NL1001237C2 - Copolymer of an olefinic monomer and 1,2-polybutadiene. - Google Patents

Description

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rOPf> T.VMFFtt OF AN OLEFINIC MONOMER AND 1.2 POLYBUTADIENE

The invention relates to a thermoplastic polyolefin which is a copolymer of at least one olefinic monomer and 0.005-10 wt% 1,2-polybutadiene.

One of the characterizing parameters of polyolefins is their molecular weight distribution, expressed in the quotient of the peanut average molecular weight, Mv, and the number average molecular weight, Mn. This parameter affects, for example, tensile strength and impact strength. An important parameter that influences the processing behavior of polyolefins is the Melt Flow Ratio (MFR). It is generally calculated as the quotient of the melt index (MI), determined according to ASTM 20 D-1238 with a weight of 21.6 Kg and the melt index determined with a weight of 2.16 kg. It is well known that in the conventional polyolefins the MFR increases as the molecular weight distribution widens or, in other words, increases the value of Mw / Mn. This implies that in some applications a compromise must be sought if a certain MFR is desired for the processing properties and a certain Mw / Mn ratio for the desired product properties.

WO-A-93/08221 discloses the production of thermoplastic polyolefins using so-called constrained geometry catalysts. With the disclosed method, it appears possible to vary the MFR at approximately the same width of the molecular weight distribution. However, the polyolefins disclosed in said application all appear to have a molecular weight distribution very close to 2. It is not taught how to manufacture polyolefins with other molecular weight distributions.

However, in order to enable optimum choice of materials in more applications, there is a need for thermoplastic polyolefins also with other combinations of MFR and molecular weight distribution than those now known.

The object of the invention is to provide such polyolefins.

This object is achieved according to the invention with the copolymers described in the preamble. The 1,2-polybutadiene will hereinafter also be referred to as (co) monomer 15. The amount of 1,2-polybutadiene is based on the total of the copolymer.

It is known from DE-A-2,123,911 to polymerize polybutadiene in the manufacture of sulfur-crosslinkable ethylene-propylene-diene rubbers. In this application, nothing is mentioned about a possible influence of the 1,2-polybutadiene on the important properties of polyolefins mentioned above and, moreover, no distinction is made between the different types, for example 1,4- or 1,2-25 polybutadiene.

DE-A-2,917,403 discloses copolymers of propylene and polybutadiene with a content of 1,2- (vinyl) unsaturations of 10-20% and a molecular weight of 10-106 g / mol, which corresponds to a chain length of about 2,000-20,000 butadiene units. The copolymers behave like a thermoplastic with elastomeric properties.

However, the polyolefin according to the invention has essentially thermoplastic and no pronounced elastomeric properties. It contains monomeric units of at least one olefin, but may also contain other α-olefinic monomeric units. A very 1001237.

- 3 - suitable combination is ethylene and octene.

It is known that in particular copolymers of ethylene with one or more α-olefins in which dienes are polymerized as a third monomer have elastomeric properties. Since the polyolefin of the present invention has thermoplastic properties, it does not contain substantial amounts of diene-derived units other than those derived from the 1,2-polybutadiene. Preferably, at most 1% by weight of the total polymer of these other diene-derived units is present, and most preferably they are completely absent.

The molecular weights, Mw and Mn of the polyolefin are determined using Size-Exclusion Chromatography in combination with a viscosity detector using polyethylene calibration samples as a reference.

For the purposes of the invention, 1,2-polybutadiene is understood to mean a polymer of butadiene in which the number of [-CH2-CH-] units is greater than hc = ch2 and the number of other butadiene-derived units such as [-CH2- CH = CH-CH2 -] - units and units in which unsaturations no longer exist.

The length of the incorporated polybutadiene chains, expressed in the number of polymerized butadiene units, should be at least 4. Preferably this length is at least 10 and more preferably it is at least 25.

The number of 1,2-vinyl unsaturations per chain is at least 3, preferably at least 6 and more preferably at least 13. Provided that the conditions regarding the chain length and the number of vinyl unsaturations remain fulfilled, it is The invention also allows the 1,2-polybutadiene 1001237 / - 4 to be partially saturated. Saturation can be accomplished by, for example, hydrogenation or copolymerization of butadiene with α-olefins. The chain length of the polybutadiene is preferably no more than 1500. At longer chain lengths, the normal properties of the polyolefin deteriorate and the polymer begins to show strong inhomogeneous behavior.

It has been found that the MFR depends relatively strongly on the amount of built-in 1,2-polybutadiene, such that the MFR also increases with increasing amount of polybutadiene, while the Mw / Mn ratio appears to be relatively less sensitive. The Mw / Mn ratio does, however, show a tendency to increase with increasing 1,2-polybutadiene content, in particular with copolymers in which 15 different α-olefinic monomer units have been incorporated, so that this ratio can also be controlled.

The Mw / Mn ratio of the polyolefin 20 according to the invention is generally greater than that of a (co) polymer manufactured under otherwise equal conditions, but which does not incorporate 1,2-polybutadiene. This increase is preferably at most a factor of 3.5. At higher increases, there is a risk of gel formation in the copolymer. Such a copolymer produces products with a less attractive appearance during processing, in particular when processing into films. In connection with the requirement to limit the Mw / Mn 30 increase, the amount of 1,2-polybutadiene is preferably at most 10% by weight if the chain length of the 1,2-polybutadiene is at least 4, with more preferably this amount is at most 5 wt% when the chain length is 10 or more and most preferably this amount is at most 3 wt% when the chain length is 25 or more. Even at an amount of 1.2-1001237.

5 - polybutadiene with a chain length of 10 or more of at most 5% by weight, the influence of the 1,2-polybutadiene is already very noticeable. Polyolefins with an amount of 1,2-polybutadiene greater than 10% 5 may exhibit an increased sensitivity to oxidation.

It has further been found that the presence of partially saturated 1,2-polybutadiene causes an increase in the Mv / Mn ratio, such that the Mw / Mn ratio increases as the number of double bonds in the polybutadiene decreases. In addition, the amount of partially saturated 1,2-polybutadiene also increases the MFR again in this case.

The polyolefins according to the invention have good processability and melt strength and are suitable for use in a wider range of products, both thin-walled objects, for example foils and thick-walled objects.

The invention also relates to a process for manufacturing a thermoplastic polyolefin by contacting one or more C2-C20 olefins with a cyclopentadienyl-containing transition metal complex as a catalyst under conditions wherein the mommers polymerize in the presence of the catalyst.

It is well known to manufacture polyolefins using non-cyclopentadiene-derived ligands containing catalysts such as Phillips and Ziegler catalysts. In polyolefins thus produced, the molecular weight distribution, Mw / Mn and the Melt Flow Ratio appear to be interrelated. At a certain value of Mw / Mn ratio, the MFR is virtually fixed, so that when choosing to produce a polymer with a certain desired Mw / Mn ratio, there is no more space available, the MFR can also be set to a desired value. .

10 01 23 7.

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From WO-A-93/08221 which is known to produce polymers of ethylene and copolymers thereof with α-olefins as catalyst under the influence of a cyclopentadienyl-containing transition metal compound as catalyst. The process disclosed in this application yields polyolefins with an Mw / Mn ratio of 1.86-2.32 and values of 5.6-16 for an MFR equivalent quantity. It is not taught how to make polyolefins with other molecular weight distributions.

There is therefore a need for a method which can also produce thermoplastic polyolefins with other combinations of Mw / Mn ratio and MFR than the known polyolefins.

This need is met according to the invention in that the polymerization takes place in the presence of 1,2-polybutadiene.

It has been found that the MFR and Mw / Mn ratio can be controlled by the amount and kind of 1,2-polybutadiene present in the polymerization medium. The manner in which this amount influences said properties has been indicated above in the discussion of the polyolefins according to the invention.

The amount of 1,2-polybutadiene that is co-polymerized is at most 10% by weight, preferably at most 5% by weight and more preferably at most 3% by weight. If too much 1,2-polybutadiene is co-polymerized, this is at the expense of the thermoplastic properties of the polyolefin obtained. It is surprising that even with very small additions of 1,2-polybutadiene as a co- and / or ter-monomer, a clearly measurable effect on the obtained polymer structure and end product properties is already observed. The allowable amounts are related to the chain length of the 1,2-polybutadiene as in the description of 1001237.

Polyolefins according to the invention have been indicated above.

The amount of 1,2-polybutadiene which must be present in the reaction mixture to obtain polyolefin with the desired amount of copolymerized 1,2-polybutadiene is inter alia related to the activity of the catalyst used and can be easily determined experimentally. From the foregoing and from the examples, it is clear what influence, for example, the 1,2-polybutadiene content has on, for example, the increase in the MFR. Those skilled in the art can establish this relationship in some experiments under the selected reaction conditions and then determine the appropriate amount and / or molecular weight for a copolymer with the desired properties.

The 1,2-polybutadiene has been found to be incorporated very efficiently. This is surprising because the vinyl unsaturated side groups can be considered as γ-20 substituted olefins, which thus have an additional alkyl group substituent in the 3-position. Such substituents are known to very strongly suppress the reactivity of an olefin in catalytic polyolefin processes due to so-called steric hindrance around the olefinic bond. It is therefore not obvious to use such a γ-substituted olefin as a comonomer to effect a high degree of incorporation of the high conversion degree 1,2-polybutadiene in a catalyzed polyolefin process.

Furthermore, the incorporation of a small amount of 1,2-polybutadiene already appears to have a significant influence on the MFR. By small is meant here: in an amount in which the demonstrable number of unsaturations in the copolymer lies in the range in which also the number of unsaturations of an otherwise corresponding thermoplastic polyolefin 1001237 lies.

- 8 - in which no 1,2-polybutadiene is co-polymerized.

A further advantage of the method according to the invention lies in the following. In WO-A-93/08221, the variation in the MFR is accomplished by appropriate selection of the amount of catalyst. This means that the reaction conditions must also be adjusted. In the process according to the invention, on the other hand, it is possible to work with a constant amount of catalyst and further equal conditions, because in principle the amount of 1,2-polybutadiene in the reaction mixture is the determining parameter.

Reference is made to the foregoing for the definitions of the copolymers to which the process according to the invention relates and for the requirements imposed on the 1,2 polybutadiene to be co-polymerized.

The polymerization is carried out by contacting C 2 -C 20 olefin monomers with a cyclopentadienyl-containing transition metal complex as a catalyst.

This metal complex contains a transition metal, preferably from Group 3 or 4 of the Periodic Table of the Elements in the new IUPAC version as depicted in the cover of the Handbook of Chemistry and Physics, 70th Edition CRC Press, 1989-1990. If the metal is in the valent state 3 *, the complex can be represented as R1MX1X2 or R1R2MX1. If the metal is in the valence state 4 *, the complex can be represented as R1R2HX1X2 or R1HX1X2X3.

In the formulas given, Rx is a substituted or unsubstituted cyclopentadienyl ligand, for example, indenyl, fluorenyl, methylcyclopentadienyl, pentamethylcyclopentadienyl or a hetero atom-containing derivative of the cyclopentadienyl ligand. In the latter group, the hetero atom may be an element of group 15 or 16 of the Periodic 1001 237. "- 9 -

System, for example N, P, As, 0 or S. The hetero atom can be as much part of the cyclopentadienyl ring as it is outside. R2 may be a Cp derivative as defined for R1, but may also be a covalent or coordinatively metal-bonded element from group 15 or 16 of the Periodic System, for example N, P, As, O or S containing substituent.

R1 and R2 may be linked by a -Si (R) 2 group, wherein R represents an aliphatic or aromatic group, by an aliphatic or aromatic group, or by a group containing an element of group 15 or 16 of the Periodic System includes.

If R2 is neutral and not a cyclopentadiene-derived compound and additionally linked to Rx in one of the aforementioned modes, then this combination of Rx and R2 is considered to be a hetero atomic derivative of the cyclopentadienyl ligand, including the description of R1 (

Xx, X2 and X3 can be the same or different and are selected from the group of: - halogens - aliphatic or aromatic substituents - sustituents, which contain an element of group 15 or 16 of the Periodic System, such as 0R3, NR3 and the like wherein R3 may be an aliphatic or aromatic optionally silicon-containing substituent.

A catalyst containing a cyclopentadienyl-containing transition metal complex of the formula R4HX1X2 is preferably used as catalyst, wherein H is a transition metal of Group 4 of the Periodic System ie, not in the highest valency state, preferably Ti3 *, wherein Xx and x2 have the same meaning as in the previous and wherein R4 is equal to 35 [Cp'-YZ (Rs) nr where Cp 'is one with aliphatic, aromatic or a 1001 237.

- heteroatom-containing groups substituted cyclopentadienyl derivative, Y is an aliphatic or aromatic group or a silicon or heteroatom-containing group, Z is an element of group 15 or 16 of the Periodic Table, preferably N or P, Rs is an aliphatic, aromatic or silicon-containing group and n equals the valence of Z minus 1.

The metal complex is usually used as a catalyst in combination with an activator. As activator, known substances can be used for this purpose, for example methylaluminoxane (MAO) or possibly (per) -fluorinated boron compounds, for example tris-pentafluorophenyl boron and tetrakis-pentafluoro-phenyl-borate compounds. In addition, organometallic compounds with a metal of group 1, 2, 12 or 13, preferably aluminum-alkyl compounds or magnesium-alkyl compounds, can be used in the catalyst system, for example trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, trioctyl aluminum, diethyl aluminum ethoxide, diethyl magnesium , dibutyl magnesium, ethyl butyl magnesium and butyl octyl magnesium. The activity of the catalyst system can be further increased by adding these main group metal-alkyl compounds.

The olefin monomers are contacted with the catalyst under conditions wherein the momomers polymerize in the presence of the catalyst. The polymerization of olefins with the aid of metal catalysts, for example classic Ziegler or Phillips catalysts, and the conditions to be selected therewith are a known technique per se, which is also applicable for the polymerization of olefins using catalysts such as those for the process according to the invention. invention.

For example, the polymerization reaction can be 1001237.

- 11 - carried out in gas phase, suspension or solution and as many (semi-) continuous as batch screw. In addition, it is also possible to use several reactors, in parallel, in series, or in a combination of these. Preferably, a solution process is used because this process is ideally suited for the production of very low crystalline polymers that are at least to some extent soluble in hydrocarbons.

Any liquid which does not adversely affect the activity of the catalyst system can be used as a dispersion or solvent for the polymerization reaction. Saturated, linear or branched aliphatic hydrocarbons, for example, butanes, pentanes, heptanes, pentamethyl heptane or petroleum fractions, for example, light or regular petrol, naphtha, kerosene or gas oil or mixtures of said substances are suitable for this. Aromatic hydrocarbons, for example benzene and toluene, can be used, but are not preferred both for cost and for safety reasons. Preferably, in technical scale polymerizations, the aliphatic hydrocarbons, or mixtures thereof, as marketed by the petrochemical industry, are used as drying or dispersing agents after drying and purification.

The polymer obtained by the process according to the invention can be further worked up in a manner known per se. In general, at some point in this work-up phase of the polymer, the catalyst is deactivated in a manner known per se.

The polymerization can be carried out under atmospheric pressure, but also at elevated pressure. If polymerization is carried out under elevated pressure, the yield of polymer per unit time can be increased even further. It is preferred to polymerize at pressures between 0.1 and 60 MPa in 1001237.

- 12 - especially between 1 and 30 hPa. Higher pressures of 100 MPa and above can be used if the polymerization is carried out in the so-called high-pressure reactors.

The molecular weight of the polymer can be controlled in the usual manner, for example by adding hydrogen or other chain length regulators or by adjusting the polymerization conditions.

The 1,2-polybutadiene is preferably added as a solution in a suitable dispersant, which is not disadvantageous for the polymerization. In a continuous process, the 1,2-polybutadiene is preferably dosed continuously to the polymerization reactor. In a multi-reactor system, it is also possible to dose the 1,2-polybutadiene to only part of the reactors used. In a batch polymerization, the 1,2-polybutadiene can be dosed before or during the polymerization. The amounts and molecular weights of the 1,2-polybutadiene to be used have already been described above.

The invention will be elucidated on the basis of the following examples, without, however, being limited thereto.

Density D23 was determined according to ASTH standard D 792-66. The melt index H1 was determined according to ASTM standard D1238 with a weight of 2.16 kg. The Helt Flow Ratio, HFR, was determined as the quotient of the 30 melt indexes determined according to ASTH D1238 weighing 21.6 and 2.16 kg, respectively. The Hw / Hn ratio was determined using a Waters H150C Gel Permation Chromatograph with DRI detector as Size Exclusion Chromatograph in combination with a Viscotek type 502 viscometer as viscosity detector and with polyethylene calibration samples as reference.

10 01 237- - 13 -

Examples I-IV

A number of polyolefins according to the invention were prepared in the following manner.

An autoclave with a volume of 2 liters was filled with boiling point petrol (boiling range 65-70 ° C) and kept at a temperature of 160 ° C. A mixture of boiling point gasoline (5.5 kg / h) and ethylene (1.2 kg / h) was continuously dosed to the autoclave. In some cases hydrogen was also dosed to achieve the desired 10 molar mass. The feed to the autoclave was adjusted to remain completely filled with the reaction medium. A solution of a catalyst, a suspension of an activator and a solution of triethyl aluminum were also continuously dosed to the autoclave. The ethylene conversion was adjusted with the amount of catalyst and activator, and was approximately 95% in all experiments.

To prepare a copolymer of ethylene and 1,2-polybutadiene, ethylene-dimethylamino-tetramethyl-cyclopentadienyl-titanium-dimethyl, Cp * (CH 2 CH 2) N (CH 3) 2, was dosed as catalyst. The concentration needed to achieve the 95% ethylene conversion was about 20 / mol per liter. Dimethylanilinium tetrakis-pentafluorophenylborate was used as activator. The concentration needed to achieve the 95% ethylene conversion was about 40 µmol per liter.

The concentration of triethyl aluminum used in the autoclave was approximately 40 μηηοΐ per liter.

In a separate vessel, a mixture of 1,2-polybutadiene (1,2-polybutadiene) with a molar mass of about 3000 g / mol, corresponding to about 50 vinyl groups per molecule (grade B-3000 from NISSOH IWAI) and boiling point petrol created. A certain amount of 1,2-polybutadiene solution was continuously pumped from this vessel to the autoclave. The desired 1,2-polybutadiene dosage was adjusted by appropriately choosing the concentration of 1,2-polybutadiene in the solution. 1 g / h 1,2-polybutadiene corresponded to 0.088 wt.% With respect to converted ethylene.

The properties of the copolymers obtained at different 1,2-polybutadiene dosages are shown in Table 1.

TABLE 1 10 example 1.2-MI MFR Mv / Mn D23 polybutadiene dosing gr / h I 0 6.1 25.8 2.5 958.9 II 0.25 4.7 27.8 2.5 959 6 15 III 2.5 4.7 30.2 2.6 959.1 I IV 5 4.1 33.0 2.8 959.1

These results show that it is possible to control the MFR 20 with the 1,2-polybutadiene dose.

Examples V-IX

Polymerizations of ethylene, 1-octene and 1,2-polybutadiene:

In an analogous manner as in Examples I-IV

Polymerizations were carried out in which octene-1 was metered into the autoclave as an additional monomer of 0.2 kg / h.

The properties of the copolymers obtained at 30 different 1,2-polybutadiene doses are shown in Table 2.

1001237.

TABLE 2 - 15 - example 1.2- MI MFR Mv / Mn D23 polybutadiene dosage gr / h V 0 4.2 29.1 2.5 914.9 5 VI 1.0 2.8 33.4 2, 6 915.4 VII 5 2.4 39.8 3.2 915.6 - VIII 15 0.68 56.7 5.0 916.2 IX 25 0.16 79.4 8.2 917.7 10

The method according to the invention has also proved suitable for the production of terpolymers. Already at a dose of 1 g / h 1,2-polybutadiene, corresponding to 0.088 wt.% With respect to the converted ethylene, a clear increase in the MFR appears.

Examples X-XIII

To investigate the influence of the molar mass of the 1,2-polybutadiene on the MFR in the terpolymerization of ethylene, octene and 1,2-polybutadiene, terpolymers of ethylene, 1-octene and 1,2- were analogous to the previous examples. polybutadiene made with two different 1,2-polybutadiene grades. The grade B-3000 and Grade B-2000 of the same company already mentioned in Examples V-IX 25 were used with a molar mass of 2000 g / mol, corresponding to approximately 33 vinyl unsaturations per molecular chain.

The results are shown in Table 3.

1001237a TABLE 3 - 16 - for 1.2-MI MFR D23 1.2-image polybu- Mw / Mn polybutadiene tadiene dosage grade 5 gr / h X 0 4.2 29.1 2.4 914.9 XI 2.5 4.1 31.1 2.7 917.0 B-2000 XII 5.0 2.2 38.6 3.0 915.6 B-2000 10

XIII 2.5 2.3 36.5 2.8 917.0 B-3000 I.

VII 5.0 2.4 39.8 3.2 915.6 B-3000 I.

I-1 I H

15

Examples XIV-XVIII

Polymerizations were carried out in an analogous manner as in Examples I-IV, with the exception that diphenylmethylene-fluorenyl-20-cyclopentadienyl-hafnium-dimethyl {[(C6H5) 2C] FluCpHfMe2} was used as the catalyst.

A grade of Aldrich with a mole was used as 1,2-polybutadiene. mass of about 1300 g / mol, about 99% unsaturated and a vinyl: trans-25 unsaturation ratio of 40:30 (referred to as grade A) and a grade of the same firm with one mol. mass of 1800 g / mol, about 60% unsaturations and distribution of the unsaturations over the various possibilities given by vinyl: trans: cis 45: 10: 5 (denoted as 30 grade B). The results are shown in Table 4.

10 012 ”- 17 - TABLE 4

Ivory- 1.2- MI MFR Mw / Mn D23 grade | image polybutadiene 1 dose 5% m / ra XIV 0 12 n.d. 3.5 956.7 |

XV 0.30 2.5 52 5.6 951.5 B

XVI 0.60 0.5 98 4.6 949.7 B

XVII 0.09 42 n.d. 3.8 955.8 A

10 XVIII 0.19 9.6 38 3.8 956.7 A

n.d. : not determined 1001237.

Claims (12)

A thermoplastic polyolefin which is a copolymer of at least one olefinic monomer and 0.005-10% by weight, included on the copolymer, of 1,2-polybutadiene. Polyolefin according to claim 1, wherein the chain length of the 1,2-polybutadiene, expressed in the number of polymerized butadiene units, is at most 1500. Polyolefin according to claim 1 or 2, containing 0.01-5% by weight of polybutadiene. Polyolefin according to claim 3, wherein the chain length of the 1,2-polybutadiene is at least 15. Polyolefin according to any one of claims 1-4, of at least ethylene as an olefinic monomer. 6. Polyolefin according to any one of claims 1-5 with at least one C2-C20 α-olefin different from the olefinic monomer 20. Polyolefin according to any one of claims 1-6, wherein the number of 1,2-vinyl unsaturations per polybutadiene chain is at least 3. 9. A method of manufacturing a thermoplastic polyolefin from at least one olefinic monomer comprising contacting one or more C2-C20 olefins with a cyclopentadienyl-containing transition metal complex as a catalyst under conditions wherein the monomers polymerize in the presence of the catalyst characterized in that the polymerization takes place in the presence of 1,2-polybutadiene 10. Process according to claim 97, in which a cyclopentadienyl-containing transition metal complex of the formula R4MXxX2 is used as the catalyst, wherein M is a transition metal of Group 10 01 23 7. - 19 - 4 of the Periodic System, not in the highest valency state, at preferably Ti3 *, wherein X3 and X2 are the same or different and are selected from the group of: 5. halogens - aliphatic or aromatic substituents - sustituents, which contain an element of group 15 or 16 of the periodic table, such as OR, NR3 and the like, wherein R3 may be an aliphatic or aromatic optionally silicon-containing substituent, wherein R4 is [Cp'-YZ (R5) J-15 where Cp 'is a cyclopentadienyl derivative substituted with aliphatic, aromatic or heteroatom , Y is an aliphatic or aromatic group or a silicon or heteroatom-containing group, Z is an element of group 15 or 16 of the periodic table, preferably N or P, Rs is an aliphatic, aromatic or silicon-containing group and n is equal to the valence of Z minus 1. 11. A method according to any one of claims 7-9, wherein the polymerization takes place in the presence of 0.01-10% by weight of 1,2-polybutadiene. A method according to any one of claims 7-10, wherein the polymerization takes place in the presence of 0.01-5% by weight of 1,2-polybutadiene. 13. Polyolefin and method as substantially described and illustrated in the examples. 1001237. COOPERATION TREATY (PCT) REPORT ON NEWNESS RESEARCH OF INTERNATIONAL TYPE OF LOAN IDENTIFICATION OF THE NATIONAL APPLICATION Characteristic of o · applicant o! of attorney 8076 NL Dutch application no. Submission date 1001237 September 19, 1995 Priority claim invoked Applicant (Name) DSM NV Oaum van nel request for an investigation of tniemaconaa / type By the Insanse voor Intematonaai Onderzoek (ISA) to the request for an investigation of international type assigned no. SN 26379'NL I. CLASSIFICATION OF THE SUBJECT (when using different design cows. specify all dassification symbols) According to the manual * classification (IPC) Int. Cl. 6: C 08 F 279/02, C 08 F 4/60, // (C 08 F 279/02, 210: 00) II. FIELDS OF TECHNIQUE RESEARCHED __Researched minimum documentation__ Classification system___Cfassificatieymoolen___ Int. Cl.6 C 08 F Untested documents other than the minimum document wet »insofar as such documents are included in the prayers examined. III.! ! NO INQUIRY FOR CERTAIN CONCLUSIONS (comments on supplement sheet) IIV. I 1 LACK OF UNITY OF INVENTION (Comments on Supplementary Sheet) I Form PC7 / ISA / 201 (a) 08 1994