CA1062693A - Catalyst and process for the polymerization of alpha-olefins - Google Patents
Catalyst and process for the polymerization of alpha-olefinsInfo
- Publication number
- CA1062693A CA1062693A CA217,918A CA217918A CA1062693A CA 1062693 A CA1062693 A CA 1062693A CA 217918 A CA217918 A CA 217918A CA 1062693 A CA1062693 A CA 1062693A
- Authority
- CA
- Canada
- Prior art keywords
- additive
- compound
- cyclic
- dialkylaluminum chloride
- sterically hindered
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000000034 method Methods 0.000 title claims abstract description 15
- 239000003054 catalyst Substances 0.000 title claims abstract description 13
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 9
- 239000004711 α-olefin Substances 0.000 title claims abstract description 6
- -1 polypropylene Polymers 0.000 claims abstract description 25
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 13
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 13
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 13
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 9
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000005977 Ethylene Substances 0.000 claims abstract description 4
- 239000002685 polymerization catalyst Substances 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 27
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 20
- 239000000654 additive Substances 0.000 claims description 17
- 230000000996 additive effect Effects 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 150000001412 amines Chemical class 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 8
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 7
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical class Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- BWZVCCNYKMEVEX-UHFFFAOYSA-N 2,4,6-Trimethylpyridine Chemical group CC1=CC(C)=NC(C)=C1 BWZVCCNYKMEVEX-UHFFFAOYSA-N 0.000 claims 4
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-Me3C6H3 Natural products CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims 2
- LIDGFHXPUOJZMK-UHFFFAOYSA-N 2,6-dimethyl-1-oxidopyridin-1-ium Chemical group CC1=CC=CC(C)=[N+]1[O-] LIDGFHXPUOJZMK-UHFFFAOYSA-N 0.000 claims 2
- GFYHSKONPJXCDE-UHFFFAOYSA-N sym-collidine Natural products CC1=CN=C(C)C(C)=C1 GFYHSKONPJXCDE-UHFFFAOYSA-N 0.000 claims 2
- XTTGYFREQJCEML-UHFFFAOYSA-N tributyl phosphite Chemical group CCCCOP(OCCCC)OCCCC XTTGYFREQJCEML-UHFFFAOYSA-N 0.000 claims 1
- 229920001155 polypropylene Polymers 0.000 abstract description 5
- 239000004743 Polypropylene Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 2
- 229910052719 titanium Inorganic materials 0.000 abstract description 2
- 239000010936 titanium Substances 0.000 abstract description 2
- 229920006125 amorphous polymer Polymers 0.000 abstract 1
- 238000012662 bulk polymerization Methods 0.000 abstract 1
- 239000000178 monomer Substances 0.000 abstract 1
- 229920005606 polypropylene copolymer Polymers 0.000 abstract 1
- 239000002002 slurry Substances 0.000 abstract 1
- 239000012808 vapor phase Substances 0.000 abstract 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000003568 thioethers Chemical class 0.000 description 3
- 101100010303 Drosophila melanogaster PolG1 gene Proteins 0.000 description 2
- 101150078890 POLG gene Proteins 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- CXENHBSYCFFKJS-OXYODPPFSA-N (Z,E)-alpha-farnesene Chemical compound CC(C)=CCC\C(C)=C\C\C=C(\C)C=C CXENHBSYCFFKJS-OXYODPPFSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- GVGLGOZIDCSQPN-PVHGPHFFSA-N Heroin Chemical compound O([C@H]1[C@H](C=C[C@H]23)OC(C)=O)C4=C5[C@@]12CCN(C)[C@@H]3CC5=CC=C4OC(C)=O GVGLGOZIDCSQPN-PVHGPHFFSA-N 0.000 description 1
- 101710199392 TATA-box-binding protein 1 Proteins 0.000 description 1
- 229910010061 TiC13 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 238000010960 commercial process Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 229960002069 diamorphine Drugs 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002338 polyhydroxyethylmethacrylate Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002195 soluble material Substances 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
Classifications
-
- 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
CATALYST AND PROCESS FOR THE POLYMERIZATION OF ALPHA-OLEFINS
ABSTRACT OF THE DISCLOSURE
Novel catalysts and processes are disclosed for producing highly crystalline polypropylene and highly crystalline copolymers of propylene with ethylene or propylene with other alpha-olefins. Such catalysts reduce the amount of low-molecular-weight and amorphous polymers formed without serious effect on the polymerization yield. These novel catalysts and processes involve treating a aluminum alkyl compound with hydrogen sulfide and using the product thereof in conjunction with a titanium halide and, optionally, a sterically hindered, cyclic, tertiary amine a sterically hindered, cyclic amine oxide or a trihydrocarbylphosphite as a polymerization catalyst. Such catalysts are useful in slurry poly-merization, bulk polymerization and techniques in which polymerization is accomplished utilizing monomer substantially in the vapor phase.
ABSTRACT OF THE DISCLOSURE
Novel catalysts and processes are disclosed for producing highly crystalline polypropylene and highly crystalline copolymers of propylene with ethylene or propylene with other alpha-olefins. Such catalysts reduce the amount of low-molecular-weight and amorphous polymers formed without serious effect on the polymerization yield. These novel catalysts and processes involve treating a aluminum alkyl compound with hydrogen sulfide and using the product thereof in conjunction with a titanium halide and, optionally, a sterically hindered, cyclic, tertiary amine a sterically hindered, cyclic amine oxide or a trihydrocarbylphosphite as a polymerization catalyst. Such catalysts are useful in slurry poly-merization, bulk polymerization and techniques in which polymerization is accomplished utilizing monomer substantially in the vapor phase.
Description
S ¦ SU~MARY OF l~E INVENT~ON
¦ Th18 ~nv nt~on relat~ to ~ovel cataly~ts and proco~eo for the ¦pol~ erlz-tlon of propylene, lt~ ~ixturee vlth thylene or ~lxture- of ¦prop~l-ne ant other alpha-oleflnJ to produce normally olld, hlghly ¦cr~t-lllne pol~ er-, nd ~ore peclflcally, to a no~el cataly-tJ and ¦proce--e- for poly2erlz-tlon of propylene, lt- d ~tur-- with ethylene or lt- lxture~ vlth other C4 to C8 lpha-ol-fln- to produc~ norm lly olld, highly cry-t-llln~ pol~ rlc protuce- vhereln coproduc-d lo~-~ol-cul-r-v lght ant a orphou polgmer- re ub-tantl-lly retuc-t nd polyu rls-tlon ylelt- r- not ~ubst-nti 11y affectet 2s In ceord nc- vlth th- ln t-nt lnv ntlon, propylene, lt~ slxture-w~th eth~l-De or lt~ tur-~ ~ith other C4 to C8 alph--ol-fin- re pol y riz-d to nor all~ ollt, hlghl~ cry-t-lline pol~mer~ u-lng alurry, bul~ or vapor t-chnlqu- ~t ono~er pre--ures of bout tw sphoric 30 pre~-ure or bove nd wterat- polymerlzatlon temperature- ~lth a catal~-t ~Y t c ~p l ln~ yl lu l~u co pound p-rtl lly r--ct-d ~Ith ¦ ~
,:
~ ~ .
' ~`:
,:. : .: . : .: : . : :.: :: ,::: ,: ,. : . : - . .- : :: : : :: :: . . :. , :::, - :
: , :: ::: - ~.:: ~ - ~ - - :
,:,,:, - : : :.,, , . .:.
:~- . . :
hydrogen sulfide, (b) a chloride of titanium, and optionally, a sterically hindered, cyclic, tertiary amine, a sterically hindered, cyclic amine oxide or a trihydrocarbylphosphite. The polymeric products produced using the above described catalysts can contain amounts of low-molecular-weight and amorphous components, as measured by room temperature extraction using n-hexane, as low as about one to two percent of the total polymer yield without seriously sacrificing polymer yield.
Thus the present invention provides a polymerization catalyst composition which comprises:
(a) an alkylaluminum compound selected from the group consisting of a trialkyl aluminum, a mixture of a trialkyl aluminum and an alkylaluminum dichloride or dibromide, a mixture of a trialkyl aluminum and a dialkylaluminum chloride or bromide and a dialkylaluminum chloride or bromide;
(b) an effective amount up to about 10 mol perccnt of hydrogen sulfide based upon the amount of alkylaluminum compound present;
(c) an activated titanium trichloride; and (d) an effective amount of an additive which is selected from the group consisting of trihydrocarbylphosphites, sterically ,i . , hindered, lower alkyl substituted, cyclic,tertiary amines and sterically hindered, lower alkyl substituted, cyclic, amine oxides;
said amounts effective to result in a substantial reduction of alkane solubles while not seriously affecting the total yield of polymer.
In a further aspect the present invention provides a ~ process for the polymerization of propylene or a mixture of -;~ 30 propylene and ethylene or propylene and another C4 to C
¦ Th18 ~nv nt~on relat~ to ~ovel cataly~ts and proco~eo for the ¦pol~ erlz-tlon of propylene, lt~ ~ixturee vlth thylene or ~lxture- of ¦prop~l-ne ant other alpha-oleflnJ to produce normally olld, hlghly ¦cr~t-lllne pol~ er-, nd ~ore peclflcally, to a no~el cataly-tJ and ¦proce--e- for poly2erlz-tlon of propylene, lt- d ~tur-- with ethylene or lt- lxture~ vlth other C4 to C8 lpha-ol-fln- to produc~ norm lly olld, highly cry-t-llln~ pol~ rlc protuce- vhereln coproduc-d lo~-~ol-cul-r-v lght ant a orphou polgmer- re ub-tantl-lly retuc-t nd polyu rls-tlon ylelt- r- not ~ubst-nti 11y affectet 2s In ceord nc- vlth th- ln t-nt lnv ntlon, propylene, lt~ slxture-w~th eth~l-De or lt~ tur-~ ~ith other C4 to C8 alph--ol-fin- re pol y riz-d to nor all~ ollt, hlghl~ cry-t-lline pol~mer~ u-lng alurry, bul~ or vapor t-chnlqu- ~t ono~er pre--ures of bout tw sphoric 30 pre~-ure or bove nd wterat- polymerlzatlon temperature- ~lth a catal~-t ~Y t c ~p l ln~ yl lu l~u co pound p-rtl lly r--ct-d ~Ith ¦ ~
,:
~ ~ .
' ~`:
,:. : .: . : .: : . : :.: :: ,::: ,: ,. : . : - . .- : :: : : :: :: . . :. , :::, - :
: , :: ::: - ~.:: ~ - ~ - - :
,:,,:, - : : :.,, , . .:.
:~- . . :
hydrogen sulfide, (b) a chloride of titanium, and optionally, a sterically hindered, cyclic, tertiary amine, a sterically hindered, cyclic amine oxide or a trihydrocarbylphosphite. The polymeric products produced using the above described catalysts can contain amounts of low-molecular-weight and amorphous components, as measured by room temperature extraction using n-hexane, as low as about one to two percent of the total polymer yield without seriously sacrificing polymer yield.
Thus the present invention provides a polymerization catalyst composition which comprises:
(a) an alkylaluminum compound selected from the group consisting of a trialkyl aluminum, a mixture of a trialkyl aluminum and an alkylaluminum dichloride or dibromide, a mixture of a trialkyl aluminum and a dialkylaluminum chloride or bromide and a dialkylaluminum chloride or bromide;
(b) an effective amount up to about 10 mol perccnt of hydrogen sulfide based upon the amount of alkylaluminum compound present;
(c) an activated titanium trichloride; and (d) an effective amount of an additive which is selected from the group consisting of trihydrocarbylphosphites, sterically ,i . , hindered, lower alkyl substituted, cyclic,tertiary amines and sterically hindered, lower alkyl substituted, cyclic, amine oxides;
said amounts effective to result in a substantial reduction of alkane solubles while not seriously affecting the total yield of polymer.
In a further aspect the present invention provides a ~ process for the polymerization of propylene or a mixture of -;~ 30 propylene and ethylene or propylene and another C4 to C
- 2 -, .
~(~6Z693 alpha-olefin to form a highly crystalline polymeric substance, :~ :
said process in~olving contacting under polymerizing conditions -~
said propylene or said mixture with a catalyst comprising~
(a) an alkylaluminum compound selected from the group :
consisting of a trialkyl aluminum, a mixture of a trialkyl aluminum and an alkylaluminum dichloride or dibromide, a mixture ~.
of a trialkyl aluminum and a dialkylaluminum chloride or bromide . .
and a dialkylaluminum chloride or bromide, said alkylaluminum ~ `
compound having been treated with an effective amount, up to j:~
10 about 10 mol percent based on the amount of said alkylaluminum . .
compound, of hydrogen sulfide; ~.
(b1 an activated titanium trichloride; and (c) an effective amount of an additive which is selected ~ ;
from the group consisting of trihydrocarbylphosphites, sterically :
hindered, lower alkyl substituted, cyclic, tertiary amines, and sterically hindered, lower alkyl substituted, cyclic, amine oxides;
said amounts effective to result in a substantial reduction of :
. .
alkane solubles while not seriously affecting the total yield :~ 20 of said polymeric substance.l BACKGROUND OF THE INVENTION
Polymers of alpha-olefins prepared in the presence of -~:: ionic catalyst systems, as for example polypropylene prepared using a catalyst comprised of diethylaluminum chloride and titanium trichloride, contain greater or lesser amounts of low-molecular-weight and amorphous components which, when taken alone, are viscous oils or soft, tacky solids. The presence of these alkane-soluble materials in the polymers lead to difficulties during the fabrication of products therefrom and to inferior physical properties in the finished items, and hence are almost ' ,~.,. ~ , ., . , ,j. . .. . ,,, ,, . . ~ , lO~Z693 always removed in commercial processes for the production of polypropylene.
Production of these components leads to an economic disability for the polymerization process as they have little usefulness and extra process steps are required to remove them from the commercial product.
In the past a number of materials and combinations thereof have been reported in the patent literature as useful additives to transition metal compound - alkylalu~inum compound catalysts to reduce the alkane-soluble fraction produced during the polymerization process. Among these additives are amines, amine oxides, ethers, organic phosphites, and mixtures of organotin sulfides and amines, amine oxides or organic phosphites. The mixtures containin~ organotin sulfides have been described as showing a greater effect on "solubles" reduction than either component of the mixture alone. However, such mixtures have a number of disadvantages including the cost of organotin sulfides.
ln ddltlon, lt h - be-n dl-clo-ed ln U.S, Patent No. 3,159,61~
th-t reactSng tho tr n-ltSon t-l component Of theso typo- Of cataly-t-~ith hydrogen ulflt- or 8elenSd- it- in protucing more highly crg-t-llln polymer.
Now lt ba- been found thst by psrtlslly reacting hydrogen ulflde ~ith the al~yl lum$num compound psrt of auch catalyet8 and, optlonally, ddlng ~terically hinderod, aromatlc, tortlary smine, ~terlcally hlndered, cycllc amlne oside or a trlhydrocarbylpho~phlte, cstaly-t~ ar formed whlch, when used for propylene polymerlzstlon, re~ult in a ~ub~t ntlal reductlon of low-~olecular-~eight and amorphous component~
~hilo t ~erloucly affectlng th- total yleld of polymer. In addltlon~
th- lnstant c-talyet- can re-ult ln an l~provement in ~olventle8s poly-morlzatlon proce~e~ ~heroin tho olefln i- polymerlzed tirectly from th-vapor or llquid phase. The cataly~t- dlsclosed herein may sl~o be u~ea for alpha-ol-fln poly~erlz-tlon- whereln supported transltlon metal compound component~ re omploy-d.
~ : ' '
~(~6Z693 alpha-olefin to form a highly crystalline polymeric substance, :~ :
said process in~olving contacting under polymerizing conditions -~
said propylene or said mixture with a catalyst comprising~
(a) an alkylaluminum compound selected from the group :
consisting of a trialkyl aluminum, a mixture of a trialkyl aluminum and an alkylaluminum dichloride or dibromide, a mixture ~.
of a trialkyl aluminum and a dialkylaluminum chloride or bromide . .
and a dialkylaluminum chloride or bromide, said alkylaluminum ~ `
compound having been treated with an effective amount, up to j:~
10 about 10 mol percent based on the amount of said alkylaluminum . .
compound, of hydrogen sulfide; ~.
(b1 an activated titanium trichloride; and (c) an effective amount of an additive which is selected ~ ;
from the group consisting of trihydrocarbylphosphites, sterically :
hindered, lower alkyl substituted, cyclic, tertiary amines, and sterically hindered, lower alkyl substituted, cyclic, amine oxides;
said amounts effective to result in a substantial reduction of :
. .
alkane solubles while not seriously affecting the total yield :~ 20 of said polymeric substance.l BACKGROUND OF THE INVENTION
Polymers of alpha-olefins prepared in the presence of -~:: ionic catalyst systems, as for example polypropylene prepared using a catalyst comprised of diethylaluminum chloride and titanium trichloride, contain greater or lesser amounts of low-molecular-weight and amorphous components which, when taken alone, are viscous oils or soft, tacky solids. The presence of these alkane-soluble materials in the polymers lead to difficulties during the fabrication of products therefrom and to inferior physical properties in the finished items, and hence are almost ' ,~.,. ~ , ., . , ,j. . .. . ,,, ,, . . ~ , lO~Z693 always removed in commercial processes for the production of polypropylene.
Production of these components leads to an economic disability for the polymerization process as they have little usefulness and extra process steps are required to remove them from the commercial product.
In the past a number of materials and combinations thereof have been reported in the patent literature as useful additives to transition metal compound - alkylalu~inum compound catalysts to reduce the alkane-soluble fraction produced during the polymerization process. Among these additives are amines, amine oxides, ethers, organic phosphites, and mixtures of organotin sulfides and amines, amine oxides or organic phosphites. The mixtures containin~ organotin sulfides have been described as showing a greater effect on "solubles" reduction than either component of the mixture alone. However, such mixtures have a number of disadvantages including the cost of organotin sulfides.
ln ddltlon, lt h - be-n dl-clo-ed ln U.S, Patent No. 3,159,61~
th-t reactSng tho tr n-ltSon t-l component Of theso typo- Of cataly-t-~ith hydrogen ulflt- or 8elenSd- it- in protucing more highly crg-t-llln polymer.
Now lt ba- been found thst by psrtlslly reacting hydrogen ulflde ~ith the al~yl lum$num compound psrt of auch catalyet8 and, optlonally, ddlng ~terically hinderod, aromatlc, tortlary smine, ~terlcally hlndered, cycllc amlne oside or a trlhydrocarbylpho~phlte, cstaly-t~ ar formed whlch, when used for propylene polymerlzstlon, re~ult in a ~ub~t ntlal reductlon of low-~olecular-~eight and amorphous component~
~hilo t ~erloucly affectlng th- total yleld of polymer. In addltlon~
th- lnstant c-talyet- can re-ult ln an l~provement in ~olventle8s poly-morlzatlon proce~e~ ~heroin tho olefln i- polymerlzed tirectly from th-vapor or llquid phase. The cataly~t- dlsclosed herein may sl~o be u~ea for alpha-ol-fln poly~erlz-tlon- whereln supported transltlon metal compound component~ re omploy-d.
~ : ' '
3 ( a ) -~, ~06:~693 ~
A~ hown ln T~ble I ~elo~ the n-he~ano soluble fractlon c-n be reduced ln a ~lurry polymeri~atlon when the al ~num alkyl cospound component of the catalyst lo flr~t partially reacted with hydrogen ~ulflde '~ ;
T~BLE I -~
Comparloon of Crystalline Polypropylene Yield ant Soluble- for Dlffercnt ~ount~
of HydroRen Sulfid-n-He~ane lG Mol Ratlo Solublec ~ /?Y ~t2AlCl/TlC13/H2S~ Crvot-lline Yi ld, g CPercent) D 1.50/1.U/o25,1 4.6 26.0 3.8 25 7 3.8 1 0/1 0/0.010 24.6 2.ô
1 0/1 0/0.030 23 6 2.7 3 0/1 0/0 010 29.7 3 3 3.0/1 0/0 030 25 6 3 4 20 ~ Lt repre~ent~ the ethyl r dlcal - 3(b) ~
~ . .. . :............... :
Il 106Z693 The r~-ult- ln T-bl~ I lndlc-t- th~t the r~ ctlon of 8m-11 portlon of the organoaluulouu alu~lnu~ co pound ~lth hgdrogen ~ulfld- prlor to I co~bln~tion ~ith the tltanlu~ trlehlorlde r -ult~ ln loN~r "-olubl--"
¦ ~lthout -rlou- ff-et on the ~l-ld.
5 ¦ The t ta et forth ln T bl~ II and III b~low ho~ the ddltlon l ¦ lo~er n8 of "-olubl -" in lurry typ propyl-n poly~risation ~h n o ~; ¦ addltiv uch a t~rie-lly hlnd-red c~elle t rtlarg ain~ or trlh~droe-rb~lpho~phlta 1~ dd-d to ~2S-tr -t-t organo lu~lnw~ co_ ¦ pound-tit nlu~ trlchlorid co bln tlon-.
- lo ¦ T~BLe II
¦Co~p-rl~on of Cr~-t-lline Polypropyl na Yl~ld Iand Solubl- for Dlff-r nt A ouot-¦ _ of~ lt- Adtltlvea n-~ ~n-Mol ~tlo Solubl-~
~ /7Y 1 ~t2AlCl/TlC13 h28JTBP* Cr~ tallln Yi lt g. (Pare nt~) `i 15 1 3.0/1.0/0.03/0 2S.6 3.4 3.0/1.0/0.03/0.05 26.4 2.6 3.0/1.0/0.03/0.20 2S.B l.S
3.0/1.0/0.03/O.~S 25.6 2.0 ~' l .
* TBP 1 trlbut~lphoaphlt-':j I '~ .
j~ 20 TABL~ III
Co p~rl-on of Cry-t-llln Polyprop~lene Yl~lt nt 8O1ubl-a for Dlff-rant A ount-of k in Additlv n-HbD~oa ~` I Mol ~tlo Solubl-~
~ //'Y/7Y ~t2 ~ /T~C13/H28!Coll* Crr-t-lllo ~lold ~. (P-rea~L
: 25 3.0/1-0/0.01/0 29.7 3.3 2.S/1.0/0.01/0.01 2~.7 2.2 2.S/1.0/0.01/0.020 22.3 2.3 i. 1 ,,,, , .. ;~
~ I * Coll i 2 4 6-eollltln~ ~ ~
I ~.
'' ..
~ 3o - 4 -:-' ~
~' ,",. .~, , . ,, , ; ~
' ~,1 l 106Z693 Th- ~lud Du~ lkyl coupound- u--ful for th- h-r-in d ~crlb-d ln~ ntlon r- lkyl-lu inu~ t-riv tlv ~ ~h-r~ln th~ lkyl r~dic l con-t-in one to bout is c-rbon ~to~ nd, re p-ciflc-lly, re tri-~ lu inu J, ~l~tur-- th r of ~lth n ~lkyl-lu inu~ dlchlorld- or dlbro id- or di lk~l~lu~inu~ chloride or bro id-, or di lkyl luoinuo chlorlt o or bro ide- ~or- pref-r bly, thi~ flr-t ~t-rl-l 1~ a trl-lkrl-lu lnu~ tur - th-r of ~ith lth-r di~l~yl lu inu chlorit or n ~lkyl lu inu dlchlorit-, or di lkylalu inu~ chlorld- Mo t pr-f-r blr, di~l~yl lu inuu chlorld- 1- u--d Th- u ount of thl-fIr-t co pooent to b- u- d i- b-J-d upon th- r--ctor ~l~e, th- UQount of (b) co po~ nt u- d nd th- ~ount of ol-fin to be poly- rl--d ~ 11 ~no~n to on klll-d in th rt Th- tlt-nlu~ co~pound- u--ful h-rein r- tlt-nlum chlorid nd, or pr f-r bly, tit-niu trichlorid- Th- ~ou~t of thi- -cond ls ~t-ri-l u--d i- b- t upon th- a~ount ~nd co po-itlon of th- ~rticul-r polyr~r to b- ~ d- nd i- ~ 11 known to on ~ill d in th- rt Sh ~-ount of hydrog n ulfid to b- r -ct d ~ith th- flr~t ~ t-ri l i- u--fully 1 -- th n --11 fr ctlon of th- tot~ ount of fir-t ct-ri l, p-rh p- up to ~J ~uch J t-n ~ol p-rc nt of the fir-t ~ t~ri-l More pr-f rabl~, n ff-ctlv ount of hydrog n ulfid up to bout fl e ol p rc nt of th fir t ~cterial i- tded to re ct with th- fir t o~t-ri l Mo-t~pr f r bl~, a~ ff-cti~e a ount of hytrogen ulfid up to bout thr - ol p rc-nt of the a~ount of flr-t ~t-rl-l u ed 1- dt-d to r ct ~ith th- fir-t ~ateri l Too uch h~drog n ulfld hould not s b- u d it ~111 ~ill th~ c t-ly-t In dditloo, furth-r at-ri l- ~r bo dded to ddltlon lly reduc " olubl -", ucb ateri l- b-lng t-ric-ll~ hinder d, cyclit, tcrti ry in - uch - 2,6-lutldine, 2,4,6-collldio and the like, t-ric lly hind-r d, cJcllc lne o~ide- uch 2,6-lutldio--N-o~lde, nd trlhydro-c rb~lpho-phlt-- uch - trlphen~lpho-phlte, trlben~ylphoophlte nd . .
Il~ 106Z693 trlbutylpho-phlt- More pr-f~rably, torlc-lly hlnd-r<d, ro atlc, t-rti ry ln - nd trlhytrocarbylphoophlt-- ~ay b- u ~d Mb-t pre-f-r bly, low r-alkyl-tl~ub-tltut-d, cycllc, tertl ry ~lne-, or l~yl-ub-tltut-t ~ln o, and trial~ylpho-phlte~ re u--t Such ttltlon l ~ terlal- whon e ploy-d re u~ot ln t l --t an ff-etlv ount Too much of th- uch adtltlonal ~terl~ ill klll th polg--rl~-tlon U -~ully, the H2S-atdltlv ~ol ratlo c n b- ln th-; ra~8 fro~ bout four to about on to bout ona to about thlrty and, r- pr-f-r bly, the H2S-adtitlve ~ol r~tlo 1 ~bout on< to bout on to ~o bout oo to -bout t n - Th d- of dtltlon 1- to add the hydrogen ulflde to the alu lnu l~yl eo~pound llo~lng ti~ for reactlon to occur, a fe~ ~lnute- or r , nd th n td th tlt-nlu co~pount nt, lf d--lr-d, th ddltloo l -t-rl l, ~ , ~ trl lkrlpho-phlte lS - ~ 1~ obvlou to on klll-t ln th- art, pr-c~utlon hould b-t ken to ~old o~yg n od ~ol-tur- eont in tlon of the e t-ly-t durl ~; lt- pr-p r tlon nd lt- tr-nJf-r C t-l~ t pr<p-r-tlon e-n b- c rrl dout uod r n i~ rt t~o-ph-r u ing ~ueh 8~J-- ~ rgon, nltrog n, h llu~ te. Nor ll~, durlng u - no pr!eautlon n d be t-~en ~
;~ po d ti~ p# ur of no- r 8-- esl-to within th re etor Th- t p r tur t ~hlch the c~taly-t -9 b- u ed 1 not crltlc l.
~o~ ~ar, t to p r tur-- belo~ bout 0-C th- r te of polg # rl- tlon 10N- do~n nd r ctor r -id-nc ti _ beco~o unrea onabl~ long uh-rc J, t t _ r tur abov bout 120-C , polymerlr-tlon rate- bec o too hlgh cd n~l~cr -e ln "-olubl -" productlon 1- fount. Pr-f-rablg, tb-t_p-r tur- r n8 ln wblch tb c-t ly-t can bc uoet i bout 2-C to `~ bout 95-C. ~o-t pr f~r blg, the t p-ratur- rang- 1~ about 50-C to bout 80-C
Th proc of th ln~ ntion can be carriet out at a no er pre--~ ur of bout t~o-ph rlc or above Pro-oure~ of about 20 p - l g to ; - 6 -'.
' ~ ' 7' ' , ' ' ' ' . . . . ..
Il 106Z693 ¦-bout 600 p ~ l 8 or hlghor r~ pr-f~rrod dop-ndlng upon ~hlch poly-¦~ rl~-tlon technique 1- u~<d ¦ Th- org nlc llquld employ d a- th~ poly~rlz-tlon ~dlu~ ln the ¦-lurry t-chnlqu c-n b~ an llph-tlc alkan~ or cycloalkane such -s ¦p nt-ne, h ~-n , h pt-n or cyclohe~ano, or a hydrogenatet romatlc ¦co~pound uch a t-tr hydron phthalene or doc-h~dronaphth-len , or hlgh ¦ ol-cul r ~ lght llqult p-raffin or ~i~tur~ of par-ffln~ uhlch re ¦llquld t the r actlon te p~raeur-, or an arom~tlc hydroc rbon ouch -¦bcn--n , toulan or ~yl n~, or h logenat-t ro atlc co~pound ouch ~
o ¦chlorob-n~c~, chloronaphth l-n or ortho-tlchlorobens-ne. Th- n tur-y/7~ ¦of the r actlon ~ dlu~ ubJ-ct to condderable varlatlon~ lthough ¦th at-rl-l uployed ehould b- llquld under the condltlon- of reactlon ; I-~t r~l tlv ly ln rt Sh- hydrocarbon llqulds re d-olr bly ~ployad.
; , ¦Oth r olv ntc ~hlch c n b- u d lnclud thylb-nrcne, l-opropylb-n~-na, ~5 ¦-thyltolu n , n-propylb ns-ne, dl-thylbens-n -, no- nd dl lkyl-¦D-phth l o--, n-p nt-s , n-oct-n , l ooct-n nt -thylcycloh x-n . Th-¦pr par-tl~ cdl- e~ploy d ln pr-ctlclDg thl- lnventlon c n b- tv-n-i It geou 1~ purlfi d prlor to uo- ln tho polg~erlzatlon reactlon by con-l t cting the -t rl l, for s-~pl-, ln dlotlll-tlon procedure or other-¦ wlae, ~lth alu inu~ alkyl co~pound to re~ove undoelrable trac l~purltl -.
¦ Alco, prlor to poly erlsatlon th catalyot c n b- contactet atv nt-g ou~1y I I ~Ith poly~ rlr-blc alph -ol-fln.
Th poly~-rlsatlon ti~o 1~ not critlcal ant wlll uoually b of th-ortcr of fro~ 30 ~inut-- to ~v~ral hourH ln batch proccos-s. Contact 2s tlnec of fro~ one to four hour~ r co ~only o~ployet ln utoclavc-typ-r actlona. Wh n contlnuou- lurry proc ~ la _ loyed, the contact tl - ln th- polyn rl~atlon ~on can alao bo regulatet a~ doclrcd, and ln eome ca-e~ lt ic not n c ~aary to o~ploy reactlon or contact tiJe~
uch b-yond on -h lf to one hour ~lnce a cycllc y~te~ can b- c ploy d by -p ratlon of th- poly r and roturn of th~ ~olvent ant e~c-c~ ~ono~er '' ~ .
ll 106Z693 to th ch rgln~ ~oo- ~h r ln th- c-t-ly-t c n b- r pl~nl-h d nd ddl-tloo l ooo -r introduc d Thc iu~ otlon lc of p-rtlcul-r i port oco ln th- pr p-r tlo~ of hlshly-cry-t-llln~ polypropyl-o- ~lthough lt c n b- u- d for pol~-s rl~ins ulstur - of prop~ nt up to bout flv~ ~ol p-rc-nt of thyl n or ooth r lph -ol f~ of up to bout lght c rbon to . It i- u--ful l o for pr p ri~S pur--block J~d t-r lnal block t~p - of copoly_ r- of othyl o nt propyl no nt propyl n nt oth r lpb -ol flo of up to bout lght c rbo~ to~ ~h-r ln tb- protuct- r tlll o blsbly cry t~ n~
~se ~ /7Y Th proc -- nd c t ly-t of thl l~ otloo r- nor lly u d ~ith o ddltl~ to cootrol l cul~r ~ l~ht uch - dl l~l d nc co pouod or hydrog o pr f-r bly hydrogco. Solld poly or- h ~lng ol cul r ~ ht- ~r t-r th~o bout SO OOO cd 1 - th n bout 5 000 000 ro-ult i 15 th rc2~. Th -ount of hydro~ o to b- uo t t p odc upoo th uclt indo~
ot l cul~r ~lght tl trlbutloc to b- obt l~ad ~t 1- ~ 11 kno~n to ;`
th - c~lll t lo th rt.
Wbll th lon otloo 1J t -erlb t lo eoonoetloo ~lth th- p elfle ~s plo- b lo~ lt 1~ to be uod r tood th t th-J- re for lllu tr~tl~ ;-pur;o - ool~. k~o~ roatl aotlflc tlon~ aot ~ ri tlon- vlll b-; ~ ~ pp r t to tho-- klll t l~ th- rt ln th- light of th- b-low kso~pl~-nt ueh lt D tl_ tlfle-tioo- ot ~ rl tloo- f ll ~ithio th-~; eop- od plrlt of th ppc~d d cl i J.
~L m~ ,L Pl~OOEDUU~ ' ,~, .
2s ~ ~ All pol~oorlotlo~ t Jerlb d h lo ~ rc c rrl d out 1~ bottl - t 70-C for 2 hour- u~i y 40 p.- l.~ of prop~l oo nt 0.20 8r of lu l-;~ ~ ou etl~ t t tlt-nlu~ triehlorit ~MTlC13).
Sh e t-l~t ~nJ up t roo to p r turo b~r atdlog th r-qul lt- -: .-oou~t of h~dro~ ~ ulflt to th- 1U~1DU~ lkyl co pound tl~-olv t ln 30 ¦ h~ ~ up to ~ hoor ~ th n ~1~4 th r~ t- ~th th-.~: -8-.
'' tlt-nlu trlchlorld , th- ttltlv , lf u--d, nt h-~ n~ tllu nt Aft-r poly rl~-tlon th co~t nt- of thc bottlo ~cr- ~lll t ~ith -, ~ ¦ _ th nol nt th- olld fllt r d off, drl-d nt ~ lgh t to 81 c th Cry t-llin Yl ld Th- up rn~t-ct llquld ~ ~ c~ por ted to dr~n--c ~nd s l tb r--ldu ~ ht, oultipll d by 100 nt dlvld-t by the Cr~t-lllD-~i ld plu- th- r ltu ~ d ght, w c-lcul t d to ~lv th- p rc-nt of n-_ 801ubl Tb Cr~-t d lino ~l ld ~ud n-~bs~n- Solubl h ~ bo n corr ct d for -r$ tio~c in dlff r nt b tch of c t~ly t co ponont-, prop~l-o- otc.
- ¦ b~ ruoniog ~ ot Qtcrd pol~ -rl~-tlon ch tlr~ u ~p-rl o~t l run ~n-_ d d corr ¢tiog th- sp ri~-ct-l ru~ for ~y dcvl tlon of th- t _ d rd'- Cr~ t-lllD- Si ld or o-~br n- 801ubl -~', , l ~
~ol ~ tio 801ubl ~t2AlCl/TlC13/~28 5E~ t lli~- Si!ld ~ ~P rc nt) ~3.0!1 0/0.010 29.7 3.3 r~ l3.0/1.0/0.030 25 6 3 ' .O/i~.O/O.OlO 24 6 2 8 0/1.010.030 23 6 2.7 l.Sll 0/0.0 26 6 4.7 2.5/1.0/0.0 2S 0 4.3 ; ~20~ ~ ~
1;
~ ~ _ 9 _ "~ 1 I
`.,''~:~'' ~;
1(~6Z693 i ~XAMPLE II
~R l/~Y/~~t2~1Cl/828/TBP/TiC13 Cr -t~lllno l-lt 8-' 3.00/0.030/0.45 25.6 2.0 0.30 27.3 1.8 ` 0.20 25.8 1.5 ~; 0.010/0.4S 23.6 1.7 0.30 28. S 1.5 ~ 0.20 2S.6 1.9 ,, 0.10 28.5 2.0 0.05 27.1 2.4 2.00/0.030/0.4S 24.5 2.3 0.30 28.0 1.6 100.2~ 26.0 1.8 _ 0.10 25.7 1.7 O.OS 24.1 2.0 ' 0.010/0.~5 24.2 2.S
~ 0.30 24.1 1.9 ,;~ 0.20 24.3 1.9 0.10 25.9 1.6 0.05 2~.9 1.9 ;
~.. ; .~ . .
'.
~ ' ~; : . : "
~ ~ .
~, ~ 20 ' - 10 - ' ~ 106Z693 I ~ I
~9~ 11Y/7~ t2AlCl/H~S/Coll/TIC13 CrV-t 111n Sl ld. ~. t rc _~) ~
2.S0/0.030/0.060 19.9 2 1 ' 5 0.030 21.3 2 2 0.020/0.0~0 20.9 2.0 0.020 22.4 2.1 0.010/0.020 22.3 2.3 0.010 24.7 2.2 o l.S010.030/0 060 18 8 2 1 ' ~ 0.02010.040 18.6 1 8 ,"~ 0.020 19.8 1 9 ,, 0 010 21o 6~ 2 2 ,,, : ., '~ ' '! 1 00/0 030/0-060 16.4 1 8 ,~ 15 0.030 18.7 2 0 0.020/0-040 18-2 2 0 0.020 17.4 2 3 0.010/0.020 21.0 2 1 Ø010~ 20.9 2 4 20~ ~ ~
i~f ~ ~ ~ ~
,~.
~ ~ .
2s f~ :
, , ~ - 1~. -'''.`' "' .
rv:~::; . -: .- : . . - : - .
A~ hown ln T~ble I ~elo~ the n-he~ano soluble fractlon c-n be reduced ln a ~lurry polymeri~atlon when the al ~num alkyl cospound component of the catalyst lo flr~t partially reacted with hydrogen ~ulflde '~ ;
T~BLE I -~
Comparloon of Crystalline Polypropylene Yield ant Soluble- for Dlffercnt ~ount~
of HydroRen Sulfid-n-He~ane lG Mol Ratlo Solublec ~ /?Y ~t2AlCl/TlC13/H2S~ Crvot-lline Yi ld, g CPercent) D 1.50/1.U/o25,1 4.6 26.0 3.8 25 7 3.8 1 0/1 0/0.010 24.6 2.ô
1 0/1 0/0.030 23 6 2.7 3 0/1 0/0 010 29.7 3 3 3.0/1 0/0 030 25 6 3 4 20 ~ Lt repre~ent~ the ethyl r dlcal - 3(b) ~
~ . .. . :............... :
Il 106Z693 The r~-ult- ln T-bl~ I lndlc-t- th~t the r~ ctlon of 8m-11 portlon of the organoaluulouu alu~lnu~ co pound ~lth hgdrogen ~ulfld- prlor to I co~bln~tion ~ith the tltanlu~ trlehlorlde r -ult~ ln loN~r "-olubl--"
¦ ~lthout -rlou- ff-et on the ~l-ld.
5 ¦ The t ta et forth ln T bl~ II and III b~low ho~ the ddltlon l ¦ lo~er n8 of "-olubl -" in lurry typ propyl-n poly~risation ~h n o ~; ¦ addltiv uch a t~rie-lly hlnd-red c~elle t rtlarg ain~ or trlh~droe-rb~lpho~phlta 1~ dd-d to ~2S-tr -t-t organo lu~lnw~ co_ ¦ pound-tit nlu~ trlchlorid co bln tlon-.
- lo ¦ T~BLe II
¦Co~p-rl~on of Cr~-t-lline Polypropyl na Yl~ld Iand Solubl- for Dlff-r nt A ouot-¦ _ of~ lt- Adtltlvea n-~ ~n-Mol ~tlo Solubl-~
~ /7Y 1 ~t2AlCl/TlC13 h28JTBP* Cr~ tallln Yi lt g. (Pare nt~) `i 15 1 3.0/1.0/0.03/0 2S.6 3.4 3.0/1.0/0.03/0.05 26.4 2.6 3.0/1.0/0.03/0.20 2S.B l.S
3.0/1.0/0.03/O.~S 25.6 2.0 ~' l .
* TBP 1 trlbut~lphoaphlt-':j I '~ .
j~ 20 TABL~ III
Co p~rl-on of Cry-t-llln Polyprop~lene Yl~lt nt 8O1ubl-a for Dlff-rant A ount-of k in Additlv n-HbD~oa ~` I Mol ~tlo Solubl-~
~ //'Y/7Y ~t2 ~ /T~C13/H28!Coll* Crr-t-lllo ~lold ~. (P-rea~L
: 25 3.0/1-0/0.01/0 29.7 3.3 2.S/1.0/0.01/0.01 2~.7 2.2 2.S/1.0/0.01/0.020 22.3 2.3 i. 1 ,,,, , .. ;~
~ I * Coll i 2 4 6-eollltln~ ~ ~
I ~.
'' ..
~ 3o - 4 -:-' ~
~' ,",. .~, , . ,, , ; ~
' ~,1 l 106Z693 Th- ~lud Du~ lkyl coupound- u--ful for th- h-r-in d ~crlb-d ln~ ntlon r- lkyl-lu inu~ t-riv tlv ~ ~h-r~ln th~ lkyl r~dic l con-t-in one to bout is c-rbon ~to~ nd, re p-ciflc-lly, re tri-~ lu inu J, ~l~tur-- th r of ~lth n ~lkyl-lu inu~ dlchlorld- or dlbro id- or di lk~l~lu~inu~ chloride or bro id-, or di lkyl luoinuo chlorlt o or bro ide- ~or- pref-r bly, thi~ flr-t ~t-rl-l 1~ a trl-lkrl-lu lnu~ tur - th-r of ~ith lth-r di~l~yl lu inu chlorit or n ~lkyl lu inu dlchlorit-, or di lkylalu inu~ chlorld- Mo t pr-f-r blr, di~l~yl lu inuu chlorld- 1- u--d Th- u ount of thl-fIr-t co pooent to b- u- d i- b-J-d upon th- r--ctor ~l~e, th- UQount of (b) co po~ nt u- d nd th- ~ount of ol-fin to be poly- rl--d ~ 11 ~no~n to on klll-d in th rt Th- tlt-nlu~ co~pound- u--ful h-rein r- tlt-nlum chlorid nd, or pr f-r bly, tit-niu trichlorid- Th- ~ou~t of thi- -cond ls ~t-ri-l u--d i- b- t upon th- a~ount ~nd co po-itlon of th- ~rticul-r polyr~r to b- ~ d- nd i- ~ 11 known to on ~ill d in th- rt Sh ~-ount of hydrog n ulfid to b- r -ct d ~ith th- flr~t ~ t-ri l i- u--fully 1 -- th n --11 fr ctlon of th- tot~ ount of fir-t ct-ri l, p-rh p- up to ~J ~uch J t-n ~ol p-rc nt of the fir-t ~ t~ri-l More pr-f rabl~, n ff-ctlv ount of hydrog n ulfid up to bout fl e ol p rc nt of th fir t ~cterial i- tded to re ct with th- fir t o~t-ri l Mo-t~pr f r bl~, a~ ff-cti~e a ount of hytrogen ulfid up to bout thr - ol p rc-nt of the a~ount of flr-t ~t-rl-l u ed 1- dt-d to r ct ~ith th- fir-t ~ateri l Too uch h~drog n ulfld hould not s b- u d it ~111 ~ill th~ c t-ly-t In dditloo, furth-r at-ri l- ~r bo dded to ddltlon lly reduc " olubl -", ucb ateri l- b-lng t-ric-ll~ hinder d, cyclit, tcrti ry in - uch - 2,6-lutldine, 2,4,6-collldio and the like, t-ric lly hind-r d, cJcllc lne o~ide- uch 2,6-lutldio--N-o~lde, nd trlhydro-c rb~lpho-phlt-- uch - trlphen~lpho-phlte, trlben~ylphoophlte nd . .
Il~ 106Z693 trlbutylpho-phlt- More pr-f~rably, torlc-lly hlnd-r<d, ro atlc, t-rti ry ln - nd trlhytrocarbylphoophlt-- ~ay b- u ~d Mb-t pre-f-r bly, low r-alkyl-tl~ub-tltut-d, cycllc, tertl ry ~lne-, or l~yl-ub-tltut-t ~ln o, and trial~ylpho-phlte~ re u--t Such ttltlon l ~ terlal- whon e ploy-d re u~ot ln t l --t an ff-etlv ount Too much of th- uch adtltlonal ~terl~ ill klll th polg--rl~-tlon U -~ully, the H2S-atdltlv ~ol ratlo c n b- ln th-; ra~8 fro~ bout four to about on to bout ona to about thlrty and, r- pr-f-r bly, the H2S-adtitlve ~ol r~tlo 1 ~bout on< to bout on to ~o bout oo to -bout t n - Th d- of dtltlon 1- to add the hydrogen ulflde to the alu lnu l~yl eo~pound llo~lng ti~ for reactlon to occur, a fe~ ~lnute- or r , nd th n td th tlt-nlu co~pount nt, lf d--lr-d, th ddltloo l -t-rl l, ~ , ~ trl lkrlpho-phlte lS - ~ 1~ obvlou to on klll-t ln th- art, pr-c~utlon hould b-t ken to ~old o~yg n od ~ol-tur- eont in tlon of the e t-ly-t durl ~; lt- pr-p r tlon nd lt- tr-nJf-r C t-l~ t pr<p-r-tlon e-n b- c rrl dout uod r n i~ rt t~o-ph-r u ing ~ueh 8~J-- ~ rgon, nltrog n, h llu~ te. Nor ll~, durlng u - no pr!eautlon n d be t-~en ~
;~ po d ti~ p# ur of no- r 8-- esl-to within th re etor Th- t p r tur t ~hlch the c~taly-t -9 b- u ed 1 not crltlc l.
~o~ ~ar, t to p r tur-- belo~ bout 0-C th- r te of polg # rl- tlon 10N- do~n nd r ctor r -id-nc ti _ beco~o unrea onabl~ long uh-rc J, t t _ r tur abov bout 120-C , polymerlr-tlon rate- bec o too hlgh cd n~l~cr -e ln "-olubl -" productlon 1- fount. Pr-f-rablg, tb-t_p-r tur- r n8 ln wblch tb c-t ly-t can bc uoet i bout 2-C to `~ bout 95-C. ~o-t pr f~r blg, the t p-ratur- rang- 1~ about 50-C to bout 80-C
Th proc of th ln~ ntion can be carriet out at a no er pre--~ ur of bout t~o-ph rlc or above Pro-oure~ of about 20 p - l g to ; - 6 -'.
' ~ ' 7' ' , ' ' ' ' . . . . ..
Il 106Z693 ¦-bout 600 p ~ l 8 or hlghor r~ pr-f~rrod dop-ndlng upon ~hlch poly-¦~ rl~-tlon technique 1- u~<d ¦ Th- org nlc llquld employ d a- th~ poly~rlz-tlon ~dlu~ ln the ¦-lurry t-chnlqu c-n b~ an llph-tlc alkan~ or cycloalkane such -s ¦p nt-ne, h ~-n , h pt-n or cyclohe~ano, or a hydrogenatet romatlc ¦co~pound uch a t-tr hydron phthalene or doc-h~dronaphth-len , or hlgh ¦ ol-cul r ~ lght llqult p-raffin or ~i~tur~ of par-ffln~ uhlch re ¦llquld t the r actlon te p~raeur-, or an arom~tlc hydroc rbon ouch -¦bcn--n , toulan or ~yl n~, or h logenat-t ro atlc co~pound ouch ~
o ¦chlorob-n~c~, chloronaphth l-n or ortho-tlchlorobens-ne. Th- n tur-y/7~ ¦of the r actlon ~ dlu~ ubJ-ct to condderable varlatlon~ lthough ¦th at-rl-l uployed ehould b- llquld under the condltlon- of reactlon ; I-~t r~l tlv ly ln rt Sh- hydrocarbon llqulds re d-olr bly ~ployad.
; , ¦Oth r olv ntc ~hlch c n b- u d lnclud thylb-nrcne, l-opropylb-n~-na, ~5 ¦-thyltolu n , n-propylb ns-ne, dl-thylbens-n -, no- nd dl lkyl-¦D-phth l o--, n-p nt-s , n-oct-n , l ooct-n nt -thylcycloh x-n . Th-¦pr par-tl~ cdl- e~ploy d ln pr-ctlclDg thl- lnventlon c n b- tv-n-i It geou 1~ purlfi d prlor to uo- ln tho polg~erlzatlon reactlon by con-l t cting the -t rl l, for s-~pl-, ln dlotlll-tlon procedure or other-¦ wlae, ~lth alu inu~ alkyl co~pound to re~ove undoelrable trac l~purltl -.
¦ Alco, prlor to poly erlsatlon th catalyot c n b- contactet atv nt-g ou~1y I I ~Ith poly~ rlr-blc alph -ol-fln.
Th poly~-rlsatlon ti~o 1~ not critlcal ant wlll uoually b of th-ortcr of fro~ 30 ~inut-- to ~v~ral hourH ln batch proccos-s. Contact 2s tlnec of fro~ one to four hour~ r co ~only o~ployet ln utoclavc-typ-r actlona. Wh n contlnuou- lurry proc ~ la _ loyed, the contact tl - ln th- polyn rl~atlon ~on can alao bo regulatet a~ doclrcd, and ln eome ca-e~ lt ic not n c ~aary to o~ploy reactlon or contact tiJe~
uch b-yond on -h lf to one hour ~lnce a cycllc y~te~ can b- c ploy d by -p ratlon of th- poly r and roturn of th~ ~olvent ant e~c-c~ ~ono~er '' ~ .
ll 106Z693 to th ch rgln~ ~oo- ~h r ln th- c-t-ly-t c n b- r pl~nl-h d nd ddl-tloo l ooo -r introduc d Thc iu~ otlon lc of p-rtlcul-r i port oco ln th- pr p-r tlo~ of hlshly-cry-t-llln~ polypropyl-o- ~lthough lt c n b- u- d for pol~-s rl~ins ulstur - of prop~ nt up to bout flv~ ~ol p-rc-nt of thyl n or ooth r lph -ol f~ of up to bout lght c rbon to . It i- u--ful l o for pr p ri~S pur--block J~d t-r lnal block t~p - of copoly_ r- of othyl o nt propyl no nt propyl n nt oth r lpb -ol flo of up to bout lght c rbo~ to~ ~h-r ln tb- protuct- r tlll o blsbly cry t~ n~
~se ~ /7Y Th proc -- nd c t ly-t of thl l~ otloo r- nor lly u d ~ith o ddltl~ to cootrol l cul~r ~ l~ht uch - dl l~l d nc co pouod or hydrog o pr f-r bly hydrogco. Solld poly or- h ~lng ol cul r ~ ht- ~r t-r th~o bout SO OOO cd 1 - th n bout 5 000 000 ro-ult i 15 th rc2~. Th -ount of hydro~ o to b- uo t t p odc upoo th uclt indo~
ot l cul~r ~lght tl trlbutloc to b- obt l~ad ~t 1- ~ 11 kno~n to ;`
th - c~lll t lo th rt.
Wbll th lon otloo 1J t -erlb t lo eoonoetloo ~lth th- p elfle ~s plo- b lo~ lt 1~ to be uod r tood th t th-J- re for lllu tr~tl~ ;-pur;o - ool~. k~o~ roatl aotlflc tlon~ aot ~ ri tlon- vlll b-; ~ ~ pp r t to tho-- klll t l~ th- rt ln th- light of th- b-low kso~pl~-nt ueh lt D tl_ tlfle-tioo- ot ~ rl tloo- f ll ~ithio th-~; eop- od plrlt of th ppc~d d cl i J.
~L m~ ,L Pl~OOEDUU~ ' ,~, .
2s ~ ~ All pol~oorlotlo~ t Jerlb d h lo ~ rc c rrl d out 1~ bottl - t 70-C for 2 hour- u~i y 40 p.- l.~ of prop~l oo nt 0.20 8r of lu l-;~ ~ ou etl~ t t tlt-nlu~ triehlorit ~MTlC13).
Sh e t-l~t ~nJ up t roo to p r turo b~r atdlog th r-qul lt- -: .-oou~t of h~dro~ ~ ulflt to th- 1U~1DU~ lkyl co pound tl~-olv t ln 30 ¦ h~ ~ up to ~ hoor ~ th n ~1~4 th r~ t- ~th th-.~: -8-.
'' tlt-nlu trlchlorld , th- ttltlv , lf u--d, nt h-~ n~ tllu nt Aft-r poly rl~-tlon th co~t nt- of thc bottlo ~cr- ~lll t ~ith -, ~ ¦ _ th nol nt th- olld fllt r d off, drl-d nt ~ lgh t to 81 c th Cry t-llin Yl ld Th- up rn~t-ct llquld ~ ~ c~ por ted to dr~n--c ~nd s l tb r--ldu ~ ht, oultipll d by 100 nt dlvld-t by the Cr~t-lllD-~i ld plu- th- r ltu ~ d ght, w c-lcul t d to ~lv th- p rc-nt of n-_ 801ubl Tb Cr~-t d lino ~l ld ~ud n-~bs~n- Solubl h ~ bo n corr ct d for -r$ tio~c in dlff r nt b tch of c t~ly t co ponont-, prop~l-o- otc.
- ¦ b~ ruoniog ~ ot Qtcrd pol~ -rl~-tlon ch tlr~ u ~p-rl o~t l run ~n-_ d d corr ¢tiog th- sp ri~-ct-l ru~ for ~y dcvl tlon of th- t _ d rd'- Cr~ t-lllD- Si ld or o-~br n- 801ubl -~', , l ~
~ol ~ tio 801ubl ~t2AlCl/TlC13/~28 5E~ t lli~- Si!ld ~ ~P rc nt) ~3.0!1 0/0.010 29.7 3.3 r~ l3.0/1.0/0.030 25 6 3 ' .O/i~.O/O.OlO 24 6 2 8 0/1.010.030 23 6 2.7 l.Sll 0/0.0 26 6 4.7 2.5/1.0/0.0 2S 0 4.3 ; ~20~ ~ ~
1;
~ ~ _ 9 _ "~ 1 I
`.,''~:~'' ~;
1(~6Z693 i ~XAMPLE II
~R l/~Y/~~t2~1Cl/828/TBP/TiC13 Cr -t~lllno l-lt 8-' 3.00/0.030/0.45 25.6 2.0 0.30 27.3 1.8 ` 0.20 25.8 1.5 ~; 0.010/0.4S 23.6 1.7 0.30 28. S 1.5 ~ 0.20 2S.6 1.9 ,, 0.10 28.5 2.0 0.05 27.1 2.4 2.00/0.030/0.4S 24.5 2.3 0.30 28.0 1.6 100.2~ 26.0 1.8 _ 0.10 25.7 1.7 O.OS 24.1 2.0 ' 0.010/0.~5 24.2 2.S
~ 0.30 24.1 1.9 ,;~ 0.20 24.3 1.9 0.10 25.9 1.6 0.05 2~.9 1.9 ;
~.. ; .~ . .
'.
~ ' ~; : . : "
~ ~ .
~, ~ 20 ' - 10 - ' ~ 106Z693 I ~ I
~9~ 11Y/7~ t2AlCl/H~S/Coll/TIC13 CrV-t 111n Sl ld. ~. t rc _~) ~
2.S0/0.030/0.060 19.9 2 1 ' 5 0.030 21.3 2 2 0.020/0.0~0 20.9 2.0 0.020 22.4 2.1 0.010/0.020 22.3 2.3 0.010 24.7 2.2 o l.S010.030/0 060 18 8 2 1 ' ~ 0.02010.040 18.6 1 8 ,"~ 0.020 19.8 1 9 ,, 0 010 21o 6~ 2 2 ,,, : ., '~ ' '! 1 00/0 030/0-060 16.4 1 8 ,~ 15 0.030 18.7 2 0 0.020/0-040 18-2 2 0 0.020 17.4 2 3 0.010/0.020 21.0 2 1 Ø010~ 20.9 2 4 20~ ~ ~
i~f ~ ~ ~ ~
,~.
~ ~ .
2s f~ :
, , ~ - 1~. -'''.`' "' .
rv:~::; . -: .- : . . - : - .
Claims (14)
1. A polymerization catalyst composition which comprises (a) an alkylaluminum compound selected from the group consisting of a trialkyl aluminum, a mixture of a trialkyl aluminum and an alkylaluminum dichloride or dibromide, a mixture of a trialkyl aluminum and a dialkylaluminum chloride or bromide and a dialkylaluminum chloride or bromide;
(b) an effective amount up to about 10 mol percent of hydrogen sulfide based upon the amount of alkylaluminum compound present;
(c) an activated titanium trichloride; and (d) an effective amount of an additive which is selected from the group consisting of trihydrocarbylphosphites, sterically hindered, lower alkyl substituted, cyclic, tertiary amines and sterically hindered, lower alkyl substituted, cyclic, amine oxides;
said amounts effective to result in a substantial reduction of alkane solubles while not seriously affecting the total yield of polymer.
(b) an effective amount up to about 10 mol percent of hydrogen sulfide based upon the amount of alkylaluminum compound present;
(c) an activated titanium trichloride; and (d) an effective amount of an additive which is selected from the group consisting of trihydrocarbylphosphites, sterically hindered, lower alkyl substituted, cyclic, tertiary amines and sterically hindered, lower alkyl substituted, cyclic, amine oxides;
said amounts effective to result in a substantial reduction of alkane solubles while not seriously affecting the total yield of polymer.
2. A polymerization catalyst composition as in Claim 1 wherein the component (a) has been pretreated by the component (b).
3. The composition of claim 1 or 2 wherein said alkylalu-minum compound is a dialkylaluminum chloride and said additive is a trihydrocarbylphosphite.
4. The composition of Claim 1 or 2 wherein said alkylalu-minum compound is a dialkylaluminum chloride and said additive is a sterically hindered, lower alkyl substituted, cyclic, tertiary amine.
5. The composition of Claim 1 or 2 wherein said alkyl-aluminum compound is a dialkylaluminum chloride and said additive is a sterically hindered, lower alkyl substituted, cyclic, amine oxide.
6. The composition of Claim 1 or 2 wherein said alkylalu-minum compound is a dialkylaluminum chloride and said additive is a lower alkyl, trialkylphosphite.
7. The composition of Claim 1 or 2 wherein said alkylaluminum compound is a dialkylaluminum chloride and said additive is a sterically hindered, di- or tri-lower alkyl substituted, cyclic, tertiary amine.
8. The composition of Claim 1 or 2 wherein said alkylalu-minum compound is a dialkylaluminum chloride and said additive is 2,6-lutidine-N-oxide.
9. The composition of Claim 1 or 2 wherein said alkylalu-minum compound is a dialkylaluminum chloride and said additive is tributylphosphite.
10. The composition of Claim 1 or 2 wherein said alkylalu-minum compound is a dialkylaluminum chloride and said additive is 2,4,6-collidine.
11. A process for the polymerization of propylene or a mixture of propylene and ethylene or propylene and another C4 to C8 alpha-olefin to form a highly crystalline polymeric substance, said process involving contacting under polymerizing conditions said propylene or said mixture with a catalyst comprising:
(a) an alkylaluminum compound selected from the group consisting of a trialkyl aluminum, a mixture of a trialkyl aluminum and an alkylaluminum dichloride or dibromide, a mixture of a trialkyl aluminum and a dialkylaluminum chloride or bromide, said alkylaluminum compound having been treated with an effective amount, up to about 10 mol percent based on the amount of said alkylaluminum compound, of hydrogen sulfide;
(b) an activated titanium trichloride; and (c) an effective amount of an additive which is selected from the group consisting of trihydrocarbylphosphites, sterically hindered, lower alkyl substituted, cyclic, tertiary amines, and sterically hindered, lower alkyl substituted, cyclic, amine oxides;
said amounts effective to result in a substantial reduction of alkane solubles while not seriously affecting the total yield of said polymeric substance.
(a) an alkylaluminum compound selected from the group consisting of a trialkyl aluminum, a mixture of a trialkyl aluminum and an alkylaluminum dichloride or dibromide, a mixture of a trialkyl aluminum and a dialkylaluminum chloride or bromide, said alkylaluminum compound having been treated with an effective amount, up to about 10 mol percent based on the amount of said alkylaluminum compound, of hydrogen sulfide;
(b) an activated titanium trichloride; and (c) an effective amount of an additive which is selected from the group consisting of trihydrocarbylphosphites, sterically hindered, lower alkyl substituted, cyclic, tertiary amines, and sterically hindered, lower alkyl substituted, cyclic, amine oxides;
said amounts effective to result in a substantial reduction of alkane solubles while not seriously affecting the total yield of said polymeric substance.
12. The process of claim 11 wherein said alkylaluminum compound is a dialkylaluminum chloride and said additive is 2,6-lutidine-N-oxide.
13. The process of Claim 11 wherein said alkylaluminun compound is a dialkylaluminum chloride and said additive is a sterically hindered, di- or tri-lower alkyl substituted, cyclic, tertiary amine.
14. The process of Claim 13 wherein said additive is 2,4,6-collidine.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US43448674A | 1974-01-18 | 1974-01-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1062693A true CA1062693A (en) | 1979-09-18 |
Family
ID=23724431
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA217,918A Expired CA1062693A (en) | 1974-01-18 | 1975-01-14 | Catalyst and process for the polymerization of alpha-olefins |
Country Status (13)
| Country | Link |
|---|---|
| US (1) | US4072809A (en) |
| JP (1) | JPS5815488B2 (en) |
| BE (1) | BE824512A (en) |
| CA (1) | CA1062693A (en) |
| CS (1) | CS196259B2 (en) |
| DD (2) | DD124254A5 (en) |
| DE (1) | DE2500505A1 (en) |
| EG (1) | EG11542A (en) |
| FR (1) | FR2258402B1 (en) |
| GB (1) | GB1488583A (en) |
| IT (1) | IT1026356B (en) |
| NL (1) | NL178511C (en) |
| RO (1) | RO71385A (en) |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4288580A (en) * | 1975-12-17 | 1981-09-08 | Standard Oil Company (Indiana) | Catalyst and process for the polymerization of alpha-olefins |
| US4334047A (en) * | 1976-06-28 | 1982-06-08 | Standard Oil Company (Indiana) | Polymerization catalysts |
| US4304684A (en) * | 1977-02-11 | 1981-12-08 | Exxon Research & Engineering Co. | Novel trialkyl aluminum cocatalyst |
| US4370457A (en) * | 1978-02-27 | 1983-01-25 | Standard Oil Company (Indiana) | Catalyst system |
| US4277370A (en) * | 1979-02-15 | 1981-07-07 | Standard Oil Company (Indiana) | Alpha-olefin polymerization catalyst |
| US4324690A (en) * | 1979-02-15 | 1982-04-13 | Standard Oil Company (Indiana) | Alpha-olefin polymerization catalyst |
| US4310439A (en) * | 1979-03-07 | 1982-01-12 | Exxon Research & Engineering Co. | Novel trialkyl aluminum cocatalyst |
| US4235747A (en) * | 1979-04-19 | 1980-11-25 | Standard Oil Company (Indiana) | Process for improving polymerization performance of brown solid titanium trichloride catalyst component |
| US4255281A (en) * | 1979-07-03 | 1981-03-10 | Standard Oil Company (Indiana) | Alpha-olefin polymerization catalyst and process |
| EP0176641B1 (en) * | 1984-10-05 | 1989-02-15 | Pony Industries Incorporated | Hydrocarbon fluid friction reducing composition containing olefin copolymer and process for producing same |
| US5270276A (en) * | 1989-04-25 | 1993-12-14 | Shell Oil Company | Process for the production of elastomeric, primarily syndiotactic polypropylene and catalysts for use in said process |
| US5270410A (en) * | 1989-04-25 | 1993-12-14 | Shell Oil Company | Process for the production of elastomeric, primarily syndiotactic polypropylene and catalysts for use in said process |
| US5089573A (en) * | 1990-02-26 | 1992-02-18 | Shell Oil Company | Process for the production of elastomeric, primarily isotactic polyolefins and catalysts for use in said process |
| US5118649A (en) * | 1990-02-26 | 1992-06-02 | Shell Oil Company | Process for the production of elastomeric primarily isotactic polyolefins and catalysts for use in said process |
| US5118767A (en) * | 1990-02-26 | 1992-06-02 | Shell Oil Company | Process for producing mildly elastomeric primarily isotatic polypropylene and poly-1-butene |
| US5118768A (en) * | 1990-05-11 | 1992-06-02 | Shell Oil Company | Process for the production of elastomeric, primarily isotactic polyolefins and catalysts for use in said process |
| US5164352A (en) * | 1990-05-11 | 1992-11-17 | Shell Oil Company | Process for the production of elastomeric, primarily isotactic polyolefins and catalysts for use in said process |
| US6180011B1 (en) * | 1993-04-07 | 2001-01-30 | Enichem Synthesis S.P.A | Method for removing hydrocarbon products from water surfaces |
| CN112745415B (en) * | 2019-10-30 | 2022-09-09 | 中国石油化工股份有限公司 | Method for preparing poly-alpha-olefin with high viscosity index |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB867139A (en) | 1960-02-22 | 1961-05-03 | Grace W R & Co | Improvements in the production of polyolefins |
| BE589260A (en) * | 1960-03-28 | |||
| DE1445225B2 (en) * | 1960-09-24 | 1971-11-18 | Badische Anilin & Soda Fabrik AG, 6700 Ludwigshafen | PROCESS FOR THE POLYMERIZATION OF MONOALPHA OLEFINS WITH THREE OR MORE CARBONS |
| NL258547A (en) * | 1960-11-30 | |||
| US3207740A (en) * | 1963-05-27 | 1965-09-21 | Shell Oil Co | Propylene polymerization by titanium trichloride, aluminum dialkyl halide and water |
| US3240773A (en) * | 1964-07-22 | 1966-03-15 | Shell Oil Co | Polymerization of alpha-monoolefins in the presence of titanium trichloride, organometallic reducing agent comprising zinc dihydrocarbyl, and an organic amine |
| US3669948A (en) * | 1970-09-04 | 1972-06-13 | Chisso Corp | Method for producing poly{60 -olefins |
-
1974
- 1974-11-10 DD DD189985A patent/DD124254A5/xx unknown
-
1975
- 1975-01-08 DE DE19752500505 patent/DE2500505A1/en not_active Withdrawn
- 1975-01-10 DD DD183595A patent/DD118439A5/xx unknown
- 1975-01-10 NL NLAANVRAGE7500306,A patent/NL178511C/en active Search and Examination
- 1975-01-14 CA CA217,918A patent/CA1062693A/en not_active Expired
- 1975-01-15 IT IT47696/75A patent/IT1026356B/en active
- 1975-01-15 GB GB1792/75A patent/GB1488583A/en not_active Expired
- 1975-01-17 BE BE152484A patent/BE824512A/en not_active IP Right Cessation
- 1975-01-17 CS CS75358A patent/CS196259B2/en unknown
- 1975-01-17 FR FR7501485A patent/FR2258402B1/fr not_active Expired
- 1975-01-18 RO RO7581155A patent/RO71385A/en unknown
- 1975-01-18 JP JP50008310A patent/JPS5815488B2/en not_active Expired
- 1975-01-18 EG EG24/75A patent/EG11542A/en active
- 1975-03-03 US US05/554,599 patent/US4072809A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| FR2258402B1 (en) | 1978-02-03 |
| JPS50106892A (en) | 1975-08-22 |
| DE2500505A1 (en) | 1975-07-24 |
| FR2258402A1 (en) | 1975-08-18 |
| GB1488583A (en) | 1977-10-12 |
| JPS5815488B2 (en) | 1983-03-25 |
| DD124254A5 (en) | 1977-02-09 |
| RO71385A (en) | 1980-12-30 |
| NL178511C (en) | 1986-04-01 |
| NL7500306A (en) | 1975-07-22 |
| IT1026356B (en) | 1978-09-20 |
| EG11542A (en) | 1977-12-31 |
| DD118439A5 (en) | 1976-03-05 |
| US4072809A (en) | 1978-02-07 |
| BE824512A (en) | 1975-07-17 |
| CS196259B2 (en) | 1980-03-31 |
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