CA1244194A - COPOLYMERS OF .alpha.-OLEFIN AND ALKYLENE CARBOXYLIC ACIDS - Google Patents

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:

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 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

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

Base Hydrolysis~ ~
6 ~CH2-CH)X -(CH2-CI)y 7 Rl l2 8 f=

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 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~

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.

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:

1 Shear ~ate Viscosity 2 sec~l cP

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) 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 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~

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 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 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:
.

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.

1 Elemental analysis showed a nitrogen content of 1.13 2 weight percent which corresponds to 8.4 mole percent 3 4-vinyl-pyridine.

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.

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 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.

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) 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

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.

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~

97.5 2.5 571 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.

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) 1~ 15 284 .

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 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.

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~

11 97~5 2.5 571 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 , .

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.

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 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.

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.

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.

Claims (11)

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:

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:

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:

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:

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:

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.

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:

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:

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 (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:

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:

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 (2) a copolymer of an alpha-olefin and a vinyl alkylene carboxylic acid having the formula:

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:

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 %.