DE2343093A1 - Ring-opening polymn. of cyclic olefins - producing polyalkenamers of broadened mol. wt. distribution and increased deform elasticity - Google Patents

Abstract

Ring-opening polymerisation of cyclic olefins (I) is effected in the presence of a catalyst contng. (a) a Gp. VB or VIB metal halide and (b) a Gp, IIA, IIIA or IVA organometallic cpd. opt. in admixture with a cocatalyst and opt. in the presence of an inert org. solvent at -70 degrees C. to 60 degrees C. during or after which polymerisation 0.01-10 wt. % (based on (I)) of a cpd. contng. C=C unsaturation in conjunction with a C=O double bond (II) is added in the presence of the catalyst. The polyalkenamers, known as per se, have higher degrees of inhomogeneity and a consequently broadened m.wt. distribution besides having greatly increased Defo elasticity.

Description

Polyalkenamers with broadened molecular weight distribution ff

It is known that cyclic olefins are made from catalysts

a) halides of metals of groups VB and VIB of the periodic table,

b) organometallic compounds of metals of groups HA, IHA and IVA of the periodic table and

c) optionally cocatalysts

to polymerize with ring opening, (German Offenlegungsschriften 1,770,491, 1,770,844 and British Patent 1,010,860).

In general, this polymerization is carried out in bulk or in an organic solvent. You can use "preformed" catalysts or, and this is preferred, prepare the catalysts from their constituents in the presence of the monomers.

In all known polymerization processes of this type, rubber-like polymers are obtained from cyclic olefins

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with polyalkenamer structure, which have a narrow molecular weight distribution. However, rubbers with a narrow molecular weight distribution are generally difficult to process, while rubbers with a broad molecular weight distribution are generally easy to process.

There is therefore a need for polyalkenamers with broad Molecular weight distribution that are easier to process.

The invention accordingly provides a process for the ring-opening polymerization of cyclic olefins over catalysts

a) a halide of a metal from groups VB or VIB of the periodic table,

b) an organometallic compound of a metal from groups ΙΙΑ, ΙΙΙΑ and IVA of the periodic table

c) optionally a cocatalyst

optionally in an inert organic solvent at temperatures from -70 to +60 ⁰ C, which is characterized in that during or after the polymerization in the presence of the active catalyst 0.01 to 10 wt .-%, based on the monomer used, adds to a compound which contains a C = C double bond and conjugated thereto a C = O double bond.

The polyalkenamers produced in this way have higher values of the compared to the products produced without the addition Inconsistency and thus a broadened molecular weight distribution. Their defo-elasticity is also strong elevated.

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Cyclic olefins which are particularly suitable for the process are, in particular, mono- or dicyclic olefins which have one or two or more unsubstituted C =C double bonds, preferred contained in a non-conjugate arrangement. Particularly preferred are cyclomonoolefins with 5 or 7 "to 12 carbon atoms in the ring, such as cyclopentene, cycloheptene, cyclooctene, cyclododecene, monocyclic, especially non-conjugated Serves with 5-12 carbon atoms in the ring, such as cyclopentadiene, cyclooctadiene or corresponding cyclic trienes, such as Cyclododecatriene. Polycyclic olefins, such as dicyclopentadiene, norbornene, norbornadiene / alkylidene norbornene, are also suitable. Various of the monomers mentioned can also be copolymerized. Cyclopentene is particularly preferred.

According to the invention for influencing the molecular weight distribution and the defo-elasticity compounds used with C = C bonds in conjugation to CO bonds are in particular ot-ß-unsaturated aliphatic mono- and polycarboxylic acids, ot-ß-unsaturated aliphatic aldehydes undo (-ß-unsaturated aliphatic ketones and derivatives of these compounds. For example, acrylic acid and methacrylic acid are suitable, as well as their C ^ -Cg alkyl esters and their nitriles, (Methyl acrylate, butyl acrylate, methyl methacrylate, acrylonitrile), maleic acid, maleic acid ester (Maleic acid diethyl ester) and maleic anhydride, acrolein, methacrolein, vinyl ketone, divinyl ketone and cyclopentenone.

The amounts in which these compounds are added are generally between 0.1 and 10% by weight, based on, ^

V <* ~. O, \ - A ^v ! ΰ * "V is the monomer. Mostly, the size of the additions is sufficient to increase the non-uniformity from 11 to 15. Non- uniform here means the quotient of the weight average of the molecular weight and the number average reduced by 1. ^ r> .

The effect of these additives is surprising because, in general, the addition of polar compounds leads to polymerizations over organometallic mixed catalysts, which is the case here

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used made difficult or even prevented entirely. Amazingly there is not even a noticeable reduction in conversion if the compound has a C = C double bond and in conjugation thereto, a CO group is added to the polymerization mixture after the organometallic Catalyst is formed but before it is deactivated. Within this time, i.e. practically during the whole Polymerization process and also, even preferably, at the end of the polymerization, the compound can be added. The actual time of addition can be chosen freely and is generally based on the type and amount of the compound added.

The polymerization process itself is known in principle. The monomer is usually dissolved in a suitable solvent and the catalyst components are then added one after the other. Usually 5-50% by weight solutions, preferably 10-30% by weight solutions, of the monomer in the organic solvent are used. Suitable solvents are for example aliphatic hydrocarbons such as butane, pentane, ^H exan, isooctane or cycloaliphatics such as cyclohexane, further aromatics such as benzene, toluene or xylene into consideration. The catalyst component a), ie the heavy metal halide, should be present in an amount of 0.1-10 mmol per 100 g of monomer, preferably 0.5-2 mmol per 100 g of monomer is used. The molar ratio of the catalyst components a): b): c) is generally 1: 0.5-15: 0-10. The polymerization is generally conducted at temperatures of -70 to +60 ⁰ C, preferably from -20 to +20 ⁰ C.

Particularly preferred catalysts are combinations of

a) tungsten or tantalum halides or oxy halides such as WCl ₆ , WBr ₅ , WCl ₄ O, TaCl,

b) organoaluminum or organotin compounds, preferably of the general formula

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Al - R ₂ II

in which R ₁ alkyl with 1-12 carbon atoms, Rp alkyl with 1-12 carbon atoms, halogen (fluorine, chlorine, bromine, iodine) R ^ alkyl with 1-12 carbon atoms, alkoxy with 1-12 carbon atoms and halogen (fluorine, chlorine , Bromine, iodine), or the formula Sn (R) ₄ , where R is an alkyl radical preferably having 1-6 carbon atoms. Triethylaluminum, trioctylaluminum, triisobutylaluminum, aluminum diethyl chloride, aluminum diethyl bromide, aluminum ethyl dichloride, ethoxyaluminum diethyl, tin tetraethyl and tin tetrabutyl are particularly preferred.

Preferred components c) are

1) Halogen-containing alcohols of the formula

R ₁ R,

R ₂ -CCR ₄ in

OH X

where X stands for chlorine, bromine or iodine, R. and R ₂ v / dss first off, chlorine, bromine, iodine, C ₁ -Cg alkyl, Cg-Cl ₂ aryl or alkylaryl, R ^ and R ₄ mean chlorine, bromine or iodine, hydrogen, C.-Cg alkyl, Cg-C ^ ₉ aryl or alkylaryl and in which R ₁ and R, together with the carbon atoms on which they are attached, can form a 5- or multi-membered hydrocarbon ring.

Particularly preferred are 2-chloroethanol, 2-bromoethanol, 2-iodoethanol, 1,3-dichloropropanol-2, 2-chlorocyclohexanol, 2-chlorocyclopentanol and 2,2,2-trichloroethanol.

2) Epoxides of the general formula

R-CH-CH-R ¹ IV

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wherein R and R ¹ is hydrogen, C ^ -CG alkyl, C ₁ -CG alkoxy, C ^ haloalkyl -CG (chloroalkyl, bromoalkyl), or oxyalkylene, preferably with 3-6 carbon atoms, mean. examples are
Ethylene oxide, propylene oxide, butylene oxide, butadiene monoxide, epichlorohydrin, epibromohydrin and allyl glycidyl ether.

The process of the invention can be batch or continuous be performed. At the end of the polymerization, the organometallic catalyst is deactivated and the polymer obtained by precipitation or steam distillation.

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example 1

250 ml of cyclopentene (96%) were dissolved in 1200 ml of toluene (containing less than 2 ppm HpO). A 1% strength butene-1 solution in toluene, corresponding to 300 ppm, based on cyclopentene, was added to this. Thereafter, after cooling to -15 ° C., 6.6 ml of a 0.1 M tungsten catalyst were added, which had been prepared by reacting WCIg with chloroethanol in toluene in a molar ratio of 1: 1.8. Then 6.6 ml of a 0.3 molar solution of diethylaluminum chloride in toluene were added. After a running time of three hours, the conversion was 85 %. 50 % of the solution was drained off, stopped by adding methanol and stabilizer and precipitated by running into isopropanol (sample A). The residue was diluted by adding 150 ml of toluene, stirred for 15 minutes and then worked up as above (sample B).

The experiment was repeated exactly. Then half of the solution was drained and worked up as above (sample C). 150 ml of a 1% strength by weight acrolein solution in toluene were added to the remainder, and the mixture was stirred for 15 minutes (0.1 % acrolein, based on cyclopentene) and worked up (sample D).

The results are summarized in Table 1.

A. toluene
25 ° C
DlJ Table 1 Defo-
hardness trans-
salary
(#) Acrolein sales
% B. 2.35 Defo-
elastic
Quote 17th without 85.0 sample C. 2.30 625 18th Il 85.5 sample D. 2.20 625 18th 79.3 It sample 2.29 550 26th 80.2 0.1 % 87.0 sample 850

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In experiment B, despite dilution with toluene and prolongation of the polymerization by 15 minutes, there was no change in the product properties compared to experiments A and C.

The addition of acrolein (experiment D) clearly improves the defo values, while the viscosity increases only very slightly will.

Example 2

Cyclopentene was polymerized as in Example 1, but 1% by weight of acrolein, based on cyclopentene (as a solution in toluene), was added just 30 minutes after the start of polymerization. The conversion of cyclopentene at this point in time was 71.0 %. The polymerization was carried out for a total of 3 hours and then worked up as described in Example 1. The final conversion was then 76.3 %, ie the addition of acrolein during the polymerization does not affect its course.

Example 3

0.1% of acrolein, based on cyclopentene , was added to a polymerization batch according to Example 1 before the catalyst constituents were added. The solution turned reddish in color. No polymerization occurred.

Example 4

A polymer solution prepared according to Example 1 was divided before the deactivation of the catalyst; one half was worked up directly, the second 0.1% by weight maleic anhydride, based on cyclopentene, was added as a solution in toluene, stirred for 15 minutes and then worked up. Final sales: 85.7 %.

Raw rubber values: JJr \ ~ J Defo- Defo-

^c "hardness viscosity

without maleic anhydride 2.61 725 17 with 0.1 % maleic anhydride 2.59 825 21

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Example 5

Example 4 was repeated. Instead of maleic anhydride, 0.1 % butyl acrylate (based on cyclopentene) was used. Final sales 82 %.

Raw rubber values: Defo hardness Defo elastic

activity

without butyl acrylate 675 15

with 0.2 % butyl acrylate 625 18

Example 6

1450 ml of a 20% strength by weight solution of cyclopentene (CPE) in dry toluene were placed in a 2 liter autoclave. The tungsten catalyst mentioned in Example 1 (0.2 mmol of W per 100 g of CPE), 0.1 mmol of iodine per 100 g of CPE and 0.4 mmol of aluminum diethyl chloride per 100 g of CPE were added in succession at room temperature. After a reaction time of 3 hours, 0.1 % acrolein (based on cyclopentene), dissolved in toluene, was added, the mixture was stirred for 15 minutes and worked as described above on (A). For comparison, a test was carried out without the addition of acrolein (B).

Acrolein added ML-4 ^f / 1CKrC Defo hardness Defo-elasticity A) 0.1 % 97 900 14th Bean 95 575 7th Example 7

The one from a continuously running cyclopentene polymerization plant obtained polymer solution was continuously a 5 wt .-% solution of acrolein in toluene in such Amount added that 0.1% by weight or 0.25% by weight of acrolein, based on the cyclopentene used. The solution was after an exposure time of the acrolein of 30 minutes continuously with an aqueous ethylenediamine

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solution deactivated. The polymer was isolated by coagulation in hot water and dried in vacuo at 7O ⁰ C. For comparison, no acrolein was added. The result is shown in Table 2.

without
0.1 %
0.25 % ML-4 ^f Tabel 2 Mon Mw
1 U
(Mw / Mn) -1 100
120
136 Defo Mn.
10 ^ g / CM CM CM , 33
, 51
, 97 11
15th
18th Acrolein added 600/6
900/12
1650/27 0.189
0.155
0.153 A)
B)
C)

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Claims (1)

Patent claim Process for the ring-opening polymerization of cyclic olefins of catalysts a) a halide of a metal from groups VB or VIB of the periodic table, b) an organometallic compound of a metal from groups IIA, IIIA and IVA of the periodic table, C) optionally a cocatalyst, optionally in an inert organic solvent at temperatures from -70 to +60 ⁰ C, characterized in that during or after the polymerization in the presence of the active catalyst, 0.01 to 10 wt .-%, based on the monomer used, one Adds compound which contains a C = C double bond and conjugated to a CO double bond. Le A 15 254 - 11 - 509809/0988