Elastomeric copolymers of ethylene and propylene

Details Elastomeric copolymers of ethylene and propylene Elastomeric copolymers of ethylene and propylene

1997-04-22

2001-12-18

Wilson, Donald R. (Department: 1713)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S281000, C526S282000, C526S943000

Reexamination Certificate

active

06331600

ABSTRACT:

The present invention relates to novel copolymers of ethylene with propylene and optionally with minor proportions of a diene or polyene having good elastomeric properties in their uncured state.
The EP and EPDM rubbers, elastomeric copolymers of ethylene with propylene and minor proportions of a diene or polyene respectively, are well known products in the state of the art.
These copolymers are generally prepared by polymerising a mixture of ethylene and propylene and optionally diene or polyene with Ziegler-Natta catalysts obtained from vanadium compounds, such as acetylacetonate, and alkyl aluminium halides.
The copolymers so obtained necessitate a vulcanisation treatment (with peroxide or sulphur) in order to acquire elastomeric behaviour of interest in industrial applications. In the their uncured state they are not endowed with elastomeric properties of interest.
Thermoplastic polyolefin rubbers (TPO) are known, which are capable of maintaining the processability characteristics of the thermoplastic polymers and at the same time are endowed with an elastomeric behaviour. These rubbers are obtained by high temperatures dynamic vulcanisation of blends of the crystalline polymer, in particular isotactic polypropylene, with EP or EPDM rubbers in the presence of crosslinking agents.
Copolymers endowed with a certain level of elasto-plastic properties are known, obtained by polymerisation of mixtures of propylene with minor proportions of ethylene using a catalyst based on a titanium compound supported on magnesium dichloride (U.S. Pat. No. 4,298,721). These copolymers are characterised by a high crystallinity content of polypropylenic type, and optionally of polyethylenic type; the elastomeric properties of these copolymers are unsatisfactory (200% tension set values are too high).
Preparing elastomeric copolymers of ethylene with propylene and/or with &agr;-olefins and optionally with minor proportion of a diene or polyene by means of the polymerization of mixtures of monomers with homogeneous catalysts obtained from Ti, Zr or Hf metallocenes and alumoxane compounds, is known.
European Patent Application EP-A-347128 describes a process for the preparation of elastomeric copolymers of ethylene with &agr;-olefins in which the catalyst used is the product obtained from the reaction of bridged dicyclopentadienyl —Zr, —Ti or Hf compounds, such as ethylene-bis(indenyl)-zirconium dichloride or ethylene-bis(tetrahydroindenyl)-zirconium dichloride or dimethyl-silanylene-bis(tetrahydroindenyl)-zirconium dichloride, with polymethyl-alumoxane.
The polymerisation is carried out in liquid monomer at a temperature between 0° and 80° C., preferably between 20° and 60° C.
European Patent Application EP-A-347129 describes a process for the preparation of elastomeric copolymers of ethylene with &agr;-olefins containing minor proportions of a non-conjugated diene, analogous to the one disclosed in European Patent Application EPA-347128.
None of the copolymers disclosed in both the above cited EP applications or in the examples shows satisfactory elasto-plastic properties in the non-vulcanized state. 200% tension set values are higher than 30% and the tensile strength is lower than 4-5 Mpa.
Until now, no copolymers of ethylene with propylene, optionally containing units deriving from dienes or polyenes, are known that have elastomeric properties of interest in their uncured state, in particular tension set values at 200%, 1 min, 25° C., of less than 15%. The tension set is determined according to the subsequently reported method.
It has now been unexpectedly found that, using particular catalysts and carrying out the polymerisation in solvents, it is possible to synthesise ethylene-propylene copolymers having the above indicated elastomeric properties.
The copolymers have an ethylene content comprised between 55 and 70% by weight, preferably between 58 and 65% by weight, a content of propylene between 30 and 45% by weight, preferably between 35 and 42% by weight, and a content of diene or polyene comprised between 0 and 10% by weight.
The copolymers are characterized by:
solubility in pentane at 25° C. higher than 95%;
substantial absence of crystallinity (fusion enthalpy lower than 15 J/g);
content of propylenic units in the form of triads comprised between 3 and 10% of propylene; at least 70% of said triads display an isotactic structure;
The content of diene or polyene units is generally comprised between 0 and 10% by weight, preferably 0.5 and 5% by weight.
The molecular weight distribution is very narrow; in particular the M
w
/M
n
ratio has relatively low values, generally less than 4, and preferably less than 3.
The copolymers of the invention are additionally characterised by an appropriate distribution of ethylene and propylene units in the macromolecular chain (values of the product of the comonomer reactivity ratios from 0.4 to 0.6.
The copolymers have an inherent viscosity higher than 3 dl/g, preferably higher than 3.5 dl/g.
In order to obtain good elastomeric properties in the uncured state, the content of ethylene and the intrinsic viscosity are particularly important parameters; copolymers having the same structure in terms of propylene content in the form of triads and in terms of the value of the product of the reactivity ratios and having a content of ethylene and intrinsic viscosity outside the values claimed, do not show interesting elastomeric properties in the uncured state, in particular they do not show tension set values at 200% of less than 15.
The copolymers of the invention, obtained by a process in solution, are additionally characterised by a good composite uniformity that can be demonstrated by solvent fractionation. Composite uniformity at such levels is not obtained when operating in liquid propylene.
The copolymers can be transformed into shaped articles by means of the normal processes of manufacturing of thermoplastic materials (compression moulding, extrusion, injection moulding, etc.) and the resulting articles display elastic properties comparable to those of vulcanized rubbers.
The copolymers of the invention are prepared by polymerising a mixture of ethylene and propylene, optionally in the presence of diene or polyene, with chiral catalysts obtained from zirconium metallocene derivatives such as ethylene-bis(tetrahydroindenyl)-zirconium dichloride or dimethylsilanyl-ene-bis(tetrahydroindenyl)-zirconium dichloride and an alkyl aluminium operating in an inert hydrocarbon solvent and in the presence of water in such quantities that the molar ratio of Al/H
2
O is higher than 1:1 and lower than 100:1 and preferably comprised between 1:1 and 50:1.
The molar ratio Al/Zr is comprised between about 100 and about 10000, preferably between 500 and 5000, more preferably between 500 and 2000.
Non-limitative examples of the alkyl-Al compound are: Al(iBu)
3
, AlH(iBu)
3
, Al(iHex)
3
, Al(C
6
H
5
)
3
, Al(CH
2
C
6
H
5
)
3
, Al(CH
2
CMe
3
)
3
, Al(CH
2
SiCMe
3
)
3
, AlMe
2
iBu, AlMe(iBu)
2
.
The hydrocarbon solvent used in the polymerisation can be both aromatic, such as for example toluene, or aliphatic such as for example, pentane, hexane, cyclohexane, heptane.
The polymerisation temperature is generally comprised between 0 and 100° C., preferably between 20 and 60° C.
The molecular weight of the copolymers of the invention can be controlled, for example, using a molecular weight regulator, among which hydrogen is preferred.
The dienes or polyenes used are preferably selected among non-conjugated linear diolefins such as 1,4-hexadiene, or internal-bridged cyclic diolefins, such as 5-ethylidene-2-norbornene.
Characterisation
The thermal behaviour of the polymer is analyzed on a sample as polymerized, by means of Differential Scanning Calorimetry, according to the following procedure: first scanning stroke from T
1
=−20° C. to T
2
=180° C., with a heating rate of 20° C./minute.
The content of bound ethylene is determined by means of infrared analysis.
The content of propylenic triads was determined by means of
13
C-NMR, with reference to the methin

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