NL1003263C2 - Catalyst for the reaction between a compound that can react with isocyanate groups and a compound that contains two or more isocyanate groups with different reactivities. - Google Patents

Description

- 1 -

Catalyst for the reaction between a compound capable of reacting with isocyanate groups and a compound 5 containing two or more groups of different isocyanate groups

INCLUDES REACTIVITIES

The invention relates to a catalyst for the reaction between a compound capable of reacting with isocyanate groups and a compound containing two or more isocyanate groups having different reactivities.

Such a reaction is described, for example, on page 42 of the Proceedings of the XIX 15 International Conference in Organic Coatings Science and Technology "(July 12-16, 1993 in Athens). In said publication, 3 (4) -isocyanatomethyl-1-methylcyclohexyl isocyanate (IMCI) as a crosslinker in powder paint formulations.

The two isocyanate groups in 3 (4) - isocyanatomethyl-1-methylcyclohexyl isocyanate (IMCI) differ in reactivity to the compounds that can react with isocyanate groups. Generally, in a compound containing two or more isocyanate groups with different reactivities, this difference in reactivity can be used to selectively react certain isocyanate groups with an isocyanate group-reactable compound while the other isocyanate groups remain unchanged and are available for later use. used in a similar or different chemical reaction. No reactions are yet known in which the selectivity is complete or almost complete under industrially applicable conditions. In the case of incomplete selectivity, for example upon reaction of a diisocyanate with an equimolar amount of alcohol, or with a compound containing alcohol groups, a more or less statistically determined mixture of 1003263 - 2 - unreacted, reacted once and twice reacted units is always obtained. A disadvantage of such a distribution is that on the one hand unreacted diisocyanate remains in the product and on the other hand many isocyanate groups are lost due to an uncontrolled reaction. In addition, significant chain elongation occurs when bivalent or polyvalent isocyanate-reactable compounds, for example OH-functional polymers, are used, resulting in greatly degraded processability. Methods that result in such distribution are described, inter alia, in Angewandte Makromolecular Chemistry 1984 (122) 83-99, and in Journal of Polymer Science (Polymer Letters Edition) 15 1985 (23) 509-515, while DE-A-4405054 describes the use of such a distribution for processing in polymers. For a successful use of said reactivity difference, hereinafter referred to as selectivity, it is of great importance that this selectivity is as great as possible under conditions which are usual and applicable under industrial conditions.

The uncatalyzed reactions between a compound containing two or more isocyanate groups with different reactivities and the compound capable of reacting with isocyanate groups show a strongly decreasing selectivity at higher temperatures. At room temperature, the selectivity of the reaction is sufficient, but the reaction speed is too slow. In addition, the processing of some compounds that can react with isocyanate groups at this temperature is problematic.

The object of the invention is to achieve a very high selectivity in the reaction between a compound containing two or more isocyanate groups with different reactivities and a compound capable of reacting with isocyanate groups, under 1003263-3 industrially customary conditions, wherein the reaction also proceeds with sufficient speed. The reaction temperature can vary from room temperature for liquid media to above 100 ° C when high is viscous media, such as, for example, polymers with a high glass transition temperature.

The invention is characterized in that an ionic metal complex based on a metallic element of groups III, IV or VII of the Periodic Table with exchangeable counterions is used as catalyst.

This ensures that the reaction proceeds quickly and that a very high selectivity is also obtained.

The coupling of the diisocyanate to, for example, a hydroxyl-functional polymer, takes place exclusively or almost exclusively via the most reactive isocyanate group by using the catalyst according to the invention. Advantages of this selective coupling are, for example, that no free diisocyanate occurs in the coating and that no chain extension occurs.

Suitable metallic elements in the appropriate valency are aluminum (III), tin (IV), manganese (III), titanium (III), titanium (IV) and zirconium (IV).

Tin (IV), titanium (IV), manganese (III) and zirconium (IV) are preferably used.

The number of counterions is between 1 and 4.

With tetravalent metals it is possible, for example, to use 4 monovalent counterions, 2 divalent counterions or to use 1 trivalent in combination with 1 monovalent counterion. Preferably 4 monovalent counterions are used.

For trivalent metals, the number of counterions is between 1 and 3 and preferably 3 monovalent counterions are used.

1003263 - 4 -

Examples of suitable counterions are halides, preferably chloride, (C 1 -C 8) alkoxides, preferably (C 1 -C 8) alkoxide, (C 2 -C 20) carboxylates, preferably (C 2 -C 8) carboxylates, enolates, preferably 2 4-pentanedione (acetylacetonates) and alkyl esters of malonic acid and acetylacetic acid, phenolates, naphthenates, cresylates and mixtures of said counterions.

Suitable catalysts are, for example, aluminum (III) acetate, aluminum (III) acetylacetonate, aluminum (III) 2,2,6,6-tetramethyl-3,5-heptanedionate, aluminum (III) ethoxide, aluminum (III) isopropoxide, aluminum (III) sec-butoxide, aluminum (III) tert-butoxide, tin (IV) chloride, tin (IV) bromide, 15 tin (IV) iodide, tin (IV) acetate, tin (IV) bis (acetylacetonate) dichloride, tin (IV) bis (acetylacetonate) dibromide, manganese (III) acetate, manganese (HI) acetylacetonate, manganese (III) fluoride, titanium (IV) chloride, titanium (IV) bromide, 20 titanium (IV) methoxide, titanium (IV) ) ethoxide, titanium (IV) isopropoxide (TYZOR TPT ™), titanium (IV) propoxide, titanium (IV) butoxide (TYZOR TBT ™), titanium (IV) 2-ethylhexoxide (TYZOR TOT ™), titanium (IV) acetylacetonate, titanium (IV) bis (acetylacetonate) 25 diisopropoxide (TYZOR AA ™), titanium (IV) bis (ethyl acetoacetato) diisopropoxide, titanium (IV) (triethanolaminato) isopropoxide (TYZOR TE ™), zirconium (IV) chloride, zirconium (IV) bromide, zircon ium (IV) acetate, zirconium (IV) 2-ethylhexanoate, 30 zirconium (IV) ethoxide, zirconium (IV) butoxide, zirconium (IV) tert-butoxide, zirconium (IV) citrate ammonium complex, zirconium (IV) isopropoxide, zirconium (IV) propoxide, zirconium (IV) acetylacetonate and zirconium (IV) trifluoroacetylacetonate.

Preferably titanium (IV) butoxide, zirconium (IV) acetylacetonate, zirconium (IV) butoxide, tin (IV) acetate, manganese (III) 1003263 - 5 - acetylacetonate, titanium (IV) isopropoxide, zirconium (IV) 2- ethyl hexanoate and tin (IV) chloride.

The catalyst complex can also contain one or more neutral elements such as, for example, alkyl cyanide, crown ether, (poly-) ether, such as, for example, polytetrahydrofuran, polyethylene glycol or tetrahydrofuran, dialkyl sulfide or tertiary amine.

The amount of catalyst is usually between 0.01 and 3% by weight (relative to the compound that can react with isocyanate groups and the compound that contains isocyanate groups).

One of the additional advantages of the catalysts of the invention when used in coating applications is that colorless catalysts can be selected.

Monomers, oligomers and polymers can be used as compounds which can react with isocyanate groups. Such compounds 20 contain reactive groups that can form a chemical bond with isocyanate groups.

Examples of suitable reactive groups are alcohols, N-hydroxyl compounds such as, for example, oximes and N-hydroxyimides, amines, amides for example N-alkoxyamides, lactams, imides, sulfides, enolates such as 1,3-dicarbonyl compounds, carboxylates, epoxides, and heterocyclic nitrogen groups containing aromatics such as pyrimidines, indoles, imidazoles, oxazoles, thiazoles, triazoles, pyrazoles and derivatives thereof.

Preferably alcohols, lactams, amines, N-hydroxy compounds and heterocyclic nitrogen containing aromatics are used.

The compound containing two or more isocyanate groups with different reactivities is preferably an aliphatic diisocyanate with one more sterically accessible isocyanate group attached to a primary 1003263-6 carbon atom and one sterically less accessible isocyanate group attached to a tertiary carbon atom. Such compounds can be represented by formula 5 (1):

NCO

R 1 -1-R 3 -CH 2 -NCO (1) 10 R 2 wherein R 1 and R 2 contain the same or different (C 1 -C 4) alkyl groups and R 3 contains a divalent, optionally branched, saturated aliphatic (C 1 -C 10) hydrocarbon radical. Preferably, cycloaliphatic diisocyanates are used having one more sterically accessible isocyanate group attached to a primary carbon atom and one sterically less accessible isocyanate group attached to a tertiary carbon atom. These compounds can be represented by formula (2)

R4 NCO

R5 R6 (2)

R7 (R8) n-CH2 - NCO

30 where: - R 4 = (C 1 -C 4 alkyl group - R 5 and R 6 * equal or different divalent, optionally branched saturated aliphatic (C 1 -C 3) hydrocarbon radical, 35 - R 7 = hydrogen or (C 1 -C 4 alkyl group, R 8 = divalent), optionally branched saturated aliphatic (C 1 -C 8) hydrocarbon residue and. 1 0 0 3 2 6 0 - 7 - n = 0 or n = 1

Examples of suitable diisocyanates are 1,4-diisocyanato-4-methyl-pentane, 1,5-diisocyanato-5-methylhexane, 3 (4) -isocyanatomethyl-1,5-methylcyclohexylisocyanate, 1,6-diisocyanato-6-methyl-heptane 1,5-diisocyanato-2,2,5-trimethylhexane and 1,7-diisocyanato-3,7-dimethyloctane, respectively 1-isocyanato-1-methyl-4- (4-isocyanatobut-2-yl) -cyclohexane, 1-isocyanato-1,2,2-trimethyl-3- (2-10 isocyanatoethyl) -cyclopentane, 1-isocyanato-1,4-dimethyl-4-isocyanatomethyl-cyclohexane, 1-isocyanato-1,3-dimethyl 3-isocyanatomethyl-cyclohexane, 1-isocyanatol-n-butyl-3- (4-isocyanatobut-1-yl) -cyclopentane, 1-isocyanato-1,2-dimethyl-3-ethyl-3-15 isocyanatomethyl-cyclopentane. The method of preparation of such diisocyanates is described in, for example, DE-A-3608354, DE-A-3620821 and EP-A-153561.

Preferably 3 (4) -isocyanotomethyl-1-methylcyclohexylisocyanate (IMCI) and 1,4-diisocyanate-20 4-methyl-pentane are used.

The reaction according to the invention can be used in many diverse fields of the art. Examples of such fields are the coating industry (both in powder paint systems and in solvent or water based system), the manufacture of construction resins, of compounds or of lenses and. acrylic-based materials, also in the preparation of resins for the adhesive and printing ink industry, and also as chain extenders in 30 engineering plastics.

In the coating industry, both in powder paint preparation as solvent and water-based coatings, the compounds that can react with isocyanate groups can be based on polymers such as, for example, amorphous and crystalline polyesters, polyurethanes, unsaturated polyesters, polyethers, polycarbonates, polybutadienes, styrene- 100326ο - 8 - maleic anhydride copolymers and fluorine-containing polymers.

Amorphous polyesters or polyacrylates are preferably used as polymer.

Polyesters are generally based on units of aliphatic polyalcohols and polycarboxylic acids. The polyester can be used, for example, as polycarboxylic acid, isophthalic acid, terephthalic acid, hexahydroterephthalic acid, 2,6-naphthalenedicarboxylic acid and 4,4-oxybisbenzoic acid, 3,6-dichlorophthalic acid, tetrachlorophthalic acid, itaconic acid, tetrahydrophthalic acid, hexachloroic acid, aphthalhydric acid, ethylene-tetrahydric acid, ethylene-tetrahydric acid , adipic acid, succinic acid, trimellitic acid and maleic acid, fumaric acid, citaconic acid and mesaconic acid. These acids can be used as such or, if available, in the form of their anhydrides, acid chlorides or lower alkyl esters.

Hydroxycarboxylic acids and / or optionally lactones, such as, for example, 12-hydroxystearic acid, hydroxypivalic acid and ε-caprolactone can be used.

Useful polyalcohols, especially diols, which can be reacted with the carboxylic acids to obtain the polyester include aliphatic diols such as, for example, ethylene glycol, propane-1,2-diol, propane-1,3-diol, butane-1 , 2-diol, butane-1,4-diol, butane-1,3-diol, 2,2-30 dimethylpropanediol-1,3 (= neopentyl glycol), hexane-2,5-diol, hexane-1,6- diol, 2,2-bis- (4-hydroxy-cyclohexyl) -propane (hydrogenated bisphenol-A), 1,4-dimethylolcyclohexane, diethylene glycol, dipropylene glycol and 2,2-bis [4-2-hydroxyethoxy) -35 phenyl] propane, the hydroxypivalin ester of neopentyl glycol.

Small amounts, such as less than 1003263-9 - about 4 wt%, but preferably less than 2 wt%, of trifunctional alcohols or acids can be used to obtain branched polyesters. Examples of useful polyols and polyacids are glycerol, hexanetriol, trimethylolethane, trimethylolpropane, tris- (2-hydroxyethyl) isocyanurate and trimellitic acid.

The preparation conditions and the COOH / OH ratio can be chosen to give final products having a hydroxyl number within the intended range of values.

For example, the hydroxy number can be between 20 and 100 mg KOH / gram and the molecular weight (Mn) between 1000 and 10000.

The polyesters can be prepared by esterification or transesterification by conventional methods both in the presence of catalysts according to the invention and in the presence of conventional catalysts.

The use of a catalyst according to the invention, preferably titanium (IV), zirconium (IV), tin (IV) or aluminum (III) complexes during the polyester synthesis has, inter alia, the advantage that in the various successive steps ( the polymer synthesis, the reaction with a compound containing two or more isocyanate groups with different reactivities, and optionally the curing step), only a catalyst has to be used and, moreover, desired reaction rates are coupled with improved selectivity. It is also possible to use conventional catalysts during polymer synthesis and during curing.

Generally, the acrylate polymer is based on alkyl esters of (meth) acrylic acid such as, for example, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, n-propyl (meth) acrylate, isobutyl (meth) acrylate ethylhexyl acrylate 1003263-10 and / or cyclohexyl (meth) acrylate, vinyl compounds such as, for example, styrene and vinyl acetate, maleate, fumarate and itaconate.

The hydroxyl functional acrylate resins are generally based on hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and alkyl (meth) acrylate.

Acrylic resins can be prepared by a polymerization in which solvent, for example toluene, xylene or butyl acetate, is first added to the reactor. Subsequently, heating takes place to the desired reaction temperature, for example the reflux temperature of the solvent used, after which monomers, initiator and optionally mercaptan are added during a period of, for example, between 2 and 4 hours. The temperature is then kept at reflux temperature for, for example, two hours. The solution is refluxed for 1 to 4 hours. The solvent is then distilled off by raising the temperature and then vacuum distillation can be carried out for, for example, one to two hours. The product is then drained and cooled.

Before the solvent is distilled off at room temperature or at an elevated temperature, modification, for example IMCI, can take place. The selective reaction produces isocyanate-functional polyacrylates without chain extension. Chain extension can lead to cross-linking in the case of highly functional polymers. A further advantage of the selective reaction is that when the optimal ratio between OH and NCO groups of at most 2 is chosen, after modification no free diisocyanate can be observed. The presence of free diisocyanate cannot be justified due to the toxic properties of the diisocyanate and the irritation caused by 1003263-11.

Isocyanate functional polyacrylates can be further modified with, for example, hydroxyethyl acrylate or hydroxybutyl vinyl ether, but can also be used as such with crosslinkers. If a ratio OH: NCO in the functionalization of the acrylate with, for example, IMCI, is chosen from 1: 1, a latent self-crosslinking system can be obtained by the selective reaction.

Since the remaining tertiary isocyanates have a low reactivity, the isocyanate functional polyacrylates can be extruded and also dispersed or emulsified in water.

After the synthesis of the polymer, for example the polyester, mixing between polymer and, for example, IMCI, can take place at a temperature at which the viscosity of the polymer is less than 5000 dPas (measured according to Emila). This can be done by applying means to obtain a homogeneous composition 20, such as, for example, static or dynamic mixers.

At the mixing temperature, the difference in reactivity is so great that the second isocyanate group of, for example, 3 (4) -isocyanatomethyl-1-25 methylcyclyhexyl isocyanate, shows (virtually) no reactivity with respect to the reactive group of the polymer.

A high selectivity due to the catalyst according to the invention results in minimal chain extension, in a better flow of the powder paint and in the absence of unreacted diisocyanate after functionalization.

The weight ratio of polymer: a compound containing two or more isocyanate groups with different reactivities is generally between 70: 30 and 99: 1, preferably between 70: 30 and 97: 3, and more particularly between 85: 15 and 95 : 5. It is possible to choose other desired ratios 1003263 - 12. Usually, at most one molecule of diisocyanate will be used per reactive group of the polymer. The OH: NCO molar ratio is usually chosen such that this ratio is between 1: 0.3 and 1: 5: 3 and preferably between 1: 0.5 and 1: 2.5. With self-crosslinking systems the ratio is preferably between 1: 0.8 and 1: 1.2 and with isocyanate functional resins between 1: 1.5 and 1: 2.0

The preparation of thermosetting powder paints and chemical curing reactions of these powder paints to cured coatings are generally described in, for example, Misev, Powder Coatings, Chemistry and Technology (1991, John Wiley), p. 44-54, p. 148 and p. 225-226. (and what is disclosed therein is incorporated by reference herein).

The curing reaction, for example between an IMCl-modified polymer and the crosslinker, as described in WO-A-95/20017, which yields the final cured coating, will generally take place in the presence of an effective amount of catalyst. If the curing reaction is based on the reaction between isocyanate and isocyanate-reactable groups, both the catalyst of the invention and any other suitable catalyst may be used. The importance of the polymer to crosslinker ratio and the amount of catalyst is set forth in Misev, Powder Coatings, Chemistry and Technology, p. 174-223 (and what is disclosed therein is incorporated by reference herein).

By modifying the polymer with IMCI, tertiary isocyanate functionalized polymers are obtained. Such functional groups do not require a blocking agent because they have a relatively low reactivity to a conventional reactive component with 1003263-13 hydroxyl groups. This makes it possible, for example, to mix such polymers during the powder paint preparation in an extruder with a hydroxy-functional crosslinker without any appreciable pre-reaction taking place.

The crosslinker and the modified polymer can be mixed together via, for example, an extruder or a static mixer. For example, it is possible to couple two static mixers together in series 10, in which the polymer can be modified in the first mixer and the crosslinker can be mixed in the second mixer. Both static mixers can have different shapes and / or be brought to different temperatures in order to control the specific processes in the in-line mixers.

It is also possible to make use of the reaction according to the invention by, for example, chemically curing a powder paint composition comprising a hydroxyl functional polymer, IMCI as crosslinker and the catalyst according to the invention into a powder coating. The temperature for this reaction is generally between 120 ° C and 200 ° C.

Examples I-VI and

Comparative Examples A-I

194 parts by weight of IMCI and 88 parts of neopentyl alcohol (2,2-dimethylpropanol) were placed in a glass flask. To the stirred suspension 30 were then added 3 parts by weight of catalyst according to Table 1 at room temperature. The temperature development of the reaction mixture during the exothermic reaction was monitored with the aid of a thermometer. After 1 hour of reaction time, a sample was taken and analyzed by proton NMR. The conversion and the degree of selectivity could be determined from the spectra obtained. The selectivity was expressed in percent (1003263-14) and represents the fraction of the most reactive isocyanate groups that have reacted with the equimolar added alcohol to form a urethane group after complete conversion of the alcohol.

At 100% selectivity, all alcohol groups present have reacted only with the most reactive isocyanate groups; at 50% selectivity, the added alcohol groups have reacted with IMCI without discrimination between the different isocyanate groups. The detection limit for the selectivity according to this method is about 99%. In case of proven low catalytic activity, ie incomplete conversion after 1 hour of reaction time, this procedure was repeated after 20 hours.

The various catalysts are summarized in

Table I.

1003263 - 15 - Table 1

Catalyst E1J Reaction% na% na selec-1 20 tivh hours I Ti (OBu) 4 +> 99> 99 5 II Zr (acac), +> 99> 99 III Zr (octoate) 4 +> 99> 99 IV SnCl4 +> 99> 99 V Mn (acac) 3 +> 99> 99 VI Ti (acac) 4 +/- 95> 99> 99 10 VII Al (iPrO) 3 +/- 92> 99> 99 A Ti ( Cp) 2C12 - 35 92> 99 B Bu2Sn +> 99 81 (laurate) 2 C BuSnCl3 +> 99 91 15 D Sn (octoate) 2 +> 99 65 E Pb (octoate) 2 - 55> 99 70 F Zn (octoate ) 2 - 70> 99 84 G Cu (octoate) 2 - 71> 99 85 H Co (octoate) 2 +> 99 90 20 I Fe (acac) 3 +> 99 90 E1): + exothermic reaction, - no exotherm detectable , +/- light eoxthermic reaction.

This table shows that when titanium (IV) butoxide, zirconium (IV) acetylacetonate, zirconium (IV) 2-ethylhexanoate, tin (IV) chloride or manganese (III) acetylacetonate were used, a rapid exothermic reaction was observed in which the reaction mixture Reached peak temperature of 60 ° C or more. Furthermore, the conversion of the reaction after 1 hour reaction time 1003263-16 was found to be complete (by NMR) and full or nearly complete selectivity was achieved: 99% or higher.

When titanium (IV) acetylacetonate and aluminum (III) isopropoxide were used, a light exothermic reaction was observed with the reaction mixture reaching a peak temperature of less than 50 ° C. Furthermore, the conversion of the reaction after 1 hour of reaction time was found to be almost complete (> 90%) (by NMR), and full or nearly complete selectivity was achieved: 99% or higher.

No exotherm was observed when using titanocene (IV) dichloride as a catalyst. Furthermore, the conversion of the reaction after 20 hours of reaction time was found to be incomplete (92%) and a full or almost complete selectivity was achieved: 99% or higher.

When using tin (II) 2-ethylhexanoate, butyltin trichloride, dibutyltin dilaurate, iron (III) acetylacetonate and cobalt (II) 2-ethylhexanoate, a rapid exothermic reaction was observed with the reaction mixture reaching a peak temperature of 40 ° C or more. Furthermore, the conversion of the reaction was found to be complete after 1 hour of reaction time, however the selectivity was found to be incomplete (65-91%).

1003263

Claims (8)

1. Catalyst for the reaction between a compound that can react with isocyanate groups and a compound containing two or more isocyanate groups with different reactivities, characterized in that as catalyst a ionic metal complex based on a metallic element from one of the groups III, IV or VII from the 10 Periodic Table with exchangeable counterion (s) is used. Catalyst according to claim 1, characterized in that the metallic element is titanium, zirconium, manganese or tin. Catalyst according to any one of claims 1-2, characterized in that the counterion is a halide, alkoxide, carboxylate or enolate. Catalyst according to any one of claims 1 to 3, characterized in that the catalyst from the group consisting of titanium (IV) butoxide, zirconium (IV) acetylacetonate, zirconium (IV) butoxide, tin (IV) acetate, titanium (IV) isopropoxide zirconium (IV) 2-ethylhexanoate, manganese (III) acetylacetonate and tin (IV) chloride are selected. Catalyst according to any one of claims 1 to 4, characterized in that as a compound containing two or more isocyanate groups with different reactivities, an aliphatic diisocyanate with one more sterically accessible isocyanate group attached to a primary carbon atom and one sterically less accessible a tertiary carbon atom-linked isocyanate group is selected. 6. Process for the reaction between a compound capable of reacting with isocyanate groups and a compound containing two or more isocyanate groups with different reactivities, characterized in that a catalyst according to any one of 1003263-18 claims 1-5 is used. Use of the reaction product obtained by the process according to claim 6. 8. Catalyst, method and application as substantially described and / or further elucidated in the examples. 1003263 ΟΜΜεΐΊϊκεη / ΜΓίαο »tnwn« u \ rw · / REPORT CONCERNING NOVELTY CREATION OF INTERNATIONAL TYPE LOENTIFIKATlE OF OE NATIONAL APPLICATION Characteristic of the applicant or oe gomaenogoe 8606NL Neoenanase nivji no. indianngseaum 1003263 June 4, 1996 In gore · pan voorangsoaum Applicant (Name) DSM NV Daftjm of jester reconcile for onoarzoon of ntamatonaai type By oe bsanoe for In lama * on aai Onoarzoen (ISA) aw nai reconcile for a type of mamaooneai type ba ga na no. SN 27663 EN I. CLASSIFICATION OF THE SUBJECT MATTER (for eapeaamg of verscniilanoe dasstAcaaas. alia dasssficaoesymboien epgavan) According to oe mamaoonae oaasificaoe (IPC) Int. Cl.6; c 07 C 269/02, C 07 B 43/00, C 07 C 271/20, C 08 F 8/30, C 08 G 63/685, C 09 D 5/03, C 08 G 18/22, C 08 G 18/75, C 09 D 175/04 II. SUGGESTED FIELDS OF TECHNIQUE Onoer2oeWe minimum flocumemaiie___ Classification system Classificationsymoolen_ Int. Cl. 6 C 08 G, C 07 C Unsolicited anoere oocumenaoo o an oe minimum do cu menace insofar as very documentaries have included the research prayers III.! ! NO RESEARCH AT ALL FOR CERTAIN CONCLUSIONS (comments on supplement plaster) JIV. ' LACK OF UNIT OF INVENTION (remarks including supplemental Dlad) I. - = orm PCT.lSA.roKai C £ tSSi • 3