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304 Lubricant Additives: Chemistry and Applications

Figures 10.17 through 10.20 summarize VM/PPD effects on MRV viscosity for each base oil

type. In these graphs, the letter Y adjacent to a vertical bar denotes a yield stress failure. For the

API Group I base oil B1 (SAE 5W-30, Figure 10.17), only PPD-3 is effective with all three viscosity

modi ers. Both VM-1 and VM-3 suffer yield stress failures with at least one PPD. In the 15W-40

formulation, VM-3 exhibits yield stress behavior with all four PPDs, even in one case in which the

MRV viscosity is quite low (PPD-1). In the author’s experience, it is quite unusual to observe yield

stress failures in the MRV test when viscosity is below ∼40,000 cP.

FIGURE 10.17 Rheological results for oil B1. SAE 5W-30 (left) and SAE 15W-40 (right).

PPD-1

PPD-2

PPD-3

PPD-4

VM-1

VM-2

VM-3

20,000

40,000

60,000

80,000

MRV viscosity (cP) at −35°C

PPD-1

PPD-2

PPD-3

PPD-4

VM-1

VM-2

VM-3

20,000

40,000

60,000

80,000

MRV viscosity (cP) at −25°C

FIGURE 10.18 Rheological results for oil B2. SAE 5W-30 (left) and SAE 15W-40 (right).

PPD-1

PPD-2

PPD-3

PPD-4

VM-1

VM-2

VM-3

20,000

40,000

60,000

80,000

MRV viscosity (cP) at −35°C

PPD-1

PPD-2

PPD-3

PPD-4

VM-1

VM-2

VM-3

20,000

40,000

60,000

80,000

MRV viscosity (cP) at −25°C

FIGURE 10.19 Rheological results for oil B3. SAE 5W-30 (left) and SAE 15W-40 (right).

PPD-1

PPD-2

PPD-3

PPD-4

VM-1

VM-2

VM-3

20,000

40,000

60,000

80,000

MRV viscosity (cP) at −35°C

PPD-1

PPD-2

PPD-3

PPD-4

VM-1

VM-2

VM-3

20,000

40,000

60,000

80,000

MRV viscosity (cP) at −25°C

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Oleﬁ n Copolymer Viscosity Modiﬁ ers 305

The other API group I blended oils, B2 (Figure 10.18), respond to PPDs in a similar manner to

B1, but only in the SAE 5W-30 formulation. In the 15W-40 case, VM-3 is the only VM to experience

yield stress failure, but only in the presence of PPD-2; all other combinations demonstrate acceptable

pumpability performance.

Figure 10.19 describes the MRV map of B3, the API Group II oil. Overall, low-temperature

viscosities are all quite low for all VM/PPD combinations, although VM-3 again experiences one

yield stress failure in each viscosity grade. VM-1 fails the yield stress criterion once.

Finally, the API Group III SAE 5W-30 formulation (Figure 10.20) was the most dif cult to pour

depress. All four oils blended with VM-3 were yield stress failures, and each of the other two VMs

showed signi cant yield stresses for one PPD each.

In summary, the number of MRV failures due to yield stress is given in Table 10.12. Clearly,

one of the LTOCP viscosity modi ers, VM-3, is substantially more sensitive to PPDs than the other

two polymers. It is especially incompatible with PPD-2. The other LTOCP in this study, VM-2, and

the amorphous VM-1 were found to be far more tolerant of PPD type. Similar to the discussion

in Section 10.5.4.2, one of the major differences between VM-3 and VM-2 is that they were

manufactured by different technologies, broadly described in Figures 10.5 and 10.4, respectively.

10.5.6 FIELD PERFORMANCE DATA

Multigrade lubricants containing EP viscosity modi ers have been tested in passenger car and

heavy-duty truck engines for over three decades, but very few studies devoted to VM effects on

engine cleanliness and wear have been published. It is generally believed that adding a polymer to

the engine lubricant will have a detrimental effect on engine varnish, sludge, and piston ring-pack

FIGURE 10.20 Rheological results for oil B4. SAE 5W-30.

PPD-1

PPD-2

PPD-3

PPD-4

VM-1

VM-2

VM-

20,000

40,000

60,000

80,000

MRV viscosity (cP) at -35°C

TABLE 10.12

Number of MRV Failures due to Yield Stress in Low-

Temperature Viscosity Modiﬁ er/Pour Point Depressant

Interaction Study

VM PPD-1 PPD-2 PPD-3 PPD-4 Total

VM-1 1 1 3 5

VM-2 1 1

VM-3 263213

Total 364619

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306 Lubricant Additives: Chemistry and Applications

deposits [1,2], but the performance additive can be formulated to compensate for these effects.

Kleiser et al. [124] ran a taxicab  eet test designed to compare the performance of a nonfunctional-

ized OCP viscosity modi er with a highly dispersant-functionalized OCP (HDOCP) as well as to

test other oil formulation effects. They were surprised to  nd that SAE 5W-30 oil containing a higher

concentration of non-DOCP showed statistically better engine deposit control when compared to a

similar SAE 15W-40 oil with lower polymer content. They also observed signi cant improvements

in sludge and varnish ratings attributed to the use of HDOCP. Others have also reported that DOCPs

can be bene cial in preventing buildup of deposits in laboratory engines such as the Sequence VE

[125], VD [1], and Caterpillar 1H2/1G2 [1] tests. These authors found that engine oils containing

certain DOCPs need less ashless dispersant to achieve an acceptable level of engine cleanliness

than NOCPs. The actual level of deposit prevention is highly in uenced by the functionalization

chemistry as well as the number of substituents per 1000 backbone carbon atoms, as shown in

Table 10.13 (MFOCP = Multi-functional OCP).

10.6 MANUFACTURERS, MARKETERS, AND OTHER ISSUES

10.6.1 EP/EPDM M

ANUFACTURERS

EP copolymers and EPDM terpolymers are manufactured by a number of companies around the

globe. Table 10.14 [126] contains a listing of those with production capacity >30,000 metric tons/

year (£65 million per annum). Not all are necessarily supplying rubber into the viscosity modi er

market. The vast majority of the capacity goes into other applications such as automotive (sealing

systems, radiator hoses, injection molded parts), construction (window gaskets, roo ng/sheeting,

cable insulation, cable  ller), and plastics modi cation.

Various grades are often classi ed by melt viscosity, EP ratio, diene type and content, and

physical form and  ller type and level (carbon black, pigments, or extender oils). Melt viscosity is

measured by two main techniques—Mooney viscosity (ASTM D1646 or ISO 289) and melt index

(ASTM D1238 or ISO 1133-1991, also called melt-mass  ow rate). Mooney viscosity is directly pro-

portional to molecular weight, whereas melt index is inversely proportional to molecular weight.

TABLE 10.13

120 h Caterpillar 1H2 Piston Deposit Ratings of SAE

10W-40 Oils Formulated with N-Vinyl Pyrollidone-

Grafted OCPs

Sample Nitrogen (wt%) TGF WTD

OCP 0 – >800

MFOCP5 0.3 46 244

MFOCP6 0.5 39 173

MFOCP7 0.7 47 149

MFOCP6

0.26 28 156

MFOCP2

0.28 11 139

Note: TGF, top groove  ll rating; WTD, weighted total (piston) demerits

rating.

OCP grafted with maleic anhydride and subsequently reacted with amines.

Source: Adapted from Spiess, G.T., Johnston, J.E., and VerStrate, G., Addit.

Schmierst. Arbeits uessigkeiten, Int. Kolloq., 5th, 2, 8.10-1, Tech.

Akad. Esslingen, 1986.

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Oleﬁ n Copolymer Viscosity Modiﬁ ers 307

TABLE 10.14

Manufacturers with Production Capacity Greater than 30,000 Metric Tons/Year

Company

Manufacturing

Location(s)

Capacity (Metric

tons/Year) Technology Trade Name Comments

Dow Chemical Plaquemine,

Louisiana

230,000 Metallocene, solution

and gas-phase

processes

Nordel IP EPDM

Seadrift, Texas Nordel MG

DSM Elastomers Geleen, The

Netherlands;

Triunfo, Brazil

185,000 Ziegler–Natta,

solution process

Keltan EP and EPDM

ExxonMobil

Chemical

Baton Rouge,

Louisiana, United

States; Notre Dame

de Gravenchon,

France; Kumbo

Polychem, South

Korea (JV)

272,500 Ziegler–Natta and

metallocene,

solution process

Vistalon EP and EPDM

JSR Corporation

(Japan Synthetic

Rubber)

Yokkaichi and

Kashima, Japan

87,500 Ziegler–Natta,

solution process

Esprene EPDM

Lanxess Orange, Texas 110,000 Ziegler–Natta,

suspension and

solution processes

Buna EP T EP and EPDM

Marl, Germany Buna EP G

Lion Copolymer Geismar, Louisiana,

United States

93,000 Ziegler–Natta,

solution process

Royalene,

Trilene

EP and EPDM

Mitsui Chiba, Japan 120,000

Ziegler–Natta and

metallocene,

solution process

Mitsui EPT EP and EPDM

Polimeri Europa Ferrara, Italy 85,000 Ziegler–Natta,

suspension process

Dutral EP and EPDM

Sumitomo Japan 45,000 Ziegler–Natta,

solution process

Esprene EPDM

Includes 75,000 metric tons/year metallocene plant to begin operation in 2007.

10.6.2 OLEFIN COPOLYMER VM MARKETERS

Companies which provide EP copolymers and EPDM terpolymers to the viscosity modi er market

are listed in Table 10.15. A wide variety of products, varying in shear stability and level of crystal-

linity, are available in both solid and liquid forms. Functionalized polymers that provide added

dispersancy and antioxidancy are available from several suppliers. The reader is advised to update

this information periodically, since each company’s product lines change over time.

Mergers and acquisitions have also contributed to signi cant  ux in the OCP market. For exam-

ple, the Paratone

product line was originally developed and marketed by the Paramins Division of

Exxon Chemical Company. When Exxon and Shell combined their lubricant additives businesses to

form In neum in 1998, the Paratone business was sold to Oronite, the lubricant additives division

of Chevron Chemical Company. Ethyl’s purchase of Amoco and Texaco OCP product technology

in the 1990s resulted in rebranding of Texaco’s TLA-XXXX products to Ethyl’s Hitec

product

line. Ethyl Additives changed its name to Afton Chemical Company in 2004. Dupont originally

marketed EPDM—manufactured at its Freeport, Texas, facility—into the viscosity modi er market

under the Ortholeum

trademark until it was sold to Octel in 1995. Thereafter, DuPont adopted

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308 Lubricant Additives: Chemistry and Applications

the NDR brand name. DuPont and Dow Chemical Company formed a 50/50 joint venture in 1995,

merging their elastomer businesses. Shortly following the successful start-up of their metallocene

plant in Plaquemine, Louisiana, 2 years later, the Freeport facility was closed. Dow Chemical Com-

pany acquired control of the EPDM product line, marketed under the Nordel

IP trade name, in

2005. Bayer transferred its EPDM business to a new company named LANXESS in 2004. Although

primarily a poly(alkylmethacrylate) company, Rohm GmbH of Darmstadt, Germany, developed

several OCP-based viscosity modi ers under the Viscoplex

trade name, currently owned and

marketed by RohMax Additives, a Degussa company. In mid-2007, Crompton sold its EPDM

business to Lion Copolymer.

10.6.3 READ ACROSS GUIDELINES

Various lubrication industry associations have published highly detailed guidelines [127–129]

for de ning conditions under which certain additive and base oil changes to a fully or partially

quali ed engine oil formulation may be permitted without requiring complete engine testing data

to support the changes. The purpose of these standards is to minimize test costs while ensuring

that commercial engine oils meet the performance requirements established by industry standards,

certi cation systems, and original equipment manufacturers (OEMs). From a viscosity modi er

perspective, changes are often driven by one or more of the following needs:

1. To optimize viscometrics within a given viscosity grade

2. To improve the shear stability of the formulation

3. To interchange one polymer for another (cost, security of supply, customer choice)

There are similarities and differences among codes of practice adopted by the American Chemistry

Council (ACC) and the two European agencies, ATC (Technical Committee of Petroleum Additive

Manufacturers of Europe) and ATIEL (Technical Association of the European Lubricants Industry).

All permit minor changes in VM concentration (no more than 15% relative on a mass basis) to accom-

plish the  rst need mentioned earlier. The European codes explicitly allow the interchange of one VM

for another (if both are from the same supplier) if the VM supplier deems them to be “equivalent and

interchangeable.” VMs from different suppliers, or those from the same supplier that are not judged to

be “equivalent,” must undergo a rigorous engine testing program such as that outlined in Table 10.16.

TABLE 10.15

Marketers of E/P Copolymers and EPDM Terpolymers as Engine Lubricating Oil Viscosity

Modiﬁ ers

Company Headquarters Trade Name Product Classes Product Form

Afton Richmond, Virginia Hitec 5700 series NDOCP, DOCP, DAOCP Liquid concentrates

Chevron Oronite Richmond, California Paratone NDOCP, DOCP Pellet, bales, and

liquid concentrates

Dow Chemical Midland, Michigan Nordel IP NDOCP Bales and pellets

In neum Linden, New Jersey In neum V8000 series NDOCP Pellets and liquid

concentrates

Lubrizol Wickliffe, Ohio Lubrizol 7000 series NDOCP, DOCP Bales and liquid

concentrates

RohMax

(Degussa AG)

Darmstadt, Germany Viscoplex NDOCP, mixed PMA/OCP Liquid concentrates

Note: DAOCP = ole n copolymer with dispersant and antioxidant functionality; DOCP = dispersant-functionalized ole n

copolymer; NDOCP = nonfunctionalized ole n copolymer; PMA = poly(alkyl methacrylate).

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Oleﬁ n Copolymer Viscosity Modiﬁ ers 309

TABLE 10.16

Engine Test Requirements for Interchanging Viscosity Modiﬁ ers within the ATIEL

Code of Practice

Performance Category NDVM to NDVM (1, 2, 3, 4) DVM to DVM or NDVM to DVM (1, 2, 3, 4)

Gasoline TU572 (8) TU572 (8)

M111 or VG (9) M111 or VG (9)

M111FE M111FE

Light-duty diesel VWICTD (9) OM602A

VW DI VWICTD (9)

M111FE XUD11 (12)

VW DI

M111FE

Gasoline/light-duty diesel TU572 (8) TU572 (8)

M111 or VG (9) M111 or VG (9)

VWICTD (9) OM602A

VW DI VWICTD (9)

M111FE XUD11 (12)

VW DI

M111FE

Gasoline/light-duty diesel with after

treatment devices

TU572 (8) TU572 (8)

M111 or VG (9) M111 or VG (9)

VW DI OM602A

M111FE XUD11 (12)

VW DI

M111FE

Heavy-duty diesel OM364LA (10) OM364LA (10)

Mack T8 (6) OM602A

Mack T8E (7) Mack T8

OM 441 LA Mack T8E

M11 (5) (11) OM 441 LA

M11 (5) (11)

Note:

1. Full testing required for any other viscosity modi er interchange (VMI) not listed above.

2. Physical mixes of non-dispersant viscosity modi er (NDVM) and DVM are treated as DVM.

3. Only the tests included in the ACEA sequence for which read across is required have to be run.

4. Where alternative tests are listed, for example, “M111 or VG,” the alternative test cannot be run to document read across

if a failing result has already been obtained on the other test.

5. Not required if the new oil formulation has the same or greater HTHS value compared with the original tested formulation.

6. The Mack T8 requirement is waived, if the replacement NDVM has the same or poorer shear stability as determined on

candidate test oil formulated to similar viscosity as the original NDVM tested formulation and measured by CEC-14-A-

93 (ASTM D 6278-98), and if the requirements of note 7 are also met.

7. The T8 or T8E requirement is waived, if the replacement NDVM is within the same chemical type as the tested NDVM

(“chemical type” means chemical family such as, but not limited to, styrene ester, polymethacrylate, styrene butadiene,

styrene isoprene, polyisoprene, ole n copolymer, and polyisobutylene).

8. TU3MH results can be used in support of A2-96 issue 3 provided the results are passing for A2-96 issue 2.

9. The VWICTD may be replaced by the VWDI (with B4 performance limit).

10. The OM364LA requirement may be met by a passing OM441LA at E5 level.

11. The M11EGR test may be used in place of the M11.

12. The XUD 11 test can be replaced by the DV4 test.

Source: Code of Practice for Developing Engine Oils Meeting the Requirements of the ACEA Oil Sequences, ATIEL, Technical

Association of the European Lubricants Industry, Issue No. 13, Appendix C, Brussels, Belgium, November 28, 2005.

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310 Lubricant Additives: Chemistry and Applications

TABLE 10.17

CAS Index of EP and EPDM Copolymers

EP/EPDM CAS Index

EP 9010-79-1

EPDM (ENB termonomer) 25038-36-2

EPDM (DCPD termonomer) 25034-71-3

EPDM (1,4-hexadiene termonomer) 25038-37-3

The ACC guidelines impose two levels of data needed to support viscosity modi er interchange.

Level 1 support is de ned as analytical and rheological test data. Level 2 support includes both

level 1 data and full-length valid ASTM engine tests, intended to demonstrate that the proposed

VM interchange presents no harm in terms of lubricant performance. There are three categories of

engine tests that can be used to satisfy the ACC level 2 criterion: (1) statistically designed engine

test matrices, (2) complete programs, or (3) partial data sets from the same technology family. This

broad de nition of additive interchange testing is more open for interpretation than the ATIEL

guidelines as represented in Table 10.16. Minor formulation modi cations needing only level 1 data

do not permit changes in VM type, de ned as polymers of a “speci c molecular architecture with

a speci c shear stability characterized by a speci c trade name, stock or code number.” When a

change in shear stability is required, level 2 support is suf cient for polymers of the same chemical

family (e.g., OCPs) and from the same manufacturer. Otherwise, a full engine testing program is

needed. The ACC guidelines also specify that if a dispersant viscosity modi er (DVM) is used in

a core multigrade formulation, the additional dispersant needed to read across to a monograde or

other multigrades with lower VM concentration requires a Sequence VG test and level 2 support in

other tests.

10.6.4 SAFETY AND HEALTH

E/P copolymers as well as EPDMs are classi ed as “nonhazardous” substances by OSHA (1910.1200)

and the European Economic Community (EEC). They are generally considered to be not acutely

toxic, similar to other high-molecular-weight polymers. Material that is heated to the molten state can

emit fumes, which can be harmful and irritating to the eyes, skin, mucous membranes, and respiratory

tract, especially copolymers containing nonconjugated diene termonomers. Proper ventilation and

respiratory protection are recommended when handling EP and EPDM copolymers under these con-

ditions. Appropriate personal protective equipment is also advised to guard against thermal burns.

EP/EPDM grades are indexed by the Chemical Abstract Service in Table 10.17.

REFERENCES

1. Spiess, G.T., J.E. Johnston and G. VerStrate, “Ethylene Propylene Copolymers as Lube Oil Viscosity

Modi ers,” Addit. Schmierst. Arbeits uessigkeiten, Int. Kolloq., 5th, 2, 8.10-1, W.J. Bartz, ed., Tech.

Akad. Esslingen, Ost ldern, Fed. Rep. Germany, 1986.

2. Marsden, K., “Literature Review of OCP Viscosity Modi ers,” Lubr. Sci., 1(3), 265, 1989.

3. Ver Strate, G. and M.J. Struglinski, “Polymers as Lubricating-Oil Viscosity Modi ers,” in Polymers

as Rheology Modi ers, D.N. Schulz and J.E. Glass, eds., ACS Symp. Ser., 462, 256, Am. Chem. Soc.,

Washington, DC, 1991.

4. Boor, J., Jr., Ziegler-Natta Catalysts and Polymerizations, Academic Press, New York, 1979.

5. Crespi, G., A. Valvassori and U. Flisi, “Ole n Copolymers,” in Stereo Rubbers, W.M. Saltman, ed.,

Wiley-Interscience, New York, NY, pp. 365–431, 1977.

6. Brandrup, J. and E.H. Immergut, eds., Polymer Handbook, 2nd Ed., Wiley , New York, p. II-193, 1975.

7. May, C.J., E. De Paz, F.N. Gixshick, K.O. Henderson, R.B. Rhodes, S. Iseregounis, and L. Ying, “Cold

Starting and Pumpability Studies in Modern Engines,” ASTM Res. Report RR-DO2-1442, 1999.

CRC_59645_Ch010.indd 310CRC_59645_Ch010.indd 310 12/6/2008 10:10:19 AM12/6/2008 10:10:19 AM

Oleﬁ n Copolymer Viscosity Modiﬁ ers 311

8. Wilkes, C.E., C.J. Carmen and R.A. Harrington, “Monomer Sequence Distribution in Ethylene-

Propylene Terpolymers Measured by

C Nuclear Magnetic Resonance,” J. Poly. Sci.: Symp. No. 43,

237, 1973.

9. Carmen, C.J. and K.C. Baranwal, “Molecular Structure of Elastomers Determined with Carbon-13

NMR,” Rubber Chem. Tech., 48, 705, 1975.

10. Carmen, C.J., R.A. Harrington and C.E. Wilkes, “Monomer Sequence Distribution in Ethylene–

Propylene Rubber Measured by

C NMR. 3. Use of Reaction Probability Model,” Macromolecules,

10(3), 536, 1977.

11. Randall, J.C., Polymer Sequence Determinations: Carbon-13 NMR Method, Academic Press, New York,

p. 53, 1977.

12. Carmen, C.J., “Carbon-13 NMR High-Resolution Characterization of Elastomer Systems,” in Carbon-13

NMR in Polymer Science, ACS Symp. Ser., W.M. Pasikan, ed. 103, 97, 1978.

13. Kapur, G.S., A.S. Sarpal, S.K. Mazumdar, S.K. Jain, S.P. Srivastava and A.K. Bhatnager, “Structure-

Performance Relationships of Viscosity Index Improvers: I. Microstructural Determination of Ole n

Copolymers by NMR Spectroscopy,” Lubr. Sci., 8-1, 49, 1995.

14. U.S. Patent 4666619, 1987.

15. U.S. Patent 4156767, 1979.

16. Olabisi, O. and M. Atiqullah, “Group 4 Metallocenes: Supported and Unsupported,” J.M.S.—Rev.

Macromol. Chem. Phys., C37(3), 519, 1997.

17. Soares, J.B.P. and A.E. Hamielec, “Metallocene/Aluminoxane Catalysts for Ole n Polymerization. A

Review,” Poly. Reaction Engr., 3(2), 131, 1995.

18. Gupta, V.K., S. Satish and I.S. Bhardwaj, “Metallocene Complexes of Group 4 Elements in the Polym-

erization of Monoole ns,” J.M.S.—Rev. Macromol. Chem. Phys., C34(3), 439, 1994.

19. Hackmann, M. and B. Rieger, “Metallocenes: Versatile Tools for Catalytic Polymerization Reactions

and Enantioselective Organic Transformations,” Cat. Tech, 79(December), 1997.

20. Chien, J.C.W. and D. He, “Ole n Copolymerization with Metallocene Catalysts. I. Comparison of

Catalysts,” J. Poly. Sci. Part A: Poly. Chem., 29, 1585, 1991.

21. Montagna, A.A., A.H. Dekmezian and R.M. Burkhart, “The Evolution of Single-Site Catalysts,”

Chemtech, 26(December), 1997.

22. McGirk, R.H., M.M. Hughes and L.C. Salazar, “Evaluation of Polyole n Elastomers Produced by

Constrained Geometry Catalyst Chemistry as Viscosity Modi ers for Engine Oil,” Soc. Automot. Eng.

Tech. Paper Ser. No. 971696, 1997.

23. Rotman, D., “Dupont Dow Dobuts Metallocene EPOM.” “Synthetic Rubber,” Chem. Week, 15,(May

14), 1997.

24. U.S. Patent 5151204, 1992.

25. Mishar, M.K. and R.G. Saxton, “Polymer Additives for Engine Oils,” Chemtech, 35(April), 1995,

pp. 35–41.

26. U.S. Patent 5698500, 1997.

27. Corbelli, L., “Ethylene-Propylene Rubbers,” Dev. Rubber Tech., 2, 87–129, 1981.

28. European Patent 199453, 1986.

29. U.S. Patent 4092255, 1978.

30. U.S. Patent 4699723, 1987.

31. U.S. Patent 4816172, 1989.

32. U.S. Patent 5814586, 1998.

33. U.S. Patent 5874389, 1999.

34. Pennewib, H. and C. Auschra, “The Contribution of New Dispersant Mixed Polymers to the Economy

of Engine Oils,” Lubr. Sci., 8(2), 179–197, 1996.

35. U.S. Patent 4089794, 1978.

36. U.S. Patent 4160739, 1979.

37. U.S. Patent 4171273, 1979.

38. U.S. Patent 4219432, 1980.

39. U.S. Patent 4320019, 1982.

40. U.S. Patent 4489194, 1985.

41. U.S. Patent 4749505, 1988.

42. U.S. Patent 5210146, 1992.

43. U.S. patent 5252238, 1993.

44. U.S. Patent 5290461, 1994.

45. U.S. Patent 5401427, 1995.

CRC_59645_Ch010.indd 311CRC_59645_Ch010.indd 311 12/6/2008 10:10:19 AM12/6/2008 10:10:19 AM

312 Lubricant Additives: Chemistry and Applications

46. U.S. Patent 5427702, 1995.

47. U.S. Patent 5534171, 1996.

48. Garbassi, F., “Long Chain Branching: An Open Question for Polymer Characterization?” Polymer

News, 19, 340–346, 1994.

49. U.S. Patent 4517104, 1985.

50. U.S. Patent 4632769, 1986.

51. U.S. Patent 5540851, 1998.

52. U.S. Patent 5811378, 2000.

53. European Patent 338672, 1989.

54. U.S. Patent 5075383, 1991.

55. U.S. Patent 4500440, 1985.

56. U.S. Patent 5035819, 1991.

57. European Patent 470698, 1992.

58. European Patent 461774, 1991.

59. U.S. Patent 5021177, 1991.

60. U.S. Patent 4790948, 1988.

61. European Patent 284234, 1988.

62. U.S. Patent 6117941, 2000.

63. Ondrey, G. and T. Kamiya “Synthetic Rubber is Resilient,” Chem. Eng., 105(12), 30, 1998.

64. Italiaander, E.T., “The Gas-Phase Process—A New Era in EPR Polymerization and Processing

Technology,” KGK Kautschuk Gummi Kunststoffe, Jahrgang, 48(October), 742–748, 1995.

65. Hüts, B., “Ethylene-Propylene Rubber,” Hydrocarbon Processing, p. 164, November 1981.

66. “EPM/EPDM,” Gosei Gomu, 85, 1–9, 1980.

67. Darribère, C., F.A. Streiff and J.E. Juvet, “Static Devolatilization Plants,” DECHEMA Monographs,

134, 689–704, 1998.

68. U.S. Patent 3726843, 1973.

69. U.S. Patent 4874820, 1989.

70. U.S. Patent 4804794, 1989.

71. U.S. Patent 5798420, 1998.

72. Corbelli, L. and F. Milani, “Recenti Sviluppi Nella Produzione Delle Gomme Sintetiche Etilene-

Proilene,” L-Industria Della Gomma, 29(5), 28–31, 53–55, 1985.

73. Young, H.W and S.D. Brignac, “The Effect of Long Chain Branching on EPDM Properties,” Proceedings

of Special Symp. Advanced Polyole n Tech., 54th Southwest Reg. Meeting, American Chemical Society,

Baton Rouge, LA, 1998.

74. British Patent 1372381, 1974.

75. Canadian Patent 991792, 1976.

76. U.S. Patent 4464493, 1984.

77. U.S. Patent 4749505, 1988.

78. U.S. Patent 5290461, 1994.

79. U.S. Patent 5391617, 1995.

80. U.S. Patent 5401427, 1995.

81. U.S. Patent 5837773, 1998.

82. U.S. Patent 3316177, 1967.

83. U.S. Patent 3326804, 1967.

84. U.S. Patent 4743391, 1988.

85. U.S. Patent 5006608, 1991.

86. U.S. Patent 4743391, 1988.

87. U.S. Patent 5006608, 1991.

88. Carman, C.J. and K.C. Baranwal, “Molecular Structure of Elastomers Determined with Carbon-13

NMR,” Rubber Chem. Technol., 48, 705–718, 1975.

89. Carman, C.J., R.A. Harrington and C.E. Wilkes, “Monomer Sequence Distribution in Ethylene-

Propylene Rubber Measured by

C NMR. 3. Use of Reaction Probability Model,” Macromolecules,

10(3), 536–544, 1977.

90. Carman, C.J., “Carbon-13 NMR High-Resolution Characterization of Elastomer Systems,” Carbon-13

NMR in Polymer Science, ACS Symp. Ser., 103, 97–121, 1978.

91. Wilkes, C.E., C.J. Carman and R.A. Harrington, “Monomer Sequence Distribution in Ethylene–

Propylene Terpolymers Measured by

C Nuclear Magnetic Resonance,” J. Poly. Sci.: Symp. No. 43,

237–250, 1973.

CRC_59645_Ch010.indd 312CRC_59645_Ch010.indd 312 12/6/2008 10:10:20 AM12/6/2008 10:10:20 AM

Oleﬁ n Copolymer Viscosity Modiﬁ ers 313

92. Di Martino, S. and M. Kelchtermans, “Determination of the Composition of Ethylene-Propylene-

Rubbers Using

C-NMR Spectroscopy,” J. Appl. Poly. Sci., 56, 1781–1787, 1995.

93. Randall, J.C., Polymer Sequence Determinations: Carbon-13 NMR Method, pp. 53–138, Academic

Press, New York, 1977.

94. Minick, J., A. Moet, A. Hiltner, E. Baer and S.P. Chum, “Crystallization of Very Low Density Copolymers

of Ethylene with α-Ole ns,” J. Appl. Poly. Sci., 58, 1371–1384, 1995.

95. Rubin, I.D. and M.M. Kapuscinski, “Viscosities of Ethylene-Propylene-Diene Terpolymer Blends in

Oil,” J. Appl. Poly. Sci., 49, 111, 1993.

96. Rubin, I.D., “Polymers as Lubricant Viscosity Modi ers,” Poly. Preprints, Am. Chem. Soc. Div. Poly.

Chem., 32(2), 84, 1991.

97. Rubin, I.D., A.J. Stipanovic and A. Sen, “Effect of OCP Structure on Viscosity in Oil,” Soc. Automot.

Eng. Tech. Paper Ser. No. 902092, 1990.

98. Kapuscinski M.M., A. Sen and I.D. Rubin, “Solution Viscosity Studies on OCP VI Improvers in Oils,”

Soc. Automot. Eng. Tech. Paper Ser. No. 892152, 1989.

99. Kucks, M.J., H.D. Ou-Yang and I.D. Rubin, “Ethylene-Propylene Copolymer Aggregation in Selective

Hydrocarbon Solvents,” Macromolecules, 26, 3846, 1993.

100. Rubin, I.D. and A. Sen, “Solution Viscosities of Ethylene-Propylene Copolymers in Oils,” J. Appl. Poly.

Sci., 40, 523–530, 1990.

101. Sen, A. and I.D. Rubin, “Molecular Structures and Solution Viscosities of Ethylene-Propylene

Copolymers,” Macromolecules, 23, 2519, 1990.

102. LaRiviere, D., A.A. Asfour, A. Hage and J.Z. Gao, “Viscometric Properties of Viscosity Index Improvers

in Lubricant Base Oil over a Wide Temperature Range. Part I: Group II Base Oil,” Lubr. Sci., 12(2),

133–143, 2000.

103. Huggins, M.L., “The viscosity or dilute solutions of Long-chain molecules. IV. Dependence on concen-

tration” J. Am. Chem. Soc., 64, 2716, 1942.

104. “Engine Oil Viscosity Classi cation,” Soc. Automot. Eng. Surface Vehicle Standard No. J300, Rev.

December 1999.

105. Rhodes, R.B., “Low-Temperature Compatibility of Engine Lubricants and the Risk of Engine

Pumpability Failure,” Soc. Automot. Eng. Tech. Paper Ser. No. 932831, 1993.

106. Papke, B.L., M.A. Dahlstrom, C.T. Mans eld, J.C. Dinklage and D.J. Rao, “Deterioration in Used Oil Low

Temperature Pumpability Properites,” Soc. Automot. Eng. Tech. Paper Ser. No. 2000-01-2942, 2000.

107. Matko, M.A. and D.W. Florkowski, “Low Temperature Rheological Properties of Aged Crankcase

Oils,” Soc. Automot. Eng. Tech. Paper Ser. No. 200-01-2943, 2000.

108. Alexander, D.L., S.A. Cryvoff, J.M. Demko, A.K. Deysarkar, T.W. Beta, R.I. Rhodes, M.F. Smith,

Jr., R.L. Stambaugh, J.A. Spearot and M.A. Vickare, “High-Temperature, High-Shear (HTHS) Oil

Viscosity: Measurement and Relationship to Engine Operation,” J.A. Spearot, ed., ASTM Special Tech.

Pub., STP 1068, 1989.

109. Bates, T.W., “Oil Rheology and Journal Bearing Performance: A Review,” Lubr. Sci., 2(2) 157–176, 1990.

110. Wardle, R.W.M., R.C. Coy, P.M. Cann and H.A. Spikes, “An ‘In Lubro’ Study of Viscosity Index

Improvers in End Contacts,” Lubr. Sci., 3(1), 45–62, 1990.

111. Alexander, D.L. and S.W. Rein, “Relationship ‘between Engine Oil Bench Shear Stability Tests,” Soc.

Automot. Eng. Tech. Paper Ser. No. 872047, 1987.

112. Bartz, W.J., “In uence of Viscosity Index Improver, Molecular Weight, and Base Oil on Thickening,

Shear Stabilit, and Evaporation Losses of Multigrade Oils,” Lubr. Sci., 12(3), 215–237, 2000.

113. Laukotka, E.M., “Shear Stability Test for Polymer Containing Lubricating Fluids—Comparison of Test

Methods and Test Results,” Third International Symposium—The Perform. Evolution of Automotive

Fuels and Lubricants, Co-ordinating European Council Paper No. 3LT, Paris, April 19–21, 1987.

114. Selby, T.W., “The Viscsosity Loss Trapezoid – Part 2: Determining General Features of VI Improver

Molecular Weight Distribution by Parameters of the VLT,” Soc. Automot. Eng. Tech. Paper Ser. No.

932836, 1993.

115. Covitch, M.J., “How Polymer Architecture Affects Permanent Viscosity Loss of Multigrade Lubricants,”

Soc. Automot. Eng. Tech. Paper Ser. No. 982638, 1998.

116. Kramer, D.C., J.N. Ziemer, M.T. Cheng, C.E. Fry, R.N.Reynolds, B.K. Lok, M.L. Sztenderowicz and

R.R. Krug, “In uence of Group II & III Base Oil Composition on VI and Oxidation Stability,” National

Lubricating Grease Inst. Publ. No. 9907, Proceedings from 66th NLGI Annual Meeting, Tucson, AZ,

October 25, 1999.

117. Rossi, A., “Lube Basestock Manufacturing Technology and Engine Oil Pumpability,” Soc. Automot.

Eng. Tech. Paper Ser. No. 940098, 1994.

CRC_59645_Ch010.indd 313CRC_59645_Ch010.indd 313 12/6/2008 10:10:20 AM12/6/2008 10:10:20 AM