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EP0000363A1 - Polyamides de haute viscosité, leur procédé de préparation et leur utilisation dans des feuilles et des fibres - Google Patents

Polyamides de haute viscosité, leur procédé de préparation et leur utilisation dans des feuilles et des fibres Download PDF

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Publication number
EP0000363A1
EP0000363A1 EP78100285A EP78100285A EP0000363A1 EP 0000363 A1 EP0000363 A1 EP 0000363A1 EP 78100285 A EP78100285 A EP 78100285A EP 78100285 A EP78100285 A EP 78100285A EP 0000363 A1 EP0000363 A1 EP 0000363A1
Authority
EP
European Patent Office
Prior art keywords
caprolactam
polyamides
salt
melt
films
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.)
Withdrawn
Application number
EP78100285A
Other languages
German (de)
English (en)
Inventor
Claus Dr. Cordes
Hans-Peter Dr. Weiss
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.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP0000363A1 publication Critical patent/EP0000363A1/fr
Withdrawn legal-status Critical Current

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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
    • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
    • C08G69/14—Lactams

Definitions

  • the invention relates to higher-viscosity polyamides which are suitable for extrusion processing and film production.
  • the object of the present invention was to provide highly viscous polyamides based on caprolactam with a melt viscosity of more than 1,500 poise, which do not have the disadvantages described and which can also be produced continuously in simple VK tubes by condensation in the melt.
  • the polyamides can also contain other polyamide-forming monomers condensed in minor amounts.
  • ⁇ -caprolactam 5 to 30 parts by weight of a salt of adipic acid and hexamethylenediamine (AH salt) and / or a salt of terephthalic acid and hexamethylenediamine (TH-salt) used as comonomers to 100 parts by weight '.
  • AH salt hexamethylenediamine
  • TH-salt a salt of terephthalic acid and hexamethylenediamine
  • 0.1 to 2.5 mmol, preferably 0.5 to 1.5 mmol, of NH2-R-NH-R-NH2 are added to the monomeric starting materials per mole of caprolactam.
  • R is a divalent saturated hydrocarbon radical with aliphatic or alicyclic character, preferably with the empirical formula C n H 2n , C m H 2m-4 or C p H 2p-8 , where n is between 2 and 10, m between 6 and 12 and p can be between 13 and 15.
  • Such amines can be prepared by known processes, for example by removing NH 3 from the corresponding diamines in the presence of protons or other catalysts.
  • H 2 N- (CH 2 ) 6 -NH- (CH 2 ) 6 -NH 2 is used as the comonomer according to the invention.
  • the polymerization is carried out by processes known per se, preferably in the presence of small amounts of water, and conventional regulators and catalysts. In the particularly preferred continuous process, the polymerization is carried out in the presence of 0.1 to 3% by weight of water, based on caprolactam, and essentially without pressure or at low negative pressures up to 0.5 bar or at low excess pressures up to 5 bar.
  • the polymerization is preferably carried out in a VK tube according to DT-AS 14 95 198.
  • the comonomers according to the invention can be added, for example, via the caprolactam fed to the VK tube, which may also contain the further comonomers.
  • the VK tube is made, on the one hand, of 100 parts by weight of melted ⁇ -caprolactam, together with the comonomer H 2 N- (CH 2 ) 6 -NH- (CH 2 ) 6 -NH 2 and, on the other hand, 5 to 30 parts by weight of AH Salt and / or TH salt metered in as highly concentrated aqueous solutions or as solid salts.
  • comonomers in solid form in the form of a prepolymer which may contain ⁇ -caprolactam and which preferably has a melting point which is below the reaction temperature prevailing in the VK tube head.
  • a prepolymer of 100 parts by weight of AH salt and / or TH salts and 5 to 100 parts by weight of ⁇ -caprolaetam is metered in.
  • the polymers produced by condensation in the melt by the process according to the invention generally contain extractable fractions of 5 to 15% by weight. After the low molecular weight components have been separated off, for example by extraction with hot water, polyamides with K values (measured according to Fikentscher Cellulosechemie 13, 58 (1932) 0.5% in 96% sulfuric acid) of 66 to 86 are obtained.
  • the melt viscosities of the Products so produced are preferably between 2,000 and 20,000 poise. (Unless otherwise noted, all melt viscosities are measured at 270 ° C measuring temperature in a KV 100 capillary viscometer from Göttfert with a shear rate of 500 sec -1 )
  • the process according to the invention surprisingly provides products without vacuum and post-condensation in the solid phase which are also excellent for the production ner monofilaments and foils.
  • a particular advantage is that production can also be carried out continuously using the cheap and easy-to-use VK pipe process.
  • the polyamides according to the invention have high, uniform and uniform viscosities.
  • the monofilaments and foils made from them are characterized by optical uniformity, are completely free of gel particles and show a surprisingly high level of transparency. The reason for the high transparency is probably the reduced roughness of the film surface due to the surprisingly favorable solidification behavior, which leads to a reduction in the amount of scattered light.
  • ⁇ -caprolactam from 100 parts by weight of ⁇ -caprolactam and 5 to 30 parts by weight of AH salt and / or TH salt as well NH 2 - (CH 2) g 6 -NH- (CH 2) 6 -NH 2 her e-set polyamides are particularly suitable for the production of highly transparent composite films with polyethylene by coextrusion by the blown film.
  • Example 1 100 parts of ⁇ -caprolactam, 13 parts of water, 0.4 part of adipic acid and 0.4 part of NH 2 - (CH 2 ) 6 -NH- (CH 2 ) 6 -NH 2 (1.17 mmol / mol caprolactam) were as condensed in Example 1. After granulation, extraction and drying, the product obtained had a K value of 78 and a melt viscosity of 2,200 poise. It could be perfectly / blown to uniform and speck-free films having a thickness of 100th
  • Example 2 a The procedure was as in Example 2 a) but with the addition of 0, 3 parts of adipic acid and 0.3 parts of NH 2 - (CH 2) 6 -NH- (CH 2) 6 -NH 2 (0.97 mmole / mole of monomer ) condenses. After granulation, extraction and drying, granules with a K value of 79 and a melt viscosity of 3,300 poise were obtained. The product was without further post-condensation, to uniform and speck-free films with a thickness of 100 / blown to.
  • the blow head of this system has three concentrically arranged annular nozzle gaps, the gap widths being 0.7 mm.
  • Each of the three ring nozzle columns is supplied with the material to be processed by its own extruder; the system is operated from top to bottom.
  • the resulting melt-plastic film tube was inflated so far by compressed air that it had a diameter of 300 mm.
  • the three individual layers joined and welded together.
  • the resulting tubular film was cooled, drawn off over a pair of rollers and then wound up.
  • the thicknesses of the individual layers were: polyethylene 0.04 mm, ternary ethylene copolymer 0.02 mm, polyamide 0.02 mm.
  • the composite film made of polyamide according to Example 2 c) was distinguished by its significantly better transparency. Microscopic images showed that films according to polyamide according to example 2 c) compared to those according to example 2 b) have a more uniform morphology of the crystallization and a smoother surface of the polyamide surface.
  • VK pipe head a stirred 1st zone
  • 3 further zones separated by heat exchangers in the cylindrical, non-stirred part.
  • the following temperatures were observed from top to bottom in the individual zones: VK pipe head 256 to 259 ° C, pipe section zone 1: 265 to 267 o C , zone 2: 269 to 271 o C , zone 3 : 249 to 251 ° C.
  • the discharge temperature from the VK pipe was 250 ° C.
  • the L Granulated product was extracted with hot water and 'dried. A K value of 74.1 was then measured.
  • the melt viscosity at 270 ° C was 1,420 poise. The product could not / be blown to blown film of 100 due to its viscosity.
  • the product had to 2 flow are post-condensed for 25 hours at 140 ° C in N. It turned slightly yellowish and the K value rose to 80.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyamides (AREA)
EP78100285A 1977-07-16 1978-06-30 Polyamides de haute viscosité, leur procédé de préparation et leur utilisation dans des feuilles et des fibres Withdrawn EP0000363A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19772732329 DE2732329A1 (de) 1977-07-16 1977-07-16 Hoeherviskose polyamide
DE2732329 1977-07-16

Publications (1)

Publication Number Publication Date
EP0000363A1 true EP0000363A1 (fr) 1979-01-24

Family

ID=6014170

Family Applications (1)

Application Number Title Priority Date Filing Date
EP78100285A Withdrawn EP0000363A1 (fr) 1977-07-16 1978-06-30 Polyamides de haute viscosité, leur procédé de préparation et leur utilisation dans des feuilles et des fibres

Country Status (5)

Country Link
EP (1) EP0000363A1 (fr)
JP (1) JPS5420096A (fr)
DE (1) DE2732329A1 (fr)
DK (1) DK315778A (fr)
IT (1) IT1105250B (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3917927A1 (de) * 1988-06-07 1989-12-14 Inventa Ag Thermoplastisch verarbeitbare polyamide
WO2003106171A1 (fr) * 2002-06-12 2003-12-24 Dsm Ip Assets B.V. Procede pour produire un film plan multicouche contenant un polyamide a ramification aleatoire, intrinsequement depourvu de gel
WO2004005026A1 (fr) * 2002-07-09 2004-01-15 Dsm Ip Assets B.V. Procede pour appliquer une couche de polyamide ramifie sur un substrat

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1078949A1 (fr) 1999-08-26 2001-02-28 Bayer Aktiengesellschaft Ramification de polyamides à l'aide d'esters d'acide carboxylique
US20180201732A1 (en) * 2017-01-18 2018-07-19 Sabic Global Technologies B.V. Dynamic Cross-Linked Poly (Amides) Prepared Via The Incorporation Of Polyamines/Ammonium Salts In The Solid State

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR860533A (fr) * 1938-09-30 1941-01-24 Du Pont Procédé de préparation de polyamides synthétiques linéaires
FR2003370A1 (fr) * 1968-03-07 1969-11-07 Allied Chem

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR860533A (fr) * 1938-09-30 1941-01-24 Du Pont Procédé de préparation de polyamides synthétiques linéaires
FR2003370A1 (fr) * 1968-03-07 1969-11-07 Allied Chem

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, Vol.71, Nr. 24, 15.Dezember 1969, 113472q, "Viscocity stabilization of polycaprolactam", Yamamoto, Ichisuke,Teijin Ltd. & JP-B-44 019 264 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3917927A1 (de) * 1988-06-07 1989-12-14 Inventa Ag Thermoplastisch verarbeitbare polyamide
WO2003106171A1 (fr) * 2002-06-12 2003-12-24 Dsm Ip Assets B.V. Procede pour produire un film plan multicouche contenant un polyamide a ramification aleatoire, intrinsequement depourvu de gel
KR100936838B1 (ko) * 2002-06-12 2010-01-14 디에스엠 아이피 어셋츠 비.브이. 본질적으로 겔이 없는 랜덤 분지쇄형 폴리아미드를함유하는 다층 평판 필름의 제조 방법
WO2004005026A1 (fr) * 2002-07-09 2004-01-15 Dsm Ip Assets B.V. Procede pour appliquer une couche de polyamide ramifie sur un substrat
CN100482463C (zh) * 2002-07-09 2009-04-29 帝斯曼知识产权资产管理有限公司 在基材上涂覆支化聚酰胺层的方法

Also Published As

Publication number Publication date
DK315778A (da) 1979-01-17
DE2732329A1 (de) 1979-02-01
JPS5420096A (en) 1979-02-15
IT1105250B (it) 1985-10-28
IT7850210A0 (it) 1978-07-07

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Inventor name: WEISS, HANS-PETER, DR.

Inventor name: CORDES, CLAUS, DR.