WO1999061509A1 - Synthese de polyphtalamides semi-cristallins par extrusion reactive d'oligomere de terephtalamide d'hexamethylene avec des polyamides semi-cristallins ou amorphes a bas point de fusion - Google Patents

Synthese de polyphtalamides semi-cristallins par extrusion reactive d'oligomere de terephtalamide d'hexamethylene avec des polyamides semi-cristallins ou amorphes a bas point de fusion Download PDF

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Publication number
WO1999061509A1
WO1999061509A1 PCT/CA1999/000415 CA9900415W WO9961509A1 WO 1999061509 A1 WO1999061509 A1 WO 1999061509A1 CA 9900415 W CA9900415 W CA 9900415W WO 9961509 A1 WO9961509 A1 WO 9961509A1
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oligomer
semi
crystalline
acid
aliphatic
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PCT/CA1999/000415
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English (en)
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WO1999061509B1 (fr
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Christian Leboeuf
David Alan Harbourne
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E.I. Du Pont De Nemours And Company
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Publication of WO1999061509A1 publication Critical patent/WO1999061509A1/fr
Publication of WO1999061509B1 publication Critical patent/WO1999061509B1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C08G69/28—Preparatory processes
    • 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
    • C08G69/04—Preparatory processes
    • 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
    • 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

  • This invention provides a flexible and economical process for the synthesis of semi-crystalline polyphthalamides through reactive extrusion of 6T oligomer with lower melting, semi-crystalline polyamides.
  • 6T/6I copolymer of hexamethylene diamine, terephthalic acid and isophthalic acid 6T/6I/66 terpolymer of hexamethylene diamine, terephthalic acid, isophthalic acid and adipic acid
  • 300°C can be made by a single step synthesis process using autoclaves (A/C).
  • the A/C process is more or less limited to copolymers containing 50 mole% 6T or less because of phase boundary considerations under which high temperatures and pressures are required for processability. These A/C processing conditions usually result in long exposure to high temperatures, thus leading to polymer degradation.
  • 6T/6I/66 [65/25/10], 6T/66 [65/35], 6T/6 [70/30] offer an attractive balance of properties, to a great extent linked to the higher level of 6T content.
  • Those competitive, higher 6T-based polymers can only be manufactured by a 2-step or 2-stage process involving overall much shorter heat histories than those typical of A/C synthesis.
  • Hei 4-53827 and Hei 4-53825 describe a 2-step process involving, as first step, the synthesis of an amine-rich (or acid rich) oligomer, which is further polymerized in the melt using an extruder.
  • An A/C reactor e.g. one which is used primarily for the batch synthesis of PA66
  • PA66 PA66
  • Japanese patent applications Kokai 3-296528, Hei 5-43681, European patent application No. EP 0744431 A2 describe a 2-step process involving, as first step, the synthesis of an essentially balanced oligomer which is further polymerized in the melt using an extruder.
  • An A/C reactor e.g. one which is used primarily for the batch synthesis of PA66
  • the oligomer' s intrinsinc viscosity is typically 0.15 dL/g and it is finished to a polymer of IV > 1.0 dL/g by extrusion on a T/S extruder with vented barrel sections.
  • Application to the synthesis of 6T/66 or 6T/6I copolymers, up to 100 mole% 6T, is claimed.
  • US patents Nos. 4,970,255 and 5,200,450 describe a process by which a superatmospheric salt solution is passed through a vaporization zone to yield a prepolymer which in turn is passed through a polycondensation zone, after which it is continuously removed from the polycondensation zone.
  • the polyamide thus obtained is passed as a liquid melt through a discharge zone with simultaneous removal of the residual water present in the melt.
  • a suitable discharge zone is for example a devolatilizing extruder.
  • Key to good polymer quality i.e. low triamine content
  • is short residence time ( ⁇ 60 sec) in the vaporizer, and the conversion at the exit of the evaporator zone is preferably
  • the present invention provides a process for the synthesis of semi- crystalline polyphthalamides of general formula 6T/y, wherein 6T represents units of hexamethylene terephthalamide and y represents units of other polyamide forming monomers, in which the proportion of 6T to y is increased by the steps of:
  • step B reacting in a reactive extruder the product of step A with further amounts of 6T oligomer to increase the proportions of 6T to y to the range of 55/45 to 99/1.
  • the present invention provides a process which comprises reactive extrusion of a 6T-based oligomer of inherent viscosity ⁇ 0.3 dL/g or of free amine ends and carboxyl ends essentially > 2000 equivalent/million grams of polymer, with a low-6T containing semi-crystalline polyphthalamide or other semi- crystalline polyamide to yield a high temperature high 6T-containing polyphthalamide, (i.e. 6T > 50 mole%) of inherent viscosity > 0.9 dL/g, and of residual free amine ends and carboxyl ends ⁇ 200 equivalents per million grams of polymer.
  • the 6T-based oligomer may be the homopolymer oligomer of hexamethylene diamine and terephthalic acid (6T).
  • composition of the 6T- based oligomer may be 6T/x, where x is a repeat unit composed of hexamethylene diamine and an aliphatic or aromatic dicarboxylic acid of 6 to 18 carbon atoms, or ⁇ -caprolactam.
  • the low 6T- containing semi-crystalline or amorphous polyphthalamide, or semi-crystalline polyamide may be a copolymer consisting of at least hexamethylene diamine, terephthalic acid, with either i) one or two additional aromatic or aliphatic dicarboxylic acids of 6 to 18 carbons, or ii) one or two additional aromatic or aliphatic diamines of 6 to 18 carbons , or iii) one aliphatic or aromatic diamine of 6 to 18 carbons and one aliphatic or aromatic dicarboxylic acid of 6 to 18 carbons, or iv) an ⁇ , ⁇ -amino acid of 6 to 18 carbons or its cyclic lactam.
  • the 6T oligomer may be obtained in powder form by a process comprising a) adding to an autoclave reactor an admixture of hexamethylene diamine, terephthalic acid and water equivalent to a 50-65 wt% hexamethylene terephthalamide salt solution in water, and in which there is excess diamine; b) heating the mixture under agitation to remove entrained oxygen; c) subsequently heating the reaction mixture to a higher temperature under pressure; d) maintaining the mixture under pressure and allowing volatile matter to vent; e) discharging the mixture by spray drying; f) collecting the oligomer powder and allowing separation of steam from the solids to yield an oligomer powder of low residual moisture.
  • the oligomer may be either 6T or 6T/y, where y is hexamethylene adipamide.
  • the oligomer is 6T. DETAILED DESCRIPTION OF THE INVENTION
  • the process of this invention involves the use of conventional stirred autoclaves for independent synthesis of (1) a 6T oligomer powder and (2) 6T- based copolymers or terpolymers finished to IV > 0.90 dL/g and having a 6T content no higher than 50 mole%.
  • the 6T oligomer and 6T-based polymers having a low 6T molar content are subsequently "coupled" during extrusion on a T/S extruder, in the presence of a coupling catalyst such as TPP (triphenyl phosphite) or SHP (sodium hypophosphite).
  • TPP triphenyl phosphite
  • SHP sodium hypophosphite
  • One additional advantage of this invention over the conversion of oligomers to finished polymer via finishing on T/S extruders is the significant reduction in moisture removal requirement, which originates only from the coupling reaction of the 6T oligomer to the main polymer chain.
  • this process is applicable to the synthesis of high temperature polyphthalamides such as, but not limited to: 6T/66 (copolymer of hexamethylene diamine, adipic acid and terephthalic acid), 6T/6 (copolymer of hexamethylene diamine, terephthalic acid and ⁇ -caprolactam), 6T/DT (copolymer of hexamethylene diamine, 2-methyl pentamethylene diamine and terephthalic acid), 6T/612 (copolymer of hexamethylene diamine, terephthalic acid and dodecanedioic acid), 6T/6I (copolymer of hexamethylene diamine, terephthalic acid and isophthalic acid), and 6T/6I
  • the final polymer composition is achieved through the extrusion finishing of an oligomer (e.g. 6T), and a semi- crystalline polyamide of inherent viscosity (IV) > 0.90 dL/g, as measured from a solution of 0.5g/L polymer in m-cresol at 25°C.
  • an oligomer e.g. 6T
  • a semi- crystalline polyamide of inherent viscosity (IV) > 0.90 dL/g as measured from a solution of 0.5g/L polymer in m-cresol at 25°C.
  • oligomer, nor the polyamide is of the composition of the target polymer.
  • oligomers or low order condensates which are converted to a high MW polymer by extrusion finishing on twin-screw (T/S) extruders are of the same monomeric composition as the final polymer.
  • the 6T oligomer of this invention has a very low MW (300 - 600). Both the 6T oligomer and the low 6T-based polymer of our invention are essentially balanced, i.e. NH 2 and CO 2 H ends are close in value.
  • the 6T oligomer powder may be obtained by a process comprising: a) adding to an autoclave reactor an admixture of hexamethylene diamine, terephthalic acid and water equivalent to a 65 wt% hexamethylene terephthalamide salt solution in water, and in which there is 2-4 mole% excess diamine; b) heating the mixture under mechanical agitation to a temperature of approximately 130degC and venting vapors for 5 minutes to remove entrained oxygen; c) subsequently heating the reaction mixture to 226degC at an autogenous pressure of 2.20 MPa; d) with the vessel pressure maintained at 2.20 MPa, venting the volatile matter up to a melt temperature of 240degC over a period of approximately 65 minutes; e) then closing the autoclave reactor's pressure control valve and discharging the reactor through a spray drying nozzle, using the autoclave's internal steam pressure; f) collecting the oligomer powder in a sufficiently large enclosure to allow separation of steam from
  • Example A Synthesis of 6T/DT (60/40 molar ratio), from reactive extrusion of 6T/DT (50/50 molar ratio) 80 wt% with 6T oligomer, 20 wt%.
  • Example B Synthesis of 6T/DT (50/50 molar ratio) from reactive extrusion of 6T/DT (30/70 molar ratio), at 70 wt%, with 6T oligomer, at 30 wt%.
  • Example C Synthesis of 6T/66 (50/50 molar ratio) from reactive extrusion of 6T/66 (38/62 molar ratio), 80 wt%, with 6T oligomer, 20 wt%.
  • Example D Synthesis of 6T/66 (65/35 molar ratio) from reactive extrusion of 6T/66 (55/45molar ratio), 80 wt%, with 6T oligomer, 20 wt%.
  • these examples reflect the fact that 20 - 30 wt% 6T oligomer powder can be conventionally compounded with 6T-based polymers (low 6T content) in a single pass. In that fashion, the 6T content of a variety of autoclave produced polymers, not limited to the examples cited above, can be increased beyond the level practical with an autoclave process.
  • Additives and reinforcements may be added at the reactive extrusion stage. This offers the additional advantage of accomplishing reactive extrusion and compounding with filler and/or other reinforcing materials and/or additives in a single step.
  • a 12 liter reaction vessel equipped with a helical ribbon agitator and a thermowell to measure reaction temperature was charged with 1907g (16.44 moles) of hexamethylene diamine as a 77.67% (wt) aqueous solution (2393g of solution), 2659g terephthalic acid (16.02 moles), 3.94g of a 1% water emulsion of Dow Corning B antifoam, and 1800g of demineralized water.
  • the reactor agitator rotating at 50 rpm the mixture was heated to 130°C and then vented to remove entrained oxygen. Subsequently, the reaction mixture was heated to 226°C at an autogenous pressure of 320 psig.
  • the oligomer thus obtained had an inherent viscosity (IV) of 0.17 dL/g; in these instances, inherent viscosity was measured on a 0.5g/L solution in m-Cresol at 25°C.
  • the oligomer had a melting point of 356°C, as measured by differential scanning calorimetry (DSC; ASTM D3418) from the remelt curve.
  • the DSC showed also a fairly broad melting peak at about 276°C, which is evidence of the presence of unreacted salt.
  • the oligomer was dried overnight at 85°C, under nitrogen, then used in reactive extrusion runs on a co-rotating non-intermeshing twin-screw extruder.
  • the reaction mixture was heated to 232°C.
  • the vessel pressure maintained at 1.71 MPa, volatile matter was vented over a period of 43 minutes up to a melt temperature of 275°C.
  • the pressure in the reactor was then reduced to atmospheric pressure over a period of 48 minutes, the temperature of the reaction mixture rising to 320°C; the rate of agitation was reduced to 5 rpm when the temperature had reached 318°C.
  • the reaction mixture obtained was maintained under a vacuum (pressure reduction) of 40 kPa for 15 minutes.
  • the polymer obtained was then discharged from the reactor and quenched in a water bath.
  • the copolyamide obtained had an inherent viscosity (IV) of 0.98 dL/g; in this instance, inherent viscosity was measured on a 0.5g/L solution in concentrated sulfuric acid at 25°C.
  • the polymer had a melting point of 301°C, as measured by differential scanning calorimetry (DSC).
  • a 12 liter reaction vessel equipped with a helical ribbon agitator and a thermowell to measure reaction temperature was charged with 585g (5.05 moles) of hexamethylene, 1392g of 2-methyl pentamethylene diamine (12.00 moles), 2659g terephthalic acid (16.01 moles), 3.94g of a 25% aqueous solution of sodium hypophosphite, 7.88g of a 1 % water emulsion of Dow Corning B antifoam, and 1200g of demineralized water.
  • the reactor agitator rotating at 50 rpm, the mixture was heated to 130°C and then vented to remove entrained oxygen.
  • the reaction mixture was heated to 231°C, at an autogenous pressure of 265 psig. With the vessel pressure maintained at 265 psig, volatile matter was vented over a period of 99 minutes up to a melt temperature of 280°C. The pressure in the reactor was then reduced to atmospheric pressure over a period of 40 minutes, the temperature of the reaction mixture rising to 296°C. The reaction mixture obtained was at atmospheric pressure for 10 minutes, while the melt temperature was maintained essentially constant. The polymer obtained was then discharged from the reactor and quenched in a water bath over a period of 73 minutes; the final melt temperature was 301°C.
  • the copolyamide obtained had an inherent viscosity (IV) of 0.97 dL/g; in this instance, inherent viscosity was measured on a 0.5g/L solution in m-Cresol at 25°C.
  • the polymer had a melting point of 244°C, as measured by differential scanning calorimetry (DSC).
  • a 12 liter reaction vessel equipped with a helical ribbon agitator and a thermowell to measure reaction temperature was charged with 1959g (16.888 moles) of hexamethylene diamine, 1118g terephthalic acid (6.735 moles), 1475g of adipic acid (10.103 moles), 0.79g of a 25% aqueous solution of sodium hypophosphite, 0.26g of a 25% solution of Carbowax 3350 in water and 1500g of demineralized water.
  • the reactor agitator rotating at 50 rpm, the mixture was heated to 130°C and then vented to remove entrained oxygen. Subsequently, the reaction mixture was heated to 221°C, at an autogenous pressure of 275 psig.
  • the vessel pressure maintained at 275 psig, volatile matter was vented over a period of 117 minutes up to a melt temperature of 274°C.
  • the pressure in the reactor was then reduced to atmospheric pressure over a period of 57 minutes, the temperature of the reaction mixture being at 298°C.
  • the reaction mixture obtained was maintained at atmospheric pressure for 2 minutes, while the melt temperature was maintained essentially constant.
  • the polymer obtained was then discharged from the reactor and quenched in a water bath over a period of 54 minutes; the final melt temperature was 307°C.
  • the copolyamide obtained had an inherent viscosity (IV) of 1.30 dL/g; in this instance, inherent viscosity was measured on a 0.5g/L solution in m-Cresol at 25°C.
  • Example A Synthesis of 6T/DT (60/40), from reactive extrusion of 6T/DT (50/50) 80 wt% with 6T oligomer, 20 wt%.
  • Screw pee s rpm Throughput: 10 lb/hr
  • the preblended mixture of polymer pellets/oligomer powder (80/20 weight ratio) was directly charged into the hopper and fed at the feed zone of the extruder (zone 1).
  • the temperature of the first zone of the extruder is kept at 490°F to prevent the oligomer powder from reacting too quickly and giving off steam which causes the oligomer powder to bridge at the feed port.
  • Example B Synthesis of 6T/DT (50/50) from reactive extrusion of 6T/DT (30/70), at 70 wt%, with 6T oligomer, at 30 wt%.
  • the preblended mixture of polymer pellets/oligomer powder (70/30 weight ratio) was directly charged into the hopper and fed at the feed zone of the extruder (zone 1).
  • the temperature of the first zone of the extruder is kept at 490°F to prevent the oligomer powder from reacting too quickly and giving off steam which causes the oligomer powder to bridge at the feed port.
  • Bl 6T/DT (30/70) as prepared B2: 6T/DT (30/70), single pass on extruder B3 : 6T/DT (30/70) + 6T oligomer (70/30 wt ratio) - single pass B4: 6T/DT (30/70) + 6T oligomer (70/30 wt ratio) - double pass B5: 6T/DT (30/70) + 6T oligomer (70/30 ratio) + 0.5% TPP catalyst single pass at 290rpm
  • Example C Synthesis of 6T/66 (50/50 molar ratio) from reactive extrusion of
  • 6T/66 38/62 molar ratio
  • 6T oligomer 20 wt%
  • Screw pee s rpm Throughput: 10 lb/hr
  • the preblended mixture of 6T/66 (38/62) polymer pellets/oligomer powder (80/20 weight ratio) was directly charged into the hopper and fed at the feed zone of the extruder (zone 1).
  • the temperature of the first zone of the extruder is kept at 490°F to prevent the oligomer powder from reacting too quickly and giving off steam which causes the oligomer powder to bridge at the feed port.
  • Example D Synthesis of 6T/66 (65/35 molar ratio) from reactive extrusion of
  • 6T/66 55/45molar ratio
  • 6T oligomer 20 wt%
  • the preblended mixture of 6T/66 (55/45) polymer pellets/oligomer powder (80/20 weight ratio) was directly charged into the hopper and fed at the feed zone of the extruder (zone 1).
  • the temperature of the first zone of the extruder is kept at 490°F to prevent the oligomer powder from reacting too quickly and giving off steam which causes the oligomer powder to bridge at the feed port.

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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)

Abstract

Cette invention concenre la synthèse de polyphtalamides semi-cristallins (c'est-à-dire contenant des unités monomères d'acide téréphtalique et d'hexaméthylène diamine) par extrusion réactive d'oligomère de téréphtalamide d'hexaméthylène ou de l'oligomère d'un autre copolymère riche en 6T, avec des polyamides semi-cristallins ou amorphes à bas point de fusion. Ce procédé est particulièrement utile du fait qu'il est fondé sur l'utilisation d'autoclaves à agitation pour effectuer la synthèse de l'oligomère 6T et des polyamides semi-cristallins ou amorphes qui sont ensuite combinés dans une extrudeuse à deux vis équipée pour extraire les substances volatiles de l'eau de réaction. Le procédé de cette invention peut également être utilisé pour modifier des polyamides semi-cristallins ou amorphes qui existent déjà (mais pas nécessairement des phtalamides) avec de faibles taux de 6T.
PCT/CA1999/000415 1998-05-21 1999-05-21 Synthese de polyphtalamides semi-cristallins par extrusion reactive d'oligomere de terephtalamide d'hexamethylene avec des polyamides semi-cristallins ou amorphes a bas point de fusion WO1999061509A1 (fr)

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US8262298A 1998-05-21 1998-05-21
US09/082,622 1998-05-21

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WO1999061509B1 WO1999061509B1 (fr) 1999-12-29

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20150037914A (ko) * 2012-07-27 2015-04-08 셋업 퍼포먼스 반응성 압출에 의한 폴리아미드의 제조 방법, 및 그러한 방법을 적용하도록 채택된 압출기
WO2019067517A1 (fr) 2017-09-28 2019-04-04 E. I. Du Pont De Nemours And Company Procédé de polymérisation
PL423004A1 (pl) * 2017-09-29 2019-04-08 Grupa Azoty Spółka Akcyjna Sposób wytwarzania poliftalamidów

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EP0364376A1 (fr) * 1988-10-13 1990-04-18 Rhone-Poulenc Chimie Procédé de préparation de polyamides amorphes à base d'acides dicarboxyliques aromatiques et de diamines aliphatiques
JPH0718072A (ja) * 1993-05-06 1995-01-20 Toray Ind Inc ポリアミド樹脂の製造方法
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EP0744431A2 (fr) * 1995-05-24 1996-11-27 Mitsui Petrochemical Industries, Ltd. Procédé pour la préparation de polyamide aromatique
US5708125A (en) * 1994-07-14 1998-01-13 Ems-Inventa Ag Process for producing precondensates of partially crystalline or amorphous, thermoplastically processable, partially aromatic polyamides or copolyamides

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EP0364376A1 (fr) * 1988-10-13 1990-04-18 Rhone-Poulenc Chimie Procédé de préparation de polyamides amorphes à base d'acides dicarboxyliques aromatiques et de diamines aliphatiques
JPH0718072A (ja) * 1993-05-06 1995-01-20 Toray Ind Inc ポリアミド樹脂の製造方法
JPH07188409A (ja) * 1993-12-28 1995-07-25 Toray Ind Inc ポリアミド樹脂の製造方法
US5708125A (en) * 1994-07-14 1998-01-13 Ems-Inventa Ag Process for producing precondensates of partially crystalline or amorphous, thermoplastically processable, partially aromatic polyamides or copolyamides
EP0744431A2 (fr) * 1995-05-24 1996-11-27 Mitsui Petrochemical Industries, Ltd. Procédé pour la préparation de polyamide aromatique

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Title
PATENT ABSTRACTS OF JAPAN vol. 199, no. 504 31 May 1995 (1995-05-31) *
PATENT ABSTRACTS OF JAPAN vol. 199, no. 510 30 November 1995 (1995-11-30) *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20150037914A (ko) * 2012-07-27 2015-04-08 셋업 퍼포먼스 반응성 압출에 의한 폴리아미드의 제조 방법, 및 그러한 방법을 적용하도록 채택된 압출기
US9453107B2 (en) 2012-07-27 2016-09-27 Setup Performance Method for preparing a polyamide by reactive extrusion, and extruder adapted for the implementation of such a method
KR102073076B1 (ko) 2012-07-27 2020-02-04 셋업 퍼포먼스 반응성 압출에 의한 폴리아미드의 제조 방법, 및 그러한 방법을 적용하도록 채택된 압출기
WO2019067517A1 (fr) 2017-09-28 2019-04-04 E. I. Du Pont De Nemours And Company Procédé de polymérisation
US11505649B2 (en) 2017-09-28 2022-11-22 Dupont Polymers, Inc. Polymerization process
PL423004A1 (pl) * 2017-09-29 2019-04-08 Grupa Azoty Spółka Akcyjna Sposób wytwarzania poliftalamidów

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