EP0000492B1 - Transparent polyamides and their use for the manufacture of moulds - Google Patents
Transparent polyamides and their use for the manufacture of moulds Download PDFInfo
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- EP0000492B1 EP0000492B1 EP78100353A EP78100353A EP0000492B1 EP 0000492 B1 EP0000492 B1 EP 0000492B1 EP 78100353 A EP78100353 A EP 78100353A EP 78100353 A EP78100353 A EP 78100353A EP 0000492 B1 EP0000492 B1 EP 0000492B1
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- EP
- European Patent Office
- Prior art keywords
- mol
- bis
- aminocyclohexyl
- methane
- polyamides
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- 239000004952 Polyamide Substances 0.000 title claims description 38
- 229920002647 polyamide Polymers 0.000 title claims description 38
- 238000004519 manufacturing process Methods 0.000 title description 4
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical class C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 claims description 28
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 23
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 23
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 20
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 18
- 150000004985 diamines Chemical class 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 235000011037 adipic acid Nutrition 0.000 claims description 11
- 239000001361 adipic acid Substances 0.000 claims description 11
- 238000006068 polycondensation reaction Methods 0.000 claims description 11
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 2
- 238000000034 method Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- -1 aromatic dicarboxylic acids Chemical class 0.000 description 4
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 3
- PYVOVMLTMWWXIS-UHFFFAOYSA-N 4-ethyldodecanedioic acid Chemical compound OC(=O)CCC(CC)CCCCCCCC(O)=O PYVOVMLTMWWXIS-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BDBZTOMUANOKRT-UHFFFAOYSA-N 4-[2-(4-aminocyclohexyl)propan-2-yl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1C(C)(C)C1CCC(N)CC1 BDBZTOMUANOKRT-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 101500021084 Locusta migratoria 5 kDa peptide Proteins 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 238000009757 thermoplastic moulding Methods 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Classifications
-
- 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
Definitions
- the present invention relates to transparent, thermoplastically deformable copolyamides with high heat resistance.
- the invention relates to polyamides which are produced by polycondensation of bis- (4-aminocyclohexyl) methane and optionally smaller amounts of aliphatic and / or further cycloaliphatic diamines as the diamine component with azelaic acid and isophthalic acid or adipic acid as the dicarboxylic acid component using customary procedures.
- polyamides based on bis- (4-aminocyclohexyl) propane and adipic acid described in DE-A 1 595 354 have less tendency to crystallize, but the thermoplastic processing of these polyamides is considerably more difficult owing to their high softening points.
- Lower-melting polyamides made from bis- (4-aminocyclohexyl) methane and aliphatic dicarboxylic acids such as adipic acid are either not transparent or tend to recrystallize and thus cloud.
- DE-A 1 933 395 describes transparent polyamides which must contain bis- (4-aminocyclohexyl) methane and hexamethylenediamine as diamine components and isophthalic acid and terephthalic acid as dicarboxylic acids in narrowly defined mixing ratios.
- a particular disadvantage of these polyamides is that the proportion of bis- (4-aminocyclohexyl) methane, which has a strongly improving influence on the heat resistance of the polyamide, is only a maximum of 50 mol%, i.e. may amount to a maximum of approx. 65% by weight. Products with a higher content of bis- (4-aminocyclohexyl) methane have too high a melt viscosity, so that they can no longer be deformed by the injection molding processes customary in practice.
- DE-A 2 125 906 describes copolyamides of bis (4-aminocyclohexyl) methane and 3-ethyl-1,10-decanedicarboxylic acid.
- the transparent products are easy to process, but due to the long and branched C-chain of the dicarboxylic acid with only 130 ° C they have an unsatisfactory heat resistance.
- the essential 3-ethyl-1,10-decanedicarboxylic acid is difficult to access.
- the previously proposed transparent polyamides therefore have disadvantages with regard to chemical resistance, softening temperature and melt formability.
- copolyamides of bis- (4-aminocyclohexyl) methane and optionally smaller amounts of an aliphatic or another cycloaliphatic diamine and a mixture of azelaic acid and isophthalic acid or of azelaic acid and adipic acid do not have the disadvantages mentioned if the isophthalic acid - or adipic acid content is selected within defined limits.
- the products can surprisingly be converted into thermoplastic moldings with high heat without difficulty Process dimensional stability, good toughness level and good resistance to solvents.
- Copolyamides obtained by polycondensation of 85 to 70 mol% of azelaic acid and 15 to 30 mol% of isophthalic acid or adipic acid and an equivalent amount of bis- (4-amino-cyclotiexyl) methane as the sole diamine component are particularly preferred.
- the bis (4-aminocyclohexyl) methane is a stereo isomer mixture consisting predominantly of trans, trans, cis-trans and to a small extent of cis, cis isomers.
- the stereo isomer mixture of bis- (4-aminocyclohexyl) -methane obtained with the hydrogenation and having a melting point above 30 ° C. is used.
- the copolyamides are produced by the processes customary for the production of polyamides from diamines and dicarboxylic acids.
- the mixture of the starting components can be heated to temperatures between 190 and 230 ° C. and precondensed in this temperature range. After this precondensation has ended, polycondensation is carried out at temperatures between 240 and 300.degree.
- Condensation can be carried out under vacuum towards the end of the polymerization, but this is in no way necessary.
- the precondensation can be carried out with or without the addition of water; it can be carried out at atmospheric pressure or in closed autoclaves under the vapor pressure of the water.
- the loss of diamine occurring during the polycondensation is preferably compensated for by using an appropriate excess of bis (4-aminocyclohexyl) methane.
- the molecular weight of the polyamides can be regulated in a known manner by monocarboxylic acids or amines.
- the relative viscosity of the copolyamides according to the invention should be at least 2.2, preferably between 2.4 and 3.5, measured on a 1% solution of the polyamide in m-cresol at 25 ° C. in an Ubbelohde viscometer.
- Polyamides according to the invention can also be added various additives, which are used for conventional polyamides, e.g. Flame retardants, heat and UV stabilizers, antioxidants and pigments, the addition being carried out during any desired stage before or after the polymerization in accordance with known approaches.
- additives e.g. Flame retardants, heat and UV stabilizers, antioxidants and pigments, the addition being carried out during any desired stage before or after the polymerization in accordance with known approaches.
- the polyamides according to the invention have excellent transparency, chemical resistance, heat stability and melt formability and are used as a molding composition for the production of various shaped and press-molded articles, e.g. Films, films, plates, tubes, bars and containers of various types are valuable.
- the mixture is heated to about 200 ° C. under an N 2 atmosphere, the agitator being switched on at 100 ° C., and the reaction mixture is kept under autogenous pressure for 4 hours. The pressure is then slowly released, heated to 270 ° C. and polycondensed for a further 7 hours at 270 ° C.
- the resulting almost colorless polyamide ( ⁇ ret 2.7) is spun through a water bath, granulated and dried.
- composition of the starting monomers and some properties of the polyamides obtained are summarized in Tab. 1, the amounts of the starting materials being given in mol%.
- the slightly yellowish polyamide had a rel. Viscosity of 3.0, a heat resistance of 145 ° C, an impact strength of 82.4 kJ / m 2 (8 samples not broken) and a notched impact strength of 4.8 kJ / m l .
- the starting monomers were weighed out in defined ratios (for molar ratios see Table 2), the reaction mixture was slowly heated to 200 ° C. under a nitrogen atmosphere and with stirring. In the further course, the mixture was heated to 270 ° C. and polycondensed for a further 6 hours at 270 ° C.
Description
Vorliegende Erfindung betrifft transparente, thermoplastisch verformbare Copolyamide mit hoher Wärmeformbeständigkeit.The present invention relates to transparent, thermoplastically deformable copolyamides with high heat resistance.
Insbesondere bezieht sich die Erfindung auf Polyamide, die durch Polykondensation von Bis-(4-aminocyclohexyl)-methan und gegebenenfalls geringeren Mengen aliphatischer und/oder weiterer cycloaliphatischer Diamine als Diaminkomponente mit Azelainsäure sowie Isophthalsäure oder Adipinsäure als Dicarbonsäurekomponente unter Verwendung üblicher Verfahrensweisen hergestellt werden.In particular, the invention relates to polyamides which are produced by polycondensation of bis- (4-aminocyclohexyl) methane and optionally smaller amounts of aliphatic and / or further cycloaliphatic diamines as the diamine component with azelaic acid and isophthalic acid or adipic acid as the dicarboxylic acid component using customary procedures.
Für viele Einsatzgebiete ist die von den üblichen Polyamiden wie 6-Polyamid oder 6,6-Polyamid bekannte günstige Eigenschaftskombination gegenüber anderen thermoplastisch verarbeitbaren Materialien von großem Vorteil. Wegen der Teilkristallinität dieser Polyamid-Typen, die einen großen Teil der besonders guten Eigenschaften verursacht, sind jedoch Formteile aus diesen Polyamiden immer opak und daher in allen Fällen, in denen transparente Formteile gefordert werden, nicht verwendbar.For many areas of application, the favorable combination of properties known from conventional polyamides such as 6-polyamide or 6,6-polyamide is of great advantage over other thermoplastically processable materials. Because of the partial crystallinity of these polyamide types, which causes a large part of the particularly good properties, molded parts made from these polyamides are always opaque and therefore cannot be used in all cases in which transparent molded parts are required.
Es hat daher nicht an Versuchen gefehlt, Polyamide herzustellen, die neben ihrem amorphen Charakter und der hiermit verbundenen Transparenz auch noch die günstigen Eigenschaften von Polyamid-6 oder -6,6 aufweisen.There has been no shortage of attempts to produce polyamides which, in addition to their amorphous character and the transparency associated therewith, also have the favorable properties of polyamide-6 or -6.6.
Einer dieser Versuche ist der Einsatz von Bis-(4-amino-cyciohexy))-methan bei der Herstellung von Polyamiden. So sind transparente Polyamide aus dem genannten Amin und aromatischen Dicarbonsäuren wie Isophthalsäure (US-A 2 696 482) oder Terephthalsäure (US-A 2 516 585) bekannt. Diese Produkte sind jedoch wegen ihrer hohen Schmelzviskosität thermoplastisch nur schwierig verarbeitbar.One of these attempts is the use of bis (4-amino-cyciohexy)) methane in the production of polyamides. Transparent polyamides of the amine mentioned and aromatic dicarboxylic acids such as isophthalic acid (US Pat. No. 2,696,482) or terephthalic acid (US Pat. No. 2,516,585) are known. However, because of their high melt viscosity, these products are difficult to process thermoplastically.
Es wurde auch versucht, transparente Polyamide aus Bis-(4-aminocyclohexyl)-methan und wieteren polyamidbjldenden Komponenten wie Adipinsäure, Hexamethylendiamin und e-Caprolactam herzustellen. Diese Polyamide sind jedoch äußerst unbeständig gegen Lösungsmittel und bilden unter Eintrübung Sphärolithe.Attempts have also been made to produce transparent polyamides from bis (4-aminocyclohexyl) methane and other polyamide-forming components such as adipic acid, hexamethylene diamine and e-caprolactam. However, these polyamides are extremely resistant to solvents and form spherulites with clouding.
Die in der DE-A 1 595 354 beschriebenen Polyamide auf Basis von Bis-(4-aminocyclohexyl)-propan und Adipinsäure neigen zwar weniger zur Kristallisation, die thermoplastische Verarbeitung dieser Polyamide ist jedoch infolge ihrer hohen Erweichungspunkte erheblich erschwert.The polyamides based on bis- (4-aminocyclohexyl) propane and adipic acid described in DE-A 1 595 354 have less tendency to crystallize, but the thermoplastic processing of these polyamides is considerably more difficult owing to their high softening points.
Dies gilt auch für die Polyamide aus Bis-(4-aminocyclohexyl)-methan und einem Säuregemisch aus Azelainsäure und Adipinsäure, die in der US-A 4 028 476 beschrieben sind.This also applies to the polyamides made from bis (4-aminocyclohexyl) methane and an acid mixture of azelaic acid and adipic acid, which are described in US Pat. No. 4,028,476.
Niedriger schmelzende Polyamide aus Bis-(4-aminocyclohexyl)-methan und aliphatischen Dicarbonsäuren wie Adipinsäure (US-A 2 585 163) sind entweder nicht transparent oder neigen zur Nachkristallisation und damit zur Eintrübung.Lower-melting polyamides made from bis- (4-aminocyclohexyl) methane and aliphatic dicarboxylic acids such as adipic acid (US Pat. No. 2,585,163) are either not transparent or tend to recrystallize and thus cloud.
In der DE-A 1 933 395 werden transparente Polyamide beschrieben, die Bis-(4-aminocyclohexyl)-methan und Hexamethylendiamin als Diaminkomponenten und Isophthalsäure und Terephthalsäure als Dicarbonsäuren in eng definierten Mischungsverhältnissen enthalten müssen.DE-A 1 933 395 describes transparent polyamides which must contain bis- (4-aminocyclohexyl) methane and hexamethylenediamine as diamine components and isophthalic acid and terephthalic acid as dicarboxylic acids in narrowly defined mixing ratios.
Ein besonderer Nachteil dieser Polyamide ist, daß der Anteil des Bis-(4-aminocyclohexyl)-methan, das einen stark verbessernden Einfluß auf die Wärmeformbeständigkeit des Polyamids hat, nur maximal 50 Mol-%, d.h. maximal ca. 65 Gew.-% betragen darf. Produkte mit höherem Gehalt an Bis-(4-aminocyclohexyl)-methan haben eine zu hohe Schmelzviskosität, so daß sie nach den in der Praxis üblichen Spritzgußverfahren nicht mehr verformt werden können.A particular disadvantage of these polyamides is that the proportion of bis- (4-aminocyclohexyl) methane, which has a strongly improving influence on the heat resistance of the polyamide, is only a maximum of 50 mol%, i.e. may amount to a maximum of approx. 65% by weight. Products with a higher content of bis- (4-aminocyclohexyl) methane have too high a melt viscosity, so that they can no longer be deformed by the injection molding processes customary in practice.
Der zwingend vorgeschriebene hohe Anteil an Hexamethylendiamin hat zur Folge, daß die Produkte eine unbefriedigende Wärmeformbeständigkeit zeigen.The mandatory high proportion of hexamethylene diamine has the consequence that the products show an unsatisfactory heat resistance.
In der DE-A 2 125 906 sind Copolyamide aus Bis-(4-aminocyclohexyl)-methan und 3-Äthyl-1,10-decandicarbonsäure beschrieben. Die transparenten Produkte sind zwar gut verarbeitbar, haben jedoch infolge der langen und verzweigten C-Kette der Dicarbonsäure mit nur 130°C eine unbefriedigende Wärmeformbeständigkeit. Darüber hinaus ist die unbedingt erforderliche 3-Äthyl-1,10-decandicarbonsäure nur schwer zugänglich.DE-A 2 125 906 describes copolyamides of bis (4-aminocyclohexyl) methane and 3-ethyl-1,10-decanedicarboxylic acid. The transparent products are easy to process, but due to the long and branched C-chain of the dicarboxylic acid with only 130 ° C they have an unsatisfactory heat resistance. In addition, the essential 3-ethyl-1,10-decanedicarboxylic acid is difficult to access.
Schließlich sind aus der DE-A 2 642 244 transparente Polyamide aus Bis-(4-aminocyclohexyl)-methan, Isophthalsäure und z.B. Salzen aus aliphatischen Dicarbonsäuren und aliphatischen Diaminen, bei denen je Amidgruppe die durchschnittliche Zahl der Methylengruppen mindestens 9 betragen muß, bekannt. Diese Polyamide zeigen aber offenbar wegen der langkettigen Anteile eine unzureichende Beständigkeit der Transparenz im kochenden Wasser und eine nicht ausreichende Wärmeformbeständigkeit.Finally, from DE-A 2 642 244 transparent polyamides made of bis (4-aminocyclohexyl) methane, isophthalic acid and e.g. Salts from aliphatic dicarboxylic acids and aliphatic diamines, in which the average number of methylene groups must be at least 9 per amide group. However, these polyamides apparently show inadequate transparency in boiling water and insufficient heat resistance due to the long-chain components.
Die bisher vorgeschlagenen transparenten Polyamide zeigen daher Nachteile bezüglich chemischer Beständigkeit, Erweichungstemperatur und Schmelzformbarkeit.The previously proposed transparent polyamides therefore have disadvantages with regard to chemical resistance, softening temperature and melt formability.
Überraschend wurde nun gefunden, daß Copolyamide aus Bis-(4-aminocyclohexyl)-methan und gegebenenfalls kleineren Mengen eines aliphatischen oder eines weiteren cycloaliphatischen Diamins sowie einem Gemisch aus Azelainsäure und Isophthalsäure bzw. aus Azelainsäure und Adipinsäure die genannten Nachteile nicht aufweisen, wenn der Isophthalsäure- bzw. Adipinsäure-Anteil in definierten Grenzen gewählt wird.Surprisingly, it has now been found that copolyamides of bis- (4-aminocyclohexyl) methane and optionally smaller amounts of an aliphatic or another cycloaliphatic diamine and a mixture of azelaic acid and isophthalic acid or of azelaic acid and adipic acid do not have the disadvantages mentioned if the isophthalic acid - or adipic acid content is selected within defined limits.
Die Produkte lassen sich trotz des sehr hohen Anteils an Bis-(4-aminocyclohexyl)-methan überraschenderweise ohne Schwierigkeiten zu thermoplastischen Formkörpern mit hoher Wärmeformbeständigkeit, gutem Zähigkeitsniveau und guter Beständigkeit gegen Lösungsmittel verarbeiten.Despite the very high proportion of bis (4-aminocyclohexyl) methane, the products can surprisingly be converted into thermoplastic moldings with high heat without difficulty Process dimensional stability, good toughness level and good resistance to solvents.
Gegenstand der Erfindung sind somit transparente, thermoplastisch verformbare Copolyamide mit einer relativen Viskosität von mindestens 2,2 (gemessen in 1% iger Lösung des Polyamids in m-Kresol bei 25°C), erhalten durch. Polykondensation von Bis-(4-aminocyclohexyl)-methanen und Dicarbonsäuregemischen, dadurch gekennzeichnet, daß man
- 1. 70 bis 100 Mol-%, vorzugsweise 80 bis 100 Mol-%, Bis-(4-aminocyclohexyl)-methane;
- 2. O bis 30 Mol-%, vorzugsweise 0 bis 20 Mol-%, Hexamethylendiamin und/oder eines von Bis-(4-aminocyclohexyl)-methan unterschiedlichen cycloaliphatischen Diamins mit C8―C15, wobei das molare Verhältnis aller cycloaliphatischen Diamine aus 1. und 2. zu Hexamethylendiamin mindestens 4:1, vorzugsweise mindestens 5:1, betragen soll, und die Summe aus 1. und 2. immer 100 Mol-% ergeben muß, und
- 3. äquivalenten Mengen eines Dicarbonsäuregemisches, bestehend aus: 70 bis 85 Mol-%, Azelainsäure, 30 bis 15 5 Moi-% Isophthalsäure oder Adipinsäure, wobei die Komponenten 3. jeweils 100 Mol-% ergeben müssen, polykondensierf.
- 1. 70 to 100 mol%, preferably 80 to 100 mol%, bis (4-aminocyclohexyl) methane;
- 2. O to 30 mol%, preferably 0 to 20 mol%, hexamethylenediamine and / or one of bis- (4-aminocyclohexyl) methane different cycloaliphatic diamine with C 8 ―C 15 , the molar ratio of all cycloaliphatic diamines from 1st and 2nd to hexamethylenediamine should be at least 4: 1, preferably at least 5: 1, and the sum of 1st and 2nd must always be 100 mol%, and
- 3. equivalent amounts of a dicarboxylic acid mixture consisting of: 70 to 85 mol%, azelaic acid, 30 to 15 5 mol% isophthalic acid or adipic acid, the components 3. must each give 100 mol%, polycondensed.
Besonders bevorzugt sind Copolyamide, die durch Polykondensation von 85 bis 70 Mol-% Azelainsäure und 15 bis 30 Mol-% Isophthalsäure oder Adipinsäure und einer äquivalenten Menge Bis-(4-amino-cyclotiexyl)-methane als alleinige Diaminkomponente erhalten werden.Copolyamides obtained by polycondensation of 85 to 70 mol% of azelaic acid and 15 to 30 mol% of isophthalic acid or adipic acid and an equivalent amount of bis- (4-amino-cyclotiexyl) methane as the sole diamine component are particularly preferred.
Das Bis-(4-aminocyclohexyl)-methan ist ein Stereo-Isomerengemisch, bestehend überwiegend aus trans, trans-, cis-trans- und zu einem geringen Anteil an cis, cis-Isomeren. Für die Kondensation wird das bei der Hydrierung anfallende Stereo-Isomerengemisch von Bis-(4-aminocyclohexyl)-methan mit einem Schmelzpunkt oberhalb 30°C eingesetzt.The bis (4-aminocyclohexyl) methane is a stereo isomer mixture consisting predominantly of trans, trans, cis-trans and to a small extent of cis, cis isomers. For the condensation, the stereo isomer mixture of bis- (4-aminocyclohexyl) -methane obtained with the hydrogenation and having a melting point above 30 ° C. is used.
Die Herstellung der Copolyamide erfolgt nach den für die Herstellung von Polyamiden aus Diaminen und Dicarbonsäuren üblichen Verfahren. Man kann das Gemisch der Ausgangskomponenten auf Temperaturen zwischen 190 und 230°C erhitzen und in diesem Temperaturbereich vorkondensieren. Nach Beendigung dieser Vorkondensation wird bei Temperaturen zwischen 240 und 300°C zu Ende polykondensiert.The copolyamides are produced by the processes customary for the production of polyamides from diamines and dicarboxylic acids. The mixture of the starting components can be heated to temperatures between 190 and 230 ° C. and precondensed in this temperature range. After this precondensation has ended, polycondensation is carried out at temperatures between 240 and 300.degree.
Gegen Ende der Polymerisation kann unter Vakuum kondensiert werden, dies ist jedoch keinesfalls erforderlich.Condensation can be carried out under vacuum towards the end of the polymerization, but this is in no way necessary.
Die Vorkondensation kann mit oder ohne Zusatz von Wasser erfolgen; sie kann bei Atmosphärendruck oder in geschlossenen Autoklaven unter dem Dampfdruck des Wassers durchgeführt werden.The precondensation can be carried out with or without the addition of water; it can be carried out at atmospheric pressure or in closed autoclaves under the vapor pressure of the water.
Vorzugsweise wird in Gegenwart von 10 bis 20 Gew.-% Wasser bei geschlossenem Autoklaven vorkondensiert. Die Polykondensation ausgehend von den Salzen der Monomeren durchzuführen, ist, besonders wenn die Vorkondensation in Gegenwart von Wasser stattfindet, nicht erforderlich.Preference is given to precondensing in the presence of 10 to 20% by weight of water in a closed autoclave. It is not necessary to carry out the polycondensation starting from the salts of the monomers, especially if the precondensation takes place in the presence of water.
Der während der Polykondensation auftretende Verlust an Diamin wird vorzugsweise durch Einsatz eines entsprechenden Überschusses an Bis-(4-aminocyclohexyl)-methan kompensiert.The loss of diamine occurring during the polycondensation is preferably compensated for by using an appropriate excess of bis (4-aminocyclohexyl) methane.
Das Molekulargewicht der Polyamide kann in bekannter Weise durch Monocarbonsäuren oder Amine geregelt werden.The molecular weight of the polyamides can be regulated in a known manner by monocarboxylic acids or amines.
Die relativ Viskosität der erfindungsgemäßen Copolyamide sollte mindestens 2.2 liegen, vorzugsweise zwischen 2, 4 und 3, 5, gemessen an einer 1 % igen Lösung des Polyamids in m-Kresol bei 25°C in einem Ubbelohde-Viskosimeter.The relative viscosity of the copolyamides according to the invention should be at least 2.2, preferably between 2.4 and 3.5, measured on a 1% solution of the polyamide in m-cresol at 25 ° C. in an Ubbelohde viscometer.
Polyamiden gemäß der Erfindung können auch verschiedene Zusätze, die für übliche Polyamide angewendet werden, zugegeben werden, z.B. Flammschutzmittel, Hitze- und UV-Stabilisatoren, Antioxydantien und Pigmente, wobei die Zugabe während irgendeiner gewünschten Stufe vor oder nach der Polymerisation in Übereinstimmung mit bekannten Ansätzen erfolgt.Polyamides according to the invention can also be added various additives, which are used for conventional polyamides, e.g. Flame retardants, heat and UV stabilizers, antioxidants and pigments, the addition being carried out during any desired stage before or after the polymerization in accordance with known approaches.
Die Polyamide gemäß der Erfindung besitzen eine ausgezeichnete Transparenz, chemische Beständigkeit, Hitzestabilität und Schmelzformbarkeit und sind als Formmasse für die Herstellung von verschiedenen gerformten und preßgeformten Gegenständen, z.B. Folien, Filmen, Platten, Rohren, Stangen und Behältern verschiedener Art wertvoll.The polyamides according to the invention have excellent transparency, chemical resistance, heat stability and melt formability and are used as a molding composition for the production of various shaped and press-molded articles, e.g. Films, films, plates, tubes, bars and containers of various types are valuable.
Man füllt 3,76 kg (20 Mol) Azelainsäure, 0,83 kg (5 Mol) Isophthalsäure und 5,25 kg (25 Mol) Bis-(4-aminocyclohexyl)-methan zusammen mit 2 I Wasser in den Autoklaven. Zur Molgewichtsstabilisierung werden 40 g Benzoesäure und zum Ausgleich während der Polykondensation auftretender Diaminverluste 50 g Bis-(4-aminocyclohexyl)-methan hinzugefügt.3.76 kg (20 mol) of azelaic acid, 0.83 kg (5 mol) of isophthalic acid and 5.25 kg (25 mol) of bis (4-aminocyclohexyl) methane are filled into the autoclave together with 2 l of water. 40 g of benzoic acid are added to stabilize the molecular weight and 50 g of bis (4-aminocyclohexyl) methane are added to compensate for diamine losses which occur during the polycondensation.
Man heizt unter N2 Atmosphäre auf ca. 200°C auf, wobei bei 100°C das Rühwerk eingeschaltet wird und hält das Reaktionsgemisch 4 h unter Eigendruck. Dann wird langsam entspannt, auf 270°C erhitzt und noch 7 h bei 270°C erhitzt polykondensiert.The mixture is heated to about 200 ° C. under an N 2 atmosphere, the agitator being switched on at 100 ° C., and the reaction mixture is kept under autogenous pressure for 4 hours. The pressure is then slowly released, heated to 270 ° C. and polycondensed for a further 7 hours at 270 ° C.
Das entstandene fast farblose Polyamid (ηret 2,7) wird durch eine Wasserbad abgesponnen, granuliert und getrocknet.The resulting almost colorless polyamide (η ret 2.7) is spun through a water bath, granulated and dried.
An Normkleinstäben wird gemäß DIN 53 460 eine Wärmeformbeständigkeit nach Vicat (Methode B) von 176°C, nach DIN 53 453 eine Kerbschlagzähigkeit von 5,9 kJ/m2, eine Biegefestigkeit von 110 MPa (DIN 53 452) gemessen. Die Prüfung auf Schlagzähigkeit (DIN 53 453) ergab bei 10 Proben keinen Bruch.On standard small bars, a heat resistance according to Vicat (method B) of 176 ° C, a notched impact strength of 5.9 kJ / m 2 and a flexural strength of 110 MPa (DIN 53 452) are measured in accordance with DIN 53 460. The impact resistance test (DIN 53 453) showed no break in 10 samples.
Die Versuche wurden entsprechend der in Beispiel 1 beschriebenen Verfahrensweise und in gleicher Größenordnung durchgeführt.The tests were carried out in accordance with the procedure described in Example 1 and in the same order of magnitude.
Die Zusammensetzung der Ausgangsmonomeren sowie einige Eingenschaften der erhaltenen Polyamide sind in Tab. 1 zusammengefaßt, wobei die Mengen der Ausgangsstoffe in Mol-% angegeben sind.The composition of the starting monomers and some properties of the polyamides obtained are summarized in Tab. 1, the amounts of the starting materials being given in mol%.
Wie in Beispiel 1 beschrieben, wurde ein transparentes Copolyamid aus 1,69 kg (9 Mol) Azelainsäure, 1,49 kg (9 Mol) Isophthalsäure und 3,82 kg (18 Mol+40 g Überschuß) Bis-(4-aminocyclohexyl)-methan hergestellt.As described in Example 1, a transparent copolyamide of 1.69 kg (9 mol) azelaic acid, 1.49 kg (9 mol) isophthalic acid and 3.82 kg (18 mol + 40 g excess) bis- (4-aminocyclohexyl) -methane manufactured.
Das erhaltene Produkt hatte eine rel. Visk. von 2,3 und eine Wärmeformbeständigkeit von 193°C. Die Verarbeitung über Spritzgußmaschinen erwies sich jedoch als so schwierig, daß das Produkt für die Praxis ungeeignet ist. Die Eigenschaften sind in der Tab. 2 zusammengefaßt.
Wie in Beispiel 1 beschrieben, wird aus 3,76 kg (20 Mol) Azelainsäure, 0,73 kg (5 Mol) Adipinsäure, 4,72 kg (22,5 Mol) Bis-(4-aminocyclohexyl)-methan und 0,29 kg (2,5 Mol) Hexamethylendiamin ein Polyamid hergestellt.As described in Example 1, 3.76 kg (20 mol) of azelaic acid, 0.73 kg (5 mol) of adipic acid, 4.72 kg (22.5 mol) of bis- (4-aminocyclohexyl) methane and 0, 29 kg (2.5 mol) of hexamethylenediamine produced a polyamide.
Das schwach gelbstichige Polyamid hatte eine rel. Viskosität von 3,0, eine Wärmeformbeständigkeit von 145°C, eine Schlagzähigkeit von 82,4 kJ/m2 (8 Proben nicht gebrochen) und eine Kerbschlagzähigkeit von 4,8 kJ/ml.The slightly yellowish polyamide had a rel. Viscosity of 3.0, a heat resistance of 145 ° C, an impact strength of 82.4 kJ / m 2 (8 samples not broken) and a notched impact strength of 4.8 kJ / m l .
Diese Versuche wurden im 100 g-Maßstab durchgeführt.These tests were carried out on a 100 g scale.
Die Ausgangsmonomeren wurden in definierten Verhältnissen (Molverhältnisse siehe Tabelle 2) eingewogen, das Reaktionsgemisch unter Stickstoffatmosphäre und Rühren langsam auf 200°C erhitzt. Im weiteren Verlauf wurde auf 270°C erhitzt und noch 6 Stunden bei 270°C polykondensiert.The starting monomers were weighed out in defined ratios (for molar ratios see Table 2), the reaction mixture was slowly heated to 200 ° C. under a nitrogen atmosphere and with stirring. In the further course, the mixture was heated to 270 ° C. and polycondensed for a further 6 hours at 270 ° C.
Wie aus den in Tabelle 2 angegebenen Bemerkungen zu den Versuchsergebnissen hervorgeht, konnte wegen zu hoher Festpunkte von niedermolekularen Anteilen in einigen Fällen die Polykondensation nicht zu Ende durchgeführt werden.As can be seen from the comments on the test results given in Table 2, In some cases the polycondensation could not be completed due to the too high fixed points of low molecular weight components.
Claims (5)
are subjected to a polycondensation reaction.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19772732928 DE2732928A1 (en) | 1977-07-21 | 1977-07-21 | TRANSPARENT POLYAMIDE |
| DE2732928 | 1977-07-21 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0000492A1 EP0000492A1 (en) | 1979-02-07 |
| EP0000492B1 true EP0000492B1 (en) | 1982-06-30 |
Family
ID=6014491
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP78100353A Expired EP0000492B1 (en) | 1977-07-21 | 1978-07-11 | Transparent polyamides and their use for the manufacture of moulds |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4205159A (en) |
| EP (1) | EP0000492B1 (en) |
| JP (1) | JPS5422495A (en) |
| DE (2) | DE2732928A1 (en) |
| IT (1) | IT1105909B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0525834Y2 (en) * | 1987-11-06 | 1993-06-29 | ||
| WO2002048239A1 (en) * | 2000-12-11 | 2002-06-20 | Asahi Kasei Kabushiki Kaisha | Polyamide |
| DE10308226A1 (en) | 2003-02-25 | 2004-09-23 | Degussa Ag | Transparent molding compound for optical applications |
| DE102008002599A1 (en) | 2008-06-24 | 2009-12-31 | Evonik Degussa Gmbh | Component with cover layer of a PA613 molding compound |
| US8857733B1 (en) * | 2009-01-14 | 2014-10-14 | Resodyn Corporation | Flameless thermal spray system using flame heat source |
| US9495397B2 (en) | 2013-03-12 | 2016-11-15 | Intel Corporation | Sensor associated data of multiple devices based computing |
| EP3772522B1 (en) | 2019-08-09 | 2023-04-26 | Ems-Chemie Ag | Polyamide moulding compound and its use and moulded bodies produced from the moulding compound |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB760025A (en) * | 1953-11-16 | 1956-10-31 | Ici Ltd | Improvements in or relating to linear polyamides |
| DE1595354C3 (en) | 1966-10-18 | 1978-12-07 | Basf Ag | Process for the production of polyamides |
| NL137599C (en) * | 1968-07-02 | |||
| DE2217016A1 (en) * | 1971-04-12 | 1972-10-26 | Phillips Petroleum Co., Bartlesville, OkIa. (V.StA.) | polyamide |
| US3842045A (en) * | 1972-07-05 | 1974-10-15 | Phillips Petroleum Co | Amorphous polyamides from bis(4-aminocyclohexyl)methane and a mixture of straight chain dicarboxylic acids |
| US3840501A (en) * | 1972-07-05 | 1974-10-08 | Phillips Petroleum Co | Copolyamides of 2,2-bis(4-aminocyclohexyl)propanes and a mixture of alkane dicarboxylic acids |
| US4028476A (en) * | 1974-07-18 | 1977-06-07 | Phillips Petroleum Company | Transparent polyamide armor |
-
1977
- 1977-07-21 DE DE19772732928 patent/DE2732928A1/en not_active Withdrawn
-
1978
- 1978-07-11 DE DE7878100353T patent/DE2861921D1/en not_active Expired
- 1978-07-11 EP EP78100353A patent/EP0000492B1/en not_active Expired
- 1978-07-17 US US05/925,409 patent/US4205159A/en not_active Expired - Lifetime
- 1978-07-20 JP JP8779778A patent/JPS5422495A/en active Granted
- 1978-07-20 IT IT50394/78A patent/IT1105909B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| EP0000492A1 (en) | 1979-02-07 |
| IT1105909B (en) | 1985-11-11 |
| JPS6120579B2 (en) | 1986-05-22 |
| JPS5422495A (en) | 1979-02-20 |
| DE2732928A1 (en) | 1979-02-01 |
| IT7850394A0 (en) | 1978-07-20 |
| DE2861921D1 (en) | 1982-08-19 |
| US4205159A (en) | 1980-05-27 |
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