GB1587659A - Polymerisation of mono-olefins and diolefins and catalyst therefor - Google Patents
Polymerisation of mono-olefins and diolefins and catalyst therefor Download PDFInfo
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- GB1587659A GB1587659A GB48445/77A GB4844577A GB1587659A GB 1587659 A GB1587659 A GB 1587659A GB 48445/77 A GB48445/77 A GB 48445/77A GB 4844577 A GB4844577 A GB 4844577A GB 1587659 A GB1587659 A GB 1587659A
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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
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- 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
- C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The process for the polymerisation of mono- and di-olefinic compounds comprises contacting compounds which are to be polymerised with a ternary catalytic system consisting of an aluminium alkyl or hydride derivative, a compound of a transition metal and a polyiminoalane.
Description
(54) POLYMERISATION OF MONO-OLEFINS AND DI-OLEFINS
AND CATALYST THEREFOR
(71) We, SNAMPROGETTI S.p.A., an Italian company, of Corso Venezia 16, Milan,
Italy, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:
This invention relates to a process for the polymerisation and copolymerisation of mono-olefines and di-olefins, which method employs a novel catalyst system enabling a higher yields of stereospecific polymers to be obtained as compared with the known systems.
It is known to polymerise unsaturated compounds by means of binary catalysts consisting of transition metals and aluminium alkyls or aluminium hydrides. We are the owners of many patents relating to the polymerisation of such compounds by means of catalyst systems consisting of transition metal compounds together with polyiminoalanes (PIA).
These patents include Patents Nos. 1,131,258 and 1,131,259. The former Patent describes and claims a catalytic composition for the production of polymers of alpha-olefins consisting of a transition metal compound and a linear aluminium iminic polymer having repeating units of the general formula: -(AlH-NR-)- in which R is an aryl, alkyl or cycloalkyl group. The latter Patent describes and claims a process for the stereo specific polymerization of conjugated dienes which comprises polymerizing at least one conjugated diene in the presence of a catalyst consisting of a compound of a Group IV to Group VIII (according to Deming) transition metal and a linear aluminium iminic polymer having repeating units of the general formula: -(AlH-NR-)- in which R is an alkyl aryl or cycloalkyl group.
According to the present invention, there is provided a catalyst system comprising (a) an aluminium compound having the general formula AlR~XHx wherein R is a hydrocarbon radical and x is 0,1,2 or 3, (b) a transition metal compound, and (c) a polyimino alane having the general formula (AlH NR')n wherein R' is a hydrocarbon radical and n is an integer, components (a) and (c) of the catalyst system being present as such and/or in the form of a product formed by reaction therebetween and/or in the form of a complex having the general formula (AIH NR')n. AlR3~XHx wherein R,R', n and x are as previously defined.
The present invention also provides a process for the polymerisation of a mono-olefin or di-olefin, wherein the polymerisation is carried out in the presence of a catalyst system of the invention.
Our Patent Specification No. 1,554,063 relates to a method for the modification of PIA by reacting the PIA with aluminium compounds having the general formula AIR3, whereby there are obtained organo aluminium imides derived from the partial or total replacement of the hydrogen atoms of the PIA radicals R with retention of the typical cage-like molecular structure, together with hydrides of aluminium having the formula AlR3~XHX.
These organo aluminium imides which are claimed in Patent Specification No. 1554063 have the general formula: (AlR NR'). (AIH NR )x wherein R and R' are the same or different and each is an alkyl group, an aryl group or a cycloalkyl group, and m is 1 to n' (wherein n' is an integer) and xis from 0 to n'-1, with the proviso that m+x is 4 or more, and with the proviso that, when m is 4, R' is other than a methyl or ethyl group. These organo aluminium imides, e.g. the specific organo aluminium imides claimed in claims 3 to 7 of Specification No. 1,554,063, can be present in the catalyst systems of the invention as the product of reaction between components (a) and (c) of the system.
As the quantity of aluminium compound AIR3 is increased, the reaction is conductive to the formation of aluminium hydrides having an increasing number of radicals R bound to aluminium until there are obtained PIA derivatives in which all of the hydrogen atoms have been replaced by radicals R.
The use of quantities of PIA in excess with respect to the aluminium compound AIR3 in the above reaction encourages the formation of simple hydrides of aluminium, namely
AlR2H, AlRH2, and AIR3, more particularly, the hydrogen-richer hydrides.
The interaction of the latter hydrides, or of the aluminium compounds AIR3 themselves, with the PIA is responsible for the formation of compounds which, together with the transition metal compound, give rise to catalyst systems suitable for use in the present invention, as has been ascertained by us on the basis of the following facts:
(1) The results which have been obtained in the polymerisation of isoprene using the catalyst systems of the invention, in comparison with the binary systems PIA + TiCl4 and
AIR3 + Tic4, indicate that the improved activity displayed by the catalyst systems of the invention can be attributed to particular interaction compounds of PIA with AIR3 or with AlR3~XHx. These results are described in detail in Examples 1 to 15 below with reference to
Figure 1 of the accompanying drawings. Similar results have been obtained in the polymerisation of ethylene with the ternary systems TiCl3 + PIA + AlR3 as compared with the binary systems TICS3 + PIA and TICS, + AIR3, as discussed in Examples 53-59 below.
(2) An activating effect due to the replacement of the hydrogen atoms of the PIA by alkyl groups is to be excluded since the totally or partially alkylated PIAs have proven to be much less active than the starting PIAs, or even inactive when used, together with Tic4, in the polymerisation of isoprene.
(3) An improved polymerisation activity towards isoprene has been observed, relative to PIA, with compounds (AlH NR)6.AlH3 obtained by chlorination of PIA and treatment with LiAIH4. In agreement with the following reaction schemes (1) and (2), such treatment results in the formation of complexes of PIA with AIH3: (AlH - NR)6 + HCI e [(AICI - NR) (AlH - NR)5] (1) [(AlCI - NR) (AlH - NR)5] + LiAlH4 H (AlH - NR)6.AlH3 + LiCl (2)
Figure 2 of the accompanying drawings. discussed in Example 15 to 35 below, refers to the activity increase as observed for compounds (AlH-NR)6.AlH3 with respect to the starting PIA.
The polymerisation is preferably carried out at a temperature ranging from -50"C to +250"C, more preferably in the range of from +10 C to 200 C, and under a pressure ranging from the vapor pressure of the monomer when the latter is liquid to 200 atmospheres, more preferably from 1 to 20 atmospheres, possibly in the presence of a solvent selected from aliphatic, aromatic and cycloaliphatic hydrocarbons.
The range of the molar ratio Al:Me (in which Al is the sum of the aluminium of the imino units and of the aluminium of the simple hydride or hydrocarbyl derivatives, and Me is the transition metal), which ratio, as is known, has an influence on the polymerisation velocity and the yield of solid polymer, is preferably from 0.1 to 500, the most preferred range depending upon the nature of the monomer which is to be polymerised.
The invention will now be illustrated by the following Examples.
Examples 1 - 15
A pop bottle, which had previously been heated and cooled under a nitrogen stream, was charged, the nitrogen atmosphere being maintained, with anhydrous n-heptane (90 ml),
TiCI4 (0.64 millimol) and then either PIA alone, or Al(C2H5)3 and PIA, in an amount consistent with the desired Al:Ti ratio. A brown precipitate formed.
The reaction mixture was aged by shaking it for 10 minutes at room temperature, and 20 grams of isoprene were added thereto. The bottle was sealed and then stirred for 2 hours in a thermostatic bath at 30"C. The polymerisation was then discontinued by adding 20 ml of methanol in which an antioxidant had been dissolved. The reaction mixture was poured into an excess of methanol. The solid polymer was dried at 500C under vacuum, and weighed.
The polymer structure was determined by infrared analysis, and the intrinsic viscosity of the polymer at 300C in toluene was measured.
Table 1 below reports the structure and the intrinsic viscosity of the polyisoprenes obtained with the above specified ternary catalyst system.
The results obtained in Examples 1 to 15 are shown in Figure 1 of the accompanying drawings. Figure 1, in which the yield of solid polymer on the ordinate is plotted against the Al:Ti ratio on the abscissa, shows the results obtained with the ternary system (A1H - N.iso-C3R7)6 + Al(C2R5)3 + TiCI4 having, in particular, a molar ratio of Al(C2H5)3: 6 (AIR - N. iso - C3H7)6 of 0.02, in comparison with the results obtained with the binary systems (AIR - N.iso - C3H7)6 + TiCl4 and A1(C2H5)3 + TiC14. In Figure 1, curve A relates to the system TiC14 + Al (C2H5)3, curve B relates to the system (AIR - N.iso C3H7)6 + TiC14, and curve C relates to the system (AIR - N.iso - C3H7)6 + Al(C2H5)3 +
TiCI4.
Examples 16 - 35
The catalysts were obtained by the following procedure. To a solution of (AIR - N.iso C3H7)6 (9.5 millimols) in diethyl ether (60 ml), there was added slowly a solution (13.5 ml) of HCI (9.5 millimols) in diethyl ether under a nitrogen atmosphere. The reaction which took place corresponded to the average substitution of an atom of hydrogen by a chlorine atom according to the reaction scheme 2 above (see S. Cucinella et al, J. Organometal.
Chem., 108, 13 (1976)). To the product thus obtained (57 x 10-3 gram-atoms of aluminum), in diethyl ether (100 ml), a solution of LiAIH4 (9.5 millimols in diethyl ether (12 ml) was added.
According to the reaction scheme 3 above, a compound II was formed. This compound was separated by evaporating the solution after separation of LiCI by filtering. The product was dried under a vacuum of 10-3 mmHg for 8 hours at room temperature.
Chemical analysis indicated that the ratio Al : N : active H of the product was 1: 0.87 1.25.
Polymerisation tests were carried out according to the procedure of Examples 1 to 15. In the case of the use of compound II + TiCI4, the polymer has a high 1,4 - cis content and a high viscosity value. For example, the polymer obtained for an AI:Ti ratio of 1.15 had the following properties : 1,4-cis content = 95.8%; 1,4-trans content = 1.3%; 1,2-unsaturated content = 0%; 3,4-unsaturated content = 2.9%; [n] 30"C toluene = 5.20.
The results obtained in Examples 15 to 35 are shown in Figure 2 of the accompanying drawings. Figure 2, in which the yield of solid polymer on the ordinate is plotted against the
Al:Ti ratio on the abscissa, shows the results obtained with the system (AIR - N.iso C3H7)6. AIR3 + TiC14 in comparison with the system (AIR - N.iso-C3R7)6 + TiC14. In
Figure 2, curve A relates to the former system and curve B relates to the latter system. The results shown in Figure 2 confirm the improved activity of the complexes formed from the (AIR - N.iso - C3H7)6 and the simple alane derivatives.
Examples 36-52
The polymerisation of isoprene was carried out, using the ternary system (AIR - N.iso - C3H7)6 + A1H(iso - C3H7)2 + TiCI4 and the binary system (AIR - N.iso - C3R7)6 +
TiCI4. Figure 3 of the accompanying drawings in which the yield of solid polymer on the ordinate is plotted against the Al:Ti ratio on the abscissa, shows the results obtained, curve
A relating to the ternary system and curve B relating to the binary system.
Polymerisation tests were carried out according to the procedure of Examples 1 to 27.
The polyisoprene obtained with the ternary system has a high content of 1,4-cis unsaturations and high viscosity []. For example, the polymer obtained using a catalyst system having an Al:Ti ratio of 1.20 had the following properties: 1,4-cis content = 95.6%; 1,4-trans content = 0%, 1,2-unsaturated content = 0.5%; 3,4-unsaturated content = 3.8%; total unsaturated content = 102; [rl 30"C toluene = 4.6.
Examples 53-59
A 5 litre autoclave equipped with stirrer was dried and deaerated by heating it under vacuum. It was filled with hydrogen at ambient pressure, and 1,600 ml of anhydrous n-heptane were then siphoned into the autoclave. The temperature was raised to 90"C, whereafter there were added 300 ml of n-heptane to which there had been added, in the order given, TiC13, PIA and Alert. The quantity of TiCI3 added to the n-heptane was 5 millimols. The quantity of PIA and AlEt3, and hence the ratio AlA,Et: AlPIA, was varied, the total quantity thereof added being 15 millimols.
On completion of the addition of the catalyst, hydrogen was added until a gauge pressure of 1.5 kg/cm2 was attained. Then, ethylene was added until a total pressure of 2.5 kg/cm2 was attained. This pressure was maintained constant with an ethylene stream adjusted by means of a pressure-stat. The absorption of ethylene was cheked continuously with a flow-meter. After two hours of polymerisation, the autoclave was cooled, the gas vented and the suspension dumped and centrifuged. The polymer was dried in an oven under vacuum at 60"C, and then weighed.
The results obtained are shown in Table 2 below. These results show the improved activity of the catalyst which contains AlEt3, particularly with a 6 or 8% molar content thereof, relative both to the catalyst containing no AlEt3 and to the complex formed from (AlR - N.iso - C3H7)6 and simple alane derivatives in agreement with the reaction schemes (1) and (2) above.
TABLE 1
Molar ratio Al* 1.4-cis 1,4-trans 1,2 3,4 Total 30"C AIR'3 Ti (%) (%) (%) (%) unsaturations toluene (AIR - NR)6 - 1.20 96.2 0 0.3 3.4 104 5.0
0.02 1.20 96.6 0 0.4 3.0 104 4.8
0.02 1.25 96.6 0 0.4 3.0 104 4.4 * Al includes the aluminium of the PIA and of the aluminium alkyl
TABLE 2
Example Polyimino AIPIA AIAI Et yield of polymer
alane (molar %) (molar %) (grams) 53 (AIH - NR)6 100 - 190 54 " 96 4 315
55 " 94 6 416
56 " 92 8 460
57 " 88 12 421
58 " - 100 217
59 (AlH-NR)6AlH3 100 - 335
WHAT WE CLAIM IS:
1. A catalyst system comprising (a) an aluminium compound having the general formula AlR~XHx wherein R is a hydrocarbon radical and x is 0, 1, 2 or 3, (b) a transition metal compound, and (c) a polyimino alane having the general formula (AIR - NR')n wherein R' is a hydrocarbon radical and n is an integer, components (a) and (c) of the catalyst system being present as such and/or in the form of a product formed by reaction therebetween and/or in the form of a complex having the general formula (AIR NR')n.AlR~xHx wherein R, R', n and x are as previously defined.
2. A catalyst system as claimed in claim 1, including, as said product, an organo aluminium imide as claimed in any of claims 1 and 3 to 7 of Specification No. 1,554,063.
3. A catalyst system as claimed in claim 1 or 2, including, as said complex, a complex having the general formula (AIR - NR')6.AIR3.
4. A catalyst system as claimed in claim 1, substantially as described in any of the foregoing Examples.
5. A process for the polymerisation of a mono-olefin or di-olefin, wherein the polymerisation is carried out in the presence of a catalyst system as claimed in any of claims 1 to 4.
**WARNING** end of DESC field may overlap start of CLMS **.
Claims (13)
- **WARNING** start of CLMS field may overlap end of DESC **.Examples 53-59 A 5 litre autoclave equipped with stirrer was dried and deaerated by heating it under vacuum. It was filled with hydrogen at ambient pressure, and 1,600 ml of anhydrous n-heptane were then siphoned into the autoclave. The temperature was raised to 90"C, whereafter there were added 300 ml of n-heptane to which there had been added, in the order given, TiC13, PIA and Alert. The quantity of TiCI3 added to the n-heptane was 5 millimols. The quantity of PIA and AlEt3, and hence the ratio AlA,Et: AlPIA, was varied, the total quantity thereof added being 15 millimols.On completion of the addition of the catalyst, hydrogen was added until a gauge pressure of 1.5 kg/cm2 was attained. Then, ethylene was added until a total pressure of 2.5 kg/cm2 was attained. This pressure was maintained constant with an ethylene stream adjusted by means of a pressure-stat. The absorption of ethylene was cheked continuously with a flow-meter. After two hours of polymerisation, the autoclave was cooled, the gas vented and the suspension dumped and centrifuged. The polymer was dried in an oven under vacuum at 60"C, and then weighed.The results obtained are shown in Table 2 below. These results show the improved activity of the catalyst which contains AlEt3, particularly with a 6 or 8% molar content thereof, relative both to the catalyst containing no AlEt3 and to the complex formed from (AlR - N.iso - C3H7)6 and simple alane derivatives in agreement with the reaction schemes (1) and (2) above.TABLE 1 Molar ratio Al* 1.4-cis 1,4-trans 1,2 3,4 Total 30"C AIR'3 Ti (%) (%) (%) (%) unsaturations toluene (AIR - NR)6 - 1.20 96.2 0 0.3 3.4 104 5.0 0.02 1.20 96.6 0 0.4 3.0 104 4.8 0.02 1.25 96.6 0 0.4 3.0 104 4.4 * Al includes the aluminium of the PIA and of the aluminium alkyl TABLE 2 Example Polyimino AIPIA AIAI Et yield of polymer alane (molar %) (molar %) (grams) 53 (AIH - NR)6 100 - 190 54 " 96 4 315 55 " 94 6 416 56 " 92 8 460 57 " 88 12 421 58 " - 100 217 59 (AlH-NR)6AlH3 100 - 335 WHAT WE CLAIM IS: 1. A catalyst system comprising (a) an aluminium compound having the general formula AlR~XHx wherein R is a hydrocarbon radical and x is 0, 1, 2 or 3, (b) a transition metal compound, and (c) a polyimino alane having the general formula (AIR - NR')n wherein R' is a hydrocarbon radical and n is an integer, components (a) and (c) of the catalyst system being present as such and/or in the form of a product formed by reaction therebetween and/or in the form of a complex having the general formula (AIR NR')n.AlR~xHx wherein R, R', n and x are as previously defined.
- 2. A catalyst system as claimed in claim 1, including, as said product, an organo aluminium imide as claimed in any of claims 1 and 3 to 7 of Specification No. 1,554,063.
- 3. A catalyst system as claimed in claim 1 or 2, including, as said complex, a complex having the general formula (AIR - NR')6.AIR3.
- 4. A catalyst system as claimed in claim 1, substantially as described in any of the foregoing Examples.
- 5. A process for the polymerisation of a mono-olefin or di-olefin, wherein the polymerisation is carried out in the presence of a catalyst system as claimed in any of claims 1 to 4.
- 6. A process according to claim 5, wherein the polymerisation is carried out at atemperature of from -50 to 2500C.
- 7. A process according to claim 6 for the polymerisation of a di-olefin, wherein the polymerisation is carried out at a temperature of from 10 to 500C.
- 8. A process according to claim 6 for the polymerisation of a mono-olefin, wherein the polymerisation is carried out at a temperature of from 50 to 1500C.
- 9. A process according to any of claims 5 to 8, wherein the polymerisation is carried out under a pressure of from the vapour pressure of the olefin to 100 atmospheres.
- 10. A process according to claim 9, wherein the polymerisation is carried out under a pressure of from 1 to 50 atmospheres.
- 11. A process according to any of claims 5 to 10, wherein the polymerisation is carried out in a solvent selected from aliphatic, aromatic and cycloaliphatic hydrocarbons.
- 12. A process according to claim 5, substantially as described in any of the foregoing Examples.
- 13. The polymerisation product of a process according to any of claims 5 to 12.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT29602/76A IT1064496B (en) | 1976-11-22 | 1976-11-22 | PROCESS FOR THE POLYMERIZATION OF MONO AND DIOLEFINIC COMPOUNDS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1587659A true GB1587659A (en) | 1981-04-08 |
Family
ID=11228082
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB48445/77A Expired GB1587659A (en) | 1976-11-22 | 1977-11-21 | Polymerisation of mono-olefins and diolefins and catalyst therefor |
Country Status (20)
| Country | Link |
|---|---|
| JP (1) | JPS6055526B2 (en) |
| AU (1) | AU510549B2 (en) |
| BE (1) | BE861062A (en) |
| CA (1) | CA1106543A (en) |
| CH (1) | CH629507A5 (en) |
| CS (1) | CS203177B2 (en) |
| DD (1) | DD133334A5 (en) |
| DE (1) | DE2751919C2 (en) |
| DK (1) | DK149127C (en) |
| FR (1) | FR2371464A1 (en) |
| GB (1) | GB1587659A (en) |
| HU (1) | HU176874B (en) |
| IL (1) | IL53366A (en) |
| IT (1) | IT1064496B (en) |
| LU (1) | LU78555A1 (en) |
| NL (1) | NL180012C (en) |
| NO (1) | NO149924C (en) |
| SE (1) | SE440362B (en) |
| YU (1) | YU39055B (en) |
| ZA (1) | ZA776811B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62127088U (en) * | 1986-02-05 | 1987-08-12 | ||
| BE1007698A3 (en) * | 1993-11-04 | 1995-10-03 | Solvay | Catalyst system used for the polymerization of alpha-olefin polymerization and method for this. |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1423016A (en) * | 1972-12-20 | 1976-01-28 | Snam Progetti | Mono-olefin-conjugated diene copolymerisation using a ternary catalyst system |
| FR2237911A1 (en) * | 1973-07-04 | 1975-02-14 | Okktinskoe Mauchno Proizv | High yield ethylene(-propylene)polymer prepn. - using titanium chloride and polyalkylalumoxane reactn. prod. as catalyst system |
| IT1019677B (en) * | 1974-07-01 | 1977-11-30 | Snam Progetti | POLYMER COMPOUNDS OF ALUMINUM OF POLYIMINIC NATURE PROCEDURE FOR THEIR PREPARATION AND THEIR USE AS COMPONENTS OF CATALYTIC SYSTEMS FOR THE POLY MERIZATION OF UNSATURATED COMPOUNDS |
-
1976
- 1976-11-22 IT IT29602/76A patent/IT1064496B/en active
-
1977
- 1977-11-09 CA CA290,496A patent/CA1106543A/en not_active Expired
- 1977-11-09 AU AU30478/77A patent/AU510549B2/en not_active Expired
- 1977-11-13 IL IL53366A patent/IL53366A/en unknown
- 1977-11-15 ZA ZA00776811A patent/ZA776811B/en unknown
- 1977-11-18 CH CH1415177A patent/CH629507A5/en not_active IP Right Cessation
- 1977-11-18 NO NO773949A patent/NO149924C/en unknown
- 1977-11-21 DE DE2751919A patent/DE2751919C2/en not_active Expired
- 1977-11-21 YU YU02770/77A patent/YU39055B/en unknown
- 1977-11-21 SE SE7713140A patent/SE440362B/en not_active IP Right Cessation
- 1977-11-21 FR FR7734946A patent/FR2371464A1/en active Granted
- 1977-11-21 GB GB48445/77A patent/GB1587659A/en not_active Expired
- 1977-11-21 CS CS777645A patent/CS203177B2/en unknown
- 1977-11-21 DK DK516077A patent/DK149127C/en not_active IP Right Cessation
- 1977-11-21 JP JP52139027A patent/JPS6055526B2/en not_active Expired
- 1977-11-21 LU LU78555A patent/LU78555A1/xx unknown
- 1977-11-22 DD DD7700202190A patent/DD133334A5/en unknown
- 1977-11-22 BE BE182820A patent/BE861062A/en not_active IP Right Cessation
- 1977-11-22 NL NLAANVRAGE7712876,A patent/NL180012C/en not_active IP Right Cessation
- 1977-12-21 HU HU77SA3076A patent/HU176874B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| NL7712876A (en) | 1978-05-24 |
| FR2371464B1 (en) | 1980-05-16 |
| IL53366A (en) | 1981-03-31 |
| IL53366A0 (en) | 1978-01-31 |
| DK149127B (en) | 1986-02-03 |
| NO149924B (en) | 1984-04-09 |
| FR2371464A1 (en) | 1978-06-16 |
| BE861062A (en) | 1978-05-22 |
| NO773949L (en) | 1978-05-23 |
| CH629507A5 (en) | 1982-04-30 |
| DE2751919C2 (en) | 1982-11-25 |
| SE440362B (en) | 1985-07-29 |
| YU277077A (en) | 1982-06-30 |
| IT1064496B (en) | 1985-02-18 |
| JPS6055526B2 (en) | 1985-12-05 |
| CA1106543A (en) | 1981-08-04 |
| NL180012C (en) | 1986-12-16 |
| JPS5365382A (en) | 1978-06-10 |
| DK149127C (en) | 1986-07-14 |
| NL180012B (en) | 1986-07-16 |
| YU39055B (en) | 1984-02-29 |
| HU176874B (en) | 1981-05-28 |
| CS203177B2 (en) | 1981-02-27 |
| SE7713140L (en) | 1978-05-23 |
| AU3047877A (en) | 1979-06-28 |
| NO149924C (en) | 1984-08-01 |
| DK516077A (en) | 1978-05-23 |
| DD133334A5 (en) | 1978-12-27 |
| DE2751919A1 (en) | 1978-05-24 |
| AU510549B2 (en) | 1980-07-03 |
| LU78555A1 (en) | 1978-04-13 |
| ZA776811B (en) | 1978-09-27 |
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