CA1137067A - Catalysts for polymerizing alpha-olefins - Google Patents
Catalysts for polymerizing alpha-olefinsInfo
- Publication number
- CA1137067A CA1137067A CA000321122A CA321122A CA1137067A CA 1137067 A CA1137067 A CA 1137067A CA 000321122 A CA000321122 A CA 000321122A CA 321122 A CA321122 A CA 321122A CA 1137067 A CA1137067 A CA 1137067A
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- Prior art keywords
- compound
- alkyl
- electron donor
- catalysts
- component
- Prior art date
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/02—Carriers therefor
- C08F4/022—Magnesium halide as support anhydrous or hydrated or complexed by means of a Lewis base for Ziegler-type catalysts
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
Abstract
ABSTRACT OF THE DISCLOSURE
New and improved catalysts for polymerizing alpha-olefins of formula CH2 = CHR in which R is a C1 to C6 alkyl, more particularly propylene, mixtures of the alpha-olefins, and mixtures thereof with ethylene are disclosed.
The catalysts are prepared form Al alkyl compounds and a solid product including a Mg dihalide and reaction products of said halide with at least one Ti compound and an electron donor compound which is an ester of and organic or inorganic oxygenated acid. The improvement consists in providing catalysts prepared from components (a) and (b) molar ratios between the alkyl Al compound and the Ti compound of component (a) in the range of from 1 to 30, preferably from 2 to 20, and in which if the alkyl Al compound is complexed with an electron donor compound, the latter is used in reduced amounts such that at least 85%
of the alkyl Al compound is in a form not combined with an electron donor compound, i.e., catalysts which are highly active and highly sterospecific but which involve a lower consumption of alkyl Al compound with respect to the Ti compound than has been required in the case of various prior art catalysts and which make it possible to use a lower amount of electron donors compound complexed with the Al alkyl compound.
New and improved catalysts for polymerizing alpha-olefins of formula CH2 = CHR in which R is a C1 to C6 alkyl, more particularly propylene, mixtures of the alpha-olefins, and mixtures thereof with ethylene are disclosed.
The catalysts are prepared form Al alkyl compounds and a solid product including a Mg dihalide and reaction products of said halide with at least one Ti compound and an electron donor compound which is an ester of and organic or inorganic oxygenated acid. The improvement consists in providing catalysts prepared from components (a) and (b) molar ratios between the alkyl Al compound and the Ti compound of component (a) in the range of from 1 to 30, preferably from 2 to 20, and in which if the alkyl Al compound is complexed with an electron donor compound, the latter is used in reduced amounts such that at least 85%
of the alkyl Al compound is in a form not combined with an electron donor compound, i.e., catalysts which are highly active and highly sterospecific but which involve a lower consumption of alkyl Al compound with respect to the Ti compound than has been required in the case of various prior art catalysts and which make it possible to use a lower amount of electron donors compound complexed with the Al alkyl compound.
Description
r?~0~
THE PRIOR ART
Processes for polymerizing alpha-olefins with catalysts comprising, as starting catalyst components, Al-alkyl compounds partially complexed with electron donor com-pounds and Ti compounds supported on Mg dihalides are known from British patent 1,387,890.
In the cata~ysts, according to khe British patent t the electron donor compound is employed in amounts of from 5 to 100% by moles with respect to the Al-alkyl compound and higher than 300% with respect to the Ti compound. Al/Ti ratios higher than 10 are used, because if lower ratios are used, the catalytic activity decreases sensibly.
German patent application No. 2,504,036 describes catalysts useful for polymerizing alpha-olefins and which com-prise a Ti compound supported on a Mg dihalide and an Al-alkyl compound employed in relatively low Al/Ti ratios, equal to or lower than 10. The activity and stereospecificity of said catalysts are high only if the catalysts are u~ilized in the absence of hydrogen as molecular weight modifier. The activity, as well as the stereospecificity notably decreases when these catalysts are used in the presence of hydrogen.
Germar~ patent application No. 2,643,143 describes catalysts improved with respect to those mentioned hereinbefore, which are endowed with high activity and stereospecificity if used at Al/Ti ratios highex than 30 40 and with amounts of electron donor compound higher than 20~30% ~y moles with respect to the Al-alkyl compound~ On the other hand, if lower -1; Al/Ti ratios are used, the activity remarkably decreases. It is not possible to employ amounts of electron donor compound lowPr ~- than those indicated hereabove, as that results in a notable , I -2- ~ ~
1 13'/'00'7 decrease in the stereospecificity of the catalyst. As to the elertron donor compound, German application No~ 2,643,143 does not suggest the use of amounts lower than 15~ by moles with respect to the Al-alkyl compound.
The high activity and high stereospecificity catalysts of the types described hereinbefore permit, on one hand, to eliminate or to simplify the treatments for purifying the polymers from the catalyst re~idues, but, on the other hand, they involve the drawbacks consisting in a high consumption of Al-alkyl compound in respect of the Ti compound and in the necessity of using substantial amounts of electron donor com-pounds, the presence of which in the polymer is not always . desirable.
; THE PRESENT INVENTION
An object o~ this invention is to provide new and ~ improved catalysts which are both highly act.ive and highly ; stereospecific in the polymerization of the alpha-olefins CH2 = CHR as defined herein, which involve a lower consumption : of alkyl Al compound with respect to the Ti compound than has . 20 been required in the case of the prior a.rt catalysts referred to above and in which an electron donor, if used, is effective in a reduced amount without appreciable decrease in the catalyst activity and stereospecificity even in the presence of hydrogen as molecular weight regulator of the polymer ~eing produced.
This and other objects are accomplished by the ~ present invention ~R accordance with which the alpha-olefins as - defined, or mixtures thereQf with ethylene, are polymerized in contact with a new and improved catalyst prepared by mixing at least the following two starting ~omponents:
37'~'7 ~
(a) a solid product including a Mg dihalide and reaction products o~ said halide with at least a Ti compound preferably selected from the halides, alcoholates, halogen alcoholates and carboxylates of Ti and an electron donor compound s lected from the esters of organic and inorganic oxygen-: ated acids, and in particular from the alkyl and aryl esters of the aromatic acids, of the halides anhydrides and amides of said acids, o~ ethers ;; 10 ROR' and of ketones R CORI, in which R and Rl~
like or unlike each other, are alkyl, cycloalkyl ¦ or aryl radicals having l to 18 carbon atoms~
: I the Mg/Ti ratio in said solid product:being from : ¦ 5 to 100, preferably from 10 to 50 and in par-:~ 15 ¦ ticular from 15 to 25, the amount of compounds ¦ extractable with TiC14 at 80C from the solid product being less than 50% and preferably less :~ ¦ than 20% of the Ti contained in the cataly.~ic ¦ component, and the molar ratio between electron ¦ . donor compound and Ti compound being comprised ¦ between 0.2 and 3, preferably between l and 2;
¦ and ¦ (b) an Al-alkyl compound selected from the Al tri-¦ alXyls, the compounds containing two or more Al atoms bound to one another through an oxygen atom . or a nitrogen atom, and the Al alkyl-aryloxy ~:~ compounds of formula AlR3 n(OR')n, in which R is an alkyl group having l to 18 Cl R' is an aryl group ortho nindered in positions 2,6 with sub-- 30 stituents capable of providing a steric hi.ndrance hi~her than that of the group -C2~5, or a naphthy L
., ' _~_ group containing at least in position 2,~ a sub-stituent capable of pro~iding a steric hindrance higher than that of group ~C2~H5, n is a number ~ ;-from 1 to 2; said Al- alkyl compound being com-1 5 plexed for at least 20-30% with an electron dono~
compound preferably selected from the alkyl, aryl :~ and cycloalkyl esters of aromatic acids.
As indicated supra, the present improvement consists in using a catalyst.component (b~ of which includes an Al-~alkyl compound as defined under (b) in amounts equal to molar ratios bet~een Al-alkyl compound and Ti compound of component (a) in the range of from 1 to 30, preferably from 2 to 20, and in which if the alkyl Al compound is complexed with an electron donor ~:
: compound, the latter is used in reduced amount such that at `: : 15 least 85% of the Al-alkyl compound is in a farm not combined : with an electron-~donor compound.
The ratio between the total moles of electron donor ~1: compound contained ln component (a), and optionally in (b), and the moles of the Ti compound is lower than 5 and preferably is comprised between 1 and 3. When no electron donor compound is -- . added to the Al-alkyl compound the ratio may be lower than 1 and correspond in practice to the ratio present in component (a) The Ti compounds useful in the practice of this inven tion arer preferably, selected from the halides of tetravalent Ti, in particular TiC14, the halogen-alcoholates of tetravalent TiJ such as for example, Ti(O-i-C4Hg)2Cl2 and Ti(O-i-C3H7)~Cl~, the Ti-carboxylates such as Ti acetate and Ti benzoate.
~ The electron donor compounds useful in preparing component (a) are selected, preferably, from the alkyl~ arylg : and cycloalkyl esters of the aromatic carboxylic acids, in particular the esters of benzoic acid,such as, e.gO, ethyl _5_ - ~37~ei7 p-anisate, ethyl p-methoxybenzoate, methyl p-toluate or ethyl p-toluate, ethyl naphthoate, ethyl benzoate and butyl benzoate.
The derivatives of the aromatic acids specified here~
inbefore are preferably used as halides, anhydrides and amides o the acids. As ethers and ketones it is possible to use n-butyl ether, diphenyl ether, ethyl-phenyl ether and benzophenone.
The electron donor compound reacted with the Al-alkyl compound of component (b) is selected, preferably, from the esters o the organic and inorganic oxygenated acids indicated for component (a). The esters of the aromatic acids are preferably utilized also for component (b).
Component (a) can be prepared according to different methods, a few of which are already known. For example, it can be prepared according to the methods described in German Patent applications Nos. 2,643,143 and 2,735,672.
Other methods for preparing component ~a) of the present catalysts are described in Canadian patent application No. 306, 4i8 (Cecchin et al3 and Canadian application No.
303,940 (Scata et al) filed May 24, 1978.
Generally component (a) can be prepared by any method that leads to the formation of a product comprising, at least on its surface, a My dihalide and complexes thereof with at least a Ti compound and an electron donor compound selected from the class of compounds (esters, halides, acids, ethers and ketones) already cited, and in which the Mg/Ti ratio is ~; comprised between 5 and 100 and the amount of Ti compounds extractable with TiCl4 at 80C is lower than 50% and after such , ' ' ' ' .
~ ' ~3 dm~
1~L3~06~
treatment the molar ratio between electron donor compound and Ti compound is from 0.2 to 3.
For instance, it is possible to employ methods based on the co-grinding ~activation) of an anhydrous Mg chloride or bromide, containing less than 2~ by weight of ~O, with an electron donor compound selected from the classes mentioned above, employed in an amount of from 0.1 to 0.3 moles per mole of Mg halide under those conditions, in which the X-ray spectrun of the ground product shows a halo in a range of interplanar distances which includes that (distance~ of the line of maximum ~:~ intensity of the spectrum of powder of the normal, non-activatec Mg halide and having the maximum intensity shifted with respect ~; to such line. The term "spectrum of powder of the non-activated Mg hallde" means the spec~ra as defined in~ASTM sheet ~`` 15 3-0854 and 15-836 for MgC12 and MgBr2, respectively. In the r: case of MgC12 the peak of the halo is comprised between 2.44 A
`~ an~ 2.97 ~. ~
The product obtained by the co-grinding is reacted with TiC14 under oonditions in which Ti compounds extractable with TiCl~ at 80C remain in the reaction product in amounts not exceeding 50~. For example, the ground product is suspendec in TiC14 and reacted at 60-130C for stretches of time suf-ficient to fix at least 0.5% by weight of Ti, and then it is separated from TiC14 at temperatures at which there is no precipitation of Ti compounds lnsoluble in TiC14 at the separation temperature.
Another m~thod of preparing component (a) of the present catalysts consists in reacting an adduct between a Mg dihalide and an alcohol or a phenol, generally containing more than 0.5 moles of organic compound per mole of halide and com-prising, in combined form, from 0.1 to 0O5 moles of an electron ll, ~37~ 7 donor compound selected from the classes of compounds cited hereinbefore (esters, halides, acids, amides, ethers, ketones), with a halogenated Ti compound liquid under the reaction con-; ditions, in particular TiC14, and in separating from the reaction mixture a solid product the Ti compounds and electron donor compounds of which satisfy the conditions already specified for the catalysts of the present invention.
Still another method of preparing component (a) con-sists in preparing a Mg dihalide or a carrier containing said dihalide in an active form havin~ a surface area larger than 80-100 m /g, in reacting said halide with an electron donor compound belonging to the classes disclosed supra in such amounts and under such conditions as to cause 0~1 to 0.3 moles per mole of dihal1de to remain fixed in the halide, and then in reacting said pro~uct with a llquid Ti compound, in particular TiC14, under the conditions specified hereinabove for the preparation of other types of catalysts.
In preparing component (a) of these catalysts, it is also possible to simultaneously react the Ti compound and the electron donor compound with the activated Mg halide.
Mg dlhalides in preactivated form are obtained, for example, by reacting an organo-magnesium compound of the type RMgX, or alcoholates of formula ROMgX', in which R is an alkyl or aryl radical hav1ng 1 to 18 C~ X is a halogen and X' is a halogen or a radical OR, ~ith a halogenating substance, such as halogenated Si compounds, in particular SiCl~, SnC14, BC13, or Al halides such as AlC13, AlR2Cl, ~lRCl~, in which R has the meaning specified.
It is also possible to obtain the Mg halides in an active form by evaporating, at a temperature up to about 200~C, s-olutions of the oxgano-magnesium compounds in ethers RORI, in ::IL13~0~
which R and R , the same or different from one to another, are alkyl, aryl and cycloalkyl radicals havi~g 3 to 18 C, or by treating said solutions with anhydrous hydrogen halides in such amounts and conditions as to cause the magnesium dihalide to precipitate.
Other methods of preparing catalyst component (a) consist in reacting a Mg alcoholate such as, e.gO, diethoxy-magnesium or a halogen-alcoholate, such as for example, chloro-ethoxy-magnesium, chloro-phenoxy-magnesium, chloro-butoxy-1 magnesium~ with the electron donor compound in such amounts and I conditions, that the solid product of the reaction contains `~ ¦ fxom 0~1 to 0.5 moles per gram atom of Mg, and in successively reacting said product with a Ti compound under the conditions - ¦ already indicated for the preparation of the catalysts useful in ¦ the practice of this invention.
; I It is also possible, in preparing component (a~, to react the Mg alcoholate wikh an anhydrous hydrogen halide, so as ¦ to form an adduct MgX2.nROH, and to treat then the adduct as ¦ disclosed hereinabove. This reaction can be conducted in one ¦ step by reacting metal Mg, an alcohol RO~ and a hydrogen halide, in which R has the significance as stated. ~
A11 of the methods disclosed lead to final products ¦ comprising~ at least on their surface, a dihalide in active ¦ form and products of addition of said dihalides with the ¦ electron donor compound and the Ti compound.
¦ The reaction of the Mg dihalide with the electron ~- donor compound and the Ti compound can be established by I~Ro and Raman spectroscopyO
¦ In the preparation of component (a), the electron donor compound is generally reacted with the alkyl Al compound p_ior to the mixing thereof with the Ti compound~ It l _g_ -~L376~
is possible, ~wever, to reaot the two compounds simultaneously, or the electron donor compound can be added after the Ti com-: pound has be~n mixed wi~h the alkyl Al. compound.
The electron donor compound present in a combined form in co~ponent (a) of the present catalysts can be intxoduced also, according to another embodiment of the present invention, by starting from a product as defined in (a)., in the absence of :~ an electron donor and then mixing such component (a) with an ~` alkyl Al compound as defined in (b), wherein the Al/Ti ratio and the molar ratio between the electron donor compound com-plexed with the alkyl Al compound and the latter are selected in such manner that the solid reaction product contains an amount of electron don~r compound corresponding to a molar ratio to . the Ti compound of from 0.2 to 3~ Also, the Al/Ti ratio be-.~. 15 tween the free Al-alkyl compound and the Ti compound:preferably ranges from 3 to 30. In the latter case, the reactlon mixture can be directly utilized as polymerization catalyst.
~: Examples of trialkyl Al compounds useful as com-ponents (b) of the present catalysts include:
Al(C2H5)3, Al(i-C4Hg)3, Al(n-C4Hg)3, Al(CH~-ClH-(CH2)2-CH3)3, .. Al(C12H25)3. CH3 Examples of alkyl A1 compounds containing two or more Al atoms bound to one another through an oxygen atom or a ~;: nitrogen atom which are useful in the practice of this inven-~: 25 tion include (C2H5)2Al-o-Al(C2H5)2 and (C2Hs)2-Al l-Al(C2H5)2-~: C6H5 Such compounds can be prepared according to conventional methods by reaction 5f an Al trialkyl with water, ammonia or primary amines.
Examples of compounds AlR3_n~OR~)n, wh~rein radical R' ~ 30 is an aryl group oxtho-hindered in positions 2 and 6, in which il3~70~
at least one of the substituents is capabl~ of giving a steric hindrance higher than that of the group -C2H5, or a naphthyl group containing at least in position 2 a substituent with a steric hindrance higher than that of group C2H5, include the S following: ~
Al(C2H5)2(2,6-di-tert.-butyl-p-cresoxy), Al(i-C4Hg)2(2,6~di-tart.butyl-p-cresoxy~, AltC2H5)2(2~6-di-tert~-butyl-phenoxy~
Al~C2H5) (2,6-di-tert.-butyl~p-cresoxy)2, Al~C2H5)2 (2,8-di-tert.butyl-naphthoxy~.
The alkyl Al compounds can be employed in admixture with one another. It is also possible to use mixtures of said compounds with organometallic compounds of the metals belonging to Groups I-IIIy in particular compounds of Al, Zn, Mg and ~` 15 compounds of B, Si, which per se fQrm with component (a) ` catalysts of little if any activity. Such compounds are utili7.ed or protecting the catalyst, or the individual com-¦ ponents thereof, ~rom the impurities, if any, contained in the polymerization system (monomer, solvent, etc.~. The use of such ~; 20 ¦ substances is particularly helpful in the case of the catalysts ~- ¦ according to the present invention, in which, due to the small ¦ amounts of catalytic components employed, lo~ amounts of ¦ impurities are sufficient to negatively affect the catalyst per-¦ formance. Preferred compounds of this kind are: Zn(C2H5)2, ¦ Al-alkyl-alkoxy compounds such as Al(i~C4Hg)2O~t-C4Hg and ¦ Al(C2H5)2~xylenoxy. Such organometallic compounds are employed in amounts generally ranging from 1 to 20 moles per mole of ¦ alkyl Al compound. They may be utilized also in the ~orm of ¦ complexes with electron donor compounds, in particular with the ~ esters of the aromatic acids.
il3'i'0i~7 Polymerization of the alpha-oleflns or mixtures ¦ thereof with ethylene with the catalysts of the present inven-tion is carried out according to conventional methods, by operatin~ either in liquid phase, the polym~rization medium being the monomer itself, or in gaseous phase. Th~ polym~riza-tion temperature i5 generally compri~ed between 40 and 90C.
~; The pressure can be atmospheric pressure or a higher pressure.
The alpha-olefins can be polymerlzed ln admixture ~ with ethylene~ in particular in such ratîos that the polymerize ; 10 ethylen~ content is from 1 to 25% ~y weight.
The catalys~ts of this invention can be also used to produce polymers, in particular polypropylene, having lmproved characteristlcs of resistance to bri*tleness, conforming to known methods in which at first the alpha-olefin is polymerized until about 60-80% of the total polymer is formed and then, in one or more steps, ethy~ene and/or mixtures thereof with the alpha-olefin are polymerized, in order that the polymexi~ed ethylene content is from 5 to 30% by ~eight.
The following examples are given to illustrate the present invention ln more detail and are not intended to be limiting. ~ ~
~ :
Q.63 millimoles of Al triisobutyl were reacted at 25~C with q.047 millimoles of methyl p-toluate in 80 ml of anhydrous and desulphurated n-heptane for 5 minutes. 50 ml of -- the resulting solution were contacted with the proper amount of a solid catalyst component prepared accordlng to Example 7 of ¦ German patent application 2,643,143, to obtain a suspension.
., I
.
3~1370c~ 7 The remaining 30 ml of the solution were diluted to lO00 ml with n-heptane and introduced, under a nitrogen pressure, into a 3000 ml steel autoclave equipped with a magnetic anchor stirrer and a thermometer, thermoregulated at 40C, and 1nto which a flow of propylene was introduced.
Successively, and in the same way, the catalytic component suspension was introduced. After closing the auto-clave, it was heated to 60C while simultaneously feeding propylene in to a total pressure of 5 atm. Such pressure was kept constant throughQut the polymerization by continuously feeding the propylene. After 4 hours, the polymerization was stopped and the polypropylene was isolated by treatment with methanol and acetone~ The results of the polymerization test are recorded in Table I.
; EXAMPLE 2 0.63 millimoles of Al triisobutyl were reacted at 25C with ~ millimoles o~ methyl p-toluate in 80 ml of anhydrous and desulphurated n-heptane for 5 minutes. 50 ml of the resulting solution were contacted with a suitable amount of a solid catalytic component prepared according to the modalities of Example 31 of Bel~ian patent No~ 857,574 and haviny a Ti content equal to l.62% by wei~ht.
The rema1ning 30 ml of the solution were diluted to ~ lO00 ml with n-heptane and were introduced, under a nitrogen -~ 25 pressure, into a steel 3000 ml autoclave equipped with a magnetic anchor stirrer and a thermometer~ thermoregulated at 40~C, and into which a flow of propylene was introduced.
In the same way, the catalytic component suspension was then introduced. After closing the autoclave, it was ~L370q3~
heated to 60C and simultaneous feeding of propylene up to a ; total pressure of 5 atm was continued. Such pressure was kept ¦ constant throughout the polymerization by feeding of the ¦ propylene. After 4 hours t the polymerization was stopped and ¦ the polypropylene was isolated by treatment with methanol and l acetone.
¦ The results of the polymerization are recorded in ¦ Table I.
I
I EXA~PLE 3 I
0.63 millimoles of Al triisobutyl were dissolved in 80 ml of (anhydrous desulphurated) n-heptane. 50 ml of such solution were contacted with a suitable amount of a solid catalytic component prepared according to Example 2 in whlch, instead of ethyl benzoate, an equlvalent amount of methyl p-toluate was used.
¦ The remaining 30 ml were diluted to 100~0 ml with ~ ¦ n-heptane and were introduced, under ~ nitrogen pressure, into - ¦ a steel 3000 ml autoclave equipped with a magnetic anchor stirrer and a thermometer, thermoregulated at 40C, and into ¦ which propylene was made to flow.
¦ Successively, the catalytic component suspension was ¦ introduced in the same manner. After closing the autoclave, it ¦ was heated to 60C while simultaneously feeding in propylene up ~ ¦ to a total pressùre of 5 atm. Such pressure was kept constant ; 25 ¦ throu~hout~the polymerization by continuing the monomer feed.
¦ After 4 hours, ~the polymerization was stopped and the poly-¦ propylene was isolated by treatment with methanol and acetone.
The results relating to the polymerization test are re~orded in Table I.
, ~1370c37 0.75 millimoles of Al triisobutyl were dissolved in ; 80 ml of (anhydrous desulphurated) n-heptane. 50 ml of suchsolution were contacted with a proper amount of a ~olid catalytic component prepared according to Example 2, with the exception that methyl benzoate was substituted by ethyl p-anisate.
The remaining 30 ml were diluted to 1000 ml with n-heptane and were introduced, under a nitrogen pressure, into a 3000 ml steel autoclave equipped with a magnetic anchor stirrer and a thermometer, thermoregulated at 40C, and into which propylene was made to flow.
Successively, the catalytic component suspension was introduced in the same manner. After having closed the auto-clave, it was heated to 60C while simultaneously feeding in ~; propylene up to a~tota1 pressure of 5 atm. Such pressure was kept constant throughout the polymerization by continuously feedin~ the monomer. After~4 hours the polymeri~ation was stopped and the polypropylene was isolated by treatment with methanol and acetone.
The results o~ the polymerization test are recorded in Table I.
0.75 millimoles of Al triisobutyl were dissolved in 80 ml of (anhydrous desulphuratad~ n-heptane. 50 ml of such solution were contacted with a suitable amount of a solid catalytic component prepared according to Example 4.
The remainin~ 30 ml were diluted to 1000 ml with n-heptane and introduced, under a nitrogen pressure, into a , ..
, . -: ' .: .
1~7~
¦ 3000 ml steel autoclave equipped with a magnetic anchor stirrer and a thermometer, thermoreyulated at 40C, and into which propylene was made to flow.
Successively, and in the same way, the ca~alykic component suspension was introduced. After having closed the autoclave, it was heated to 60C and V~l atm of H2 and propylene were introduced up to a total pressure of 5 atm. Such pressure was kept constant throughout the polymerization by continuously feeding the monomer. A~ter 4 hours the polymerization was stopped and the polypropylene was isolated by treatment with methanol and acetone.
The results of the polymerization test are recorded in Table I.
' , EX~MPLE 6 0.40 millimoles of Al triisobutyl were reacted at 25C with 0.04 millimoles of methyl p-toluate in 80 ml of (anhydrous desulphurated) n-heptane for 5 minutes~ 50 ml of such solution were contacted with a proper amount of a solid catalyst component prepared according to Example 1.
The remaining 30 ml were diluted to 1000 ml with n-heptane containing 2.5 millimoles of Zn(n-C4H9~2 and intro-duced, under a nitrogen pressure, into a 3000 ml steel auto-clave equipped with a ma~netic anchor stirrer and a thermometer, thermoregulated at 40C, and into which propylene was made to flow.
SuccessiV ly, and in the same way, the catalytic co~ponent suspension was introduced. After having closed the autoclave, it was heated to 60 C while simultaneously feeding in propylene up to a total pressure of 5 atm. Such pressure was ~3~7 kept constant thro~ghout the polymerization by continuously feeding the monomer. After 4 hours the polymerization was ¦ stopped and the polypropylene was isolated by treatment with ¦ methanol and acetone.
¦ The results of the polymerization test are recorded l in Table I.
' I
0.19 millimoles of Al triisobutyl were dissolved in l 80 ml of (anhydrous desulphurated~ n-heptane. 50 ml of such ¦ solution were contactéd with a suitable amount of a solid catalyst component prepared according to Example 1. The remain-¦ ing 30 ml were diluted to 1000 ml with n-heptane containing 2.5 ¦ millimoles of Zn(n-C4Hg)2 and were introduced, under a nitrogen ¦ pressure, into a 3000 ml steel autoclave equipped with a 1 magnetic anchor stirrer and a thermometer, thermoregulated at ¦ 40C~ into which propylene was caused to flow.
Successively, and in the same way, the catalytic ; ¦ component suspension was introduced. After having closed the autoclave, it was heated to 60C with simultaneous feeding of ~0 ¦ propylene up to a total pressure of 5 atm. Such pressure was kept constant throughout the polymerization by continuously ¦ feeding the monomer. After 4 hours the polymerization was ¦ stopped and the polypropylene was isolated by treatment with ¦ methanol and acetone.
l The results of the polymerization test are recorded ¦ in Table I.
' I
:, I
~37~7 0.63 millimoles of Al trilsobutyl were reacted at 25C with 0.041 millimoles of methyl p-toluate in 80 ml of (anhydrous desulphurated) n-heptane for 5 minutes. 50 ml of such solution were contacted with a solid catalyst component prepared according to Example 24 of the above-mentionéd Canadian application Serial No. 306,478 and used in the amount recorded in Table I.
The remaining 30 ml were diluted to 1000 ml with n-heptane and introduced, under a nitrogen pressure, into a 3000 ml steel autoclave equipped with a magnetic anchor stirrer and a ~hermometer, thermoregulated at 40C, and into -~
which propylene was cSused to flow.
Successively, and in the same way, the catalytic component suspension was introduced. After having closed the autoclave, it was heated to 60C with simultaneous feeding of propylene up to a total pressure of 5 atm. Such pressure was kept constant throughout the polymerization by continuously feeding the monomer. After 4 hours the polymerization was stopped and the polypropylene was isolated by treatment with methanol and acetone.
The results relating to the polymerization test are recorded in Table I.
EX~MPLE 9 0.113 millimoles of Al triisobutyl were dissolved in 80 ml of tanhydrous desulphurated) n-heptane. 50 ml of such solution were contacted with a solid catalytic component -prepared according to Example 2 and used in the amount indicated in Table I. ~he remaining 3Q ml were diluted to 1000 ml with - 30 n-heptane containlng 2.5 millimoles of (C~H5)2Al ~OC~Hs(CH~) 2]
;~ and introduced, under a nitrogen pressure, into a 3000 ml steel ~,`,, bmo --.3 ~.37~
autoclave equipped with a magnetic anchor stirrer and a thermometer, thermoregulated at 40C, and into which propylene was made to flow.
Successively, and in the same way, the catalytic component suspension was introduced. After having closed the autoclave, it was heated to 60C while simultaneously feeding in propylene up to a total pressurç of 5 atm. Such pressure was kep~ constant throughout the polymerization by continuously feeding the monomer. After 4 hours the polymerization was ;~ 10 stopped and the polypropylene was isolated by treatment with ~-methanol and acetone.
The results of the polymerization test are recorded in Table I.
0.63 millimoles of Al-triisobutyl were reacted at 25C with 0.041 millimoles of methyl p-toluate in 80 ml of (anhydrous desulphurated) n-heptane for S minutes. 50 ml of such solution were contacted with a solid catalyst component prepared according to an example set out in the above-mentioned Canadian appllcation Serial No. 303,940 and used in the amount specified in Table I. The remaining 30 ml were diluted to 1000 ml with n-heptane and introduced, undex a nitrogen pressure; into a 3000 ml steel autoclave equipped with a magnetic anchor~stirrer~and a thermometer, thermoregulated ; at 40C, and into which propylene was made to flow.
Successively, and Ln the same way, the catalytic -~ component suspension was introduced. After having closed the autoclave, it was heated to 60C while simultaneously feeding in propylene up to a total pressure of 5 atm. Such pressure was kept constant throughout the polymerization by continuously .
, ~ bm:
113`~7o~7 feeding the monomer~ ~fter 4 hours the polymerization was stopped and the polypropylene was isolated by treatment with methanol and acetone.
The results of the polymerization test are recorded in Table I~
0 65 millimoles of (C2H5)2Al[OC6H2tt 4 9 2 3 ¦ dissolved in 80 ml of (anhydrous desulphurated3 n-heptane. 50 ml of such solution were~contacted with a proper amount of a solid catalytic component prepared according to Example 31 of Belgian patent No~ 85~,574, while suitably varying conditions in order to have a titanium content equal to 1~7% and an ethyl benzoate content equal to 6.5% by weight.
The remaining 30 ml were diluted to 1000 ml with n-heptane and introduced, under a nitrogen pressure, into a 3000 ml steel autoclave equipped with a magnetic anchor stirrer and a thermometer, thermoregulated at 40C, and into which propylene was made to f low .
Successively, and in the same way, the catalytic component suspension was introduced. After having closed the autoclave, it was heated to 60C while simultaneously feeding in propylene up to a total pressure of 5 atm. Such pxessure was kept constant throughout the polymerization by continuously feeding the monomer. After 4 hours the polymerization was stopped and the polypropylene was isolated by treatment with methanol and a~etone.
The results relating to the polymerization test are recorded in Table I.
THE PRIOR ART
Processes for polymerizing alpha-olefins with catalysts comprising, as starting catalyst components, Al-alkyl compounds partially complexed with electron donor com-pounds and Ti compounds supported on Mg dihalides are known from British patent 1,387,890.
In the cata~ysts, according to khe British patent t the electron donor compound is employed in amounts of from 5 to 100% by moles with respect to the Al-alkyl compound and higher than 300% with respect to the Ti compound. Al/Ti ratios higher than 10 are used, because if lower ratios are used, the catalytic activity decreases sensibly.
German patent application No. 2,504,036 describes catalysts useful for polymerizing alpha-olefins and which com-prise a Ti compound supported on a Mg dihalide and an Al-alkyl compound employed in relatively low Al/Ti ratios, equal to or lower than 10. The activity and stereospecificity of said catalysts are high only if the catalysts are u~ilized in the absence of hydrogen as molecular weight modifier. The activity, as well as the stereospecificity notably decreases when these catalysts are used in the presence of hydrogen.
Germar~ patent application No. 2,643,143 describes catalysts improved with respect to those mentioned hereinbefore, which are endowed with high activity and stereospecificity if used at Al/Ti ratios highex than 30 40 and with amounts of electron donor compound higher than 20~30% ~y moles with respect to the Al-alkyl compound~ On the other hand, if lower -1; Al/Ti ratios are used, the activity remarkably decreases. It is not possible to employ amounts of electron donor compound lowPr ~- than those indicated hereabove, as that results in a notable , I -2- ~ ~
1 13'/'00'7 decrease in the stereospecificity of the catalyst. As to the elertron donor compound, German application No~ 2,643,143 does not suggest the use of amounts lower than 15~ by moles with respect to the Al-alkyl compound.
The high activity and high stereospecificity catalysts of the types described hereinbefore permit, on one hand, to eliminate or to simplify the treatments for purifying the polymers from the catalyst re~idues, but, on the other hand, they involve the drawbacks consisting in a high consumption of Al-alkyl compound in respect of the Ti compound and in the necessity of using substantial amounts of electron donor com-pounds, the presence of which in the polymer is not always . desirable.
; THE PRESENT INVENTION
An object o~ this invention is to provide new and ~ improved catalysts which are both highly act.ive and highly ; stereospecific in the polymerization of the alpha-olefins CH2 = CHR as defined herein, which involve a lower consumption : of alkyl Al compound with respect to the Ti compound than has . 20 been required in the case of the prior a.rt catalysts referred to above and in which an electron donor, if used, is effective in a reduced amount without appreciable decrease in the catalyst activity and stereospecificity even in the presence of hydrogen as molecular weight regulator of the polymer ~eing produced.
This and other objects are accomplished by the ~ present invention ~R accordance with which the alpha-olefins as - defined, or mixtures thereQf with ethylene, are polymerized in contact with a new and improved catalyst prepared by mixing at least the following two starting ~omponents:
37'~'7 ~
(a) a solid product including a Mg dihalide and reaction products o~ said halide with at least a Ti compound preferably selected from the halides, alcoholates, halogen alcoholates and carboxylates of Ti and an electron donor compound s lected from the esters of organic and inorganic oxygen-: ated acids, and in particular from the alkyl and aryl esters of the aromatic acids, of the halides anhydrides and amides of said acids, o~ ethers ;; 10 ROR' and of ketones R CORI, in which R and Rl~
like or unlike each other, are alkyl, cycloalkyl ¦ or aryl radicals having l to 18 carbon atoms~
: I the Mg/Ti ratio in said solid product:being from : ¦ 5 to 100, preferably from 10 to 50 and in par-:~ 15 ¦ ticular from 15 to 25, the amount of compounds ¦ extractable with TiC14 at 80C from the solid product being less than 50% and preferably less :~ ¦ than 20% of the Ti contained in the cataly.~ic ¦ component, and the molar ratio between electron ¦ . donor compound and Ti compound being comprised ¦ between 0.2 and 3, preferably between l and 2;
¦ and ¦ (b) an Al-alkyl compound selected from the Al tri-¦ alXyls, the compounds containing two or more Al atoms bound to one another through an oxygen atom . or a nitrogen atom, and the Al alkyl-aryloxy ~:~ compounds of formula AlR3 n(OR')n, in which R is an alkyl group having l to 18 Cl R' is an aryl group ortho nindered in positions 2,6 with sub-- 30 stituents capable of providing a steric hi.ndrance hi~her than that of the group -C2~5, or a naphthy L
., ' _~_ group containing at least in position 2,~ a sub-stituent capable of pro~iding a steric hindrance higher than that of group ~C2~H5, n is a number ~ ;-from 1 to 2; said Al- alkyl compound being com-1 5 plexed for at least 20-30% with an electron dono~
compound preferably selected from the alkyl, aryl :~ and cycloalkyl esters of aromatic acids.
As indicated supra, the present improvement consists in using a catalyst.component (b~ of which includes an Al-~alkyl compound as defined under (b) in amounts equal to molar ratios bet~een Al-alkyl compound and Ti compound of component (a) in the range of from 1 to 30, preferably from 2 to 20, and in which if the alkyl Al compound is complexed with an electron donor ~:
: compound, the latter is used in reduced amount such that at `: : 15 least 85% of the Al-alkyl compound is in a farm not combined : with an electron-~donor compound.
The ratio between the total moles of electron donor ~1: compound contained ln component (a), and optionally in (b), and the moles of the Ti compound is lower than 5 and preferably is comprised between 1 and 3. When no electron donor compound is -- . added to the Al-alkyl compound the ratio may be lower than 1 and correspond in practice to the ratio present in component (a) The Ti compounds useful in the practice of this inven tion arer preferably, selected from the halides of tetravalent Ti, in particular TiC14, the halogen-alcoholates of tetravalent TiJ such as for example, Ti(O-i-C4Hg)2Cl2 and Ti(O-i-C3H7)~Cl~, the Ti-carboxylates such as Ti acetate and Ti benzoate.
~ The electron donor compounds useful in preparing component (a) are selected, preferably, from the alkyl~ arylg : and cycloalkyl esters of the aromatic carboxylic acids, in particular the esters of benzoic acid,such as, e.gO, ethyl _5_ - ~37~ei7 p-anisate, ethyl p-methoxybenzoate, methyl p-toluate or ethyl p-toluate, ethyl naphthoate, ethyl benzoate and butyl benzoate.
The derivatives of the aromatic acids specified here~
inbefore are preferably used as halides, anhydrides and amides o the acids. As ethers and ketones it is possible to use n-butyl ether, diphenyl ether, ethyl-phenyl ether and benzophenone.
The electron donor compound reacted with the Al-alkyl compound of component (b) is selected, preferably, from the esters o the organic and inorganic oxygenated acids indicated for component (a). The esters of the aromatic acids are preferably utilized also for component (b).
Component (a) can be prepared according to different methods, a few of which are already known. For example, it can be prepared according to the methods described in German Patent applications Nos. 2,643,143 and 2,735,672.
Other methods for preparing component ~a) of the present catalysts are described in Canadian patent application No. 306, 4i8 (Cecchin et al3 and Canadian application No.
303,940 (Scata et al) filed May 24, 1978.
Generally component (a) can be prepared by any method that leads to the formation of a product comprising, at least on its surface, a My dihalide and complexes thereof with at least a Ti compound and an electron donor compound selected from the class of compounds (esters, halides, acids, ethers and ketones) already cited, and in which the Mg/Ti ratio is ~; comprised between 5 and 100 and the amount of Ti compounds extractable with TiCl4 at 80C is lower than 50% and after such , ' ' ' ' .
~ ' ~3 dm~
1~L3~06~
treatment the molar ratio between electron donor compound and Ti compound is from 0.2 to 3.
For instance, it is possible to employ methods based on the co-grinding ~activation) of an anhydrous Mg chloride or bromide, containing less than 2~ by weight of ~O, with an electron donor compound selected from the classes mentioned above, employed in an amount of from 0.1 to 0.3 moles per mole of Mg halide under those conditions, in which the X-ray spectrun of the ground product shows a halo in a range of interplanar distances which includes that (distance~ of the line of maximum ~:~ intensity of the spectrum of powder of the normal, non-activatec Mg halide and having the maximum intensity shifted with respect ~; to such line. The term "spectrum of powder of the non-activated Mg hallde" means the spec~ra as defined in~ASTM sheet ~`` 15 3-0854 and 15-836 for MgC12 and MgBr2, respectively. In the r: case of MgC12 the peak of the halo is comprised between 2.44 A
`~ an~ 2.97 ~. ~
The product obtained by the co-grinding is reacted with TiC14 under oonditions in which Ti compounds extractable with TiCl~ at 80C remain in the reaction product in amounts not exceeding 50~. For example, the ground product is suspendec in TiC14 and reacted at 60-130C for stretches of time suf-ficient to fix at least 0.5% by weight of Ti, and then it is separated from TiC14 at temperatures at which there is no precipitation of Ti compounds lnsoluble in TiC14 at the separation temperature.
Another m~thod of preparing component (a) of the present catalysts consists in reacting an adduct between a Mg dihalide and an alcohol or a phenol, generally containing more than 0.5 moles of organic compound per mole of halide and com-prising, in combined form, from 0.1 to 0O5 moles of an electron ll, ~37~ 7 donor compound selected from the classes of compounds cited hereinbefore (esters, halides, acids, amides, ethers, ketones), with a halogenated Ti compound liquid under the reaction con-; ditions, in particular TiC14, and in separating from the reaction mixture a solid product the Ti compounds and electron donor compounds of which satisfy the conditions already specified for the catalysts of the present invention.
Still another method of preparing component (a) con-sists in preparing a Mg dihalide or a carrier containing said dihalide in an active form havin~ a surface area larger than 80-100 m /g, in reacting said halide with an electron donor compound belonging to the classes disclosed supra in such amounts and under such conditions as to cause 0~1 to 0.3 moles per mole of dihal1de to remain fixed in the halide, and then in reacting said pro~uct with a llquid Ti compound, in particular TiC14, under the conditions specified hereinabove for the preparation of other types of catalysts.
In preparing component (a) of these catalysts, it is also possible to simultaneously react the Ti compound and the electron donor compound with the activated Mg halide.
Mg dlhalides in preactivated form are obtained, for example, by reacting an organo-magnesium compound of the type RMgX, or alcoholates of formula ROMgX', in which R is an alkyl or aryl radical hav1ng 1 to 18 C~ X is a halogen and X' is a halogen or a radical OR, ~ith a halogenating substance, such as halogenated Si compounds, in particular SiCl~, SnC14, BC13, or Al halides such as AlC13, AlR2Cl, ~lRCl~, in which R has the meaning specified.
It is also possible to obtain the Mg halides in an active form by evaporating, at a temperature up to about 200~C, s-olutions of the oxgano-magnesium compounds in ethers RORI, in ::IL13~0~
which R and R , the same or different from one to another, are alkyl, aryl and cycloalkyl radicals havi~g 3 to 18 C, or by treating said solutions with anhydrous hydrogen halides in such amounts and conditions as to cause the magnesium dihalide to precipitate.
Other methods of preparing catalyst component (a) consist in reacting a Mg alcoholate such as, e.gO, diethoxy-magnesium or a halogen-alcoholate, such as for example, chloro-ethoxy-magnesium, chloro-phenoxy-magnesium, chloro-butoxy-1 magnesium~ with the electron donor compound in such amounts and I conditions, that the solid product of the reaction contains `~ ¦ fxom 0~1 to 0.5 moles per gram atom of Mg, and in successively reacting said product with a Ti compound under the conditions - ¦ already indicated for the preparation of the catalysts useful in ¦ the practice of this invention.
; I It is also possible, in preparing component (a~, to react the Mg alcoholate wikh an anhydrous hydrogen halide, so as ¦ to form an adduct MgX2.nROH, and to treat then the adduct as ¦ disclosed hereinabove. This reaction can be conducted in one ¦ step by reacting metal Mg, an alcohol RO~ and a hydrogen halide, in which R has the significance as stated. ~
A11 of the methods disclosed lead to final products ¦ comprising~ at least on their surface, a dihalide in active ¦ form and products of addition of said dihalides with the ¦ electron donor compound and the Ti compound.
¦ The reaction of the Mg dihalide with the electron ~- donor compound and the Ti compound can be established by I~Ro and Raman spectroscopyO
¦ In the preparation of component (a), the electron donor compound is generally reacted with the alkyl Al compound p_ior to the mixing thereof with the Ti compound~ It l _g_ -~L376~
is possible, ~wever, to reaot the two compounds simultaneously, or the electron donor compound can be added after the Ti com-: pound has be~n mixed wi~h the alkyl Al. compound.
The electron donor compound present in a combined form in co~ponent (a) of the present catalysts can be intxoduced also, according to another embodiment of the present invention, by starting from a product as defined in (a)., in the absence of :~ an electron donor and then mixing such component (a) with an ~` alkyl Al compound as defined in (b), wherein the Al/Ti ratio and the molar ratio between the electron donor compound com-plexed with the alkyl Al compound and the latter are selected in such manner that the solid reaction product contains an amount of electron don~r compound corresponding to a molar ratio to . the Ti compound of from 0.2 to 3~ Also, the Al/Ti ratio be-.~. 15 tween the free Al-alkyl compound and the Ti compound:preferably ranges from 3 to 30. In the latter case, the reactlon mixture can be directly utilized as polymerization catalyst.
~: Examples of trialkyl Al compounds useful as com-ponents (b) of the present catalysts include:
Al(C2H5)3, Al(i-C4Hg)3, Al(n-C4Hg)3, Al(CH~-ClH-(CH2)2-CH3)3, .. Al(C12H25)3. CH3 Examples of alkyl A1 compounds containing two or more Al atoms bound to one another through an oxygen atom or a ~;: nitrogen atom which are useful in the practice of this inven-~: 25 tion include (C2H5)2Al-o-Al(C2H5)2 and (C2Hs)2-Al l-Al(C2H5)2-~: C6H5 Such compounds can be prepared according to conventional methods by reaction 5f an Al trialkyl with water, ammonia or primary amines.
Examples of compounds AlR3_n~OR~)n, wh~rein radical R' ~ 30 is an aryl group oxtho-hindered in positions 2 and 6, in which il3~70~
at least one of the substituents is capabl~ of giving a steric hindrance higher than that of the group -C2H5, or a naphthyl group containing at least in position 2 a substituent with a steric hindrance higher than that of group C2H5, include the S following: ~
Al(C2H5)2(2,6-di-tert.-butyl-p-cresoxy), Al(i-C4Hg)2(2,6~di-tart.butyl-p-cresoxy~, AltC2H5)2(2~6-di-tert~-butyl-phenoxy~
Al~C2H5) (2,6-di-tert.-butyl~p-cresoxy)2, Al~C2H5)2 (2,8-di-tert.butyl-naphthoxy~.
The alkyl Al compounds can be employed in admixture with one another. It is also possible to use mixtures of said compounds with organometallic compounds of the metals belonging to Groups I-IIIy in particular compounds of Al, Zn, Mg and ~` 15 compounds of B, Si, which per se fQrm with component (a) ` catalysts of little if any activity. Such compounds are utili7.ed or protecting the catalyst, or the individual com-¦ ponents thereof, ~rom the impurities, if any, contained in the polymerization system (monomer, solvent, etc.~. The use of such ~; 20 ¦ substances is particularly helpful in the case of the catalysts ~- ¦ according to the present invention, in which, due to the small ¦ amounts of catalytic components employed, lo~ amounts of ¦ impurities are sufficient to negatively affect the catalyst per-¦ formance. Preferred compounds of this kind are: Zn(C2H5)2, ¦ Al-alkyl-alkoxy compounds such as Al(i~C4Hg)2O~t-C4Hg and ¦ Al(C2H5)2~xylenoxy. Such organometallic compounds are employed in amounts generally ranging from 1 to 20 moles per mole of ¦ alkyl Al compound. They may be utilized also in the ~orm of ¦ complexes with electron donor compounds, in particular with the ~ esters of the aromatic acids.
il3'i'0i~7 Polymerization of the alpha-oleflns or mixtures ¦ thereof with ethylene with the catalysts of the present inven-tion is carried out according to conventional methods, by operatin~ either in liquid phase, the polym~rization medium being the monomer itself, or in gaseous phase. Th~ polym~riza-tion temperature i5 generally compri~ed between 40 and 90C.
~; The pressure can be atmospheric pressure or a higher pressure.
The alpha-olefins can be polymerlzed ln admixture ~ with ethylene~ in particular in such ratîos that the polymerize ; 10 ethylen~ content is from 1 to 25% ~y weight.
The catalys~ts of this invention can be also used to produce polymers, in particular polypropylene, having lmproved characteristlcs of resistance to bri*tleness, conforming to known methods in which at first the alpha-olefin is polymerized until about 60-80% of the total polymer is formed and then, in one or more steps, ethy~ene and/or mixtures thereof with the alpha-olefin are polymerized, in order that the polymexi~ed ethylene content is from 5 to 30% by ~eight.
The following examples are given to illustrate the present invention ln more detail and are not intended to be limiting. ~ ~
~ :
Q.63 millimoles of Al triisobutyl were reacted at 25~C with q.047 millimoles of methyl p-toluate in 80 ml of anhydrous and desulphurated n-heptane for 5 minutes. 50 ml of -- the resulting solution were contacted with the proper amount of a solid catalyst component prepared accordlng to Example 7 of ¦ German patent application 2,643,143, to obtain a suspension.
., I
.
3~1370c~ 7 The remaining 30 ml of the solution were diluted to lO00 ml with n-heptane and introduced, under a nitrogen pressure, into a 3000 ml steel autoclave equipped with a magnetic anchor stirrer and a thermometer, thermoregulated at 40C, and 1nto which a flow of propylene was introduced.
Successively, and in the same way, the catalytic component suspension was introduced. After closing the auto-clave, it was heated to 60C while simultaneously feeding propylene in to a total pressure of 5 atm. Such pressure was kept constant throughQut the polymerization by continuously feeding the propylene. After 4 hours, the polymerization was stopped and the polypropylene was isolated by treatment with methanol and acetone~ The results of the polymerization test are recorded in Table I.
; EXAMPLE 2 0.63 millimoles of Al triisobutyl were reacted at 25C with ~ millimoles o~ methyl p-toluate in 80 ml of anhydrous and desulphurated n-heptane for 5 minutes. 50 ml of the resulting solution were contacted with a suitable amount of a solid catalytic component prepared according to the modalities of Example 31 of Bel~ian patent No~ 857,574 and haviny a Ti content equal to l.62% by wei~ht.
The rema1ning 30 ml of the solution were diluted to ~ lO00 ml with n-heptane and were introduced, under a nitrogen -~ 25 pressure, into a steel 3000 ml autoclave equipped with a magnetic anchor stirrer and a thermometer~ thermoregulated at 40~C, and into which a flow of propylene was introduced.
In the same way, the catalytic component suspension was then introduced. After closing the autoclave, it was ~L370q3~
heated to 60C and simultaneous feeding of propylene up to a ; total pressure of 5 atm was continued. Such pressure was kept ¦ constant throughout the polymerization by feeding of the ¦ propylene. After 4 hours t the polymerization was stopped and ¦ the polypropylene was isolated by treatment with methanol and l acetone.
¦ The results of the polymerization are recorded in ¦ Table I.
I
I EXA~PLE 3 I
0.63 millimoles of Al triisobutyl were dissolved in 80 ml of (anhydrous desulphurated) n-heptane. 50 ml of such solution were contacted with a suitable amount of a solid catalytic component prepared according to Example 2 in whlch, instead of ethyl benzoate, an equlvalent amount of methyl p-toluate was used.
¦ The remaining 30 ml were diluted to 100~0 ml with ~ ¦ n-heptane and were introduced, under ~ nitrogen pressure, into - ¦ a steel 3000 ml autoclave equipped with a magnetic anchor stirrer and a thermometer, thermoregulated at 40C, and into ¦ which propylene was made to flow.
¦ Successively, the catalytic component suspension was ¦ introduced in the same manner. After closing the autoclave, it ¦ was heated to 60C while simultaneously feeding in propylene up ~ ¦ to a total pressùre of 5 atm. Such pressure was kept constant ; 25 ¦ throu~hout~the polymerization by continuing the monomer feed.
¦ After 4 hours, ~the polymerization was stopped and the poly-¦ propylene was isolated by treatment with methanol and acetone.
The results relating to the polymerization test are re~orded in Table I.
, ~1370c37 0.75 millimoles of Al triisobutyl were dissolved in ; 80 ml of (anhydrous desulphurated) n-heptane. 50 ml of suchsolution were contacted with a proper amount of a ~olid catalytic component prepared according to Example 2, with the exception that methyl benzoate was substituted by ethyl p-anisate.
The remaining 30 ml were diluted to 1000 ml with n-heptane and were introduced, under a nitrogen pressure, into a 3000 ml steel autoclave equipped with a magnetic anchor stirrer and a thermometer, thermoregulated at 40C, and into which propylene was made to flow.
Successively, the catalytic component suspension was introduced in the same manner. After having closed the auto-clave, it was heated to 60C while simultaneously feeding in ~; propylene up to a~tota1 pressure of 5 atm. Such pressure was kept constant throughout the polymerization by continuously feedin~ the monomer. After~4 hours the polymeri~ation was stopped and the polypropylene was isolated by treatment with methanol and acetone.
The results o~ the polymerization test are recorded in Table I.
0.75 millimoles of Al triisobutyl were dissolved in 80 ml of (anhydrous desulphuratad~ n-heptane. 50 ml of such solution were contacted with a suitable amount of a solid catalytic component prepared according to Example 4.
The remainin~ 30 ml were diluted to 1000 ml with n-heptane and introduced, under a nitrogen pressure, into a , ..
, . -: ' .: .
1~7~
¦ 3000 ml steel autoclave equipped with a magnetic anchor stirrer and a thermometer, thermoreyulated at 40C, and into which propylene was made to flow.
Successively, and in the same way, the ca~alykic component suspension was introduced. After having closed the autoclave, it was heated to 60C and V~l atm of H2 and propylene were introduced up to a total pressure of 5 atm. Such pressure was kept constant throughout the polymerization by continuously feeding the monomer. A~ter 4 hours the polymerization was stopped and the polypropylene was isolated by treatment with methanol and acetone.
The results of the polymerization test are recorded in Table I.
' , EX~MPLE 6 0.40 millimoles of Al triisobutyl were reacted at 25C with 0.04 millimoles of methyl p-toluate in 80 ml of (anhydrous desulphurated) n-heptane for 5 minutes~ 50 ml of such solution were contacted with a proper amount of a solid catalyst component prepared according to Example 1.
The remaining 30 ml were diluted to 1000 ml with n-heptane containing 2.5 millimoles of Zn(n-C4H9~2 and intro-duced, under a nitrogen pressure, into a 3000 ml steel auto-clave equipped with a ma~netic anchor stirrer and a thermometer, thermoregulated at 40C, and into which propylene was made to flow.
SuccessiV ly, and in the same way, the catalytic co~ponent suspension was introduced. After having closed the autoclave, it was heated to 60 C while simultaneously feeding in propylene up to a total pressure of 5 atm. Such pressure was ~3~7 kept constant thro~ghout the polymerization by continuously feeding the monomer. After 4 hours the polymerization was ¦ stopped and the polypropylene was isolated by treatment with ¦ methanol and acetone.
¦ The results of the polymerization test are recorded l in Table I.
' I
0.19 millimoles of Al triisobutyl were dissolved in l 80 ml of (anhydrous desulphurated~ n-heptane. 50 ml of such ¦ solution were contactéd with a suitable amount of a solid catalyst component prepared according to Example 1. The remain-¦ ing 30 ml were diluted to 1000 ml with n-heptane containing 2.5 ¦ millimoles of Zn(n-C4Hg)2 and were introduced, under a nitrogen ¦ pressure, into a 3000 ml steel autoclave equipped with a 1 magnetic anchor stirrer and a thermometer, thermoregulated at ¦ 40C~ into which propylene was caused to flow.
Successively, and in the same way, the catalytic ; ¦ component suspension was introduced. After having closed the autoclave, it was heated to 60C with simultaneous feeding of ~0 ¦ propylene up to a total pressure of 5 atm. Such pressure was kept constant throughout the polymerization by continuously ¦ feeding the monomer. After 4 hours the polymerization was ¦ stopped and the polypropylene was isolated by treatment with ¦ methanol and acetone.
l The results of the polymerization test are recorded ¦ in Table I.
' I
:, I
~37~7 0.63 millimoles of Al trilsobutyl were reacted at 25C with 0.041 millimoles of methyl p-toluate in 80 ml of (anhydrous desulphurated) n-heptane for 5 minutes. 50 ml of such solution were contacted with a solid catalyst component prepared according to Example 24 of the above-mentionéd Canadian application Serial No. 306,478 and used in the amount recorded in Table I.
The remaining 30 ml were diluted to 1000 ml with n-heptane and introduced, under a nitrogen pressure, into a 3000 ml steel autoclave equipped with a magnetic anchor stirrer and a ~hermometer, thermoregulated at 40C, and into -~
which propylene was cSused to flow.
Successively, and in the same way, the catalytic component suspension was introduced. After having closed the autoclave, it was heated to 60C with simultaneous feeding of propylene up to a total pressure of 5 atm. Such pressure was kept constant throughout the polymerization by continuously feeding the monomer. After 4 hours the polymerization was stopped and the polypropylene was isolated by treatment with methanol and acetone.
The results relating to the polymerization test are recorded in Table I.
EX~MPLE 9 0.113 millimoles of Al triisobutyl were dissolved in 80 ml of tanhydrous desulphurated) n-heptane. 50 ml of such solution were contacted with a solid catalytic component -prepared according to Example 2 and used in the amount indicated in Table I. ~he remaining 3Q ml were diluted to 1000 ml with - 30 n-heptane containlng 2.5 millimoles of (C~H5)2Al ~OC~Hs(CH~) 2]
;~ and introduced, under a nitrogen pressure, into a 3000 ml steel ~,`,, bmo --.3 ~.37~
autoclave equipped with a magnetic anchor stirrer and a thermometer, thermoregulated at 40C, and into which propylene was made to flow.
Successively, and in the same way, the catalytic component suspension was introduced. After having closed the autoclave, it was heated to 60C while simultaneously feeding in propylene up to a total pressurç of 5 atm. Such pressure was kep~ constant throughout the polymerization by continuously feeding the monomer. After 4 hours the polymerization was ;~ 10 stopped and the polypropylene was isolated by treatment with ~-methanol and acetone.
The results of the polymerization test are recorded in Table I.
0.63 millimoles of Al-triisobutyl were reacted at 25C with 0.041 millimoles of methyl p-toluate in 80 ml of (anhydrous desulphurated) n-heptane for S minutes. 50 ml of such solution were contacted with a solid catalyst component prepared according to an example set out in the above-mentioned Canadian appllcation Serial No. 303,940 and used in the amount specified in Table I. The remaining 30 ml were diluted to 1000 ml with n-heptane and introduced, undex a nitrogen pressure; into a 3000 ml steel autoclave equipped with a magnetic anchor~stirrer~and a thermometer, thermoregulated ; at 40C, and into which propylene was made to flow.
Successively, and Ln the same way, the catalytic -~ component suspension was introduced. After having closed the autoclave, it was heated to 60C while simultaneously feeding in propylene up to a total pressure of 5 atm. Such pressure was kept constant throughout the polymerization by continuously .
, ~ bm:
113`~7o~7 feeding the monomer~ ~fter 4 hours the polymerization was stopped and the polypropylene was isolated by treatment with methanol and acetone.
The results of the polymerization test are recorded in Table I~
0 65 millimoles of (C2H5)2Al[OC6H2tt 4 9 2 3 ¦ dissolved in 80 ml of (anhydrous desulphurated3 n-heptane. 50 ml of such solution were~contacted with a proper amount of a solid catalytic component prepared according to Example 31 of Belgian patent No~ 85~,574, while suitably varying conditions in order to have a titanium content equal to 1~7% and an ethyl benzoate content equal to 6.5% by weight.
The remaining 30 ml were diluted to 1000 ml with n-heptane and introduced, under a nitrogen pressure, into a 3000 ml steel autoclave equipped with a magnetic anchor stirrer and a thermometer, thermoregulated at 40C, and into which propylene was made to f low .
Successively, and in the same way, the catalytic component suspension was introduced. After having closed the autoclave, it was heated to 60C while simultaneously feeding in propylene up to a total pressure of 5 atm. Such pxessure was kept constant throughout the polymerization by continuously feeding the monomer. After 4 hours the polymerization was stopped and the polypropylene was isolated by treatment with methanol and a~etone.
The results relating to the polymerization test are recorded in Table I.
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Polymerization of ~op~lene at atmos heric ressure.
. P P _ 450 ml o anhydrous and desulphurated n~heptane and 1.25 millimoles of aluminum alkyl~alcoholate were introduced, while flowing in propylene, into a cylindrical glass reactor having a 1 liter volume and equipped with a stirrer r a ther-mometer and a plunging pipe for the gas inflow. The whole was brought to a temperature of 60C and heptane was saturated with the monomer for 10 minut~s. After this time pPriod, 50 ml of heptane suspension containin~ a proper amount of (a) solid catalytic component (equal to about O.12 millimoles/titanium liter~ prepared according to Example 11~ and of (b) aluminum triisobutyl were added. Polymerization was carried out at 60~
under normal pressure; after l hour the reaction was sto~ped with ethanol.
~ The results xelating to the polymerization test con-;1~ ducted under such conditions, ~arying the aluminum alkyl-alcoholate or employing an aluminum trialkyl reacted with Si(OC2~5)4, are recorded in Table II.
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~7q3~7 !¦ EXAMPLE 15 i l millimole of aluminum triisobutyl were reacted at 25~C with 0.09 millimoles of methyl p-toluate in 80 ml of I (anhydrous desulphurated) n-heptane for 5 minutes. 50 ml of ¦ such solution were contacted with a proper amount of the solid catalytic component described in Example lll in such a way as to obtain an Al/Ti molar ratio equal to 20 and a donor/Ti molar ratio equal to 2.9.
The remaining 30 ml of the solution were diluted to 1000 ml with n-heptane and introduced, under a nitro~gen pressuxe into a 3000 ml steel autoclave equipped with a magnetic anchor stirrer and a thermometer, thermoregulated at 40C, and into ¦ which propylene was made to flow.
Successively, the catalytic component suspension was ¦ introduced in the same manner. After having closed the auto-¦ clave, i~ was heated to 60C and 0.1 atm of H2 and propylene ¦ up to a total pressure of 5 atm were introduced. Such pressure ¦ was kept constant throu~hout the polymeri~ation by continuously ¦ feeding the monomer. After 4 hours the polymerization was ¦ stopped and, by treatment with methanol and acetone, a poly-propylene amount corresponding to a yield of 250 kg/g of Ti, haying a n = 2.0 dljg and a residue of the extraction thereof with heptane equal to 91.3% was isolated.
~ :
Example 15 was repeated usin~ aluminum triethyl instead of aluminum triisobutyl, but keeping the molar ratios unchanged.
A polypropylene amount corresponding to a yield of 182 kg/g of Ti, having a " = 2.20 dl/g and a residue after the extraction thereof with heptane of 94~8% was obtained.
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Polymerization of ~op~lene at atmos heric ressure.
. P P _ 450 ml o anhydrous and desulphurated n~heptane and 1.25 millimoles of aluminum alkyl~alcoholate were introduced, while flowing in propylene, into a cylindrical glass reactor having a 1 liter volume and equipped with a stirrer r a ther-mometer and a plunging pipe for the gas inflow. The whole was brought to a temperature of 60C and heptane was saturated with the monomer for 10 minut~s. After this time pPriod, 50 ml of heptane suspension containin~ a proper amount of (a) solid catalytic component (equal to about O.12 millimoles/titanium liter~ prepared according to Example 11~ and of (b) aluminum triisobutyl were added. Polymerization was carried out at 60~
under normal pressure; after l hour the reaction was sto~ped with ethanol.
~ The results xelating to the polymerization test con-;1~ ducted under such conditions, ~arying the aluminum alkyl-alcoholate or employing an aluminum trialkyl reacted with Si(OC2~5)4, are recorded in Table II.
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~7q3~7 !¦ EXAMPLE 15 i l millimole of aluminum triisobutyl were reacted at 25~C with 0.09 millimoles of methyl p-toluate in 80 ml of I (anhydrous desulphurated) n-heptane for 5 minutes. 50 ml of ¦ such solution were contacted with a proper amount of the solid catalytic component described in Example lll in such a way as to obtain an Al/Ti molar ratio equal to 20 and a donor/Ti molar ratio equal to 2.9.
The remaining 30 ml of the solution were diluted to 1000 ml with n-heptane and introduced, under a nitro~gen pressuxe into a 3000 ml steel autoclave equipped with a magnetic anchor stirrer and a thermometer, thermoregulated at 40C, and into ¦ which propylene was made to flow.
Successively, the catalytic component suspension was ¦ introduced in the same manner. After having closed the auto-¦ clave, i~ was heated to 60C and 0.1 atm of H2 and propylene ¦ up to a total pressure of 5 atm were introduced. Such pressure ¦ was kept constant throu~hout the polymeri~ation by continuously ¦ feeding the monomer. After 4 hours the polymerization was ¦ stopped and, by treatment with methanol and acetone, a poly-propylene amount corresponding to a yield of 250 kg/g of Ti, haying a n = 2.0 dljg and a residue of the extraction thereof with heptane equal to 91.3% was isolated.
~ :
Example 15 was repeated usin~ aluminum triethyl instead of aluminum triisobutyl, but keeping the molar ratios unchanged.
A polypropylene amount corresponding to a yield of 182 kg/g of Ti, having a " = 2.20 dl/g and a residue after the extraction thereof with heptane of 94~8% was obtained.
-2~-
3~7 l millimole of Al triisobutyl was dissolved in 80 ml of (anhydrous desulphurated) n-heptane. 50 ml of such solution were contacted with a proper amount of the solid catalytic com-ponent prepared according to Example 2 of British Patent No.
.~ l,387,890, with a titanium content equal to 5% by weightD
The remaining 30 ml of the solution were diluted to l000 ml with n-heptane and introduced, under a nitrogen pres-sure, into a 3000 ml steel autoclave e~uipped with a magnetic anchor stirrer and a thermometer, thermoregulated at 40C, and into which propylene was made to flow.
Successively; and in the same way, the catalytic component suspension was introduced. After having closed -the autoclave, it was heated to 60C while simultaneously feeding in propylene up to a total pressure of 5 atm. Such pressure was kept constant throughout the polymerization by continuously feeding the monomer. After 4 hours the polymerization was stopped and the polyprop~lene was isolated by treatment with methanol and acetone.
The results relating to the polymerization test are ~; xecorded in Table III.
-;; l.0 millimole of Al triisobutyl was reacted at 25C
with 0.15 millimoles of methyl p-toluate in 80 ml of ~anhydxous desulphurated~ n~heptane for 5 minutes. 50 ml of such solution were contacted with a proper amount of a solid catalyst com-ponent prepared according to Comparison Example l.
The remaining 30 ml of the solution were diluted to l000 ml with n-heptane and introduced, under a nitrogen ~L 37~t7 pressure, into a 3000 ml steel autoclave equipped wlth a magnetic anchor stirrer and a thermometer, thermoregulated at 40~C, and into which propylene was made to flow.
Successively, and in the same way, the catalytic component suspension was introduced. After having closed the autocla~e, it was heated to 60C while simultaneously feeding propylene up to a total pressure of 5 atm. Such pressure was kept constant throughout the polymerization by going on feeding I the monomer. After 4 hours the polymerization was stopped and the polypropylene was isolated by treatment with methanol and acetone. ~
The results relating to the polymerization test are recorded in Table III.
1.3 millimoles of Al triisobutyl we~e dissolved in ~0 ml of (anhydrous desulphuxated~ n-heptane. 50 ml of such solution were contacted with a suitable amount of a solid catalytic component prepared accordiny to Comparison Example 1 having a titanium content equal to 2.64% by weight.
The remaining 30 ml were diluted to 1000 ml with n~heptane and introduced, under a nitrogen pressure, into a 3000 ml steel autoclave equipped with a magnetic anchor stirrer and a thermometer, thermoregulated at 40C, and into which propylene was made to flow ¦ Successively, and in the same way, the catalytic ; component suspension was introduced. ~fter having closed the autoclave, it was heated to 60CC while simultaneously feeding propylene up to a total pressure of 5 atm. Such pressure was kept constant throu~hout the polymerization by continuously ; ~ -26-li370~7 ¦ feeding the monomer. AEter 4 hours the polymeri~ation was ~:
stopped and the polypropylene was isolated by treatment with methanol and acetone.
The results relating to the polymerization test are recorded in Table III.
~ COMPARISON EXAMPLE 4 ; 2.45 millimoles of Al triisobutyl were reacted at ~5C with 0.49 millimoles of methyl p-toluate in 80 ml of (anhydrous desulphurated) n-heptane for S minutes. 50 ml of ~` such solution were contacted with a proper amount of a solid catalyst component prepared according to Comparison Example 3O
The remaining 30 ml were diluted to I000 ml with n-heptane and introduced, under a nitrogen pressure, into a 3000 ml steel autoclave equipped with a magnetic anchor stirrer and a thermometer, thermoregulated at 40~C, and into which propylene was made to flow.
Successively, and in the same way, the catalytic ~ component suspension was introduced. Aft~r having closed the ; autoclave, it was heated to 60C while simultaneously feeding propylene up to a total pressure of 5 atm. Such pressure was ~ kept constant throughout the polymerization by contlnuously : feeding the monomer. After 4 hours the polymerization was stopped and the polypropylene was isolated by treatment with methanol and acetone.
- 25 The results relating to the polymerization test are recorded in Table III.
11;~7(~7 5.0 millimoles of Al triiso~utyl were reacted at ; 25C with 1.3 millimoles of methyl p-toluate in 80 ml of (anhydrous desulphurated) n-heptane for 5 minutes. 50 ml of such solution we.re contacted with a proper amount of the solid catalytic component employed in Example 1.
The remaining 30 ml of the solution were diluted to 1000 ml with n-heptane and introduced, under a nitrogen pres-sure, into a 3000 ml steel autocla~e equipped with a magnetic anchor stirrer and a thermometer, thermoregulated at 40C, and into which propylene was made to flow.
:~ Successively, and in the same way, the catalytic component suspension was introduced. After having closed the autoclave, it was heated to 60C while simultaneously feeding in propylene up to a total pressure of 5 atm. Such pressure was kept constant throughout the polymerization by continuously feeding the monomer. After 4 hours, the polymerization was stopped and the polypropylene was isolated by treatment with methanol and acetone.
The results relating to the polymerization test are recorded in Table III.
. . - :
COMPARISoN EX~PLE 6 , --~ 5.0 millimolès of Al triisobutyl were reacted at 25C
~ith 1 5 millimoles of methyI p-toluate in 80 ml of (anhydrou~
desulphurated) n-heptane for 5 minutes~ 50 ml of such solution were contacted with a prope~ amount of the solid catalytic component employed in Example 2, The remalning 30 ml were diluted to 1000 ml with n-hept~ne and introduced, under a nitrogen pressure, into a . , :- ~
3000 ml steel autoclave equipped with a magnetic anchox stlrrer and a ~hermometer, thermoregulated at 40C, and into which propylene was caused to flow.
Successively, and in the same wa~, the catalytic component suspension was introduced. After having closed the autoclave, it was heated to 60C while simultaneously feeding propylene in up to a total pressure o 5 atm. Such pressure was kept constant throughout the polymerization by continuously feeding the monomer~ After 4 hours the polymerization was stopped and thè polypropylene was isolated by treatment with methanol and acetone.
The results relating to the polymerization test are shown in Table III.
COMPARISON EXAMPLE 7 -~
0.19 millimoles of Al triisobutyl were reacted at - -25C with 0.057 millimoles of methyl p-toluate in 80 ml of (anhydrous desulphurated) n-heptane for 5 minutes. 50 ml of ~ such solution were ~ontacted with a proper amount of the ; solid catalytic component prepared according to Comparison Example 5.
The remaining 30 ml were diluted to 1000 ml with ~`
n-heptane and introduced, under a nitrogen pressure, into : ~ :
a 3000 ml steel autoclave equipped with a magnetic anchor stirrer and a thermometer, thermoregulated at 40C, and into which propylene was made to flow.
Successlvely, and in the same way, the catalytic component suspension was introduced. After having closed the autoclave, it was h~ated to~60C while simultaneollsly feeding propylene up to a total pressure of 5 atm. Such pressure was kept constant throughout the polymerization by continu~usly feedin~ the monomer. After 4 houFs the polymerization was , C dm ~ 2 ~3~
~topped and the polypropylene was isolated by treatment wlth methanol and acetone.
Table III shows the results of the polymerization test.
0~38 millimoles of Al triisobutyl were dissolved in sn ml of (anhydrous desulpllurated~ n~heptane. 50 ml of such solution were contacted with a sultable amount of the solid catalytic component prepared according ~o Example 1 of publish~d German patent appli~cation No. 2 504 036.
The remaining 30 ml were diluted to 1000 ml wlth n-heptane and introduced, under a nitrogen pressure, into a 3000 ml steel autoclave equipped with a magnetlc anchor stirrer and a thermometer, thermoregulated at 40C, and into which propylene was made to flow. ~ .
Successively, and in the same way, the catalytic component suspenslon was in~roduced. After having closed the autoclave, it was heated to 60C while simultaneously feeaing propylene in up to a total pressure of 5 atm~ Such pressure was kept constant throughout the polymeriæation by con-tinuously feeding the monomer. After 4 hours the poly-merization was stopped and the polypropylene was isolated by treatment wlth methanol and acetonen The results relating to the polymerization test are recorded in Table III.
.: , 0~38 millimoles~of Al triisobutyl were dissolved in , 80 ml of (anhydrous desulphurated) n-hep~ane~ ~0 ml o~ such solution wexe contacted with a suitable a~ount of the solid catalytic component prepared a~cording to Example 1 of German . ~ .
.
~ .
dms \c~ 3 , ' ~37~3~7 Patent No. 2,504,036. The remaining 30 ml were diluted to 10Q0 ml with n-heptane and were introduced, under a nitrogen pressure, into a 3000 ml steel autoclave equipped with a magnetic anchor stirrer and a thermometer, thermoregulated at 40~C, and into which propylene was mads to f low .
: Successively, the catalytic component suspension was : introduced in the same way. Ater having closed the autoclave,it was heated to 60C while simultaneously feeding in propylene up to a pressure of 4.8 atm and H2 up to 5 atm. Such pressure was kept cons~ant throughout the polymerization by continuous feed of the monomer. After 4 hours the polymerization was stopped and the polypropylene was isolated by treatment with methanol and acetone.
The results relating to the polymerization test are - 15 recorded in Table III.
.= .
: ~ _MPARISON EX~MPLE 10 Example 15 Was repe~ted Var~ing the molar ratios as . follows: Al/Ti = 40; electron-donor/Ti = 2.9. After a poly-merization time of 30 minutes, an amount of polypropylene was isolated oorresponding to a yield of 25Q kg/g of Ti having an inherent n = 1.62 dl/g and a residue after extraction thereof with heptane of 76.5~.
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.~ l,387,890, with a titanium content equal to 5% by weightD
The remaining 30 ml of the solution were diluted to l000 ml with n-heptane and introduced, under a nitrogen pres-sure, into a 3000 ml steel autoclave e~uipped with a magnetic anchor stirrer and a thermometer, thermoregulated at 40C, and into which propylene was made to flow.
Successively; and in the same way, the catalytic component suspension was introduced. After having closed -the autoclave, it was heated to 60C while simultaneously feeding in propylene up to a total pressure of 5 atm. Such pressure was kept constant throughout the polymerization by continuously feeding the monomer. After 4 hours the polymerization was stopped and the polyprop~lene was isolated by treatment with methanol and acetone.
The results relating to the polymerization test are ~; xecorded in Table III.
-;; l.0 millimole of Al triisobutyl was reacted at 25C
with 0.15 millimoles of methyl p-toluate in 80 ml of ~anhydxous desulphurated~ n~heptane for 5 minutes. 50 ml of such solution were contacted with a proper amount of a solid catalyst com-ponent prepared according to Comparison Example l.
The remaining 30 ml of the solution were diluted to l000 ml with n-heptane and introduced, under a nitrogen ~L 37~t7 pressure, into a 3000 ml steel autoclave equipped wlth a magnetic anchor stirrer and a thermometer, thermoregulated at 40~C, and into which propylene was made to flow.
Successively, and in the same way, the catalytic component suspension was introduced. After having closed the autocla~e, it was heated to 60C while simultaneously feeding propylene up to a total pressure of 5 atm. Such pressure was kept constant throughout the polymerization by going on feeding I the monomer. After 4 hours the polymerization was stopped and the polypropylene was isolated by treatment with methanol and acetone. ~
The results relating to the polymerization test are recorded in Table III.
1.3 millimoles of Al triisobutyl we~e dissolved in ~0 ml of (anhydrous desulphuxated~ n-heptane. 50 ml of such solution were contacted with a suitable amount of a solid catalytic component prepared accordiny to Comparison Example 1 having a titanium content equal to 2.64% by weight.
The remaining 30 ml were diluted to 1000 ml with n~heptane and introduced, under a nitrogen pressure, into a 3000 ml steel autoclave equipped with a magnetic anchor stirrer and a thermometer, thermoregulated at 40C, and into which propylene was made to flow ¦ Successively, and in the same way, the catalytic ; component suspension was introduced. ~fter having closed the autoclave, it was heated to 60CC while simultaneously feeding propylene up to a total pressure of 5 atm. Such pressure was kept constant throu~hout the polymerization by continuously ; ~ -26-li370~7 ¦ feeding the monomer. AEter 4 hours the polymeri~ation was ~:
stopped and the polypropylene was isolated by treatment with methanol and acetone.
The results relating to the polymerization test are recorded in Table III.
~ COMPARISON EXAMPLE 4 ; 2.45 millimoles of Al triisobutyl were reacted at ~5C with 0.49 millimoles of methyl p-toluate in 80 ml of (anhydrous desulphurated) n-heptane for S minutes. 50 ml of ~` such solution were contacted with a proper amount of a solid catalyst component prepared according to Comparison Example 3O
The remaining 30 ml were diluted to I000 ml with n-heptane and introduced, under a nitrogen pressure, into a 3000 ml steel autoclave equipped with a magnetic anchor stirrer and a thermometer, thermoregulated at 40~C, and into which propylene was made to flow.
Successively, and in the same way, the catalytic ~ component suspension was introduced. Aft~r having closed the ; autoclave, it was heated to 60C while simultaneously feeding propylene up to a total pressure of 5 atm. Such pressure was ~ kept constant throughout the polymerization by contlnuously : feeding the monomer. After 4 hours the polymerization was stopped and the polypropylene was isolated by treatment with methanol and acetone.
- 25 The results relating to the polymerization test are recorded in Table III.
11;~7(~7 5.0 millimoles of Al triiso~utyl were reacted at ; 25C with 1.3 millimoles of methyl p-toluate in 80 ml of (anhydrous desulphurated) n-heptane for 5 minutes. 50 ml of such solution we.re contacted with a proper amount of the solid catalytic component employed in Example 1.
The remaining 30 ml of the solution were diluted to 1000 ml with n-heptane and introduced, under a nitrogen pres-sure, into a 3000 ml steel autocla~e equipped with a magnetic anchor stirrer and a thermometer, thermoregulated at 40C, and into which propylene was made to flow.
:~ Successively, and in the same way, the catalytic component suspension was introduced. After having closed the autoclave, it was heated to 60C while simultaneously feeding in propylene up to a total pressure of 5 atm. Such pressure was kept constant throughout the polymerization by continuously feeding the monomer. After 4 hours, the polymerization was stopped and the polypropylene was isolated by treatment with methanol and acetone.
The results relating to the polymerization test are recorded in Table III.
. . - :
COMPARISoN EX~PLE 6 , --~ 5.0 millimolès of Al triisobutyl were reacted at 25C
~ith 1 5 millimoles of methyI p-toluate in 80 ml of (anhydrou~
desulphurated) n-heptane for 5 minutes~ 50 ml of such solution were contacted with a prope~ amount of the solid catalytic component employed in Example 2, The remalning 30 ml were diluted to 1000 ml with n-hept~ne and introduced, under a nitrogen pressure, into a . , :- ~
3000 ml steel autoclave equipped with a magnetic anchox stlrrer and a ~hermometer, thermoregulated at 40C, and into which propylene was caused to flow.
Successively, and in the same wa~, the catalytic component suspension was introduced. After having closed the autoclave, it was heated to 60C while simultaneously feeding propylene in up to a total pressure o 5 atm. Such pressure was kept constant throughout the polymerization by continuously feeding the monomer~ After 4 hours the polymerization was stopped and thè polypropylene was isolated by treatment with methanol and acetone.
The results relating to the polymerization test are shown in Table III.
COMPARISON EXAMPLE 7 -~
0.19 millimoles of Al triisobutyl were reacted at - -25C with 0.057 millimoles of methyl p-toluate in 80 ml of (anhydrous desulphurated) n-heptane for 5 minutes. 50 ml of ~ such solution were ~ontacted with a proper amount of the ; solid catalytic component prepared according to Comparison Example 5.
The remaining 30 ml were diluted to 1000 ml with ~`
n-heptane and introduced, under a nitrogen pressure, into : ~ :
a 3000 ml steel autoclave equipped with a magnetic anchor stirrer and a thermometer, thermoregulated at 40C, and into which propylene was made to flow.
Successlvely, and in the same way, the catalytic component suspension was introduced. After having closed the autoclave, it was h~ated to~60C while simultaneollsly feeding propylene up to a total pressure of 5 atm. Such pressure was kept constant throughout the polymerization by continu~usly feedin~ the monomer. After 4 houFs the polymerization was , C dm ~ 2 ~3~
~topped and the polypropylene was isolated by treatment wlth methanol and acetone.
Table III shows the results of the polymerization test.
0~38 millimoles of Al triisobutyl were dissolved in sn ml of (anhydrous desulpllurated~ n~heptane. 50 ml of such solution were contacted with a sultable amount of the solid catalytic component prepared according ~o Example 1 of publish~d German patent appli~cation No. 2 504 036.
The remaining 30 ml were diluted to 1000 ml wlth n-heptane and introduced, under a nitrogen pressure, into a 3000 ml steel autoclave equipped with a magnetlc anchor stirrer and a thermometer, thermoregulated at 40C, and into which propylene was made to flow. ~ .
Successively, and in the same way, the catalytic component suspenslon was in~roduced. After having closed the autoclave, it was heated to 60C while simultaneously feeaing propylene in up to a total pressure of 5 atm~ Such pressure was kept constant throughout the polymeriæation by con-tinuously feeding the monomer. After 4 hours the poly-merization was stopped and the polypropylene was isolated by treatment wlth methanol and acetonen The results relating to the polymerization test are recorded in Table III.
.: , 0~38 millimoles~of Al triisobutyl were dissolved in , 80 ml of (anhydrous desulphurated) n-hep~ane~ ~0 ml o~ such solution wexe contacted with a suitable a~ount of the solid catalytic component prepared a~cording to Example 1 of German . ~ .
.
~ .
dms \c~ 3 , ' ~37~3~7 Patent No. 2,504,036. The remaining 30 ml were diluted to 10Q0 ml with n-heptane and were introduced, under a nitrogen pressure, into a 3000 ml steel autoclave equipped with a magnetic anchor stirrer and a thermometer, thermoregulated at 40~C, and into which propylene was mads to f low .
: Successively, the catalytic component suspension was : introduced in the same way. Ater having closed the autoclave,it was heated to 60C while simultaneously feeding in propylene up to a pressure of 4.8 atm and H2 up to 5 atm. Such pressure was kept cons~ant throughout the polymerization by continuous feed of the monomer. After 4 hours the polymerization was stopped and the polypropylene was isolated by treatment with methanol and acetone.
The results relating to the polymerization test are - 15 recorded in Table III.
.= .
: ~ _MPARISON EX~MPLE 10 Example 15 Was repe~ted Var~ing the molar ratios as . follows: Al/Ti = 40; electron-donor/Ti = 2.9. After a poly-merization time of 30 minutes, an amount of polypropylene was isolated oorresponding to a yield of 25Q kg/g of Ti having an inherent n = 1.62 dl/g and a residue after extraction thereof with heptane of 76.5~.
~. .
':~
'~ I
7~
~ _ D _ . _ a U~
~d~ ~ .
~ ~ I~ O ~ o ~ r~
~ d~ .
m .
E~
~ P~ o~ I co o o u~ ~
:~ _ _ _ o E~ ~ oo o~cn 5~ In ~ ~ ~ ~
O ~ ~ , ~; . ,_, ~D ~e_~
.~ ~ U~
~E~ ~ o o ~ ~ o o ;~ ~ ~ ei ~
:~ .
. ~ . _ _ _ z; IY; :~ ~ m ~ m a~ :q Z Z; __ _ _ ~ ~ oP ~ . .
V 'n 'n c~ 9 o ~ r~
H _ . _ E~ oP ~ ~r In ~ n O
.~ ~ ~" . . ~ n ~ ~ N
.. ~ E~ Ln ~ Q
~ g ~ ~ . . . . . . . . ~
.. , ~ ~ o co o ~ ~ ~t~ ~ oo ~:
a~ c~ o o u _ n ~ . ~
O H ~ O ,1 ~ ~) ~ !1~ ~ CO ~ m -: ~E~
~:~
~ --3~-': :
Claims (10)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. Catalysts for polymerizing alpha-olefins CH2 =
CHR, in which R is an alkyl radical having 1 to 6 carbon atoms, mixtures thereof, and mixtures thereof with ethylene, including the product of the reaction between at least the following two components:
(a) a solid product comprising a Mg dihalide and complexes of said halide with at least a Ti compound and an electron donor compound selected from the group consisting of the esters of the organic and inorganic oxygenated acids, the anhydrides, halides, and amides of said acids, ethers ROR' and ketones RCOR', in which R and R', the same or different from one another, are alkyl, cycloalkyl or aryl radicals having 1 to 18 carbon atoms; in which the Mg/Ti ratio between Mg dihalide and Ti compound ranges from 5 to 100, the amount of Ti compound extractable with TiCl4 at 80°C is lower than 50% and the molar ratio between electron donor compound and Ti compound ranges, after extraction with TiCl4, from 0.2 to 3, and (b) an Al alkyl compound selected from the group consisting of trialkyls, the Al alkyl compounds containing two or more Al atoms bound to one another through an oxygen atom or a nitrogen atom, and compounds AlR3-n(OR')n, in which R is an alkyl radical having 1 to 18 carbon atoms, R' is an aryl radical ortho-hindered in positions 2,6 with substituents capable of giving a steric hindrance higher than that of the group -C2H5, or a naphthyl group containing at least in position 2 a substituent with a steric hindrance higher than that of the group -C2H5, and n is a number comprised in the range from 1 to 2 said Al alkyl compound being present for at least 85% in a non-combined form with an electron donor compound and being employed in amounts corresponding to a molar ratio to the Ti compound of component (a) ranging from 1 to 30; and the ratio between the total moles of electron donor compound and the moles of titanium compound is lower than 5.
CHR, in which R is an alkyl radical having 1 to 6 carbon atoms, mixtures thereof, and mixtures thereof with ethylene, including the product of the reaction between at least the following two components:
(a) a solid product comprising a Mg dihalide and complexes of said halide with at least a Ti compound and an electron donor compound selected from the group consisting of the esters of the organic and inorganic oxygenated acids, the anhydrides, halides, and amides of said acids, ethers ROR' and ketones RCOR', in which R and R', the same or different from one another, are alkyl, cycloalkyl or aryl radicals having 1 to 18 carbon atoms; in which the Mg/Ti ratio between Mg dihalide and Ti compound ranges from 5 to 100, the amount of Ti compound extractable with TiCl4 at 80°C is lower than 50% and the molar ratio between electron donor compound and Ti compound ranges, after extraction with TiCl4, from 0.2 to 3, and (b) an Al alkyl compound selected from the group consisting of trialkyls, the Al alkyl compounds containing two or more Al atoms bound to one another through an oxygen atom or a nitrogen atom, and compounds AlR3-n(OR')n, in which R is an alkyl radical having 1 to 18 carbon atoms, R' is an aryl radical ortho-hindered in positions 2,6 with substituents capable of giving a steric hindrance higher than that of the group -C2H5, or a naphthyl group containing at least in position 2 a substituent with a steric hindrance higher than that of the group -C2H5, and n is a number comprised in the range from 1 to 2 said Al alkyl compound being present for at least 85% in a non-combined form with an electron donor compound and being employed in amounts corresponding to a molar ratio to the Ti compound of component (a) ranging from 1 to 30; and the ratio between the total moles of electron donor compound and the moles of titanium compound is lower than 5.
2. Catalysts according to claim 1, in which the Mg/Ti ratio between Mg dihalide and Ti compound ranges from 10 to 50.
3. Catalysts according to claim 1, in which the Mg/Ti ratio between Mg dihalide and Ti compound ranges from 15 to 25.
4. Catalysts according to claim 1, in which the molar ratio between the electron donor compound and Ti compound ranges, after the extraction with TiCl4, from 1 to 2.
5. Catalysts according to claim 1, in which the Al alkyl compound of component (b) is employed in amounts corresponding to a molar ratio to the Ti compound of component (a) ranging from 2 to 20.
6. Catalysts according to claim 1, in which the Mg/Ti ratio between the Mg dihalide and Ti compound ranges from 15 to 25, the molar ratio between electron donor compound and Ti compound ranges, after the extraction with TiCl4, from 1 to 2, and the Al alkyl compound of component (b) is employed in amounts corresponding to a molar ratio to the Ti compound of component (a) ranging from 2 to 20.
7. Catalysts according to claim 1, in which component (b) comprises, in a combined form with the Al alkyl compound, an electron donor compound selected from the group consisting of the esters of the organic and inorganic oxygenated acids in amounts up to 10% by moles with respect to the Al alkyl compound, and in which the molar ratio between the total amount of the electron donor compound contained in components (a) and (b) and the Ti compound is comprised between 1 and 5.
8. Catalysts according to claim 1, in which component (a) comprises, in addition to the Al alkyl compound, an organometallic compound of Al different from the Al alkyl compound as defined in (b) or an organometallic compound of an element selected from the group consisting of Zn, Mg, B and Si.
9. A process for polymerizing alpha-olefins CH2 =
CHR, in which R is an alkyl radical containing 1 to 6 carbon atoms, and mixtures thereof with each other or with ethylene, characterized in that polymerization is carried out in the presence of a catalyst according to claim 1.
CHR, in which R is an alkyl radical containing 1 to 6 carbon atoms, and mixtures thereof with each other or with ethylene, characterized in that polymerization is carried out in the presence of a catalyst according to claim 1.
10. A process for polymerizing alpha-olefins CH2 =
CHR, in which R is an alkyl radical containing 1 to 6 carbon atoms, and mixtures thereof with each other or with ethylene, characterized in that polymerization is carried out in the presence of a catalyst according to claim 7.
CHR, in which R is an alkyl radical containing 1 to 6 carbon atoms, and mixtures thereof with each other or with ethylene, characterized in that polymerization is carried out in the presence of a catalyst according to claim 7.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT20096A/78 | 1978-02-09 | ||
| IT20096/78A IT1092448B (en) | 1978-02-09 | 1978-02-09 | CATALYSTS FOR THE POLYMERIZATION OF ALPHA-OLEFINS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1137067A true CA1137067A (en) | 1982-12-07 |
Family
ID=11163764
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000321122A Expired CA1137067A (en) | 1978-02-09 | 1979-02-08 | Catalysts for polymerizing alpha-olefins |
Country Status (17)
| Country | Link |
|---|---|
| US (1) | US4315836A (en) |
| JP (1) | JPS54126684A (en) |
| AR (1) | AR226416A1 (en) |
| AT (1) | AT362933B (en) |
| AU (1) | AU530611B2 (en) |
| BE (1) | BE874033A (en) |
| BR (1) | BR7900790A (en) |
| CA (1) | CA1137067A (en) |
| DE (1) | DE2904598A1 (en) |
| ES (1) | ES477551A1 (en) |
| FR (1) | FR2416903A1 (en) |
| GB (1) | GB2014592B (en) |
| IT (1) | IT1092448B (en) |
| MX (1) | MX150889A (en) |
| NL (1) | NL7900915A (en) |
| NO (1) | NO155776C (en) |
| SE (1) | SE446868B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4521541A (en) * | 1983-02-09 | 1985-06-04 | International Flavors & Fragrances Inc. | Process for forming functional fluid and solid-containing thermoplastic films, uses thereof and process for producing same |
| WO2017143174A1 (en) | 2016-02-18 | 2017-08-24 | International Flavors & Fragrances Inc. | Polyurea capsule compositions |
| EP4209264A1 (en) | 2016-09-16 | 2023-07-12 | International Flavors & Fragrances Inc. | Microcapsule compositions stabilized with viscosity control agents |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0041362A1 (en) * | 1980-06-02 | 1981-12-09 | Hercules Incorporated | 1-Olefin polymerization process and catalyst |
| JPS5778408A (en) * | 1980-11-05 | 1982-05-17 | Mitsui Petrochem Ind Ltd | Production of ethylene copolymer |
| IT1190683B (en) * | 1982-02-12 | 1988-02-24 | Montedison Spa | COMPONENTS AND CATALYSTS FOR THE POLYMERIZATION OF OLEFINE |
| IT1190682B (en) * | 1982-02-12 | 1988-02-24 | Montedison Spa | CATALYSTS FOR THE POLYMERIZATION OF OLEFINE |
| IT1190681B (en) * | 1982-02-12 | 1988-02-24 | Montedison Spa | COMPONENTS AND CATALYSTS FOR THE POLYMERIZATION OF OLEFINE |
| KR850008494A (en) * | 1984-05-17 | 1985-12-18 | 로버트 씨. 슬리반 | Olefin polymerization catalyst and its manufacturing method |
| US4680351A (en) * | 1985-09-06 | 1987-07-14 | Phillips Petroleum Company | Supported polyolefin catalyst components and methods of making and using same |
| IT1213474B (en) * | 1986-07-31 | 1989-12-20 | Montedison Spa | PROCEDURE FOR PREPARING SOLID COMPONENTS OF CATALYSTS, OR PRECURSORS OF SUCH COMPONENTS, IN THE FORM OF MICROSPHEROIDAL PARTICLES FOR THE POLYMERIZATION OF ALPHA-OLEFINS. |
| US5068212A (en) * | 1990-08-20 | 1991-11-26 | Phillips Ptroleum Company | Olefin polymerization catalyst and method for production and use |
| US5095080A (en) * | 1990-08-20 | 1992-03-10 | Phillips Petroleum Company | Olefin polymerization catalyst and method for production and use |
| KR101677694B1 (en) | 2012-09-24 | 2016-11-18 | 인디언 오일 코퍼레이션 리미티드 | Catalyst for polymerization of olefins and process thereof |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3549717A (en) * | 1968-02-28 | 1970-12-22 | Gosei Chem Ind Co Ltd | Process for the production of 1,5,9-cyclododecatriene |
| US4107413A (en) * | 1971-06-25 | 1978-08-15 | Montedison S.P.A. | Process for the stereoregular polymerization of alpha olefins |
| JPS5236786B2 (en) * | 1974-02-01 | 1977-09-17 | ||
| JPS5128189A (en) * | 1974-09-03 | 1976-03-09 | Mitsui Petrochemical Ind | KOKETSUSHOSEIHORIOREFUIN NO KOKATSUSEI JUGOHOHO |
| JPS565404B2 (en) * | 1975-02-14 | 1981-02-04 | ||
| IT1037112B (en) * | 1975-03-28 | 1979-11-10 | Montedison Spa | CATALYSTS FOR THE POLYMERIZATION OF OLFINES |
| IT1039828B (en) * | 1975-07-09 | 1979-12-10 | Montedison Spa | COMPONENTS OF PEARL CATALYSTS POLYMERIZATION OF OLEFINS AND CATALYSTS OBTAINED FROM THEM |
| IT1042711B (en) * | 1975-09-19 | 1980-01-30 | Montedison Spa | COMPONENTS OF CATALYSTS FOR THE POLYMERIZATION OF OLEFINS |
| IT1054410B (en) * | 1975-11-21 | 1981-11-10 | Mitsui Petrochemical Ind | CATALYSTS FOR THE POLYMERIZATION OF ALPHA OLEFINS |
| IT1068112B (en) * | 1976-08-09 | 1985-03-21 | Montedison Spa | COMPONENTS OF CATALYSTS FOR THE POLYMERIZATION OF ALPHA OLEFINS AND CATALYSTS FROM THEM OBTAINED |
| GB1603724A (en) * | 1977-05-25 | 1981-11-25 | Montedison Spa | Components and catalysts for the polymerisation of alpha-olefins |
| IT1114822B (en) * | 1977-07-04 | 1986-01-27 | Montedison Spa | COMPONENTS OF CATALYSTS FOR THE POLYMERIZATION OF ALPHA-OLEFINS |
-
1978
- 1978-02-09 IT IT20096/78A patent/IT1092448B/en active
-
1979
- 1979-02-05 NO NO790364A patent/NO155776C/en unknown
- 1979-02-05 NL NL7900915A patent/NL7900915A/en active Search and Examination
- 1979-02-05 SE SE7900999A patent/SE446868B/en not_active IP Right Cessation
- 1979-02-06 AT AT0088479A patent/AT362933B/en not_active IP Right Cessation
- 1979-02-06 AR AR275412A patent/AR226416A1/en active
- 1979-02-06 AU AU43986/79A patent/AU530611B2/en not_active Expired
- 1979-02-07 JP JP1236379A patent/JPS54126684A/en active Granted
- 1979-02-07 FR FR7903089A patent/FR2416903A1/en active Granted
- 1979-02-07 DE DE19792904598 patent/DE2904598A1/en active Granted
- 1979-02-07 GB GB7904350A patent/GB2014592B/en not_active Expired
- 1979-02-08 BE BE0/193348A patent/BE874033A/en not_active IP Right Cessation
- 1979-02-08 BR BR7900790A patent/BR7900790A/en unknown
- 1979-02-08 ES ES477551A patent/ES477551A1/en not_active Expired
- 1979-02-08 MX MX176537A patent/MX150889A/en unknown
- 1979-02-08 CA CA000321122A patent/CA1137067A/en not_active Expired
-
1980
- 1980-04-04 US US06/137,256 patent/US4315836A/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4521541A (en) * | 1983-02-09 | 1985-06-04 | International Flavors & Fragrances Inc. | Process for forming functional fluid and solid-containing thermoplastic films, uses thereof and process for producing same |
| WO2017143174A1 (en) | 2016-02-18 | 2017-08-24 | International Flavors & Fragrances Inc. | Polyurea capsule compositions |
| EP4209264A1 (en) | 2016-09-16 | 2023-07-12 | International Flavors & Fragrances Inc. | Microcapsule compositions stabilized with viscosity control agents |
Also Published As
| Publication number | Publication date |
|---|---|
| AR226416A1 (en) | 1982-07-15 |
| BE874033A (en) | 1979-08-08 |
| FR2416903A1 (en) | 1979-09-07 |
| AU4398679A (en) | 1979-08-16 |
| AU530611B2 (en) | 1983-07-21 |
| NO155776C (en) | 1987-05-27 |
| NL7900915A (en) | 1979-08-13 |
| DE2904598A1 (en) | 1979-08-16 |
| GB2014592A (en) | 1979-08-30 |
| FR2416903B1 (en) | 1985-01-04 |
| MX150889A (en) | 1984-08-09 |
| NO790364L (en) | 1979-08-10 |
| SE446868B (en) | 1986-10-13 |
| GB2014592B (en) | 1982-08-04 |
| US4315836A (en) | 1982-02-16 |
| JPS54126684A (en) | 1979-10-02 |
| IT1092448B (en) | 1985-07-12 |
| DE2904598C2 (en) | 1989-03-02 |
| JPS6224442B2 (en) | 1987-05-28 |
| NO155776B (en) | 1987-02-16 |
| SE7900999L (en) | 1979-08-10 |
| BR7900790A (en) | 1979-09-04 |
| IT7820096A0 (en) | 1978-02-09 |
| ES477551A1 (en) | 1980-05-16 |
| AT362933B (en) | 1981-06-25 |
| ATA88479A (en) | 1980-11-15 |
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