SI9620102A - Polymer material, process for its production and use thereof - Google Patents

Abstract

The invention concerns a polymer material based on renewable raw materials and containing a reaction product comprising 10 to 90 mass % of a triglyceride having at least two epoxy and/or aziridine groups, and 5 to 90 mass % of a polycarboxylic acid anhydride with 0.01 to 20 mass % of a polycarboxylic acid.

Description

PREFORM GMBH

Polymeric material, process for its production and use

The invention relates to a polymeric material based on renewable raw materials, to a process for preparing this material and to its use. Organic plastics, which are widely used in the art today, are almost exclusively produced on a petrochemical basis. For example, they are used in the furniture and construction industries of UF-bonded wood (UF = ureaformaldehyde resins), PF (PF = phenolformaldehyde) or, more rarely, PUR (PUR = polyurethane). Cover plates, end pieces, cable ducts, etc. they mainly consist of polyvinyl chloride (PVC). Also, plastic windows with frames made of PVC are nowadays used in the field of windows. PVC, as a material for such construction parts, has decisive disadvantages. One is unsatisfactory recycling, and the other is that PVC develops dangerous gases in the event of a fire. Qualitatively valuable compression elements for machines and devices often consist of fibers or interlaces reinforced with PF, MF (MF = melamine-formaldehyde resins), EP (EP = epoxy resins) or UP (UP = unsaturated polyester resins), which they are used, for example, in the motor vehicle industry. In conjunction with the increasing discussion of CO ₂ and the associated potential global climate change, there is a great need today for mainly new type CO ₂ neutral plastics that will meet the high profile requirements of currently used plastics on a petrochemical basis and which would they can be compensated relatively. It is reasonable that such polymeric materials will be obtained from educts based on renewable raw materials.

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Prior art is known in the art. combinations of binders that also partially contain renewable raw materials. These developments are particularly relevant to the polyurethane field. Thus, it is known from US PS 458 2891 that castor oil, and thus also a renewable feedstock, is converted by polyisocyanate and inorganic filler.

EP 01 51 585 discloses a two-component polyurethane adhesive system using oleochemical polyol as a ring opening product for epoxidized fatty alcohols, fatty acid esters (especially triglycerides) or fatty acid amides with alcohol. It is further known that epoxidized triglycerides are used as plasticizers. One such procedure is described e.g. in PCT / EP94 / 02284.

US 35 78 633 discloses a process for curing polypoxides with polycarboxylic acid anhydride with the addition of special alkali salts of selected carboxylic acids. Only polypoxides with more than one vicinal epoxy group per molecule are used here. The polymers obtained by this document, however, have the disadvantage that they, on the one hand, originate from physiologically problematic starting materials (eg lithium salts) and, on the other, contain polymers that lack the required strength. This clearly indicates that a basic reaction is proceeding under the US patent, which supports the crosslinking of external epoxy groups, which in no way exist in epoxidized triglycerides.

DE 41 35 664 discloses polymeric products which are prepared from epoxides of triglycerides and partial esters of polycarboxylic acids with at least two free carboxylic groups and a hydrophobic agent. However, according to DE 41 35 664, elastic plastics with increased water resistance are obtained, which also lack satisfactory properties regarding the strength and variation width of the polymer system.

Therefore, it is an object of the present invention to provide a material of a new kind that is made on the basis of renewable raw materials and which leads to polymeric substances which, in view of their strength, allow a wide range of applications.

With respect to the polymeric material, the problem is solved by the characteristic features of claim 1, in conjunction with the process given by the characteristic features of claims 15 and 16. Dependent claims indicate preferred further embodiments.

The invention therefore proposes a polymeric material which essentially contains a reaction product of three components, namely from 10-90% by weight of triglyceride, 5-90% by weight of polycarboxylic acid anhydride with 0.01-20% by weight of polycarboxylic acid . The Applicant was able to demonstrate that, surprisingly, polymeric materials containing the reaction product in the manner previously described have surprising strength properties and the variational width of the material properties. Crucially, the material of the invention is the use of polycarboxylic acid anhydrides, which act as crosslinkers, so that the crosslinking density of the resulting polymer is significantly increased. Hard polymers are obtained as a result.

The main components of the reaction product are both epoxidized triglycerides and polycarboxylic acid anhydrides which are crosslinked. The crosslinking reaction is then started with the addition of small amounts of polycarboxylic acid (0.01 to 20% by weight). Thus, polycarboxylic acid clearly has a useful initiator function for internally existing epoxy triglyceride groups.

With the addition of polycarboxylic acid anhydrides, the adjacent OH groups formed by opening the epoxy ring are then crosslinked in the form of an addition reaction. The free carboxyl group thus formed on the polycarboxylic anhydride thus apparently reopens one further epoxy ring, thereby also obtaining one adjacent OH group, which reacts with the additional carboxyl anhydride group upon further addition. The reaction begins when the epoxy ring is opened and adjacent OH groups are formed. The crosslinking initiation is carried out by the addition of smaller amounts of polycarboxylic acid. It is important that the opening of the epoxy group occurs as a reaction start. The possible reaction course is schematically presented below.

H OH

Ri — C— έ— R2 i i O H

O initiation r, _r_C_R2 ”HOOC - Ra- (epoxide triglyceride) (polycarboxyl k.) O

P o

(cyclic polycarboxylic acid anhydride)

Ra

OOC ^Z —COOH -C — t-R2 OOC — Ra ο _χ .0 — c — R1 (epoxide triglyceride) polycarboxylic acid anhydride ⁺

Ra

OOC R1 - C R2

OOC — R3

Ra / \ λ

OOC-COO-C-C-R:

/ \

-— ČOO - C — C — R2

Ra / \ OOC — COOH

R1

OH

R:

epoxidized triglyceride repeat reaction scheme

I

Unlike pure polycarboxylic acid crosslinking, the resulting hydroxyl groups react with polycarboxylic anhydride upon polyaddition. This was also confirmed by DSC and IR investigations.

For the polymeric material of the invention, it is essential that it contains a reaction product consisting of 10-90% by weight of triglyceride and 5-90% by weight of carboxylic acid anhydride, the reaction being initiated with smaller amounts of polycarboxylic acid (0.01 -20 wt.%). Preferably, the reaction product contains 35-70% by weight of triglyceride and 10-60% by weight of polycarboxylic acid anhydride, as well as 0.05-10% by weight of polycarboxylic acid.

Examples of epoxidized triglycerides that can be used in the polymeric material to prepare the reaction products of the invention are soybean oil, linseed oil, linen oil, tung oil, oitikik oil, saffron oil, poppy seed oil, hemp oil, cottonseed oil, sunflower oil, sun oil rapeseed oil, triglycerides from Euphorbia plants, e.g. Euphorbia-Iagascae oil and high oleic triglycerides such as e.g. high oleic sunflower oil or Euphorbia-Iathyris oil, peanut oil, olive oil, olive oil, almond oil, kapok oil, hazelnut oil, apricot oil, acorn oil, lupine oil, corn oil, sesame oil, grape seed oil, grape seed oil lalemantia oil, castor oil, marine animal oils such as brine oil and sardine oil or menhaden oil, whale oil as well as triglycerides with a high content of saturated fatty acids, which are subsequently ex. by dehydrogenation, they are converted into an unsaturated state, or mixtures thereof. Due to the reaction with hydroxyl groups, it is possible to use hydroxylated triglycerides in addition to the epoxidized triglycerides as a further component. Such hydroxylated triglycerides are e.g. hydroxylated high oleic or castor oil. In this way, the physical properties of the polymers can be greatly altered. It is important, however, that epoxidized triglycerides are always present, as otherwise the chain will break. The use of triglycerides with aziridine groups is also possible. Various synthesis pathways are known for the preparation of aziridines. One route of preparation is cycloaddition e.g. carbenes on azomethines (Breitmaier E., G. Jung, Org. Chemie Bd. 1, E. Thieme Berlag, Stuttgart) or nitrenes on olefins. Synthesis by reduction of a6 chloronitriles or oximes with LiAlH _{4 is also possible} (Buli. Chem. Soc. Jpn. 40, 432 (1967) and Tetrahedra 24, 3681 (1968).

For polycarboxylic acid anhydrides, those having a cyclic base framework, i.e. polycarboxylic acid anhydrides prepared from cyclic polycarboxylic acids with at least two free carboxylic groups. Examples are cyclohexanedicarboxylic anhydride, cyclohexendicarboxylic anhydride, phthalic anhydride, trimellitic anhydride, hemimellitic acid anhydride, pyromellitic anhydride 1,2-cyclic acid anhydride, 1,2-cyclic acid anhydride, anhydride quinolinic acids, norbomendicarboxylic acid anhydride (NADICAN), as well as methyl substituted MNA compounds, pinic acid anhydride, norpinic acid anhydride, truxic acid anhydride, perylene 1,2-dicarboxylic acid anhydride, anhydrous anhydride anhydride isatoic acids, caffeic anhydride, 1,8-naphthalic acid anhydride, diphenic acid anhydride, o-carboxyphenylacetic acid anhydride, 1,4,5,8 naphthalenecarboxylic acid anhydride or mixtures thereof.

Polycarboxylic acid anhydrides of open-chain di- and polycarboxylic acids having at least two free carboxylic groups, such as e.g. acotinic acid anhydride, citric acid anhydride, glutamic acid anhydride, itaconic acid anhydride, tartaric acid anhydride, diglycolic acid anhydride, ethylenediaminetetraacetic acid anhydride or mixtures thereof.

In the initiators used according to the invention, i.e. for polycarboxylic acids, di- and tri-carboxylic acids are preferred. Examples of these are citric acid derivatives, polymerized tallow oils, azelaic acid, gallic acid, di- or polymerized resin acids, di- or polymerized anacardic acid, also cashew nut, polyuronic acid, polyalginic acid, trimeic acid, myelamic acid di- and polycarboxylic acids, such as e.g. phthalic acid, trimellitic acid, hemimellitic acid, pyromellitic acid, as well as their aromatically substituted derivatives, such as e.g. hydroxy or alkylphthalic acid, unsaturated cyclic di-

Ί polycarboxylic acids such as e.g. norpic acid, heterocyclic di- and polycarboxylic acids, such as e.g. loiponic acid or quincholoiponic acid, bicyclic di- and polycarboxylic acids, such as e.g. norbomandicarboxylic acids, open-chain di- and polycarboxylic acids such as e.g. malonic acid and their long-chain homologs, as well as their substituted compounds, such as e.g. hydroxy- and keto- and polycarboxylic acids, pectic acids, humic acids, the polymeric liquid of the shell of indium with at least two free carboxylic groups in the molecule, or mixtures thereof.

A further preferred embodiment of the invention proposes that the polymeric material contains a reaction product prepared from the starting components described above but additionally with a catalyst. The catalyst may be added in a quantity ratio of from 0.01 to 10% by weight. %, preferably 0.05 to 5% by weight. Essentially, all the compounds that serve to promote crosslinking of epoxy resins can serve as catalysts. Examples of these are tertiary amines, such as e.g. Ν, Ν'-benzyldimethylaniline, imidazole and their derivatives, alcohols, phenols and their substituted compounds, hydroxycarboxylic acids, such as lactic acid or salicylic acid, organometallic compounds such as triethanolaminititanate, di-n-butyl zinc lauric acid, especially boron alumina, boron trichloride and their amine complex compounds, Lewis bases, in particular alcoholates, multifunctional mercapto compounds and thio acids, as well as organophosphorus compounds, in particular triphenylphosphite, trisnonylphenylphosphite and bis-β-chloroethyl ethyl phosphite, bicyclic amines such as [2.2.2] -diazabicyclooxydecane, or k-diazabicycloidocyanide, , alkali and alkaline earth hydroxides, Grinard compounds or mixtures thereof.

It is particularly advantageous that the polymeric material of the invention may consist solely of the reaction product described previously or may, depending on the profile required, contain one additional filler or flame retardant. When the polymeric material contains exclusively the reaction product and the filler, it is preferred that it contains 2-98% by weight of the reaction product and 98-2% by weight of the filler.

It is particularly preferred that the polymeric material contains 6-90% by weight of the reaction product and 10-94% by weight 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 chaff, straw and flax based on protein, in particular sheep wool, as well as inorganic silicate based fillers and carbonates such as sand, quartz, corundum, silicon carbide and glass fibers, or mixtures thereof. The polymeric material of the invention may also contain up to 50% by weight of a fire retardant. Preferred flame retardants are: aluminum hydroxide, halogen, antimony, bismuth, boron or phosphorus compounds, silicate compounds or mixtures thereof.

In the preparation of the material, in a preferred embodiment with the filler, it is possible to proceed by first preparing a mixture of the starting components, i.e. triglyceride, polycarboxylic acid anhydride and carboxylic acid, then the mixture is prepolymerized to a high density of 0.2-20000 mPas at 20 ° C to 200 ° C and then the filler is added. Finally, after design, optional hardening can be carried out - optionally under pressure. However, it is also possible to mix all the additives and then carry out the pre-polymerization.

On the other hand, we can also handle all starting materials i.e. triglycerides, polycarboxylic acid anhydrides and carboxylic acids, as well as optionally further additives such as fillers and / or flame retardants, are mixed and subsequently cured at elevated temperature and elevated pressure.

Curing may take place in the range> 20 ° C to 200 ° C at a pressure of 1 bar to 100 bar. The duration of cure depends on the temperature, pressure and, optionally, the catalyst added. Curing time can range from 10 seconds to 24 hours. We preferably operate in the temperature range from 50 to 150 ° C.

The polymeric material of the invention may also be infiltrated into the web or web. In this way we can prepare molded fibers.

By the process of the invention, the resulting mixture can be individually molded and pressed, and can also be used in endless production. Endless production can also be accomplished by extrusion or hot rolling.

After curing, the reaction mixture forms a closed and developed smooth surface, with plastic dissolution, i.e. the size of the plastics still geometric figures is very high. The material can very accurately replicate the finest filigree patterns.

The material of the invention is particularly distinguished by being toxicologically sound and thus free from defects in PVC and / or other comparable materials, such as e.g. those based on polyurethane. It is worth mentioning that the material of the new type may have similar mechanical properties as PVC, EP or PES. These material variants are rigid and have high strength. High-grade cellulose-containing polymeric materials of the invention which can be obtained by compression or extrusion have high mechanical strengths. In mechanical point loading, such as e.g. the structure of the surrounding material is retained when fastening wood screws or hammering wood nails. Cracks like you can eg. appear on wood, we do not notice. The material can be machined without problems. No sawing of the border surfaces or peeling of smaller pieces is observed when sawing or milling.

With additional proportions of hydroxylated triglycerides, molds can be obtained which, at room temperature, have a partially plastic behavior and at the same time have exceptional tear resistance. Depending on the degree of crosslinking, which can in principle be influenced by the composition of the output components, molds can be obtained that allow the thermal transformation of bodies from polymeric material. A noticeable improvement in fire behavior was especially found in the flammability tests by the incorporation of aluminum hydroxide. The installation of aluminum hydroxide and the associated cleavage of water prevent the direct onset of flames. This complies with the BS 4102 fire protection class.

Numerous experiments have shown that the material of the invention does not exhibit a noticeable absorption of water, so that the high-filled cellulose-containing presses were immersed in water for an extended period of time. After 80 hours, the material did not absorb any significant amount of water. No physical or chemical changes could be observed on the material.

The invention is further explained by the following examples:

EXAMPLE 1

53.5% by weight of oxygenated flaxseed oil with an oxygen content of 9% by weight is mixed with

42.8% by weight of caffeic anhydride and 2.7% by weight of a mixture of di- and trimeme abietic acid. This mixture was homogenized with 1 wt% 50% ethanol quinuclidine solution. 10% by weight of this mixture is mixed with 90% by weight of straw and pressed for 10 minutes at a pressure of 15 bar and a temperature of 180 ° C. The resulting fibreboard has a physical density of 0.62 (g / cm), is characterized by quality mechanical properties and has exceptional water resistance. It can be used as fiber board in the construction and furniture industries.

EXAMPLE 2 parts by weight of an epoxidized linen oil with an oxygen content of 8% by weight are mixed with 16 parts by weight of pyromellic acid anhydride and 4% by weight of trimerized fatty acid. Apply 30% by weight of this mixture to 70% by weight of jute-hemp fiber net so that the fiber net is homogeneously wetted. The infiltrated fiber strand is then pressed at 10 bar and 170 ° C for 10 minutes. The resulting fiber product has high elasticity, breaking strength and water resistance. It can be used in many areas where fiber reinforced or fiber reinforced plastics are used, such as e.g. fiber reinforced shuttering and forming parts or cladding elements.

EXAMPLE 3

42.9% by weight of epoxidized soybean oil with an oxygen content of 6.5% by weight is mixed with

21.5% by weight of hydroxylated high oleic oil. To this mixture was added 34.3 wt.% Of norbomendicarboxylic acid anhydride and 1.3 wt.% Of methanolic DABCO solution. The mixture was homogenized and then crosslinked at 140 ° C for 15 minutes. The resulting product is transparent, plastically resizable and has high tear resistance. This product can be used for the coating of materials and construction components that must have the ability to transform plastically, such as e.g. electrical cables.

EXAMPLE 4

72.7% by weight of epoxidized hemp oil with an oxygen content of 10.5% by weight is mixed with 27.3% by weight of trimethylic anhydride. 8% by weight of this mixture is mixed with 92% by weight of dried chaff of multi-purée puree and at a pressure of 15 bar and at a temperature of 170 ° C.

Λ Walk for 8 minutes. The resulting fibreboard has a physical density of 0.88 (g / cm), is characterized by high water resistance and extremely mechanical strength and can be used as a fibreboard in the construction and furniture industries.

EXAMPLE 5

54.7% by weight of epoxidized linseed oil with an oxygen content of 9.6% by weight are mixed with

43.7% by weight of tetrahydrophthalic anhydride and 1.1% by weight of adipic acid. This mixture was homogenized with 0.5 wt% DBN and crosslinked into a solid, transparent mold at 145 ° C for 5 minutes. The resulting material is resistant to water and boiling water (cf. Figs. 1 and 2) and has high mechanical strengths. The material can be heated to 300 ° C without decomposing. It can be used e.g. as a lining element for machines and machines of all kinds.

EXAMPLE 6% of epoxidized soybean oil with oxygen content of 6.5% by weight was mixed with 36% by weight of 1,2 cyclohexanedicarboxylic acid anhydride and 1.1% by weight of dimerized rosin with an acid number of 154. The mixture was homogenized with 50% butanol solution of imidazole and crosslinked at 140 ° C for 10 minutes. The polymer material obtained is transparent, characterized by high water resistance and a temperature of approx. 90 ° C can be warmly transformed. It has high mechanical strength below this temperature.

EXAMPLE 7

69.9% by weight of high oleic oil containing aziridene groups from Euphorbia Lathyris with an oxygen content of 4.3% by weight is mixed with 28% by weight of phthalic anhydride,

1.5% by weight of sebacic acid and 0.6% by weight of isopropanol quinuclidine solution. The mixture at 145 ° C was crosslinked for 5 minutes in a hard-elastic transparent polymeric material with high water resistance and abrasion resistance.

EXAMPLE 8

51.5% by weight of epoxidized tung oil with an oxygen content of 10.5% by weight is mixed with

45.5% by weight of caffeic anhydride and 2.5% by weight of 70% citric acid ethanol solution. To this mixture was added 0.5 wt% DABCO and the mixture was homogenized. 30% by weight of this mixture is applied to 70% by weight of dry coconut fiber so that the fibers are homogeneously infiltrated with the reaction mixture. The infiltrated coconut fibers are then preheated at 130 ° C for 20 minutes. The reaction mixture is reacted to the prepolymer with a viscosity of approx. 10000 (mPas). The pretreated netting is then molded and stirred at 15 bar for 1 minute. The resulting fiber product has high mechanical strength, is highly water resistant and very temperature resistant. It can be used in areas where fiberglass reinforced plastics or fiber reinforced plastics are used with plastics.

EXAMPLE 9

Mixture of 61.6% by weight of epoxidised flaxseed oil with an oxygen content of 9.6% by weight and

15.4% by weight of epoxidized sardine oil with an oxygen content of 10.5% by weight is mixed with 19.2 parts by weight of pyrromylic acid anhydride and 3.8% by weight of trimerized fatty acid. 25% by weight of this mixture is homogenized with 75% by weight of wood flour with an average fiber length of 300 µm. The powdered dust is then treated with infinite molds using a RAM extruder at 160 ° C and a pressure of 40 bar. The obtained products have high mechanical stability and are extremely resistant to water.

EXAMPLE 10

53.2% by weight of epoxidized saffron oil with an oxygen content of 9% by weight is mixed with 10% by weight of acotinic acid anhydride, 32.5% by weight of methylnorbonendicarboxylic acid anhydride and 2.6% by weight of dimerized anacardic acid. To this mixture was added 1.7 wt% propanol DABCO solution and then the mixture was homogenized. 10% by weight of this mixture was mixed with 90% by weight of dried and ground rice paddies with a mean grain size of 0.5 mm to give a homogeneous wettable powder. This mixture was then stirred at 15 bar for 15 minutes at a temperature of 130 ° C. The material obtained has a physical density of 0.9 (g / cm ³ ) and can be treated by cutting.

This material is suitable everywhere where Medium Density Fibreboard (MDF) is used.

EXAMPLE

50.5% by weight of epoxidized linseed oil is mixed with 42.5% by weight of tetrahydrophthalic anhydride and 2.5% by weight of trimerized abietic acid. This mixture was homogenized with 1.8 wt% 50% isobutanol quinuclidine solution. 30% by weight of this mixture is homogenized with 35% by weight of barite, 5% by weight of pigment such as e.g. rutile and 30% by weight of muscovite, chlorite and quartz flour mixtures. The mixture is then crosslinked at 30 bar and 140 ° C for 8 minutes into rigid elastomeric molds having high resistance to water and boiling water as well as high mechanical strength. The material can be used e.g. as a lining element for apparatus and machines of all kinds.

Claims (15)

PATENT APPLICATIONS A polymeric material based on renewable raw materials, characterized in that it contains a reaction product obtained by crosslinking 10-90% by weight of triglyceride with at least two epoxy and / or aziridine groups and 5-90% by weight of polycarboxylic acid anhydride, which is prepared from cyclic polycarboxylic acids with at least two free carboxylic groups, with 0.01-20% by weight of polycarboxylic acid as initiator. Polymeric material according to claim 1, characterized in that the epoxidized triglycerides are selected from soybean oil, linseed oil, linen oil, tung oil, oitikik oil, saffron oil, poppy seed oil, hemp oil, cottonseed oil, sunflower oil, sunflower oil, sunflower oil oils, triglycerides from Euphorbia plants such as e.g. Euphorbia-Iagascae oil and high oleic triglycerides, such as e.g. high oleic sunflower oil or Euphorbia-Iathyris oil, peanut oil, olive oil, olive oil, almond oil, kapok oil, hazelnut oil, apricot oil oil, acorn oil, lupine oil, corn oil, sesame oil, sesame oil, sesame oil lalemantia oil, castor oil, marine animal oil such as brine oil, sardine oil or menhaden oil, whale oil, as well as triglycerides with a high content of saturated fatty acids, which are subsequently ex. by dehydrogenation, they are converted into an unsaturated state, or mixtures thereof. Polymeric material according to claim 1 or 2, characterized in that the epoxidized triglycerides additionally contain hydroxylated triglycerides as castor oil. Polymeric material according to at least one of claims 1 to 3, characterized in that the polycarboxylic acid anhydrides are composed of cyclohexanedicarboxylic anhydride, cyclohexendicarboxylic anhydride, phthalic anhydride, trimethyl anhydride anhydride, pyridine anhydride, anhydride , 3-naphthalic acid, 1,2-cyclopendanedicarboxylic acid anhydride, 1,2-cyclobutandicarboxylic acid anhydride, quinolinic acid anhydride, norbomendicarboxylic acid anhydride (NADICAN), as well as from methyl substituted MNA compounds, anhydrins, norhydride, pinotinic anhydrides truxic anhydride, perylene anhydride 1,2-dicarboxylic acid, caronic acid anhydride, narcamphandicarboxylic acid anhydride, isoic acid anhydride, caffeic anhydride, 1,8-naphthalenic acid anhydride acid anhydride acid anhydride 4,5,8 naphthalenecarboxylic acid or mixtures thereof. Polymeric material according to at least one of claims 1 to 4, characterized in that di- or tricarboxylic acid is used as a polycarboxylic acid. Polymeric material according to claim 5, characterized in that the polycarboxylic acid is selected from citric acid derivatives, polymerized tallow oils, azelaic acid, galus acid, di- or polymerized resin acids, di- or polymerized anacardic acid, including cashew nuts , polyuronic acids, polyalginic acids, melitic acid, trimesic acid, aromatic di- and polycarboxylic acids such as e.g. phthalic acids, trimellitic acids, hemimellitic acids, pyromellitic acids, as well as aromatic substituted derivatives such as e.g. hydroxy or alkyl phthalic acids, unsaturated cyclic di- and polycarboxylic acids such as e.g. norpinic acids, heterocyclic di- and polycarboxylic acids, such as e.g. loiponic acid or quincholoiponic acid, bicyclic di- and polycarboxylic acids such as e.g. norbonandicarboxylic acids, open-chain di- and polycarboxylic acids such as e.g. malonic acids and their long-chain homologs, as well as their substituted compounds, such as e.g. hydroxy- and keto-, di- and poly-carboxylic acids, pectic acids, humic acids, polymer nut of cashew nuts with at least two free carboxylic groups in the molecule, or mixtures thereof. A polymeric material according to at least one of claims 1 to 6, characterized in that it contains 2-98% by weight of the reaction product according to claim 1 and 98-2% by weight of the filler. Polymeric material according to at least one of claims 1 to 7, characterized in that the filler is selected from the group of organic fillers on the basis of cellulose-containing materials such as wood flour, sawdust or wood waste, rice weeds, straw and flax fibers. proteins, in particular sheep wool, as well as inorganic fillers based on silicates and carbonates such as sand, quartz, corundum, silicon carbide and glass fibers, or mixtures thereof. Polymeric material according to at least one of claims 1 to 8, characterized in that 0.01-10% by weight of catalyst is added in the preparation of the reaction product. Polymeric material according to claim 9, characterized in that the catalyst is selected from tertiary amines such as Ν, Ν'-benzyldimethylaniline, imidazole and their derivatives, alcohols, hydroxycarboxylic acids, such as lactic acid or salicylic acid, thio acids, as well as organophosphorus compounds, in particular triphenylphosphite, trisnonylphenylphosphite and bis-p-chloroethylphosphite, bicyclic amines such as [2.2.2] diazabicyclooctane, quinuclidine or diazabickloundecene, or mixtures thereof. A polymeric material according to at least one of claims 1 to 10, characterized in that it further comprises a flame retardant selected from the group consisting of aluminum hydroxide, halogen, antimony, bismuth boron or phosphorus compounds, silicate compounds or mixtures thereof . A process for the preparation of a polymeric material according to at least one of claims 1 to 11, characterized in that the triglyceride, the polycarboxylic acid anhydride, the polycarboxylic acid and optionally further additives such as fillers and / or catalysts and / or a flame retardant are mixed and then cured. Process for the preparation of a polymeric material according to at least one of claims 1 to 12, characterized in that the triglyceride, polycarboxylic acid anhydride and polycarboxylic acid, and optionally the pre-crosslinked catalyst to a viscosity of 0.2 to 20000 mPas at 20 ° C-200 ° C and then add filler and / or flame retardant and then cure. Process according to Claims 12 and 13, characterized in that the curing is carried out at a temperature in the range of> 20 ° C to 200 ° C and at a pressure of 1 bar to 100 bar over a period of 10 seconds to 24 hours. 15. The use of a polymeric material according to at least one of claims 1 to 11 for pre-fabricated space dividing systems, as a replacement material for plastic and metal frames, as material for lacquer rails and lining elements, as a profile material, as a sealing material, for linings and high abrasion resistant moldings, such as protective layers for bridging cracks, for non-slip coatings, insulating or conductive masses, tribologically applicable films, underwater ship coatings, rosy synth systems for laden device components and molded parts, for molded elements as infiltrated fibers and fiber interlaces, plywood, MDF substitutes and hard fiber boards in the construction and furniture industries, endless profiles.