DE1962853C3 - Process for the production of curable amorphous olefin interpolymers - Google Patents

Description

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The invention relates to a process for the preparation of curable amorphous olefin polymers by polymerizing two different -olefins with up to 10 carbon atoms and a polycyclic polyene in the presence of a polymerization catalyst which consists of a compound of a transition metal of groups IV to VIII of the Periodic Table of the Elements and an aluminum compound of the general formula AlRXiX ₂ ■ m Z, in which R is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, Xi and X ₂ , which can be identical or different, each have a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms or a secondary amino group, Z is a Lewis base and m is 0 or an integer, or a polyiminoalane of the general formula (-AIH-NRi-), in which Ri is an alkyl, aryl or cycloalkyl radical.

It is known that from ethylene, propylene or other A-olefins and dicyclopentadiene or one similar, one double bond in the endomethylene ring and another double bond in one with the first ring orthocondensed second ring containing compound as third monomer terpolymers can be produced (see, for example, French patents 14 47 671 and 14 54 300 and British patent specification 10 07 908). It has been shown, however, that these terpolymers are indeed a high utilization of the diene monomer and, because of its low unsaturation content, a very good hi Have resistance to chemical agents, but that they have the disadvantage that they are a have a fairly slow cure rate. In addition, the vulcanization ac sometimes sets infinitum without ever stopping. This disadvantage naturally affects the properties of the on them Terpolymers produced wisely and considerably restricts their usability, although this does not only the properties of these polymers are adversely affected; it is also not possible together with other common elastomers which have a high rate of vulcanization, one to achieve satisfactory covulcanization.

The object of the invention is therefore to provide a method Specify the production of terpolymers which do not have the disadvantages outlined above.

It has now been found that this object can be achieved by preparing the olefin interpolymers very specific polycyclic polyhydric hydrocarbons are used as the third monomer will.

The invention relates to a process for the production of curable amorphous olefin interpolymers by polymerizing two different α-olefins having up to 10 carbon atoms and a polycyclic polyene in the presence of a polymerization catalyst which consists of a compound; Transition metal of groups IV to VIII of the Periodic Table of the Elements and an aluminum compound of the general formula AlRXiX ₂ ■ m Z wherein R is a hydrogen atom or an alkyl group with 1 to 10 carbon atoms, Xi and X ₂ , which can be the same or different, are each a hydrogen atom a halogen atom, an alkyl group with 1 to IC carbon atoms or a secondary amino group Z is a Lewis base and m is 0 or an integer, or a polyiminoalane of the general formula (- AlH -NR, -), in which R, an alkyl- aryl or cycloalkyl radical, which is characterized in that the polyene Allyldicyclopentadi ene, Crotyldicyclopentadiene, (l'3'-dimethyl) -allyldicy · clopentadiene, Vinyldicyclopentadiene, Isopropenyldi cyclopentadienes, Divinyldicyclopentadiene, üiallyldicy clopentadiene, Vinylendomethylenhexahydronaphthali ne, Vinyltricyclopentadiene and Allyltricyclopentadien "used will.

As shown in Example 11 below it can be seen that olefin interpolymers are obtained by the process according to the invention which, in terms of their Properties clearly outperform the olefin interpolymers which can be prepared by the known process genes are. In particular, they have a considerably high vulcanization rate, which is often more than! 100% above that of a corresponding be produced using dicyclopentadiene known terpolymer is.

The polycyclic used to produce the olefin interpolymers according to the process of the invention see Polyhydrocarbons can be produced according to processes like those in German Offenlegungsschrift 19 62 854 are described.

Examples of polyenes which can be used according to the invention are as follows:

i '\ V CH ₂ --CH CH ₂

2- or? -Ally! -Dicyclopenladien

-CH ₂ -CH = CH-CH ₃
2- or 3-crotyldicycopentadiene

CH-CH = CH-CH ₃

Γ 2 '3 "

(HIj

2- or -S-O '^' - Dimethyty-allyldicyclopentadieiii

C = CH ₂

(IV)

1- or 2- or -3-vinyldicyclopentadiene (R = H): 1- or -2- or -S-isopropenyldicyclopentadiene
(R = CH ₃ )

Divinyl dicyclopentadiene

CH = CH,

(VI)

6-vinyl- [1,4-endomethylene-1,4,5,8,9,10-hexahydro] naphthalene

^ CH = CH ₂

(VII)

7-vinyl- [1,4-endomethylene-1,4,7,8,9,10-hexahydro] naphthalene

(VIII)

6-vinyl- [1,4-endomethylene-1,4,7,8,9,10-hexahyd: ro] naphthalene

_/ -CH = - CH ₂

S g I

2- or -i-vinyl-tricyclopentadiene

CH ₂ -CH = CH ₂

2- or 3-, -5- or -o-diallyl-dicyclopentadiene

For carrying out the process according to the invention, suitable jJ-olefins are ethylene, propylene, Butenes, pentenes, methylpentenes and hexenes. The ethylene-propylene pair is preferably used

Examples of suitable aluminum compounds which are a component of that used according to the invention Polymerization catalyst are the following:

AKn-C ₁₀ H ₂ O ₃ ,

Al (n-C <sHi3) 3,

AKn-C ₄ H ₉ J ₃ ,

AlClKC ₂ H ₅ ),

AKC ₂ Hs) ₂ Cl,
2, AKi-C ₄ Hg) ₂ Cl,

Al (IC ₄ H ₉ ) Cl ₂ ,

AlHCl ₂ · 0 (C ₂ Hs) ₂ ,

AIH ₂ N (CK ₃ K

AlHClN (CH ₃ J ₂ and
3u AlH ₃ · N (CH _{3 I 3} .

Examples of suitable transition metal compounds which can be used as components in the catalyst used according to the invention are VCl ₄ , VOCl ₃ , vanadium triacetylacetonate, VCIO (OC ₂ H ₅ ) J ₁ VCl, 3 THF and TiCl ₄ .

The process of the invention can be carried out in the presence of an inert hydrocarbon solvent or in the liquid monomers (α-olefins) as solvents. The catalyst used in the present invention can be prepared either in advance in the presence or absence of a monomer or in situ. The temperatures used are the same as are usually used in such 4 ^r > reactions, and they are, for example, within the range of -60 to + 100 ⁰ C. The pressures used are between the pressure that is required to achieve the To keep monomers at least partially in the liquid state, and 100 atmospheres, preferably between 1 and 80 atmospheres.

If ethylene and propylene are used as -olefins, the ratio between these two monomers is preferably within the range from 5 ^r > 1: 4 to 4: 1, in particular 1.5: 1 to 1: 1.5. The polyene used in the process according to the invention preferably makes up 1 to 20% by weight of the terpolymer produced therefrom.

The invention is illustrated in more detail by the following examples bo.

In the following examples, the course of the vulcanization reaction was determined using the torque tracked by a Vulcameter (rheometer from the Zwick type) with an oscillating plate during the IIX) b <i vulcanization was recorded. The torque is proportional to the degree of vulcanization. The maximum change in torque corresponds to the difference between after the first 250 minutes of the

Vulcanization measured torque and the torque measured at the beginning d. H. the equation

G250 - Gmin ⁼ Gij23x.

Another prerequisite is that the concentration of the double bonds on the side t is equal to the difference between the assumed maximum and the torque at time t , i.e. corresponds to equation G250-G. The vulcanization rates measured under the specified conditions with an excess of sulfur essentially depend only depends on the concentration of the double bonds.

The course of the vulcanization reaction corresponds to a kinetic equation of the second order, which by the following equation can be expressed:

dG,

dr

Once G _m "and / 90, the time required to achieve 90% of G _max - G _W i" , are known, the vulcanization rate constant K can be calculated from this equation according to the following equation:

K =

example 1

1000 ml of η-hexane was placed in an inert atmosphere in a 1500 ml tubular reactor equipped with a mechanical stirrer, a thermometer sleeve and a jacket for a thermostatically regulated liquid. At the same time, a mixture of propylene and ethylene with a molar ratio of 2: 1 and a flow rate of 12001 (measured under standard conditions) per hour was introduced into the bottom of the reactor the temperature of the solvent was maintained at 0 ⁰ C by a controlled by a cryostat cooling mixture was circulated within the reactor shell.

After the monomer mixture had been blown for 20 minutes, it was believed that equilibrium had been established. The reactor was then charged with 4 mmol (C ₂ H ₅ ) 2A1C1 and 11.6 mmol allyldicyclopentadiene (Formula I) per liter. While the introduction of the monomer gas stream continued, the polymerization reactor became. initiated by introducing 0.5 mmol of vanadium triacetylacetonate per liter. The polymerization was continued for 9 minutes; it was stopped by adding 1 ml of n-butanol in the reactor. The reaction solution was washed with water, acidified with HCl and washed again with water until neutral; then it was coagulated by slowly adding an excess of acetone containing an amine antioxidant. After drying for 15 hours under reduced pressure at 50 ° C., an elastomeric composition was obtained which weighed 14.8 g and which in its appearance resembled uncured rubber. Eiin X-ray pattern showed that it was essentially amorphous and a CVGehaii of 62 wt .-% had as their intrinsic viscosity, measured in toluene at 30 ⁰ C, 136 dl / g was. The iodometric investigation showed a termonomer (I) content of 5.1% by weight in the terpolymer

Part of the terpolymer was cured using the following composition in a Zwick rheometer with an oscillating plate with an angle of rotation & = 45 °:

Polymer 100 parts

H AF carbon black (carbon) 50 parts
ZnO 5 parts

Naphthenic oil 5 parts

Mercaptobenzothiazole 0.5 parts

Tetramethylthiuram disulfide 1 part

Sulfur 2 parts

Vulcanization temperature 145 ° C

The following results were obtained:

(Induction time) = 3'30 ";

(the time required to reach 90% of the maximum modulus) = 81 ';
(Rate constant for the entire vulcanization reaction) = 0.386 min- ¹ ■ m- '· kg-' and

Gmax (the maximum torque measured at the end of vulcanization) = 0.508 m · kg.

The IR spectrum of the terpolymer showed the absorption bands characteristic of the vinyl group at 908 and 990 cm- '.

Example 2

The process of Example 1 was repeated using 4 mmol of Al (C2Hs) 2Cl and 0.5 mmol of V (acetylacetonate) 3 in n-heptane as the catalyst system. As Termonomeres 10.7 mmol Crotyldicyclopentadien were of the above formula II is used and the polymerization temperature was kept constant at 0 ⁰ C. After 8 minutes of polymerization, 16 g of terpolymer were obtained with an unsaturation content corresponding to 4.85% by weight of termonomer, an intrinsic viscosity of 1.25 dl / g and one

Ethylene content of 65% by weight. The technological data obtained were as follows:

ti = 3'30 " 1 -1 . kg-> fco - 39 '; kg- K - 0.333 min Gmax = 0.511 m

mouth

Example 3

The polymerization described in Example 2 was repeated, this time as a termonomer 11.2 mmol of the compound of formula III were used. After 8 minutes of polymerization, one obtained 15 g of a terpolymer with an unsaturation content corresponding to 43% by weight of termonomer, an intrinsic viscosity of 132 dl / g and an ethylene content of 63% by weight. The received technological data were as follows:

rn ~ 'and

please , = 3 '; min -1 . kg- twi = 42 '; m kg- K = 0.320 G _ma , = 0.505

Example 4

The polymerization was carried out in 1000 ml of toluene at -20 ° C. using 0.5 mmol of VCU, 2.5 mmol of AI (C ₂ Hs) ₂ CI and 1.25 mmol of anisole as a catalyst and 12.2 mmol of vinyldicyclopentadiene of the above formula IV , in which R is a hydrogen atom, carried out as a termonomer. After 6 minutes, 18 g of a terpolymer with an unsaturation content corresponding to 4.3% by weight of termonomer, an intrinsic viscosity [ή] = 1.3 dl / g and an ethylene content of 55% by weight were obtained. The technological data obtained were as follows:

t, = 3 ';

f90 = 60 ';

K = 0350min- '■ kg-' · m-'and

G _m * x = 0.450 m kg.

Example 5

The polymerization was 3.2 mmol of AI (C ₂ Hs) ₂ Cl and 0.4 mmol of V (acetylacetonate) 3 existing catalyst and using 8.0 mmol of a compound of the above at 0 ⁰ C in n-heptane having a Formula V carried out as a termonomer. After 9 minutes, 13.5 g of terpolymer were obtained with an unsaturation content corresponding to 4% by weight of termonomer, an intrinsic viscosity of 1.57 dl / g and an ethylene content of 64% by weight. The technological data were as follows:

20th

25th

30th

= 2'45 "; -I. k g- '· m-' and (90 = 35 '; ■ kg. K = 0.41 min G _max = 0.490 m

Example 6

The polymerization was conducted at 20 ⁰ C in 1000 ml of toluene using 0.5 mmol VCI +, 2.5 mmoles of Al (C ₂ Hs) ₂ Cl and 1.25 mmol of anisole as a catalyst and 10.2 mmol of a compound of the above Formula VI carried out as termonomers After 8 minutes , 16 g of terpolymer were obtained with an unsaturation content corresponding to 4.5% by weight of termonomers, [ή] = 1.45 dl / g and an ethylene content of 56%. The technological data were as follows:

ti = 2'30 ";

fco = 50 ';

K = 0,360min- ¹ · ^kg-1 ■ m-'and

G "= 0.440 m · kg.

Example 7

In this example, as Termonomeres 8.5 mmol of a compound of the above formula VII and 3.2 mmol of AJ (QHs) ₂ Cl and 0.4 mmol of V (acetylacetonate) 3 were used as the catalyst, the polymerization was carried out at 0 ° C. in n-heptane. After 10 minutes 14.5 g of a terpolymer with an unsaturation content corresponding to 4.9% by weight, [tj] = 132 dl / g and an ethylene content of 64% by weight were obtained. The technological data were as follows:

t, = 3'30 ";

feo = 42 ';

K = 0390min- '-kg-'

G ₀₁₁ X = 0.495 m kg.

mouth

Example 8

As Termonomeres 10.5 mmol of time of a compound of formula VIII is used, the catalyst consisted of 3.2 mmoles AI (C ₂ Hs) ₂ CI, and 0.4 mmol of V (acetylacetonate) 3, the polymerization was conducted at 0 ⁰ C carried out in n-heptane. After 10 minutes, 13.5 g of a terpolymer with an unsaturation content corresponding to 4.4%, [η] - 1.4 dl / g and an ethylene content of 63% by weight were obtained. The technological data obtained were as follows:

1, = 3 ';

to = 70 ';

K = 0.330 min- 'kg>m-' and

C _m3 , = 0.460 m kg.

Example 9

In this example, 11.5 mmol of a compound of the above formula IX were used as the termonomer and 0.5 mmol of VCl ₄ , 2.5 mmol of Al (C ₂ Hs) ₂ Cl and 1.25 mmol of anisole were used as the catalyst; -20 ⁰ C carried out in toluene. After 6 minutes, 16 g of a terpolymer with an unsaturation content corresponding to 3.8%, [η] = 1.36 dl / g and an ethylene content of 57% by weight were obtained. The technological data obtained were as follows:

ti = 3'45 ";

iw = 60 ';

K = 0345min- 'kg- ¹ m-' and

Gmax = 0.515 m kg.

Example 10

The procedure described in Example 1 was repeated, but this time ₂ Cl and 1 mmol of V (acetylacetonate) was ml n-heptane at 0 ⁰ C was used in 1000 as a catalyst ₃ 8 mmol Al (C ₂ Hs). The termonomers were 18.9 mMo! a compound of the above formula X used. After 22 minutes, 15.1 g of a terpolymer with an unsaturation content corresponding to 5.7% by weight were obtained

Termonomerem, [ij] = 1.05 dl / g and an ethyl acetate content of 65% by weight. The technological data obtained were as follows:

ti = 3'45 ";

Ϊ90 = 107 ';

K = 0,16min- '· kg-m ·-'and

G _mlx = 0.408 m kg.

Example 11

To demonstrate the technical progress achieved according to the invention compared to that achieved by the French Patent Nos. 1,447,671 and 1,454,300 and represented by British Patent No. 10 07 908 Prior art, the comparative tests described below were carried out.

When using 3-methyl-l, 4,6-heptatriet and 1,4,7-octatriene (French patent 14 47 671) as Termonomerem could after The process of the invention in both cases involves terpolymers with the desired properties and vulcanized products with good elastomeric properties could not be obtained therefrom getting produced.

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65

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For the preparation of the terpolymers using 3-methyl-l, 4,6-heptatriene were Twelve experiments carried out in which VCU and aluminum hydride compounds were used as the catalyst became. In all cases a saturated copolymer was obtained without any unsaturation, even if when a large amount of polyene was used. There were also seven more attempts with other catalyst systems carried out, the various vanadium compounds and aluminum alkyl compounds contained. In these cases, even when a large amount of polyene (15 ml 3-methyl-l, 4,6-heptatriene in 400 ml of solvent) only achieved a very low degree of vulcanization.

! In any case, if the usual amount was considered

Termonomer was used, no curable terpolymer, but only a saturated copolymer obtain. As the analyzes carried out on the basis of the IR spectra and the ICI reaction showed, no unsaturation could be determined. The 3-methyl-1,46-heptatriene used in these experiments was according to the information from S. O t s u k a et al. in "). Am. Chem. Soc ", 85, 3809 (1963).

In addition, terpolymers were prepared using the 1,4,7-octatriene known from French patent 14 47671 as a termonomer and using catalysts which contained VCU and AlAtCl ₂ . The results obtained are summarized in the following table:

Vcr Termono Catalyst T

look for more

(mmol / l) (mmol / 1) (mmol / 1) (C)

Time C ₃ / C ₂ Yield Termono Comments

in min. in g / l meres

1 8.3 AIAt ₂ Cl VCl ₄ -20 10 2.5 26.8 0.6

12.0 2.0

2 8.3 Al ₂ At ₃ Cl ₃ VOCl ₃ +30 10 2.5 34.4 0.2

40.0 4.0

3 16.7 M ₂ At ₃ Cl ₃ VOCl ₃ +30 10 2.5 50.7 nd

60 6.0

n.d. = not determined.

semi-liquid
Polymer

viscous oil

viscous oil

The results reported above show that none of these experiments were high molecular weight solid polymer was obtained.

In addition, the following comparative tests were carried out in which the vulcanization genetic Values of terpolymers produced by the process according to the invention with the corresponding values of commercial products were compared. As can be produced according to the invention Terpolymer was used such that using 2- or 3-crotyldicyclopentadiene as Termonomerem had been made.

Type of used (Mol / kg) Vis C ₂ H ₄ (min) '90 K A, 10 ³ Termonomers 0-470 kosity 6th 0.630 (dl / g) (Wt .-%) 5 (min) (kg "'m"' min ~ ¹ ) (min ' ¹ ) 1,4-trans hexadiene 0.470 1.78 58 5 30th 0.14 5.00 2-ethylidene norbornene 0.440 1.65 63 7.5 35 0.14 0.26 2-methylidene norbornene 0.250 1.68 55 3.5 73 0.12 - Endodicyclopentadiene 1.70 65 115 0.07 0.20 According to the invention 1.25 64 39 0.33 used termono meres

*) / £, = the reverse reaction rate constant (breakage of the vulcanization bonds formed).

The above data show that the present invention makes a surprising technical Progress is being made that was not readily to be expected.

Claims (1)

Claim: Process for the preparation of curable amorphous olefin interpolymers by polymerizing two different α-olefins with up to 10 carbon atoms and a polycyclic polyene in the presence of a polymerization catalyst consisting of a compound of a transition metal of groups IV to VIII of the Periodic Table of the Elements and an aluminum compound of the general Formula AIRX1X2 m Z, where R is a hydrogen atom or an alkyl group with 1 to 10 carbon atoms, Xi and X2, which can be identical or different, each have a hydrogen atom, a halogen atom, an alkyl group with 1 to 10 carbon atoms or a secondary amino group, Z denotes a Lewis base and m denotes 0 or an integer, or a polyiminoalane of the general formula (—AlH-NRj—), in which Ri denotes an alkyl, aryl or cycloalkyl radical, characterized in that the polyene is allyldicylopentadienes, crotyldicyclopentadienes , (1 ', 3'-dimethyl) allyldicyclopentadienes, vinyl di cyclopentadienes, isopropenyldicyclopentadienes, divinyldicyclopentadienes, diallyldicyclopentadienes, vinylendomethylene hexahydronaphthalenes, vinyltricyclopentadienes or allyltricyclopentadienes can be used. 50