CA1338368C - Crystalline copolymers of propylene - Google Patents

Crystalline copolymers of propylene

Info

Publication number
CA1338368C
CA1338368C CA000584234A CA584234A CA1338368C CA 1338368 C CA1338368 C CA 1338368C CA 000584234 A CA000584234 A CA 000584234A CA 584234 A CA584234 A CA 584234A CA 1338368 C CA1338368 C CA 1338368C
Authority
CA
Canada
Prior art keywords
ethylene
propylene
alpha
olefins
copolymers
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CA000584234A
Other languages
French (fr)
Inventor
Luigi Maria Resconi
Enrico Albizzati
Romano Mazzocchi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Montell Technology Co BV
Original Assignee
Montedison SpA
Ausimont SpA
Montell North America Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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Application filed by Montedison SpA, Ausimont SpA, Montell North America Inc filed Critical Montedison SpA
Application granted granted Critical
Publication of CA1338368C publication Critical patent/CA1338368C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04Monomers containing three or four carbon atoms
    • C08F210/06Propene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/42Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62Refractory metals or compounds thereof
    • C08F4/64Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/42Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62Refractory metals or compounds thereof
    • C08F4/64Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65927Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/943Polymerization with metallocene catalysts

Abstract

Novel crystalline copolymers of propylene with minor proportions of ethylene and/or alpha-olefins, endowed with very good mechanical properties, a low melting point and a limited solubility in xylene at 25 °C, and the process for preparing them by means of the polymerization of mixtures of propylene with ethylene and/or alpha-olefins of suitable composition, by using catalysts obtained from stereorigid and chiral compounds of zirconium, and methylalumoxanic compounds.

Description

( - 2 - l 338 368 * * * * *
The present invention is concerned with new crystalline copolymers of propylene, and with the process for preparing them.
Those skilled in the art know that polypropylene can be modified by introducing small amounts of comonomers, mainly ethylene and l-butene, during the polymerization reaction.
The purpose of this modification is of lowering the melting point of the polymer, and hence obtaining films showing improved characteristics of weldability.
However, the polymers obtained by means of the processes known to date suffer from the drawback of a non-homogeneous distribution of the comonomers; this causes the polymers to show high solubility characteristics in cold xylene, and the manufactured articles obtained from them to have decreased mechanical p operties.
~ ~ p~ sh~
From European~ patent application N. 0 185 918, polymerizing propylene with stereospecifc catalysts is known, wherein such stereospecific catalysts are obtained from stereorigid and chiral compounds of zirconium, such as ethylene-bis-indenyl-zirconium dichloride, and ethylene-bis(4,5,6,7-tetrahydroindenyl)zirconium dichloride, and from methylalumoxanic compounds.
The catalysts are also used in the polymerization of mixtures of propylene with ethylene or other olefins, with ~ 3 ~ 1 338368 copolymers being obtained which, in the examples, are rich of ethylene and are soluble in xylene, and show an isotactic configuration of the propylenic sequences.
The present Applicants have unexpectedly found now that by using catalytic systems obtained from:
a) ~ stereorigid and chiral compound of zirconium of formula / I
R3 R, ~ Z r - R2 X

wherein:
Rl and Rz are halogens or alkyl groups of from 1 to 6 G
atoms;
X and Y are asymmetrical single-ring or multi-ring organic groups;
R3 is a linear group of from 1 to 4 C atoms, or a cyclic group containing from 3 to 6 C atoms;
b) an alumoxanic compound of formula (Al O)n with n being comprised within the range of from 2 to 25;
or CH3 (Al O)n Al(CH3 )2 with n being comprised within the range of from 1 to 25;
propylene copolymers with minor amounts of ethylene and/or . ~ 4 ~ l 338368 alpha-olefins CH2=CHR
wherein R is an alkyl radical of from 2 to 20 C atoms, which are endowed with a high crystallinity, and with very good mechanical properties (very similar to propylene homopolymer), have a melting point comprised within the range of from 110 to 140C and show a limited solubility in (soluble polymer fraction in xylene at 25C lower than 10%) cold xylene/, can be obtained if the polymerization of the monomers is carried out under conditions under which the formed copolymer has a composition similar to the composition of the monomers present in the gas phase.
The present Applicants have found, and this is an at all unexpected aspect of the present invention, that the composition of the copolymers is similar to that of the mixture of the monomers present in the gas phase, when the content of the monomers which are not propylene of said mixture is comprised within the range of from 2 to 10 mol %.
More particularly, in case of copolymers with ethylene, the ethylene content in the gas-phase mixture is comprised within the range of from 2 to 6 mol %; in case of propylene-ethylene-butene terpolymers, the content of ethylene and butene is comprised within the range of from 2 to 10 mol %.
By operating under the above stated conditions, copolymers are obtained, in which the distribution of the comonomers is perfectly homogeneous. This is demonstrated, _ 5 - I 338368 in case of the copolymers with ethylene, by the analysis by means of l3C-N.M.R.: the presence is not observed of the characteristic signals of the sequences of more than one ethylene units, as described in Macromolecules 10 (3) 536 (1977).
The preparation of the copolymers by using the above stated catalysts is carried out by operating both in the gas phase and in the liquid phase (in the presence of a solvent consisting of an inert hydrocarbon, or in liquid propylene).
The composition of the gas phase, comprised within the above stated critical range, is maintained constant during the polymerization. For example, in case of polymerization of propylene-ethylene mixtures by operating in liquid propylene, a constant overpressure of ethylene is maintained.
On the contrary, in case the polymerization is carried out in the gas phase, or in the presence of an inert hydrocarbon solvent, a gaseous mixture of the monomers with a constant composition is fed. The polymerization is carried out at temperatures lower than 20C, and preferably comprised within the range of from 0 to 10C.
The copolymers obtained by operating under the above stated conditions have an intrinsic viscosity in tetralin at 135C higher than 0.2 dl/g. As already stated, the copolymers are mainly used in the field of films; this, . - 6 - I 338368 thanks to the high weldability characteristics of the films obtained from them.
The following examples are given for the purpose of merely illustrating the invention, without limiting it.
ExamPles 1 - 8 PolymethYlalumoxane sYnthesis To a flask of 500 ml of capacity, equipped with thermometer, bubble-condenser with stopcock connected to the gas meter, 100-ml dripping funnel, nitrogen stopcock and magnetic stirrer, 44.5 g of Al2 (S04 )3 .18H20 and 200 ml of toluene are charged under a nitrogen atmosphere, and to the dripping funnel 60 ml of pure trimethyl-Al is charged.
The nitrogen supply is discontinued, the connection to the gas meter is opened and, at room temperature, trimethyl-Al is rapidly added dropwise to the suspension of Alz (S04 )3 .18H20, with this latter being kept vigorously stirred.
The temperature rises up to 55C; it is increased up to 60OC by means of a heating bath, and is maintained constant at this value. The reaction is complete after 4 hours. The suspension is filtered, and the solution is dried: 15.8 g of product, corresponding to a yield of 44%, is obtained.
Cryoscopic average molecular weight 1,160; average oligomerization degree 20.
Zirconium comPound sYnthesis _ 7 - t338368 The synthesis of ethylene-bis-indenyl-ZrCl2 (EBIZ) and of ethylene-bis(tetrahydroindenyl)-ZrCl2 (EBTHIZ) was carried out according to Journal of Organometallic Chemistry (1985) 288, 63.

PolYmeriZation All operations were carried out under nitrogen.
To a three-neck flask equipped with bubbling tube, thermometer and gas vent stopcock, with mechanical stirring means, and kept at the controlled temperature of 0C, a solution of 20 ml of toluene, containing 45 mg of polymethylalumoxane and 0.8 mg of zirconium compound is charged.
After evacuating nitrogen, the gas mixture, the composition of which is specified in the following Table, is continuously added (flow rate 20 litres/hour).
The polymerization time, the catalyst type and the characteristics of the polymer are shown in the Table.
Comparative ExamPle 1 To a glass autoclave of 300 ml, under a propylene stream a solution of 150 ml of toluene containing 350 mg of polymethylalumoxane is charged, the temperature of the autoclave is adjusted at the controlled value of 0C, and then 5 mg of EBTHIZ dissolved in toluene is injected. The pressure inside the autoclave is increased up to 4 atm, and the polymerization is allowed to proceed for 4 hours at 0C.

30.5 g of polymer is obtained, the data of which is reported in the Table.
ComParative ExamPle 2 The process is carried out as in Example 1, with the exception that as the zirconium compound, EBIZ is used ~the data relevant to the polymer is reported in the Table).
ComParative ExamPle 3 Example 7 of EP 0 185 938 is repeated, with 20 g being obtained of a polymer which contains 47 mol % of ethylene, with (~) = 0.15 dl/g, and a fraction soluble in xylene at 20C of 81.3%.
On l3C-N.M.R- investigation, the polymer shows ethylenic sequences.

~1, o, C~ ~
lQ P O '' X o oo o ~ a~ ~ o ~ o O O O O C~l C~ C~ In I
--~ a),Q
. D ~

.
~ O ~ ~ ~ C~ ~ N C`~
-~ ~ X ~ C`3 0 0 ~
_I ...... ...
~ _I O ~ O _~ O O _~ O
-O O
1~ 0 0 C

~ O
P.--( ~ I I . .
' O
e C~ o ., II ......

_~ ~ O U~ O O O U~ X ~
o ~ o c~ , ~ O _, ._, o ~ _ _I
D
~n L~
O
E~ ~
-u~
O O : X ~D ~ a~ ~ cr, o~
o o cn ~ o~
o ~
~ _ .,, D~
o u, e _~
8 e s , L 0 5 ~1 r r~ r ~ r ~ ~ ~
e ~s m I m s m s m I m o ~ ~ s ~3 s ~ s ~3 s ~

.
t,~ . ~ ~
Z ~ x e E
r~

Claims (4)

1. Crystalline copolymers of propylene with ethylene and/or alpha-olefins CH2=CHR

wherein R is an alkyl radical of from 2 to 10 C atoms, containing from 2 to 10 mol % of ethylene and/or alpha-olefin, said ethylene and/or alpha-olefins being homogeneously distributed along the copolymer chain, as demonstrated by the substantial absence of signals due to sequences of comonomer units at the 13C-N.M.R. analysis, having a melting point comprised within the range of from 110 to 140°C, and a solubility in xylene at 25°C lower than 10% by weight.
2. Copolymers according to claim 1, containing from 2 to 6 mol % of ethylene, having a melting point comprised within the range of from 120° to 135° C.
3. Copolymers according to claim 1, containing from 2 to 10 mol % of ethylene and butene.
4. Process for preparing the copolymers according to claim 1, 2 or 3, comprising polymerizing mixtures of propylene with ethylene and/or alpha-olefins CH2=CHR

wherein R is an alkyl radical of from 2 to 10 C atoms, with catalysts obtained from:
- stereorigid and chiral compounds of zirconium, of formula:

wherein:
CA000584234A 1987-11-27 1988-11-25 Crystalline copolymers of propylene Expired - Fee Related CA1338368C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT41012/87A IT1221653B (en) 1987-11-27 1987-11-27 PROPYLENE CRYSTALLINE COPOLYMERS
IT41012A/87 1987-11-27

Publications (1)

Publication Number Publication Date
CA1338368C true CA1338368C (en) 1996-06-04

Family

ID=11250144

Family Applications (1)

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Country Status (15)

Country Link
US (2) US5516866A (en)
EP (1) EP0318049B2 (en)
JP (1) JP3112908B2 (en)
KR (1) KR950013682B1 (en)
CN (1) CN1040217C (en)
AU (1) AU604582B2 (en)
BR (1) BR8806244A (en)
CA (1) CA1338368C (en)
DE (1) DE3869921D1 (en)
DK (1) DK660088A (en)
ES (1) ES2031986T3 (en)
FI (1) FI96770C (en)
IT (1) IT1221653B (en)
NO (1) NO171791C (en)
ZA (1) ZA888859B (en)

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US6355758B1 (en) 2002-03-12
NO885281L (en) 1989-05-29
BR8806244A (en) 1989-08-15
AU604582B2 (en) 1990-12-20
CN1040217C (en) 1998-10-14
FI885462A0 (en) 1988-11-24
JP3112908B2 (en) 2000-11-27
JPH01266116A (en) 1989-10-24
FI885462A (en) 1989-05-28
US5516866A (en) 1996-05-14
EP0318049A1 (en) 1989-05-31
CN1034551A (en) 1989-08-09
DE3869921D1 (en) 1992-05-14
IT8741012A0 (en) 1987-11-27
IT1221653B (en) 1990-07-12
KR890008188A (en) 1989-07-10
DK660088A (en) 1989-05-28
DK660088D0 (en) 1988-11-25
KR950013682B1 (en) 1995-11-13
NO171791B (en) 1993-01-25
ZA888859B (en) 1989-08-30
FI96770C (en) 1996-08-26
EP0318049B2 (en) 2003-07-16
ES2031986T3 (en) 1993-01-01
FI96770B (en) 1996-05-15
NO885281D0 (en) 1988-11-25
NO171791C (en) 1993-05-05
AU2595288A (en) 1989-06-01
EP0318049B1 (en) 1992-04-08

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