EP0000492A1 - Polyamides transparents et leur application à la fabrication d'objets moulés - Google Patents

Polyamides transparents et leur application à la fabrication d'objets moulés Download PDF

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Publication number
EP0000492A1
EP0000492A1 EP78100353A EP78100353A EP0000492A1 EP 0000492 A1 EP0000492 A1 EP 0000492A1 EP 78100353 A EP78100353 A EP 78100353A EP 78100353 A EP78100353 A EP 78100353A EP 0000492 A1 EP0000492 A1 EP 0000492A1
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EP
European Patent Office
Prior art keywords
mol
bis
methane
acid
aminocyclohexyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP78100353A
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German (de)
English (en)
Other versions
EP0000492B1 (fr
Inventor
Rolf-Volker Dr. Meyer
Rolf Dr. Dhein
Friedrich Fahnler
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
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Bayer AG
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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 prepared 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 DOS 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 (US Pat. No. 2,585,163) are either not transparent or tend to recrystallize and thus cloud.
  • DOS 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.
  • DOS 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 they have an unsatisfactory heat resistance at only 130 ° C.
  • 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 processed without difficulty into thermoplastic molded articles with high heat resistance, good toughness level and good resistance to solvents.
  • copolyamides which are obtained as the sole diamine component by polycondensation of 85 to 70 mol% azelaic acid and 15 to 30 mol% isophthalic acid or adipic acid and an equivalent amount of bis- (4-amino-cyclohexyl) methane.
  • 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 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 2300C and pre-condensed 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% strength 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 h at 270 ° C.
  • the resulting almost colorless polyamide ( ⁇ rel 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%.
  • Example 1 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 a polyamide.
  • the slightly yellowish polyamide had a rel. Viscosity of 3.0, heat resistance of 145 ° C, impact strength of 82.4 kJ / m 2 (8 samples not broken) and notched impact strength of 4.8 k J / m 2 .
  • the starting monomers were weighed in defined ratios (mol ratios see Table 2), the The reaction mixture is 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.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyamides (AREA)
EP78100353A 1977-07-21 1978-07-11 Polyamides transparents et leur application à la fabrication d'objets moulés Expired EP0000492B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19772732928 DE2732928A1 (de) 1977-07-21 1977-07-21 Transparente polyamide
DE2732928 1977-07-21

Publications (2)

Publication Number Publication Date
EP0000492A1 true EP0000492A1 (fr) 1979-02-07
EP0000492B1 EP0000492B1 (fr) 1982-06-30

Family

ID=6014491

Family Applications (1)

Application Number Title Priority Date Filing Date
EP78100353A Expired EP0000492B1 (fr) 1977-07-21 1978-07-11 Polyamides transparents et leur application à la fabrication d'objets moulés

Country Status (5)

Country Link
US (1) US4205159A (fr)
EP (1) EP0000492B1 (fr)
JP (1) JPS5422495A (fr)
DE (2) DE2732928A1 (fr)
IT (1) IT1105909B (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014163799A1 (fr) 2013-03-12 2014-10-09 Intel Corporation Données associées à des capteurs pour informatique basée sur plusieurs dispositifs
US20150182989A1 (en) * 2009-01-14 2015-07-02 Resodyn Corporation Flameless thermal spray system using flame heat source

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0525834Y2 (fr) * 1987-11-06 1993-06-29
US6936682B2 (en) * 2000-12-11 2005-08-30 Asahi Kasei Kabushiki Kaisha Polyamide
DE10308226A1 (de) 2003-02-25 2004-09-23 Degussa Ag Transparente Formmasse für optische Anwendungen
DE102008002599A1 (de) 2008-06-24 2009-12-31 Evonik Degussa Gmbh Bauteil mit Deckschicht aus einer PA613-Formmasse
FR3086946B1 (fr) * 2018-10-03 2021-06-25 Arkema France Procede ameliore pour la fabrication de polyamides transparents
EP3772522B1 (fr) 2019-08-09 2023-04-26 Ems-Chemie Ag Matière de moulage de polyamide et son utilisation ainsi que corps moulé fabriqué à partir de la matière de moulage

Citations (6)

* Cited by examiner, † Cited by third party
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
FR2012193A1 (fr) * 1968-07-02 1970-03-13 Toyo Rayon Co Ltd
DE2217016A1 (de) * 1971-04-12 1972-10-26 Phillips Petroleum Co., Bartlesville, OkIa. (V.StA.) Polyamid
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
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
US4028476A (en) * 1974-07-18 1977-06-07 Phillips Petroleum Company Transparent polyamide armor

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1595354C3 (de) 1966-10-18 1978-12-07 Basf Ag Verfahren zur Herstellung von Polyamiden

Patent Citations (6)

* Cited by examiner, † Cited by third party
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
FR2012193A1 (fr) * 1968-07-02 1970-03-13 Toyo Rayon Co Ltd
DE2217016A1 (de) * 1971-04-12 1972-10-26 Phillips Petroleum Co., Bartlesville, OkIa. (V.StA.) Polyamid
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
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
US4028476A (en) * 1974-07-18 1977-06-07 Phillips Petroleum Company Transparent polyamide armor

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150182989A1 (en) * 2009-01-14 2015-07-02 Resodyn Corporation Flameless thermal spray system using flame heat source
WO2014163799A1 (fr) 2013-03-12 2014-10-09 Intel Corporation Données associées à des capteurs pour informatique basée sur plusieurs dispositifs

Also Published As

Publication number Publication date
DE2732928A1 (de) 1979-02-01
DE2861921D1 (en) 1982-08-19
JPS5422495A (en) 1979-02-20
US4205159A (en) 1980-05-27
JPS6120579B2 (fr) 1986-05-22
IT1105909B (it) 1985-11-11
IT7850394A0 (it) 1978-07-20
EP0000492B1 (fr) 1982-06-30

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