 1 to 25 carbon
atoms, R2 is an alkylene group having 3 to 17 carbon
atoms, x is 95.0 to 99.95 mole % and y is .05 to 5.0
mole %.
5. An antimisting hydrocarbon solution com-
prising a hydrocarbon mixed with a copolymer of an
alpha-olefin and a vinyl alkylenecarboxylic acid,
wherein the concentration of said copolymer in said
hydrocarbon is 0.05 to 2 grams per 100 ml of said
solution, wherein such copolymer has the formula:
<IMG>
wherein R1 is an alkyl group having 1 to 25 carbon
atoms, R2 is an alkylene group having 3 to 17 carbon
atoms, Z is a mixture of hydrogen and an alkyl group
having 1 to 25 carbon atoms, x is 95.0 to 99.99 mole %
and y is 0.01 to 5 mole %, wherein hydrogen comprises 55
to 99 mole% of Z.

- 41 -
6. An antimisting hydrocarbon solution com-
prising a hydrocarbon mixed with a copolymer of an
alphaolefin and a vinyl alkylenecarboxylic acid,
wherein the concentration of said copolymer in said
hydrocarbon is 0.05 to 2 grams per 100 ml of said
solution, wherein said copolymer has the formula:
<IMG>
wherein R1 is an alkyl group having 1 to 25 carbon
atoms, R2 is an alkylene group having 3 to 17 carbon
atoms, x is 95.0 to 99.99 mole % and y is 0.01 to 5
mole %.
7. A process for increasing the viscosity of
a hydrocarbon liquid having a viscosity of at least 10
cP which includes the steps of:
(a) forming a first solution of an organic
hydrocarbon liquid and a copolymer of an alpha-olefin
and a vinyl alkylenecarboxylic acid having an acid
content of from 0.01 to 10 mole percent, wherein said
copolymer of said alpha-olefin and said vinyl alkylene-
carboxylic acid has the formula:

- 42 -
<IMG>
wherein Z is a mixture of H and an alkyl group having 1
to 25 carbon atoms, wherein H comprises 55 to 99 mole %
of Z, R1 is an alkyl group having 1 to 25 carbon atoms,
R2 is an alkylene group having 1 to 17 carbon atoms, and
x is 99.99 to 95.0 mole %, and
(b) forming a second solution of an organic
hydrocarbon liquid and an amine containing polymer
which contains basic nitrogen atoms wherein the basic
nitrogen content ranges from 4 to 500 milliequivalents
per 100 gms. of polymer;
(c) mixing said first and said second solu-
tions to form a hydrocarbon solution liquid having an
interpolymer complex of said neutralized copolymer of
an alpha-olefin and a vinyl alkylenecarboxylic acid and
said amine containing polymer therein, wherein said
complex is present at a level of from 0.01% to 10%;
and
(d) subjecting said hydrocarbon solution of
said interpolymer complex to an increasing shear rate
thereby causing the viscosity of said hydrocarbon
solution of said interpolymer complex to increase.
8. A solution which comprises:
(a) an organic liquid; and

- 43 -
(b) 0.01 to 10 weight percent of an inter-
polymer complex of:
(1) a copolymer of styrene/vinyl pyridine; and
(2) a copolymer of an alpha-olefin and a vinyl
alkylene carboxylic acid having the formula:
<IMG>
wherein Z is a mixture of H and an alkyl group having 1
to 25 carbon atoms, wherein H comprises 55 to 99 mole%
of Z, R1 is an alkyl group having 1 to 25 carbon atoms,
R2 is an alkylene group having 3 to 17 carbon atoms,
and x is 99.99 to 95.0 mole%.
9. A process for forming a shear thickening
hydrocarbon liquid having a viscosity of at least 10
cP which includes the steps of:
(a) forming a first solution of an organic
hydrocarbon liquid and a copolymer of an alpha-olefin
and a vinyl alkylenecarboxylic acid having an acid
content of from 0.01 to 10 mole percent, wherein said
copolymer of said alpha-olefin and said vinyl alkylene-
carboxylic acid has the formula:

- 44 -
<IMG>
wherein Z is a mixture of H and R3, R1 is an alkyl
group having 1 to 25 carbon atoms, R2 is an alkylene
group having 3 to 17 carbon atoms, R3 is an alkyl group
having 1 to 25 carbon atoms, and x is 99.99 to 95.0 mole%;
(b) forming a second solution of an organic
hydrocarbon liquid and an amine containing polymer
which contains basic nitrogen atoms wherein the basic
nitrogen content ranges from 4 to 500 milliequivalents
per 100 gms. of polymer; and
(c) mixing said first and said second solu-
tions to form an organic hydrocarbon liquid having an
interpolymer complex of said neutralized copolymer of
an alpha-olefin and a vinyl alkylenecarboxylic acid and
said amine containing polymer therein, wherein said
complex is present at a level of from 0.01% to 10% and
the viscosity of said solution increases by at least
10% as shear rate increases.
10. A solution which comprises:
(a) an organic liquid; and
(b) 0.01 to 10 weight percent of an inter-
polymer complex of:
(1) a copolymer of styrene/vinyl pyridene; and

- 45 -
(2) a copolymer of an alpha-olefin and a vinyl
alkylene carboxylic acid having the formula:
<IMG>
wherein Z is a mixture of H and R, R1 is an alkyl group
having 1 to 25 carbon atoms, R2 is an alkylene group
having 3 to 17 carbon atoms, R is an alkyl group having
1 to 25 carbon atoms, x is 99.99 to 95.0 mole %,
wherein H comprises 55 to 99 mole % of Z.
11. A method for reducing the frictional drag of
an organic liquid in flow through pipes or conduits having
a continuous bore therethrough which comprises adding a
polymeric complex to said organic liquid, in a
concentration of 0.001 to 0.5 grams of polymeric complex
per 100 ml of organic liquid, wherein the polymeric complex
is the reaction product of a copolymer containing an
alpha-olefin and vinyl alkylenecarboxylic acid and a basic
nitrogen-containing copolymer, wherein said acid copolymer
of alpha-olefin and vinyl alkylenecarboxylic acid has the
formula:
<IMG>

- 46 -
wberein R1 is an alkyl group having 1 to 25 carbon
atoms, Z is a mixture of hydrogen and an alkyl group
having 1 to 25 carbon atoms and R2 is an alkylene group
having 3 to 17 carbon atoms, x is 95.0 to 99.99 mole %
and y is 5.0 to 0.01 mole %.

Description

_UMMARY OF THE INVE~TION
1 It has been discovered that the vlscosity of
2 organic liquids may be conveniently controlled by
3 incorporating in said organic liquid a minor amount of
4 a copolymer which is the reaction product of an alpha
olefin and a vinyl alkylenecarboxylic acid. The
6 copolymer is characterized as having a polymeric
7 backbone which is substantially soluble in the organic
8 liquid.
g The number of acid groups contained in the
copolymer is a critical parameter affecting this
11 invention. The number of acid groups present in the
12 copolymer can be described in a variety of ways such as
13 weight percent, mole percent, number per polymer chain,
14 etc. Mole percent will be employed to describe the
copolymers in this invention.
16 The copolymer of the instant invention which
17 is a copolymer containing an alpha olefin and a mixture
18 of vinyl alkylenecarboxylic acid and vinyl alkylene-
19 carboxylic esters having 4 to 20 carbon atoms, more
prefera'oly 9 to 18 and most preferably 10 to 16,
21 wherein an alkyl styrene group is situated between the
22 acid or ester group and the carbon of the double bond
23 of the monomer, wherein the resulting alkylenecar-
24 boxylic acid side groups are randomly distributed along
the alpha olefin backbone. The alpha olefin has 2 to
26 27 carbon atoms, more preferably 6 to 2 , and most
27 preferably 6 to 18. The copolymer contains 0.01 to 5
28 mole % of the alkylenecarboxylic acid and ester side
29 groups, more preferably 0.05 to 3 and most preferably
0.1 to 2. The number average molecular weight as
31 measured by GPC of the alpha olefin copolymer is

-- 2
1 10,000 to 20,000,000, more preferably 50,000 to
2 15,000,000, and most preferably 100,000 to 10,000,000.
3 A copolymer of the alpha olefin and vinyl
4 alkylenecarboxylic acid/ester is formed by partially
hydrolyzing with concentrated sulfuric acid or other
6 suitable acids having a sufficiently low Ph to effect
7 hydrolysis, wherein the hydrolysis occurs in solvent
8 which is inert itself to hydrolysis such as an alipha-
9 tic or aromatic hydrocarbon. A copolymer of an alpha
olefin and a vinyl alkylene ester is partially
11 hydrolyzed according to the reaction scheme:
12 - (CH2-7H)X -(CH2 TH)y
13 Rl R2
I
14 C=O
I
OR3
16 Acid Hydrolysis
17 - (CH2-CH) x -(CH2-fH)y
18 Rl R2
I
19 C=O
lz
21 wherein Z i5 a mixture of H and R3, Rl is an alkyl g~oup
22 having 1 to 25 carbon atoms, R2 is an alkylene group
23 having 1 to 17 carbon atoms (preferably 3 to 17 carbon
24 atoms), R3 is an alkyl group having 1 to 25 carbon
atoms. x is 99.99 to 95.0 mole ~, more preferably 99.95 to
26 97.0, and most preferably 99.90 to 98Ø The balance (y)
comprises both carboxy-

- 3 ~ g~
1 lic acid and ester containing units, since the
2 hydrolysis is only partial, wherein only a portion of
3 the sster groups axe hydrolyzed~to carboxylic acid
4 groups. The final hydrolyzed product is a mixture of
ester species and acid species, wherein the mixture
6 contains 0.1 to 45 weight percent of the acid species,
7 more preferably 2 to 40, and most preferably 4 to 20.
8 The hydrocarbon solution of the copolymee of
g the alpha-olefin and the vinyl alkenecarboxylic
acid/ester exhibits antimisting properties and is
11 formed by forming a solution of the copolymer in an
12 organic liquid, wherein the organic liquid preferably has a
13 solubility parameter of less than 9.5 and is ~refera~1~ selected
14 from the group consisting of mineral oil, synthetic
oil, alkanes, cycloalkanes and aromatics and mixtures
16 thereof. The concentration of the copolymer in the
17 solution is 0.05 to 2 grams per 100 ml of organic,
18 liquid, more preferably 0.1 to 0.5.
19 A copolymer of the alpha olefin and vinyl
alkylenecarboxylic acid is formed by first hydrolyzing
21 the organic ester with a base and optionally further
22 treating with concentrated sulfuric acid or other
23 suitable acids having a sufficiently low Ph to effect
24 hydeolysis, wherein the hydrolysis occurs in a solvent
which is inert itself to hydrolysis such as an alipha-
26 tic or aromatic hydrocarbon. The substantially
27 complete hydrolysis o the copolymer of an alpha olefin
28 and a vinyl alkylene ester and the optional acid
29 treatment is represented by the reaction scheme:
1~?

- ~\
_ 4
~2~
~CH2-CH) X - (CH2-CH) y
2 Rl . ~2
3 C=O
4 OR3
Base Hydrolysis~ ~
6 ~CH2-CH)X -(CH2-CI)y
7 Rl l2
8 f=
9 OH
Acid Treatment
11 ~CH2-CH) X - (CH2-CH) y
12 Rl lR2
13 C=O
14 lz
wherein Z is a mixture of H and an alkyl group having 1 to
16 2S carbon atoms, wherein H comprises 55 to 99 mole % of z,
17 more preferably 65 to 95 mole %, and most preferably 70 to
17 9O mole %. R1 i5 an alkyl group having 1 to 25 carbon
18 atoms, R2 is an alkylene group having 1 to 17 carbon
atoms (preferably 3 to 17 carbon atoms), R3 is an alkyl
21 group having 1 to 25 carbon atoms, x is 99~99 to 95.0 mole
22 %, more preferably 99.95 to 97.0, and most preferably 99.9O
23 to 98.0,
24 The bases used in the hydrolysis of the ester
species are sel2cted from the group consisting of
26 _ ~, OH ~, EtO ~, nBuO ~ and Pro ~.
~1

_ 5 - ~ 94
1 The hydrocarbon solution of the copolymer of
2 the alpha-olefin and the vinylalkylenecarboxylic acid
3 exhibits antimisting properties and is formed by
4 forming a solution of copolymer in an organic liquid,
wherein the organic liquid prefe~bly has a solubility
6 parameter o. les.s than 9.5 and is~referabl~selected from the
7 group consisting of mineral oil,synthetic oil, alkanes,
8 cycloalkanes and aromatics and mixtures thereof. The
9 concenteation of the copolymer in the solution is 0.05
to 2 grams per 100 ml of organic liquid, more prefer~
11 ably 0.1 to 0.5.
12 It is evident that the copolymers covered
13 within this invention encompass a broad class of
14 hydrocarbon polymer systems. I. is important that
these hydrocarbon polymer backbones (in the absence of
16 the acid groups) be soluble in the organic liquid,
17 whose viscosity is to be controlled. To achieve the
18 desired solubility, it is required that the polymer to
19 be employed possess a deg~ee of polarity consistent
with that solvent. This solubility relationship can be
21 readily established by anyone skilled in the art simply
22 by appropriate texts te.g., Polymer Handbook-edited by
23 Brandrup and Immergut, Interscience Publishers, 1967,
24 section VI-341). In the absence of appropriate
polymer-solvent compatibility knowledge, this can be
26 determined experimentally by observing whether the
27 selected polymer will be .soluble in the solvent at a
28 level of lg polymer per 100 ml solvent. I~ the polymer
29 is soluble, then this demonstrates that it is an
appropriate backbone for modification with acid groups
31 to achieve the objectives of this invention. It is
32 also apparent that polymers which are too polar will
33 not be soluble in the relatively nonpolar organic
34 liquids of this invention. Therefore, only those

- 6 - ~0~
1 polymer backbones (i.e., as measured in the absence of
2 ionic groups) having a solubility parameter less than
3 10.5 are suitable in this invention.
4 The solutions of the instant invention are
prepared by dissolving the copolymer in an organic
6 liquid which has a solubility parameter of less than
7 9.5 and a viscosity of less than 35 centipoises and is
8 selected from the group consisting of mineral oil,
9 synthetic oil, lubricating oils, alkanes, cycloalkanes
and aromatics and mixtures thereof. The concentration
11 of the copolymer in the solution is 0.4 to 10 grams
12 per 100 ml of organic liquid, more preferably 0.5 to 2.
13 The viscosity of the solutions are 10 to 10,000 cp,
14 when the concentration level o the polymer in solution
is less than 1 weight percent. When the concentration
16 of the polymer in the solution is greater than 1.0
17 weight percent, the viscosity of the solution can
18 exceed 50,000 cps and extends to a gelled state.
19 The copolymers of the alpha olefin and vinyl
alkylenecarboxylic acid are improved viscosification
21 agents for organic hydrocarbon liquids as compared to
22 the copolymers of the alpha olefin and vinyl alkyl-
23 enecarboxylic acid/ester because the hydrolysis level
24 is higher and more controlled than in the case of the
acid hydrolyzed examples.
26 The present invention also relates to a
27 process for the viscosification of an organic hydro-
28 carbon liquid having a viscosity typically, but not
29 necessarily, less than 10 cps. which includes the steps
of forming a first solution of a polymer containing
31 carboxylic acid groups in the organic hydrocarbon
32 liquid, forming a second solution of a cationic polymer
33 in the organic hydrocarbon liquid and mixing the first

- 7 -
1 and second solutions to form a solution of the organic
2 hydrocarbon liquid and an interpolymer complex o~ the
3 two polymers, wherein the resultant solution o the
4 organic hydrocarbon liquid has a viscosity of at least
10 cps, and furthermore exhibits shear thickening
6 behavior. The component mateeials of the instant
7 process generally include a water insoluble inter-
8 polymer complex in an organic hydrocarbon solvent
9 system to Eorm a solution with a concentration le~el of
0.01 to 10 weight percent. The acid content of said
11 first solution is preferabl~ from 0.01 to 10 mole percent.
12 The polymer containing the carboxylic acid
13 groups can be either the copolymer of the alpha-olefin
14 and carboxylic acid or the alpha-olefin and carboxylic
acid/ester.
16 The basic nitrogen-containing copolymer such
17 as styrene-vinyl pyridine copolymer (polymer B of the
18 interacting polymer complex) can be formed by free
19 radical copolymerization using techcniques well-known
2C in the polymer literature. Such polymers can be
21 prepared by polymerizing by a variety of techniques a
22 basic nitrogen-containing monomer, such as vinyl
23 pyridine, with styrene, t-butyl styrene, alkyl acry-
24 lates, alkyl methacrylates, butadiene, isoprene vinyl
chloride, acrylonitrile, butadiene/styrene monomer
26 mixtures and copolymers, or more complex mixtures. An
27 emulsion polymerization process is generally preferred,
28 but other processes are also acceptable.
29 The amount of vinyl pyridine in the basic
nitrogen-containing polymer can vary widely, but should
31 range from less than 50 weight percent down to at least
32 0.5 weight percent.
`-,p;~

- 8 ~
1 Preerably, the amine content in the basic
2 polymer is expressed in terms of basic nitrogen. In
3 this respect, the nitrogen content in amides and
4 similar nonbasic nitrogen functionally is not part of
the interacting species.
6 The water insoluble base nitrogen-containing
7 copolymer will comprise from 0.5 to 50 weight percent
8 basic groups situated along the chain backbone, or
9 alternatively the basic groups content will range from
4 milliequivalents to 500 milliequivalents per 100 g of
11 polymer. The basic groups may be conveniently
12 selected from the groups containing polymerizable
13 primary, secondary and tertiary amine groups. Included
14 in these categories are pyridine, anilines, pyrroles,
and other basic polymerizable ammonia derivatives.
16 Specific polymers include styrene-4-vinylpyridine,
17 t-butyl styrene-4-vinylpyridine, ethylene-4-vinyl-
18 pyridine copolymers, propylene-4-vinylpyridine copoly-
19 mers, acrylonitrile-4-vinylpyridine, methyl meteh-
acrylate-4-vinylpyridine copolymers, block copolymers
21 and ethylene oxide/4-vinylpyridine, acrylic acid-4-
22 vinylpyridine copolymers, ethylene-propylene 4-vinyl-
23 pyridine terpolymers, isoprene-4-vinylpyridine,
24 4-vinylpyridine-elastomers, copolymers and the like.
The preferred base-containing polymers of the instant
26 invention are styrene and 4-vinylpyridine and ethylene-
27 propylene terpolymers with grafted 4-vinylpyridine.
28 The former polymers are the preferred species.
2g These materials are prepared through conven-
tional solution, suspension and emulsion copoly-
31 meriation techniques.
. .

9 ~2~
1 The copolymer of styrene/vinyl py~idine is
2 typically formed by the emulsion copolymerization of
3 freshly distilled styrene and n-vinylpyridine monomers.
4 This method of copolymerization is generally known to
those well-versed in the art~ As noted previously,
6 solution or suspension techniques may also be used to
7 prepare those base-containing polymeric materials.
8 The interpolymer complex of the copolymer of
9 the alpha-olefin and the alkylenecarboxylic acid or
alkylenecarboxylic acid/ester and the copolymer of
11 styrene/vinyl pyridine is formed, for example, by
12 forming 'a first solution of the copolymer of the
13 alpha-olefin and alkylene carboxylic acid in the
14 previously described solvent system. A second solution
of the copolymer of styrene/vinyl pyridine is formed by
16 dissolving the copolymer of styrene/vinyl pyridine in
17 an aromatic solvent such as xylene or benzene. Alterna-
18 tively, both polymers can be dissolved simultaneously
19 in the same solvent. The concentration of the copoly-
mer of the alpha-olefin and alkylenecarboxylic acid in.
21 the solution is 0.001 to 5 g/dl, more preferably 0.01
22 to 4, and most preferably 0.01 to 1.5. The concentra-
23 tion OL the copolymer of styrene/vinyl pyridine in the
24 second solution is 0.001 to 5 g/dl, more preferably
0.01 to 4, and most preferably 0.01 to 1.5. The first
26 solution of the copolymer of 'the alpha-olefin and
27 alkyle'necarboxylic acid and the second solution of the
28 copolymer of styrene/vinyl pyridine a~e mixed together,
29 thereby permitting the inter'action of the copolymer of
the'alpha-olefin and alkylenecarboxylic acid and the
31 copolymer of styrene/vinyl pyridine to form the water
32 insoluble interpolymer complex. The molar ratio of the
33 ~opolymer of the alpha-olefin, alkylenecarboxylic acid
34 to the copolymer of styrene/vinyl pyridine in the
interpolymer complex is 0.1 ~o 20, more preferably 0.5

- 10 ~
1 to 10, and most preferably 1 to 5. The concentration
2 of the interpolymer complex in the hydrocarbon organic
3 liquid is 0.01 to 10 weight percent, more preferably
4 0.1 to 7, and most preferably 1.0 to 5.
The amount of vinyl pyridine in the amine-
6 containing polymer can vary widely, but should range
7 from less than 50 weight percent down to at least 0.5
8 weight percent.
g Preferably, the amine content in the basic
polymer is expressed in terms of basic nitrogen. In
11 this respect, the nitrogen content in amides and
12 similar nonbasic nitrogen functionality is not part of
13 the interacting species.
14 A minimum of three basic groups must be
present on the average per polymer molecule and the
16 basic nitrogen content generally will range fr~m 4 meq.
17 per 100 grams of polymer up to 500 meq. per 100 g. A
18 range of 8 to 200 meq. per 100 g. is preferred.
19 The organic liquids, which may be utilized in
the instant invention, are selected with relation to
21 the ionic polymer and vice-versa. The organic liquid
22 is selected from the group consisting of aromatic
23 hydrocarbons, cyclic aliphatic eth~rs, aliphatic
24 ethers, or organic aliphatic esters and mixtures
thereof.
26 SpeciEic examples of organic liquids to be
27 employed with the various types of polymers are:
28 benzene, toluene, ethyl benzene, methylethyl ketone,
29 xylene, styrene, ethylene dichloride, methylene
chloride, styrene, t-butyl styrene,aliphatic oils,
31 aromatic oils, hexane, heptane, decane, nonane,

1 pentane, aliphatic and aromatic solvents, oils such as
2 Solvent 'llO0 Neutral", 'l150 Neutral" and similar oils,
3 diesel oil, octane, isooctane, aromatic solvents,
4 ketone solvents, dloxane, halogenated aliphatics, e.g.,
methylene chloride, tetrahydrofuran~
6 The viscosity of organic hydrocarbon solution
7 of the interpolymer complex having an increased
8 viscosity can be reduced by the addition of a polar
9 cosolvent, for example, a polar cosolvent in the
mixture of organic liquid and water insoluble inter-
11 polymer complex to solubilize the pendant carboxylic
12 acid groups. The po]ar cosolvent will have a solu-
13 bility parameter of at least 10.0, more preferably at
14 least 11.0 and is water miscible and may comprise from
0.1 to 15.0 weight percent, preferably 0.1 to 5.0
16 weight percent of the total mixture of organic liquid,
17 water insoluble carboxylic acid copolymer, and polar
18 cosolvent.
19 Normally,the polar cosolvent will be a liquid
at room temperature; however, this is not a require-
21 ment. It is preferred, but not required, that the
22 polar cosolvent be soluble or miscible with the organic
23 liquid at the levels employed in this invention. The
24 polar cosolvent is selected from the group consisting
essentially of water soluble alcohols, amines, di- or
26 trifunctional alcohols, amides, acetamides, phos-
27 phates, or lactones and mixtures thereof. Especially
28 preferred polar cosolvents are aliphatic alcohols such
29 as methanol, ethanol, n-propanol, isopropanol, 1,
2-propane diol, monoethyl ether or ethylene glycol, and
31 n-ethylformamide.

- 12 - ~2~
1 DESCRIPTION OF THE PREFER D EMBODIMENT
2 The following are preferred embodiments of
3 the instant invention.
4 Example 1
Base Hydrolysis
6 A flask was charged with a solution of
7 l-octene-methyl-10-undecanoate copolymer (4.0 g) in 200
8 g THF and 0.82 g t-BuOK. The solution was heated to
9 50-60C. After one hour another 150 ml of T~F was
added and 3.6 ml of 2N H2SO4 was added to neutralize
11 the solution (pH = 5). After cooling, the polymer was
12 precipitated in 600 ml of water/isopranol (1:1
13 vol/vol.). The polymer was filtered, washed with water
14 and isopranol, and dried to yield 4.0 g of product
which had 100~ of the original ester groups hydrolyzed
16 to carboxyl groups by IR. The viscosity of this
17 polymer in xylene (2~) was 19 cP at 30s~1.
18 Example 2
19 Acid Treatment
.
2.0 g of the polymer prepared according to
21 Example 1 was dissolved in 100 g xylene. A 3 ml
22 quantity of concentrated H2SO4 was added at room
23 temperature. The batch was stirred for 1 hour at room
24 temperature and subsequently precipitated in iso-
pranol/water and dried under vacuum with heating. The
26 polymer showed carbonyl and ester groups in the IR (75~
27 COOH) and surprisingly showed an enhanced viscosity of
28 34 cP at 30s-l at 2% concentration in xylene, which is
29 higher than the solution viscosity shown in Example l~

- 13 ~
1 This Example shows that there is an advantage
2 in viscosification with an acid copolymer which was
3 first hydrolyzed by a base. It is a surprising result
4 since the acid content based on IR decxeased after the
treatment.
6 Example 3
7 A two liter flask was charged with a solution
8 of l-octene-methyl-10-undecenoate copolymer (10 g) in
9 xylene (500 g), and the solution was heated up to 40C.
Concentrated sulfuric acid (20 ml) was then added.
11 After atirring for one hour, the mixture was cooled
12 down. The hydrocarbon layer was washed with a mixture
13 of isopropyl alcohol and water three times and poured
14 into 3 liters of isopropyl alcohol. The resulting
white product was purified by reprecipitation and dried
16 in a vacuum oven at 50C. Finally, 8.0 g of colorless
17 rubbery polymer was obtained. The product was quite
18 soluble in a variety of hydrocarbon solvents.
19 Example 4
The procedure described in Example 3 was
21 repeated, but the reaction was carried out at 60C.
22 Example 5
23 The procedure described in Example 3 was
24 repeated, but the reaction was carried out at 25C for
two hours.

- 14 - ~2
1 Example 6
_
2 A copolymer of l-octene and methyl-10-
3 undecenoate was partially hydrolyzed as in Example 5.
4 The polymer had a backbone of 2 million weight average
molecular weight and 1 mole percent of ester groups
6 before hydropyrolysis. The partial hydrolysis resulted
7 in 0.1-0.5 mole percent of carboxylic acid groups.
8 The partially hydrolyzed copolymer was
9 dissolved in xylene at a concentration of 1 weight
percent. The backbone used for the hydrolysis was also
11 dissolved in xylene at a concentration of 1 weight
12 percent. The viscosity of the two solutions at 2SC
13 and at a shear rate of 60 sec_l were 378 cP (centi-
14 poise) and 6 cP, respectively.
This Example demonstrates an unexpectedly
16 high viscosity for a solution of a partially hydrolyzed
17 polymer at a relatively low level of carboxylic acid
18 content. The nonhydrolyzed copolymer solution exhibit-
19 ed a normally expected viscosity.
Example 7
21 Synthesis of Polytl-octene) having alkylenecarboxylic
22 acid side chains.
23 (a) Copolymerization of l-octene and methyl-10-
24 undecenoate
A 2-liter flask was charged with a mixture of
26 n-heptane (480 ml), l-octene (500 ml), methyl-10-
27 undecenoate (6.4 g), and diethyl aluminum chloride (72
28 m mole), were heated to 60C. The catalyst containing
29 TiC13 (2.0g) in n-heptane (20 ml) (described in U. S.

- 15 -
1 Patent No. 4,240,928) was then added. After stirring
2 for 1 hour, the reaction was terminated with a small
3 amount of isopropyl alcohol. The polymer was preci-
4 pitated and washed with isopropyl alcohol and vacuum
dried at 60C to yield 87.g g of colorless material. IR
6 spectrum showed that the copolymer contains 0.8 mole ~
7 of methyl-10-undecenoate unit. The inherent viscosity
8 was 4.3 dl/g in a decalin solution. Mn was 4.6 x 106
9 as measured by GPC.
(b) Hydrolysis of l-octene-methyl-10-undecenoate
11 copolymer
12 l-octene-methyl-10-undecenoate copolymer was
13 converted to a respective sa~ple having alkylene-
14 carboxylic acid side chains as described below.
A solution of the copolymer (lOg) in xylene
16 (500 g) was placed in a 2-liter flask and heated to
17 40C. Concentrated sulfuric acid (20 ml) was then
18 added. After stirring for one hour, the reaction
19 mixture was cooled down and washed with a mixture of
water and isopropyl alcohol three times. A white
21 product was obtained by precipitating from the solution
22 with isopropyl alcohol. Further purification by
23 reprPcipitation and drying in a vacuum oven at 50C
24 gave 8.0 g of colorless rubbery polymer. IR spectrum
showed that 3 percent of methyl ester group was
26 converted into corresponding acid form. The partially
27 hydrolyzed copolymer was then dissolved in xylene at a
28 concentration of 1 weight percent. The resulting
29 viscosity of this solution at 25C as a function of
shear rate was:

- 16 -
1 Shear ~ate Viscosity
2 sec~l cP
3 3 63
4 10 72
99
6 30 171
7 60 378
8 These data demonstrate a high effectiveness
9 in viscosification, as well as dilatancy or shear
thickening. The high viscosi~ication can be demon-
11 strated by comparing the above viscosity data to
12 viscosity of a high molecular weight polyisobutylene
13 (Exxon L-200, with a weight average molecular weight
14 above 2 million) in xylene at the same concentration of
1 weight percent. The later solution has a low shear
16 viscosity of 24 cP at 3 sec~l and is shear thinning
17 such that the viscosity drops to 14 cP at 300 sec~l.
18 Another comparison could be made to a solution of the
19 non-hydrolyzed copolymer which was used to prepare the
above partially hydrolyzed copolymer. The viscosity of
21 this last copolymer in a xylene solution at 1 weight
22 percent concentration was 6 cP.
23 Example 8
24 Destruction of Viscosification and Shear Thickening
A solution of a partially hydrolyzed copoly-
26 mer of l-octene and methyl 10-undecenoate was prepared
27 in xylene at a concentration of 0.5 weight percent.
28 The copolymer was similar in molecular architecture to
29 the one described in Example 7, except that it had a
3Q higher degree of hydrolysis conversion of 13 percent.
31 The viscosity of this 0.5 weight percent solution was

- 17 - '~2~
l 30 cP at 6 sec~l and 420 cP at 18 sec~l and at 25C.
2 After adding 0.5 percent by weig'nt of methanol to the
3 solution the viscosity dropped to 205 cP. When 0.1
4 weight percent of stearic acid was added to the
S solution rather than methanol the viscosity dropped to
6 approximately the same value of 2.5 cP. In both cases
7 the modified solutions exhibited a Newtonian nature.
8 This Example demonstrates that some polar
9 additives, such as methanol or stearic acid, can be
effective agents for reversing the viscosification and
ll shear thickening exemplified by the class of material
12 claimed in this instant invention.
13 Example 9
14 Flow in a Tubeless Siphon for Solutions in Jet Fuel
A solution of a partially hydrolyzed copoly-
16 mer of l-octene and methyl-10-undecenoate was prepared
17 in jet fuel. The polymer was the same as that in
18 Examp;e 7 and the solution was prepared at a concentra~
19 tion of 0~5 weight percent. The solution was then
studied in a tubeless siphon flow and the height at
21 which the unsupported fluid column broke was recorded.
22 The solution was then diluted to various lower concen-
23 trations which were also studied in tubeless siphon
24 flow. The column heights at break for the various
concentrations of the polymer solution in jet fuel
26 were:

- 18 - ~2~
1 Polymer Concentration Column Height
2 (Wt.~) (mm)
0 5 16
4 0.4 12
0.3 4
6 0.2 2-3
7 0.1 1-2
8 The siphon height at bre~k for the 0.5 weight
9 percent solution was changed from 16 mm to less than 6
mm upon addition of 1,000 ppm of stearic acid.
11 Since tubeless siphon height has been
12 correlated with antimisting activity, this Example
13 demonstrates that the polymer of the instant invention
14 is expected to be an effective agent for antimisting of
jet fuel by virtue of its ability to affect a high
16 extensional viscosity in jet fuel solutions. The
17 Example also shows that a polar additive, such as
18 stearic acid, can be effective for significantly
l9 reversing the antimisting characteristics.
Example 10
21 Synthesis of Poly(l-octene) having alkylenecarboxyllc
22 acid side chains
23 Copolymerization of l-octene and methyl-10-undecenoate
24 A 2-liter flask was charged with a mixture of
n-heptane (480 ml), l-octene (500 ml), and methyl-10-
26 undecenoate (6.4 g), and diethyl aluminum chloride (72
27 m mole), were heated at 60C. The catalyst containing
28 TiC13 (2.0 g) in n-heptane (20 ml) (described in U. S.
29 Patent No. 4,240,928) was then added. After stirring

-- 19 --
1 for 1 hour, the reaction was terminated with a small
2 amoun~ of isopropyl alcohol. The polymer was preci-
3 pitated and washed with isopropyl alcohol and vacuum
4 dried at 60C to yield 87.9 g of colorless material. IR
spectrum showed that the copolymer contains 0.8 mole %
6 of mathyl-10-undecenoate unit. The inherent viscosity
7 was 4.3 dl/g in a decalin solution. ~n was 4.6 x 106
8 a.s measured by GPC.
9 Example 11
Base Hydrolysis
11 A flask was charged with a solution of
12 l-octene-methyl-10-undecanoate copolymer (40.9) in 200
13 g THF and 0.82 g t-BuOK. The solution was heated to
14 50-6DC. After one hour another 150 ml THF was added
and 3.6 ml of 2N H2SO4 was added to neutralize the
16 solution (p~ = 5). After cooling, the polymer was
17 precipitated in 600 ml of water/isopropanol (1:1
18 vol./vol.). The polymer was filtered, washed with
19 water and isopronol, and dried to yield 4.0 g of
product which had 100% of the original ester groups
21 hydrolyzed by IR. The viscosity of this polymer in
22 xylene (2%) was 19 cps. at 30 s-l.
23 Example 12
24 Flow in a Tubeless Siphon for Solutions in Jet Fuel
A solution of hydrolyzed copolymer of
26 l-octene and methyl-10-undecenoate was prepared in jet
27 fuel A. The copolymer was hydrolyzed by base hydroly~
28 sis and was similar to the one in Example 11. The
29 solution was prepared by first dissolving 5 weight
percent of the copolymer in xylene and then diluting it

~L2~
- 20 -
1 with jet fuel A to obtain a O.S weight percent copoly-
2 mer in a mixture of xylene and jet fuel A where jet
3 fuel A was 90 weight percent of the mixture. This
4 solution was then studied in a tubeless siphon flow and
the height at which the unsupported fluid column broke
6 was recorded. The solution was then further diluted
7 with jet fuel A to various lower concentrations which
8 were also studied in tubeless siphon flow. The column
9 heights at break for the various concentrations of the
polymer solutions in jet fuel A (and a minor proportion
11 of xylene) were:
12 Polymer Concentration Column Height
13 (Wt.~) (mm)
14 0.5 8
0.4 5.8
16 0 3
17 0.2 4
18 0.1 2
19 The above solution at 0.3 weight percent
polymer was nearly Newtonian with a shear viscosity of
21 2.87 cP at 30 sec~l and a slight decrease to 2.67 cP at
22 300 sec~l.
23 This Example demonstrates the low shear
24 viscosity of a jet fuel solution with a base hydrolyzed
copolymer while demonstrating flow in a tubeless
26 siphon. Therefore, such solutions are expected to be
27 antimisting with the advantage of pumpability and ease
28 of flow.

~L2~
- 21 ~
l Example 13
2 Destruction of Antimisting Properties
3 A solution of jet fuel A containing a
4 copolymer similar to the ones used in Examples 11 and
12 was prepared at a polymer concentration of 0.3
6 weight percent. The solution was subjected to a flow
7 in a tubeless siphon and it produced a 5.5 mm unsup-
8 ported column of fluid before break which is the same
9 height shown for the identical concentration in E~ample
12.
ll Upon addition of stearic acid to the solution
12 the siphon heights before break as a function of
13 stearic acid concentrations were:
14Stearic Acid Column Height
-
15.(ppm) (mm)
16 o 5.5
171,500 4.5
182,500 3.8
l94,000 3.0
,
This demonstrates that an addition of a polar
21 material, such as stearic acid, can act to reduce the
22 antimisting capability of a solution that incorporates
23 the novel polymer.
24 Example 14
Synthesis of Polymers Al and A2 Having
26 Alkylenecarboxylic Acid Side Chains
~7 (a) Copolymerization of l-Octene
28 and methyl-10-undecenoate

- 22 -
1 A 2-liter flask was charged with a mixture of
2 n-heptane (480 ml), l-octene (500 ml), methyl-10-
3 undecenoate (6.4 g), and diethyl aluminum chloride (72
4 m mole), and heated to 60C.
.
The catalyst containing TiC13 (described in
6 U. ~. Patent No. 4,240,928) (2.0 g) was then added with
7 n-heptane (20 ml). After stirring for one hour, the
8 reaction was terminated with a small amount of iso-
g propyl alcohol.
The polymer was precipitated and washed with
11 isopropyl alcohol and vacuum dried at 60C to yield
12 87.9 g of colorless material. IR spectrum showed that
13 the copolymer contained 0.8 mole % of methyl-10-
14 undecenoate unit. Intrinsic viscosity was 4.3 dl/g in a
decalin solution. ~n was 4.6 x 106 by means of GPC.
16 (b) Base H~drolysis - Polymer Al
.
17 A flask was charged with a solution of
18 l-octene-methyl-10-undecanoate copolymer similar to the
19 one described in (a) above (4.0g) in 200 g THF and 0.82
20 g t-BuOK. The solution was heated to 50-60C. After
21 one hour, another 150 ml THF was added and 3.6 ml of 211
22 H2SO4 was added to neutralize the solution (ph = 5).
23 After cooling, the polymer was precipitated in 600 ml
24 of water/isopranol (1:1 vol/vol.). The polymer was
25 filter washed with water and isopranol and dried to
26 yield 4.0 g of product which had 100% of the original
27 ester groups hydrolyzed to carboxyl groups by IR. The
28 viscosity of this polymer in xylene (2%) was 19 cP at
29 30s-1.

- 23 ~
1 (c) Acid Treatment - Polymer A2
2 2.0 g of the polymer prepared according to
3 Example l(b) was dissolved in 100 g xylene. A 3 ml
4 quantity of concentrated H2SO4 was added at room
temperature. The batch was stirred for 1 hour at room
6 temperature and subsequently precipitated in isopra-
7 nol/water and dried under vacuum while heating. The
8 polymer showed an enhanced viscosity of 34 cP at 809-l
9 at 2~ concentration in xylene which is higher than the
solution viscosity shown in (b) above.
11 EXAMPLE 15:
.
12 SYNTHESIS OF STYRENE-VINYLPYRIDINE COPOLYMER-POLYMER B
13 A representative example for the synthesis of
14 styrene-4-vinylpyridine copolymer (SVP) is outlined
below.
16 Into a l-liter 4-neck flask the following
17 ingredients were introduced:
18 100 g distilled styrene
19 6.4 g sodium lauryl sulfate
240 ml. distilled water
21 0.4 g potassium persulfate
22 9.4 g 4-vinylpyridine
23 The solution was purged with nitrogen for 10
24 minutes to remove dissolved oxygen. As the nitrogen
gas purge began, the solution was heated to 55C. After
26 24 hours, the polymer was precipitated from solution
27 with methanol. Subsequently, the resulting polymer was
28 washed several times with a large excess of methanol
29 and dried in a vacuum oven at 60C for 24 hours.

- 24 -
1 Elemental analysis showed a nitrogen content of 1.13
2 weight percent which corresponds to 8.4 mole percent
3 4-vinyl-pyridine.
4 EXAMPLE 16
VISCOSIFICATION BY NETWORK FORMATION
6 Polymers Al and A2 of Example 14 having acid
7 functionalities and polymer B of Example 15 having base
8 functionalities were separately dissolved in xylene at
9 0.5 weight percent concentration. Various mixtures of
these two solutions were prepared in order to form
11 polymer networks in solution via acid base inter-
12 actions.
13 The resulting solution viscosities at 25~C
14 and 30 sec~l are shown in Table 1.
TABLE 1
16 VISCOSITIES OF ACID-BASE NETWORK SOLUTIONS IN XYLENE
17 AT 0 5 WEIGHT PERCENT POLYMER (TOTAL)
18 Composition Viscosity (cP)*
19 Parts Al or A2/Parts B Al/B A2/B
100/0 2.1 2.2
21 95/5 2.0 92
22 90/10 - 140
23 85/15 - 38
24 50/50 - 10
0/100 2.6 2.6
26 * at 25C and 30 sec~l

- 25 ~
1 This example shows that a copolymer con-
2 taining carboxylic acid groups which was base
3 hydrolyzed (Polymer Al) may not interact well with a
4 base containing Polymer (B), but a strong interpolymer
formation is made possible by acid treating a base
6 hydrolyzed copolymer (A2). Acid treating is a single
7 procedure as shown in Example 14(c) and it enables
8 control over the degree of hydrolysis or ability to
9 form a network with a basic polymer.
EXAMPLE 17
11 SHEAR THICKENING
12 The polymer complex solution shown in Example
13 16 as composition 90/10 of polymer A2/polymer B was
14 studied with respect to its viscosity vs. shear rate at
25C in a Haake CV-100 viscometer. This solution at a
16 total polymer concentration of 0.5 weight percent
17 showed dilatant (shear thickening) behavior:
18Shear Rate (sec~lViscosity (cP)
19 3 85
9 90
21 21 108
22 30 140
23 70 158
24 Shear thickening behavior is a useful property for
applications such as antimisting. Shear thickening is
26 displayed in this example for an interpolymer network
27 solution where the polymer containing carboxylic acid
28 groups was prepared via base hydrolysis followed by
29 acid treatment (polymer A2 of Example 14). Solutions

- 26 ~
1 of polymer Al (which i9 the precursor of polymer A2
2 before acid treatment) or the mixtures of polymer Al
3 and polymer ~ in xylene at 0.5 weight percent did not
4 exhibit shear thickening behavior.
This example demonstrates the importance of
6 acid treating of a base hydrolyzed copolymer when shear
7 thickening solutions are required.
8 EXAMPLE 18: Synthesis of Polymer (A) Having Alkylene-
9 carboxylic Acid Side Chains
10 ~a) Copolymerization of l-Octene
11 and Methyl-10-undecenoate
12 A 2-liter flask was charged with a mixture of
13 n-heptane (480 ml), l-octene (500ml), methyl-10-
14 undecenoate (6.4 g), and diethyl aluminum chloride (72
mmole), and heated to 60C.
16 The catalyst containing TiC13 (described in
17 U.S. Patent 4,240,928) (2.0 g) was then added with
18 n-heptane (20 ml). After stirring for 1 hour, the
19 reaction was terminated with a small amount of iso-
propyl alcohol.
21 The polymer was precipitated and washed with
22 isopropyl alcohol and vacuum dried at 60C to yield
23 87.9 g of colorless material. IR spectrum showed that
24 the copolymer contained 0.8 mole % of methyl-10-
undecanoate unit. Intrinsic viscosity was 4.3 dl/g in
26 a decalin solution. Mff was 4.6 x 106 by means of
27 GPC.
28 (b) Hydrolysis of l-octene-methyl
29 l-undecenoate copolymer - Polymer A

- 27 -
1 l-octene-methyl~10-undecenoate copolymer
2 similar to the one described in (a) above was converted
3 to a respective copolymer having alkylenecarboxylic
4 acid side chains as described below:
A solution of the copolymer (10 g) in xylene
6 (500 g) was placed in a 2-liter flask and heated to
7 40C. Concentrated sulfuric acid (20 ml) was then
8 added. After stirring for one hour, the reaction
9 mixture was cooled down and washed with a mixture of
water and isopropyl alcohol three times.
11 A white product was finally obtained by
12 precipitating from the solution with isopropyl alcohol.
13 Further purification by reprecipitation and drying in a
14 vacuum oven at 50C gave 8.0 g of colorless rubbery
polymer (polymer A).
16 EXAMPLE 19: Viscosification b~ Network Formation
~.
17 Polymer A of Example 18 having acid func-
18 tionalities and polymer B of Example 14 having base
19 functionalities were separately dissolved in xylene at
1 weight percent concentrationO Various mixtures of
21 these two solutions were prepared in order to form
22 polymer networks in solution via acid-base inter-
23 actions.
24 Polymer A of Example 18 has a l-octene
backbone with -(CH2)8-COOH alkyl carboxylic acid groups
26 randomly attached along the backbone. The carboxylic
27 level is on the order of 0.1-0.5 mole percent. The
28 average molecular weight is 2 million based on an
29 intrinsic viscosity in xylene of 3.5.

- 28 -
1 Polymer B of Example 2 is a copolymer of
2 styrene and vinyl pyridine with a pyridine level of 8
3 mole percent and a viscosity average molecular weight
4 of 2 million.
Mixtures of the xylene solutions at 1 weight
6 percent each were blended, and the resulting solution
7 viscosities at 25C and 30 sec~l are shown in Table llo
8 Table II
9 Viscosities of Acid-Base Network Solutions
in Xylene at 1 Weight Percent Polymer
11 Composition Viscosity
12 Polymer A Polymer B cP at 25C
13 Parts Parts and 30 sec~
14 100 0 171
97.5 2.5 571
16 95 5 879
17 90 10 358
18 0 100 8.5
19 The mixture viscosities increased signi-
ficantly over the viscosities of the individual
21 components and peaked at a ratio of 95/5 by weight for
22 polymer A to polymer B. The peak ratio is approxi-
23 mately at a stoichiometric concentration of acid to
24 base functionalities.

- 29 -
1 This example shows that polymers A and B can
2 interact to increase solution viscosity, as would be
3 expected from increasing molecular weig'nt. It sug-
4 gests, therefore, that larger structures are formed as
a result of the interactions.
6 EXAMPLE 20: Shear Thickening
7 The solution blends dPscribed in Example 3
8 were measured with respect to their viscosity-shear
9 rate behavior in a Haake CV-100 viscometer at 25C. All
the blends showed increased viscosities at higher shear
11 rates (i.e., dilatant behavior).
12 A specific example is the blend of 90/10 of
13 polymer A/polymer B from Example 19 at a total concen-
14 tration of 1 weight percent in xylene. Viscosities for
this blend were measured with shear rates of up to 60
16 sec~1 with the following results:
17 Shear Rate (sec~l) Viscosity (cP)
18 3 248
1~ 15 284
20 30 358
21 60 427
.
22 This example shows that hydrocarbon solutions
23 of networks made of acid-base interacting polymers may
24 exhibit significant shear thickening of dilatant
behavior.

- 30 ~ 9~
l EXAMPLE 21: Destruction of a Network in Solution
2 A network of acid-base interacting polymers in
3 solution was prepared by blending solutions of two
4 polymers at 0.5 weight percent concentration in xylene
each.
6 One polymer, polymer C is similar to polymer A
7 of Example 18, the only difference being the level of
8 carboxylic acid which was on the order of 0.3-1.0 mole
9 percent. The other polymer was polymer B of Example
19.
ll The two solutions were mixed at a ratio of
12 97.S parts of polymer C to 2.5 parts of polymer B. The
13 resulting viscosity was 400 cP at 25C and 20 sec~l.
14 Upon addition of l weight percent methanol to this
polymer network solution the viscosity dropped to 2.4
16 cP at 25C and 20 sec~l and shear thickening was
17 eliminated.
18 This example shows that a network of acid-base
19 interacting polymers in solution can be effectively and
selectively destroyed by the addition of a proper agent
21 such as methanol, at relatively low concentration. This
22 is useful in reversing viscosification or antimisting
23 properties which are introduced by acid-base interac-
24 tians.
The present invention also relates to a method
26 for reducing the frictional drag of an organic hydro-
27 carbon liquid in flow through pipes or conduits having
28 a continuous bore therethrough, which method comprises
29 adding a quantity of the previously described polymeric
complex to the organic hydrocarbon liquid, wherein the
31 polymeric complexes are the reaction products of an

- 31 -
1 alpha-olefin polymer having alkylenecarboxylic acid
2 side groups randomly distributed along the polymeric
3 backbone of the alpha-olefin and a basic nitrogen-
4 containing polymer.
The final concentration of the polymeric
6 complex as a drag reduction agent in the organic
7 hydrocarbon liquid is 0.001 to 0.5 grams per 100 ml of
8 the organic hydrocarbon liquid, more preferably 0.005
9 to 0.1.
EXAMPLE 22
11 Polymeric Systems and Solutions
12 Polymer Al having acid functionalities and
13 polymer B having base functionalities were separately
14 dissolved in xylene at 1 weight percent concentration.
Various mixtures of these two solutions were prepared.
16 Polymer Al, prepared by acid hydrolysis
17 according to the procedure of Example 14(b), has a
18 l-octene backbone with -(CH2)g-COOH alkylenecarboxyllc
19 acid side groups randomly attached along the backbone.
The carboxylic acid level is in the order of 0.02-0.5
21 mole percent. The average molecular weight is 2
22 million based on an intrinsic viscosity in xylene of
23 3.5.
24 Polymer B, prepared according to the procedure
of Example 15, is a copolymer of styrene and vinyl
26 pyridine with a pyridine level of 8 mole percent and
27 viscosity average molecular weight of 2 million.

- 32 ~
l Mixtures of the xylene solutions at l weight
2 percent each were blended and the resulting solution
3 viscosities at 25 and 30 sec~l are shown in Table III.
4 Table III
Viscosities of Acid-Base Network Solutions
6 in Xylene at 1 Weight Percent Polymer
7 Composition Viscosity
8 Polymer Al Polymer B cP at 25C
9 Parts _ Parts _ and 30 sec~
100 0 171
11 97~5 2.5 571
12 95 5 879
13 go 10 358
14 0 lO0 8.5
The mixture viscosities in Table III increased
16 significantly over the viscosities of the individual
17 components and peaked at a ratio of 95/5 by weight for
18 Polymer ~l to Polymer 3. The peak ratio is approxi-
19 mately at a stoichiometric concentration of acid to
base functionalities.
21 Polymer A2 having acid functionalities and
22 prepared by base hydrolysis followed by acid treatment
23 was interacted in xylene solution with polymer B
24 described above. Both polymers were separately
dissolved in xylene at 0.5 weight percent and various
26 mixtures of the two solutions were prepared yielding a
27 total polymer complex concentration in xylene of 0.5
,
.

- 33 -
1 weight percent. The solution viscosities at 25~ .and
2 30 sec~l were mea5ured by a Haake CV-100 viscometer and
3 are shown in Table IV.
4 TABLE IV
Viscosities of Acid--Base Network
6 Solutions in Xylene at 0.5 Weight Percent Polymer
7 Composition Viscosity
8 Polymer Al Polymer B cP at 25C
9 Parts_Parts and 30 sec~
10 100 0 2~2
11 95 5 92
12 90 10 140
13 85 15 38
14 50 50 10
0 100 2.6
16 In Table IV, mixture viscosities are signifi-
17 cantly higher than the viscosities of the individual
18 components as was shown in Table I.
19 This example shows that polymers Al and B, and
A2 and B can interact to increase solution viscosity as
21 would be expected from increasing molecular weight. It
22 suggests therefore that larger structures are formed as
23 a result of the interation.

- 34 ~
1 EXAMPLE_23
2 Destruction of a Network in Solution
3 A network of acid-base interacting polymers in
4 solution was prepared by blending solutions of two
polymers at 0.5 weight percent concentration in xylene
6 each.
7 One polymer, polymer C, prepared by acid
8 hydrolysis is similar to polymer Al of Example 21 the
9 only difference being the level of carboxylic acid
which was in the order of 0.3-1.0 mole percent. The
11 other polymer was polymer B of Example 21.
12 The two solutions were mixed at a ratio of 97.5
13 parts of polymer A to 2.5 parts of polymer B. The
14 resulting viscosity was 400'cP at 25C and 20 sec~l.
Upon addition of 1 weight percent methanol to this
16 polymer network solution the viscosity dropped to 2.4
17 cP at 25C and 20 sec~l.
18 This example shows that a network of acid-base
19 interacting polymers in solution can be effectively and
selectively destroyed by the addition of a proper agent
21 such as methanol, at relatively low concentration.
22 EXAMPLE 24
23 Drag Reduction of Novel Acid-Base Interacting Polymers
24 Drag reduction was evaluated by flowing
polymer/xylene solutions through a 2.13 mm inside
26 diameter stainless steel tube and measuring the
27 resulting frictional pressure drops and flow rates. The
28 flows were generated by loading a pair oE stainless

- 35 ~
1 ste21 tanks (1 liter each) with a previously dissolved
2 polymer/xylene solution, pressurizing the tanks with
3 nitrogen gas (300 kPa) and discharging the solution
4 through the tube test section. Pressure drops were
measured across a 50 cm straight segment of the tube
6 with a pair of flush mounted tube wall pressure taps
7 and a differential pressure transmitter. Flow rates
8 were measured by weighing samples of the effluent
g liquid collected over measured time periods.
Flow rates in the drag reduction experiments
11 ranged from 12 to 25 g/s; these corresponded to solvent
12 Reynolds numbers from 12,000 to 25,000 (solvent
13 Reynolds number = mean flow velocity x tube diameter -
14 solvent kinematic viscosity). Drag reduction was
measured by comparing flow rates of the polymer/xylene
16 solutions with flow rates of the xylene solvent at
17 equal pressure drops. Results were expressed as
18 percent flow enhancement which is defined as:
19 Flow Rate Flo~ Rate
Percent Flow = 100 X of solution - of solvent
21 Enhancement ~-~rb~ l~nD~cDr ..nr~
22 The sensitivity of the solutions to flow degradation
23 was evaluated by recycling solutions through the
24 system. Under these conditions flow enhancement values
decrease on successive passes when flow degradation
26 occurs.
27 (a) Typical drag reduction results for a pair of
28 novel acid-base interacting polymers and a similar pair
29 of non-interacting polymers are given in Table V.
These results demonstrate that the acid-base inter-
31 acting polymer solution, where the polymer was prepared
32 by acid hydrolysis, has a higher initial level of flow

- 36 - ~ ~4~
1 enhancement and a greater r0sistance to flow degrada-
2 tion. Both effects are attributed to the acid-base
3 interactions among the polymers.
4Table V
5Flow Enhancement Results For Acid-Base
6Interacting and Similar Non-Interacting Polymers
7 ~ Flow Enhancement ~or Pressure Drop of 112 kPa/m
8 375 ppm Polymer Al 375 ppm Polymer D
9Pass 375 ppm Po ymer B 375 ppm Polymer B
10 1 105 69.2
11 2 106 57.4
12 3 105 55.4
13 4 107 51.6
14 5 107 52.7
15 6 108 52.5
,
16 Polymers Al and B are the same polymers described in
17 Example 21. Polymer D is a l-octane homopolymer with
18 an average molecular weight and poly-dispersity
19 approximately equal to those of Polymer Al.
(b) Drag reduction results for a second pair
21 of acid-base interacting polymers where the acid
22 polymer was prepared by base hydrolysis followed by
23 acid treating, are shown in Table VI.

- 37
1TABLE VI
2Flow Enhancement Results for
3Acid-Base Interacting Polymers in Xylene
4% Flow Enhancement for Pressure Drop of 112 kPa/m
Pass250 ppm Polymer A3/250 ppm Polymer B
6 1 93.2
7 3' 95.3
8 4 92.2
9 5 93.1
6 93.8
11 The results in Table VI demonstrate effective
12 drag reduction and stability for a polymeric acid-base
13 interacting agent where followed by acid treatment.