SK25796A3 - A binder based on reaction product and its use - Google Patents

Abstract

Reaction products have more than 1,500 molecular weight and are produced by reacting: A) fats having 1 to 10, preferably 1.5 to 6 units of at least one of the functional groups -OH, -COOH, -SH, -NH2, -C=C-, an epoxide group or an acid anhydride group in the fat radical, the fat containing at least 1 % by moles of at least three-functional fats, with B) at least one mono- or multifunctional compound capable of reacting with the functional groups of the fats. The reaction products are preferably dispersed as liquids in water. These binders are suitable for coating, sealing and binding, in particular gluing, alone or combined with known glues and polymer dispersions. Glue dispersions, pressure-sensitive masses, universal glues and glue sticks may in particular be produced from these binders.

Description

Binder based on the reaction product and its use

Technical field

BACKGROUND OF THE INVENTION The present invention relates to binders based on the reaction products of fat chemistry and their use for the formation of layers, sealing, casting and bonding.

BACKGROUND OF THE INVENTION

The term binders refers to those substances which can bond the same or different materials, or can themselves be firmly held. They are generally based on substances or mixtures of substances that form a chemical and / or physical bond. In addition to inorganic substances, in particular organic substances, and in particular synthetic high-molecular compounds, play an important role, and the high molecular weight can be achieved gradually. Said substances are generally modified with additives to better suit for bonding, layering, sealing or casting. Said additives are, for example, resins, plasticizers, solvents, fillers, pigments, accelerators, stabilizers and dispersants. Glues, sealants, layers and coatings, casting resins are then based on the types of modified binders.

Thus, the most important binder bases are synthetic polymers such as polyacrylates, polyvinyl acetates, polyamides, polyisobutene, polyvinyl ether, polyurethane, styrene / butadiene copolymer, ethylene / vinyl acetate copolymer, polyvinyl chloride, phenolic resin and the like.

However, all of the above polymers have the disadvantage that they come from basic petrochemical sources and are derived from oil or natural gas. For the production of these basic chemicals, multi-stage syntheses that are environmentally harmful are essential. The resulting dispersions of petroleum products and wastes in the processing of natural gas also cause difficulties in their degradation due to their poor biodegradability in water and landfills.

On this basis, efforts have been made to prepare polymers based on fats and oils. Thus, WO 91/00305 describes plastics obtained by reacting unsaturated and / or hydroxyl groups containing fatty acids or their esters with two functional esters and / or amide-forming compounds and subsequently converting the two functional monomeric basic building units with a second bifunctional compound. Since only two functional compounds are prepared and used, linear polymers are obtained which are moldable and meltable. Thus, a film was produced at 230 ° C which was used to bond two glass plates at 190 ° C.

DE 43 05 309 describes an aqueous dispersion of fats and oil-based polymers. An ionic polymer is prepared from polyvalent metal ions and from carboxylic acids based on fats and oils. The carboxylic acids have from one to ten members and preferably have a molecular weight (Mn) of more than 400. Said carboxylic acids bind together with metal ions such as calcium, magnesium, zinc, zirconium, selenium, aluminum and titanium to form an ionic bond in the main chain. Such ionic polymers can also be further processed in the form of aqueous dispersions. Their disadvantage is that they exhibit properties that are associated with a certain dissociation equilibrium of ionic groups in the backbone, such as the susceptibility to flowing of a dried film under tension or at elevated temperature. This property is known to those skilled in the art as cold flow.

SUMMARY OF THE INVENTION

Accordingly, the present invention provides fats and oil-based binders which are not only environmentally compatible, but also for a wide range of applicability at a favorable price level, and in particular for high initial adhesion, ease of manufacture and good biodegradability can be used to prepare binder systems.

The solution according to the invention is apparent from the description of the invention below. Firstly, the solution consists in using the product of reaction A) of at least one fatty substance with an average of 1 to 10, preferably 1.5 to 6, with at least one of the following functional groups -OH, -SH, -NH2, -C = C-, -C00H, an acid anhydride or epoxide group in the fatty residue, wherein the fatty substance comprises at least 1% (mole) of at least a tri-functional fat substance with B) at least one mono- or poly-functional compound capable of reacting with functional groups of the fatty substance.

The reaction product has an average molecular weight (Mn, osmotically determined value) of at least 1500, preferably of at least 5000 and preferably of at least 8000 for certain uses. The molecular weight may still be spread after the reaction and before use, for example after dispersion of the binder. The increase in molecular weight can also lead to slight crosslinking, but the binder still remains castable or at least moldable in use. In use, the reaction is carried out at a temperature between 0 and 250 ° C, preferably between 20 and 150 ° C. The binder is still workable. The molecular weight is particularly increased by the addition of a reactive system, for example by the addition of radical initiators such as benzoyl peroxide, or by the addition of curing agents such as epoxy resin, polyisocyanate and polyamine.

The term fatty substances herein refers to fatty acids, fatty alcohols and derivatives thereof having at least one of the following functional groups on the chain: -OH, -SH, -NH 2, -C ,C-, -COOH, an acid anhydride group or an epoxide group . The fat substance is not a single substance but more often a mixture of substances. This is particularly true when expressing functional groups. At least 1% (mole) of fatty substance molecules have at least three functional groups of the same kind or different, preferably at least 3%. The person skilled in the art is

The fatty substances have the term oily or oily

Carboxyl groups, unbranched or known, depending on the stage to which the reaction is carried out and the branching or slight crosslinking of the molecules associated thereto, affect the processability of the reaction product. Preferably, fatty substances with a molecular weight (mean) > 300 or an oligomerized fatty substance with a molecular weight > 800 are used. Generally, the molecular weight is> 200.

lipophilic.

acids are acids that have multiple carboxyl groups (-COOH). they may have a saturated or unsaturated, branched alkyl radical having more than 8, preferably more than 12, carbon atoms. In addition to the above -OH, -SH, -C CC-, -COOH, amino-, acid anhydride or epoxide groups, the fatty acids may contain other groups such as ether, ester, halogen, amide, amine, urethane and urea. Preferably, the carboxylic acids are in the form of natural fatty acids or mixtures thereof, dicarboxylic fatty acids, and tricarboxylic fatty acids.

Examples of the fatty acids of the present invention are, in addition to saturated acids, preferably one or more unsaturated acids: palmitoleic acid, oleic acid, elaidic acid, petroselinic acid, erucic acid, ricinoleic acid, hydroxymethoxystearic acid, 12-hydroxystearic acid, linoleic acid and gadoleic acid.

In addition to naturally occurring fatty acids, polyhydroxy fatty acids can also be used. These can be prepared, for example, by epoxidation of unsaturated fats and oils or fatty acid esters with alcohols, cleavage of the ring with active hydrogen compounds such as alcohols, amines and carboxylic acids and subsequent saponification. Both vegetable and animal fats and oils can be used as starting material of a suitable fat or oil, or, optionally, products synthesized in a targeted manner by the petrochemical method.

Fatty acids can also be derived from fatty or oleic raw materials, for example, by En-reaction, Diels-Adler reaction, transesterification, condensation reactions, grafting (e.g. maleic anhydride or acrylic acid and the like) and epoxidizing. Examples are: a) unsaturated fatty acid epoxides such as palmitooleate, oleic, alaidic, petroselinic, erucic, linoleic, linoilenic and gadoleic acid, b) reaction products of unsaturated fatty acids with maleic acid, maleic anhydride or methacrylic acid c) condensation products of hydroxycarboxylic acids such as ricinooleic acid, or 12-hydroxystearic acid and polyhydroxycarboxylic acids.

Not all of these fatty acids are still at room temperature. If necessary, derivatives of said fatty acids, for example esters or amides, may be used for use herein.

In a preferred embodiment of the invention, an ester or a partial ester of said fatty acids with alcohols with one or more hydroxyl groups is used. The term alcohols includes hydroxy derivatives of aliphatic and alicyclic, saturated or unsaturated, unbranched or branched hydrocarbons. These include, in addition to monohydric alcohols, low-molecular-weight chain-extending groups known from polyurethane chemistry and, optionally, crosslinking agents with hydroxyl groups. Examples of this low molecular weight region are methanol, ethanol, propanol, butanol, pentanol, decanol, octadecanol, 2-ethylhexanol, 2-octanol, ethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, butylene glycol-2,3, hexamethylenediol, neopamethylenediol, octamethylene ethylene. 4-bishydroxymethylcyclohexane, queret alcohol, 2-methyl-1,3-propanediol, hexanetriol- (1,2,6), glycerol, trimethylolpropane, trimethylolethane, pentaerythritol, sorbitol, formite, methylglycoside, butylene glycol, which are derived by tricarboxylic acid reduction and tricarboxylic acid reduction acids. Likewise, monophenyl glycol or rosin-derived alcohols such as abiethyl alcohol may be used for the transesterification.

Instead of alcohols, it is also possible to use tertiary amines having an OH group, a polyglycerol or a partially hydrolyzed polyvinyl ester.

Pre-esterification with alcohols may also be accomplished by the addition of saturated and branched fatty acids such as caproic, caprylic, capric, lauric, myristic, palmitic, stearic, isostearic, isopalmitic, peanutic, behenic, cerotic and melisic. In addition, polycarboxylic or hydroxycarboxylic acids can be used for oligomerization. Examples are oxalic, malonic, succinic, maleic, fumaric, glutaric, adipic, cork, sebacic, 1,11-undecanedioic acid, 1,12-dodecanedioic acid, phthalic acid, isophthalic, terephthalic, hexyhydrophthalic, tetrahydrophthalic, or fatty acids, acid, lactic acid, tartaric acid, castoric acid, 12-hydroxystearic acid.

Examples of esters according to the invention are, in addition to partially saponified fats, such as glycerol monostearate, especially esters of natural fats and oils from rapeseed, sunflower, soybean, rope, ricinus, coconut, oil palm, oil palm and olive kernels and their methyl esters. Preferred fats and oils are, for example, beef tallow with chains of oleic acid (67%), stearic acid (2%), heptadecane acid (1%), saturated acids having a chain length of C ^ 2 to (10%), linoleic acid (12%) and saturated acids with more than 18 carbon atoms (2%), or, for example, new sunflower oil (NSb) having a composition of about 80% oleic acid, 5% stearic acid, 8% linoleic acid, and about 7% palmitic acid. Of course, the corresponding epoxides and reaction products with maleic anhydride can of course also be used. Further examples are partially or totally dehydrated castor oil, partially acetylated castor oil, open ring epoxidized soybean oil products with fatty diacids.

Fatty acid esters and derivatives accessible thereto by epoxidation are preferably used. Examples of these fatty acids are: soybean oil fatty acid methyl ester, linseed fatty acid methyl ester, castor oil methyl ester, epoxistearic acid methyl ester, epoxistearic acid 2-ethylhexyl ester. Of the glycerides, triglycerides are preferred, for example rapeseed oil, rope oil, soybean oil, castor oil, partially or totally dehydrated castor oil, partially acetylated castor oil, soy epoxy, linseed epoxide, epoxidized rapeseed oil, epoxidized sunflower oil.

In another preferred embodiment of the invention, nucleophile open rings of epoxidized unsaturated fatty acid triglycerides may be used. Nucleophiles are alcohols such as methanol, ethanol, ethylene glycol, glycerol, or trimethylolpropane, amines such as ethanolamine, diethanolamine, triethanolamine, ethylenediamine, or hexamethylenediamine, or carboxylic acids such as acetic acid, fatty acids, phthalic acid, maleic acid, or a mixture of fatty acids of 6 to 36 carbon atoms.

Conveniently, fats and oils (triglycerides) may be used in their natural form, but also after their thermal and / or oxidative treatment or their derivatives, resulting from the epoxidation or addition of maleic anhydride or acrylic acid. Examples are palm oil, peanut oil, rapeseed oil, cottonseed oil, soybean oil, castor oil, partially or totally dehydrated castor oil, sunflower oil, linseed oil, blown oils, epoxidized soybean oil, epoxidized rope oil, rapeseed oil, coconut oil, palm kernel oil and tallow. After modification, the product should contain at least 50% (w / w), preferably at least 80% (w / w) fat substances with triglyceride structures.

Amides of the above fatty acids can also be used as derivatives. The amides may be obtained by reaction with primary or secondary amines or polyamines, for example with monoethanolamine, diethanolamine, ethylenediamine, hexamethylene diamine, ammonia, and the like.

The term fatty alcohols refers to compounds containing one or more hydroxyl groups. The hydroxyl groups may be bonded to saturated, unsaturated, unbranched or branched alkyl groups having more than 8, preferably more than 12, carbon atoms. In addition to the -SH, -C =C-, rCOOH, amino, acid anhydride or epoxide groups necessary for later oligomerization, the fatty alcohols may contain other groups, for example ester groups, ether, halogen, amide, amine, urea and urethane. Examples of fatty alcohols according to the invention are ricinooleyl alcohol, 12-hydroxystearyl alcohol, oleyl alcohol, erucyl alcohol, linoleyl alcohol, arachidyl alcohol, gadoleyl alcohol, brazidyl alcohol, dimerdiol (= hydrogenation product of fatty acid methyl esters).

Symmetrical or asymmetric ether or ester with mono- or polycarboxylic acids can be used as fatty alcohol derivatives. Monocarboxylic acids are those such as formic, acetic, propionic, butyric, valeric, caproic, enantic, caprylic, pelargonic, capric, undecanoic, lauric, tridecanoic, myristic, pentadecanoic, palmitic, heptadecylic, stearene, stearene, stearene, stearene, stearene, stearene, stearene, stearene, stearene, lignoceric, ceric and melisic acids. Polycarboxylic acids are, for example, oxalic, adipic, maleic, tartaric and citric acids. The fatty acids described above, such as, for example, oleic acid oleyl ester, can also be used as carboxylic acids.

Fatty alcohols can be converted to ethers, especially with the same or another fatty alcohol, but also with another alcohol with multiple hydroxyl groups, for example as alkylpolyglycoside, dioleyl ether, dimer diol ether, diepoxydistearyl ether, oleyl butyl ether.

Of course, mixtures of the above-mentioned fatty substances may also be used.

In the case of unsaturated fatty substances, it is expedient to add siccatives in an amount of from 1 to 5% (w / w) based on the fatty substance. Examples are naphthenates, octaates, linoleate or resins of cobalt, manganese, lead, or mixtures thereof.

Multifunctional compounds which are capable of reacting with functional groups of the fatty substance (reactant B) refer in particular to one of the following compounds: vinyl ester, (meth) acrylic ester of up to 18 carbon atoms in the alcohol component, ethylene, styrene, butadiene, acrylonitrile , vinyl chloride, polyhydric alcohols, polyamines, aminoalcohols, polymercaptans, aminomercaptans, alcohol mercaptans, amino acids, hydroxyacids, mercaptoacids, polycarboxylic acids - also with higher molecular weight such as fatty diacids - and their anhydrides, polyepoxides and polyacid chlorides, all aliphatic and acidic polymers preferably difunctional isocyanates and NCO-terminated short chain prepolymers prepared therefrom (molecular weight < 8000). Generally, the reactant has a molecular weight of less than 2000 (mean).

The proportion of reactant B is at most 80% by weight, preferably at most 50% by weight, based on the weight of reactants A and B together. The equivalent ratio of the functional groups of reactant A) to reactant B) is decisive. After thorough mixing, components A) and B) are reacted to such an extent that a formable reaction product is formed first, which can also be converted to cured plastic by further cross-linking.

In the reaction, more or less branched macromolecules or polymers are formed, which also means oligomers. It is the announcement of polymer formation reactions, ie polyaddition, polycondensation and polymerization. In particular, these are transesterification, condensation reactions, En-reactions, grafting (for example with maleic anhydride and subsequent chain extension with polyols or polyamines) and ring opening of epoxy groups. The triglyceride structures of oils and fats are retained. By re-esterification or amidation, said structure can be partially destroyed or can be intentionally altered by said reactions.

It is essential that the polyreaction results in reaction products with an average relative molecular weight (MG) of at least 1500, preferably at least 5000 (determined by GPC). On the other hand, the reaction product should not gel in the melt. However, certain flow properties are required for subsequent use, especially when dispersed in water at elevated temperatures. Said properties can be improved by the addition of emulsifiers or special additives, such as the addition of a plasticizer to the polymer melt.

By the addition of stabilizers, the reaction can be accelerated so rapidly that even at room temperature the reaction proceeds within a reasonable time. Thus, for example, the process can be greatly accelerated by reacting carboxylic acid anhydride groups (containing alcohol groups) with heteroaromatic amines containing additional ring heteroatoms. Catalysts of this kind are: pyrrole derivatives, indolizine, indole, isoindole, benztriazole, carbazole, pyrazole, imidazole, oxazole, isooxazole, isothiazole, triazole, tetrazole, thiazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, pyridazine, pyrimidine, pyrimidine, pyrimidine triazine and compounds containing the corresponding structural moieties. Particularly suitable are 1-methylimidazole, 2-methyl-1-vinylimidazole, 1-allylimidazole, 1-phenylimidazole, 1,2,4,5-tetramethylimidazole, 1- (3-aminopropyl) imidazole, pyrimidazole, 4-dimethylaminopyridine, 4-pyrrolidinylpyridine 4-morpholinylpyridine, 4-methylpyridine.

The end of the polyreaction results from a calculation based on the average fat and oil functional content on the one hand and on the functional component content of the reactant B as well as the mixing ratio of the two components. More practical than evaluating the course of the reaction by calculation is to conduct a series of experiments with increasing concentrations of Compound B and possibly increasing the reaction time. This provides a quick and safe statement of the position of the respective gel point, from which thermoplastic treatment with the corresponding softening interval is no longer possible.

Advantageously, the reaction products are so constructed, that poly-functional compounds having from 1 to 10, preferably from 1.5 to 6, functional groups can in general be used in place of the described di-functional compounds.

1) Reaction products based on epoxides of fats or oils.

The preparation of typical fat epoxides and suitable oils and fats are described in DE 43 05 309. Fat or oil epoxides can be partially or fully epoxidized. The number of functional groups in the open epoxy ring reaction product is preferably from 1.5 to 5, particularly preferably two, with diols, diamines and dicarboxylic acids being particularly preferred for ring opening. Monofunctional amines, alcohols, and carboxylic acids can also be added to control the molecular weight or the opening of the epoxy ring. Fatty and oily epoxides open the ring with polyhydric alcohols, amines, aminoalcohols, mercaptans, aminomercaptans, alcohol mercaptans. carboxylic acids, amino acids, hydroxy acids, mercaptan acids, etc. However, diamines and diols which are suitable for preparing polyurethanes may also be used. Carboxylic diacids, also of higher molecular weight, such as a fatty diacid, are also suitable for reaction with the fatty epoxide. The ring-formed OH groups, optionally preferred OH groups or NH 2 groups, can also be reacted with polyisocyanates, preferably diisocyanates. The reaction of isocyanates with amines and alcohol groups found in modified or polymerized fat and oil molecules can also occur after dispersion in water. Curing with curing initiators such as dibenzoyl peroxide is also possible. For such subsequent crosslinking there are

suitable water-insoluble as isocyanates. and water dispersible 2) Reaction products based on 0H- and NH2- fat groups and ole- jov. Oils and fats derivatives with OH-

and NH 2 ', such as castor oil derivatives, fat conversion epoxide products with monoalcohols or monoamines can be converted to polymers by reactive multifunctional substances - preferably dual functional groups such as acid anhydride, diisocyanate, diepoxide and diacid chloride. All aliphatic and aromatic, preferably bifunctional, isocyanates and NCO-terminated short chain prepolymers prepared therefrom (Mn < 20,000, preferably &lt; 8,000) are suitable for this purpose. Also in this case, as described in 1), a subsequent dispersion can be carried out using polyisocyanates.

Of particular interest for the two-component reactive adhesives or for the formation of layers are diepoxides.

Suitable acid anhydrides are, for example, the saturated or unsaturated species used in the synthesis of polyester and polyamide.

3) Reaction products based on unsaturated fats and oils with acid anhydride groups.

The unsaturated fats and oils are reacted (grafted) with acid anhydrides, especially maleic anhydride at elevated temperature. These types of conversion are described in DE 43 05 397 for example on rapeseed oil and soybean oil. Acid anhydride groups modified by fat and oil molecules are reacted with the aforementioned, preferably bifunctional, compounds, such as diamines, dialcohols (diols), aminoalcohols and mercaptan variants thereof, to form polymer molecules. Also in this case, stoichiometry, depending on the number of functional groups of the fat or oil molecules as well as the number of bound acid anhydride groups in the center of the triglyceride molecule, determines the position and approach to the gel formation point.

However, it is also possible to react fatty substances containing C = C double bonds first with a dienophilic substance such as maleic anhydride, methacrylic acid and acrylic acid and then further with polyamines, polyols or aminoalcohols, the average number of functional groups being preferably 1, 5 to 5.

It is useful to modify the fat containing C = C double bonds in the presence of oxygen, initiator or at elevated temperature, in certain circumstances, prior to piling or addition. This can be done in the absence, but more preferably in the presence of radically polymerizable compounds with olefinic C = C double bonds, preferably in the presence of at least one of the monomers: styrene, vinyl ester, vinyl chloride, butadiene, ethylene, acrylic acid, (meth) acrylic ester, crotonic acid, acrylonitrile or in the presence of a mixture of these monomers.

The reaction may be carried out in solution, in dispersion or in the melt. Which form of reaction is expedient depends in particular on the purpose for which the binder is to be used. It is generally preferred to carry out the melt reaction and then convert the reaction product to an aqueous dispersion.

Generally, the dispersion can be prepared as follows: the polymer is heated to a temperature of 50 ° C to 150 ° C, preferably to 80 ° C to 130 ° C and then dispersed in water by high shear, which can also be inverted, mixed water into the polymer melt. Other additives such as a polymer, plasticizer, resin, stabilizer, etc. may be mixed prior to dispersion. up to a maximum of 50% content, preferably up to 30%. Due to the melt viscosity, it may be advantageous to heat the water to the melt temperature prior to addition. Pressurized emulsification is required at mixing temperatures between 95 ° C and 100 ° C.

Emulsifiers which are either added (external emulsifiers such as nonionic surfactants, ether sulfonic acids as well as ether carboxylic acids) or already incorporated in polymers (internal emulsifiers) are necessary for dispersion. Internal emulsifiers can be, for example, -COOH groups, neutralized with sodium hydroxide or amines (anionic disubstitutions). Internal emulsifiers are formed, for example, in the preparation of polymers by method 3). Acid-protonated or alkylated amine groups of polymer chains (cationic dispersions) can also play the role of internal emulsifiers. The external emulsifiers may also be low molecular weight compounds as well as polymers. Such emulsifiers or surfactants are known to those skilled in the art and are available in manuals (e.g., Tensid-Taschenbuch by Dr. Helmut Stache, 2nd edition, 1981, Ed. Carl Hanser, Munich-Vienna, especially pages 771 to 978). Other emulsifiers or surfactants such as ionic or non-ionic stabilized polymer dispersions (e.g. acrylic or polyurethane) may be used, and it is known that the emulsifying effect increases with increasing hydrophilicity of the substance. Protective colloids (e.g. starches, starch derivatives, cellulose derivatives, polyvinyl alcohols and the like) may be added in each case as added in the production of polymer dispersions (e.g. polyvinyl acetate).

Thus, dispersions are obtained in which the reaction product is finely dispersed in water. It can be dispersed so finely that the dispersion looks clear (molecular or colloidal dispersion). Generally, however, the dispersion is cloudy.

After dispersion, it is expedient to increase the molecular weight of the reaction product. Known curing agents and / or initiators are used for this purpose. In this case, slight crosslinking is possible, but in any case the processability must still be guaranteed.

In the macromolecules of the fatty chemicals obtained according to the invention, the building blocks of the molecules are bound together covalently. Therefore, they have a different technical applicability than the known ionomers based on fats and oils. This is particularly true in relation to heat resistance, possibly temperature-dependent strength and flowability, or in relation to water behavior. The binders of the present invention, despite the high fat content, have the ability to bond joints having at least the strength of the pressure-bonded joints. They do not have to be permanent sticky.

The binders according to the invention are therefore suitable for bonding layers, sealing, casting and bonding, especially for bonding or bonding inorganic mixtures such as cement and gypsum.

Depending on the purpose of use, the binder is formulated with a suitable additive, for example, by adding waxes, fillers, pigments, dispersants, stabilizers, viscosity regulators, preservatives, solvents and resins, to the adhesive, casting resin, sealant or layer binder. These are known as well as mixing them.

The binder according to the invention can also be formulated for the polymer dispersions or gels customary in the commercial network, with a proportion of 2 to 90, preferably up to 50% by weight, expressed as binder polymer content in the polymer dispersion or in the gel. The polymer dispersions and polymer gels are based on conventional polymers such as casein, glutin, cellulose ethers, starches, dextrin, polyvinylpyrrolidone, polyvinyl alcohol, polymethacrylates, polyvinyl chloride, polybutadiene, polystyrene, styrene / acrylate copolymers, styrene copolymers, styrene copolymers, styrene / polymers. Said polymer dispersions and gels have a solids content of from 20 to 80% by weight.

The person skilled in the art knows the rules which determine the compatibility with each other in mixtures of the species mentioned. For example, cationic and anionically stabilized dispersions are generally intolerant, and similarly, a greater pH change results in coagulation of the dispersion or dispersion mixture. Nonionic stabilized dispersions are generally the least sensitive to changes in pH values and to the addition of ions.

By virtue of their properties, the binders of the present invention are suitable for the production of adhesives, adhesive sealants, adhesive casting resins and coatings and layers, especially when it is less important to achieve peak strength values than the cost-effectiveness of the product. They are particularly suitable for substrates with different elastic properties or with different coefficients of thermal expansion, which is a rule when bonding different materials together. The bonded materials may be wood, paper, cardboard, wall cladding materials such as wallpaper, cork, leather, rubber, felt, textiles, plastics - preferably PVC floor coverings, linoleum and polyolefins in the form of foils or forming textile coverings - mineral substrates such as glass, quartz, debris, stone and ceramics, as well as metals.

The binders according to the invention are particularly suitable for the preparation of dispersion adhesives, pressure-bonding adhesives, contact adhesives, liquid adhesives, pencil-roller adhesives, plastisols and hot-melt adhesives. They are also particularly suitable as joint sealants, adhesive resins and coatings on hard materials as well as on textiles and paper.

The invention is illustrated by the following examples.

DETAILED DESCRIPTION OF THE INVENTION

Example 1 g of the reaction product of 1 mole of soybean oil with 3 moles of maleic anhydride (at 240 ° C under nitrogen for 6 hours of stirring then distilled) was mixed at 80 ° C with 239 g of Jeffamine D 2000 (propylene glycol with Mn 2000) with the amino terminus), with Jeffamin D 2000 added dropwise over 10 minutes. The temperature of the highly viscous mixture was raised to 100 ° C. With vigorous stirring, 47.7 ml of water containing 3.8 g of sodium hydroxide previously heated to 50 ° C were added rapidly. Cooling to room temperature over 20 minutes gave a strongly tacky, clear to opaque dispersion having a viscosity of 10,000 mPa · s and a solids content of 65%. The dispersion has a pH of 7.5 and has a shelf life of at least 3 months.

Example II

The preparation was carried out in a similar manner to Example I (6 hours at 200 ° C and then 4 hours at 220 ° C under a nitrogen atmosphere with stirring, without distillation) with 29 g of Jeffamine D 2000 replaced by an equimolar amount of isophorone diamine and the amount of hydroxide used. of sodium for neutralization upon dispersion remains constant. A dispersion having a solids content of 50% and a pH of 7.6 is formed. The dispersion provides a weakly sticky film which is clear after drying.

Example III g of the reaction product of 1 mole of soybean oil with 3 moles of maleic anhydride was reacted with 8.6 g of polydiol 200 (polyethylene glycol with molecular weight Mn 200) for 1 hour at about 150 ° C. The temperature of the mixture was then reduced to 90 ° C. With vigorous stirring, 65 ml of water containing 4.6 g of sodium hydroxide previously heated to 50 ° C were added rapidly. Upon cooling to room temperature, an adhesive clear dispersion is formed having a solids content of 50%. The dispersion must be stored for at least 6 months.

Example IV

The preparation was carried out similarly to Example III, whereby 50 g of the reaction product from 1 mole of soybean oil with 2 moles of maleic anhydride were reacted with 12.7 g of polytetrahydrofuran 2000 (Mn = 2000). 65 g of water and 5.1 g of sodium hydroxide are used for dispersion. A clear dispersion with a solids content of 50% is formed. The dispersion provides a sticky film that is clear after drying. Shelf life is at least 6 months.

Example V

The preparation is carried out in a similar manner to Example III, whereby 50 g of the reaction product from 1 mole of soybean oil with 2 moles of maleic anhydride is reacted with 8.6 g of polydiol 600 (polyethylene glycol with Mn = 600). 68 g of water and 8.0 g of sodium hydroxide are used for dispersion. A clear dispersion with a solids content of 50% is formed. The dispersion provides an adhesive film which is clear after drying.

Shelf life is at least 6 months.

Example VI

The soybean oil epoxide derivative is reacted with the dicarboxylic acid at a molar ratio of 1: 1 (at 160 ° C, 1 hour stirring) to open the ring. 40 g of the resulting fat reaction product are dispersed with vigorous stirring at 90 ° C with 124 g of water containing 3.3 g of sodium hydride and preheated to 90 ° C. Upon cooling to 20 ° C, a low viscous, milky dispersion is formed with a solids content of 25%. The dispersion provides a clear, low tack film. Shelf life is at least 6 months.

Example VII

The castor oil was reacted with phthalic anhydride at a molar ratio of 1: 2 (at 140 ° C under a nitrogen atmosphere with stirring for 2 hours). 40 g of the reaction product thus obtained were dispersed with vigorous stirring at 90 ° C in 100 ml of water containing 5.2 g of sodium hydroxide and preheated to 90 ° C. Upon cooling to room temperature, a moderately viscous, milky dispersion is formed with a solids content of 31%. The dispersion provides a clear, low tack film. Shelf life is at least 6 months.

Example VIII

278.3 of the maleic anhydride (MSA) soybean oil adduct in a molar ratio of 1: 2 is heated with 188.1 g of partially dehydrated castor oil having a hydroxyl number of 120 with stirring, for 1.5 hours, to 150-160 ° C. After cooling to 90-95 ° C, a solution of 3.26 g of NaOH in 20 g of hot water is added with vigorous stirring. With stirring, the dispersion was cooled to room temperature (1,000 g). The dispersion dries onto a highly sticky film.

Example IX

268.1 g of partially dehydrated castor oil (hydroxyl value 120), 40.2 g of Desmodur 44 V 10 (technical methylenediphenyl diisocyanate) and 61.7 g of Eumulgin KP 92 (mixture of fatty acids with 9.2 EO) were heated for 2 hours at 50 ° C. C. Then 630 g of warm water (60 ° C) was added slowly and with stirring. The mixture was allowed to cool to room temperature. About 1000 g of beige dispersion was obtained.

Example X

Reaction of Polyvest C 150 (polycarboxylic anhydride from butadiene, maleic anhydride and succinic anhydride from Hulsj with polyester / polyetherpolyol (reaction product of epoxidized soybean oil and methanol in a ratio of 1: 6, produced by dripping and 1 hour post-reaction by Henkel) : N-methylimidazole

Reagent A: Polyvest C 150

Reagent B: Polyester / polyether-polyol

Reaction temperature: 20 ^° C

A íg] B [G] Catalyst [% wt. ] Response time [days] 1 2 3 30 23 - The mixture remains viscous 30 23 1 weakly sticky gummy sticky cured rubbery 40 15 1 weakly sticky gummy non-sticky cured rubbery 30 15 1 weakly sticky gummy sticky cured rubbery

Example XI

Reaction of reaction products of soybean oil and maleic anhydride (100 g oil: 30 g MSA, reactant A) with glycerol + 5 E0 ‘(reactant B) at 20 ° C catalyst: N-methylimidazole

A [G] B [G] Catalyst [% wt. ] Response time [days] 1 2 3 20 4 - The mixture remains viscous 20 4 1.4 gummy gummy non-sticky cured rubbery

Example XII

Reaction reaction of linseed oil and maleic anhydride (100 g oil: 20 g MSA, reactant A) with glycerol + 30 EO (reactant B) catalyst: 1.6% (w / w) N-methylimidazole reactant A: 10 g reactant B: 8 g weakly sticky after 60 minutes cured after 10 hours.

Example XIII

Reaction reaction of rope oil and maleic anhydride reaction product (100 g oil: 30 g MSA, reactant A) with glycerol + 30 EO (reactant B) catalyst: 1.4% (w / w) N-methylimidazole reactant A: 10 g reactant B: 10.8 g dry surface after 30 minutes cured after 3 hours.

Fatty chemistry reaction products of Examples X to XIII suitable for use as sticky cast resins which cure even at room temperature.

Claims (15)

PATENT CLAIMS A binder based on a reaction product, obtainable from: A) at least one fatty substance with an average of 1 to 10, preferably 1.5 to 6, at least one of the above -OH, -COOH, -SH, -NH 2, -C = C-, epoxide or acid anhydride functional groups in the fatty chain, wherein the fatty substance comprises at least 1 mole% of at least a tri-functional fat molecule; B) at least a mono- or multifunctional compound capable of reacting with functional groups of a fatty substance having a relative molecular weight of at least 1500. Binder according to claim 1, characterized in that at least one substance from the following group of fatty substances is used: saturated, unsaturated, unbranched or branched fatty acids, fatty alcohols having at least 8 carbon atoms and their esters, in particular triglycerides of higher fatty acids, preferably natural fats and oils both in the natural state and after their thermal and / or oxidative treatment, optionally after epoxidation or after addition of the nucleophilic substance, the fatty substance having a relative molecular weight higher than 200, preferably higher than 300 and particularly preferably higher than 800. Binder according to claim 1 or 2, characterized in that the fatty substance is lipophilic. Binder according to claim 1, 2 or 3, characterized in that the relative molecular weight of the functional compound B) is less than 20 000, preferably less than 8000 and particularly preferably less than 2000. Binder according to at least one of Claims 1 to 4, characterized in that the fatty substances used are those with epoxy groups and multifunctional compounds (B) which are polyols, polyamines, aminoalcohols and polycarboxylic acids, preferably fatty diacids and dialcohols, the number of functional groups is on average 1.5 to 5. Binder according to at least one of Claims 1 to 4, characterized in that substances with -OH and / or -NH 2 groups are used as fatty substances and the following multifunctional compounds B) are polycarboxylic anhydrides, polyisocyanates, polyepoxides and / or polycarboxylic acid chlorides, the preferred number of functional groups being an average of 1.5 to 5. Binder according to at least one of Claims 1 to 4, characterized in that the fatty substances used are C = C double bonds which are first converted with dienophilic substances such as maleic anhydride, methacrylic acid and acrylic acid. and then reacted with polyamines, polyols or aminoalcohols, the preferred number of functional groups being on average 1.5 to 5. Binder according to at least one of Claims 1 to 4, characterized in that C-C double bonds are used as fatty substances, which are converted in the presence of oxygen, radical initiators or at elevated temperatures. Binder according to at least one of Claims 1 to 4 and 8, characterized in that the fatty substances used are C = C double bonded fatty substances which are converted in the presence of radically polymerizable compounds with olefinic C = C double bonds, preferably in the presence of at least one of the following monomers such as styrene, vinyl ester, vinyl chloride, butadiene, ethylene, acrylic acid, (meth) acrylic acid ester, crotonic acid, acrylonitrile or mixtures of these monomers. Binder according to at least one of Claims 1 to 9, characterized in that it is prepared in the form of an aqueous dispersion, which is preferably prepared by dispersing the reaction product in the liquid state, optionally after heating to 50 to 150 ° C, into water, or vice versa, water into the reaction product, preferably under high shear stress, conveniently using auxiliaries such as bases, for example NaOH or amines, emulsifiers, for example nonionic surfactants, ether sulfonic acids and ether-carboxylic acids, and / or protective colloids. Binder according to claim 10, characterized in that the molecular weight of the reaction product is increased after dispersion, using a suitable curing agent and / or initiator. Use of a binder according to at least one of the preceding claims for forming layers, coatings, for sealing and bonding, preferably in admixture with conventional polymer dispersions or gels with a proportion of from 2 to 90% by weight, based on the binder polymer. Use according to claim 12, characterized in that dispersions of polymers and gels based on casein, glutin, cellulose ethers, starches, dextrin, polyvinylpyrrolidone, polyvinyl alcohol, polymethacrylates, polyvinyl chloride, polybutadiene, polystyrene, styrene / acrylene are used. % butadiene copolymers, polyvinyl ester and polyurethane having a solids content of from 20 to 80% by weight. Use of the dispersions according to at least one of claims 1 to 13, characterized in that the adhesive is an adhesive dispersion, contact adhesive, pressure-bonding adhesive, general adhesive, solvent-based adhesive or pencil adhesive, and that the sealant is a sealant or filling joints and that coatings on hard surface fabrics as well as on textiles and paper can be formed. Use according to at least one of claims 12 to 15 14, characterized in that it is used for gluing, coating and sealing wood, cardboard, paper, wall coverings such as wallpaper, cork, rubber products, felt, textiles, plastics, preferably PVC, linoleum and polyolefin floor coverings, either in the form of foils or coverings with textile surfaces, minerals such as glass, quartz, slag, stone and ceramics, as well as metals.