AU713023B2 - Polymeric material, method for its manufacture, and its utilisation - Google Patents
Polymeric material, method for its manufacture, and its utilisation Download PDFInfo
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- AU713023B2 AU713023B2 AU63530/96A AU6353096A AU713023B2 AU 713023 B2 AU713023 B2 AU 713023B2 AU 63530/96 A AU63530/96 A AU 63530/96A AU 6353096 A AU6353096 A AU 6353096A AU 713023 B2 AU713023 B2 AU 713023B2
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/10—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B26/18—Polyesters; Polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/34—Epoxy compounds containing three or more epoxy groups obtained by epoxidation of an unsaturated polymer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/027—Polycondensates containing more than one epoxy group per molecule obtained by epoxidation of unsaturated precursor, e.g. polymer or monomer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/08—Epoxidised polymerised polyenes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2200/04—Non-macromolecular organic compounds
- C09K2200/0441—Carboxylic acids, salts, anhydrides or esters thereof
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2200/04—Non-macromolecular organic compounds
- C09K2200/0447—Fats, fatty oils, higher fatty acids or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
- C09K2200/0645—Macromolecular organic compounds, e.g. prepolymers obtained otherwise than by reactions involving carbon-to-carbon unsaturated bonds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Polyesters Or Polycarbonates (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Graft Or Block Polymers (AREA)
- Paints Or Removers (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
Abstract
Polymer (P) based on renewable materials contains a reaction prod. (R) comprising: (A) 10 - 90 mass % triglyceride contg. at least 2 epoxy and/or aziridine gps.; (B) 5 - 90 mass % polycarboxylic acid anhydride; and (C) 0.01 - 20 mass % polycarboxylic acid. The prepn. of (P) by mixing (A) - (C) and opt. additives (e.g. filler, catalyst and flame-retardant) and then curing, is also claimed.
Description
PREFORM
'WERKSTOFF II' (TO) Polymeric Material, Method for its Manufacture, and its Utilisation The invention relates to a polymeric material on the basis of renewable raw materials, to a method of manufacturing this material, and to its utilisation.
Organic plastics, which are today used on a large scale in industry, are obtained almost exclusively on a petrochemical basis. For example, in the furniture and building industries, wood materials are used, which are bonded with UF (urea formaldehyde), MUF, PF or more rarely PUR. Cladding panels, endpieces, cable ducts etc.
mostly consist of polyvinyl chloride (PVC). In the area of windows, plastics windows are also used today in large numbers with frames made of PVC. PVC as a material for numbers with frames made of PVC. PVC as a material for such components however has serious disadvantages. On the one hand the recycling problem has not yet been satisfactorily solved, and on the other hand PVC develops dangerous gases when burning. Covering members for machines and apparatus, high-quality pressed mouldings, frequently consist of PF, MF, EP or UP-reinforced fibre materials or mats, which are for example used in the automobile industry. In the course of the growing C02 discussion and a possible global climatic change entailed therewith, there is today an urgent requirement for novel, extensively C0 2 -neutral plastics which satisfy the requirements set for plastics on a petrochemical basis used at present, and which could partly replace these.
More appropriately such polymeric materials are obtained from educts on the basis of renewable materials.
There have already become known in prior art binders or binder combinations which also partly contain renewable raw materials. These developments refer in particular to the field of polyurethane. Thus it is known from US-PS 458 2891 to convert castor oil, i.e. a renewable material, with polyisocyanate and an inorganic filler.
From EP 01 51 585 there is known a two-component polyurethane adhesive system, in which there are used as an oleochemical polyol ring-scission products of epoxidised fatty alcohols, fatty acid esters (particularly triglycerides) or fatty acid amides with alcohol. It is further known to use epoxidised triglycerides as softeners. Such a method is described for example in PCT/EP94/02284.
From US 35 78 633 there is known a method of hardening polyepoxides with polycarboxylic acid anhydride, using special alkali salts of selected carboxylic acids.
According to this, polyepoxides with more than one vicinal epoxy group per molecule are used exclusively.
The polymers obtained according to this document however have the drawback that on the one hand they originate from physiologically harmful initial substances (e.g.
lithium salts), and on the other hand that the polymers obtained do not have the necessary strength. This is clearly ascribed to the fact that according to the US Patent a basic reaction takes place which reinforces the cross-linking of external epoxy groups which however are in no way present in epoxidised triglycerides.
Polymeric products are known from DE 41 35 664 which are produced from epoxidised triglycerides and part esters of polycarboxylic acids with at least two free carboxylic acid groups and with water-repellent agents. According to DE 41 35 664 however resilient coating compounds are obtained with increased water resistance, which likewise do not have any satisfactory properties with respect -:o strength and the range of variation of polymeric sys:em.
Proceeding from this point it is therefore the objec: of the present invention to indicate a novel material whih is constructed on the basis of renewable raw materials, and which leads to polymeric materials which allow a wide range of applications due to their strength.
The object is achieved as regards the polymeric material by the characterising features of claim 1, and as regards the method by the characterising features of claims and 16. The sub-claims illustrate advantageous further developments.
Thus there is proposed according to the invention a polymeric material which substantially contains a reaction product from three components, i.e. 10 90% by mass of a triglyceride, 5 90% by mass of a polycarboxylic acid anhydride with 0.01 20% by mass of a polycarboxylic acid. The Applicant has been able to demonstrate that, surprisingly, polymeric materials, which contain a reaction product in the prescribed way, have surprising properties with regard to the strength N M and the range of variation of the properties of the material.
A decisive factor in the material according to the Application is that polycarboxylic acid anhydrides are used which function as cross-linkers, so that the crosslinking density of the polymer obtained is decisively increased. As a result of this, hard polymers are obtained.
The main ingredients of the reaction product are thus epoxidised triglycerides and polycarboxylic acid anhydrides, which are cross-linked with one another. The cross-linking reaction is started by the addition of small quantities of polycarboxylic acid (0/01 to 20% by mass). The polycarboxylic acid thus clearly has the advantageous function of an initiator for the internallypresent epoxy groups of the triglycerides.
Accordingly, by means of the use of polycarboxylic acid anhydrides, the adjacent OH groups originating from epoxy ring scission are cross-linked in the form of an additional reaction. The free carboxylic acid group resulting on the polycarboxylic acid anhydride thus clearly in turn opens another epoxy ring, an adjacent OH group likewise being obtained which reacts with an additional carboxylic acid anhydride group, with further addition. The reaction is then started when an epoxy ring has been opened and the adjacent OH group has originated.
This initiation of the cross-linking is effected by the addition of small quantities of polycarboxylic acid. Thus it is essential that an opening of the epoxy group is present as a reaction starter. A possible reaction procedure is shown diagrammatically in the following.
-6a- 0 R1- -C--R2 (Epoxyd.Trig.) H OH HOOC R3 Initiation i-Rl-C- R2 O H (Polycarboxylic/ acid) 0 5,C\R 0 (Polycarboxylic acid anhydride) R4 000 -COGH Ri,-C- '-R2 00C -R3 0 R-C--C-R2 (Epoxyd. Trigi.) R4
O
0OC-C0O-C- -R2 R -C R2 Ri O0C-R3 polycarboxylic anhxdrid R4 OC COOH OOC-COO0-C-C-R2 Rl -CRR doe R3 epoxidised triglyceride Repetition of reaction diagram In contrast to prior art with the cross-linking in pure polycarboxylic acids, the hydroxy groups formed reacunder polyaddition with the polycarboxylic acid anhydride. it was also possible to prove this by DSC and IR tests.
Thus an essential feature in the polymeric material according to the invention is that it contains a reac:ion product comprising 10-90% by mass of a trigelyceride and 5-90% by mass of a carboxylic acid anhydride, the reaction being initiated by small amounts of carboxylic acid (0.01-20% by mass). It is preferred in this resDect if the reaction product contains 35-70& by mass of a triglyceride and 10-60% by mass of a polycarboxylic acid anhydride, and 0.05-10% by mass of the polycarboxylic acid.
Examples of epoxidised triglycerides which can be used to produce the reaction product according to the invention are soya oil, linseed oil, perilla oil, tung oil, oiticica oil, safflower oil, poppy oil, hemp oil, cottonseed oil, sunflower oil, rape oil, triglycerides from euphorbia plants such for example as euphorbiaiagascae oil, and highly-oleic triglycerides such for example as highly-oleic sunflower oil or euphorbia N M iathyris oil, groundnut oil, olive oil, olive seed oil, almond oil, kapok oil, hazelnut oil, apricot seed oil, beechnut oil, lupin oil, maize oil, sesame oil, grapeseed oil, lallemantia oil, castor oil, oils of sea creatures such as herring oil and sardine oil or menhaden oil, whale oil and triglycerides with a high proportion of saturated fatty acids which are subsequently converted to an unsaturated condition by dehydration, or mixtures thereof. Due to the reaction with the hydroxy groups it is possible, in addition to epoxidised triglycerides, also partly to use hydroxylised triglycerides as further ingredients. Such hydroxylised triglycerides are for example hydroxylised highly-oleic or castor oil. In this way the physical properties of the polymers can be altered to a large extent. An essential feature however is that epoxidised triglycerides are always present, as otherwise chain termination will occur. It is also possible to use triglycerides with azaridine groups.
Various synthesising methods are known for producing aziridines. One method of production is cycloaddition, e.g. of carbenes to azomethines (Breitmaier G. Jung, Org. Chemie vol. 1, E. Thieme Verlag, Stuttgart), or of nitrenes to olefines. A synthesis by reduction of achloronitriles or oximes with LiA1H 4 is likewise possible (Bull. Chem. Soc. Jpn. 40, 432 (1967) and Tetrahedro 24, 3681 (1968)).
With polycarboxylic acid anhydrides, those which have a cyclic basic framework, i.e. polycarboxylic acid anhydrides produced from cyclic polycarboxylic acids with at least two free carboxylic acid groups, are preferred.
Examples of this are cyclohexane dicarboxylic acid anhydride, cyclohexene dicarboxylic acid anhydride, phthalic acid anhydride, trimellitic acid anhydride, hemimellitic acid anhydride, pyromellitic acid anhydride, 2,3-naphthalic acid anhydride, 1,2 cyclopentane dicarboxylic acid anhydride, 1,2 cyclobutane dicarboxylic acid anhydride, quinolinic acid anhydride, norbornene dicarboxylic acid anhydride (NADICAN), and the methylsubstituted compounds MNA, pinic acid anhydride, norpinic acid anhydride, truxillic acid anhydride, perylene 1,2dicarboxylic acid anhydride, caronic acid anhydride, narcamphane dicarboxylic acid anhydride, isatoic acid anhydride, camphoric acid anhydride, 1,8-naphthalic acid anhydride, diphenic acid anhydride, ocarboxyphenylbenzoic acid anhydride, 1,4,5,8-naphthalic intera carboxylic acid anhydride or mixtures thereof.
Also usable are polycarboxylic acid anhydrides from openchained di- and polycarboxylic acids with at least two free carboxylic acid groups, such for example as aconitic acid anhydride, citraconic acid anhydride, glutaric acid anhydride, itaconic acid anhydride, tartaric acid anhydride, diglycolic acid anhydride, ethylenediamineinterabenzoic acid anhydride or mixtures thereof.
In the case of the initiators used according to mhe invention, i.e. in the case of the polycarboxylic acids, the di- and tri-carboxylic acids are preferred. Examples of this are citric acid derivates, polymerised tall oils, azelaic acid, gallic acid, di- or polymerised oleoresin acids, di- or polymerised anacardic acid, also cashew nut shell liquid, polyuronic acids, polyalginic acids, mellitic acids, trimesic acids, aromatic di- and polycarboxylic acids such for example as phthalic acid, trimellitic acid, hemimellitic acid, pyromellitic acid and their aromatically substituted derivates such for example as hydroxy or alkyl phthalic acid, unsaturated cyclic di- and polycarboxylic acids such for example as norpinic acid, heterocyclic di- and polycarboxylic acids such for example as loiponic acid or cincholoiponic acid, bi-cyclic di- and polycarboxylic acids such for example as norbornene dicarboxylic acids, open-chained di- and polycarboxylic acids such for example as malonic acid and its longer-chained homologues and its substituted compounds such for example as hydroxy- and keto- di- and polycarboxylic acids, pectinic acids, humic acids, polymeric cashew nut shell liquid with at least two free carboxylic acid groups in the molecule, or mixtures thereof.
A further preferred embodiment of the invention proposes that the polymeric material contains a reaction product produced from the initial ingredients described above, yet with an added catalyst. In this case the catalyst can be added in a quantitative ratio of 0.01 10% by mass, preferably of 0.05-5% by mass. There could basically serve as a catalyst all compounds serving to accelerate cross-linkings of epoxy resins. Examples of this are tertiary amines such as N, N'benzyldimenthyl aniline, imidazol and its derivates, alcohols, phenols and their -substituted compounds, hydroxycarboxylic acids such as lactic acid or solicylic acid, organometallic compounds such as triethanolamine titanate, di-n-butyl tin laurate, Lewis acids, particularly boron trifluoride, aluminium trichloride and its aminic complex compounds, Lewis bases, particularly alcoholates, multifunctional mercapto compounds and thio acids and organophosphorus compounds, particularly triphenylphosphite, and bis-Bchloroethylphosphite, bi-cyclic amines such as diazabicyclooctane, chinuclidine or diazabicycloundecene, alkali and alkaline earth hydroxides, Grignard compounds or mixtures thereof.
It should be particularly emphasised that the polymeric material according to the invention can consist exclusively of the reaction product as described above or, depending on the scale of requirements, can also additionally contain a filler or flame-retardant means.
When the polymeric material contains only a reaction product and a filler, it is preferred that it should contain 2-98% by mass of the reaction product and 98-2% by mass of the filler. It is particular preferred if the polymeric material contains 6-90% by mass of the reaction product and 10-94% by mass of the filler.
Particularly preferred examples of fillers are organic fillers on the basis of cellulose-containing materials such as wood flour, sawdust or timber waste, rice husks, straw and flax fibres on the basis of proteins, particularly sheep wool and inorganic fillers on the basis of silicates and carbonates such as sand, quartz, corundum, silicon carbide and glass fibres, or mixtures thereof. The polymeric material according to the invention can also contain up to 50% by mass of a flameretardant agent. Preferred flame retardants are: aluminium hydroxide, halogen, antimony, bismuth, boron or phosphorus compounds, silicate compounds or mixtures thereof.
In producing the material according to the preferred embodiment with the filler, the procedure can be such that on the one hand firstly a mixture of the initial ingredients, i.e. the triglyceride of the polycarbcxylic acid anhydride and of the carboxylic acid is produced, and then that this mixture is pre-polymerised to a viscosity of 0.2 20,000 CPS at 20°C 200°C, the filler then being added. In connection therewith if necessary, also after shaping, if necessary under pressure, hardening can be effected. It is however also possible to mix all the additive materials and then carry out prepolymerisation.
On the other hand, the procedure can be such that all the ingredients, i.e. the triglycerides, the polycarboxylic acid anhydrides and the carboxylic acids as well if necessary as the further additive materials, such as filler and flame-retardants, are mixed, and that hardening is then subsequently carried out at an increased temperature, and increased temperature and increased pressure.
Hardening can be carried out in ranges from >20 0 C to 200'C at a pressure of 1 bar to 100 bar. Duration of hardening depends on the temperature, the pressure and f necessary the added catalyst. Hardening time can lie in a range from 10 seconds to 24 hours. A temperature range of 150°C is preferred.
The polymeric material according to the invention can also be infiltrated into fleeces or mats. In this way fibre-reinforced materials can be produced.
With the method according to the invention the mixture obtained can be placed individually into moulds and pressed, or endless production can be carried out.
Endless production can also be carried out by extrusion or hot-rolling.
After hardening the reaction mixture forms an enclosed and extremely smooth surface; the plastic definition, i.e. the size of geometric shapes, is extremely large.
The finest filigreed patterns can be extremely precisely reproduced by the material.
The material according to the invention is particularly characterised by the fact that it is toxologically harmless, and thus does not have the disadvantages of PVC and/or other comparable materials such, for example, as those on a polyurethane base. It should be mentioned that the novel material can have similar mechanical properties to PVC, EP or PES. These variant materials are rigidly elastic and of high strength. Highly-filled cellulosecontaining polymeric materials according to the invention, obtained by pressing or extrusion, have high mechanical strengths. In the case of mechanical spotloading such for example as occurs when fastening wood screws or driving in wood nails, the structure of the surrounding material is retained, splintering such as is observed for example with wood, is not observed. The material can be mechanically processed without problems.
When sawn or milled, no splintering of the lateral surfaces, or even breakage of smaller particles, is observed.
By means of added proportions of hydroxylised triglycerides, mouldings can be obtained which at ambient temperature have a partly-plastic behaviour and at the same time excellent tear strength. Depending on the degree of cross-linking, which is in theory influenced by the composition of the initial ingredients, mouldings can be obtained which permit heat-shaping of the polymeric material members. In particular, when aluminium hydroxide is incorporated, an appreciable improvement in fire resistance is noted during flame tests. The incorporation of aluminium hydroxide and the emission of water entailed prevent the direct attack of flames. Thus fire resistance class BS according to DIN 4102 is fulfilled.
In numerous tests it has also become apparent that the material according to the invention has a notable waterabsorbency; for this purpose cellulose-containing highlyfilled blanks were submerged in water for a lengthy period. After 80 hours no appreciable quantity of water had been absorbed by the material. No physical or chemical changes could be observed in the material.
The invention will be explained in more detail by the following examples: Example 1 53.5% by mass of epoxidised linseed oil with an acid content of 9% by mass are mixed with 42.8% by mass of camphoric acid anhydride and 2.7% by mass of a mixture of di- and trimeric abietic acid. This mixture is homogenised with 1% by mass of a 50% ethanolic chinuclidine solution. 10% by mass of this mixture is mixed with 90% by mass of straw and pressed for minutes at a pressure of 15 bar and at a temperature of 1800°C. The fibreboard obtained has a physical density of 0.62 [g/cm 3 is characterised by high-quality mechanical properties and has outstanding water resistance. It can be used in the building and furniture industries as a fibreboard material.
Example 2 80% by mass of epoxidised perilla oil with an acid content of 8% by mass are mixed with 16 parts by mass of pyromellitic acid anhydride and 4% by mass of a trimerised fatty acid. 30% by mass of this mixture is applied to 70% by mass of a jute-hemp fibre fleece in such a way that the fibre fleece is homogeneously wetted.
The infiltrated fibre mat is then pressed at a pressure of 10 bar and a temperature of 170°C for 10 minutes. The fibre product obtained has high elasticity, resistance to breakage and water-resistance. It may be used in many areas in which plastic-reinforced fibres or fibrereinforces plastics are used, such for example as fibrereinforced shell or mould members of covering members.
Example 3 42.9% by mass of epoxidised soya oil with an acid content of 6.5% by mass are mixed with 21.5% by mass of a hydroxylised highly-oleic oil. To this mixture there is added 34.3% by mass of a norbornene dicarboxylic acid anhydride and 1.3% by mass of a 50% methanolic DABCO solution. The mixture is homogenised and then crosslinked at a temperature of 140°C within 15 minutes. The product obtained is transparent, plastically deformable and has a high tear strength. This product can be suitable for coating materials and components which must be plastically deformable, such for example as electrical cables.
Example 4 72.7% by mass of epoxidised hemp oil with an acid content of 10.5% by mass are mixed with 27.3% by mass of trimellitic acid anhydride. 8% by mass of this mixture are mixed with 92% by mass of dried grain husks and pressed at a pressure of 15 bar and a temperature of 170°C for 8 minutes. The fibreboard obtained has a physical density of 0.88 [g/cm 3 is characterised by high water-resistance and excellent mechanical strength, and can be used as a fibreboard in the building and furniture industries.
Example 54.7% by mass of epoxidised linseed oil with an acid content of 9.6% by mass are mixed with 43.7% by mass of tetrahydrophthalic acid anhydride and 1.1% by mass of adipic acid. This mixture is homogenised with 0.5% by mass of DBN and cross-linked at 145 0 C within 5 minutes to form a hard, transparent moulding. The material obtained is resistant to water and boiling water (see Figs. 1 and 2) and has high mechanical strengths. The material can be heated up to 300 0 C without decomposition. It can be suitable for example as a covering member for apparatus and machinery of the most varied types.
Example 6 by mass of epoxidised soya oil with an acid content of 6.5% by mass are mixed with 36% by mass of 1,2 cyclohexane dicarboxylic acid anhydride and 1.1% by mass of dimerised pine resin with an acid number of 154. The mixture is homogenised with a 50% butanolic imidazol solution and cross-linked within 10 minutes at 140°C. The polymeric material obtained is transparent, is characterised by high water resistance and can be hotshaped at a temperature of approx. 90°C. Below this temperature it has high mechanical strengths.
Example 7 69.9% by mass of a highly-oleic oil from euphorbia lathyris with a nitrogen content of 4.3% by mass are mixed with 28% by mass phthalic acid anhydride, 1.5% by mass of sebacid acid and 0.6% by mass of an isopropanolic chinuclidine solution. The mixture is cross-linked at 145 0 C in a period of 5 minutes to form a hard elastic, transparent polymeric material which has a high water resistance and wear resistance.
Example 8 51.5% by mass of epoxidised tung oil with an acid content of 10.5% by mass are mixed with 45.5% by mass of camphoric acid anhydride and 2.5% by mass of a ethanolic citric acid solution. 0.5% by mass of DABCO are added to this mixture, and the mixture is homogenised.
30% by mass of this mixture is applied to 70% by mass of a dry coco fibre fleece, so that the fibres are homogeneously infiltrated by the reactive mixture. The infiltrated coco fibre is than preheated at 130°C for minutes. The reactive mixture in this case reacts to form a prepolymer with a viscosity of approx. 10,000 [mPas].
The pre-treated fleece is then placed in a mould and pressed at 15 bar for 1 minute at a temperature of 160°C.
The fibre product obtained has high mechanical strength, is extremely water resistant and temperature resistant.
It can be used in areas in which plastics-reinforced fibre fleece materials or fibre-reinforced plastics are used.
Example 9 A mixture of 61.6% by mass of epoxidised linseed oil with an acid content of 9.6% by mass, and 15.4 by mass of epoxidised sardine oil with an acid content of 10.5% by mass are mixed with 19.2 parts by mass of pyromellitic acid dianhydride and 3.8% by mass of trimerised fatty acid. 25% by mass of this mixture are homogenised with by mass of wood flour with an average fibre length of 300 pm. The wetted powder is then processed with the aid of a RAM extruder at 160 0 C and a pressure of 40 bar, forming endless mouldings. The products obtained have high mechanical stability and are characterised by outstanding water resistance.
Example 53.2% by mass of epoxidised safflower oil with an acid content of 9% by mass are mixed with 10% by mass of aconitic acid anhydride, 32,5% by mass of methyl norbornene dicarboxylic acid anhydride and 2.6% by mass of dimerised anacardic acid. To this mixture there are added 1.7% by mass of a propanolic DABCO solution, and the mixture is then homogenised. 10% by mass of this mixture are mixed with 90% by mass of dried and ground rice husks with an average grain size of 0.5 mm, until a homogeneously wetted powder is obtained. This mixture is then pressed at a temperature of 130 0 C for 15 minutes at a pressure of 15 bar. The material obtained has a physical density of 0.9 [g/m 3 and can be processed by chip-removal. This material is suitable in all cases where middle-density fibreboards (MDF) are used.
Example 11 50.5% by mass of epoxidised linseed oil are mixed with 2.5% by mass of trimerised abietic acid. This mixture is homogenised with 1.8% by mass of a 50% isobutanolic chinuclidine solution. 30% by mass of this mixture is homogenised with 35% by mass of barytes, 5% by mass of a pigment such for example as rutile and 30% by mass of a conglomerate of muscovite, chlorite and quartz powders.
The mixture is then cross-linked in a mould at a pressure of 30 bar and a temperature of 140°C within 8 minutes to form hard elastic duroplastic mouldings which have a high resistance to water and boiling water, and high mechanical strengths. The material can for example be used as a cover member for apparatus and machinery of he most varied types.
Claims (14)
1. Polymeric material on the basis of renewable raw materials, containing a reaction product produced by cross-linking from 10-90% by mass of a triglyceride with at least 2 epoxy and/or aziridine groups and 5-90% by mass of a polycarboxylic acid anhydride, manufactured from cycl;ic polycarboxylic acids with at least 2 free carboxylic acid groups, with 0.01-20% by mass of a polycarboxylic acid as an initiator.
2. Polymeric material according to claim 1, characterised in that the epoxidised triglycerides are selected from soya oil, linseed oil, perilla oil, tung oil, oiticica oil, safflower oil, poppy oil, hemp oil, cottonseed oil, sunflower oil, rape oil, triglycerides from euphorbia plants such for example as euphorbia- iagascae oil, and highly-oleic triglycerides such for example as highly-oleic sunflower oil or euphorbia iathyris oil, groundnut oil, olive oil, olive seed oil, almond oil, kapok oil, hazelnut oil, apricot seed oil, beechnut oil, lupin oil, maize oil, sesame oil, grapeseed oil, lallemantia oil, castor oil, oils of sea creatures such as herring oil and sardine oil or menhaden oil, whale oil and triglycerides with a high proportion of saturated fatty acids which are subsequently converted to an unsaturated condition by dehydration, or mixtures thereof. 4
3. Polymeric material according to claim 1 or 2, characterised in that the epoxidised triglycerides additionally contain hydroxylised triglycerides such as castor oil.
4. Polymeric material according to at least one of claims 1 to 3, characterised in that the polycarboxylic acid anhydrides are selected from cyclohexane dicarboxylic acid anhydride, cyclohexene dicarboxylic acid anhydride, phthalic acid anhydride, trimellitic acid anhydride, hemimellitic acid anhydride, pyromellitic acid anhydride, 2,3-naphthalic acid anhydride, 1,2 cyclopentane dicarboxylic acid anhydride, 1,2 cyclobutane dicarboxylic acid anhydride, quinolinic acid anhydride, norbornene dicarboxylic acid anhydride (NADICAN), and the methyl-substituted compounds MNA, pinic acid anhydride, norpinic acid anhydride, truxillic acid anhydride, perylene 1,2- dicarboxylic acid anhydride, caronic acid anhydride, narcamphane dicarboxylic acid anhydride, isatoic acid anhydride, camphoric acid anhydride, 1,8-naphthalic acid anhydride, diphenic acid anhydride, o- carboxyphenylbenzoic acid anhydride, 1,4,5,8-naphthalic intera carboxylic acid anhydride or mixtures thereof.
Polymeric material according to at least one of claims 1 to 4, characterised in that a di- or tricarboxylic acid is used as a polycarboxylic acid.
6. Polymeric material according to claim characterised in that the polycarboxylic acid is selected from citric acid derivates, polymerised tall oils, azelaic acid, gallic acid, di- or polymerised oleoresin acids, di- or polymerised anacardic acid, also cashew nut shell liquid, polyuronic acids, polyalginic acids, mellitic acids, trimesic acids, aromatic di- and polycarboxylic acids such for example as phthalic acid, trimellitic acid, hemimellitic acid, pyromellitic acid and their aromatically substituted derivates such for example as hydroxy or alkyl phthalic acid, unsaturated cyclic di- and polycarboxylic acids such for example as norpinic acid, heterocyclic di- and polycarboxylic acids such for example as loiponic acid or cincholoiponic acid, bi-cyclic di- and polycarboxylic acids such for example as norbornene dicarboxylic acids, open-chained di- and polycarboxylic acids such for example as malonic acid and its longer- chained homoiogues and its substituted compounds such for example as hydroxy- and keto- di- and polycarboxylic acids, pectinic acids, humic acids, polymeric cashew nut shell liquid with at least two 1 1 free carboxylic acid groups in the molecule, or mixtures thereof.
7. Polymeric material according to at least one of claims 1 to 6, characterised in that it contains 2-98% by mass of a reaction product according to claim 1 and 98-2% by mass of a filler.
8. Polymeric material according to at least one of claims 1 to 7, characterised 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 timber waste, rice husks, straw and flax fibres on the basis of proteins, particularly sheep wool and inorganic fillers on the basis of silicates and carbonates such as sand, quartz, corundum, silicon carbide and glass fibres, or mixtures thereof.
9. Polymeric material according to at least one of claims 1 to 8, characterised in that during production of the reaction product, 0.01-10% by mass of a catalyst are added.
Polymeric material according to claim 9, 62 0 characterised in that the catalyst is selected from tertiary amines such as N, N'benzyldimenthyl aniline, imidazol and its derivates, alcohols, hydroxycarboxylic acids such as lactic acid or salicylic acid, and thio acids and organophosphorus compounds, particularly triphenylphosphite, trisnonylphenylphosphite, and bis-8- chloroethylphosphite, bi-cyclic amines such as diazabicyclooctane, chinuclidine or diazabicycloundecenes, or mixtures thereof.
11. Polymeric material according to at least one of claims 1 to characterised in that it contains in addition a flame- retardant selected from the group aluminium hydroxide, halogen, antimony, bismuth, boron or phosphorus compounds, silicate compounds or mixtures thereof.
12. Method of producing the polymeric material according to at least one of claims 1 to 11, characterised in that the triglyceride, the polycarboxylic acid anhydride, the polycarboxylic acid and if necessary the further additives such as fillers and/or catalyst and/or flame retardants are mixed, and in that hardening is then carried out. I L I I?
13. Method of producing the polymeric material according to at least one of claims 1 to 12, characterised in that the triglyceride, the polycarboxylic acid anhydride, the polycarboxylic acid and if necessary the catalyst are previously cross- linked to a viscosity of 0.2-20,000 CPS at 200C -200°C, in that then the filler and/or the flame retardant are added, and in that hardening is then carried out.
14. Method according to claims 12 and 13, characterised in that hardening is carried out at a temperature in the range of 200C to 2000C and at a pressure of 1 bar to 100 bar for a period in the range of 10 seconds to 24 hours. Utilisation of the polymeric material according to at least one of claims 1 to 11, in prefabricated room-dividing systems, as a substitute material for plastics and metal frames, as a material for paint strips and covering members, as a profiled material, as a sealing material, highly abrasion- resistant coatings and mouldings, as a crack-covering protective skin, non-slip coverings, electrically insulating or conductive compounds, tribologically usable films, paints for the underwater hulls of ships, fluidised-bed sintering systems for apparatus and mouldings subject to stress, moulded members as infiltrated fibres and fibre mats, chipboards, substitutes for MDF and hard-fibre panels in the building and furniture industries, endless profiles.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19524514 | 1995-07-05 | ||
DE19524514 | 1995-07-05 | ||
PCT/DE1996/001243 WO1997002307A1 (en) | 1995-07-05 | 1996-07-05 | Polymer material, process for its production and use thereof |
Publications (2)
Publication Number | Publication Date |
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AU6353096A AU6353096A (en) | 1997-02-05 |
AU713023B2 true AU713023B2 (en) | 1999-11-18 |
Family
ID=7766089
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
AU63530/96A Ceased AU713023B2 (en) | 1995-07-05 | 1996-07-05 | Polymeric material, method for its manufacture, and its utilisation |
Country Status (24)
Country | Link |
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EP (1) | EP0836627B2 (en) |
JP (1) | JP2000501119A (en) |
KR (1) | KR19990028734A (en) |
CN (1) | CN1103791C (en) |
AT (1) | ATE207092T1 (en) |
AU (1) | AU713023B2 (en) |
BG (1) | BG63603B1 (en) |
BR (1) | BR9609342A (en) |
CA (1) | CA2224714A1 (en) |
CZ (1) | CZ417797A3 (en) |
DE (2) | DE19627165C2 (en) |
DK (1) | DK0836627T3 (en) |
EA (1) | EA000565B1 (en) |
ES (1) | ES2165508T5 (en) |
HU (1) | HUP9802994A3 (en) |
MX (1) | MX9800135A (en) |
NZ (1) | NZ312082A (en) |
PL (1) | PL324348A1 (en) |
PT (1) | PT836627E (en) |
SI (1) | SI9620102A (en) |
SK (1) | SK1598A3 (en) |
TR (1) | TR199701758T1 (en) |
UA (1) | UA49837C2 (en) |
WO (1) | WO1997002307A1 (en) |
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1996
- 1996-07-05 HU HU9802994A patent/HUP9802994A3/en unknown
- 1996-07-05 EA EA199800004A patent/EA000565B1/en not_active IP Right Cessation
- 1996-07-05 CZ CZ974177A patent/CZ417797A3/en unknown
- 1996-07-05 CA CA002224714A patent/CA2224714A1/en not_active Abandoned
- 1996-07-05 SK SK15-98A patent/SK1598A3/en unknown
- 1996-07-05 NZ NZ312082A patent/NZ312082A/en unknown
- 1996-07-05 AU AU63530/96A patent/AU713023B2/en not_active Ceased
- 1996-07-05 CN CN96196748A patent/CN1103791C/en not_active Expired - Fee Related
- 1996-07-05 AT AT96922761T patent/ATE207092T1/en not_active IP Right Cessation
- 1996-07-05 ES ES96922761T patent/ES2165508T5/en not_active Expired - Lifetime
- 1996-07-05 WO PCT/DE1996/001243 patent/WO1997002307A1/en not_active Application Discontinuation
- 1996-07-05 PT PT96922761T patent/PT836627E/en unknown
- 1996-07-05 BR BR9609342-0A patent/BR9609342A/en unknown
- 1996-07-05 KR KR1019980700032A patent/KR19990028734A/en not_active Application Discontinuation
- 1996-07-05 UA UA97126299A patent/UA49837C2/en unknown
- 1996-07-05 DE DE19627165A patent/DE19627165C2/en not_active Expired - Fee Related
- 1996-07-05 EP EP96922761A patent/EP0836627B2/en not_active Expired - Lifetime
- 1996-07-05 DE DE59607956T patent/DE59607956D1/en not_active Expired - Lifetime
- 1996-07-05 DK DK96922761T patent/DK0836627T3/en active
- 1996-07-05 JP JP9504723A patent/JP2000501119A/en active Pending
- 1996-07-05 PL PL96324348A patent/PL324348A1/en unknown
- 1996-07-05 TR TR97/01758T patent/TR199701758T1/en unknown
- 1996-07-05 SI SI9620102A patent/SI9620102A/en unknown
-
1997
- 1997-12-29 BG BG102153A patent/BG63603B1/en unknown
-
1998
- 1998-01-07 MX MX9800135A patent/MX9800135A/en not_active Application Discontinuation
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CH486755A (en) * | 1965-11-09 | 1970-02-28 | Liebknecht Transformat | Process for increasing the tracking resistance of surfaces of electrical insulating parts |
Also Published As
Publication number | Publication date |
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PL324348A1 (en) | 1998-05-25 |
BG102153A (en) | 1998-08-31 |
DK0836627T3 (en) | 2001-11-19 |
EP0836627A1 (en) | 1998-04-22 |
HUP9802994A3 (en) | 2000-04-28 |
NZ312082A (en) | 2000-04-28 |
EA199800004A1 (en) | 1998-08-27 |
EP0836627B2 (en) | 2005-06-01 |
CA2224714A1 (en) | 1997-01-23 |
TR199701758T1 (en) | 1998-03-21 |
SK1598A3 (en) | 1998-09-09 |
DE19627165C2 (en) | 1999-02-25 |
UA49837C2 (en) | 2002-10-15 |
CN1195357A (en) | 1998-10-07 |
CZ417797A3 (en) | 1998-05-13 |
EP0836627B1 (en) | 2001-10-17 |
PT836627E (en) | 2002-02-28 |
KR19990028734A (en) | 1999-04-15 |
SI9620102A (en) | 1998-10-31 |
JP2000501119A (en) | 2000-02-02 |
MX9800135A (en) | 1998-11-29 |
BG63603B1 (en) | 2002-06-28 |
CN1103791C (en) | 2003-03-26 |
BR9609342A (en) | 2002-04-30 |
WO1997002307A1 (en) | 1997-01-23 |
DE59607956D1 (en) | 2001-11-22 |
AU6353096A (en) | 1997-02-05 |
DE19627165A1 (en) | 1997-01-09 |
HUP9802994A2 (en) | 1999-04-28 |
ES2165508T5 (en) | 2005-12-01 |
ES2165508T3 (en) | 2002-03-16 |
ATE207092T1 (en) | 2001-11-15 |
EA000565B1 (en) | 1999-12-29 |
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