MXPA01008541A - Polycondensation resins and polyaddition resins produced by heterogeneous catalysis - Google Patents

Abstract

The invention relates to polycondensation resins which are prepared by polycondensation of compounds having a low molecular weight and separation of small molecules in the presence of at least one heterogeneous catalyst. The invention also relates to polyaddition resins which are prepared by polyaddition in the presence of at least one heterogeneous catalyst. The invention further relates to the use of said polycondensation resins and polyaddition resins for the preparation of moulded parts, adhesives and coating materials.

Description

POLYCONDENSATION RESINS AND POLYADENTION RESINS PRODUCED BY HETEROGENIC CATALYSIS The present invention relates to the use of heterogeneous catalysts for the preparation of polycondensation resins and polyaddition resins. In addition, the present invention relates to polycondensation resins and polyaddition resins which can be made from heterogeneous catalysis. Furthermore, the present invention relates to novel processes for the manufacture of polycondensation resins and polyaddition resins. The present invention also relates to the use of polycondensation resins for the manufacture of polyaddition resins. It is treated in the polycondensation of a reaction in stages of compounds of low molecular weights in oligomers and / or polymers. The reaction rate of the polycondensation can be increased by increasing the reaction temperature. However, limits are placed on a discretional increase in the reaction temperature in short periods of time because, especially in the case of large reactors, sufficient thermal energy can not be fed to melt the reaction mixture more rapidly and for its condensation. Additional limiting parameters are the useful thermal energy present, the heat transfer coefficients, the formation of foam, which is caused by the distillation of water for example, or the increasing viscosity of the polycondensate during the reaction in stage, which makes it increasingly difficult plus the rapid removal of water, for example. In addition, high reaction temperatures are frequently detrimental to the color of the polycondensate. It is known to increase the polycondensation reaction rate through catalysts such as, for example, lithium octoate, dibutyltin oxide, dibutyltin dilaurate, stannic acid or para-toluolsulfonic acid and consequently reduce the synthesis time. However, these catalysts are often not desired in products made with the polycondensation resins. If the polycondensation resins are used, for example for the preparation of polyaddition resins, these catalysts can cause unwanted side reactions that worsen the possibility of using the polyaddition resins. A typical example is the preparation of polyurethane prepolymers containing isocyanate groups from polyesters with terminal hydroxyl groups (polyester polyols). The catalysts used usually also catalyze isocyanate group reactions in such a way that large quantities of numerous side products are produced which worsen the properties profile of the polyaddition resins. If the polycondensation resins are used directly for the manufacture of coating materials, the catalysts can accelerate so much the reaction with the crosslinking agents that a crosslinked product can be formed too early. This shows in the finished lacquer. Therefore, it is necessary to remove the aforementioned catalysts from the polycondensation resins, which, however, is not possible in a simple manner. The object of the present invention is to provide novel processes for the polycondensation and polyaddition of low molecular weight compounds that do not have the drawbacks of the state of the art, but allow the reaction speed to be increased without problem with the help of catalysts without producing thermal damage to polycondensation resins or polyaddition resins. In addition, the catalysts used in the new processes must not cause any unwanted side reactions in the successive products of the polycondensation resins and polyaddition resins. In addition, the catalysts must be removed in a simple manner if required after the reactions in stages. In accordance with the above, the novel process for the preparation of polycondensation resins through the polycondensation of low molecular weight compounds with separation of small molecules in a reactor was found., which is characterized in that heterogeneous catalysts are used here. In addition, a novel process was found for the preparation of polyaddition resins by means of polyaddition in a reactor that is also characterized by the use of heterogeneous catalysts. Next, the new processes for the preparation of polycondensation resins and as "processes in accordance with the present invention" will be known. In addition, novel polycondensation resins and novel polyaddition resins were found that can be made in the presence of heterogeneous catalysts. In addition, novel polyaddition resins were found which can be made with the use of polycondensation resins according to the present invention. Next, the novel polycondensation resins will be known as "polycondensation resins according to the present invention" and the novel polyaddition resins will be known as "polyaddition resins according to the present invention. surprising and not foreseeable for the person skilled in the art that the object of the present invention could be solved through the use of heterogeneous catalysts according to the present invention It was even more surprising that numerous organic and inorganic materials could be used as heterogeneous catalysts. The wide range of catalysts which are available in accordance with the present invention makes it possible in an extremely advantageous and simple way to select the optimal catalyst for polycondensation and specific polyaddition, as well as the exceptionally wide range of ways in which the catalysts Heterogeneous aligners are available allows its useful and simple adaptation to the geometries of existing reactors and their simple separation of the products of the reaction. It was also not predictable that the advantages of the processes according to the present invention and of the polycondensation resins or polyaddition resins according to the present invention would have complete repercussions on the products made with them. Thus, coating materials based on the resins according to the present invention have particularly advantageous properties profiles for use. The same is true in the case of polyaddition resins according to the present invention which can be made by the use of polycondensation resins according to the present invention. The first process according to the present invention is used for the formation of polycondensation resins. It is a reaction in stages that takes place under the separation of small molecules such as water,• alcohols, phenols or halogen hydrogens. Examples of polycondensation resins that can be made according to the process of the present invention are polyamides, polyimides, polyesters, polycarbonates, inoplatants, phenoplasts, polysulfides or urea resins, especially polyesters. The second process according to the present invention • 10 is used for the preparation of polyaddition resins. The polyaddition resins are formed in reactions in stages in reactive oligomers as discrete intermediate stages. Addition reactions are carried out without separation of small molecules frequently under displacement of hydrogen atoms. Reactive oligomers are also known as prepolymers. They contain functional groups that are still reactive and participate in the synthesis of polymers in the final polymer formation. Examples of polyaddition resins in accordance with The present invention that can be made with the process according to the present invention are polyurethanes or polyureas, especially polyurethanes, as will be used in particular for the production of coating materials. Examples of prepolymers that can be made according to the process of the present invention are polyurethane prepolymers which still contain free isocyanate groups.

• The main characteristic of the processes according to the present invention is the use of at least one heterogeneous catalyst which is totally or essentially insoluble in the reaction mixture. Within the framework of the present invention, the concept "essentially insoluble" means that only a quantity of dissolved parts of the heterogeneous catalyst is present in the mixture of the The reaction does not adversely affect the profile of properties of the polycondensation resins according to the present invention and of the polyaddition resins according to the present invention. As heterogeneous catalysts to be used in accordance with The present invention especially contemplates oxides of metals and non-metals, salts, sulphides, selenides, tellurides, zeolites, phosphates, heteropoly acids and / or resins of • exchange of coated or uncoated acidic or alkaline ions, insoluble or hardly soluble. The heterogeneous catalysts to be used according to the present invention can present compounds of the first and seventh main groups of the periodic table. Examples of suitable compounds of this type are lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium chloride, Sodium chloride, potassium chloride, lithium fluoride, sodium fluoride, potassium fluoride, magnesium fluoride, calcium fluoride or barium fluoride. Within the framework of the present invention under the concept "periodic table system" is understood the periodic system 5 of the elements developed by Mendelejeff and Meyer and described in numerous books. In addition, the heterogeneous catalysts to be used according to the present invention can contain up to 50% by weight, preferably up to 40% by weight and especially • 10 to 30% by weight of copper, silver, tin, zinc, manganese, rhenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum and / or vanadium. Examples of suitable metal and non-metal oxides are acidic, basic or amphoteric oxides of the latter, third and fourth main group of periodic table system such as calcium oxide, magnesium oxide, boron oxide, aluminum oxide, silicon dioxide, • especially pyrogenic silicon dioxide, silica gel, kieselguhr and / or quartz, or tin dioxide; oxides acids, basic or amphoteric from the second to the sixth subgroups of the system of the periodic table such as titanium dioxide, especially amorphous titanium dioxide, anata or rutile, zirconium oxide, zinc oxide, manganese oxide, vanadium oxide, niobium oxide, oxide iron, chromium oxide, molybdenum oxide or tungsten oxide; either lanthanide or actinide oxides such as cerium oxide, praseodymium oxide, neodymium oxide, samarium oxide, europium oxide, gadolinium oxide, terbium oxide, dysprosium oxide, holmium oxide, erbium oxide, thulium oxide, ytterbium oxide, lutetium oxide or thorium oxide; or mixed oxides of the mentioned elements or mixtures of these mixed oxides and / or oxides. An example of a suitable salt is sulfuric acid titandioxide. Examples of suitable sulfides, selenides and tellurides are zinc telluride, tin selenide, molybdenum sulphide, tungsten sulfide, nickel sulphide, zinc sulphide or chromium sulfide. Examples of suitable zeolites are ion exchangers such as for example alkyl zeolites ("Permutite®") or molecular sieves such as chabasite, gyllinite or heroinite. Examples of suitable phosphates are calcium phosphate or iron phosphate. Examples of suitable heteropolyacids are heteropolyacids which are formed from polyacids of tungsten, molybdenum and / or vanadium with boric acid, silicic acid, phosphoric acid, arsenic acid, telluric acid or periodic acid. Examples of suitable acid or alkali ion exchange resins are organic polymers containing anionic groups and / or acid groups or cationic groups and / or cation forming groups. Examples of suitable anionic groups or acidic groups are sulphonate or sulfonic acid groups. Examples of suitable cationic groups or cation forming groups are primary, secondary, tertiary or quaternary ammonium groups or primary, secondary or tertiary amines. Examples of suitable organic polymers are perfluorinated polymers, polybenzenimidazoles, polyetherketones, polysulfones, polyethersulfones or polyetherketosulfones. The heterogeneous catalyst to be used according to the present invention is, depending on its configuration, a complete contact catalyst or a vehicle catalyst. For example, titanium dioxide or tin dioxide can be used as titanium dioxide chain or tin dioxide chain (complete contact catalyst) or as thin layers on a vehicle (vehicle catalyst). Examples of suitable vehicles are silicon dioxide, aluminum oxide, or zirconium oxide. The layers of titanium dioxide or tin dioxide can be applied, for example, by hydrolysis of titanium tetrachloride or tin tetrachloride. Sols containing titanium dioxide or tin dioxide can also be used.

The heterogeneous catalyst to be used in accordance with the The present invention can be employed for the process according to the present invention in various forms. For example, in a suitable polycondensation reactor or in a a polyaddition reactor, the reactor wall or other reactor parts that come into contact with the reaction mixture can be coated in an adhesive manner with the heterogeneous catalysts. A typical example of a reactor ^ k of suitable polycondensation is described in the document of Patent WO 97/35902. In this variant the process according to the present invention effects the separation of the heterogeneous catalyst automatically when the product of the reaction is extracted from the reactor. The heterogeneous catalyst to be used in accordance with the present invention can, however, also be introduced into the reaction mixture in the form of powders, chains, cakes and / or meshes or it can be permanently or removably anchored in sieve receptacles or networks in the reactor. The variant selected depends in the first instance on the geometry of the reactor. After the polycondensation or the polyaddition the catalyst according to the present invention can be removed by filtration and / or by extraction of the mixture of the reaction, which is a special advantage of the process according to the present invention. The first process according to the present invention is • especially suitable for the production of polyester resins. Special advantages are obtained when, with the aid of the process according to the present invention, polyester resins which are usually used in polyester lacquers are prepared. The process according to the present invention is especially suitable for the preparation of polyester resins containing hydroxyl groups (polyester polyols) which are used for the preparation of polyaddition resins. As is known, polyester resins are obtained by the reaction of: optionally sulfonated polycarboxylic acids or their derivatives capable of esterification, optionally together with monocarboxylic acids, as well as polyols, optionally together with monooles. Examples of suitable polycarboxylic acids are aromatic, aliphatic and cycloaliphatic polycarboxylic acids. HE prefers to use aromatic and / or aliphatic polycarboxylic acids. Examples of suitable aromatic polycarboxylic acids are italic acid, isophthalic acid, terephthalic acid, italic acid monosulfonate, acid monosulfonate.

Isophthalic or monosulfonate of terephthalic acid, or halogenphthalic acids such as tetrachloric acid or tetrabromphthalic acid, among which isophthalic acid is especially advantageous and therefore preferred. Examples of suitable acyclic aliphatic polycarboxylic acids to be used according to the present invention are oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelainic acid, sebacic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, or Dimeric fatty acids, among which adipic acid, glutaric acid, azelaic acid, sebacic acid and / or dimeric fatty acids are of special benefit and are therefore preferably used. Examples of suitable cycloaliphatic polycarboxylic acids to be used according to the present invention are 1,2-cyclobutanedicarboxylic acid, 1,3-cyclobutanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, hexahydrophthalic acid, 1,3-acid. -cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 4-methylhexahydrophthalic acid, tricyclodecanedicarboxylic acid. The cycloaliphatic dicarboxylic acids can be used both in their cis form and in their trans form as well as mixture of both forms. According to the present invention, derivatives capable of esterification of the aforementioned polycarboxylic acids, such as, for example, their monovalent or polyvalent esters with aliphatic alcohols, are also suitable. • with 1 to 4 carbon atoms or hydroxyalcohols with 1 to 4 carbon atoms. In addition, the 5 anhydrides of the aforementioned polycarboxylic acids can also be used insofar as they exist. If desired, together with the polycarboxylic acids, monocarboxylic acids such as, for example, benzoic acid, tert.-butylbenzoic acid, • 10 lauric, isononanic acid and fatty acids from natural oils. It is preferred to use isononanic acid as the monocarboxylic acid. Examples of suitable polyols are diols and trifunctional alcohols and / or with higher functionality, especially diols. Usually the trifunctional alcohols and / or with higher functionality are used alongside the diols in lower amounts to promote branching in the polyester resins. Suitable diols (a2) are ethylene glycol, 1,2-propanediol or 1, 3-propanediol, 1,2-, 1,3- or 1,4-butanediol, 1,2-, 1,3-, 1,4- or 1,5-pentanediol, 1,2- , 1,3-, 1,4-, 1,5- or 1,6-hexanediol, neopentyl ester of hydroxypivalinic acid, neopentyl glycol, diethylene glycol, 1,2-, 1,3- or 1,4-cyclohexanediol, 1,2-, 1,3- or 1,4-cyclohexanedimethanol, Trimethylpentanediol, ethylbutylpropanediol or the isomeric diethyl octanediols. Additional examples of suitable diols are diols of the formula I or of the formula II: wherein R1 and R2 each represent an equal or different radical and represent an alkyl radical having 1 to 18 carbon atoms, an aryl radical or a cycloaliphatic radical, provided that R; and / or R; do not be methyl; where R3, R4, Re and R? each represents identical or different radicals and represents an alkyl radical with 1 to 6 carbon atoms, a cycloalkyl radical or an aryl radical and R represents an alkyl radical having 1 to 6 carbon atoms, an aryl radical or an alkyl radical unsaturated with 1 to 6 carbon atoms, and n is 0 or 1.

As diols I of the general formula I, all propandiols of the formula (a21) are suitable, in which either Ri or R2 or Ri and R2 are not methyl, such as 2-butyl-2-ethylpropanediol-1 , 3, 2-butyl-2-methylpropanediol-1,3, 2-phenyl-5-methylpropan-diol-1,3, 2-propyl-2-ethylpropanediol-1,2,3-di-tert-butylpropanediol -1, 3, 2-butyl-2-propanediol-1,3,1-dihydroxymethyl-bicyclo [2.2.1] heptane, 2,2-diethylpropandiol-1,3,2,2-dipropylpropanediol-1,3 or 2-cyclohexyl-2- ^ fc methylpropanediol-1, 3 and others. As diols II of the general formula II, there can be used, for example, 2,5-dimethyl-hexanediol-2,5, 2,5-diethylhexandiol-2,5-, 2-ethyl-5-methylhexandiol-2, 5, 2, 4-dimethylpentanediol-2,4,4,3-dimethylbutanediol-2, 3, 1, 4- (2'-hydroxypropyl) -benzole and 1,3- (2'-hydroxypropyl) -benzole. Among these diols, hexanediol and neopentyl glycol are especially advantageous and therefore are preferably used. Suitable examples of triols are trimethylolethane, trimethylolpropane or glycerin, especially trimethylolpropane. Examples of suitable higher functional alcohols are dimethylolpropane, pentaerythritol, diglycerin, triglycerin, homopentaerythritol or sugar alcohols such as, for example, mannose. If necessary, lower amounts of monooles can also be used. Examples of suitable monooles are alcohols such as for example phenols such as ethanol, propanol, n'-butanol, sec. -butanol, tert-butanol, amyl allyl alcohols, hexanols, fatty alcohols or phenol. The preparation of the polyester resins according to the present invention can be carried out in the presence of small amounts of a suitable solvent as entrainer. Suitable entraining agents are, for example, aromatic hydrocarbons, especially xylene and (cyclo) aliphatic hydrocarbons, for example cyclohexane or methylcyclohexane. The second process according to the present invention is especially suitable for the preparation of polyaddition resins. Advantages are obtained especially when, for the preparation of the polyaddition resins according to the present invention, the polycondensation resins of the present invention or the polycondensation resins prepared without catalyst are used. The process according to the present invention is used with special benefit for the production of polyurethanes, especially polyurethane prepolymers, which have ionic (potential) functional groups or which do not have said groups. These polyurethanes are usually used as thermoplastic plastics or foams or in polyurethane adhesives or polyurethane lacquers.

When used in polyurethane lacquers, the polyurethanes generally have groups which can be dispersed in water, such as, for example, ionic (potential) groups such as sulfonic, phosphonic or carboxylic acid groups or amino groups and / or hydrophilic nonionic groups such as polyalkylene ether groups. The preparation of polyurethane prepolymers containing isocyanate groups according to the present invention is carried out through the reaction of polyols with excess polyisocyanates at temperatures of up to 150 ° C, preferably at 50 and 130 ° C, in organic solvents which they can not react with isocyanates. The equivalent ratio between NCO groups and OH groups is preferably between 2.0: 1.0 and >; 1.0: 1.0, preferably between 1.4: 1 and 1.1: 1. Suitable polyols are conventional and known polyether polyols and / or polyester polyols, especially polyester polyols. According to the present invention, it is an advantage when the polyether polyols and polyester polyols no longer contain customary catalysts. In the case of polyester polyols this can be achieved insofar as they are processed without catalysts as described above, in accordance with the first process of the present invention. In accordance with the present invention it is an advantage to use polyester polyols according to the present invention made through the first process of the present invention since in this way an additional shortening of the overall process time is obtained. In addition to these polyols, it is also possible to use the diols and / or triols and / or compounds described above which have at least two functional groups which react with isocyanate and at least one functional group capable of forming cations and / or anions (functional groups) potentially ionic), especially potentially anionic functional groups).

Functional groups reactive with suitable isocyanate groups are especially hydroxyl groups as well as primary and / or secondary amino groups, among which the hydroxyl groups have specific advantages and are therefore preferably used. Functional groups which can facilitate the formation of anions are carboxylic acid, sulfonic acid and / or phosphonic acid groups among which the carboxylic groups have advantages and therefore are preferably used. Preferably, alkanic acids with two substituents on the carbon atom in the alpha position are used. The substituent may be a hydroxyl group, an alkyl group or an alkylol group. These polyols have at least one carboxyl group in the molecule, in general from 1 to 3 carboxyl groups. Examples of suitable compounds of this type are dimethylolpropionic acid, dimethylolbutyric acid, dimethylolpropanphosphonic acid or dimethylolbutanephosphonic acid or dimethylolpropanesulfonic acid or dimethylolbutanesulfonic acid, especially dimethylolpropionic acid. Examples of suitable polyisocyanates are aliphatic diisocyanates and aromatic cycloaliphatics, acyclics. Within the scope of the present invention, the term "cycloaliphatic diisocyanate" refers to a diisocyanate in which at least one isocyanate group is linked to a cycloaliphatic radical. Examples of suitable aromatic diisocyanates are toluylene diisocyanate, xylylene diisocyanate, bisphenylene diisocyanate, naphthylene diisocyanate or diphenylmethane diisocyanate. Examples of suitable cycloaliphatic diisocyanates are isophorone diisocyanate (= 5-isocyanato-l-isocyanatomethyl-1,3,3-trimethyl-cyclohexane), 5-isocyanato-1- (2-isocyanatoet-1-yl) -1,3, 3-trimethyl-cyclohexane, 5-isocyanato-l- (3-isocyanatoprop-1-yl) -1,3,3-trimethyl-cyclohexane, 5-isocyanato- (4-isocyanatobut-1-yl) -1, 3, 3-trimethyl-cyclohexane, l-isocyanato-2- (3-isocyanatoprop-1-yl) -cciohexane, 1-isocyanato-2- (3-isocyanatoet-1-yl) ciciohexane, 1-isocyanato-2- (4- isocyanatobut-1-yl) -cydohexane, 1,2-diisocyanatocyclobutane, 1,3-diisocyanatocyclobutane, 1,2-diisocyanatocyclopentane, 1,3-diisocyanatocyclopentane, 1,2-diisocyanatocyclohexane, 1,3-diisocyanatocyclohexane, 1,4-diisocyanatocyclohexanedicyclohexylmethane -2,4 '-diisocyanate or dicyclohexylmethane-4,' -diisocyanate, especially isophorone diisocyanate. Examples of suitable acyclic aliphatic diisocyanates to be used according to the present invention are trimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, ethylethylene diisocyanate, trimethylhexane diisocyanate, heptanmethylene diisocyanate or diisocyanates of dimeric fatty acids such as those sold by Henkel under the trademark DDI 1410 and such as those described in WO 97/49745 and WO 97/49747, especially 2-heptyl-3,4-bis (9 -isocyanthononyl) -1-pentyl-cyclohexane, or 1,2-, 1,4- or 1,3-bis (isocyanatomethyl) cydohexane, 1,2-, 1,4- or 1,3-bis ( 2-isocyanatoet-1-yl) cyclohexane, 1,3-bis (3-isocyanatoprop-1-yl) cydohexane or 1,2-, 1,4- or 1,3-bis (4-isocyanatobut-1-) il) cyclohexane. The latter must be considered among the acyclic aliphatic diisocyanates due to their two isocyanate groups exclusively attached to alkyl groups despite their cyclic groups. Among them, hexamethylene diisocyanate is advantageous according to the present invention and is therefore preferably used. The polyurethane prepolymers according to the present invention have a constant isocyanate content after processing, which also does not change after prolonged storage. This is a special advantage for the practice since the polyurethane prepolymer according to the present invention can be manufactured in large quantities, stored for long periods of time and used according to the need for the production of polyurethanes and polyurethane dispersions with beneficial properties. These specific advantages of the process according to the present invention and of the polyester polyols according to the present invention therefore extends to the coating materials, lacquers and sheets, adhesives and adhesive layers as well as the molded shapes which are made based on These polymers, polyurethane prepolymers, polyurethanes and polyurethane dispersions. Accordingly, these polymers, polyurethane prepolymers, polyurethanes and polyurethane dispersions according to the present invention are excellent for the preparation of thermoplastic and thermoset molded shapes as well as physical, thermal and / or actinic radiation adhesives and coating materials. such as are used for the manufacture of adhesive layers or in the lacquering of automobiles, • automotive repair lacquering, industrial lacquering, including coatings of containers and 5-coil coatings, or for lacquering furniture in order to form transparent lacquers and / or color formers and / or effects of one or more layers, leaves or lacquered sheets. It should be emphasized that property profiles can always reproduce reliably, which means that The molded shapes, coating layers, lacquers, sheets and sheets lacquered in accordance with the present invention as well as adhesives and adhesive layers are attractive both from the product's perspective and from the consumer's perspective. The adhesive layers, molded forms, lacquered and corresponding sheets have excellent use properties that can be adjusted and reproduced reliably.

• Examples and comparison experiments Examples 1 and 2 and comparison experiments VI and V2 Preparation of polyester polyols according to the present invention according to the process of the present invention (examples 1 and 2) and preparation of polyester polyols not in accordance with the present invention according to a process of the state of the art (experiments of Comparison VI and V2) In a 41 stainless steel reactor suitable for the production of polyesters, 446.8 g of a • Dimeric fatty acid (Pripol 1013), 307.9 g of hexanediol, 271. 5 g of neopentyl glycol, 557.9 g of isophthalic acid and 40 g of cyclohexane and heated to a temperature of 140 ° C. The residue was condensed for so long until distillation of a water amount of 170 to 180 g. The production of water was measured according to the reaction time. During the reaction period, the reactor was rinsed with • 10 a nitrogen stream of 30 1 / h to make it inert. The reaction mixture was heated in such a way that a column head temperature of 69 to 70 ° was maintained.

C. In Example 1 0.19% by weight of pyrogenic silicon dioxide was used as a heterogeneous catalyst. In Example 2, 0.065% by weight of titanium dioxide in powder form was used as a heterogeneous catalyst. In the comparison experiment VI, no catalyst was used. In the comparison experiment V2 Fascat 4100 (hydrousized monobutyltin oxide from Atochem) was used as the catalyst. The table provides an overview of the results obtained in the experiments. 25 Table: Acceleration of the polycondensation reaction rate through heterogeneous catalysts Examples: Examples of co-adaptation • 1 2 VI V2 t (min) H20 t (min) H20 t (min) H20 t (min) H20 5 (ml) (ml) (ml) (ml) 13 10 9 10 15 3 13 12 42 23 23 16 34 7 39 24 71 31 58 25 52 10.5 71 35 105 37 83 35 99 19.5 111 51 • 10 132 43 105 41 126 24.5 147 67 163 57 115 43 150 30.5 177 85 182 68 130 46 170 36.5 216 111 192 76 145 52 192 44.5 247 139 213 93 155 55 213 52.5 286 159 15 232 106 165 61 229 61.5 303 167 247 118 175 67 245 70.5 333 178 288 146 199 86 266 83 297 152 225 103 314 102 20 321 161 243 116 368 130 497 173 261 132 419 136 273 143 434 149 288 155 501 158 297 161 592 164 25 340 177 708 170 The results of the table highlight the high catalytic effect of the heterogeneous catalysts (examples 1 and 2). The • polycondensation carried out with the usual catalyst (comparison experiment V2) with a remarkably reduced reaction time compared to the non-catalyzed polycondensation (comparison experiment VI). However, the resulting polyester polyol V2 was unsuitable for the production of polyurethane prepolymers. Examples 3 and 4 and comparison experiments V3 and V4 • Preparation of polyurethane prepolymers with polyester polyols according to the present invention (examples 3 and 4) and with customary polyester polyols (comparison experiments V3 and V4) In a 41 stainless steel reactor suitable for the In the polyurethane synthesis, 497.64 g of a 72% solution of a polyester polyol and 154.1 g of meta-tetramethylxylylene diisocyanate were introduced and heated to a • temperature of 90 ° C. The resulting reaction mixture was heated for a sufficient time to adjust a constant content of isocyanate within limits of 2 to 2.5% by weight. In the case of Example 3, the polyester polyol of Example 1 was used. A constant isocyanate content of 2.05% by weight was achieved. In the case of Example 4, the polyester polyol of Example 2 was used. A constant isocyanate content of 2.3% by weight was reached. In the comparison experiment V3, a polyester polyol was used that was made without a catalyst. A constant isocyanate content of 2.04% by weight was reached. In the comparison example V4, the polyester polyol of the comparison experiment V2 was used. No constant isocyanate content was reached, but the isocyanate content decreased more and more due to collateral reactions.

Examples 3 and 4 prove that the polyester polyols made with the processes according to the present invention are excellent for the preparation of polyurethane prepolymers. The polyester polyols prepared with the use of a conventional catalyst from the experiment of comparison V2 were inadequate. Example 5 and comparison experiments V5 and V6 Production of polyurethane prepolymers according to the process of the present invention (example 5) and in accordance with the usual process (comparison experiments V5 and V6) For the comparison experiment V5, the comparison experiment V3 was repeated. For example 5, and for comparison experiment V6, the comparison experiment V3 was repeated, only that used: - in the case of example 5, 0.16 g of titanium dioxide powder and in the case of the comparison experiment V6, 0.01 g of Fascat 4100. In all cases, polyaddition was attempted for as long as necessary to reach a constant isocyanate content. In the case of the comparison experiment V5, this was reached after 7 hours, in example 5 after 5 hours. This establishes a significant shortening of the reaction time. In the comparison experiment V6, a constant isocyanate content was not reached but the isocyanate content constantly decreased due to side reactions.

Claims (12)

1. CLAIMS 1. Polycondensation resins that can be prepared to • through the polycondensation of low molecular weight compounds with separation of small molecules 5 and polyaddition resins which can be prepared by polyaddition, which are characterized in that at least one heterogeneous catalyst is employed.
2. 2. Polycondensation resins and polyaddition resins according to claim 1, • characterized in that heterogeneous catalysts are metal and non-metallic oxides, salts, sulphides, selenides, tellurides, zeolites, phosphates, heteropoly acids and / or coated or uncoated acid or alkaline ion exchanger resins, 15 insoluble or poorly soluble.
3. 3. The polycondensation resins and polyaddition resins according to claim 1 or according to claim 2, characterized in that the heterogeneous catalysts 20 present compounds of the first main group and seventh main group of the Periodic Table of the elements.
4. 4. Polycondensation resins and polyaddition resins in accordance with any of the 25 claims 1 to 3, characterized in that the heterogeneous catalysts contain up to 50% by weight of copper, silver, tin, zinc, manganese, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum and / or vanadium.
5. 5. The polycondensation resins and polyaddition resins according to any of claims 1 to 4, characterized in that in the case of the polycondensation resins they are polyester resins and in the case of the polyaddition resins are It deals with polyurethane and polyurethane prepolymers.
6. 6. Process for the preparation of polycondensation resins through the polycondensation of low molecular weight compounds with separation of small molecules in a reactor, characterized in that at least one heterogeneous catalyst is used.
7. 7. Process for the preparation of polyaddition resins through polyaddition, characterized in that at least one heterogeneous catalyst is used. The process according to claim 6 and the process according to claim 7, characterized in that the heterogeneous catalyst is introduced as a solid constituent in the form of powder, chains, cakes and / or meshes in the reaction mixture or it is brought into contact with the reaction mixture by coating parts of the reactor. The process according to claim 6 or according to claim 8, and the process according to claim 7 or according to claim 8, characterized in that the heterogeneous catalyst is placed in sieve receptacles or networks in catalyst or is anchored in a removable manner. The process according to any of claims 6, 8 or 9 and the process according to any of claims 7 to 9, characterized in that the heterogeneous catalyst is removed after the reaction through filtration and / or extraction of the reaction mixture and / or separated by removal of the reaction mixture from the reactor. The process according to claim 6 and the process according to claim 7, characterized in that the reactor wall and / or other parts of the reactor in contact with the reaction mixture are adhesively coated with catalyst. 12. Polyaddition resins, which can be prepared by using polycondensation resins according to any of claims 1 to 5. The use of polycondensation resins according to any of claims 1 to 5, of polyaddition resins in accordance with with any of claims 1 to 5 or 12, of polycondensation resins prepared in accordance with the process according to any of claims 6 or 8 to 11 and of polyaddition resins prepared in accordance with the process in accordance with any of claims 7 to 11 for the preparation of thermoplastic or thermoplastic molded parts as well as coating materials and hardenable physical adhesives, thermally and / or with actinic radiations. Thermoplastic and thermoplastic molded parts as well as coating materials and adhesives hardenable physically, thermally and / or with actinic radiation, containing polycondensation resins according to any of claims 1 to 5, polyaddition resins according to any of claims 1 to 5 or 12, polycondensation resins prepared according to the process according to claims 6 or 8 to 11 and / or polyaddition resins prepared according to the process according to any of claims 7 to 11. The use of coating materials and adhesives according to claim 14 for the preparation of transparent and / or color and / or lacquered adhesive layers and / or which provide effects of one or more layers, sheets or lacquered sheets as used in the original automotive lacquering , the lacquering of car repair, the industrial lacquering, including going for coatings of containers and coatings of coil, or the lacquering of furniture. Adhesive and transparent lacquered layers, and / or color and / or that provide effects of one or several layers, sheets or lacquered sheets, as used in the original lacquering of automobiles, in the lacquering of car repairs, in industrial lacquering, including coating of containers and coil coatings, or in the lacquering of furniture, made with the aid of the coating materials and adhesives according to claim 14.