CA1091643A - Catalysts for the polymerization of olefins - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE:
New components of catalysts for the polymerization of olefins, consist of metal complexes having the general formula MM'TY . n E, wherein M = Mg, Mn or Ca; M' = Ti, V or Zr;
T = oxygen, the anion CO3", or a pair of monovalent groups selected from the group consisting of:

, , and in which R is an alkyl, cycloalkyl, aryl or arylalkyl radical having up to 20 C atoms; Y = one or more atoms or groups selected among halogen atoms, halogen atoms and, contemporane-ously, oxygen atoms, -NR'2, -OR', -SR', ,

Description

` 1091~i43 .

In the canadian pending application Serial No. 249,104, filed March 26, 1976, we disclosed catalys~ sy~tem~ ~or poly-merizing olefin~ and prepared ~rom organometallic compounds of metals belonging to Groups I to III inclu3ive of the (Mendelyeev) Periodic ~able and metal complexe~ having the general formula (I) MmMt X2mY nE
in which M = Mg7 Mn and/or Ca;
m = a number ~rom 0.5 to 2;
M~ 3 Ti, V and/or Zr;
X = Cl, ~r or I;
Y = one or more atoms or group~ of atom~ which are the same or different and selected from atom~ of halogen;
atoms of halogen and, contexporaneo~sly, atom~ o~
O' O
I~
oxygen; -~R2; -OR; SR; -O-C-R; -O-S-R;
O
(in which R is a hydrocarbon radical, ln partioular an alkyl, aryl, cycloalkyl or aralkyl radical), acetylacetonate anion; aoetylacetonate anion a~d, contemporaneously, oXygen atom~; ~aid ~tom~ or group~ being pre~ent in ~uoh an amount a~ to ~ati~y the valence o~ M~;
n = a number ~rom 0.5 m to 20 m; and E 3 ~n eleotron-donor compound ~eleoted ~rom the following classes of compound~:
(a~ e~ter~ o~ organio carboxylic aoid3;
(b) alcohols;
~c) eth2rs;
(d) amine~;
(a) ester~ o~ carbonic acids;
(f) n~trile~;

l_ ~09:16~3 (g) phoaphoramides, ester~ of phosphoric acid, and phosphorus oxy~hloride.
A~ ob~ect of this i~v~ntion i~ to pro~lde new cataly~ts which are highly active in the polym~rization o~ ole~in~ and, more particularly, in the polymeri2ation of ethylene, alpha-olefin~ and mixtures of ethylene with alpha-olefin~ and/or with multi-olefins, including diolefin~ and which are bases on metal complexes different from tho~e of ~ormula (I) a~d which ha~e the following general formula (II): MM'TY.nE
in which M - Mg, Mn or Ca;
Mi= ~i, V or Zr;
1 = oxygen, the anion C03", or a pair of monovalent groups selected from ~ OH, ~-OH, ~-OR, d ~-OR, ~-OH ~-Cl s~OR ~Cl in which R i8 an alkyl, cycloalkyl, aryl or alkylaryl radical containing from 1 to 20 carbon atoms;
Y = one or more atoms or group~, aliks or different, and selected from halogen atoms, halogen atom~ and, contemporaneously, oxygen atoms, -~R'2~ -OR'?
O O

-SRI, -O-C-RI, -O-S-RI, (R' being a hydrocarbon Il .

raAical, in particular an alkyl, aryl~ c~clo~lkyl or aralkyl radical); acetyla~etonate anion;
acetylacetonate a~ion and, GontemporaneouslyJ
oxygen atoms; such atom~ or group~ being pre~ent in ~uch number a~ to ~atisfy the valenc~ of M';
n _ a number from 0.5 to 20; and E = an electron-donor compound selected ~rom Ogl643 (a) esters o~ organic carboxylic acids;
(b) alcohols;
(c) ethers;
(d) amines;
(e) esters of carbonic acid;
(~) nitriles; and (g) esters of phosphoric and phosphorous acid and phosphorous oxychloride.
~he presentl~ preferred electron-donor compounds E are alkyl ester~ of aliphatic or aromatic acids in which the alkyl radical contains from 1 to 8 carbon atoms, inclu~ive; ethers ROR' in which R and R', which may be the ~ame or different, repre~ent alk~l radicals containing from 1 to 8 carbon~atom~, inclusive, aryl radicals, aromatic nitriles, or alkyl ester~ of phosphoric or pho~phorous acid in which the alkyl contain~ from 1 to 8 carbon atoms, inclusive.
lypical preferred electron-donor~ include: ethyl aoetate, ethyl benzoate, methanol, ethanol, ethyl ether, tetrahydrofuran, pyridine, ethylene carbonate, ben20nitrile, and pho~phorus oxyohloride.
~ he complexe~ of the invention are prepared by reaoting equimolar amounts of compounds M~ and MIY, in which M, ~, M~ and Y have the sàme significance as in ~ormula tII~, a~ a tempera-ture from room temperature to 150C, inclu~ive, in solvent~ E
which are electron-donor compounds of one of the olas~es (a) to ~g) disclo~ed hereinabove. The complexes found in the reaction can be isolated from the reaction mass by crystalliza-tion from the ~olvent E, by ev~poration Gf the solvent, or by precipitation with a solvent in which the eomplexe~ are in~oluble.
If either compound M~ or compound M'Y is, or i~ both are, poorly ~oluble in solvent E, the reaction of those compound~

, ~109~6;43 can be carried out in a~ alternative electron-don~r ~olvent E', in which at least one of those compound~ is soluble, to obtain a complex MM'IY.nE' which, after i~olation from the ~olvent E', c~n be treated, at a temperature from room temperature to 150C, in¢lu~ive, with an exce~ o~ a ~olvent E, which treat~en-t shift~
~olvent E'. Such shifting o~ a solvent E' can al30 be accom-plished by adding an excess of a ~olvent E to the ~olution o~
the complex MM'~Y.nE' in solvent El.
. According to another embodiment of the invention, components whi¢h yield final catalysts of good actlvity in the polymerization of olefin~ can be obtained b~ reaction of the compounds M~ and M'Y in a molar ratio other than 1:1. In this embodiment, the reaction product isolated by crystallization ~ro~ the aolvent, by evaporation of the solvent, or b~ precipi~a-tion of the reactio~ product with a suitable solvent, i~ a mixture which consists of the desired complex (or of such a complex comprising a solvent E') and of a complex consi~ting of oompound M~, or compound M'Y, and solvent E or sol~ent E'.
Compounds of Ti, V or Zr which can be used to prepare the metal complex (which i9 component (A) of the present catalyst~) include: ~iC13, TiC14, ~iOC12, ~iBr4, ~iI4, 3 3~ C12~i(a4Hg)2- ~i(OC4Hg)4, C13~iN(C6~5)?, al3~iOCOC6H5, 013~iSC6H5, C13~i-acetylacetonate, C13~iOSO~C6H5, C13~iO06H5, VC13, VC14, VOC13, C12VOC4Hg, V(Oa4~9~3, alV(acetyl~cetonate)2, Cl~VOCOC6H5, VO-acetylacetonate, ZrO14 and 13 r 4Hg Some examples of metal complexes comprised in ge~eral formula (II3 are the following:
Mg~iOC14.2CH3COOC2H5 Mg~iOC13.4CH3COOC2H5 Mg~iOC13 . 5C2H50H
Mg~iC150H . 2C~3C00(~2H5 _ 4 _ gTi( C2H5)2( CH3)C13 CH3 2H5 Mg~iCl4(0C2Hs)2 CH3COOC2H5 Mg~iOCl3-2tn-C3H7)20 Mg~iOCl3.5POCl~.
Organometallic compounds of the Groups I to III metal~
which are particularly ~uitable for u~e as component (B) of the present catalysts include: Al(C2~5)3, Al(C2E5)2Cl, Alti-C4H9)3. Al(i-C4Hg)2Cl~ A12(C2H5)3Cl~;, Al(C2H5)2H, Al(i-c4H9)2H~ Al(C2H5)2~r' (C2H5)2Al ( 2 5 2 o (C2H5)2Al-I-Al(c2H5)27 (C2H5)2Al-O-ll-OAl(c2H5)2 ~l~l(i-C4Hg)4, ~ C4Hg, and Zn(C4H9)2-~ he molar ratio between the organometallic compound and the complex containing ~i, V or Zr i~ not critical, ~or the (co)polymeri~ation of ethylene and of alpha-ol~fins it ic preferably comprised between 10 and 100, ~ he catalysts according to this invention are utilized in the (co)polymerization of olefins, in paxticular ethylene, propylene, butene-1 and ~-methylpente~e-1, according to conventional techniques, i,e. 9 în a liquid phase, in the presence or in the absence of an inert solvent, or in a gas phase. An aliphatio or cycloallphatic hydrocarbon such a~, for example, hexane, heptane9 cyclohexane, may be used as the inert ~olvent.
~ he (co)polymerization temperature may range from ~80 to 2G0C, preferably from 50~ to 1 ooa, operating at atmospheric pressure or under increased pressure During (co)polymeri~ation, the molecular weight of the polymer or oopolymer can be regulated according to known methods, by operating, for iRstanoe, in the presence of alkyl halides, orgsnometallio compounds of Zn or Cd, or hydrogcn.

)9~i43 `
The ~ollowing examples are given to illu~trate the invention9 and are-not intended to be limiting.
EXAMP~E 1

2.02 g (50.1 m. mole~) o~ MgO were suspended, in a nitrogen atmo~phere, in 160 ml of anhydrou~ ethyl acetate. 5,57 ml (50.1 m. moles) of TiC14 were added dropwiqe and the whole was reacted ~or 3 hour~ at 40C; a yellow solution waQ obtained.
~ he reaction product wa~q isolated by evaporation of the sol~ent and the resulti~g yellow powder exhibited, on analy3is, a compo~ition corre ponding to ~ormula Mg~iOC14.2CH3COOC2H5. ~he result obtained by polymerizing ethylene in contact with a final catalyst prepared from said complex and a component (B) i3 reported in the ~ollowing Table, (~est I).
~XAMPLE 2 1.75 g (11.3 m. m~les) of ~iC13HR were dissolved, in a nitrogen atmo~phere, in 250 ml of anhydrous ethyl aoetate at 60C. 0.46 g (11.3 m. mole~) of MgO were added to the solution.
~ he reaction was allowed to proceed at 60C for 20 hours. A black ~qolution was obtai~ed and evaporated to dr~ne~qs.
On analysis the re~qulting black powder had a compoqi~
tion of the formula MgTiOC13.4CH3COOC2H5. ~he re~ult~ obtained by polymeriæing ethylene in contact with a ~inal catalgst prepared ~rom said complex and a component (B) are reported ln the ~able (Te~t II).

1.85 g (12 m. moles) o~ liC13 were di~sol~ed, in a nitrogen atmosphere, in 180 ml of anhydrous ethyl alcohol at 60C. Subsequently, 0.484 g (12 m. mole~) of MgO were added to the solution. The reaction was allowed to proce~d at 60C for 8 hours. A brown solution ¢omprising a brown powder in ~u~pen-sion was obtai~ed~ The suspen~ion wa~ evaporated to dryneRs 10~1643 and, on analy9i8, the brown powder was found to have a compo~i-tion corresponding to the for~ula Mg~iOC13.5C2~50H.
~ eflt III of the ~able shows the re~ults obtained by polymerizing ethylene in contact with a catalyst prepared from the complex.

1.88 g (24.4 m~ moles) of HO-Mg-Cl were partially di~ol~ed, in a nitrogen atmo~phere, in 160 ml of anhydrous ethyl a¢etate at 60C. 2.68 ~1 ~2404 m. mole~) of ~iC14 were added dropwi~e ~nd the whole was reacted for 3 hour~ and 30 minutes. A yellow solution was obtained and evaporated to dry-ness. ~he yellow powder thus obtained wa~ found, on analysis, to correspond to for~ula Mg~iC150H.2CH3COOC2H5, ~ he results o~ polymerizing ethylene in oontact with a cataly~t prepared ~rom ~aid oomplex a~ one component thereof are reported in the ~able (~est IV).

1.68 g (14.7 m. moles~ o~ ~g(OC2H5)2 were ~uspended~
in a nitrogen atmoæphere, in 100 ml of anhydrous ethyl acetate at 60C.
A 301ution of 2.73 g (14.7 m. moles) of C13~iOCH3 in 50 ml of ethyl acetate was added dropwise to the ~uspen~ion.
~he whole wa~ reacted at 60C ~or 4 hour~, thu3 obtain1ng a colorle~ solution.
~ he reaction product was isolated by evaporation of the solvent, and the resulting white powder revealed, on analysi~t a composition corresponding to ~ormula MgTi(OC2H5)2(0CH3)C13 .CH3COOC2H5.
The ethylene polymerization test using that complex as catalyst component i3 reported in the ~able (~e3t V).
AMP~E 6

3.6 g (33 m. moles) of Mg(OC2H5)2 were ~uspended, in a '`, ` ~Ogl643 nitrogen atmo~phere, in 200 ml of anhydrous ethyl acetate at 60C, and 3.6 ml (33 m. moles) of ~iC14 were added dropwi~e thereto. After reaction at 60C fvr 4 hour~, a light brown solution was obtained.
- ~he reaction product wa~ isolated by e~aporation of the solvent, and the re~ulting brown powder exhibited, on analy~is, a composition corre~ponding to formula Mg~iC14(0C2H5)2.
.CH3COOC2H5. The result~ of polymerizing ethylene using such complex as cataly~t componen~ is reported in th~ ~able (Test VI).
EXAMP~E 7 0.5 g o~ complex Mg~iOCl~.4CH3COOC2H5 (prepared accord-ing to Example 2) was added to 20 ml of anhydrou~ dipropyl ethex; the whole was reacted ~t 60C for 8 hour~ and a black ~olution wa~ thus obtained.
~he shift reaction was terminated by evaporation of CH3COOC2H5, the resulting product being then isolated through evaporation of dipropyl etherO
A black powder was ~o obtained tha~ on analysis, revealed a compo6ition corre~ponding to formula Mg~iOC13.
.2(n-C3H7)20. The ethylene polymerization test carxied out by using ~uch complex as oataly~t oomponent i9 reported in the ~able (~est VII).
EXAMP~E 8 1.2 g of oomplex MgTiO013.4CH3000C2H5 (prepared accord-ln~ to Example 2) were added to 20 ml af pho~phorus oxy¢hloride;
the whole was reacted at 60C ~or 8 hours, thu~ obtaining a green solution.
The ~hift reaction was terminated by evaporation o~
CH3COOC2H5, and the produc* wa~ successively isolated by evaporation of pho6phorus oxychloride. A light bxown powder wa~
obtained that, on analysis, revealed a composition oorre6ponding to formula Mg~iOC13.5POC13.

6~1L3 ~he ethylene polymerlzation test conducted by using such complex as catalytic component is reported in the Table (Test VIII).
Eth~lene Pol~merization ~ A suitable amount of one of the catalytic complexes prepared in the foregoing examples and 1000 ml of deaerated anhydrous desulphurized n-heptane were introduced, along with 1 or 2 ml of Al(i-C4~9)3, in a nitrogen atmosphere~ into a stainles~ ~teel autoclave, having a 3-liter capacity, equipped with an anchor stirrer and heated to the de~ired temper~ture.
Hydrogen and ethylene at prefixed partial pre~ures were added thereto, and the total pres~ure was kept con8tant throughout the polymerization by continuou~ feeding of ethylene.
After a 4-hour reaction, the polymerization was ~topped, the reaction mas~ was filtered, and the resulting polymer was dried. ~he polymer inherent viscosity1~in was determined in tetrahydronaphthalene at 135C, employing concentrations of 0.25 g of polymer in 100 ml of solvent; the yield i8 expressed in grams of polymer obtained per gram Of ?i.
~he operating condition~ and ~he result~ of the di~ferent tests are reported in the following table.

lQ9~43 . . . _ . . .
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Claims (15)

The embodiments of the invention in which an exclusive property or privilege as claimed are defined as follows:

1. Components for catalysts useful in the polymeriza-tion of olefins, said components having the general formula MM'TY . nE
in which M = Mg, Mn or Ca;
M' = Ti, V or Zr;
T = oxygen, the anion CO3", or a pair of mono-valent groups selected from the group consisting of , , , in which groups R is an alkyl cycloalkyl, aryl or alkylaryl radical containing from 1 to 20 carbon atoms;
Y = one or more groups, the same or different, and selected from the group consisting of halogen atoms, halogen atoms and, contemporaneously, oxygen atoms -NR'2, - OR', -SR', , (R' being a hydrocarbon radical); acetylacetonate anion; acetylacetonate anion and, contemporaneously, oxygen atoms; said atoms or groups being present in a number to satisfy the valence of the metal M';
n = a number from 0.5 to 20, inclusive; and E = an electron donor compound selected from the group consisting of (a) esters of organic carboxylic acids;

(b) alcohols;
(c) ethers;
(d) amines;
(e) esters of carbonic acid;
(f) nitriles; and (g) esters of phosphoric or phosphorous acid and phosphorous oxychloride.

2. Catalyst-forming components according to Claim 1 in which, in the groups Y, R' is an alkyl, aryl, cycloalkyl or aralkyl radical.

3. A catalytic component according to Claim 1, having the formula MgTiOCl4.2CH3COOC2H5.

4. A catalytic component according to Claim 1, having the formula MgTiOCl3.4CH3COOC2H5.

5. A catalytic component according to Claim 1, having the formula MgTiOCl3.5C2H5OH.

6. A catalytic component according to Claim 1, having the formula MgTiCl5OH.2CH3COOC2H5.

7. A catalytic component according to Claim 1, having the formula MgTi[OC2H5)2(OCH3)Cl3.CH3COOC2H5.

8. A catalytic component according to Claim 1, having the formula MgTiCl4(OC2H5)2.CH3COOC2H5.

9. A catalytic component according to Claim 1, having the formula MgTiOCl3.2(n-C3H7)2O.

10. A catalytic component according to Claim 1, having the formula MgTiOCl3.5POCl3.

11. Process for preparing the catalyst components according to claim 1, characterized in that a compound MT is reacted, at a temperature from room temperature to 150°C, with a compound of M'Y in an electron-donor solvent E in which both of the compounds MT and M'Y are soluble, and the resulting complex is isolated from said solvent by crystallization from the same solvent, by evaporation of said solvent, or by precipi-tation with a solvent in which the complex formed in the reaction is insoluble, the thus obtained complex being optionally treated with an excess of a second solvent E at a temperature ranging from room temperature to 150°C, before or after the isolation of said complex, for the formation of a second complex comprising the second solvent E as the desired electron-donor compound, and said second complex in turn is isolated from said second solvent by crystallization from the same solvent, by evaporation of said second solvent, or by precipitation with a solvent in which the second complex is insoluble.

12. The process of claim 11, in which the compounds MT and M'Y are used in a MT/M'Y molar ratio of 1:1.

13. The process of claim 11, in which the compounds MT and M'Y are used in a MT/M'Y molar ratio different from 1:1.

14. Catalysts for the (co)polymerization of olefins, prepared by mixing (A) a catalyst-forming component having the general formula MM'TY.nE

wherein M = Mg, Mn or Ca;
M' = Ti, V or Zr;

T = oxygen, the anion CO3", or a pair of monovalent groups selected from the group consisting of , , and in which R is an alkyl, cycloalkyl, aryl or alkylaryl having from 1 to 20 carbon atoms;
Y = one or more atoms or groups, the same or different, and selected from the group con-sisting of halogen atoms, halogen atoms and, contemporaneously, oxygen atoms, -NR'2, -OR', SR', , (R = being a hydrocarbon radical) acetylacetonate anion; acetylacetonate anion and contemporaneously, oxygen atoms; said atoms or groups being present in such number as to satisfy the valency of M';
n = a number from 0.5 to 20, inclusive, and E = an electron-donor compound selected from the group consisting of (a) esters of organic carboxylic acids (b) alcohols;
(c) ethers;
(d) amines;
(e) esters of carbonic acid;
(f) nitriles;
(g) esters of phosphoric and phosphorous acid and phosphorus oxychloride;
with (B) a catalyst-forming-component which is an organo-metallic compound of a metal belonging to Groups I - III, inclusive, of the Mendelyeev Periodic Table.

15. Process for polymerizing ethylene, alpha-olefins, or mixtures of ethylene with alpha-olefins and/or with multi-olefins, characterized in that the monomer or mixture of monomers is polymerized in contact with a catalyst according to claim 14.