SK1598A3 - 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

Polymeric material, process for its preparation and use

Technical field

The invention relates to a polymeric material based on renewable raw materials and to a process for its production and use.

BACKGROUND OF THE INVENTION

Organic plastics, which are currently widely used in industry, are almost exclusively based on petrochemical bases. For example, in the manufacture of furniture and construction, wood materials are used that contain UF-, MUF-, PF-, or rarer PUR-binders. Cladding boards, endings, cable strips, etc. ' consist mostly of polyvinyl chloride (PVC). In the case of windows, plastic windows with PVC frames are also widely used today. However, polyvinyl chloride as a material for components of this type exhibits decisive disadvantages. On the one hand, recycling of this material has not been satisfactorily solved, and on the other hand, in the event of a fire from PVC, hazardous gases are generated. The components of the sheaths of the devices and apparatus, as well as the qualitatively high-quality moldings, are often formed of PF-, MF-, EP- or UP-reinforced matrices or nets, which are used, for example, in the automotive industry. In the context of the growing debate on carbon dioxide and its possible global climate change, there is now a great demand for modern carbon dioxide-neutral plastics that meet the high standards of petrochemical-based plastics currently used and which could partially replace these plastics. In a meaningful manner, such polymeric materials are obtained from sources based on renewable raw materials.

Binders are known from the prior art.

binder combinations which also partially contain renewable raw materials. This development applies in particular to the polyurethane field. Thus, it is known from U.S. Pat. No. 458,291 to replace castor oil, also a renewable raw material, with a polyisocyanate and an inorganic filler.

EP 01 51 585 discloses a two-component polyurethane adhesive system in which ring opening products of epoxylated fatty alcohols, fatty acid esters (especially triglycerides) or fatty acid amides with alcohols are used as oleochemical polyols. It is also known that epoxylated triglycerides can be used as plasticizers. A method of this type is described e.g. PCT / EP94 / 02284.

US 35 78 633 discloses a process for curing polyepoxides with polycarboxylic anhydrides using special alkali salts of selected carboxylic acids. According to this method, only polyepoxides with more than one vicinal epoxy group per molecule were used. However, the polymers obtained in this way have the disadvantage that, however, the starting materials are physiologically harmful substances (e.g. lithium salts) and, nevertheless, the polymers obtained do not have the desired strength values. From this, it can be reasonably concluded that, according to the US patent, there is a basic reaction which promotes cross-linking of external epoxy groups, but which in no way occur in epoxylated triglycerides.

DE 41 35 664 discloses polymer products which are produced from epoxylated triglycerides and partial polycarboxylic acid esters with at least two free carboxyl groups using a hydrophobising agent. According to DE 41 35 664, however, elastic coating materials with improved water resistance are obtained which also do not show any satisfactory properties with regard to the strength and variation width of the polymer system.

SUMMARY OF THE INVENTION

Accordingly, it is an object of the present invention to provide a novel material based on renewable raw materials which leads to polymeric materials which, in view of their strength, offer a wide range of applications.

With respect to the polymer material itself, the problem has been solved by the characterizing features of claim 1 in terms of the method, then by the characterizing features of claims 15 and 16. The dependent claims provide detailed information for preferred embodiments of the invention.

According to the invention, a polymeric material which is essentially composed of three components is 10 to 90% by weight of triglyceride, 5 to 90% by weight of polycarboxylic anhydride and 0.01 to 20% by weight of polycarboxylic acid. It has been found that unexpectedly polymeric materials containing a reaction product prepared as described above exhibit unexpected properties with respect to the strength and variation width of the material properties. Crucial to this material is that polycarboxylic anhydrides are used which act as crosslinking agents. In this way, polymers with a significantly increased cross-linking rate are obtained. The result is hard polymeric materials.

Thus, the basic components of the reaction product are epoxylated triglycerides and polycarboxylic acid anhydrides which are crosslinked with each other. The crosslinking reaction is initiated by the addition of a small amount of polycarboxylic acid (0.01 to 20% by weight). The polycarboxylic acid here appears to have a positive initiator function for the existing epoxy groups of the triglyceride.

The use of polycarboxylic anhydrides in this way leads to a cross-linking addition reaction of adjacent hydroxyl groups formed by the opening of the epoxy ring. The free carboxyl group which is formed on the polycarboxylic anhydride then obviously opens another epoxy ring, again forming an adjacent hydroxyl group, which in the next addition step reacts with another carboxylic anhydride group. Thus, the reaction is initiated at the moment of opening of the first epoxy ring when adjacent hydroxyl groups are formed. This crosslinking initiation is achieved by adding a small amount of polycarboxylic acid. Essentially, the opening of the epoxy ring represents the initiation of the reaction. The possible course of the reaction is shown in the following scheme.

0 R1-C-C-R; initiation H OH • c-B-R 2 2 + HOOC-Ra ^ -R1 - epoxidised polycarbonates I I 0 H triglyceride anthracenecarboxylic acid J FROM acid- ^X R3

cyclic polycarboxylic anhydride

R4

O 0 - COOH -C 1 - R 2 OOC - R 3

epoxylated triglyceride polycarboxylic anhydride

I

OOC — r ₃

R4

R4 / \

OOC-coo R1-e-C-R2

60c — R3 (poc / \

COOH — C — C — R2 I

R1 is an epoxylated triglyceride

In contrast to the prior art, where polycarboxylic acid crosslinking is mentioned, the hydroxyl groups formed here react by polyaddition with polycarboxylic anhydride. The progress of this reaction can be monitored by thin-layer chromatography and infrared spectroscopy.

The polymeric material according to the invention is characterized in that it comprises a reaction product consisting of 10 to 90% by weight of triglyceride and 5 to 90% by weight of polycarboxylic acid anhydride, the reaction being initiated by a small amount of polycarboxylic acid (0.01 to 20% by weight). It is particularly preferred that the reaction product comprises 35 to 70% by weight of triglyceride, 10 to 60% by weight of polycarboxylic anhydride and 0.05 to 10% by weight of polycarboxylic acid.

Examples of epoxylated triglycerides that can be used to prepare the reaction product in the polymeric material of the invention are soybean oil, linseed oil, pearl oil, Chinese wood oil, oitic oil, safflower oil, poppy oil, hemp oil, cottonseed oil, sunflower oil, rapeseed oil, triglycerides derived from Euphorbia plants, e.g. iagas oil and high oil triglycerides such as e.g. high-oil sunflower oil or iathyris oil from Euphorbia, peanut oil, olive oil, olive kernel oil, almond oil, kapok oil, hazelnut oil, apricot kernel oil, lupine oil, lupine oil, corn oil, sesame oil, grape seed oil, lalemanti oil, castor oil, marine animal oils such as e.g. herring oil, sardine oil, menhaden oil, whale oil and triglycerides with a high content of saturated fatty acids, which are subsequently converted e.g. by dehydrogenation to an unsaturated form, or to a mixture of saturated and unsaturated forms. Due to the basic reaction with hydroxyl groups, in addition to epoxylated triglycerides, another group of substances which are hydroxylated triglycerides can be used. Hydroxylated triglycerides of this type are e.g. hydroxylated high-oil triglycerides, or hydroxylated castor oil. In this way, the physical properties of the polymer can be altered in various ways. What is important, however, is that they always contain epoxylated triglycerides, since otherwise the chain is cleaved also triglycerides are used for the preparation of aziridines. One of them is azomethines (Breitmaier E., E. Thieme publishing house, olefins. Another option is or oximes using LiAlH ₄ (1967) and Tetrahedron 24, 3681 polymer. Various raw cycloadditions can be used as raw materials containing aziridine groups. Carbenes on

G. Jung: Org. Chemistry, Vol. 1, Stuttgart), or nitrenes also for the reduction of the chloronitriles, Bull. Chem. Soc. Jpn. 40, 432 (1968)].

With regard to polycarboxylic anhydrides, they are most preferably those having a cyclic backbone, i.e. polycarboxylic anhydrides which are prepared from cyclic polycarboxylic acids with at least two free carboxylic groups. Examples of such substances are cyclohexanedicarboxylic anhydride, cyclohexene dicarboxylic anhydride, phthalic anhydride, trimellitecarboxylic anhydride, hemimellitecarboxylic anhydride, pyromellitecarboxylic acid,

2,3-naphthalenedicarboxylic,

1,2-cyclopentanedicarboxylic acid, acid anhydride acid anhydride acid acids

1.2-cyclobutanedicarboxylic acid, quinolinic anhydride, norbornane dicarboxylic anhydride (NADICAN) and further methyl-substituted MNA compounds, pinenic anhydride, norpinenic anhydride, truxilic anhydride, perylene anhydride

1,2-dicarboxylic acid, carboxylic acid anhydride, narcamphane dicarboxylic acid anhydride, isic acid anhydride, camphoric anhydride, acid anhydride

1,8-naphthalenedicarboxylic acid, diphenylcarboxylic anhydride, o-carboxyphenylacetic anhydride, 1,4,5,8-naphthalenetretracarboxylic anhydride, or mixtures thereof.

Also useful are polycarboxylic anhydrides obtained from open-chain di- and polycarboxylic acids containing at least two free carboxylic groups such as aconitic anhydride, citraconic anhydride, glutaric anhydride, itaconic anhydride, tartaric anhydride, diglycolic anhydride, ethylenediaminetetraacetic anhydride, or mixtures thereof.

Among the initiators used according to the invention, i.e. polycarboxylic acids, dicarboxylic and tricarboxylic acids are particularly preferred. Examples are citric acid derivatives, polymerized tall oils, azelaic acid, gallic acid, di- or polymerized bitumen acids, di- or polymerized anacardic acid, keshu nut shell, polyuronic acid, polyalginic acid, mellitic acid, trimesic acid, aromatic di- and polycarboxylic acids such as e.g. phthalic acid, trimellitic acid, hemimellitic acid, pyromellitic acid and aromatic substituted derivatives thereof such as e.g. hydroxy- or alkylphthalic acid, unsaturated cyclic di- and polycarboxylic acids, such as e.g. norpinic acid, heterocyclic di- and polycarboxylic acids, such as e.g. loiponic acid, or cincholoiponic acid, bicyclic di- and polycarboxylic acids, such as e.g. norbannanedicarboxylic acids, di- and polycarboxylic acids with an open chain, such as e.g. malonic acid and its longer chain homologues as well as substituted compounds thereof, e.g. hydroxy- and keto-dicarboxylic and polycarboxylic acids, pectic acids, humic acids, polymeric keshu nut shell liquid with at least two free carboxyl groups per molecule, or mixtures thereof.

Another preferred embodiment of the invention suggests that the polymeric material comprises a reaction product made from the above starting items using a catalyst. The catalyst may be added in an amount of 0.01-10% by weight, preferably 0.05-5% by weight. In principle, all compounds which serve to accelerate the crosslinking of epoxy resins can be used as catalysts. Examples of such substances are tertiary amines, such as e.g. N, N'-benzyldimethylaniline, imidazole and its derivatives, alcohols, phenols and their substituted compounds, hydroxycarboxylic acids such as lactic or salicylic acid, organometallic compounds such as e.g. triethanolamine titanate, di-n-butyltin laurate, Lewis acids, especially borotrifluoride, aluminum trichloride and complexes thereof with amines, Lewis bases, especially alcoholates, multifunctional mercapto compounds and thioacids, as well as organophosphorus compounds, especially bisphenylphosphite phosphite, trisphenylphosphite, trisphenylphosphite, trisphenylphosphite, trisphenylphosphite amines such as [2,2,2] diazabicyclooctane, quinuclidine or diazabicycloundecene, alkali and alkaline earth metal hydroxides, Grinard compounds, or mixtures thereof.

In particular, it should be pointed out that the polymeric material of the invention may be composed solely of the reaction product as described above, or may optionally contain a filler or flame retardant to achieve the desired properties. If the polymeric material exclusively comprises 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 comprises 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, chips, straw or rope fibers based on proteins, in particular: sheep 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 of the present invention may also contain up to 50% by weight of the flame retardant. Preferred flame retardants are aluminum hydroxide, halogenated compounds, antimony, bismuth, boron, or phosphorus compounds, and silicate compounds, or mixtures thereof.

In the preparation of the preferred filler material, a mixture of the starting components, i.e. triglyceride, polycarboxylic anhydride and carboxylic acid, is first prepared, and the mixture thus prepared is prepolymerized to a viscosity of 0.220,000 CPS at 20 ° C. ° - 200 ° C, and then the filler is added. Finally, it is possible, according to one process, to carry out: curing, possibly under pressure. However, it is also possible that all the ingredients are mixed and subsequently prepolymerized.

On the other hand, it is also possible to first mix all the starting materials, i.e. triglycerides, polycarboxylic anhydrides and carboxylic acids, as well as, optionally, other additives such as fillers and / or flame retardants, and subsequently cure at elevated temperature. , or at elevated temperature and elevated pressure.

Curing may be performed: at temperatures in the 20 ° - 200 ° C at a pressure of 10 ⁵ - ^ lO Pa. The curing time depends on the temperature, pressure and, optionally, the catalyst to be added and can range from 10 seconds to 24 hours. The preferred curing temperature is in the region of 50 ° -150C.

The polymeric material according to the invention can also be incorporated into nonwovens and mats. In this way it is possible to produce fiber-reinforced moldings.

Heat can also be used in the process according to the invention to individually meter the molds into a continuous process.

it is possible to either obtain the obtained mixture and to compress it or to produce. Continuous extrusion and rolling process

After curing, the reaction mixture forms a closed and explicitly smooth surface, whereby the plastic resolution, i.e. the size of the geometric forms which can still be plasticized, is very high. Therefore, the finest filigree patterns can be made very precisely from this material.

The material according to the invention is particularly characterized in that it is toxicologically sound and therefore does not have the disadvantages of PVC and / or other comparable materials such as e.g. materials based on polyurethanes. It should also be noted that this new material may have similar mechanical properties to PVC, EP, or PES. These material variants are highly elastic and have great strength. The highly filled cellulosic polymeric materials of the invention obtained by compression or extrusion are characterized by high mechanical strengths. Under the mechanical point stresses to which the material is subjected e.g. When fastening screws in wood or nails, the structure of the material remains intact in the immediate vicinity. The tearing that may occur e.g. for wood, not observed with this material. The material can be machined without any problems. When cutting or milling, no rupture of the boundary surfaces is observed, and at all no peeling of smaller material particles.

By additionally adding proportions of hydroxylated triglycerides, it is possible to obtain moldings which, at normal room temperature, exhibit partially plastic properties but at the same time have excellent tear strength. Depending on the degree of crosslinking, which can in principle be influenced by the composition of the starting components, it is possible to obtain moldings in which the polymer material can be thermoformed. In attempts to ignite, it has been found that, in particular by incorporating aluminum hydroxide into the material, a noticeable improvement in the non-flammability of the material is achieved. The incorporation of aluminum hydroxide and the associated cleavage of water molecules suppresses the direct effect of the flames. In this way, the flammability class BS according to DIN 4102 is achieved.

In addition, it has been shown in many experiments that there is no appreciable water uptake for the material according to the invention. For this purpose, the highly filled cellulose-containing moldings were immersed in water for a long time. After 80 seconds, no appreciable amounts of water collected by the material were observed. The material also showed no change in physical or chemical properties.

The following examples illustrate the invention in more detail.

Examples

Example 1

53.5% by weight of epoxyated rope oil with an oxygen content of 9% by weight was mixed with 42.8% by weight of camphoric anhydride and 2.7% by weight of a mixture of di- and trimeric abietic acid. This mixture was homogenized by adding 1% by weight of a 50% ethanolic quinuclidine solution. 10% by weight of this mixture was mixed with 90% by weight of straw, and this mixture was then at a pressure of 15 x 10 ⁵ Pa and at 180 ° C for 10 minutes the fiber board obtained had a physical specific gravity.

thus

0,62 pressed. weight g / cm * has high mechanical properties and excellent water resistance. It can be used as a fiber board material in the building and furniture industries.

Example 2 parts by weight of epoxydated perilla oil with an oxygen content of 8% by weight were mixed with 16 parts by weight of pyromellitic dianhydride and 4% by weight of trimerized fatty acid. 30% by weight of this mixture was applied to 70% by weight of jute and hemp fiber carpet in such a way that the fiber carpet is wetted homogeneously. The infiltrated fibrous material was subsequently pressed at 10 x 10 ⁵ Pa and at 170 ° C for 10 minutes. The fibrous product thus obtained is characterized by high elasticity, fracture strength and water resistance. It can be used in many areas where fiber-filled fibers or fiber-filled plastics are used, such as fiber-filled moldings, mold parts, or cladding elements.

Example 3

42.9% by weight of soybean oil with an oxygen content of 6.5% by weight was mixed with 21.5% by weight of hydroxylated high-oil oil. To this mixture was added 34.3% by weight norbornene dicarboxylic anhydride and 1.3% by weight 50% methanolic DABCO solution. This mixture was homogenized and then cross-linked at 140 ° C for 15 minutes. The product thus obtained is transparent, plastically deformable and has a high tensile strength. This product is possible

S can be used for coating materials and components which must be plastically deformable, such as e.g. electric cables.

Example 4

72.7% by weight of epoxylated hemp oil with an oxygen content of 10.5% by weight were mixed with 27.3% by weight of trimellitic anhydride. 8% by weight of this mixture was mixed with 92% by weight of dried wheat husk, and the mixture was then pressed for 8 minutes at 15 x 10 ⁵ Pa at 170 ° C. The fiber board thus obtained has a physical density of 0.88 g / cm ³ , characterized by high water resistance and excellent mechanical strength. It can be used as a fiber board material in the building and furniture industries.

Example 5

54.7% by weight of epoxyated linseed oil with an oxygen content of 9.6% by weight was mixed with 43.7% by weight of tetrahydrophthalic anhydride and 1.1% by weight of adipic acid. This mixture was homogenized with 0.5% DBN and then crosslinked at 145 ° C for 5 minutes to give a hard, transparent material. The material thus obtained is resistant to both water and boiling water (cf. FIGS. 1 and 2) and is characterized by high mechanical strengths. This material can be heated to 300 ° C without decomposition. It is suitable for production of e.g. cover elements of apparatus and equipment of all kinds.

Example 6% by weight of epoxylated soybean oil with an 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 having an acid number of 154. This mixture was homogenized with 50% by weight. of a butanolic solution of imidazole and then crosslinked at 140 ° C for 10 minutes. The polymer material thus obtained is transparent, has a high water resistance and can be heat treated at a temperature of about 90 C. At a lower temperature, the material is characterized by high mechanical strengths.

Example 7

69.9% Euphorbia Lathyris aziridine-functional high-oil oil having a nitrogen content of 4.3% by weight was mixed with 28% by weight of phthalic anhydride, 1.5% by weight of sebacic acid and 0.6% by weight of an isopropanolic quinuclidine solution. The mixture was crosslinked at 145 ° C for 5 minutes to give a hard, flexible, and transparent polymeric material that is characterized by high water resistance and abrasion resistance.

Example 8 by weight of lemon. The

51.5% by weight of epoxylated Chinese wood oil with an oxygen content of 10.5% by weight was mixed with 45.5% by weight of camphoric anhydride and 2.5% by weight of an ethanolic acid solution of this mixture was added 0.5% by weight.

DABCO and the resulting mixture was homogenized. 30% by weight of this mixture was applied to 70% by weight of dried coconut fiber carpet in such a way that the fibers were homogeneously infiltrated by the reaction mixture. The infiltrated coconut fiber was then heated to 130 ° C for 20 minutes. The reaction mixture reacts to form a prepolymer having a viscosity of about 10,000 mPas. Subsequently, the fiber prepared above was filled into a mold and pressed at 160 ° C and 15 x 10 ⁵ Pa for one minute. The obtained fibrous product is characterized by high mechanical strength, is very resistant to water and characterized by high heat resistance. This material can be used in those areas where fibrous materials filled with plastics or plastics filled with fibrous materials are used.

Example 9

A blend consisting of 61.6% epoxylated rope oil with an oxygen content of 9.6% and 15.4% epoxylated sardine oil with an oxygen content of 10.5% was mixed with 19.2 parts by weight of pyromellitic dianhydride and 3% by weight. 8% trimerized fatty acid. 25% of this mixture was homogenized with 75% wood flour with an average particle size at 300 µm by weight.

The wetted powder was then processed into an endless molding by means of a RAM extruder at a temperature of 160 ° C and a pressure of 4 x 10 ⁶ Pa. The products thus obtained are characterized by high mechanical stability and excellent water resistance.

Example 10

53.2% by weight of an epoxylated safflower oil with an oxygen content of 9% by weight was mixed with 10% by weight of aconitic anhydride, 32.5% by weight of methylnorbornene dicarboxylic anhydride and 2.6% by weight of dimerized anacardic acid. To this mixture was added a 1.7 wt% propanolic solution of DABCO, and the resulting mixture was then homogenized. 10% by weight of this mixture was then mixed with 90% by weight of dried and ground rice chaff with a mean particle size of 0.5 mm to form a homogeneously wetted powder. The mixture was then pressed at 130 ° C and 15 x 10 ⁵ Pa for 15 minutes. The material obtained has a physical density of 0.9 g / cm ³ and can be processed without the formation of undesirable chips.

Example 11

50.5% by weight of epoxyated rope oil was 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% by weight of a 50% isobutanolic quinuclidine solution. 30% by weight of the thus obtained mixture was homogenized with 35% by weight of barite, 5% by weight of pigment, such as e.g. % rutile and 30% by weight of a mixture of muscovite, chlorite and silicon meal. The resulting mixture was then transferred to a mold where it was crosslinked for 8 minutes at 30 x 10 ⁵ Pa at 140 ° C. The result is a hard and elastic, duroplastic molding that exhibits high water and boiling water resistance as well as high mechanical strength. The material can be used e.g. for the manufacture of coverings for apparatus and equipment of a wide variety.

Industrial usability

The polymer material prepared according to the invention offers a wide range of applications in a variety of industries, such as e.g. construction, engineering, or furniture industry.

9 ...... 7TL ^ / ~

Percent change in weight (%)

Time (min)

Water-resistant polymer material of triglycerides and polycarboxylic acid anhydrides based on linseed oil and THPSA according to DIN 53 476 fig. 1? Er

Percent change in weight (%)

Resistance to boiling water of polymer material of polycarboxylic acid triglycerides and anhydrides based on linseed oil and THPSA according to DIN 53 471 fig. 2

Claims (15)

PATENT CLAIMS Renewable raw material polymeric material comprising a reaction product obtained by crosslinking 10 to 90% by weight of triglycerides with at least two epoxy and / or aziridine groups and 5 to 90% by weight of polycarboxylic anhydride prepared from cyclic polycarboxylic acid with at least two free carboxyl groups, with 0.01 to 20% by weight of polycarboxylic acid initiator. Polymeric material according to claim 1, characterized in that epoxylated soybean oil, linseed oil, perilla oil, Chinese wood oil, oitic oil, safflower oil, poppy oil, hemp oil, cottonseed oil, sunflower oil, rapeseed oil are selected oil, triglycerides derived from Euphorbia plants, e.g. from iagas oil and high-oil triglycerides such as e.g. high-oil sunflower oil or Iathyris oil from Euphorbia, peanut oil, olive oil, olive kernel oil, almond oil, kapok oil, hazelnut oil, apricot oil, lupine oil, lupine oil, corn oil, sesame oil, grape seed oil, lalemanti oil, castor oil, marine animal oils such as e.g. herring oil, sardine oil, menhaden oil, whey oil and triglycerides with a high content of saturated fatty acids, which are subsequently converted e.g. by dehydrogenation to the unsaturated form, or mixtures thereof. Polymeric material according to claim 1 or 2, characterized in that the epoxylated triglycerides additionally contain hydroxylated triglycerides as castor oil. Polymeric material according to at least one of Claims 1 to 3, characterized in that the anhydrides AMENDED SHEET 'of polycarboxylic acids are selected from the group consisting of cyclohexanedicarboxylic anhydride, cyclohexene dicarboxylic anhydride, phthalic anhydride, trimellitecarboxylic anhydride, hemimellitecarboxylic anhydride, pyromellitecarboxylic anhydride, 2,3-naphthalenedicarboxylic, 1,2-cyclopentanedicarboxylic acid, acid acid anhydride anhydride anhydride 1.2-cyclobutanedicarboxylic acid, quinolinic anhydride, norbornane dicarboxylic anhydride (NADICAN) as well as methyl-substituted MNA compounds, pinenic anhydride, norpinenic anhydride, truxilic anhydride, perylene anhydride 1,2-dicarboxylic acid, carboxylic acid anhydride, narcamphane dicarboxylic acid anhydride, isic acid anhydride, camphoric anhydride, 1,8-naphthalenedicarboxylic acid anhydride, diphenylcarboxylic acid anhydride, o-carboxyphenylacetic anhydride, 1,4,5,8-naphthalenetetric anhydride, 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 the polycarboxylic acid. 6. The polymeric material of claim 5, wherein the polycarboxylic acids are selected from the group consisting of citric acid derivatives, polymerized tall oils, azelaic acid, gallic acid, di- or polymerized bitumen acids, di- or polymerized anacardic acid. keshu nut shell, polyuric acid, polyalginic acid, mellitic acid, trimesic acid, aromatic dia polycarboxylic acids such as e.g. phthalic acid, trimellitic acid, hemimellitic acid, pyromellitic acid and aromatic substituted derivatives thereof such as e.g. Hydroxy- or alkylphthalic acid, unsaturated cyclic di- and polycarboxylic acids, e.g. norpinic acid, heterocyclic di- and polycarboxylic acids, such as e.g. loiponic acid, or cincholoiponic acid, bicyclic di- and polycarboxylic acids, such as e.g. norbannanedicarboxylic acids, di- and polycarboxylic acids with open chain, such as e.g. malonic acid and its longer chain homologs as well as substituted compounds thereof, e.g. hydroxy- and keto-dicarboxylic and polycarboxylic acids, pectic acids, humic acids, a keshu nut shell liquid polymer with at least two free carboxyl groups per molecule, or mixtures thereof. Polymeric material according to at least one of Claims 1 to 7 6, characterized in that it contains 2 to 98% by weight of the reaction product according to claim 1 and 98 to 2% by weight of a filler. Polymeric material according to at least one of Claims 1 to 8 7, characterized in that the filler is selected from the group comprising organic fillers based on cellulose-containing materials, such as wood flour, sawdust or wood waste, chips, straw and rope fibers based on proteins, in particular sheep wool and further inorganic fillers silicate and carbonate bases such as sand, quartz, corundum, silicon carbide and glass fibers, or mixtures thereof. Polymeric material according to at least one of Claims 1 to 9 8, characterized in that 0.01 to 10% by weight of catalyst is added in the preparation of the reaction product. 10. The polymer material of claim 9, wherein the catalyst is selected from the group consisting of tertiary amines, such as e.g. N, N-benzyldimethylaniline, imidazole and its derivatives, alcohols, hydroxycarboxylic acids such as lactic or salicylic acid, thioacids, AMENDMENT SHEET as well as organophosphorus compounds, especially triphenylphosphite, trisnonylphenyl phosphite and bis-beta-chloroethyl phosphite, bicyclic amines such as [2,2,2] diazabicyclooctane, quinuclidine or diazabicycloundecene, or mixtures thereof. The polymeric material according to at least one of claims 1 to 10, further comprising a flame retardant selected from the group consisting of aluminum hydroxide, halogenated compounds, antimony, bismuth, boron or phosphorus compounds, and silicate compounds or mixtures thereof. Process for the production of polymeric material according to at least one of Claims 1 to 11, characterized in that the triglyceride, polycarboxylic anhydride, polycarboxylic acid and optionally other additives such as fillers and / or catalyst and / or flame retardant are mixed and subsequently carried out. curing. Process for the production of polymeric material according to at least one of Claims 1 to 12, characterized in that the triglyceride, polycarboxylic anhydride, polycarboxylic acid and optionally the catalyst are pre-crosslinked to a viscosity of 0.2 to 20,000 CPS at a temperature of 20 ° C to 200 C, the filler and / or the flame retardant is then added, followed by curing. Production method according to claims 12 and 13, characterized in that the curing is carried out at a temperature in the region of 20 ° C to 200 ° C and at a pressure in the range of 1 x 10 ⁵ Pa to 1 X 10 ⁷ Pa for a period of time from 10 seconds to 24 hours. Use of claims 1 to systems like or metal, polymeric material according to at least one of 11, in prefabricated spatial element replacement of material for plastic frames, as cladding material and lacquered "CHANGED SHEETS" as profile material, as sealing material , for coating and moldings highly abrasion-resistant, as crack-bridging protection elements, for non-slip coatings, for electrically-insulating or electrically-conductive materials, for tribologically usable films, for underwater coating of ships, fluid sintering systems for demanding equipment parts and moldings, for mold elements such as infiltrated fibers and fiber mats, particle board, MDF- and hard fiber boards as substitutes in the building and furniture industries, endless profiles.