(O 03/055921 Al s (12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (19) World Intellectual Property Organization International Burea (43) International Publication Date 10 July 2003 (10.07.2003) PCT (10) International Publication Number WO 03/055921 Al (51) International Patent Classifiation iss ‘COSF 10/00, (2) International Application Number: PCTVEPO2/14252 (22) International Filing Date 13 December 2002 (13.12.2002), (25) Filing Language: (26) Publication Language: (G0) Priority Data: 01205091024 December 2001 24.12.2001) EP (71) Applicant (or all designated States excep US: BASELL, POLIOLEFINE ITALIA S.PA, [T/IT]; Via Pergolesi25, 120124 Milano (I). m 75) Inventors; and Inventors/Applicants (for US only): COLLINA, Giana (ITAT]; Via XI Apuile 1945, 3, 14044 Ferrara (T) BRITA, Diego [T/T]; Via Mulineto, 63, 144100 Ferrara (81) Designated States (national): AE, AG, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, BZ, CA, CH,CN, CO, CR. CU CZ, DE, DK, DM, D7, EC, EE, ES, 1, GB, GD, GE, GH, GM, HR, HU, ID, TL, IN, IS, JP KE, KG, KP, KR, KZ, L LK, LR,LS, LT, LU, LY, MA, MD, MG, MK, MN, MW. MX, MZ, NO, NZ, OM, PH, PL, PT, RO, RU, SD, Si SK, SL, TJ, TM, TN, TR, TT, TZ, UA, UG, US, YU, ZA, 7M, ZW, (84) Designated States (regional): ARIPO patent (GH, GM, KE, LS, MW, MZ, SD, SL, SZ, TZ, UG, ZM, ZW), Eurasian patent (AM, AZ, BY, KG, KZ, MD, RU, TI. TM) European patent (NT, BE, BG, CH, CY, CZ, DE, DK, El BS, FI, FR, GB, GR. IB, IT, LU, MC, NL, PT, SE, Sl SK. TR), OAPI patent (BF, BJ, CE, CG, Cl, CM, GA, GN, GQ, GW, ML, MR, NE, SN, TD, 1) Declarations under Rule 4.17: ‘10 the applican’s entitlement to claim the priority of the earlier application (Rule 4.17(i) for all designations of mentorship (Rule 4.174) for US ony Published: an, with international search report (74) Agent: COLUCCI, Giuseppe; Basel Polioleline lala For avo-letter codes and other abbreviations, refer fo the "Guid S.p.A. Intellectual Property, Ple G. Donegan, 12,1-4100 ance Notes on Codes and Abbreviations” appearing at the begin Ferrara (IT, ning of each regular issue ofthe PCT Gazette (54) Title: ZIEGLER NATTA CATALYST FOR THE POLYMERIZATION OF OLEFINS (57) Abstract: Catalyst forthe polymerization of olefins CH:=CHR, wherein R is hydrogen or a hydrocarbon radical having 1-12 cearhon atoms, comprising (1) a sold catalyst component comprising Mg, Ti, C1, and OR groups, where Ris a C1-C10 alkyl group ‘optionally containing heteroatoms, in which the TiMg weight radio is from 2 to 6.5 the CI/T weight rato is from 1.5 © 35 (0 and the OR/T weight rato is from 0.7 to 2 and at least $O% of the titanium atoms are ina valence state lower than 4 and (II) an alkyaluminum halide as eocatalyst. The sad catalyst allow the preparation of ethylene copolymers with a Tow content of xylene soluble fractions,Wo 03/055921 PCTIEPOR/I4252 ZIEGLER NATTA CATALYST FOR THE POLYMERIZATION OF OLEFINS ‘The present invention relates to catalysts for the polymerization of olefins CHz=CHR, wherein R is hydrogen or a hydrocarbon radical having 1-12 carbon atoms. In particular, the present invention relates to a catalyst comprising (1) a solid catalyst component based on Mg, Ti, halogen and OR groups, and ([I) halogenated aluminum alkyls as cocatalyst. This catalyst is particularly suitable for the preparation of copolymers of ethylene with o-olefins due to its capability of randomly distribute the c-olefins along the polymer chain, Accordingly, another object of the present invention is the use of said catalysts in a process for the copolymerization of olefins in order to produce ethylene/.-olefin copolymers Linear low-density polyethylene (LLDPE) is one of the most important products in the polyolefin field. Due to its characteristics, it finds application in many sectors and in particular in the field of wrapping and packaging of goods where, for example, the use of stretchable films based on LLDPE constitutes an application of significant commercial importance. LLDPE is commercially produced with liquid phase processes (solution or slurry) or via the more economical gas-phase process. Both processes involve the widespread use of Ziegler-Natta catalysts that are generally formed by the reaction of a solid catalyst component, comprising a titanium compound, deposited on a Mg containing support, with an alkylaluminium compound. As far as the preparation of LLDPE is concerned, said catalysts are required to show good comonomer distribution suitably coupled with high yields. The good comonomer distribution ensures the achievement of an ethylene copolymer which has a density sufficiently lower with respect to HDPE while at the same is not affected by too high values of fractions soluble in hydrocarbon solvent like hexane or xylene which worsen certain properties of the said copolymers, and in particular tend to increase the blocking phenomenon observed for example in the rolls of LLDPE film. USP 4,218,339 discloses catalyst components for the polymerization of olefins obtained by the reacting a Mg compound, preferably a Mg halide with an oxygen containing compound of a metal M selected from Ti, V or Zr and then by contacting the so obtained product with a compound, or a mixture of compounds in order to explicate on said reaction product an halogenating and reducing action. The said catalyst components are transformed in active catalyst for the polymerization of olefins by reaction with aluminum trialkyls in particular triisobutyl aluminum. Although generically stated that the catalysts are active also in the copolymerization of ethylene with alpha olefins, their use and effectiveness in this type of polymerization is not reported. CONFIRMATION COPYWo 03/055921 PCTIEPO2/I4252 EP 155682 discloses the use of the same kind of catalyst components in the preparation of LLDPE polymers. From the comparison of Example 11 and comparative example 7 it is apparent that the said catalyst components are endowed with a good capability of distributing the comonomer only when a specific nitrogen containing external donor is used. together with the aluminum trialkyl. The presence of nitrogen containing extemal donor has. ‘two negative effects: it may decrease the activity of the catalyst and increase the cost of the catalyst. No mention is made of the possibility of using a halogenated aluminum alkyl as cocatalyst. ‘The applicant has now found catalysts for the polymerization of olefins that are particularly suitable for the prepar n of LLDPE polymers comprising (1) a solid catalyst component comprising Mg, Ti, Cl, and OR groups, where R is a C1-C10 alkyl group optionally containing heteroatoms, in which the Ti/Mg weight ratio is from 2 to 6.5 the CUTi weight ratio is from 1.5 to 3.5 and the OR/Ti weight ratio is from 0.7 to 2.5 and at least 50% of the titanium atoms is in a valence state lower than 4 and (11) an alkyaluminum halide as cocatalyst. The alkylaluminum halide is suitably selected among alkylaluminum chlorides and in particular among diethylaluminum chloride, diisobutylaluminum chloride, Al- sesquichloride and dimethylaluminum chloride. Dimethylaluminum chloride is especially preferred. In the solid catalyst component (I) the Ti/Mg weight ratio is preferably from 2.25 to 6 and more preferably from 2.4 to 5.5 the CVTi weight ratio is preferably from 1.75 to 3.25 and preferably from 2 to 3, the OR/Ti weight ratio is preferably from 0.8 to 2.25 and more preferably fiom 1 to 2; it is moreover preferred that at least 70%, and more preferably 80%, of the titanium atoms is in a valence state lower than 4. The solid catalyst component (1) can be prepared according to the general disclosure of USP 4,218,339. In particular it can be obtained by reacting: (A) a magnesium compound of formula X:Mq(ORi)z-, wherein X is a halogen atom, hydroxyl group or an alkyl, aryl or cycloalkyl radical containing 1-20 carbon atoms; R’ is an alkyl, aryl or cycloalkyl radical containing 1-20 carbon atoms, or a~COR’ radical in which R” has the same meaning as R; 0S1S2, oF products of reaction of said compounds with electron-donor compounds; with (B) a compound of Ti, containing at least two titaniumoxygen bonds Ti-OR? wherein R’ is an alkyl. aryl or cycloalkyl radical having 1-20 carbon atoms, and (C) a compound or a mixture of compounds, other than the aluminium halides, capable of exerting a halogenating and a reducing action on compound (B), ic. capable of substituting in the compound (B) at least one group —OR? with a halogen atom and of reducing the titanium 2Wo 03/055921 PCT/EPON/14252 of compound (B) to a lower valence. As mentioned above a mixture of a halogenating ‘compound with a compound having a reducing ability can be used. Examples of (A) compounds are the Mg dihalides, the Mg mono-and dialcoholates, examples of which are Mg(OCzHs)2, Mg(O-n-CsHs)2, CoHsO-MgCl, n-Csl1p0-MgCl, the Mg carboxylates such as Mg acetates. As Mg dihalides the following compounds can be employed MgCk, which is the preferred one, MgBr, Mgh, MgChenR°OH (R*=alkyl group, n=1-6), for example MgCh3C2HsOH, or MgClen H2O (0Sn<6), and adducts of MgCh with electron donor compounds not containing active hydrogen atoms, like the esters of carboxylic acids, the ethers, ketones or amines, Example of components (B) are: Ti(OC:Hs)s, Ti(O-m-CiH)s, Ti(O-i-Cali)s, Ti(OCsHs)s, ‘Tictriacetylacetonate Ti (OCHs)2 (OC:H:)z. However, haloalcoholates can be also used, as. for instance (n-CsHo0);TiCl. Examples of compounds or mixture of components (C) comprise a halogen-containing, preferably a chlorine-containing compounds, capable of substituting a halogen atom for at least one group -OR? in component (B). Specific examples of such compounds include organic acid halides R°COX (in which X is halogen, preferably chlorine, and R* is an aliphatic or aromatic radical); hydrogen halides such as HCI, SOCb, COCh, TiC, BCh, and others. Particularly satisfactory results are achieved by using as halogenating agents halogen- containing silicon compounds or halogen and hydrogen-containing silicon compounds. The latter act as both reducing agents and halogenating agents. Specific examples of such silicon compounds include: = silicon halides having formula SiXsaYo, in which X and Y represent halogen atoms, ¢.g., Cl and Br, and n is anumber varying from zero to 3, inclusive as SiCls, - chlorosiloxanes of formula SisOn-1Clns2, in which n is a number varying form 2 to 7 inclusive, e.g., Si0Cls; = Halogenated polysilanes having formula SixXzui2, wherein X is halogen and n is a number varying form 2 to 6, inclusive, for instance SisClio; = Alkoxy-halogensilanes of formula Si(OR)sXn in which X is halogen, R is alkyl or aryl having 1 to 20 carbon atoms and n is a number from 1 to 3, inclusive, e.g., Si(OCzHS)Ch. - Halogensilanes having formula SiH,Xn in which X is halogen and n is a number varying form 1 to 3, inclusive, e.g., SiHCls; - Alkyl-halogensilanes having formula RxSiH.X, wherein R is an aliphatic or aromatic 3WO 031055921 PCTIEPO2/I4252 radical, X is halogen, n is a number from 1 to 3, inclusive, x is a number varying form zero to 2, inclusive, and y is a number varying form 1 to 3, inclusive, e.g., CaHsSiCls; CH3SiCLH; (CHs)2SiCh; Examples of agents having a reducing activity to be used as compound (C) include Na-~ alkyls, Li-alkyls, Zn-alkyls, Mg-alkyls and corresponding aryl-derivatives, Grignard compounds of the type RMgX(R is an aliphatic or aromatic hydrocarbon radical; X is halogen), the Natalcohol system, and furthermore NaH and Lill. Particularly effective as reducing agents are the polyhydrodiloxanes in which the monomer unit has the general formula Wherein R is H, halogen, alkyl with 1 to 10 carbon atoms, aryl, alkoxyl, aryloxyl or carboxyl, and the polymerization grade ranges from 2 to 1,000, preferably from 3 to 100. Specific examples of such polyhydrosyloxanes include the compounds: (CHs)sSi-O[(CH3)HSiO};-Si(CHs)s, (CHSHSiO)s, (CH3HSiO)s, HsSi-O-Sitz-OSiFb, phenylhydropolysiloxanes in which the hydrogen atoms can be partially replaced by methyl group. Other silicon compounds useful as reducing agent in the practice of this invention are: = Silanes SisHzat2, in which n is a number equal to or higher that 1, preferably equal to or higher than 3, e.g., SisHs; - Polysilanes that contain the group (SiH) in which x22 - Alkyl or aryl silanes R,SiH+x, in which R is alkyl or aryl and x is a number varying from 1 to 3, inclusive, e.g., (CoHls)sSiH; - Alkoxy — of atyloxy — silanes (RO),SiHe.y in which R is alkyl or aryl and x is a number varying for 1 to 3, inclusive, e.g., (CsHs0)2SiH. ‘The new catalyst-forming components of the invention can be obtained by reacting (A) and (B) and (©) in an aliphatic or aromatic hydrocarbon diluent or in the absence of diluent. ‘When at least one of the reagents is in the liquid state at the reaction temperature and pressure, the use of a solvent can be omitted. (A) and (B) can be reacted preferably until a homogeneous product is obtained which isWo 03/055921 PCTIEPO2/I4252 then reacted with component (C). However, if (C) consists of a halogenating compound plus a reducing compound, the order of addition makes no difference: i.e., either the halogenating compound or the reducing ‘compound can be reacted first. It is also possible to add the compounds simultaneously. ‘The reactions are conducted at a temperature ranging from -10°C. to +250°C, preferably fiom 20°C. to 200°C. The selection of the temperature depends also on the type of component (C), because the higher its reducing power, the lower the preferred reaction temperatures. Since (C) is both a halogenating agent and a reducing agent, or it consists of a halogenating compound plus a reducing compound, the titanium, in the final catalyst-forming component is prevailingly in the trivalent state, provided that a sufficient quantity of reducing agent is used. ‘The component (1) can be used to prepare the catalyst system of the invention directly as obtained from its preparation process. Alternatively, it can be pre-polymerized before being used in the main polymerization process. This is particularly preferred when the main polymerization process is carried out in the gas phase. The prepolymerization can be carried cout with any of the olefins CHa-CHR, where R is H or a C1-C10 hydrocarbon group. In particular, it is especially preferred to pre-polymerize ethylene or mixtures thereof with one or more c-olefins, said mixtures containing up to 20% in moles of a-olefin, forming amounts of polymer from about 0.1 g per gram of solid component up to about 100 g per gram of solid catalyst component. The pre-polymerization step can be carried out at temperatures from 0 to 80°C, preferably from 5 to 50°C, in the liquid or gas phase. The co-catalyst can be the same as, of different from, the cocatalyst (II). Therefore it can be used an aluminumalkyl halide or the corresponding not halogenated ones such as aluminum triethyl, aluminum triisobutyl, aluminum tri-n-octyl ete. In a particular embodiment of the present invention, a halogenated aluminumalkyl compound is used also in the prepolymerization step. The pre-polymerization step can be performed in-line as a part of a continuous polymerization process or separately in a batch process. The batch pre-polymerization of the catalyst of the invention with ethylene in order to produce an amount of polymer ranging from 0.5 to 200 g per gram of catalyst component is particularly preferred. The prepolymerized catalyst component can also be subject to a further treatment with a titanium compound before being used in’ the main polymerization step. In this case the use of TiCly is particularly preferred. The reaction with the Ti compound can be carried out by suspending the prepolymerized catalyst component in the liquid Ti compound optionally in mixture with a liquid diluent; the mixture is heated to 5WO 03/055921 PCT/EPO2/14252 60-120°C and kept at this temperature for 0.5-2 hours. Examples of gas-phase processes wherein it is possible to use the catalysts of the invention are described in WO 92/21706, USP 5,733,987 and WO 93/03078. These processes comprise a pre-contact step of the catalyst components, a pre-polymerization step and a gas phase polymerization step in one or more reactors in a series of fluidized or mechanically stirred bed. The catalysts of the present invention are particularly suitable for preparing linear low density polyethylenes (LLDPE, having a density lower than 0.940 g/cm’) and very-low-density and ultra-low-density polyethylenes (VLDPE and ULDPE, having a density lower than 0.920 g/cm’, to 0.880 g/cm’) consisting of copolymers of ethylene with one or more alpha- olefins having from 3 to 12 carbon atoms, having a mole content of units derived from ethylene of higher than 80%, However, they can also be used to prepare a broad range of polyolefin products including, for example, high density ethylene polymers (HDPE, having a density higher than 0.940 g/cm’), comprising ethylene homopolymers and copolymers of ethylene with alpha-olefins having 3-12 carbon atoms; elastomeric copolymers of ethylene and propylene and elastomeric terpolymers of ethylene and propylene with smaller proportions of a diene having a content by weight of units derived from ethylene of between about 30 and 70%; isotactic polypropylenes and crystalline copolymers of propylene and ethylene and/or other alpha-olefins having a content of units derived from propylene of higher than 85% by weight; impact resistant polymers of propylene obtained by sequential polymerization of propylene and mixtures of propylene with ethylene, containing up to 30% by weight of ethylene; copolymers of propylene and i-butene having a number of units derived from 1-butene of between 10 and 40% by weight. ‘The following examples are given in order to further describe the present invention in a non- limiting manner. CHARACTERIZATION ‘The properties are determined according to the following methods: Melt Index: measured at 190°C according to ASTM D-1238 condition “E” (load of 2.16 Kg) and “F* (load of 21.6 Kg); Fraction soluble in xylene. The solubility in xylene at 25°C was determined according to the following method: About 2.5 g of polymer and 250 ml of o-xylene were placed in a round- bottomed flask provided with cooler and a reflux condenser and kept under nitrogen. The mixture obtained was heated to 135°C and was kept under stirring for about 60 minutes. ‘The final solution was allowed to cool to 25°C under continuous stitting, and was then 6Wo 03/055921 PCTIEPO2/I4252 filtered. The filtrate was then evaporated in a nitrogen flow at 140°C to reach a constant weight. The content of said xylene-soluble fraction is expressed as a percentage of the original 2.5 grams. Comonomer content 1-Butene was determined via Inftared Spectrometry. ‘The o-olefins higher than 1-butene were determined via Infra-Red analysis. Effective density: ASTM-D 1505 EXAMPLES Example 1 Preparation of the Solid Component Preparation of solution A MgCl: (69g) and 510 ml of Ti(OBu)s are stirred in a flask under nitrogen at a temperature of 140°C obtaining after 5 hours a complete dissolution of the MgCl. Ina 2 L reactor equipped with blase stirrer were introduced 660ml of heptane and, at a temperature of 60°C, under stirring 225 ml of solution A prepared as described above. After that 165 ml of polymethylhydrosiloxane (PMHS) were added. After 10 minutes the mixture was cooled down to 50°C. At this point a first aliquot of SiCly (20ml) was added in 30 min while a second aliquot (155ml) was added in the subsequent 30min. The temperature was brought to 65°C and left under stirring for two hours. After this period the solid was allowed to settle and the supernatant siphoned off. The solid obtained was washed three times with heptane at 60°C and three times with heptane at room temperature. ‘The solid obtained had the following composition: Ti (total) 15.3 wi.% Tired. 13.6% Mg Swt% a 36.3 wi.% Si 4S%wt -OBu 22 wt% Preparation of the pre-polymer The catalyst prepared above was prepolymerized in hexane slurry with ethylene in the presence of Dimethylatuminum chloride (DMAC) at a temperature of 0°C for the timeWo 03/055921 PCTIEPO2/I4252 necessary to reach a prepolymer/catalyst weight ratio of about 1. Ethylene copolymerization ‘A 15.0 liter stainless-steel fluidized reactor equipped with gas-circulation system, cyclone separator, thermal exchanger, temperature and pressure indicator, feeding line for ethylene, propane, I-butene and hydrogen was used. The gas-phase apparatus was purified by fluxing pure nitrogen at 40°C for 12 hours and then was circulated a propane (10 bar, partial pressure) mixture containing 1.5 g of TEAL at 80°C for 30 minutes. It was then depressurized and the reactor washed with pure propane, heated to 75°C and finally loaded with propane (2 bar partial pressure), I-butene, ethylene (7.1 bar, partial pressure) and hydrogen (2.1 bar, partial pressure). The prepolymer as prepared above, and the aluminum alkyl halide reported in table 1 were jected into the gas-phase reactor by using a propane overpressure (1 bar increase in the gas-phase reactor), The final pressure, in the fluidized reactor, was maintained constant during the polymerization at 75 °C for 180 minutes by feeding a 10 wt.% 1-butene/ethylene mixture. [At the end, the reactor was depressurised and the temperature was dropped to 30°C. The collected polymer was dried at 70 °C under a nitrogen flow and weighted. The polymer characteristics are collected in table 1. Examples 2-3 and comparison Example 1 The polymerization was carried out according to the same procedure of example 1 with the difference that a different cocatalyst was used (Ex.3 and Comp. Ex. 1) or a polymer with a lower butene-1 content was produced (Ex. 2). The polymer characteristics are shown in table 1.WO 03/055921 PCT/EPON/14252 Table 1 Ex.1 Ex.2 Ex.3 Comp. Ex. 1 Cocat DMAC |DMAC |DEAC [TEAL MIE 0.87 08 1.09 0.87 ~ YowtCr 105 99 104 108 Density 0916 | 0.917 0.918 0917 | Solubles wi | i 88 115 149WO 03/055921 PCT/EPO2/14252 CLAIMS ib 10. Catalyst for the (co)polymerization of olefins CH2=CHR, wherein R is hydrogen or a hydrocarbon radical having 1-12 carbon atoms, comprising (1) a solid catalyst component comprising Mg, Ti, Cl, and OR groups, where R is a C1-C10 alkyl group optionally containing heteroatoms, in which the Ti/Mg weight ratio is from 2 to 6.5 the CVTi weight ratio is from 1.5 to 3.5 and the OR/Ti weight ratio is from 0.7 to 2.5 and at least 50% of the titanium atoms are in a valence state lower than 4 and (I) an alkyaluminum halide as cocatalyst. Catalyst according to claim 1 in which the alkylaluminum halide is an alkylaluminum chloride. Catalyst according to claim 2 in which the alkylaluminum halide is diethylaluminum chloride, diisobutylalumunum chloride, Al-sesquichloride or dimethylaluminum chloride. Catalyst according to claim 1 or 3 in which the Ti/Mg weight ratio is from 2.25 to 6, the CVTi weight ratio is from 1.75 to 3.25, the OR/Ti weight ratio is from 0.8 to 2.25. Catalyst according to claim 1 in which at least 70% of the titanium atoms are in a valence state lower than 4, Catalyst according to claim 4 in which the Ti/Mg weight ratio is from 2.4 to 5.5, the CITi weight ratio is from 2 to 3 and the OR/Ti weight ratio is from 1 to 2. Catalyst according to claim 5 in which at least 80% of the titanium atoms are in a valence state lower than 4, Catalyst according to claim 1 in which the solid catalyst component (1) is prepolymerized with one or more of the olefins CH2=CHR, where R is H or a C1-C12 hydrocarbon group. Catalyst according to claim 8 prepolymerized with one or more olefins up to forming amounts of polymer from about 0.1 g per gram of solid component to about 100 g per ‘gram of solid catalyst component. Process for the polymerization of olefins CH2-CHR, where R is H or a C1-Cl0 hydrocarbon group, carried out in the presence of the catalyst according to any one of the claims 1-9, 10mprnarionay SEARCH REPORT In pions Appteaton wo PCT/EP 02/14252 7 SLASSPOATON OF RIOT MATTER Tre? COBF10/00° COBF4/634 Accorangointmaios Pater leatcaon (PO ort ot nan escaion ad PC 'B. FIELDS SEARCHED IPC 7 COBF "Wb donmeniaton searched (Gasaiclon sar lowed by Camcaion aOR) Dsaanaon seca oh Bsn Haim Goa naton oa ae Wa uch Geri vs HED He ae ST EP0-Internal "laa daa Wass consul ugha Placa snare (sie Oa aba aFa, Wher PSC aT eS vA) (DOCUMENTS CONSIDERED TO BE RELEVANT ‘cateeoy* | Cision of ocart wit noston, whew aprontia, othe love paseanee ebrorte came examples 2,10,18 examples 12-14 9 March 1993 (1993-03-09) example 26 x US 4 703 026 A (MATSUURA MITSUYUKI ET AL) 1-10 27 October 1987 (1987-10-27) x Us 4 399 055 A (MATSUURA MITSUYUKI ET AL) 1-10 16 August 1983 (1983-08-16) z EP 0 306 939 A (SUMITOMO CHEM IND) 1-10 15 March 1989 (1989-03-15) example 10 y Us 5 192 731 A (KIOKA MAMORU ET AL) 1-10 J] Furteraecunris ar tsa he contusion ot box Dk] Patsy mentor ar tte in nex. pda calagotae of od deamon “Ar soca! dt th gnea state ote an wash nat oeisredte bo pa ance "cater coca tt punated ono otto nemo ing da "1 socio when ay to cuts on pry ami ‘ls ced elation na pubealon ee aah: ‘lion or ener specalrssoy ee apache) "0" einer ring oan les ose, ein of ** aperentpbhe ios enema ona ng but Biarhon he pron dee clare 7 rar a Seevonmisiersce chy ane coer tenten are cer item toast ana “+ cea per tts ti Se a aoe line iearalaec wires ieee omnaony sameeren “et nt a et ly aie of eal corpOn A ara Sea ‘ala naling a he Wiarton coach PE Fae (eo) 30-98 24 March 2003, 28/03/2003 Tae and aing waar of fo SA ‘Aaoraad oir Suchen Fall Oc. 10 Puentan 2 Tal fo 70) 940° So, 91 5p Balmer, J-P Fam PaTacaIO al anprmarionat SEARCH REPORT Tnigppors Aonicaion No PCT/EP 02/14252 ‘[Cantnation) BOCUUENTS CONSIDERED TOBE RELEVANT Talegoy™ | Clalon of aoaan wah acon ware HORNE Te OA PSS i Us: 4 530 983 A (MATSUURA MITSUYUKI ET AL) 23 July 1985 (1985-07-23) the whole document A EP 0 595 565 A (MITSUBISHI PETROCHEMICAL CO) 4 May 1994 (1994-05-04) the whole document A US 4 540 680 A (SPECA ANTHONY N) 10 September 1985 (1985-09-10) the whole document 1-10 1-10 1-10NATIONAL SEARCH REPORT capac esac formation on pte fay members POMEP 02/14252 Patent dosument Puniaton Paton famty ubcatton cad in search report ae members) ale us 4703026 A 27-10-1987 oP. 1996693 ¢ 08-12-1995 oP 7025814 B 22-03-1995 OP 61285203 A 16-12-1986 oP. 1996694 ¢ 08-12-1995 oP. 7025815 B 22-03-1995 OP 61285205 A 16-12-1986 3671022 Di 13-06-1990 0205159 AL 17-12-1986 Us 4399055 A 16-08-1983 JP 151822 ¢ 21-06-1994 oP 4063886 B 13-10-1992 OP 58127706 A 29-07-1983 oP 1034247 B 18-07-1989 oP 1550704 ¢ 23-03-1990 op 57180612 A 06-11-1982 oP 1018927 B 07-04-1989 oP 1537657 C 16-01-1990 OP 58005310 A 12-01-1983 DE 3215893 Al 09-12-1982 6B 2102438 A 02-02-1983 EP 0306939 A 15-03-1989 JP 1069610 15-03-1989 oP 2045921 25-04-1996 oP. 7080968 30-08-1995 cA 1325004 07-12-1993 cN 1031844 22-03-1989 DE 3876550 21-01-1993, DE 3876550 24-06-1993 EP 0306939 15-03-1989 ES 2036640 01-06-1993, HU. 52121 28-06-1990 KR 9512332 17-10-1995 No 283981 10-03-1989 sé 112994 & 25-11-1994 us 4916099 A 10-04-1990 us 5192731 A 09-03-1993 CA 1335094 AL 04-04-1995 oP 1287106 A 17-11-1989 oP 2613621 82 28-05-1997 oP 1287107 A 17-11-1989 oP 2656946 B2 24-09-1997 oP 1292010 A 24-11-1989 oP 2617988 82 11-06-1997 oP 1292008 A 24-11-1989 oP 2723134 B2 (09-03-1998 oP 2032104 A 01-02-1990 a 2667453 82 27-10-1997 oP 2032103 A 01-02-1990 oP 2732597 82 30-03-1998 EP 0408750 AL 23-01-1991 EP 0494084 AL 08-07-1992 Wo 8910942 AL 16-11-1989 us 5155078 A 13-10-1992 aT 190072 T 15-03-2000 aT 155799 T 15-08-1997 DE 68928204 D1 04-09-1997 DE 68928204 12 22-01-1998 DE 68929161 D1 06-04-2000 Fa RSW baer ty oy TDINTERNATIONAL SEARCH REPORT formation on patent family members Inigypons Apptetion No PCTVEP 02/14252 Patent document Pubicaton Patent fly Publeaton citadin aren report ale mrbers} ‘sate Us 5192731 A DE 68929161 T2 14-09-2000 KR 9209615 BL 22-10-1992 KR 9209614 B1 22-10-1992 Us 4530983, A 23-07-1985 1673709 ¢ 26-06-1992 3036841 B 03-06-1991 58125706 A 26-07-1983 395667 AL 16-05-1983 3302009 AL 28-07-1983 EP 0595565, A 04-05-1994 69330044 D1 26-04-2001 69330044 T2 19-07-2001 0595565 AL 04-05-1994 6199927 A 19-07-1994 272738 B1 15-11-2000 5488022 A 30-01-1996 us 4540680 A 10-09-1985 AT 386212 B 25-07-1988 aT 505981 A 15-12-1987 at 386214 B 25-07-1988 aT 506081 A 15-12-1987 Au 550723 B2 10-04-1986 AU 7781581 A 03-06-1982 AU 551320 B2 24-04-1986 AU 7781681 A 03-06-1982 BE 891234 AL 24-05-1982 BE 891235 AL 24-05-1982 BR 8107638 A 24-08-1982 BR 8107639 A 24-08-1982 cA 1206353 Al 24-06-1986 CA 117812 Al 13-11-1984 DE 3146524 Al 24-06-1982 DE 3146568 AL 08-07-1982 DK 520381 A 25-05-1982 DK 520481 A 25-05-1982 ES 8307010 Al 01-10-1983 ES 8305004 Al 16-06-1983 FI 813744 A ,B, 25-05-1982 FI 813745 A .B, 25-05-1982 FR 2494694 AL 28-05-1982 FR 2494700 AL 28-05-1982 6B 2088862 A ,B 16-06-1982 6B 2087907 A ,B 03-06-1982 IN 156404 AL 20-07-1985 IN 156133 Al 18-05-1985 1 1139827 8 24-09-1986 T 1139828 B 24-09-1986 a 1703739 14-10-1992 oP 3072089 B 15-11-1991 OP 57117507 A 22-07-1982 KR 3900023 B1 06-03-1989 KR 2801327 B1 25-07-1988 MX. 6918 E 11-11-1986 x 160802 A 25-05-1990 NL 8105318 A jC 16-06-1982 NL 8105319 A,B, . 16-06-1982 NO 813991 A \B, - 25-05-1982 No 813992 A ,B,. 25-05-1982 Fam BOTAN pa yerINTERNATIONAL SEARCH REPORT tormation on patent ramty members ne coe EP 02/14252 Patent document Publeation Patent family Publeation ced In search report cae members) ate Us 4540680 A NO. 870751 A ,B, 25-05-1982 NZ 199047 A 14-12-1984 NZ 199048 A 31-01-1985 SE 461100 B 08-01-1990 SE 8106988 A 25-05-1982 SE 451587 B 19-10-1987 SE 8106989 A 25-05-1982 TR 21347 A 18-04-1984 TR 22074 A 18-04-1986 Fae PHENO oy yD