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    • 专利摘要:
    A molding mass based on a copolyamide containing terephthalic acid and trimethylhexamethylenediamine units, molding part, film, filament, and fiber composite material The present invention relates to a molding mass containing at least 30% by weight of a copolyamide derived from the following monomers: (a) by 50 to 95 mole% of the combination of a diamine selected from the group 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine and 1,12 dodecanediamine as well as terephthalic acid and b) in 5 to 50 mol% of a diamine combination selected from the group 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine and mixtures thereof as well As terephthalic acid, it is crystalline and has a low water absorption.
    公开号:BR112012000509B1
    申请号:R112012000509-0
    申请日:2010-07-08
    公开日:2019-07-16
    发明作者:Andreas Pawlik；Martin Roos；Franz-Erich Baumann；Harald Häger
    申请人:Evonik Degussa Gmbh；
    IPC主号:
    专利说明:

    Invention Patent Descriptive Report for MOLDING MASS BASED ON A COPOLYAMIDE CONTAINING TEREFTALLIC ACID AND TRIMETHYL-HEXAMETHYLENODYAMINE UNITS, MOLDED PIECE, FILM, FILAMENT, AND FIBER COMPOSITE MATERIAL.
    [001] The present invention relates to molds based on a copolyamide, which contains units, which are derived from terephthalic acid, a linear diamine with 9 to 12 carbon atoms, as well as trimethylhexamethylenediamine (TMD).
    [002] Known standardized polyamides, such as PA6 and PA66, can be easily processed and have high melting points and high dimensional stability under heat, particularly when they are reinforced with glass fibers or contain mineral fillers. However, they have typically high water absorptions of up to 10% when stored in water. For many applications with high demands on dimensional stability, even in wet or damp conditions, these aliphatic polyamides cannot be used. With water absorption, not only the dimensions change, but also the mechanical properties. Stiffness and stability are reduced several times. Thus, in applications with mechanical stress in contact with water or ambient humidity, the use of these standardized polyamides is problematic.
    [003] Partially aromatic polyamides of type PA6T / 6I, as described in US 4,607,073, have a reduced water absorption, compared to PA6 and PA66; the mechanical properties remain largely intact after water absorption. For precision parts, water absorption is still too high due to swelling; the melting points are also too high, and due to the use of isophthalic acid, crystallinity, as well as the speed of crystallization, strongly decrease. With
    Petition 870190017936, of 02/21/2019, p. 6/30
    2/19 this, processability is problematic.
    [004] PA10T, on the other hand, as it is also published in US 4,607,073, presents a strongly reduced water absorption; in water storage, the mechanical properties do not change in a way worth mentioning. The material has a high melting point with a melting point of the crystallite Tm of 316 o C; this is highly crystalline and crystallizes very quickly, so that in the injection molding the nozzles freeze. The surfaces of PA10T molded parts reinforced with glass fibers are severely disturbed.
    [005] In publications EP 0.659.799 A2, EP 0.976.774 A2, EP 1.186.634 A1 and EP 1.375.578 A1, partially aromatic polyamides of 60 to 100 mol%, of terephthalic acid and 60 to 100% in mol, of a diamine component of 1,9-nonanediamine and 2-methyl-1,8octanediamine. These products stand out for their good processability, excellent crystallinity, good dimensional stability under heat, low water absorption, good chemical resistance, dimensional stability and toughness. However, in Europe, 2-methyl-1,8octanediamine is currently not covered either in the new decree or in the existing substances decree and is therefore not authorized. This prevents a rapid introduction of the product on the European market.
    [006] The applicant sells with TROGAMID ® T5000, a polyamide formed from terephthalic acid and a mixture of 2,2,4-TMD and
    2,4,4-TMD. This stands out for its high mechanical stability and high toughness. However, the material, conditioned by the bulky diamine component, is amorphous and shows, therefore, only a conditioned resistance to chemicals, which is especially visible in relation to polar organic media in the formation of cracks due to tension. Due to the lack of crystalline parts, also the resistance
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    3/19 as the form in the heat is limited; maximum water absorption is relatively high at 7.5% by weight. In general, the exchange of linear aliphatic diamines for bulky monomers, such as TMD in polyamides, does in fact lead to increased glass transition points, but at the same time it dramatically decreases crystallinity.
    [007] US 4,495,328 describes partially crystalline polyamides of terephthalic acid and mixtures of hexamethylenediamine and TMD. As an example there is cited PA6T / TMDT (60/40 in mol%), which has a melting point of 310 o C. US 4,476,280 describes copolyamides of terephthalic acid, isophthalic acid and adipic acid in combination with hexamethylenediamine and TMD. Corresponding systems are also described in US 4,617,342. In all of these publications, no indications are given about dimensional stability in contact with water or about mechanics or stability to chemicals in a conditioned state.
    [008] EP 1,988,113 A1 describes a polyamide molding based on a 10T / 6T copolyamide, which is formed from the monomers 1,10-decanediamine, 1,6-hexanediamine and terephthalic acid. However, the high melting point of PA10T is only insufficiently reduced by coutilization of 1,6-hexanediamine.
    [009] The purpose of the invention is based on providing easily processable polyamide molds, which stand out by melting points in the range of approximately 250 o C to approximately 300 o C, even better, up to approximately 290 o C with crystallinity high enough combined with the smallest possible differences in mechanical properties, dimensional stability under heat and dimensional stability in the newly atomized state, as well as conditioned by humidity.
    [0010] This objective is solved by a molding dough, which contains at least 30% by weight, preferably at least 40%
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    4/19 by weight, particularly preferably at least 50% by weight and especially preferably at least 60% by weight of a copolyamide, which is derived from the following monomers:
    [0011] a) 50 to 95 mol%, preferably 55 to 90 mol% and particularly preferably 60 to 85 mol%, of the combination of a diamine, selected from the group 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine and 1,12-dodecanediamine, as well as terephthalic acid and [0012] b) by 5 to 50 mol%, preferably by 10 to 45 mol% and particularly preferred , in 15 to 40 mol%, of the combination of a diamine, selected from the group 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine and mixtures thereof, as well as terephthalic acid, in which the% in mol indicated, refer to the sum of components a) and b).
    [0013] In a preferred embodiment, the copolyamide does not contain any elements of composition, which are derived from other monomers. In other embodiments, the copolyamide contains a maximum of 30 mol%, a maximum of 25 mol%, a maximum 20 mol%, a maximum 15 mol%, a maximum 10 mol% or a maximum 5 mol% , of composition elements, which are derived from other monomers. Here, it should be considered that in this case, diamine and dicarboxylic acid, as well as any lactam or eventual aminocarboxylic acid are counted, in each case, individually in the composition calculation.
    [0014] In addition to the molding mass, 0 to 70% by weight, preferably 0 to 60% by weight, more preferably 0 to 50% by weight and most preferably 0 , 1 to 40% by weight of additives. Therefore, the molding paste can also consist of pure copolyamide.
    [0015] The elements of composition, which derive from other motions 870190017936, of 02/21/2019, p. 9/30
    5/19 numbers, fall into the following categories:
    [0016] - or they are derived from the combination of a diamine and a dicarboxylic acid. Here, the following cases can be distinguished: [0017] a) Dicarboxylic acid is terephthalic acid, diamine is different from 1,9-nonanediamine, 1,10-decanediamine, 1,11undecanediamine, 1,12-decanediamine, 2,2,4-TMD and 2,4,4-TMD according to the claims.
    [0018] b) Dicarboxylic acid is different from terephthalic acid; diamine is one of the diamine according to the claims already cited.
    [0019] c) Both dicarboxylic acid is different from terephthalic acid, and also diamine is different from diamines according to the claims already mentioned.
    [0020] - Either they are derived from a lactam or an aminocarboxylic acid.
    [0021] Other suitable diamines are, for example, diamines with 4 to 22 carbon atoms, such as 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,8-octanediamine, 1,14tetradecanediamine, 1, 18-octadecanediamine, 2-methyl-1,5-diaminopentane, 2,2-dimethyl-1,5-diaminopentane, 4,4'-diaminodicyclohexylmethane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 3,3 ', 5 , 5'-tetramethyl-4,4'-diaminodicyclohexylmethane, m- or pxylylenediamine or isophoronediamine.
    [0022] Other suitable dicarboxylic acids are, for example, dicarboxylic acids with 6 to 22 carbon atoms, for example, adipic acid, cortic acid, azelaic acid, sebacic acid, undecanoic diacid, dodecanoic diacid, tridecanoic diacid, tetradecano diacid, diacid hexadecanoic, octadecanoic diacid, diacid
    2,2,4- or 2,4,4-trimethylhexanoic acid, isophthalic acid, 2,6naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid or 2Petition 870190017936, of 02/21/2019, pg. 10/30
    6/19 methyl-1,4-cyclohexanedicarboxylic.
    [0023] Suitable lactams or aminocarboxylic acids are, for example, caprolactam, laurinlactam or ω-aminoundecanoic acid.
    [0024] Here, mixtures of other diamines, mixtures of other dicarboxylic acids, mixtures of lactams or aminocarboxylic acids, as well as mixtures of another diamine or other dicarboxylic acid or lactam or aminocarboxylic acid can also be used.
    [0025] As a rule, copolyamide is produced by melting polycondensation. Corresponding processes are state of the art. Alternatively, however, any other known polyamide synthesis process can also be used.
    [0026] Suitable additives in the molding compound are, for example:
    [0027] a) other polymers;
    [0028] b) fibrous reinforcement materials;
    [0029] c) filling materials;
    [0030] d) plasticizers;
    [0031] e) pigments and / or dyes;
    [0032] f) flame protection agents;
    [0033] g) auxiliary processing agents and [0034] h) stabilizers.
    [0035] Other polymers are, for example, polyamides, polyphenyl ether and / or impact modifiers.
    Suitable polyamides are, for example, PA46, PA66, PA68, PA620, PA612, PA613, PA410, PA412, PA810, PA1010, PA1012, PA1013, PA1014, PA1018, PA1212, PA6, PA11 and PA12, as well as copoliamides, that derive from these types. Fundamentally, it is also possible to use partially crystalline aromatic polyamides, for example, PA6T / 6I, PA6T / 66, PA6T / 6 or PA6T / 6I / 66.
    [0037] Suitable polyphenylene ethers are produced by conventional processes from phenols disubstituted by alPetition groups 870190017936, of 02/21/2019, p. 11/30
    7/19 kilo in ortho position or through coupling. A particularly preferred polyphenyl ether is poly (2,6-dimethyl-1,4-phenylenic) ether, optionally in combination with 2,3,6-trimethylphenol units. According to the state of the art, polyphenylene ether contains functional groups for binding to the polyamide matrix; these functional groups are introduced, for example, through treatment with maleic acid anhydride.
    [0038] Suitable impact modifiers are, for example, olefinic polymers, which contain functional groups, which are either grafted into the main olefinic chain or are included in the main chain by polymerization; suitable types and combinations are published, for example, in EP 1,170,334 A2. In addition, polyacrylate rubber or ionomers can also be used.
    [0039] The dough contains in other polymers preferably at most 40% by weight, particularly preferably at most 30% by weight and most preferably at most 25% by weight.
    [0040] Suitable fibrous reinforcing materials are, for example, glass fibers, carbon fibers, aramid fibers, stainless steel fibers or potassium titanate whiskers.
    [0041] Suitable reinforcement materials are, for example, talc, mica, silicate, quartz, graphite, molybdenum disulfide, titanium dioxide, wolastonite, kaolin, amorphous silicic acids, magnesium carbonate, chalk, lime, feldspar, sulfate barium, conductive soot, graphite fibrils, solid or hollow glass spheres or ground glass.
    [0042] Plasticizers and their use in polyamides are known. A general synopsis about plasticizers, which are suitable for polyamides, can be found at Gachter / Müller, Kunststoffadditive,
    C. Hanser Verlag, 2nd edition, page 296.
    [0043] Conventional compounds, suitable as plasticizers
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    8/19 are, for example, esters of p-hydroxybenzoic acid with 2 to 20 carbon atoms in the alcoholic component or amides of arylsulfonic acids with 2 to 12 carbon atoms in the amine component, preferably amides of benzenesulfonic acid.
    [0044] As plasticizers, among others, include the ethyl ester of p-hydroxybenzoic acid, octyl ester of p-hydroxybenzoic acid, i-hexadecyl ester of p-hydroxybenzoic acid, n-octylamide of toluenesulfonic acid, n-butylamide of benzenesulfonic acid or benzenesulfonic acid 2-ethylhexylamide.
    [0045] Suitable pigments and / or dyes are, for example, soot, fero oxide, zinc sulphide, oversea, nigrosine, pearly luster pigments and metal flakes.
    [0046] Suitable flame retardants are, for example, antimony trioxide, hexabromocyclododecane, tetrabromobisphenol, borates, red phosphorus, magnesium hydroxide, aluminum hydroxide, melamine cyanurate and their condensation products, such as melam, melem, melon, melamine compounds, such as pyro- and melamine polyphosphate, ammonium polyphosphate, as well as phosphorus-organic compounds or their salts, such as, for example, resorcinol diphenylphosphate, phosphonic acid ester or metal phosphinates.
    Suitable processing aids are, for example, paraffins, fatty alcohols, fatty acid amides, paraffin waxes, montanates or polysiloxanes.
    [0048] Suitable stabilizers are, for example, copper salts, molybdenum salts, copper complexes, phosphites, sterically hindered phenols, secondary amines, ultraviolet absorbers and HALS stabilizers.
    [0049] The dough according to the invention can be processed, for example, through injection molding, extrusion
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    9/19 or blow on molded parts. Typical application examples in the field of injection molding are represented by connectors or housings for the automotive or electronics industry, as well as frames, filter cups or housings for drinking water applications. In the scope of extrusion, for example, tubes or also mono- or multilayer films may be mentioned. In addition, powders for composites can be manufactured from these molding compounds, for example, with glass or carbon fibers. Finally, let us mention air intake tubes in the car as an example of blow molded parts.
    [0050] The polyamide moldings according to the invention are excellently suited for the production of monofilaments (single fibers) as well as multifilaments (for example, lines with 100 single fibers respectively). The temperature of the dough varies, in this case, according to the method and viscosity of the use of the molding dough between approximately 280 o C and approximately 340 o C. Typical drawing temperatures are in the range of about 160 o C to approximately 180 o C. Filaments can be used, for example, for textile fabrics, as reinforcement fibers in composites, for example, together with a duromeric matrix or as bristles. [0051] Moldable powders according to the invention can be produced, for example, by grinding, by precipitation or by all other known processes. The powder can be used, for example, for layered molding processes (rapid prototyping), for surface coating or for the production of fiber composite materials (composites). As a rule, the powder has a grain size d90, determined by means of laser diffraction according to ISO 13320: 2009, of a maximum of 500 pm, preferably a maximum of 400 pm, particularly preferably, of a maximum 300 pm and particularly preferably not
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    10/19 maximum 200 pm.
    [0052] Fiber composite materials consist of reinforcement fibers and a plastic matrix. The fibers are joined in an adhesive or cohesive way with the matrix that completely surrounds them. Through the orientation of reinforcement fibers, fiber-plastic composites have anisotropic mechanical properties. As a rule, they have specific high stabilities and stiffness. This makes them suitable materials for light construction applications. Based on fiber composite materials, predominantly flat structures are produced.
    [0053] In the present case, the fibers used may be of an inorganic nature (for example, glass or basalt fibers) or of an organic nature (for example, aramid or carbon fibers). Mixtures of various fibers can also be used. Fiber composite materials can be produced, for example, by impregnating flat fiber structures with dough powders according to the claims and hot pressing; then, the composites obtained in this way can be thermally transformed.
    [0054] When impregnating the fiber structure with powder, two processes are mainly applied:
    [0055] - impregnation through a suspension, in which the polymer as a fine powder, suspended in a liquid, is put in contact with the fibers or [0056] - impregnation through the powder spreading process.
    [0057] In addition, fiber composite materials of the molding paste according to the claims, can also be produced by impregnating the reinforcing fibers in fusion or by compressing the polymeric films with the reinforcing fibers (film stacking) ).
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    11/19 [0058] In the production of composites from powder, it is fundamentally also possible the common use of molding powder according to the invention, together with other thermoplastic powders and especially also the combination with starting materials for duraplastic matrices (eg powder together with two-component epoxy resin components). In such systems reinforced with fibers or not reinforced with a duraplastic or thermoplastic matrix (eg bismaleinimide resin), the powder acts as a component that increases the impact resistance.
    [0059] In the following, the invention is clarified by means of examples. [0060] For the production of the higher melting point types of copolyamide according to the invention, for example, the apparatus shown in Figure 2 of US 2,361,717 is provided. When adjusting to the laboratory scale, positions 23, 24 and 25 from there can be replaced by an autoclave resistant to high pressure, which, by means of an overlay of inert gas, can guarantee a constant transport pressure through the reactors. In the following examples, the first tubular reactor (corresponds to position 26) had a length of 6 m and an internal diameter of 1.4 mm and the second tubular reactor (corresponds to position 27 '), a length of 10 m and an internal diameter of 2 mm. The two reactors were operated with an oil inlet of 360 o C.
    Example 1: CoPA 10T / TMDT (80: 20) [0061] 675.2 g of 1.10-decanediamine (98.6%), 150.3 g of a mixture of 2,2,4- and 2, 4,4-TMD, 789.3 g of terephthalic acid, 452 g of totally desalinated water (VE water), 3.1 g of a heat stabilizer and 2.88 g of a 5% aqueous solution of H3PO2 in the autoclave, inerted three times with nitrogen, the autoclave was locked and heated to an inlet oil temperature
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    12/19
    230 o C. In this case, a homogeneous, clear saline solution was formed. The autoclave was adjusted with nitrogen to a constant pressure of 4400 KPa (44 bar); this pressure carried the material through the installation. In the flasher (position 30), 16.5 g / h was obtained. The results of the analysis were:
    [0062] carboxyl end group ratio: 113 mmol / kg [0063] amino end group ratio: 106 mmol / kg [0064] relative solution viscosity q re l, measured according to ISO 307 in a solution a 0.5% by weight, in m-cresol at 23 o C: 1.59 [0065] Tg (according to ISO 11357): 126 o C [0066] Tm1 (according to ISO 11357): 256 o C (measured on the second heating) [0067] Tm2 (according to ISO 11357): 278 o C (main peak;
    measured on the second heating) [0068] The product was post-condensed for 30 hours at 180 o C in a light stream of nitrogen in solid phase for a material with Qrel = 1.79.
    Example 2: CoPA 10T / MDT (94: 6) [0069] 654.9 g of 1.10-decanediamine (98.6%), 38.0 g of a mixture of 2,2,4- and 2, 4,4-TMD, 664.6 g of terephthalic acid, 372.5 g of VE water, 1.2 g of sodium hypophosphite, 2.4 g of a heat stabilizer and 1.2 g of an aqueous solution of 5% H3PO2 were filled in the autoclave, inerted three times with nitrogen, the autoclave was locked and heated with an oil inlet temperature of 230 o C. In this case, a clear, homogeneous saline solution was formed. The autoclave was adjusted with nitrogen to a constant pressure of 4200 KPa (42 bar); this pressure carried the material through the installation. In the flasher, 17.9 g / h were obtained. The results of the analysis were:
    Petition 870190017936, of 02/21/2019, p. 17/30
    13/19 [0070] carboxyl end group rate: 172 mmol / kg [0071] amino end group rate: 167 mmol / kg [0072] Qrel: 1.42 [0073] Tg: 122 [0074] Tm: 297 o C (main peak) [0075] The product was post-condensed for 40 hours at 180 ° C in a light stream of nitrogen in solid phase for a material with Qrel = 1.74.
    Example 3:
    [0076] According to example 1, the other copolyamide listed in the following tables was produced with a decanodiamine / TMD ratio of 85: 15.
    Reference example 1:
    [0077] According to example 1, the homopolymer PA10T was produced.
    Example 4:
    [0078] To produce a CoPA 10T / TMDT (70: 30), a 30 liter autoclave stirrer was fed with the following ingredients: [0079] 3,962 kg of 1.10-decanediamine (as an aqueous solution at
    99.3%), [0080] 1,549 kg of isomeric mixture of 2,2,4- and 2,4,4-trimethylhexamethylenediamine [0081] 5.563 kg of terephthalic acid, as well as [0082] 1.12 g of a solution 50% aqueous hypophosphorous acid (corresponds to 0.006% by weight) with [0083] 5.96 kg of water VE [0084] The ingredients were melted in a nitrogen atmosphere and under stirring, heated in the closed autoclave at about 220 o C, with an internal pressure of about 2000 KPa (20 bar) adjusted. This internal pressure was maintained for 2 hours; then the
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    14/19 melting mass continued to be heated to 305 o C under continuous decompression at normal pressure and then maintained at that temperature for 1.5 hours in the nitrogen stream. Then, within 3 hours, it was decompressed at atmospheric pressure and for another 3 hours the nitrogen was conducted through the melting mass, until, based on the torque, no further increase in the viscosity of the melting mass was recorded. Then, the molten mass was discharged by means of a sprocket pump and granulated as an extrusion. The granulate was dried at 110 o C for 24 hours under nitrogen.
    [0085] Discharge: 7.4 kg.
    [0086] The product had the following characteristic values: [0087] melting point of the crystallite Tm: 270 o C [0088] viscosity of relative solution qreli 1.76 [0089] COOH end groups: 291 mmol / kg [0090] NH2 terminal groups: 17 mmol / kg
    Example 5:
    [0091] To produce a CoPA 12T / TMDT (60: 40), a 30 liter stirrer autoclave was loaded with the following ingredients: [0092] 3,788 kg of 1,12-dodecanediamine (as 99.4% aqueous solution) , [0093] 1,982 kg of isomeric mixture of 2,2,4- and 2,4,4-trimethylhexamethylenediamine [0094] 5.305 kg of terephthalic acid, as well as [0095] 1.13 g of a 50% aqueous solution of hypophosphorous acid (corresponds to 0.006% by weight) with 5.96 kg of VE water.
    [0096] The ingredients were melted in a nitrogen atmosphere and under stirring, they were heated to about 220 o C in the closed autoclave, and an internal pressure of about 2000 KPa (20 bar) was adjusted. This internal pressure was maintained for 2 hours; then the
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    15/19 melting mass continued to be heated to 295 o C under continuous decompression at normal pressure and then maintained at that temperature for 1.5 hours in the nitrogen stream. Then, it was decompressed within 3 hours at atmospheric pressure and for another 3 hours the nitrogen was conducted through the melting mass, until, based on the torque, no further increase in the viscosity of the melting mass is recorded. Then, the molten mass was discharged by means of a sprocket pump and granulated as an extrusion. The granulate was dried at 110 o C for 24 hours under nitrogen. [0097] Discharge: 8.9 kg.
    [0098] The product had the following characteristic values: [0099] melting point of the crystallite Tm: 232 o C [00100] viscosity of relative solution qrel: 1.53 [00101] COOH end groups: 275 mmol / kg [00102 ] NH2 terminal groups: 84 mmol / kg
    Example 6:
    [00103] To produce a CoPA 12T / TMDT (70: 30), a 30 liter agitator autoclave was loaded with the following ingredients: [00104] 4,356 kg of 1,12-dodecanediamine (as 99.4% aqueous solution) , [00105] 1,465 kg of isomeric mixture of 2,2,4- and 2,4,4-trimethylhexamethylenediamine [00106] 5,258 kg of terephthalic acid, and [00107] 1.13 g of a 50% aqueous solution hypophosphorous acid (corresponds to 0.006% by weight) with 5.97 kg of VE water.
    [00108] The ingredients were melted in a nitrogen atmosphere and under stirring, they were heated to about 220 o C in the closed autoclave, and an internal pressure of about 2000 KPa (20 bar) was adjusted. This internal pressure was maintained for 2 hours; then, the melting mass continued to be heated to 295 o C under continuous dispensation 870190017936, of 02/21/2019, p. 20/30
    16/19 compression at normal pressure and then maintained at that temperature for 1.5 hours in the nitrogen stream. Then, it was decompressed within 3 hours at atmospheric pressure and for another 3 hours the nitrogen was conducted through the melting mass, until, based on the torque, no further increase in the viscosity of the melting mass is recorded. Then, the molten mass was discharged by means of a sprocket pump and granulated as an extrusion. The granulate was dried at 110 o C for 24 hours under nitrogen. [00109] Discharge: 9.1 kg.
    [00110] The product had the following characteristic values: [00111] melting point of the crystallite Tm: 257 o C [00112] viscosity of relative solution q re : 1.56 [00113] COOH end groups: 269 mmol / kg [00114] NH2 terminal groups: 17 mmol / kg
    Example 7:
    [00115] According to example 6, a copolyamide with a dodecanediamine / TMD ratio of 75: 25 was produced.
    Examples 8 and 9:
    [00116] According to example 4, two copolyamides were produced with a dodecanediamine / TMD ratio of 60: 40, respectively, 52: 48.
    Comparative examples 1 and 2:
    [00117] According to example 4, two copolyamides were produced with a dodecanediamine / TMD ratio of 33: 67, respectively, 12: 88.
    [00118] The properties of the polyamides or copolyamides produced are shown in the following tables.
    Petition 870190017936, of 02/21/2019, p. 21/30
    Table 1: Calorimetric data of 10T / TMDT copolyamides, determined according to ISO 11357 in the second heating
    Co-PA 10T / TMDT reference 1 example2 example3 example1 example4 example8 example9 comparative example 1 comparative example 2 10-part [mol%] 100 94 85 80 70 60 52 33 12 TMD-share [mol%] 0 6 15 20 30 40 48 67 88 enthalpy of melting mass [J / g] 64 62 62 52 49 45 17 0 0 Tm [ the C] 309 297 282 274 270 263 251 - - Tg [ o C] 119 122 123 125 128 133 134 137 145
    Table 2: Calorimetric data of 12T / TMDT copolyamides, determined according to ISO 11357 in the second heating
    17/19
    Co-PA12T / TMDT example 7 example 6 example 5 12-part [mol%] 75 70 60 TMD-share [mol%] 25 30 40 enthalpy of melting mass [J / g] 51 52 38 Tm [ the C] 263 258 247 Tg [ o C] 116 116 118
    Petition 870190017936, of 02/21/2019, p. 22/30
    18/19 [00119] In Figure 1, the relative water absorption of the product of example 3 (full contact storage at 23 o C) compared to that of a commercially available PPA produced from 1,6-hexamethylenediamine and a mixture of 65 mol% dicarboxylic acid, terephthalic acid, 25 mol%, isophthalic acid and 10 mol%, adipic acid. It is evident that the water absorption in the copolyamide according to the invention is considerably less.
    [00120] Table 3 shows that the product of example 3 after conditioning by humidity (here: total contact storage at 120 o C in the autoclave) essentially maintains its mechanical properties. The increase in module E in the first case must be attributed to recrystallization.
    Table 3: Mechanical properties in the dry state as well as in the condition conditioned by humidity
    example product3 storage[H] module E according to ISO 527 [MPa] breaking stress according to ISO 527 [MPa] elongation at break according to ISO 527 [MPa] Pure 0 2594 81 5100 2819 80 6 with 30% by weight 0 8702 273 3 glass fiber 24 8404 269 3
    Powder production:
    [00121] The product of example 8 was milled as extrusion granules about 5 cm long and about 3 mm in diameter in a disc friction mill (Alpine CW 160). Using a cooling coil, the use granulate was cooled to -50 o C, accelerated in the grinding space to 220 m / s and crushed between the opposite grinding disc pins. Here, with a passage of 15 kg / h, a ground material was formed, in which the fraction with a grain diameter of less than 100 pm, made up 50% by weight. The ground material 870190017936, of 02/21/2019, p. 23/30
    19/19 do was sieved at 63 pm; the fine fraction obtained had a grain size distribution (determined by means of laser diffraction) of dio = 14.9 pm, d50 = 43.7 pm and d90 = 75.4 pm.
    [00122] This fine powder was used for the production of fiber composite materials.
    权利要求:
    Claims (8)
    [1]
    1. Molding mass, characterized by the fact that it comprises at least 30% by weight of a copolyamide, which is derived from the following monomers:
    (a) in 50 to 95 mol% of the combination of a diamine, selected from the group 1,10-decanediamine, 1,11-undecanediamine and 1,12-dodecanediamine, as well as terephthalic acid, and (b) in 5 to 50 mol% of the combination of a diamine, selected from the group 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine and mixtures thereof, as well as terephthalic acid, with the stated mol% referring to sum of components (a) and (b), and said copolyamide comprises from 0 to 5 mol% of units derived from other monomers, and said units derived from other monomers can be categorized as follows :
    - first, they can be derived from the combination of a diamine and a dicarboxylic acid; a distinction can be drawn between the following cases here:
    (a) dicarboxylic acid is terephthalic acid; diamine is a different diamine from 1,10-decanediamine, 1,11undecanediamine, 1,12-decanediamine, 2,2,4-DTM and 2,4,4-DTM, (b) dicarboxylic acid is a different acid terephthalic acid; diamine is one of the aforementioned, (c) not only is dicarboxylic acid an acid other than terephthalic acid, but diamine is a diamine other than that mentioned above;
    - second, they can be derived from a lactam or an aminocarboxylic acid.
    Petition 870190017936, of 02/21/2019, p. 25/30
    [2]
    2/2
    2. Molding compound according to claim 1, characterized by the fact that it is composed of pure copolyamide.
    [3]
    Molding material according to claim 1, characterized in that it comprises, in addition to copolyamide, at least 0.1% by weight of additives.
    [4]
    Molding paste according to any one of claims 1 to 3, characterized in that it is a powder.
    [5]
    Molded part, produced from the molding paste, as defined in any one of claims 1 to 4.
    [6]
    6. Film, produced from the molding compound, as defined in any one of claims 1 to 4.
    [7]
    7. Filament, produced from the dough, as defined in any one of claims 1 to 4.
    [8]
    8. Fiber composite material, characterized in that it comprises the molding compound, as defined in any one of claims 1 to 4.
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    同族专利:
    公开号 | 公开日
    KR101792890B1|2017-11-02|
    US20120095161A1|2012-04-19|
    EP2451862A2|2012-05-16|
    CN102471482A|2012-05-23|
    DE102009027611A1|2011-01-13|
    BR112012000509A2|2016-02-16|
    US8871862B2|2014-10-28|
    RU2559328C2|2015-08-10|
    RU2012104509A|2013-08-20|
    JP5847078B2|2016-01-20|
    CN102471482B|2014-01-01|
    EP2451862B1|2018-10-03|
    WO2011003973A2|2011-01-13|
    WO2011003973A3|2011-03-10|
    KR20120036343A|2012-04-17|
    JP2012532943A|2012-12-20|
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    法律状态:
    2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-02-05| B06T| Formal requirements before examination|
    2019-05-28| B09A| Decision: intention to grant|
    2019-07-16| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 08/07/2010, OBSERVADAS AS CONDICOES LEGAIS. (CO) 20 (VINTE) ANOS CONTADOS A PARTIR DE 08/07/2010, OBSERVADAS AS CONDICOES LEGAIS |
    2020-05-12| B25D| Requested change of name of applicant approved|Owner name: EVONIK OPERATIONS GMBH (DE) |
    优先权:
    申请号 | 申请日 | 专利标题
    DE200910027611|DE102009027611A1|2009-07-10|2009-07-10|Molding composition based on a copolyamide containing terephthalic acid and trimethylhexamethylenediamine unit|
    DE102009027611.4|2009-07-10|
    PCT/EP2010/059809|WO2011003973A2|2009-07-10|2010-07-08|Molding compound on the basis of a copolyamide containing terephthalic acid and trimethylhexamethylene diamine units|
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