Ethylene-Propylene Co - and Terpolymer Rubber, Supp.

B, July 1981

PROGRAM
SRI INTERNATIONAL
Mod0 Pd.

Abstract
Process Economics Program Report No. 4B
ETHYLENE-PROPYLENE TERPOLYMER RUBBER
(July 1981)

Most commercial ethylene-propylenecopolymer rubber now includes a

small amount of diene to permit conventional vulcanization with sulfur.
This EPDM terpolymer is used in non-tire automotive parts, and is used
increasingly as an impact modifier for plastics.
Asymmetric nonconjugated dienes are preferred for making EPDM, and
three different dienes are used commercially. They are trans-1,4hexadiene (HD), dicyclopentadiene (DCPD), and 5-ethylidene-norbornene-2
(ENB). These dienes vary in price and also confer different combinations of properties on the final rubber product.
No new EPDM processes have been proposed in recent years, and processes evaluated here are refinements of processes evaluated earlier.
Process Improvements have focused on reducing reactor fouling while
making more concentrated solutions, increasing catalyst efficiency, and
reducing energy requirements for polymer workup.
This report presents technical and economic evaluations of the two
processes that are used commercially for making EPDM.

Solution pro-

cesses for making EPDM with HD and for making EPDM with ENB are
evaluated. A suspension process for making EPDM with ENB is also
evaluated.
The suspension process appears to have capital and operating cost
advantages over the solution process, largely because of its lower utllity costs. The solution process that uses hexadiene has a lower cost
than the process that uses ENB.

This lower cost is attributable to the

assumed lower cost for the diene, and to the simplified recovery procedure (which may also

be applicable

to ENB-containing terpolymers).

PEP'79 RHS
c-lx

CJifomia

Ethylene-Propylene Co - and Terpolymer Rubber, Supp. B, July 1981

Report No. 4B

ETHYLENE-PROPYLENE
TERPOLYMER

RUBBER
SUPPLEMENT B

by ROBERT H. SCHWAAR
and CHAO-HA0

CHI EN

with contributions by
M. KOORSE
R. MAGOVERN
A. MILLARD

July 1981

A private

report by the

PROCESS ECONOMICS PROGRAM

Menlo Park, California

94025

Ethylene-Propylene Co - and Terpolymer Rubber, Supp. B, July 1981

For detailed
referred
research.

marketing

data and information,

to one df the SRI programs specializing

the reader

is

in marketing

The CHEMICAL
ECONOMICS
HANDBOOK
Program covers

most major chemicals and chemical products produced in the

United States and the WORLD PETROCHEMICALS Program covers
major hydrocarbons and their derivatives on a worldwide basis.
In addition, the SRI DIRECTORY OF CHEMICAL PRODUCERS services
provide detailed lists of chemical producers by company, product, and plant for the United States and Western Europe.

ii

Ethylene-Propylene Co - and Terpolymer Rubber, Supp. B, July 1981

CONTENTS

INTRODUCTION . . . . . . . . . . . . . . . . . . . . . . . .

SUMMARY

..........................

Economic Aspects ......................

Technical Aspects .....................
Solution Process with Hexadiene ..............
Solution Process with ENB .................
Suspension Process with ENB ................
Gas-Phase Process .....................
3

INDUSTRY STATUS

......................

3
4
7
8
9
10
13

Consumption of EPM and EPDM Rubber .............

Production Capacity for EPM and EPDM Rubber ........

13
16

PROCESSES FOR MAKING EPDM BY SOLUTION POLYMERIZATION ....

19

Modified Catalysts for EPDM Solution Processes .......

Polymerization Systems ...................
Polymerization Modifiers ..................
Catalyst Deactivation and Removal .............
Removal and Recovery of Unreacted Monomer .........
Solvent Recovery ......................
Product Variations .....................

20
23
26
26
28
29
30

SOLUTION PROCESS FOR EPDM CONTAINING 1,4-HEXADIENE . . . . .

59

Process Description ....................

Polymerization (Section 100) ...............
Conversion of Polymer Solution to Dry Product
(Section 200) .......................
Solvent Recovery (Section 300) ..............
Process Discussion .....................
Plant Capacity ......................
Polymerization ......................
Catalyst Deactivation ..................
Product Recovery .....................
Process Wastes ......................
Materials of Construction ................
Cost Estimates. ......................
Capital-Costs ......................
Production Costs .....................

61
61

iii

62
64
72
72
72
72
73
75
75
77
77
77

Ethylene-Propylene Co - and Terpolymer Rubber, Supp. B, July 1981

CONTENTS

SOLUTION PROCESS FOR EPDM CONTAINING ENB ..........

87

Process Description ....................

Polymerization (Section 100) ...............
Catalyst Removal (Section 100) ..............
..............
Solvent Removal (Section
100)
Dryer Regeneration (Section 100) .,............
Solvent Recovery (Section
200) ..............
Monomer Recovery (Section 200) ..............
Polymer Drying (Section 300) ...............
Process Discussion .....................
Catalyst System .....................
Solvent Recovery .....................
Polymer Drying and Finishing ...............
Process Wastes ......................
Materials of Construction ................
......................
Capital Costs
Production Costs .....................

89
89

;:
91
92
102
102
103
103
104
104
104
106

SUSPENSION PROCESS FOR EPDM CONTAINING ENB .........

117

Process Review .......................

Diluents .........................
Catalysts ........................
Polymer Handling .....................
Process Description ....................
Polymerization (Section 100) ...............
Polymer Recovery (Section 200) ..............
Monomers and Solvent Recovery (Section 300) .......
Process Discussion .....................
Catalyst .........................
Reactor Liquid Composition ................
Polymer Purification and Solvent Recovery ........
Waste Streams ......................
Materials of Construction ................
Cost of Estimates .....................
Capital Costs ......................
Production Costs .....................

118
118
125
126
129
131
132
133
142
142
143
143
145
145
145
145
147

CONVERSION OF RUBBER SOLUTION TO DRY PRODUCT ........

157

Non-aqueous Solvent Removal ................

Steam Stripping ......................
Water Removal from Rubber Crumb ..............

162
163
164

i.V

9:

Ethylene-Propylene Co - and Terpolymer Rubber, Supp. B, July 1981

CONTENTS

TERMONOMERS FOR EPDM ....................

167

Dicyclopentadiene .....................
Ethylidene Norbornene ...................
Production of VNB ....................
Isomerieation of VNB to ENB ...............
Other Ways of Making ENB .................
Hexadiene .........................

167
169
169
175
176
177

APPENDIX

DESIGN AND COST BASES

................

CITED REFEEENCES ........................

PATENTED REFERENCES BY COMPANY

.................

183
191
201

Ethylene-Propylene Co - and Terpolymer Rubber, Supp. B, July 1981

ILLUSTRATIONS

2.1

Manufacture of EPDM Rubber

Effect of Plant Capacity on Total Fixed Capital

. . . . .

4.1

Du Pont EPDM Reactor. . . . . . . . . . . . . . . . . . .

24

4.2

Flow Scheme and Material Balance for Solution Blending

Copolymer -Rubberand Chemical Corporation . . . . . . . .

27

Solution Process for EPDM Containing HD

Flow Diagram. . . . . . . . . . . . . . . . . . . . . . .

205

5.1
5.2

Phase Diagram of EP/HD and Hexane

. . . . . . . . . . . .

73

5.3

Solution Process for EPDM Containing 1,4-Hexadiene

Effect of Raw Material Prices on Production Cost . . . . .

85

Solution Process for EPDM Containing 1,4-Hexadlene

Effect of Operating Level and Plant Capacity on
Production Cost . . . . . . . . . . . . . . . . . . . . .

86

Solution Process for EPDM Containing ENB

Flow Diagram....
. . . . . . . . . . . . . . . . . . .

209

Solution Process for EPDM Containing ENB

Effect of Raw Material Prices on Production Cost . . . . .

114

Solution Process for EPDM Containing ENB

Effect of Operating Level and Plant Capacity on
Production Cost . . . . . . . . . . . . . . . . . . . . .

115

5.4

6.1
6.2
6.3

7.1
7.2
7.3
7.4

EPDM By a Suspension Reaction

Du Pont Reactor Design . . . . . . . . . . . . . . . . . .
Suspension Processfor EPDM Containing ENB
Flow Diagram.......................

215

Suspension Process for EPDM Containing ENB

Effect of Raw Material Prices on Production Cost . . . . .

155

Suspension Process for EPDM Containing ENB

Effect of Operating Level and Plant Capacity on
Production Cost . . . . . . . . . . . . . . . . . . . . .

156

Vii

128

Ethylene-Propylene Co - and Terpolymer Rubber, Supp. B, July 1981

TABLES

2.1

Summary of Cost Estimates for EPDM Manufacture . . . . . .

3.1

Estimated U.S. Domestic Consumption of EPM and

EPIC Rubber - 1978 . . . . . . . . . . . . . . . . . . .

14

3.2

EPM and EDPM Plant Capacities . . . . . . . . . . . . . .

17

4.1

Catalysts for EPDM by Solution Process

Patent Summary..
. . . . . . . . . . . . . . . . . . . .

34

EPDM Solution Polymerization Reactors

Patent Summary . . . . . . . . . . . . . . . . . . . . . .

40

EPDM Solution Polymerization Modifiers

Patent Summary. . . . . . . . . . . . . . . . . . . . . .

44

EPDM Solution Catalyst Deactivation and Removal

Patent Summary. . . . . . . . . . . . . . . . . . . . . .

48

EPJM Monomer Removal (Solution Process)

Patent Summary . . . . . . . . . . . . . . . . . . . . . .

50

EPDM Solvent Removal (Solution Process)

Patent Summary . . . . . . . . . . . . . . . . . . . . . .

52

EPDM Product Variations (Solution Process)

Patent Summary . . . . . . . . . . . . . . . . . . . . . .

57

4.2
4.3
4.4
4.5
4.6
4.7

SOLUTION PROCESS FOR EPLM CONTAINING 1,4-HEXADIENE

5.1

Bases and Assumptions ..................

60

5.2

Major Equipment .....................

65

5.3

Utilities Summary

5.4

Stream Flows .......................

5.5

Summary of Waste Products

5.6

Total Capital Investment .................

5.7

Major Capital Equipment Costs

5.8

Production Costs .....................

....................

................

ix

..............

68
69
76
79
81
82

Ethylene-Propylene Co - and Terpolymer Rubber, Supp. B, July 1981

TABLES

SOLUTION PROCESS FOR EPDM CONTAINING ENB

6.1

Bases and Assumptions ..................

88

6.2

Major Equipment .....................

93

6.3

Utilities Summary

6.4

Stream Flows.

6.5

Summary of Waste Products

6.6

Total Capital Investment .................

6.7

Major Capital Equipment Costs

6.8

Production Costs .....................

111

7.1

EPDM by a Suspension Process

Patent Summary......................

119

96

....................

97

......................

105

................

108
110

..............

SUSPENSION PROCESS FOR EPDM CONTAINING ENB

7.2

Design Bases and Assumptions ...............

7.3

Major Equipment

7.4

Utilities Summary ....................

137

7.5

Stream Flows .......................

138

7.6

Summary of Waste Products ................

146

7.7

Total Capital Investment .................

149

7.8

Major Capital Equipment Costs

7.9

Production Costs .....................

8.1

Treatment of Rubber Solutions with Steam or Hot Water

Patent Stunmary.
. . . . . . . . . . . . . . . . . . . .

158

Devolatilization and Drying of Rubber Crumb or Melt

Patent Summary.
. . . . . . . . . . . . . . . . . .

160

8.2
9.1

9.2

9.3

130
134

.....................

..............

151
152

Manufacture of 5-Vinyl-2-Norbornenefrom 1,3-Butadlene

and 1,3-Cyclopentadiene
Patent Summary . . . . . . . . . . . . . . . . . . . . . .

170

Isomerization of 5-Vinyl-2-Norbornene to
5-Ethylldene-2-Norbornene
Patent Summary . ..~..................

172

Manufacture of Hexadiene from Butadiene and Ethylene

Patent Summary.......
. . . . . . . . . . . . . . .

179