DE2137524A1 - Copolymers of cyclic monoolefins and cyclic polyolefins and process for their preparation - Google Patents

Description

The preparation of polymers by polymerizing cyclic monoolefins is known. Examples of such fabrications of polymers are the polymerization of cyclopentene in the presence of tungsten or molybdenum chlorides together with organic aluminum compounds; linear polymers with a very high gel content (see Natta et al, Angew.Chem.internat.Edit. 3, 723, 725 (1964)). Recently other catalyst systems were found, according to which linear polymers of cyclic monoolefins are obtained which are essentially gel free. However, the cycloolefin polymers produced by the known processes show which have a considerable range of molecular weights, also have a strong cold flow, which means that the

ORIGINAL INSPECTED 109886/1696

Products difficult to access during storage and transport are handled. In addition, the polymerization of cyclic moleolefins to give low, cold-flowing polymers results in polymers with high molecular weight.These polymers with very high molecular weights are suitable for processing in the not suitable for most industrial uses.

The invention relates to new copolymers of cyclic monoolefins with cyclic polyolefins and of cyclic monoolefins with ^ J -alkenyl polycycloalkenes.

The invention also relates to copolymers which are terpolymers of cyclic monoolefins, cyclic polyolefins or of Cu - \ lkenyl polycycloalkenes and acyclic olefins.

The invention also relates to a method for production of copolymers of cyclic monoolefins and cyclic polyolefins or ko'-alkenyl polycycloalkenes, that consists in treating the monomers with a catalyst which is suitable for the olefin disproportionation reaction, treated.

The copolymers of cyclic monoolefins and cyclic polyolefins or ^ ° -alkenyl polycycloalkenes show reduced cold flow compared with the homopolymers of cyclic monoolefins with a similar molecular weight.

The copolymers of cyclic monoolefins, cyclic polyolefins and acyclic olefins show a reduced Molecular weight at a certain cold flow, if you use them with homopolymers of cyclic monoolefins with a compares similar cold flow value. The copolymers also show a significantly reduced cold flow in one

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"certain molecular weight value when compared with homopolymers of the cyclic monoolefins with a similar molecular weight compares. In other words, the copolymers of cyclic monoolefins show cyclic polyenes and acyclic olefins balance their molecular weight and cold flow properties, which makes these polymers special in industrial uses Have utility such as elastomeric products.

Cyclic monoolefin monomers ,, used to prepare the inventive Polymers that can be used include cyclic monoolefins having 5 and 7 to 10 carbon atoms iming, including their alkyl substituted derivatives, wherein the alkyl group has 1 to about 6 carbon atoms contains in the molecule and is no closer than the 4-position, based on the double bond. Examples of such compounds include cyclopentene, cycloheptene, cyclooctene, cyclonones, cyclodecene, 4-methylcyclopentene, 4-ethylcyclopentene, 4-hexylcyclodecene and 4-pentylcyclopentene and similar. Preferably the cyclic monoolefin is not substituted.

The cyclic polyolefins that can be used are cyclic hydrocarbons with at least two carbon double bonds, which are separated from one another by a carbon-carbon single bond, or cyclic polyolefins with a condensed ring that has at least one. Carbon = _ Carbon double bond in each jyon at least two rings possess »The term" cyclic polyolefin "is intended to be cyclic Hydrocarbons or cyclic hydrocarbons with a condensed ring, in which each ring is aromatic in its own way is not include. Preferred cyclic polyolefins are conjugated diolefins having 5 to 12 carbon atoms in Molecule. Cyclopentadiene, 1,3-Cyelohexadian, 1,! S-Cyolooctadiene,

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1,3,5-cyclooctatriene, 1,3,5-cyelododecatriene and 1,2,3,4,4a, 8a-hexahydronaphthalene are examples of "preferred cyclic conjugated dienes used in the present invention v / can ground.

Preferred hydrocarbons having fused rings which can be used in the invention are those having about 7 to about 20 carbon atoms in the molecule. Examples of preferred compounds include dieyclopentadiene, Bixyclo- (2,2,1) -hepta-2,5-diene, tricyolo- (5,2,3,0,4,9) -dodeca-2,5,11-triene, Bicyclo- (2,2,2) -octa-2,5,7-triene and bicyclo- (8,6,4) -eicosa-2,11-diene.

The acyclic olefins that are used to prepare the inventive Cycloolefin, cyclic polyolefin, acyliocheii olefin interpolymers Can be used are non-tertiary, acyclic mono- and polyenes that have at least 2 carbon atoms contained in the molecule, including their cycloalkyl, cycloalkenyl and aryl derivatives and mixtures of these olefins. Acyclic olefins having 2 to about 30 carbon atoms are preferred. You get particularly good results with acyclic monoolefins and diolefins derived from about 5 contain up to about 10 carbon atoms in the molecule. Non-tertiary Olefins are olefins that contain at least one double bond, in which the carbon atoms are mutually exclusive are connected via a double bond, contain at least one hydrogen atom.

Some specific examples of acyclic olefins which can be used as comonomers include ethylene, propylene, 1-butene, 2-butene, 1-pentene, 2-pentene, 1-hexene, 1,4-hexadiene, 2 -Heptene, 1-octene, 2,5-octadiene, 2-nonene, 1- do & eeen, 2-terradecene, 1-hexadecene, 3-methyl-1-butene, 1- phenyl-2-butene, 4-octene, 3 -Eicosen, 3-heptene, 3-hexene, 1,3-

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Pentadiene, 1., 4-pentadiene, 1, 4,7-dodecatriene, 2-methyl-4-octexi ₉ 4-vinyloyclohexene, 1,3-octadiene, 1,7-octadiene ₉ 3,5-decadiene _s 1.5 Eieosadiene, 2-triaconts, 2,6-dodecadiene, 1,4,7,10,13-octadecapentaene, 8-cyclopentyl-4,5-dimethyl-1-yl-decene and 6,6-dimethyl-1,4-octadiene .

The (- $ -alkenyl-polycycloalkenes which can be used in the present invention are dienes containing a terminal unsaturation of the yinyl type in an aliphatic chain and an unsaturation in a polycyclic system. Examples of LQ -alkenyl-polycycloalkenes used in the copolymerization processes according to the invention can be used, and other compounds can also be used, are:

CH »CII ₂

2-vinyl-bicycio (2 _> 2, i) hspten'-5 · ( also known as 5-Yynyl-2-.:·■ .. .-. Norbornene)

, CH ₂ - CH ₂ - CH = CH ₂

CH ₂ CH

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; ■ 2-vinyl bicyclo (2,2,2) octen.-r.5 "'

CH «CH ₂

- CU ■ CH ₂

3-AUylinden

Most of these monomers can easily be made by Diels-Alder condensation reactions can be obtained.

For example, 2-Yinyl-Mcyclo- (2,2,1) -hepten-5 can by Condensation of 1 mole of cyclopentadiene and 1 mole of butadiene- "!, 3 and 2 ~ buten-3'-yl-bicyclo- (2,2,1) -hepten-5 can be produced by the condensation of cyclopentadiene and diallyl.

Mixtures of the abovementioned CaI -alkenyl-polycycloalkene compounds and the cyclic polyolefins can be used to prepare the compounds according to the invention.

The polymerization of the monomers described above is achieved by using a catalyst which acts as an olefin disproportionation catalyst is known. These catalysts have previously been used to convert olefinic materials into to convert other olefinic materials, a conversion that can be expressed as a conversion between two carbons atom pairs, the two carbon atoms of the first Pairs are linked by a double bond, and where a new pair of carbon atoms is formed from the first pair,

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and where the two carbon atoms of each new pair are connected to one another via a double bond. Although this implementation is not fully understood, one takes indicates that the disproportionation reaction is above a saturated Intermediate in the transition state · proceeds. The implementation can be represented by the following equations:

IIC ¹ - C ² -

1 'I.

ο ... ό-

ι ι

- £ ■ i ² ^

It 11

-C

Other terms have been used to refer to olefin disproportionation reactions and describe catalysts that effect this reaction. Jüan, for example, has such expressions such as "olefin conversion", "olefin dismutation", "transalkylation reaction" and "olefin metathesis" is used.

To produce the copolymers according to the invention can all catalysts having activity in the conversion of olefins according to the olefin disproportionation reactions described above have to be used. Includes both heterogeneous catalysts that are in the presence or Absence of liquid hydrocarbon solvents. Olefin disproportionation activity have, and homogeneous catalysts, generally together with a diluent used during implementation. Of course, the olefin or the monomer, if it is under normal conditions is liquid, act as a diluent for the homogeneous catalysts. For the production of the invention Non-polymers are preferred, homogeneous catalysts

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The heterogeneous catalysts "especially for the polymerization reactions Suitable include tungsten oxide on silicon dioxide, tungsten oxide on aluminum oxide, molybdenum oxide and aluminum oxide, rhenium oxide on aluminum oxide, molybdenum oxide on aluminum phosphate, molybdenum hexacarbonyl on aluminum oxide and all of the above compounds mixed with an organometallic reducing agent such as methyl aluminum sesquichloride. These catalysts are described in U.S. Patents 3,261,879, 3,365,513, and 3,463,827, as well as the United Kingdom U.S. Patent 1,054,864.

The different solid catalysts exhibit different optimal reaction temperatures, pressures and contact times the polymerization of the monomers according to the invention. In general the preferred temperatures, pressures and times in the polymerization reactions are essentially the same like the optimal conditions at which the olefin disproportionation catalyst acyclic? Low molecular weight olefins such as propylene, butenes and pentenes. Extremely high reaction temperatures at which the monomers decompose should be avoided.

The homogeneous catalysts, which are particularly suitable for the polymerization reaction, contain (a) a transition metal compound, mixed with (b) an organometallic compound. These catalysts are known. Particularly suitable catalysts are described in U.S. Patent 3,492,278. The most preferred homogeneous catalysts are those which contain a metal from Group VIB mixed with an organoaluminum halogen compound, as described in US Pat French patents 1,561,026 and 1,575,778 are.

Some suitable examples of homogeneous catalysts that can be used include mob pentachloride with tri-

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Q _

isobutylaluminum; Tantalum pentachloride with triisobutyl aluminum; Molybdenum trichloride distearate with diethyl aluminum chloride; Ethyl aluminum dichloride, methyl aluminum sesquichloride or ethyl aluminum sesquichloride; Until ~ (triphenyl ~ phosphine) molybdenum tetrachloride with methyl aluminum sesquichloride; Molybdenum hexacarbonyl or triphenylphosphine molybdenum pentacarbonyl with ethyl aluminum dichloride; Molybdenum trichloride dioctanoate with diethylaluminium chloride; Y / olefin tetrachloride distearate with diethyl aluminum chloride; Molybdenum trichloride dilaurate, molybdenum trichloride distearate, molybdenum oxychloride stearate or tungsten tetrachloride distearate with di- ethyl magnesium; Bis-ctriphenylphosphineJ-rheniumoxytrilDromide, Bis (triphenylphosphine) rhenium oxytrichloride or bis (triphenylphosphine) rhenium tetrachloride with ethyl aluminum dichloride and dinitrosyl ruthenium chloride or bis- / l; ri- (? T - allyl) rhodium chloride / mi "fc methyl aluminum sesquichloride.

The production and processing of homogeneous catalysts for olefin disproportionation are known. In general, in the polymerization reaction using the optimum conditions - in which the catalyst olefin disproportionation of acyclic olefins of low molecular weight, such as of pentenes and hexenes effected, ie, temperatures in the range from -30 ⁰ C to 150 ⁰ C. Using homogeneous catalysts, the choice of the molar proportions of the organometallic reducing agent and the transition metal compound is also a function of the purity of the monomer. Monoolefin cyclic and polyolefin cyclic monomers often contain impurities that can react with the catalyst components. Accordingly, the monomers are preferably purified prior to contact with the homogeneous or heterogeneous catalysts. Molecular sieves can be used to purify the monomers. The success of the cleaning process determines the optimal molar ratio of metal-

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organic compound to the transition metal compound. If the feed material contains impurities, the organometallic compound is preferably used in a molar excess with respect to the transition metal compound. the The amount of catalyst in the homogeneous system is expediently based on the amount of organometallic compound used and is generally in the range of 0.15 to 150 g mmol per 100 g of monomer.

As mentioned above, the homogeneous catalyst becomes the polymerization reaction generally used in the presence of a diluent. Any diluent that is used in the implementation is essentially inert (except when the monomer is used as a diluent) can be used will. Aliphatic, cycloaliphatic and aromatic hydrocarbons that have 4 to 10 carbon atoms in the molecule can be used. Examples of such hydrocarbons are n-pentane, n-butane, η-hexane, isooctane, n-decane, Cyclohezane, cyclopentane, methylcyclohexane, benzene, toluene and xylene. Other suitable solvents are halogenated Compounds such as chlorobenzene, letrachlorethylene and 1,2-dichloroethylene. Mixtures of these diluents can also used v / earth.

The amount of cyclic polyolefin copolymers used in the present Invention used can be varied over a wide range. The resulting copolymers show a much smaller cold flow than the corresponding polycyclic monoolefin homopolymers. The degree of desired Cold flow reduction will of course determine the amount of cyclic polyolefin that is used. In general a noticeable reduction in catalytic converter flow is achieved with amounts ranging from 0.1 to 500 mmol / 100 g of that used oyolic monoolefin monomers (mhm) vary,

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preferably in the range from 10 "to 200 mhm. However, if desired also use larger quantities. For example, you can use up to 50 parts by weight of cyclic polyolefin per 100 Parts by weight of the total cyclic monoolefins and cyclic polyolefins when carrying out the process according to the invention i.e., cyclic monoolefin / cyclic polyolefin weight ratios of at least 50/50 be used. The cyclic conjugated diene and / or the hydrocarbon with a condensed ring can simultaneously or at any time before the polymerization reaction is stopped.

The amount of lo. Alkenyl polycycloalkene or mixtures thereof with cyclic polyolefins can be varied within a wide range in the present invention. The resulting copolymer has a remarkably lower cold flow than the corresponding homopolymer of the cyclic monoolefin. The amount of cold flow reduction that is desired will accordingly determine the amount of comonomer (s) that are used. In general, a remarkable reduction in cold flow is achieved with amounts of CO -alkenyl-polycycloalkene which vary in the range from 0.001 to 50 parts by weight per 100 g of the other monomers used (cyclic monoolefin and / or acyclic olefin) (phm), but preferred is a range of 0.025 to 5 phm. If desired, however, larger amounts can also be used. For example, up to 50 parts by weight of U) -alkenyl-polycycloalkene per 100 parts by weight of total other monomers can be used in the present invention, ie weight ratios of cyclic monoolefin / CO -alkenyl-polycycloalkene of at least 50/50 can be used will. The 60-alkenyl polycycloalkene or mixtures thereof with polycyclic olefins can be added at the beginning or at any time before the polymerization reaction is terminated.

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At higher concentrations, comonomers of the U) -alkenyl polycycloalkene type tend to "form products that contain gels. This tendency can, however, be reduced by adding the amount of acyclic olefin that is present in the polymerization formulation" in the preparation of the polymers containing the acylic olefin monomers are used. If the copolymers according to the invention are prepared in the absence of acyclic olefin monomers, suitable low amounts of ^ o-alkenyl-polycycloalkene monomers can be used if gel-free products are desired.

If terpolymers according to the invention are prepared, so will Low molecular weight acyclic olefins such as ethylene, propylene, butenes, pentenes and hexenes are most commonly used. The Terpolynierisate show a desired balance in the cold flow and molecular weight properties. The amount of low molecular weight acyclic olefin that is used generally determines the extent of the reduction in the intrinsic viscosity time. Individual olefins or mixtures of olefins can be used in the process be used. The amounts are generally in the range from 0.01 to 10, preferably from about 0.05 "to 1.0 parts by weight per 100 Parts by weight of the other monomer.

Any known treatment method can be used to prepare the polymers can be used, and one can batch with both the heterogeneous and the homogeneous catalysts or work continuously. Subject to the reaction time, the polymer can by known methods, such as by Precipitation, coagulation, steam stripping and the like can be separated and isolated. Spruce-converted monomers or unwanted products can be recycled or discarded as required. If desired, the Catalyst can be destroyed using various materials such as oil or alcohol, which are well known,

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or, the catalyst can be removed before the products are separated off deactivate.

It is assumed that the copolymers of cyclic monoolefins and cyclic polyolefins or. ^ Ü.-alkenyl-polycycloalkenes contain linear chains of cyclomonoolefins, which are formed by ring opening of the cyclomonoolefins and the cyelopolyolefins or the U) -alkenyl-polycyeloalkene monomer units, those within the cycloalkene part according to the. Incorporation into the polymer retain their double bond. The cyclic polyolefin or the £ 0 -alkenyl-polycycloalkene can be incorporated into the polymer chain in a random or non-random manner. It is assumed that the reduction in the cold flow which is obtained is due to the incorporation of the cyclic polyolefin or the ^ -alkenyl-polycycloalkene into the polymer backbone, a double bond reacting and branching occurring. It is believed that branching occurs on the available double bond of the comonomer. Obviously, as can be seen from the reduction in the intrinsic molecular viscosity, the terpolymers of the present invention are obtained by incorporating the low molecular weight olefin into the monomer feed. The lowering of the molecular weight and the broadening of the molecular weight distribution are believed to proceed via an olefin disproportionation-cleavage reaction of the polymer and the low molecular weight olefin.

The rubbery products made in accordance with the invention have a good balance in their properties. They can be stretched with oil and mixed with soot, whereby vulcanizates with recorded properties are obtained. The Rphpolymerisate have a high green strength. These properties make it possible that the inventive poly

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merisate find a wide area of application. You can alone as tire tread compound or carcass stock or mixed used with other rubbers or plastics. They can be used to provide adhesive and green strength of rubbers, such as butadiene-styrene emulsion copolymers, cis-polybutadiene and others, in solution to improve polymerized, conjugated diene polymers. They can also be used in adhesive formulations or in adhesive formulations be used. In the above applications, these polymers can be mixed with conventional fillers, extenders, Plasticizers, antioxidants, hardening accelerators, crosslinking or hardening agents, pigments, stabilizers and the like Substances are compounded and cured.

The following examples illustrate the invention without, however, restricting it.

example 1

In a series of experiments, cyclopentene was present in the presence different amounts of cyclopentadiene polymerized to the effect of this compound on the cold flow of the copolymer, compared to the homopolymer of cyclopentene. The polymerization recipe and the ones obtained Results are shown in Table I.

Table I.

1. Conditions

Polymerization recipe Toluene, parts by weight 435 Cyclopentene, parts by weight 100

Molybdenum trichloride dilaurate, mtim (a) 2.9 Diethylaluminum chloride, mhm (a) 4,4 cyclopentadiene, mhm (a) various.

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3.06 0 1.83 3.05 0 1.64 2.99 0 0.38 3.02 0 0.45 3.71 0 0

9 1 % 1 R 7 L 15 -

Temperature, ° C · 5 Time, hours 4

(a) mhm = mmol / 100 g of the monomers introduced (cyclopentene)

2 results.

(c)

Yers.Cyclopenta- Unsät- Conversion- Trans basic Gel Cold flow no. Dien, mhm - tigung, lung, fo (b) mol.Yis- ° / Ό mg / min

Io (a) ^c / o . . kosit. (c) (d)

_______ number

1 '0 99 55 91

2 1.2 - 56 -

3 10.0 98 47 89

5 20 - 54 -

6 200 100 55 83

(a) Iodine monochloride titration suggested that there was one double bond per monomer unit.

(b) Infrared analysis in carbon disulfide solutions of the polymer using an absorption band "at 10.35 microns.

(c) determined in accordance with U.S. Patent 3,278,508 ₅ column 20, comments (a) and (b)

(d) The cold flow is determined by extruding the rubber through a 6 ram (1/4 ") nozzle at 246 g / cm2 (3.5 psi) and a temperature of 50 ⁰ G, then waiting 10 min the steady state is reached and the extent of the extrusion is determined and recorded in mg / min.

These results show that the amount of cyclopentadiene can be varied over a wide range without gel products are formed. It can also be seen that only small amounts of cyclopentadiene are required to ensure the cold flow of the Remarkably diminish products.

In these polymerization reactions, toluene was first added to the reactor, and the intestine was flushed with nitrogen. "

1 09886 / 1.6 96

The reactor was closed and purged with argon, and then argon was admitted to a pressure of 24 atm.abs. (20 psig) into the reactor. The molybdenum compound was then charged and then the reactor contents were ^{cooled to approximately 0 °} C. in an ice bath. Cyclopentene was then incorporated, and then the organic aluminum compound was added. The temperature of the reactor was then adjusted to the desired polymerization temperature.

Towards the end of the polymerization, the reaction was stopped with a 10 percent by weight solution of 2.2 ^l -methylene bis (4-methyl-6-ter.butylphenol) in isopropyl alcohol, the amount being sufficient for one part of antioxidant per 100 wt . -leile of the filled cyclopentene was present. The reaction mixture was then diluted with 435 parts by weight of toluene per 100 parts by weight of the filled-cyclopentene, and the mixture was stirred at 30 ⁰ C. After mixing well, stop mixing, add isopropyl alcohol to coagulate the polymer. The liquid phase was discarded and the polymer is dried over spurred on in vacuo at 60 ⁰ C in a nitrogen stream.

Example 2

In a further series of experiments, cyclopentene was polymerized in the presence of various amounts of dicyclopentadiene, to determine the effect of this compound on the cold flow of the copolymers in comparison with the homopolymer of cyclopentene. The same polymerization and polymerist recovery procedures were used as used in the experiments of Example 1 are described. The polymerization recipe and results are shown in Table II.

Table II

1. Conditions

Polymerization recipe

Xoliiol, parts by weight "435

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Cyclopentene, parts by weight 100

Molybdenum trichloride

dilaurate, mhm 2.9

Diethyl aluminum chloride, mhm 4.4

Dieyclöpentadien, mhm various

Temperature, ° 0 5

Time, hrs. 4

2 results Dieyclö
pentadiene
mhm Around
Wall
lung fa Inappropriateness
activity grimdmol.
Yiskosit.
number Trans gel Cold
flow
mg / min Ver
search
ITr. 0 55. 99 3.06 91 0 1.83 1 1.0 59 - 2.93 - 0 0.91 2 10.0 61 99 3.07 88 0 0 3 0 60 98 3.03 95 0 2.06 4th 20th 64 100 3.43 88 0 0 5 0 59 - 2.87 88 0 2.12 6th 20th 64 3.34 89 0 0 7th

The results clearly show the effect of small amounts of Dieyclöpentadiene, "for example, have the copolymers a significantly reduced cold flow compared to the homopolymers.

Example 3

In a manner similar to that described in Example 1, cyclopentene was polymerized using a molybdenum trichloride dioctanoate diethylaluminum chloride catalyst system. Toluene was used as a diluent and the polymerization was carried out in the presence and absence of diyclopentadiene and 1-hexene. The monomers were charged in the following order: cyclopentene, 1-hexene and

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213752A

Dicyclopentadiene. The recipe and the results are summarized in Table III.

Table III

1. Conditions

Polymerization recipe

Toluene, parts by weight 450 (3 , 32 mhm) Cyclopentene, parts by weight 100 (2 , 28 mhm) 1-hexene, parts by weight various Oj, ) Dicyclopentadiene (DCPD), Parts by weight various Diethyl aluminum chloride 0.40 Molybdenum trichloride dioctanoate 0.76 Temperature, ° C 5 (41 Time, hours 4.3

2 results

Trial Fr. 1-Hexen phm ^ ^a ^ DCPD, phiJ ¹ ) Conversion, fo

intrinsic viscosity (b)

Cold flow, mg / min

(a) Parts by weight per 100 parts of cyclopentene.

(b) determined in tetrahydrofuran at 25 ^° C.

The effect of the presence of 1-hexene and dicyclopentadiene is evident. In Experiment 4, the molecular weight of the

36 0 2 0 3 4th 6th 0 , 117 4th , 117 - 62 - 66 , 6 4, 27 3 1 1 69 0 5, 70 , 58 27 , 56 5, 0, , 4 , 7 0,

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Copolymer recognizable by the intrinsic molecular viscosity number is so high that the copolymer is most common Devices for elastomers cannot be processed. If 1-hexene is used in Experiment 2, the molecular weight becomes scaled down to a desirable value. However, this occurs at the expense of increased cold flow. attempt 3 shows how the terpolymers according to the invention have a desirable Possess union of molecular weight and cold flow properties.

Example 4

To the structure of the inventive cj ^ clischen Monoolefin- «, To "determine cyclic polyolefin polymers" became two Terpolymers prepared using essentially the same procedure of Example 2, except that the in Table IV indicated amounts of dicyclopentadiene used " Toluene was used as a diluent and 1-hexene was used to control molecular weight. One used the same catalyst as in Example 2. The recipe is given in Table IV below.

Table IV Attempt ITr. 1 2 Cyclopentene / DCPD, weight ratio 70/30 80/20 1-witches, phm (a) 0.075 0.117 Temperature, ⁰ C 5 5 conversion 49 . 64 Time, hours 0.75 4.2

(a) calculated as cyclopentene and DCPD as monomers.

These polymers were precipitated three times and placed in GlasfXa-see-rinsed and stored rafcbStickstoff at 0 ⁰ C "

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No antioxidant or detergent was used to prevent this Materials "did not interfere with the HMR and infrared analyzes.

Quantitative MR and infrared measurements showed that the cyclopentene / DCPD Weight ratio for the polymer from experiment Hr. 1 55/45 and the ratio for the polymer from experiment Br. 2 81/19 ". The analysis also showed that the cyclopentene monomer unit in the polymer as

was present and the DOPD monomer unit was present as

: ■. ■ - a

- CII = CK - CE CII -

r ι

"- ' ^: ■. CH - CH _n

CE = CB

available.

Example 5

Essentially in the same way as described in Example 1 ", cyclopentene was copolymerized with various cyclic diolefins in the presence of 1-hexene. When the reactions were stopped" after conversion with 100 ml of 80/20 toluene-isopropanol, the polymers were with Isopropanol eoagulated. The reaction mixture was mixed with 0.5 g of an industrial antioxidant per 100 ml of the total coagulated mixture, then the polymers were dried in an air oven for 1 hour and then in a vacuum oven. The recipe and the results are summarized in Table V.

! Table V

1. Conditions

Polymerization recipe

Toluene parts by weight 450

.-Parts 100 109886/1696

1-hexene, parts by weight 0.050

Comonomer 2.0 mhm

MoCl, (stearate) ₂ 1.72 (2.25 mhm)

Diethyl aluminum chloride 0.29 (2.38 mhm)

Temperature, ⁰ C 5

2 results

Oomonomers cold flow, mg / min

none (comparison) 18th 4th Dicyclopentadiene 9, 5 Bicycl0-2,2,1-hepta-2,5-diene 12, Example 6

Cyclopentene polymers were in the presence and absence of dieyclopentadiene comonomers using a MoCl ^ Oct ^ -DEAO catalyst system produced. When a acyclic olefin was used, it was 1-pentene. the The polymerization recipe and the properties of the polymers are summarized in Table VI.

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O CD OO OO

Table YI ...

Verse. DEAC tooth Joctl Pcnten —J DCED · ■■ "-" CTm- '"■
^ walled. Mooaey basic moi, ¹ ■ cold flow .No. ,. 1.1 »
1.1 »
1.75
2.50 KoCl ο ο ο ο t ■ phm (k) ' irihra % ■ ML-It ·. number ... . ..ijjff / inin 1
2
3
U 1.
1.
1.
1. O.Ol »
0.02
0.05
'O.Ol » 18.9
18.9 . δο
78
- 71 35 ·
·. 69.
. -79 " 1.91
2.30
1.90
2.1 »2 • 7.9 ·
0.2
O ·.

ill

The polymers were calculated to be gel-free only for cyclopentene.

Mixtures of the above polymers were prepared ', whereby one polymers that had a desired Mooney range (50-60 ML-4). the Properties of the mixtures are summarized in Table YII below.

mixture

K L

Yersuch ^;

Kr. ■

• 3

Table YII

Yer.s. ITr ". In basic mol.

the mixture,. Vigkasite. Mooney. ' Traas

37
63
8k 16-

number .·.
2.12
1.98

ML-It
53
51

81 »
QO

The polymer mixtures were in a standard tire profile * formulation, which is given in Table YIII, incorporated, and the proportions of the stocks incorporated are listed in Tables IX and X.

Table YIII basic recipes

Polymer names KL

weight

IRB #> ^(a) Zinc Oxide Stearic Acid Philrich * Sulfur HOBS Special (c)

a) Industry name Black No. 2 bV Highly aromatic oil. Type 101 according to ASTM D 2226-63T IT-Oxydiethylen-2-Benzothiazolsulfenamid.

100 , 75 100 75 50 , 0 50 0 3 3 2 2 10 10 1 1, 1 ■ 1,

Table IX Polymer K _L Processing conditions Raw MD-4 53 51 processed ML — 4 80 69 Extrusion, g / min ^ ^a ' 80 84 Loading speed
0-10, 1o best 7th 7th Shrinkage during extrusion, 5 ί 66 68 Green tensile strength, kg / cm
(psi) 2.8
(4θ5 2.0
(295

(a) Ind.Eng.Chem., 3 ± o 1309 (

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Table X

Physical properties of the vulcanizates

Polymer * K ^ L

Raw. ML-4 53 51

Total oil, phr 10 10

hardened for 30 minutes at 153

° C

(ά)

permanent deformation ^{K <XJ} 18 20

300 $ module, kg / cm ² (psi) ^ 106 (1500) 116 (1650)

² ^

p
Tensile Strength, kg / cm ² (psi) ^ 173 (2450) 173 (2450)

Elongation, % ^, ^ 400 390

Tensile strength at 93 ° C (2OO ^C P) 74 (1050) 77 (1100)

Tear strength, kg / cm ² at 93 ^° C

(200 ⁰ P, Ib / in.) (C) 27kg / 2.54cm 41kg / 2.54cm

(60) (90)

Heat accumulation, (^ T) ⁰ O ( ⁰ F) ^ '38 (69) 43 (77

Rebound, f <r- ^Q ^ 72 66

Flexural fatigue strength, M ^ '0.7 1.9

Shore A hardness ^ '64 64

cured for 24 hr. at 100 ⁰ C

Module, kg / cm ² (psi) 107 (1450) 112 (1600)

Tensile Strength, kg / cm ² (psi) 112 (1600) 134 (1900)

Elongation, % 210 220

Δ I, ⁰ C ( ⁰ P) 32 (57) 37 (66)

Rebound, $> 77 73

Flexural fatigue strength, M <0.1 <dO, 1

ASTM D 395-61
ASTM D 412-66

ie
ί

ASTM D 624-54
ASTM D 623-62
ASTM D 945-59
ASTM D 813-59
ASTM D 1706-61

109886/1696

In general, the cyclopentene-dicyclopentadiene-i-pentene copolymers show improved processing properties during Goaipounding compared with cyelopentene-pentene-1 copolymers. The OMGE Table ΙΣ ze IGT _s that the DCPD-cyclopentene-i-pentene copolymer shows good Yerarbeitungseigensbhaften, although the cold flow of Rohpolymerisatmischung "is considerably reduced.

Example 7

Experiments have been carried out in which mixtures of cyclopentene and 1-hexene with 2-vinyl-bieyclo- (2 _y 2,1) -heptene ~ 5 (generally referred to as 5-vinyl-2-norbornene) or with dicyclopentadiene (DCPD) were polymerized as the third monomer. The polymerization recipe is given below and the results are shown in Table XI.

P olymerisat! Onsrezeptur

Parts by weight !Toluene 450 Cyclopentene 100 1 witches 0.05 5-vinyl-2-norbornem (VKB) various Dicyclopentadiene (DGPD) vers.ch. MoCl, (octanoate) p 1.22 (2.25 mhm) Diethyl aluminum chloride
(DEAG) 0.44 (3.60 mhm) Temperature, ⁰ G 5 Time, hours 4.2

In each experiment , ΦοΙαοΧ was first added to the reactor and then cyclopentene. Then 1-hexene was added and then 5-vinyl-2-nor "bornene or dioyclopeatadiene with the exception

109886/1696

Vergle.ichsversuchs, "this experiment was used in which none of these compounds. At the end were added to each Polymerisationsmisehung a solution of the antioxidant ^2,2-f methylene bis- (4-methyl-6-tert.butylph.enol) in a 20/80 volume mixture of isopropyl alcohol (toluene, the amount added being sufficient to give approximately 1 part by weight of antioxidant / 100 g of the charged monomer. Each polymerization mixture was then coagulated with isopropyl alcohol and then the polymer was separated and dried.

VHB , 24 PCPD
phm Table XI 2.17 Gel ^(a) Cold flow ^
mg / min Verse.
Mr. , 45 _ base mol.
Conversion viscosity.
! us, io number (a) 1.08 0 9.97 1 O , 44 - 62 0.67 79 0 CVJ 1 - 65 0.82 71 0 3 O _ 62 74 0 4th 68

5 - 0.29 67 2.98 ο 5.84

(a) Determined according to the method of U.S. Patent 3 278 508, column 20, remarks a and b.

(b) The cold flow is determined by the rubber extruded through a 6 mm (1/4 ") nozzle at a pressure of 246 g / cm2 (3.5 psi) and a temperature of 50 ⁰ C. Fachdem to 10 min had waited until the steady state was reached, the extrusion rate is determined and given in mg / min.

The results in Table XI show that with the amounts of 5-vinyl-2-norbornene used, products were obtained which showed no cold flow and contained the gel.

JThe results of Experiment 5 show that dicyclopentadiene (DGPB) in an amount comparable to that of 5-vinyl-2-norbornene in experiment 2 the cold flow in the same way as in

109886/1696

Example 1 decreased and that no gel was formed.

Example 8

Other experiments were carried out using those in Example 7 ″ and the method also described there for isolating the polymers was used. Smaller amounts of 5-vinyl-2-norborneii were used in these experiments (VIiB) is used. The results of these experiments are shown in Table XII.

VEB Conversion Tabel XII Cold flow, Verse. phm lung, $ basal molars Gel Io mg / min Mr. _ 64 Viscous number 9.99 1 0.022 60 2.16 0 0.33 CvJ 0.044 66 2.25 0 0 3 0.088 65 2.37 0 0 4th 2.71 3

The results of Table XII show that VHB levels of approximately 1/10 of the amount of dicyclopentadiene (DCPD) used in Experiment 5 of Example 7 gave products which showed no cold flow and contained no gel.

Example 9

Further tests were carried out, in which even smaller ones Amounts of 5-vinyl-2-norbornene were used in a series of experiments using the polymerization recipes described in Example 7 and methods for isolating the polymers used. The results of this series of tests are in Table XIII listed.

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Act XIII

attempt ¹ O, VNB Conversion basal molars GeIj Cold flow, Mr. - 0, phm lung, $ Viscosity number ί ms / min 1 0, _ 63 2.16 0 8.79 2 0019 61 2.14 0 7.48 3 0094 57 2.24 0 2.12 4th 0187 59 2.25 0 0.78

109886/1696

Claims (12)

Claims ^ 1 / Process for the production of a rubbery hydrocarbon copolymer, characterized in that one A. a major amount of a cyclic monoolefin with 5 or 7 "to 10 carbon atoms in ring ₉ to which an alkyl substituent with up to 6 carbon atoms can be attached, but which is not closer to the double bond than In the 4-position; and B. a smaller amount of 1) a cyclic polyolefin with at least 2 carbon-carbon double bonds, which are separated from each other by a single carbon bond, or from one? link with condensed ringj the at least one carbon-carbon - Has a double bond in each of at least two rings, or 2) a ^ O.-alkenyl-polycycloalkeni in the presence of an olefin ice proportioning catalyst lysators copolymerized to 2. Procedure "according to" _:. Claim 1 ₉ characterized ₈ _ that by interpolymerization doe cyclic monoolefin with the cyclic polyolefin or the ^ j -alkenyl-poly- cycloalkene and a small amount of an acyclic ^ nich.t-tert.mono- or polyene with 2 Me 30 carbon atoms per Molecule <a ± n Serpolymerisat is formed « 3. The method according to claim. 1 © ä @ w 2 ₉ dadureh that the cyclic monoolefic is Oyolopsnten . 109888/1696 4. The method according to claim 1, 2 or 3, characterized in that the comonomer of B. is cyclopentadiene, dicyclopentadiene or bicyclo {2,2, i] -hepta-2,5-diene. 5. Process for the preparation of a terpolymer according to one of Claims 2 "to 4, characterized in that the acyclic mono- or polyene is 1-pentene or 1-hexene. 6. The method according to any one of claims 1, 2, 3 and 5, characterized in that the comonomer under B 2-vinyl-bieyclo- (2,2,1) ~ hepten-5, 2-butene-3 ^! -yl-Mcyolo- (2,2,1) -hepten-5,2-allyl-bicyclo »(2,2,1) -hepten-5,2-vinyl-bieyelo- (2,2,1) -heptene -5, 2-vinyl-1,4-endomethylene-i ^^^^ ySajS / Sa-octahydro- naphibhalen or 3-Allyllinden is. 7. A method for producing a copolymer according to any one of the preceding claims, characterized in that that the catalyst is formed by adding a compound of a metal from group VIB and an organoaluminum Mixed halide. 8. The method according to claim 7? characterized in that the metal compound of group VI B molybdenum trichloride dilauratej molybdenum trichloride dioctanoate. or molybdenum trichloride distearate is » 9. The method according to claim 7 or 8, characterized in that the organoaluminum halide is diethylaluminum chloride « 10. The method g © according to one of the preceding claims, characterized gekennz © lehnet that the copolymerization in one 109888/1698 Temperature in the range from -30® to + 15O®O carried out will. 11. Chewable hydrocarbon copolymer containing: A. a major amount of a cyclic monoolefin with 5 or with 7 "to 10 carbon atoms in ring ₉ to which further alkyl substituents with up to β carbon atoms can be bonded, but which are not closer to the double bond than to the 4-position; and B. a small amount of 1) a cyclic polyolefin having at least 2 carbon-carbon double bonds separated by a carbon-carbon single bond or a fused ring compound with at least one carbon-carbon double bond in each of at least 2 rings or 2) a U) -alkenyl-polycycloalkene. 12. Copolymer of cyclopentene and dicyclopentadiene according to claim 11, characterized in that the cyclopentene units by the following structural formula -CH ₂ - CH = CH - CH ₂ - CH ₂ - are represented, and that the dicyclopentadiene units by the following structure - CH = CH = CH can be represented. 109886/1696 - CH ₂ N CH - CH I. I. CH ν CH - _