DE2451848A1 - METHOD FOR MIXED POLYMERIZATION OF CYCLOPENTENE WITH DICYCLOPENTADIENE IN THE PRESENCE OF AN UNCONJUGATED ACYCLIC OLEFIN - Google Patents

Description

COLOGNE 1, DEICHMANNHAUS

Cologne, October 3rd 1974 13o3 AvK / IM

The B.P. Goodrich Company, Akron, Ohio / USA

Process for the copolymerization of cyclopentene with dicyclopentadiene in the presence of a non conjugated acyclic olefin

Because of their olefin structure, cycloolefins can be polymerized to give polycycloaliphatics or, by ring-opening processes, to give unsaturated linear polymers. That ; ^; The latter process is particularly interesting because the polymers obtained in this way can be vulcanized with sulfur. Since cyclopentene is a readily available by-product of ethylene production, efforts in this area have focused on ring-opening polymerization and copolymerization of cyclopentene.

According to the prior art, the ring-opening polymerization of cyclopentene can be achieved by a mixture of a tungsten salt, a molybdenum salt or mixtures thereof and ■ an organometallic compound or organometallic Ilalogenidverbindungen a metal of the III. Group of the periodic table. Molecular oxygen or a compound an oxygen-oxygen or an oxygen-hydrogen bond can be used as activators. In addition, the molecular weight modifying agent can be used.

The general application of these prior art methods to the copolymerization of cyclopentene with di-

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The result of cyclopentadiene is that either no reaction takes place at all or, if a reaction occurs, the polymer obtained is essentially insoluble, ie more than 10 % insoluble in a solvent, as defined below. Significant insolubility is indicative of the presence of a gel and / or pre-dicyclopentadiene homopolymer. It is therefore desirable to develop a process for the preparation of a copolymer of cyclopentene with dicyclopentadiene in which the copolymer obtained is more than 90% soluble in a solvent defined below.

The invention relates to a process for the copolymerization of cyclopentene with dicyclopentadiene in the presence a non-conjugated acyclic olefin which has at least one hydrogen on each double bond Has carbon and in the presence of a catalyst, the at least one in a solvent or a monomer soluble tungsten compound and at least one alkyl aluminum iodide compound or a mixture of elemental iodine and at least one alkyl aluminum compound. The catalytically effective aluminum / tungsten molar ratio is about 1 to 40 moles per mole, the aluminum monomer ratio must be from about 0.15 to about 0.35 µmoles per mole and the alkyl aluminum iodide compound or mixture of elemental iodine and an alkyl aluminum compound must be added to the reaction mixture be added before the tungsten compound is added. This improved process results in a copolymer which is more than 90% soluble in a solvent defined below, even if the copolymer is more contains than 90% dicyclopentadiene.

Cyclopentene is copolymerized with dicyclopentadiene to form a linear, unsaturated copolymer, the has repeating units in a random arrangement, which are mainly of the following types, in which

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below formula "m"

Numbers that are proportional to the concentrations of the cyclopentene used and dicyclopentadiene ionomers are:

(CEL) o -C =

and

The alkyl aluminum iodide compounds are from the group selected from dialkyl aluminum iodides and alkyl aluminum iodides where each alkyl group has 2 to 8 carbon atoms, preferably 2 to 4 carbon atoms has, such as diethylaluminum iodide, ethylaluminum iodide, Propyl aluminum iodide, ethyl propyl aluminum iodide and the like A mixture of a trialkyl aluminum compound with iodine can also be used, the alkyl group having 2 to 8 carbon atoms, preferably 2 to Has 4 carbon atoms, such as a mixture of Triethylaluminum and iodine. Other organoaluminum compounds and also organoaluminum halide compounds proved unsuitable for the process of the present invention. These compounds include trialkylaluminum compounds, if they are used without iodine, e.g. Triethylaluminum and the like, dialkylaluminum halides and Alkylaluminum dihalides in which the halogen is selected from the group consisting of fluorine, chlorine and bromine, such as diethy! aluminum chloride, ethyl aluminum dichloride, Diethyl aluminum chloride, diethyl aluminum fluoride and the like.

The tungsten compounds used according to the invention are soluble in the monomers or in the inert solvents used. Suitable inert solvents include aliphatic or cycloaliphatic hydrocarbon '■ solvents having 4 to 10 carbon atoms such as

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Pentane, hexane, heptane, octane, cyclohexane and cyclooctane; aromatic hydrocarbon solvents with 6 to 14 carbon atoms that are liquid or easily liquefiable are such as benzene, toluene and naphthalene and substituted hydrocarbons in which the substituents are inert such as dichloromethane, chloroform and chlorobenzene. Benzene has been found to be an excellent solvent is. j

Suitable tungsten compounds include tungsten carbonyl / ßiCO) // , tungsten oxytetrachloride, etc. Also suitable are tungsten halides such as the chlorides, bromides, iodides and fluorides such as tungsten hexachloride and tungsten hexafluoride. More preferred are tungsten halides, which include the chlorides, bromides, iodides and fluorides, such as tungsten hexachloride and tungsten hexafluoride. Excellent results are obtained using tungsten hexachloride. ;

The alkyl aluminum iodide or alkyl aluminum compound is in an amount from about 0.15 to about 0.35 rimoles per mole Monomer used. The alkyl aluminum iodide or alkyl aluminum compound becomes catalytically active molar ratio to the tungsten compound of about 1 to about 40 moles per mole, preferably from about 1 to about Moles per mole used. The elemental iodine becomes elemental iodine in a range from about 0.25 moles to about 6 moles per mole of alkyl aluminum compound, preferably from about 0.5 to about 3 moles per mole. The catalyst components can be added directly or in solution.

A polymerization activator can be used, but is generally not necessary. Examples of activators include water, methanol, ethanol, isopropyl alcohol, benzyl alcohol, Phenol, ethyl mercaptan, 2-chloroethanol, 1,3-dichloropropanol, p-bromophenol, epichlorohydrin, ethylene oxide, Cyclopenten-2-hydroperoxide, cumene hydroperoxide,

"5Ö9S19 / 1Ö33

tert-butyl peroxide, benzoyl peroxide and air or acid: material. Excellent activation is achieved when air or a peroxide or hydroperoxide is used as the actuator, in particular organic peroxides such as benzoyl peroxide can be used.

The activator can be used in an amount from about 0 to about 3 ^;

Moles per mole of aluminum organic compound, preferably ^: from about 0 to about 1 mole per mole, are used. The: activator can be added at any stage of the feed; however, it is preferred to add it as the last ingredient after the addition of the tungsten compound. I.

i is at least one nonconjugated acyclic Oils- 'used fin having at least one hydrogen atom on each in a double bond standing carbon atom and 2 to 12, preferably 2 to 8 carbon atoms corresponds [holds. Inert substituents on the remaining carbon atoms are selected from the group consisting of hydrogen; and alkyl groups having 2 to 8 carbon atoms. Examples of suitable compounds include 1-olefins such as 1-butene and 3-methyl-1-butene, 2-olefins such as 2-pentene and 4-methyl-2-pentene, 3-olefins such as eg S-ethyl 3-octene, non-conjugated diolefins such as;

1,6-hexadiene, non-conjugated triolefins such as! 1,4,7-octatriene and similar compounds. The nonconjugated acyclic olefin is more preferably selected from the group consisting of 1-olefins and 2-olefins having 2 to 8 ^: carbon atoms, e.g. 1-butene, 3-methyl-1-butene, 2-pentene, 4-methyl- 2-pentene. Compounds which do not have a hydrogen atom on the carbon atoms on the double bonds do not react in the process according to the invention. Conjugated olefins such as butadiene and iso-: prene and the like are active inhibitors. The nonconjugated acyclic olefin is used in a molar ratio to monomer of from about 0.01 to about 0.3 moles per mole. The non-conjugated acyclic olefin can be directly or

^l ---—— 5Ϊ98Τ9710ΊΠ ~ ^:

-c-

in solution at any point in the feed, but it is preferred to feed it with the monomers. If it's the last to be admitted
the non-conjugated acyclic olefin is preferably added before the start of the reaction,

The polymerization can be carried out batchwise or continuously and in bulk or in solution. The polymerization is usually carried out in a solvent or diluent as defined above and is therefore a solvent polymerization process. The solvent can be added at any point in the charge, but it is preferred added before adding the catalyst. ;

The process is effectively used for the production of cyclopentene-dicyclopentadiene copolymers. Up to about 98% by weight of dicyclopentadiene, based on the total weight of the copolymer, can be copolymerized. Preferably, the dicyclopentadiene is in a range from about 35 to about 98 wt .-% and especially from about 50
up to about 98 wt%, based on the total weight of the
Copolymers, polymerized. Small amounts of others
Monomers such as norbornylene can also be copolymerized. j

The monomers can be added at any point in the feed process. Usually the monomers, the solvent - if used - and the
non-conjugated acyclic olefins are added to the reaction vessel first. These ingredients can be added separately or as a mixture. Next, the alkyl aluminum iodide compound or the mixture of one
Trialkylaluminum compound with elemental iodine added, usually as a solution in a solvent such as benzene and the like. Then the tungsten compound is usually added as a solution in a solvent such as benzene and the like.

T / 1UT3 "~" ~ ~ ' ^j

- - - 2-451548. .,

-7-

and then the activator if one is used. The tungsten compound must follow the alkyl aluminum iodide compound or to the mixture of a trialkylaluminum compound with the elemental iodine and at the polymerization temperature. The reaction mixture in The reaction vessel can be cooled to the polymerization temperature or heated at the start of the additions or: at any other point in time before the tungsten compound is added will.

Monomeric impurities such as water and the like should be removed before adding the tungsten compound. The alkyl aluminum iodide compound or the mixture of a trialkylaluminum compound with elemental iodine can be used for this purpose to titrate the monomers or the mixture of monomers with solvent, until a color change from pink to colorless or slightly yellow. A catalytically effective amount of an alkyl aluminum iodide compound or a mixture of a trialkylaluminum compound with elemental iodine can then be added whereupon the tungsten compound is added. The end point of the titration is typically difficult to pinpoint

determine. If small amounts of impurities are present, it may be necessary to use up to ten times the catalytically active substance Amount and even more of the alkyl aluminum iodide compound or triacyl aluminum compound to use to render the impurities harmless. !

The polymerization can be terminated by adding alcohols, amines or carboxylic acids. Examples include ethanol, t-butyl phenol _# diethylamine and acetic acid.

The polymers can be isolated by all known methods such as direct drying under reduced Pressure, by precipitation using alcohols such as methanol, ethanol and isopropanol, or

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by steam or hot water stripping. The polymer is recovered and can be further washed with water or alcohol and then be dried.

The copolymers according to the invention are high molecular weight products with an intrinsic viscosity of about 0.1 to about 10, more generally. ¹ of about 0.5 to 5 and more than 90% soluble in the solvents mentioned above. Substantial insolubility indicates the presence of gels and / or dicyclopentadiene homopolymer. With inherent viscosity <7j. ,) denotes the value obtained by dividing the natural logarithm of the relative viscosity (*] ■ = the ratio of solution viscosity to solvent viscosity) by the concentration (c), which is in g of polymer per loo ml of solvent at a given temperature in this Case 0.1 g in 100 ml of toluene at 25 ° C is obtained:

¹¹ V ⁼ In (η / ηο)

The inherent viscosity is regarded as a measure of the molecular weight and is given in the dimension dl / g.

The copolymers according to the invention easily become rubbers - Vulcanized with high tensile strength (both at 25 ° C and at 1oo ° C), suitable for use in tires, particularly in truck tires, and in other articles made of rubber. For example can be elemental sulfur or a thiuram di or polysulphide together with a wide range of accelerators and other processing materials and auxiliaries with those made according to the present invention polymers are used. Copolymers that do not work with oil processed have plastic properties.

The following examples illustrate the invention.

Examples 1-14

Cyclopentene was copolymerized with dicyclopentadiene by the following method. Glass or glass-lined reaction vessels were used. Before the polymerization, the reaction vessel was carefully cleaned with soap and water, then rinsed with acetone and blown dry with nitrogen. Cyclopentene and dicyclopentadiene were mixed with benzene and added to the reaction vessel. 1-butene was added as a 2 wt% solution in benzene, if used. The alkylaluminum halide or the trxalkylaluminum compound (diethylaluminum iodide, diethylaluminum chloride, ethylaluminum dichloride or triethylaluminum as o, 5, o, 5, o, 25 and c, 5 molar solutions in benzene in the order given) and WoIframhexaChlorid (o, o5) molar solution put in different order in the reaction vessel. The polymerization was ^{carried out at about .22 0} C and developed little heat. Little agitation (stirring) was necessary for effective polymerization to occur. The reactions were terminated by adding ethanol and the polymers were precipitated using ethanol, washed with ethanol and recovered. About 1 part by weight of di-t-butyl paracresol was added to the polymer as an antioxidant and the polymer was dried in a vacuum oven at 50 ° C. The yield in% was based on the total weight of the cyclopentene, dicyclopentadiene and 1-butene used. The grams and moles of the reactants, the yields, the percentages of dicyclopentadiene in the polymer, the inherent viscosities (IV) and the percent insolubility of the polymers are given in Tables I and II. _t

Example. Figure 1 shows the preparation of a highly soluble copolymer in good yields with the appropriate reactants and conditions as described above.

5 09819 / 1Ö3 3 Γ

-Ιοί-butene, diethyl aluminum iodide and tungsten hexachloride are made with suitable aluminum / ^ onomer and aluminum / Tungsten molar ratios are used. The aluminum compound was added before the tungsten salt. Examples 2, 3 4 and 5 show the production of no polymer or only sparingly soluble polymer with too high a molar ratio of Al / monomer, to low molar ratio of Al / monomer, without the use of! -butene and unsuitable order of addition of the aluminum compound, in all examples a diethyl aluminum iodide and tungsten hexachloride catalyst system has been used.

Examples 6, 7 and 8 use dietary aluminum chloride previously identified as unsuitable and show no or little polymer production soluble polymer with all other conditions and reactants as previously described (see Example 6); with too high an Al / monomer molar ratio in Example 7 and with a wrong order of addition of the aluminum compound in Example 8.

Examples 9, to and 11 use ethyl aluminum sealant, which, as previously stated, is unsuitable, and show the production of no polymer or poor solubility. chera polymer, all other conditions and reactions being as previously described (Example 9); too high an Al / monomer molar ratio in Example 1o .and! an incorrect order of addition of the aluminum bond in Example 11 can be used.

Examples 12, 13 and 14 use triethylaluminum, cäas has been previously identified as unsuitable and shows no polymer production or leaks soluble polymer, with all other conditions and reactants as described above (Example 12); with too high an Al / monomer molar ratio in example 13 and a wrong order of

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j Addition of the aluminum compound in Example 14, '■

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Table I.

O C *? CaJ

example

Benzene, g

Moles of cyclopentene, g

Moles of DCPD ,, g

Moles of 1-butene, g

mmol Et-AlX, g

mmol Et ₂ AlCl, g

mmol WCl ₆ , g

mmol

mmol Al- Compound / mol monomer Al / W molar ratio 1.25

Al or W-Verbdg. first admitted Al time, hours Polymer yield, g

Wt%

% By weight DCPD in polymer IV 0.92

insoluble polymer,%

DCPD = dicyclopentadiene Et ₂ AlI = diethyl aluminum iodide

Et ₂ AlCl = diethylaluminum chloride = tungsten-hexachloride

73.0 74.7 74.1 0.93 O.96 0.95 4.6 4.5 4.6 0.07 0.07 0.07 5-9 5.7 5.9, O.o4 o.o4 o.o4 0.85 0.9 0.9 15th 16 16 0.005 0.011 0.003 0.025 0.05 0.012 0 0 0 0 0 0 0.008 0.008 0.008 0.02 0.02 0.02

0.4
2.5

0.1 0.6

76.1 73.7 0.97 0.94 4.5 4.6 0.07 0.C7 5.8 5.9 o.o4 o.o4 0 0.85 0 15th 0.005 0.005 Oo 025 0.025 0 0 0 - 0 0.008 0.008 0.02 0.02

0.2
1.25

Al .9 Al Al .1 1 0.6 5. 0 7- 53 .38 · 0 68 .68 _ 82 1. _ 1. 98 66

0.2
I.25

1.75
6.4

'
92

0.86
62

72.4

p.93

4.6
0.07
5.8
o.o4
0.9
16
0
0

0.003
0.025
0.008
0.02

0.2
1.25

Al

1.75

75.4 0.97

4.6 0.07

5.8,

0.9 16
0
0

0.006 0.05 0.008 0.02

0.4 2.5

Al

6Γ3 55

⁹² ο I.18

94.6

75.2 0.96 4.6: 0.07:

5.8!

0.04 '

0.9

16 0

o.oo3'-i

0.025 '

0. oo5 ^;

0.02 ■ - · 0.2

1.25

¥ 1.75:

4.8

42

95.1

'ι ¹
example DCPD, g i Benzene, g MoI ; Cyclopentene, g 1-butene, g MoI mmol EtAlCl ^ g. ·
mmol Et ₃ Al, g WCl ₆ , g ^riMo1 mmol mmol of Al compound / mol of monomer cn
ο
co Al / W molar ratio CD * Al or W-Verbdg. first admitted CO Time, hours O Polymer yield, g to Wt%. co % By weight DCPD in the polymer I V. insoluble polymer,%

Table II

10

0.4

2.5

Al

6.3
56
92

0.36
76

11

76.3 ' 72.7 73-7, O.98 0.93 0.94 4.5 4.6 4.5 0.07 0.07 ■ 0.07 5-9 5.8 5.9 o.o4 o.o4 0.04 0.9 0.85 0.8 16 15th 14th 0.003 0.006 ' 0.003 ■ 0.025 0.05 0.025 0 0 0 0 0 0 0.008 0.008 0.008 0.02 0.02 0.02

0.2

1.25

6.6
58
89

1.2
98

12th

76.4
O.98
4.6
0.97
5.7
o.o4

0.9
16
0
0

0.003
0.025
0.008
0.02

0.2
1.25

Al

4.5

70.1
0.90

4.9

0.07

5.8

o.o4

0.9
16
0
0

0.006
0.05
0.008
0.02

0.4
2.5

Al

3-5

1.2
10
96 *

0.88
38

DCPD = dicyclopentadiene EtAlCl- = ethyl aluminum dichloride Et ₃ Al = triethyl aluminum = tungsten exachloride

DCPD in the polymer chain are additional polymerization units of the structure

76.4 0.98 4.6 0.07 5.8 o.o4

0.9 16 0 0 0.003

0.025 0.00 & 0.02

0.2

1.25:

3.4 30 95 *

0.95 82

Examples 15-2o

Cyclopentene was with dicyclopentadiene following the same general procedure as in Examples 1 to 14 copolymerized, with the exception that diethyl aluminum bromide and diethylaluminum fluoride as catalysts in each case as an o, 2omolar solution in benzene and 0.7 molar solution in heptane were rated. In each case, the alkyl aluminum halide was preceded by the tungsten hexachloride admitted. :

Examples 15-17 encompass a range of Al / monomer and Al / W-Mo! Ratios, with diethylaluminum bromide is used but does not give less than 10% insoluble polymer as does diethylaluminum iodide is possible. Similarly, Examples 18-2o include a range of Al / Ilonomer and Al / W-MoI ratios, diethylaluminum fluoride being used but no less than 10% insoluble polymers being obtained as is possible with diethylaluminum oxide. The g and moles of the reactants that Yields, the percentages of dicyclopentadiene in the polymer, the inherent viscosities (IV) and the percentage of. Insolubility of the polymers is given in Table III. j

5 09819/1033

Table III

CD CO CO

example

Benzene, g

Moles of cyclopentene, g

MoI DCPD, g

MoI 1-butene, g

mmol Et ₂ AlBr, g

mmol Et ₂ AlF, g

mmol WCl ₆ , g

mmol

mmole Al compound / mole monomer Al / W molar ratio

Al or W-Verbdg. first admitted Time, hours polymer yield, 'g

Wt%

% By weight of DCPD in polymer IV. Insoluble polymer,%

Et ₂ AlBr = diethyl aluminum bromide Et ₂ AlF = diethyl aluminum fluoride = tungsten hexachloride 16

18th

20th

74.5 75-9 72.4 74.1 71.9 .74.9 0.95 p.97 0.93 0.95 0.92 0.96 4.5 4.6 4.6 4.5 4.6 4.6 0.07 0.07 0.07 0.07 0.07 0.07 5.9, 5-9, 5.8 5.9 5.9 5-9 0.04 0.04 0..04 o.o4 • o.o4 o.o4 0.9 0.85 0.85 "0.8 0.9 0.9 16 15th 15th 15th 16 16 0.004 0.008 0.016 0 0 0 0.025 0.05 0.10 0 0 0 0 0 0 0.003 0.005 0.010 0 0 0 0.025 0.05 0.10 ο.οοδ 0.008 ο.οοδ ' 0.008 0.008 0.008 0.02 0.02 . 0.02 0.02 0.02 0.02 0.2 0.4 0.8 0.2 0.4 0.8 1.25 2.5 • .5.0 1.25 2.5 5.0 Al Al Al Al Al Al IQ 1 1.5 - '1.5 0 4.9 6.9 6.2 0 6.8 0 43 · 61 55 0 • 59 > 95 > 95 > 95 - > 95 mm ο.βΐ · 0.51 - 0.54 mm 17th 94 . 90 - 62

Examples 21-28

Cyclopentene-dicyclopentadiene copolymers with various Dicyclopentadiene contents were determined by the general catalyst preparation and addition method according to of the invention as shown in Example 1. The copolymers obtained were processed with processing agents mixed and vulcanized according to the recipes given in Table IV. The mixing was taking Made use of a two-roll roller, the roller temperature was about 4o to about 9o ° C. on Materials produced other than by the method according to the present invention were unsuitable because they were very difficult or impossible to process.

The copolymers were tested for their physical properties. The results are shown in Table V. 300 % modules tensile strength and elongation at break (ultimate elongation) were determined according to ASTM D412-68 using die D dumbbells. The printing fatigue

(ΔΤ, ⁰ F) was measured according to ASTM D623-67 at 212 ° F using a Goodrich Flexometer with o.175 inch travel

(stroke), 55 Ib. static load (143 lb / in. ), 20 minutes ", conditioning time and 25 minutes run time tested". ι

The durometer hardness was determined using ASTM D224o-68 of the Shore type A durometer and a 1 second indentation hardness time interval (one second indentation hardness time interval). Low temperature stiffening was made according to ASTM D1o53-65 using a

yellow marked torsion wire measured in a nitrogen heat transfer medium, the torsion (twist) was measured after a 10 second exposure interval. The values given for the stiffening test include T ₉ , T ₅ , T-. and T, values a «The hot tear strength was determined according to that of Vieth

in Rubber Chemistry and Technology, Bd ₀ 38, No. ₀ 4 "

W U w y I * y f iiaflfc ^ w

November 1965, pp. 7oo - 718 described method determined. The pico abrasion resistance ¹ was measured according to ASTM D2228-69 using a weight of 4.5 kg, 60 rpm speed and 24 ° revolutions. The abrasion index was calculated according to §11.3 of the method.

The physical test data show that the polymers tested had a good physical balance Have properties that make them suitable for use in tire manufacture. The most extraordinary Property is the high tensile strength at high temperatures, which is particularly important in Truck Tire Rubbers are because truck tires are "hotter" under heavier loads than other tires are in use.

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Table IV

Example 21. 22. 2 £ 24 £ 5 2β 27 28

Copolymer 100 100 100 100 100 100 100 100

Soot HAF N 33ο 75 ■ 75. 75 75 75 75 'βθ 75

naphthenic oil 50 50 50 50 50 50 · 2β 50

Stearic acid 3 3 5 5 3 3 3 ς

Zinc Oxide. 3 '3 ^J 5 · 5' 3 3 3 5

Sulfur. 2.5 2.5 1.3 1.3 2.5 2.5 2.5 1.

N-Cyclohexyl-2-benzothiazole- ^

α, sulfenamide _ 1 1 1.3 ..1.3

CO

CD CO CO

CO
I.

ΟΊ; CX) 'OO

Table V

cn
ο
co

Examples

Wt. % Dicyclopentadiene

Cure Time © 160 ° C, minutes

300 $ modulus © 25 ° C, psig

300 $ modulus © 100 ⁰ C, Psig

Tensile © 25 C, psig Tensile © 100 ⁰ C, psig

Low Temp. Stiffening,

rn o-rn

-T ₅ , F
Low Temp. Stiffening,

21 22nd 2! 24 25th 26th 21 28 28
3.5
33
1900 ■ 35
2.5
2-2
I85O 42
2.5
20th
1420 52
1.7
20th
I345 56
1.7.
4i
2500 65
1.5
60
3200 68
1.0
20-
1975 92
2-9
3440 2450
io4o I36O
3OOO
I56O 1240
38OO
I92O 9OO
3215 '
I540 ' OO
I QVO
• = t CM
COH 3200
1280 740
2290
740 1615
3860
2150 350 400 545 565 375 305 345 315 250
34
62 330
40
63 4oo
63
65 440
86
66 ^ 52
65 230 '
47
74 300
• κ *
82 34ο
63
80 -51 -42 -39 * -29 * -6 -5 + 10 * -10 * -57 -47 . .-41 * -31 * -30 -19 -9 * -15 * -59 -49 -43 * -32 * -32 -22 -12 * -16 * -64 -55 -48 * -37 * -38 -30 '-20 * -23 * - - coin
VOCh 120
89 - mm 105
98 67
122

Ultimate Elongation @

25 ° C, fo

o ° j Ultimate Elongation · ©

- * I 100 ° C, % 250 330 400 440 255 230 300 340 £

2J | Compression Fatigue (AT, ° F) 34 40 63 86 52 47 ** 63 _ * I Durometer Hardness, Type ο j Low Temp. Stiffening,

<- * Cl -1—1 '

Low Temp. Stiffening,

^T 100 ^F '· " ^{D <q} · · -55 -W * -SC * -jjo - ^ u -UU * _ -ϋ ^ *; K3

Hof Tear Strength. cn

© ICO '' Cs.lbs / in. - ~ 63 120 - 105 '67 I-- »

Pico Abrasion Index - - 95. 89 - - 98 122 '..

* Low Temperature stiffening measured using ** Blow out, i.e., sample shattered * ^

uncured mixture of rubber and oil. . °°

Claims (6)

Claims j Process for the interpolymerization of cyclopentene with dicyclopentadiene in the presence of a non-conjugated one acyclic olefin that has at least one hydrogen atom on each double bond Has carbon atom, 2 to 12 carbon atoms and inert substituents on the remaining carbon atoms: has tuenten selected from the group consisting of hydrogen and alkyl groups with 2 to 8 carbon atoms are selected, with, a catalyst containing i (A) at least one compound selected from the group consisting of dialkyl aluminum iodides, alkyl aluminum iodides and their mixtures and mixtures of elemental iodine with trialky aluminum compounds in which each Alkyl group has 2 to 8 carbon atoms and the catalytically effective amount of the compound of " consists from 0.15 to about 0.35 mfuol per mole of monomer, / and J (B) at least one tungsten compound that is soluble in the monomer mixture or a solvent from aliphatic or cycloaliphatic hydrocarbon solvents with 4 to 10 carbon atoms and liquid or easily liquefied aromatic hydrocarbon solvents with 6 to 14 carbon atoms, | and the molar ratios of A / B are from about 15 to about 40; 1 mole per mole, the mole ratio of elemental iodine to trialkylaluminum compound from about 0.25: 1 to about 6: 1 moles per mole, and the nonconjugated acyclic olefin in a molar ratio . ι to monomer of about o, o1: 1 to about o, 3: 1 moles \ per mole is used. j 2. The method according to claim 1, characterized in that the non-conjugated acyclic olefin from the 509819/1033 Group of 1-olefins and 2-olefins with 2 to 8 carbon atoms each trialkylaluminum compound has alkyl groups of 2 to 4 carbon atoms, the tungsten compound is a tungsten halide, the molar ratio of A / B from about 1: 1 to about to: 1 moles per mole and the molar ratio of elemental iodine to trialkylaluminum compound is about 0.5: 1 to about 3: 1 moles per mole. 3. Process according to claims 1 and 2 _f characterized in that the nonconjugated acyclic olefin is 1-butene and the catalyst (A) is at least one compound from the group consisting of diethylaluminum iodide, ethylaluminum iodide and a mixture of elemental iodine and Contains triethylaluminum and (B) tungsten hexachloride., 4. Copolymers containing cyclopentene, dicyclopentadiene and about o, o1 to about o, 3 moles of at least one with J copolymerized non-conjugated acyclic olefin per mole of cyclopentene and dicyclopentadiene monomer, the nonconjugated acyclic olefin at least one water · substance atom on each carbon atom on a double bond has and has 2 to 12 carbon atoms, and dicyclopentadiene is present in amounts of from about 35 to about 98% by weight of the total weight of the copolymers. : 5. Copolymers according to claim 4, characterized in that the non-conjugated acyclic olefin is selected from the group of 1-olefins and 2-01efins with 2 to 8 carbon atoms and dicyclopentadiene with about 50 to ', about 98 wt .-% of the total weight of the copolymer is present . . ■ 6. Copolymers according to Claims 4 and 5, characterized in that the non-conjugated acyclic olefin is 1-butene. . '< 509819/1 033