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WO2015057557A1 - Procédé de préparation de terpolyamide semi-aromatique - Google Patents

Procédé de préparation de terpolyamide semi-aromatique Download PDF

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Publication number
WO2015057557A1
WO2015057557A1 PCT/US2014/060247 US2014060247W WO2015057557A1 WO 2015057557 A1 WO2015057557 A1 WO 2015057557A1 US 2014060247 W US2014060247 W US 2014060247W WO 2015057557 A1 WO2015057557 A1 WO 2015057557A1
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WIPO (PCT)
Prior art keywords
aromatic
semi
terpolyamide
psia
mole
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PCT/US2014/060247
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English (en)
Inventor
Annakutty Mathew
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EIDP Inc
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EI Du Pont de Nemours and Co
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Publication of WO2015057557A1 publication Critical patent/WO2015057557A1/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
    • C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, 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
    • C08G69/04—Preparatory processes

Definitions

  • the present invention relates to a process for making a semi-aromatic terpolyamide.
  • Polyamides having melting points of 290 °C or higher (high melting polyamides) are very desirable for injection molded articles that may experience high temperatures under normal operation. Such applications include many under hood- applications in the automotive area.
  • high temperature polyamides is using a copolymer comprising repeat units of poly(hexamethylene terephthaiamide/ hexamethyiene isophthalamide) (PA6T/6I), and adjusting the 81 repeat unit concentration to obtain the desired melting point and crystallinity.
  • PA6T/6I poly(hexamethylene terephthaiamide/ hexamethyiene isophthalamide)
  • US 3,787,373 discloses a process for providing PA 6T/6I/6 in various weight per cents of repeat units, but with high levels of ⁇ -caprolactam providing terpolymers with melting points less than 280 °C.
  • EP 0592996 discloses processes, including an autoclave process, for providing PA 6T/6I/6 in various weight per cents of repeat units.
  • the autoclave process did not include two constant pressure stages and did not provide a polymer demonstrated to be extrudabie through a die.
  • US 8,324,307 discloses high melting polyamides including PA 6T/6I/6 in various weight per cents of repeat units and recommends a one-step batch process, described in US 3,843,61 1 and US 3,839,296, for their manufacture.
  • US 1 ,528,329 discloses PA 6T/6I/66 terpolyamides prepared in a one-step constant pressure process.
  • JP 2012-122066 discloses terpolyamides including PA 8T/8I/8.
  • a process for making 6T/6I/6 semi-aromatic terpolyamide comprising: a) charging a reactor with a polymerization salt mixture comprising water, a1 ) 55 to 62 mole % hexamethylene diammonium terephthalate, a2) 13 to 29 mole % hexamethylene diammonium isophthalate, and a3) 9 to 28 mole % ⁇ -caprolactam, wherein the sum of a1 ), a2) and a3) equals 100 mole % of polymer components;
  • b) heating said polymerization mixture, in at least two constant pressure stages comprising: b1 ) first heating with venting of volatiles at a first constant pressure of 180 psia to 285 psia to a temperature of 225 °C to 240 °C; followed by b2) second heating and venting of volatiles at a second constant pressure of 320 psia to 450 psia to a temperature of 285 °C to 310 °C; followed by
  • terpolyamide made by any of the processes of the invention.
  • Figure 1 illustrates a batch process profile for the process of the invention including two constant pressure stages.
  • the terms “comprises,” “comprising,” “includes,” “including,” “containing,” “characterized by,” “has,” “having” or any other variation thereof, are intended to cover a non-exclusive inclusion.
  • a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
  • the semi-aromatic terpolyamides consists essentially of the ranges of repeat units, including the stated preferences, as disclosed above.
  • the term as applied to the semi-aromatic terpolyamides means the semi-aromatic terpolyamides includes the repeat units 6T/6I/6, and may include additional repeat units in small amounts, so long as the additional repeat units do not materially affect the basic and novel properties of the invention.
  • the basic properties of the semi-aromatic terpolyamides include a melting point of at least 290 °C, preferably in the range of 290 °C to 320 °C and more preferably 290 °C and 310 °C; and preferably a melt viscosity in the range of 80 Pa-s to 160 Pa-s; and, independently a
  • Additional repeat units in small amounts means less than 5 mole percent repeat units, and preferably, less than 3 mole percent, less than 2 mole percent, and 1 mole percent or less, other than 6T/6I/6.
  • compositions, a process, a structure, or a portion of a composition, a process, or a structure is described herein using an open-ended term such as "comprising,” unless otherwise stated the description also includes an embodiment that "consists essentially of or “consists of the elements of the composition, the process, the structure, or the portion of the composition, the process, or the structure.
  • substantially free refers to a composition that includes no more than an adventitious amount of the component. Stated alternatively, the composition includes no added amount of the component, only the amount that is commonly present in the raw materials from which the composition is produced. In some commercially available materials, the level of adventitious components is less than less than 2.5%, 1 .0%, less than 0.5%, or less than 0.1 % by weight, based on the weight of the
  • ranges set forth herein include their endpoints unless expressly stated otherwise.
  • an amount, concentration, or other value or parameter is given as a range, one or more preferred ranges or a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether such pairs are separately disclosed.
  • the scope of the invention is not limited to the specific values recited when defining a range.
  • melting points are as determined with differential scanning calorimetry (DSC) at a scan rate of 10 °C/min in the first heating scan, wherein the melting point is taken at the maximum of the endothermic peak.
  • the process for making 6T/6I/6 semi-aromatic terpo!yamide disclosed herein provides polyamide resins having a high melting point, in the range of 290 °C to 320 °C, preferably 290 °C to 310 °C. as determined with differential scanning calorimetry (DSC) at a scan rate of 10 °C/min in the first heating scan.
  • DSC differential scanning calorimetry
  • terpolyamide resins have a melt viscosity in the range of 80 Pa-s to 160 Pa-s, as determined at 1000 s "1 shear rate and 325 °C with terpolyamides having a moisture content of 125 to 550 parts per million (ppm).
  • the terpolyamides have a bsshexamethylene triamine content of 60 mequiv/Kg or less, and preferably 52 mequiv/Kg or less, as determined with hydrolysis of the
  • the semi-aromatic terpolyamides are identified by their respective repeat units.
  • the following list exemplifies the abbreviations used to identify monomers and repeat units in the terpolymer polyamides (PA) disclosed herein:
  • the term "6" when used alone designates a polymer repeat unit formed from ⁇ -caprolactam.
  • a diacid such as adipic acid
  • the “6” refers to HMD.
  • the diamine is designated first.
  • the first "6” refers to the diamine HMD
  • the second "6” refers to adipic acid.
  • repeat units derived from other amino acids or lactams are designated as single numbers designating the number of carbon atoms.
  • the semi-aromatic terpolyamide repeat units are separated by a slash (that is, /). For instance poly(hexametbyiene terephthalamide/ hexamethylene
  • PA 6T/6I/6 (62/23/15), wherein the values in parentheses are the mole % repeat unit of each repeat unit in the
  • the semi-aromatic terpolyamides provided by the process disclosed herein comprise a1 ) 55 to 62 mole % hexamethylene terephthalamide (6T), a2) 13 to 29 mole % hexamethylene isophthalamide (6i), and a3) 9 to 26 mole % caprolactam (6), wherein the sum of a1 ), a2) and a3) equals 100 mole % of polymer components.
  • the semi-aromatic terpolyamides provided by the process disclosed herein comprise 58 to 62 mole % 6T, 20-24 mole % 6!, and 16 to 20 mole % caprolactam.
  • One embodiment is a process for making 6T/6I/6 semi-aromatic terpolyamide, said semi-aromatic terpolyamide having a melting point of at least 290 °C and not more than 320 °C, comprising:
  • the reactor is preferably an autoclave capable of a safe operating pressure range of 1 to 500 psia, and an operating temperature range of 23 °C to 350 °C.
  • the polymerization salt mixture may comprise additional reagents including excess hexamethylenediamine, acetic acid or other organic monocarboxylic acids, amine capping agents, thermal stabilizers, and other functional agents known in the art to be useful in polyamide polymerization.
  • additional reagents including excess hexamethylenediamine, acetic acid or other organic monocarboxylic acids, amine capping agents, thermal stabilizers, and other functional agents known in the art to be useful in polyamide polymerization.
  • excess hexamethylenediamine, acetic acid or another organic acid, and/or amine capping agents can be added to manipulate the type of end group and the amount of end group in the polymer which ultimately affects the melt viscosity.
  • Volatiles include water vapor, amines such as HMD, organic acids, monoamines and other capping reagents which may be used to control end group concentration.
  • Figure 1 shows the batch process profile in graphic terms indicating the temperature and pressure of process.
  • the polymerization salt mixture is heated in at least two constant pressure stages: b1 ) (corresponds to Stage 2-1 in Fig 1 ) a first heating with venting of volatiles at a first constant pressure of 180 to 265 psia to a temperature of 225 °C to 240 °C; and b2) (corresponds to Stage 2-3 in Fig 1 ) a second heating and venting of volatiles at a second constant pressure of 320 to 450 psia, preferably 330 to 450 psia, and more preferably at 330 to 400 psia, to a temperature of 285 °C to 310 °C.
  • the salt mixture As the salt mixture is heated, water boils, and the pressure is raised to a first constant pressure selected between 180 and 265 psia.
  • the salt mixture is held at the first constant pressure at +/- 2 psia as volatiles (steam, and small amounts of HMD and/organic acids, if present) are vented until the temperature reaches 225 °C to 240 °C. Then the venting is terminated or reduced to allow the pressure to rise to the second constant pressure.
  • the polymerization salt mixture is held at the second constant pressure as volatiles (steam, and small amounts of HMD and/organic acids, if present) are vented until the temperature reaches 285 °C to 310°C.
  • the selected two constant pressure stages allow the polymerization to progress without encountering a phase boundary.
  • step b) heating may comprise three or more constant pressure stages.
  • Heating steps c) and d) (corresponding to Stage 3 and Stage 4 in Fig 1 ) drive the polymerization to provide a molten semi-aromatic terpolyamide with the desired molecular weight, as evidenced by the melt viscosity range.
  • step c) is performed over a period of 30 to 80 minutes; and step d) is performed over a period of 15 to 45 minutes, and more preferably 20 to 30 minutes.
  • the 6T/6I/6 semi-aromatic terpolyamide provided by the process disclosed herein may be melt-blended with reinforcing agents, polymeric tougheners, flame retardants and/or additional functional additives to provide thermoplastic
  • compositions useful in injection molding to provide thermoplastic molded articles are provided.
  • melting points were as determined with DSC (TA Instruments Q2000, TA Instruments, New Castle, Delaware, USA) at a scan rate of 10 °C/min in the first heating scan, wherein the melting point is taken at the maximum of the endothermic peak per ASTM D3418.
  • freezing points were as determined with DSC (TA Instruments Q2000, TA Instruments, New Castle, DE, USA) at a scan rate of 10 °C/min in the cooling cycle as per ASTM D3418.
  • Inherent Viscosity Inherent Viscosity (IV) was measured on a 0.5% solution of terpolyamide in m ⁇ cresol at 25 °C, using a Schott AVS310 viscosity measuring unit, a Schott CK300 cooling unit, and a Schott CT52 constant temperature bath according to the method described in ISO 307.
  • Amine ends were determined by titrating a 1 percent solution of polyamide in a phenol/methanol mixture (90:10 by volume) with 0.025 N perchloric acid solution. The end point was determined potentiometrically, using a Metrohm "Tiamo" operating system with a Titrando 809 and Dosino 800 burette, along with a Metrohm pH electrode, all available from Metrohm USA, Riverview, Florida, USA.
  • BHMT content was determined by hydrolysis of the polyamide samples, liberation of free amines (diamines, triamines) by basification, followed by GC analysis of the resulting amine mixture using the following procedure.
  • the hydrolysis of the polyamide sample was carried out as follows: a polymer sample was hydrolyzed in concentrated hydrochloric acid solution for 2 hours in a sealed tube at 175 °C. The resulting solution of hydrolysis products was diluted with water and then saturated with potassium hydroxide. The basic and neutral fractions of the hydrolysis products were then extracted from the diluted hydrolysate into an organic layer. It was then analyzed by using a Bruker 450 gas chromatograph with a DB-5 column (10 m long, 0.25 mm ID, 1 .0 ⁇ film), available from Brucker Corp., Billerica, Massachusetts, USA.
  • the oven temperature was raised from 50 °C to 235 °C at 15 degrees per minute and a hold time of 8 minutes (total run time of 18.3 minutes).
  • the concentrations of degradation products in the orginal polymer sample was calculated using the appropriate dilution factors, accounting the proportion of the sample that was hydrolyzed.
  • Stage 1 The agitator was then set to 50 rpm, the pressure control valve was set to 55 psia and the autoclave was heated. When pressure reached 55 psia, a small amount of steam was allowed to vent (-50 grams of condensate). The pressure control valve was then set to 200 psia and heat Input to the autoclave was raised and the pressure was allowed to rise.
  • Stage 2-1 (corresponds to step b1 ): At a constant reactor pressure of 200 psia steam began to vent at a rate determined by the heat input. This stage was terminated after 30 minutes.
  • Step 2-2 The pressure control valve was then set at 345 psia and pressure was allowed to rise to 345 psia in 25 minutes.
  • Stage 2-3 (corresponds to step b2): The pressure was then maintained 345 psia during which steam was vented and the temperature of the contents were allowed to rise further to 285 °C.
  • Stage 3 At 285 °C, the pressure was reduced to 14.5 psia over about 45 minutes while the heating continued to approximately 315 °C.
  • Stage 4 The autoclave pressure was reduced to 5 psia by applying vacuum and held there for 20 minutes.
  • Stage 5 The autoclave was then pressurized with 65 psia nitrogen and the molten polymer was extruded into strands, quenched with cold water and cut into pellets.
  • Examples 2A, 3 to 7 were performed by charging the reactor with the materials listed in Table 1 .
  • the process conditions were the same as Example 1 except that the temperature at initiation of pressure reduction was raised by 5 to 20 °C and the final finish temperature of the polymer melt was raised by 5 to 7 °C higher than that used in Example 1 .
  • Example 2B was made in a manner similar to that used in Examples 3 to 7, except the first constant pressure hold was at 285 psia.
  • Tables 2 and 3 list the properties of the terpolyamides prepared in Examples 1 -7.
  • Aqueous SHP (1 wt %, 71 g) and aqueous Carbowax 8000 (1 wt %, 14 g) were each added to each polymerization salt mixture.
  • HMD hexamethyiene diamine
  • T terephthalic acid
  • l isophthaiic acid
  • SHP sodium hypophosphite
  • Example 4 The ingredients used for examples C1 to C3 are listed in Table 4.
  • the process conditions for making comparative examples C1 and C2 were similar to those described in Example 1 .
  • the process conditions for C3 were the same as Example 1 except that the temperature at Initiation of pressure reduction was raised by 15 °C and the final finish temperature of the polymer melt was raised by 5 °C higher than that used in Example 1 .
  • Comparative Example C1 had a melting point lower than the desired 290 °C - 320 °C and a BHMT level within the range of Examples.
  • C2 and C3 show that as the level of 6T is increased, the melting point increased as expected, but also the level of BHMT increased to undesirable levels.
  • terpolyamide provided the desired high melting points, and low BHMT levels consistent with low branching of the terpolyamide.
  • Aqueous SHP (1 wt %, 68 g) and aqueous Carbowax 8000 (1 wt %, 10 g) added to each
  • HMD hexamethyiene diamine
  • T terephtha!ic acid
  • l isophthaiic acid
  • SHP sodium
  • Comparative Example 4 is identical to Example 1 in composition but the process conditions included a single constant pressure stage, rather than the at least two constant pressure stages of Example 1 .
  • PA6T/6I/6 (55/27/18) salt mixture was prepared in the lab as follows: A 500 ml 3-necked round bottomed flask was equipped with a high efficient condenser, nitrogen purge, thermocouple, heating mantle and magnetic stirring. The flask was first charged with 88 grams of water and 87.24 grams of an aqueous solution of hexamethyiene diamine of 79.2% concentration. The flask was magnetically stirred and was kept under nitrogen purge. The flask was then slowly heated to 40 °C.
  • the flask When the temperature was above 40 °C, the flask was charged with 50.4051 gram of terephthalic acid, 25.22 grams of isophthaiic acid and 1 1 .48 grams of ⁇ - caproiactam. Then, an additional 88 grams of water were added to the flask. The temperature of the flask was then slowly raised to approximately 90 °C. The salt was completely dissolved at this point. Then, 42.2 grams of hot salt solution was transferred to a quartz tube of approximately 60 mL volume. A magnetic stirrer bar was also added to the quartz tube. The quartz tube was then sealed with a plastic film and allowed to cool overnight to room temperature during which time the salt froze.
  • the quartz tube was installed in the quartz tube reactor.
  • the pressure controller of the quartz tube reactor was set at 285 psia.
  • the head space of the quartz tube was purged with nitrogen.
  • the magnetic stirring was turned on and the heating started.
  • the temperature of the salt solution gradually rose and the salt completely melted at 80 0 C.
  • the heating was continued and the pressure of the reactor was allowed to rise to 265 psia.
  • the pressure was kept constant at 265 psia and the temperature of the contents was allowed to rise further.
  • the temperature was about 237 °C, the solution started to become hazy.
  • the venting continued and temperature increased.

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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)
  • Life Sciences & Earth Sciences (AREA)
  • Proteomics, Peptides & Aminoacids (AREA)
  • Polyamides (AREA)

Abstract

La présente invention concerne un procédé de préparation de terpolyamide 6T/6I/6 semi-aromatique, le terpolyamide semi-aromatique ayant un point de fusion supérieur ou égal à 290 °C et inférieur ou égal à 320 °C, ledit procédé consistant à : chauffer un mélange de sels de polymérisation comprenant de l'eau, a1) de 55 à 62 % en moles de téréphtalate d'hexaméthylène diammonium, a2) de 13 à 29 % en moles d'isophtalate d'hexaméthylène diammonium, et a3) de 9 à 26 % en moles d'ε-caprolactame, à au moins deux paliers de pression constante ; et éventuellement extruder ledit terpolyamide semi-aromatique fondu à travers une filière.
PCT/US2014/060247 2013-10-16 2014-10-13 Procédé de préparation de terpolyamide semi-aromatique Ceased WO2015057557A1 (fr)

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US61/891,467 2013-10-16

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107057342A (zh) * 2017-01-20 2017-08-18 金发科技股份有限公司 一种半芳香族聚酰胺树脂及其制备方法和由其组成的聚酰胺模塑组合物
WO2019060117A1 (fr) 2017-09-21 2019-03-28 E. I. Du Pont De Nemours And Company Compositions de polyamide retardatrices de flamme
WO2019067517A1 (fr) 2017-09-28 2019-04-04 E. I. Du Pont De Nemours And Company Procédé de polymérisation
WO2020210656A1 (fr) 2019-04-10 2020-10-15 E I Du Pont De Nemours And Company Compositions de polyamides
CN114736369A (zh) * 2022-05-25 2022-07-12 北京化工大学 改性尼龙及其制备方法
JP2023548227A (ja) * 2020-11-02 2023-11-15 キャセイ バイオテック インコーポレイテッド 高温耐性ポリアミドを製造するための方法、高温耐性ポリアミド及びその使用

Citations (3)

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FR2331633A1 (fr) * 1975-11-12 1977-06-10 Monsanto Co Copolyamides statistiques formant des fibres, derivees d'hexamethylenediamine, d'acide terephtalique, d'acide isophtalique et d'un diacide aliphatique en c5 a c10
EP0592996A2 (fr) * 1992-10-15 1994-04-20 BASF Aktiengesellschaft Copolyamides partiellement aromatiques
WO2013091737A1 (fr) * 2011-12-23 2013-06-27 Ems-Patent Ag Matière moulable à base de polyamides, son utilisation ainsi que les pièces moulées fabriquées à partir de celle-ci

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2331633A1 (fr) * 1975-11-12 1977-06-10 Monsanto Co Copolyamides statistiques formant des fibres, derivees d'hexamethylenediamine, d'acide terephtalique, d'acide isophtalique et d'un diacide aliphatique en c5 a c10
EP0592996A2 (fr) * 1992-10-15 1994-04-20 BASF Aktiengesellschaft Copolyamides partiellement aromatiques
WO2013091737A1 (fr) * 2011-12-23 2013-06-27 Ems-Patent Ag Matière moulable à base de polyamides, son utilisation ainsi que les pièces moulées fabriquées à partir de celle-ci

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107057342A (zh) * 2017-01-20 2017-08-18 金发科技股份有限公司 一种半芳香族聚酰胺树脂及其制备方法和由其组成的聚酰胺模塑组合物
WO2019060117A1 (fr) 2017-09-21 2019-03-28 E. I. Du Pont De Nemours And Company Compositions de polyamide retardatrices de flamme
EP4219594A2 (fr) 2017-09-21 2023-08-02 DuPont Polymers, Inc. Compositions de polyamide ignifuges
US12152108B2 (en) 2017-09-21 2024-11-26 Celanese Polymers Holding, Inc. Flame retardant polyamide compositions
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
WO2020210656A1 (fr) 2019-04-10 2020-10-15 E I Du Pont De Nemours And Company Compositions de polyamides
US20220169850A1 (en) * 2019-04-10 2022-06-02 Dupont Polymers, Inc. Polyamide compositions
US12187892B2 (en) * 2019-04-10 2025-01-07 Celanese Polymers Holding, Inc. Polyamide compositions
JP2023548227A (ja) * 2020-11-02 2023-11-15 キャセイ バイオテック インコーポレイテッド 高温耐性ポリアミドを製造するための方法、高温耐性ポリアミド及びその使用
JP7759945B2 (ja) 2020-11-02 2025-10-24 キャセイ バイオテック インコーポレイテッド 高温耐性ポリアミドを製造するための方法、高温耐性ポリアミド及びその使用
CN114736369A (zh) * 2022-05-25 2022-07-12 北京化工大学 改性尼龙及其制备方法

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