HK1014969A - Polymer material, process for its production and use thereof - Google Patents

Description

Polymeric material, method for the production and use thereof

The invention relates to a polymer material based on renewable raw materials, to a method for producing said material and to the use thereof.

Organic plastics now used in large quantities in industry are almost exclusively produced on the petrochemical basis. For example: furnitureAnd in the construction industry, wood is used in conjunction with UF (urea formaldehyde resins), MUF, PF or, less rarely, PUR. The facing plates, end pieces, cable ducts, etc. are mostly made of polyvinyl chloride (PVC). In the field of windows, plastic windows using PVC window frames are also widely used. PVC has become a bulk material for window frames, however PVC, as the material for such members, has some serious drawbacks. On the one hand, the recycling problem has not been satisfactorily solved, and on the other hand PVC generates harmful gases when burned. Machine and equipment covers, high-quality press-molded parts, are frequently made of fibrous materials of phenol-formaldehyde resins, melamine-formaldehyde resins, epoxy resins (EP) or Unsaturated Polyesters (UP) or reinforcing materials of mats thereof, as are used in the automotive industry, for example. According to the increasing CO₂And by CO₂The possible change of global climate caused by the change of global climate, the need of CO and the like is urgent₂Completely unrelated (CO)₂Neutral) plastic, which should meet the requirements for the petrochemically based plastics currently used, and thus be able to partially replace the above plastics. More precisely, such polymeric materials are prepared from educts on the basis of renewable raw materials.

It is known in the prior art that the binder or binder combination also contains a portion of the recycled material. These developments relate in particular to the field of polyurethanes. For example: it is known from us patent 4582891 that castor oil, a renewable raw material, can be modified with polyisocyanates and inorganic fillers.

From EP0151585 a two-component polyurethane adhesive system is known, in which the ring-opening product of an oil-chemical polyol of an epoxidized aliphatic alcohol, an aliphatic acid ester (in particular a triglyceride) or an aliphatic acid amide with an alcohol is used. It is also known to use epoxidized triglycerides as softeners. Such a process is described, for example, in PCT/EP 94/02284.

From us patent 3578633 a process is known for curing polyepoxides with polycarboxylic anhydrides using specific alkali metal salts of selected carboxylic acids. This patent specifically applies to polyepoxides having more than one vicinal epoxy group per molecule. However, the polymers obtained according to this document have the disadvantage that, on the one hand, they are produced from physiologically harmful materials (e.g.lithium salts) and, on the other hand, the resulting polymers do not have the necessary strength. Clearly, this is due to: the basic reaction according to this us patent enhances the crosslinking of the outer epoxy groups, which however are never present in the epoxidized triglycerides.

From DE4135664 a class of polymerization products is known, which are prepared from epoxidised triglycerides together with polycarboxylic acid partial esters having at least two free carboxylic acid groups and a water repellent. However, the resilient coating compounds obtained according to DE4135664 have increased water resistance, but both the strength properties and the variation range of the polymerization system are unsatisfactory.

Starting from this point, therefore, the object of the present invention is to specify a new material based on renewable raw materials, which polymeric material has been widely used because of its good strength.

The object of the invention is achieved both in the characterizing polymer material of claim 1 and in the characterizing production method according to claims 15 and 16. The dependent claims describe advantageous further developments.

The invention therefore proposes a polymeric material which essentially comprises the reaction product of three components, namely 10 to 90% by mass of triglycerides, 5 to 90% by mass of polycarboxylic anhydrides and 0.01 to 20% by mass of polycarboxylic acids. The applicant has been able to demonstrate that polymeric materials containing the reaction product in the specified manner have unexpected properties both with respect to the strength of the material and to the range of variation of its properties.

The decisive factor in the materials according to the application is that the polycarboxylic anhydride used acts as a crosslinker, so that the crosslinking density of the resulting polymer is decisively increased. As a result, a hard polymer is produced.

The main constituents of the reaction product are therefore epoxidized triglycerides and polycarboxylic anhydrides, which are crosslinked to one another. The crosslinking reaction is started by adding a small amount of polycarboxylic acid (0.01 to 20% by mass). It is therefore clear that the polycarboxylic acids act as good initiators for the internal epoxy groups present in the triglycerides.

Therefore, by using a polycarboxylic anhydride, adjacent OH groups resulting from ring opening of epoxy groups are crosslinked in the form of addition reaction. It is thus clear that the free carboxylic acid groups which are produced on the polycarboxylic anhydride additionally open the other epoxide rings, and the adjacent OH groups thus obtained react with further carboxylic anhydride groups in a further addition reaction. Then, when the epoxy ring is opened and an adjacent OH group is generated, the reaction starts again. The small amount of polycarboxylic acid added effects the initiation of this crosslinking. Thus, essentially epoxy group ring opening is the initiator of the reaction. Possible reaction steps are shown below.

In contrast to the prior art relating to crosslinking in pure polycarboxylic acids, the hydroxyl groups formed are reacted by means of polyaddition with polycarboxylic anhydrides. This can be confirmed by Differential Scanning Calorimetry (DSC) or infrared spectroscopy tests.

The polymer material of the present invention is basically characterized in that the polymer material contains a reaction product comprising 10 to 90% by mass of a triglyceride and 5 to 90% by mass of a carboxylic acid anhydride, the reaction being initiated with a small amount of a carboxylic acid [ 0.01 to 20% by mass ]. In this regard, it is preferable if the reaction product contains 35 to 70% by mass of triglyceride and 10 to 60% by mass of polycarboxylic anhydride and 0.05 to 10% by mass of polycarboxylic acid.

Examples of epoxidized triglycerides which can be used to prepare the reaction product of the present invention are soybean oil, linseed oil, perilla oil, tung oil, oiticica oil, safflower oil, poppy seed oil, hemp oil, cottonseed oil, sunflower oil, rapeseed oil, triglycerides from euphorbia plants such as euphorbia-iagascae oil, and higher oleic acid triglycerides such as higher oleic sunflower oil or euphorbia-lathyris (euphorbia-latiris) oil. Peanut oil, olive oil, almond oil (almondol), kapok oil, hazelnut oil and almondOil (apricot seed oil), lindera glauca oil, lupin oil, corn oil. Sesame oil, grapeseed oil, raman oil, castor oil, marine oils such as menhaden and sardine oils or menhaden oil, whale oil and triglycerides with a high amount of saturated fatty acids converted to unsaturated states by dehydration, or mixtures thereof. Due to the reaction with hydroxyl groups, it is also possible to use partially hydroxylated triglycerides as further components in addition to epoxidized triglycerides. Such hydroxylated triglycerides are, for example, hydroxylated higher oleic oils or castor oils. In this way, the physical properties of the polymer can be changed to a large extent. However, one essential feature is that epoxidized triglycerides are always present, otherwise chain termination will occur. Triglycerides with aziridine groups may also be used. Various synthetic methods for producing aziridines are well known. One method of preparation is cycloaddition, for example addition of carbene to azomethine [ Breitmaier E., G.Jung, organic chemistry (org. Chemie) Vol.1, E.Thieme Verlag, Stuttgart ] or addition of nitrene to alkenes. By using LiAlH₄Synthetic methods for reducing α -chloronitriles or oximes are also available [ the japanese chemical society report (bull. chem. soc. jpn.40, 432 (1967)) and tetrahedron (tetrahedron) 24, 3681(1968) ].

As the polycarboxylic anhydride, a polycarboxylic anhydride having a cyclic basic skeleton, that is, a polycarboxylic anhydride produced from a cyclic polycarboxylic acid having at least two free carboxylic acid groups is preferable. Examples of such are cyclohexane dicarboxylic anhydride, cyclohexene dicarboxylic anhydride, phthalic anhydride, 1, 2, 4-trimellitic anhydride, hemimellitic anhydride, 1, 2, 4, 5-pyromellitic anhydride, 2, 3-naphthalic anhydride, 1, 2-cyclopentane dicarboxylic anhydride, 1, 2-cyclobutane dicarboxylic anhydride, quinoline anhydride, norbornene dicarboxylic anhydride (NADICAN) and the methyl-substituted compounds methylnonyl acetaldehyde (MNA) pinac anhydride, norpinac anhydride, tobionic anhydride, perylene 1, 2-dicarboxylic anhydride, caronic anhydride, norzane (narcamhane) dicarboxylic anhydride, N-carboxyaminobenzoic anhydride, camphor anhydride, 1, 8-naphthalic anhydride, bibenzoic anhydride, o-carboxyphenylbenzoic anhydride, 1, 4, 5, 8-naphthalenetetracarboxylic anhydride and mixtures thereof.

Also applicable are polycarboxylic anhydrides derived from open-chain dicarboxylic and polycarboxylic acids having at least two free carboxylic acid groups, such as: aconitic anhydride, citraconic anhydride, glutaric anhydride, itaconic anhydride, tartaric anhydride, diethanol anhydride, ethylenediaminetetraacetic anhydride or mixtures thereof.

As regards the initiator, i.e.the polycarboxylic acid, used according to the invention, preference is given to dicarboxylic acids and tricarboxylic acids. Examples thereof are citric acid derivatives, polymeric tall oil, azelaic acid, gallic acid, dimeric or pimaric acid, dimeric or polymeric cashew acid, also cashew nut shell liquid, polyuronic acid, alginic acid, mellitic acid, 1, 3, 5-trimellitic acid, aromatic di-or polycarboxylic acids such as phthalic acid, 1, 2, 4-trimellitic acid, hemimellitic acid, 1, 2, 4, 5-pyromellitic acid and aromatic substituted derivatives thereof such as hydroxy or alkyl phthalic acid, unsaturated ring di-and polycarboxylic acids such as norpinanic acid, heterocyclic di-and polycarboxylic acids such as lobapontic acid or cinchocanoic acid (cincholeinic acid), bicyclic di-and polycarboxylic acids such as norbornene dicarboxylic acid, open chain di-and polycarboxylic acids such as malonic acid and its long chain homologues and substituted compounds thereof such as hydroxy and keto di-and polycarboxylic acids, pectinic acid, humic acid, polymacanic acid having at least two free carboxylic acid groups in its molecule such as nut shell liquid, or mixtures thereof.

Another preferred embodiment of the present invention provides that the polymeric material comprises a reaction product prepared from the above-mentioned starting components together with the added catalyst. In this case, the amount ratio of the catalyst to be added is 0.01 to 10% by mass, preferably 0.05 to 5% by mass. Essentially all compounds which accelerate the crosslinking of epoxy resins can be used as catalysts. Examples thereof are tertiary amines such as N, N' -benzyldimethylaniline, imidazole and derivatives thereof, alcohols, phenols and substituted compounds thereof, hydroxycarboxylic acids such as lactic acid or salicylic acid (salicylic acid), organometallic compounds such as triethanolamine titanate, dibutyltin laurate, Lewis acids, in particular boron trifluoride, aluminum trichloride and formic acid complex compounds thereof, Lewis bases, in particular alcoholates, polyfunctional mercapto compounds and thioacids and organophosphorus compounds, in particular triphenyl phosphite and bis-. beta. -chloroethylphosphinite, bicyclic amines such as [ 2.2.2. ] -diazabicyclooctane, Chinuclidine or diazabicycloundecene, alkali metal and alkaline earth metal hydroxides, Grignard compounds or mixtures thereof.

It should be particularly emphasized that the polymer materials according to the invention may consist solely of the above-mentioned reaction products or, depending on the technical requirements, may also contain fillers or flame retardants. When the polymer material contains only the reaction product and the filler, it is preferable that it contains 2 to 98% by mass of the reaction product and 98 to 2% by mass of the filler. It is particularly preferable if the polymer material contains 6 to 90% by mass of the reaction product and 10 to 94% by mass of the filler.

Particularly preferred examples of fillers are organic fillers based on cellulose-containing materials, such as wood flour, sawdust or wood waste, rice husks, straw and flax fibers based on protein, in particular wool, and inorganic fillers based on silicates and carbonates, such as sand, quartz, corundum, silicon carbide and glass fibers, or mixtures thereof. The polymeric material according to the invention can also contain up to 50% by mass of flame retardants. Preferred flame retardants are aluminum hydroxide, halogens, antimony, bismuth, boron or phosphorus compounds, silicate compounds or mixtures thereof.

The procedure for producing the material with filler according to the preferred embodiment is, on the one hand, to first prepare a mixture of the starting components, i.e. the triglycerides of polycarboxylic anhydride and of carboxylic acid, then prepolymerize this mixture at 20 to 200 ℃ to a viscosity of 0.2 to 20000 cps, and then add the filler. In connection with this, the hardening is carried out under pressure (if necessary), if necessary, which can also be carried out after the shaping. However, it is also possible to mix all the additional materials and then to carry out a prepolymerization.

In another aspect, the process step may be to mix all of the ingredients, i.e., the triglycerides, first. The polycarboxylic acid anhydride and the polycarboxylic acid and, if necessary, other additives such as fillers and flame retardants are then hardened under elevated temperature and pressure.

The curing can be carried out at temperatures of > 20 ℃ to 200 ℃ and under a pressure of 1 to 100 bar. The time for hardening depends on the temperature, pressure and, if desired, the catalyst added. The hardening time may vary from 10 seconds to 24 hours. The preferable temperature range is 50-150 ℃.

The polymeric material of the present invention can also penetrate into a felt or mat. In this way a fibre-reinforced material can be produced.

The mixture obtained by the process of the invention can be charged into a mould and pressed separately or can be produced continuously. Continuous production is also possible by extrusion or hot rollers.

After hardening, the reaction mixture forms a closed, very smooth surface; the limits of the plastic, i.e. the geometrical dimensions, can be very large, with which very fine filigree patterns can be reproduced very accurately.

A significant feature of the material of the present invention is that it is non-toxic and therefore does not suffer from the disadvantages of PVC and/or other comparable materials such as polyurethane based materials. It should be noted that. Such new materials may have mechanical properties similar to PVC, EP or PES. Such modified materials are hard elastomeric materials with high strength. The highly filled polymeric material of the present invention, which contains cellulose and is obtained by pressing or extrusion, has high mechanical strength. The structure of the surrounding material can be retained in the case of mechanical point loads, for example in the fixing of wood screws or in the driving of wood nails. No splitting as seen with wood was found. This material can be machined without any problems. When sawn or cut, no side splitting was found, even with smaller particles broken.

By virtue of the addition ratio of the hydroxylated triglyceride, it is possible to obtain molded articles having partial plasticity at ambient temperature, while having excellent tear strength. The degree of crosslinking is theoretically influenced by the composition of the starting components, and controlling the appropriate degree of crosslinking enables the production of molded articles, which enable the thermoforming of polymeric material members. In particular, in the flame test, considerable improvement in flame retardancy has been noted with the addition of aluminum hydroxide. The addition of aluminium hydroxide with the consequent production of water prevents the direct destruction of the flame. Thus, the fire rating to DIN4102 reaches BS.

In many tests it is also evident that the material according to the invention does not have a significant water absorption. For this purpose, highly filled semifinished products containing cellulose are immersed in water for a long time. After 80 hours, the material did not absorb appreciable amounts of water. Physical or chemical changes to the material have not been observed.

The invention is now illustrated in more detail by the following examples:

example 1

53.5% by mass of epoxidized linseed oil having an acid content of 9% by mass was mixed with 42.8% by mass of camphoric anhydride and 2.7% by mass of a mixture of dimerized and trimerized abietic acids. The mixture was homogenized with 1% by mass of 50% ethanol solution of Chinuclidine. 10% by mass of this mixture was mixed with 90% by mass of straw. And pressurized at 15 bar, 180 ℃ for 10 minutes. The resulting fiberboard had a physical density of 0.62 g/cm³Its advantages are high mechanical performance and high water resistance. Can be used as fiber board in the building and furniture industries.

Example 2

80 mass% of epoxidized perilla oil having an acid content of 8 mass% was mixed with 16 parts by mass of 1, 2, 4, 5-pyromellitic anhydride and 4 mass% of trimerized fatty acid. 30% by mass of the mixture was applied to 70% by mass of a jute-hemp fiber mat so that the fiber mat was uniformly wetted. The impregnated fiber mat was then pressed at 170 ℃ for 10 minutes at 10 bar. The obtained fiber product has high elasticity. Fracture resistance and water resistance. It can be used in many fields of plastic-reinforced fibers or fiber-reinforced plastics, such as molded articles of fiber-reinforced housings or covers.

Example 3

Epoxidized soybean oil 42.9% by mass having an acid content of 6.5% by mass was mixed with hydroxylated higher oleic oil 21.5% by mass. To the mixture were added 34.3 mass% of norbornene dicarboxylic anhydride and 1.3 mass% of 50 mass% methanol-1, 4-diazobicyclo (2.2.2.) octane (DABCO) solution. The mixture was homogenized and then crosslinked at 140 ℃ for 15 minutes. The product obtained is transparent, can be plastically deformed and has a high tear strength. The product is suitable for coating materials and articles which must have plastic deformability, such as cables.

Example 4

Epoxidized hemp oil 72.7% by mass having an acid content of 10.5% by mass was mixed with 1, 2, 4-trimellitic anhydride 27.3% by mass. This mixture was 8% by mass and 92% by mass of dried chaff were mixed and pressurized at 15 bar at 170 ℃ for 8 minutes. The resulting fiberboard had a physical density of 0.88 g/cm³. It features high water resistance and mechanical strength, and may be used as fibre board in building and furniture.

Example 5

54.7% by mass of epoxidized linseed oil having an acid content of 9.6% by mass was mixed with 43.7% by mass of tetrahydrophthalic anhydride and 1.1% by mass of adipic acid. The mixture is homogenized with 0.5% by mass of 1, 5-diazobicyclo (4.3.0) -5-nonene (DBN) and crosslinked at 145 ℃ for 5 minutes to form transparent rigid moldings. The resulting material is resistant to water and boiling water (see fig. 1 and 2) and has high mechanical strength. The material can be heated up to 300 ℃ without decomposition. It can be applied to a coated article such as various types of machine equipment.

Example 6

60% by mass of epoxidized soybean oil having an acid content of 6.5% by mass was mixed with 36% by mass of 1, 2-cyclohexanedicarboxylic anhydride and 1.1% by mass of dimer rosin having an acid value of 154. The mixture was homogenized with a 50% butanol imidazole solution and then crosslinked at 140 ℃ for 10 minutes. The resulting polymeric material is transparent, is characterized by high water resistance, and is capable of being thermoformed at about 90 ℃ and has high mechanical strength below that temperature.

Example 7

69.9 mass% of higher oleic oil having a nitrogen content of 4.3 mass% of free-follower was mixed with 28 mass% of phthalic anhydride, 1.5 mass% of sebacic acid and 0.6 mass% of an isopropyl alcohol solution of Chinuclidine. The mixture is crosslinked at 145 ℃ for 5 minutes to form an elastic, transparent, rigid polymeric material having high water and abrasion resistance.

Example 8

51.5% by mass of epoxidized tung oil having an acid content of 10.5% by mass was mixed with 45.5% by mass of camphoric anhydride and 2.5% by mass of an ethanol solution of 70% citric acid. To this mixture was added 0.5% by mass of DABCO and homogenized. The resulting mixture was applied to a coconut tree fiber mat in an amount of 30% by mass to allow the reaction mixture to be uniformly impregnated into the fibers. The soaked coconut fibre was then preheated at 130 ℃ for 20 minutes. In this case, the reaction mixture reacts to form a prepolymer having a viscosity of about 10000 mPas. The pre-treated felt was then placed in a mold and pressurized at 160 ℃ for 1 minute at 15 bar. The resulting fiber product has high mechanical strength, excellent water and temperature resistance. It can be used in the field of plastic reinforced fiber felt materials and fiber reinforced plastics.

Example 9

A mixture of 61.6% by mass of epoxidized linseed oil having an acid content of 9.6% by mass and 15.4% by mass of epoxidized sardine oil having an acid content of 10.5% by mass was mixed with 19.2 parts by mass of 1, 2, 4, 5-pyromellitic dianhydride and 3.8% by mass of trimeric fatty acid. 25% by mass of this mixture was homogenized together with 75% by mass of wood chips having an average fiber length of 300 μm. The moist powder is then processed by means of a piston extruder at 160 ℃ and 40 bar to form endless moldings. The obtained product has high mechanical stability and is characterized by excellent water resistance.

Example 10

Mixing epoxidized safflower oil 53.2% (by mass) with acid content of 9% (by mass), aconitic anhydride 10% (by mass), and methyl norice32.5% by mass of schisenedicarboxylic anhydride and 2.6% by mass of dimeric anacardic acid. To this mixture was added 1.7 mass% of a solution of DABCO in propanol, which was then homogenized. 10% by mass of the resulting mixture was mixed with 90% by mass of dry chaff having an average particle size of 0.5 mm grains until a uniform wet powder was obtained. The mixture was then pressurized at 130 ℃ under 15 bar for 15 minutes. The resulting material had a physical density of 0.9 g/cm³Chip removal can be adopted for processing. The material is suitable for all occasions of using various Medium Density Fiberboards (MDF).

Example 11

Epoxidized linseed oil (50.5 mass%) was mixed with trimeric abietic acid (2.5 mass%). The mixture was homogenized with 1.8% by mass of a 50% solution of Chinuclidine in isobutanol. The resulting mixture was homogenized by 30% by mass together with 35% by mass of barite, 5% by mass of a pigment such as rutile, and 30% by mass of muscovite conglomerate, chlorite and quartz powder. The mixture is then crosslinked in a mold at 30 bar, 140 ℃ for 8 minutes to form an elastic hard plastic molded article having high water and hot water resistance and high mechanical strength. The material can be used for covering parts such as various types of equipment and machines.

Claims (18)

1. A polymer material based on a renewable raw material, comprising a reaction product of 10 to 90 mass% of a triglyceride having at least 2 epoxy groups and/or aziridine groups and 5 to 90 mass% of a polycarboxylic anhydride with 0.01 to 20 mass% of a polycarboxylic acid.

2. Polymeric material according to claim 1, characterized in that the epoxidized triglycerides are selected from the group consisting of soybean oil, linseed oil, perilla oil, tung oil, oiticica oil, safflower oil, poppy seed oil, hemp oil, cottonseed oil, sunflower oil, rapeseed oil, triglycerides from euphorbia plants such as euphorbia-iagascae oil, and higher oleic triglycerides such as higher oleic sunflower oil or euphorbia lathyris (eupolyphylla-latiris) oil, peanut oil, olive oil, almond oil (almondoil), kapok oil, hazelnut oil, almond oil (apricot seed oil), lindera glauca nut oil, lupin oil, corn oil, sesame oil, grapeseed oil, raman oil, castor oil, marine oils such as menhaden and sardine oils or menhaden oil, whale oil and triglycerides with a high amount of saturated fatty acids which are converted to unsaturated conditions by dehydration, or mixtures thereof.

3. Polymeric material according to claim 1 or 2, characterized in that the epoxidized triglyceride further comprises a hydroxylated triglyceride such as castor oil.

4. A polymeric material according to at least one of claims 1 to 3, characterized in that the polycarboxylic anhydride is prepared from a cyclic polycarboxylic acid having at least two free carboxylic acid groups.

5. A polymeric material according to claim 4, characterized in that the polycarboxylic acid anhydride is selected from the group consisting of cyclohexanedicarboxylic anhydride, cyclohexene dicarboxylic anhydride, phthalic anhydride, 1, 2, 4-trimellitic anhydride, hemimellitic anhydride, 1, 2, 4, 5-pyromellitic anhydride, 2, 3-naphthalic anhydride, 1, 2-cyclopentanedicarboxylic anhydride, 1, 2-cyclobutanedicarboxylic anhydride, quinoline anhydride, norbornene dicarboxylic anhydride (NADICAN) and the methyl-substituted compounds methylnonyl acetaldehyde (MNA), pinanic anhydride, norpinanic anhydride, tobionic anhydride, perylene 1, 2-dicarboxylic anhydride, caronic anhydride, norzane (narcamhane) dicarboxylic anhydride, N-carboxyaminobenzoic anhydride, camphoric anhydride, 1, 8-naphthalic anhydride, bibenzoic anhydride, o-carboxyphenylbenzoic anhydride, 1, 4, 5, 8-naphthalenetetracarboxylic anhydride, or mixtures thereof.

6. A polymeric material according to at least one of claims 1 to 3, characterized in that the polycarboxylic anhydride is prepared from open-chain di-and polycarboxylic acids having at least two free carboxylic acid groups.

7. Polymeric material according to claim 6, characterized in that the polycarboxylic anhydride is selected from the group consisting of aconitic anhydride, citraconic anhydride, glutaric anhydride, itaconic anhydride, tartaric anhydride, diethanol anhydride, ethylenediaminetetraacetic anhydride or mixtures thereof.

8. Polymer material according to at least one of claims 1 to 7, characterized in that di-or tricarboxylic acids are used as polycarboxylic acids.

9. Polymeric material according to claim 8, characterized in that the polycarboxylic acid is selected from the group consisting of citric acid derivatives, polymerized tall oil, azelaic acid, gallic acid, dimeric or pinolenic acid, dimeric or cashew acid, cashew nut shell liquid, polyuronic acid, alginic acid, mellitic acid, 1, 3, 5-trimellitic acid, aromatic di-or polycarboxylic acids such as phthalic acid, 1, 2, 4-trimellitic acid, hemimellitic acid, 1, 2, 4, 5-pyromellitic acid and aromatic substituted derivatives thereof such as hydroxy or alkyl phthalic acid, unsaturated di-and polycarboxylic acids such as norpinac acid, heterocyclic di-and polycarboxylic acids such as lobatenoic acid or octanenic acid (cinicoholponic acid), bicyclic di-and polycarboxylic acids such as norbornene dicarboxylic acid, open-chain di-and polycarboxylic acids such as malonic acid and its long-chain homologues and substituted compounds thereof such as hydroxy and keto di-and polycarboxylic acids, pectinic acid, humic acid, cashew nut shell liquid having at least two free carboxylic acid groups in its molecule, or mixtures thereof.

10. A polymeric material according to at least one of claims 1 to 9, characterized in that it comprises 2 to 98% by mass of the reaction product of claim 1 and 98 to 2% by mass of the filler.

11. Polymer material according to at least one of claims 1 to 10, wherein the filler is selected from organic fillers based on cellulose-containing materials, such as wood flour, sawdust or wood waste, rice husks, straw and flax fibers based on proteins, in particular wool, and inorganic fillers based on silicates and carbonates, such as sand, quartz, corundum, silicon carbide and glass fibers, or mixtures thereof.

12. The polymer material according to claim 1 to 11, wherein 0.01 to 10% by mass of a catalyst is added to the reaction product.

13. Polymeric material according to claim 12, characterized in that the catalyst is selected from tertiary amines such as N, N' -benzyldimethylaniline, imidazole and its derivatives, alcohols, phenols and their substituted compounds, hydroxycarboxylic acids such as lactic acid or salicylic acid (solicylic acid), organometallic compounds such as triethanolamine titanate, dibutyltin laurate, lewis acids, in particular boron trifluoride, aluminium trichloride and their formic acid complex compounds, lewis bases, in particular alcoholates, polyfunctional mercapto compounds and thioacids and organophosphorus compounds, in particular triphenyl phosphite and bis- β -chloroethylphosphinite, bicyclic amines such as [ 2.2.2 ] -diazabicyclooctane, Chinuclidine or diazabicycloundecene, alkali metal and alkaline earth metal hydroxides, grignard compounds or mixtures thereof.

14. Polymer material according to at least one of claims 1 to 13, characterized in that it further comprises a flame retardant selected from the group consisting of aluminium hydroxide, halogens, antimony, bismuth, boron or phosphorus compounds, silicate compounds or mixtures thereof.

15. Process for producing a polymeric material according to at least one of claims 1 to 14, characterized in that a triglyceride, a polycarboxylic anhydride, a polycarboxylic acid and, if desired, additives such as additives and/or catalysts and/or flame retardants are mixed and in that hardening is then carried out.

16. Process for producing a polymeric material according to at least one of claims 1 to 14, characterized in that a triglyceride, a polycarboxylic anhydride, a polycarboxylic acid and, if desired, a catalyst are first crosslinked to a viscosity of 0.2 to 20000 cps at 20 to 200 ℃, in that then a filler and/or a flame retardant is added, and in that then hardening is carried out.

17. A method according to claims 15 and 16, characterized in that the hardening is carried out at > 20 ℃ to 200 ℃ for 10 seconds to 24 hours at 1 to 100 bar.

18. Use of the polymeric material according to at least one of claims 1 to 14 in prefabricated indoor partition systems, as a substitute material for plastic and metal frames, as a material for paint boards and coverings, as profile materials, as sealing materials, high abrasion resistant coatings and moldings, as covering crack protection skins, non-slip coverings, electrical insulating or conductive compounds, abrasion resistant films, paints for ship hull underwater parts, equipment fluidized bed sintering parts and moldings subjected to stress, as moldings of penetrating fibers and fiber mats, chipboards, MDF substitutes, hard fiber boards and endless profiles for the building and furniture industry.