WO2018152761A1 - Résine à base de polyamide améliorée destinée à des formulations élaborées de matières plastiques - Google Patents

Résine à base de polyamide améliorée destinée à des formulations élaborées de matières plastiques Download PDF

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WO2018152761A1
WO2018152761A1 PCT/CN2017/074718 CN2017074718W WO2018152761A1 WO 2018152761 A1 WO2018152761 A1 WO 2018152761A1 CN 2017074718 W CN2017074718 W CN 2017074718W WO 2018152761 A1 WO2018152761 A1 WO 2018152761A1
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polyamide
mol
copolymer
monomers
article
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PCT/CN2017/074718
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English (en)
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Haiming Chen
Min Wang
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Advansix Resins & Chemicals Llc
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Priority to PCT/CN2017/074718 priority Critical patent/WO2018152761A1/fr
Priority to PCT/CN2017/100107 priority patent/WO2018153048A1/fr
Priority to TW107106225A priority patent/TW201837079A/zh
Priority to US15/903,185 priority patent/US20180244918A1/en
Publication of WO2018152761A1 publication Critical patent/WO2018152761A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/40—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic

Definitions

  • the present disclosure relates to polyamide materials and, in particular, to a copolymer of polyamide 6 and polyamide 66 for use as base resin for fiber reinforced manufactured plastic articles, for example.
  • both polyamide 6 (PA 6) and polyamide 66 (PA 66) homopolymers are used as base resins for fiber filled or reinforced compositions of the type that are processed, typically via injection molding, for example, into finished articles that are commonly used in automotive, consumer goods, power tools, electrical, electronic, and other applications.
  • polyamide 6 has good mechanical strength, thermal stability and chemical resistance, and is one of the most widely used engineering plastics, especially in the automobile industry worldwide.
  • Polyamide 6 is commonly compounded with glass fiber and/or other additives such as carbon black, impact modifiers and processing aids, for example.
  • new requirements are either now present or are foreseen, such as the need for properties such as better surface finish, lower shrinkage and warpage, and higher toughness.
  • Improved surface finish may be described as a smooth surface with less “floating” of glass fibers in or on the surface of the molded parts, which will reduce the post treatment steps of the articles and the dependence on paint or other coverings, thereby also making the product more environmentally friendly and saving costs.
  • Automobile parts producers also desire high dimensional accuracy of finished articles and, in this context, lower warpage is another highly desirable property of automobile parts, especially for larger sized parts.
  • the present disclosure provides polyamide base resins with improved crystallization dynamics for the production of reinforced polyamide compositions having improved surface, shrink, warpage and mechanical properties such as toughness.
  • the polyamide base resins are copolymers of polyamide 6 and polyamide 66, formed of ratios that are tailored to reduce the crystallization rate and final crystallization extent when used in melt processing to produce glass filled articles.
  • the copolymers demonstrate improved polyamide morphology dynamics that in turn impart improved final properties in reinforced molded articles, such as improved surface finish, improved toughness/impact resistance, reduced warpage, and more symmetrical shrinkage properties.
  • the low warpage, low shrinkage and high toughness properties provided to finished articles made with the present base resins enable the production of relatively larger sized parts such as pillars, frame reinforcements, and door components.
  • the smooth surface finish of finished parts made from the present base resins enable the production of parts that are visibly exposed, such as body panels and bumpers, for example, and the relatively wide processing window enabled by the relatively slower crystallization time of the present base resins allows for relatively high reinforcement loading, such as with glass fibers, for increased toughness while also preserving a smooth surface finish.
  • manufactured articles made with the present base resin may be used in applications such as appliances, electrical equipment, and building and construction components, for example.
  • the present disclosure provides a polymeric base composition for use in manufacturing a finished article via melt processing, the polymeric base composition including at least one polyamide 6/66 copolymer polymerized from caprolactam and adipic acid/hexamethylenediamine monomers and including between 84 mol%and 99 mol%monomers based on caprolactam and between 1 mol%and 16 mol%monomers based on adipic acid and hexamethylenediamine, based on the total moles of caprolactam and adipic acid/hexamethylenediamine monomers, wherein the polyamide 6/66 copolymer has; and at least one reinforcement component.
  • the present disclosure provides an article formed via a melt processing method, the article including at least one polyamide 6/66 copolymer polymerized from caprolactam and adipic acid/hexamethylenediamine monomers and including between 84 mol%and 99 mol%monomers based on caprolactam and between 1 mol%and 16 mol%monomers based on adipic acid and hexamethylenediamine, based on the total moles of caprolactam and adipic acid/hexamethylenediamine monomers; and at least one reinforcement component.
  • Fig. 1 is related to Example 1 and provides the crystallization rate as a function of temperature for various formulations.
  • Fig. 2A is related to Example 4 and provides the melt temperature for copolymers formed from compositions having varying levels of monomers.
  • Fig. 2B is related to Example 4 and provides the peak isothermal crystallization time (in minutes) at 170°C for copolymers formed from compositions having varying levels of monomers.
  • Fig. 3 is related to Example 4 and provides the 13 C NMR spectra for Ex. 3B and Comp. Ex. 3 copolymers formed from compositions having varying levels of monomers.
  • Fig. 4 is related to Example 4 and provides the degree of randomness for copolymers formed from compositions having varying levels of monomers.
  • Fig. 5 is related to Example 5 and provides warpage comparison data.
  • Fig. 6 is related to Example 5 and provides shrinkage data.
  • the present disclosure provides polyamide base resins inthe form of copolymers of polyamide 6 and polyamide 66 (polyamide 6/66 copolymers) that are synthesized from caprolactam monomers and adipic acid/hexamethylenediamine monomers.
  • the adipic acid and hexamethylenediamine components of the adipic acid/hexamethylenediamine monomers may be provided in a salt of 1: 1 molar proportion, referredto as “AH salt” , which may be either in solid form or in the form of an aqueous solution.
  • AH salt a salt of 1: 1 molar proportion
  • Caprolactam is traditionally used to form polyamide 6 via ring opening hydrolysis, followed by polymerization.
  • AH salts are traditionally used to form polyamide 66 via condensation polymerization.
  • caprolactam monomers and AH salt monomers are polymerized together to produce polyamide 6/66 copolymers including a majority component of monomers based on caprolactam and a minority component of monomers based on AH salt, i.e., adipic acid and hexamethylenediamine.
  • the polymer chains include monomers, or repeating units, based on caprolactam and monomers, or repeating units, based on adipic acid/hexamethylenediamine which are mutually present in the polymer chains according to a random or near random distribution.
  • the caprolactam monomers make up as little as 84 mol. %, 90 mol. %, 94 mol. %, 95 mol. %, 96 mol. %, or as great as 97 mol. %, 98 mol. %, or 99 mol. %, of the total moles of caprolactam and AH salt monomers, or within any range defined between any two of the foregoing values, such as 84 mol. %to 99 mol. %, 90 mol. %to 99 mol. %, 94 mol. %to 99 mol. %, or 94 mol. %to 96 mol. %, for example.
  • the AH salt monomers make up as little as 1 mol. %, 2 mol. %, 3 mol. %, or as great as 4 mol. %, 5 mol. %, 6 mol. %, 10 mol. %, 16 mol. %, of the total moles of caprolactam and AH salt monomers, or within any range defined between any two of the foregoing values, such as 1 mol. %to 16 mol. %, 1 mol. %to 10 mol. %, 1 mol. %to 6 mol. %, or 4 mol. %to 6 mol. %, for example.
  • caprolactam and AH salt are blended together at elevated temperatures, such as low as about 150°C, 155°C, as great as 160°C, 165°C, 170°C, or within any range defined between any two of the foregoing values, such 150°C to 170°C, or 155°C to 165°C for example.
  • the caprolactam and AH salt may be mildly agitated during heating to provide more uniform heat transfer and mixing.
  • the AH salt may be combined with the caprolactam as a dry powder, or may be combined with the caprolactam as an aqueous solution, such as an aqueous solution containing as little as about 50 wt. %, 52 wt.
  • the caprolactam and AH salt may be blended in the presence of added water.
  • the mixture of caprolactam and AH salt, and optionally water, is polymerized to form the polyamide composition.
  • the polymerization may be carried out using a batch continuously stirred tank reactor (CSTR) , a VK tube, or by using a continuous polymerization train, for example.
  • CSTR batch continuously stirred tank reactor
  • the polyamide 6/66 copolymers may have a relative viscosity (RV) as low as 2.0, 2.1, or 2.2, or as high as 2.5, 2.7, or 3.0, or within any range defined between any two of the foregoing values, such as 2.0 to 3.0, 2.1 to 2.5, or 2.2 to 2.7, for example.
  • RV relative viscosity
  • Relative viscosity is mainly determined by the molecular weight and molecular weight distribution.
  • the polyamide 6/66 copolymers have a relatively low melt point as measured by Differential Scanning Calorimetry (DSC) using ASTM D3418 compared to either a polyamide 6 or polyamide 66 homopolymer, as well as a polyamide compositions that are formed from a physical melt blend of polyamide 6 and polyamide 66 homopolymers.
  • DSC Differential Scanning Calorimetry
  • the polyamide 6/66 copolymers may have a melt point as low as 190°C, 195°C, 200°C, or as high as 205°C, 210°C, 215°C, 220°C, 225°C, or within any range defined between any two of the foregoing values, such as 190°C to 225°C, 195°C to 215°C, or 200°C to 210°C, for example.
  • the polyamide 6/66 copolymers have a relatively low crystallization temperature as measured by Differential Scanning Calorimetry (DSC) using ASTM D3418 compared to either a polyamide 6 or polyamide 66 homopolymer, as well as polyamide compositions that are formed from a physical melt blend of polyamide 6 and polyamide 66 homopolymers.
  • DSC Differential Scanning Calorimetry
  • the polyamide 6/66 copolymers may have a crystallization temperature as low as 150°C, 155°C, 160°C, 165°C, or as high as 170°C, 175°C, 180°C, or within any range defined between any two of the foregoing values, such as 150°C to 180°C, 155°C to 175°C, or 160°C to 170°C, for example.
  • the polyamide 6/66 copolymers have a relatively long isothermal crystallization time as measured by Differential Scanning Calorimetry (DSC) using ASTM E2070 compared to either a polyamide 6 or polyamide 66 homopolymer, as well as polyamide compositions that are formed from a physical melt blend of polyamide 6 and polyamide 66 homopolymers.
  • the polyamide 6/66 copolymers may have an isothermal crystallization time as little as 1 min, 2 min, 4 min, 6 min, or as high as 8 min, 10 min, 12 min, 14 min or within any range defined between any two of the foregoing values, such as 1.5 min to 4 min, 2 min to 4 min, or 2.1 min to 3.7 min, for example.
  • isothermal crystallization was performed at 170°C to measure isothermal crystallization time, among other properties.
  • the polyamide 6/66 copolymers may have a relatively high degree of randomness in connection with the monomers or repeating units based on caprolactam and the monomers or repeating units based on AH salt.
  • the degree of randomness is calculated (with equations I and II shown below) from the intensities of carbonyl peaks in the spectra obtained by.
  • the measured degree of randomness may be as little as 0.4, 0.55, 0.7, as high as 0.975, 1.00, 1.25, or within any range defined by any two of the foregoing values, such as 0.6 to 1.1, 0.82 to 1.01, or 0.95 to 1.01, for example.
  • copolymerizing monomers of caprolactam and AH salt in the relative amounts and using the conditions according to the present disclosure provides a highly randomized distribution of the AH salt monomers and the caprolactam monomers in the copolymer chains.
  • the polyamide 6/66 copolymer After the polyamide 6/66 copolymer is produced as discussed above, same may be combined with a reinforcement component, such as short or long glass and/or mineral fibers, and/or other additives to form a ready to process reinforced polymer base resin in a suitable form such as pellets, bars, or sheets, for example, for further melt processing.
  • a reinforcement component such as short or long glass and/or mineral fibers, and/or other additives to form a ready to process reinforced polymer base resin in a suitable form such as pellets, bars, or sheets, for example, for further melt processing.
  • the reinforcement component may be added or combined with the polyamide 6/66 copolymer during the melt processing operation, such as injection molding, extrusion, or other suitable techniques by which the finished manufactured article is formed.
  • Suitable glass and/or mineral fibers include short fibers, sometimes referred to as “chopped” fibers, having an average length of between 1 mm and 5 mm, or long fibers having an average length of between 6 mm and 25 mm.
  • short fibers sometimes referred to as “chopped” fibers, having an average length of between 1 mm and 5 mm, or long fibers having an average length of between 6 mm and 25 mm.
  • average diameters of between 1 ⁇ m and 150 ⁇ m are suitable.
  • both short and long fibers may be used in combination.
  • other reinforcement components such as carbon nanotubes, nanoglass fibers and nanocarbon fibers may also be used.
  • Exemplary loading amounts of the reinforcement component may be as little as 5 wt. %, 15 wt. %, or 30 wt. %, or as great as 45 wt. %, 50 wt. %, or 60 wt. %, or may be between any pair of the forgoing values, such as between 5 wt. %and 60 wt.%, 15 wt. %and 50 wt. %, and 30 wt. %and 45 wt. %, based on the total weight of the polyamide 6/66 copolymer and the reinforcement component.
  • Other reinforcement components may alternatively, or additionally, include one or more types of particulate fillers, for example, having an average particle size as little as 10 nm, 1 ⁇ m, or 8 ⁇ m, or as great as 15 ⁇ m, 100 ⁇ m, or 500 ⁇ m, or may be between any pair of the forgoing values, such as between 10 nm and 15 ⁇ m, 8 ⁇ m and 15 ⁇ m, and 8 ⁇ m and 500 ⁇ m, based on the total weight of the polyamide 6/66 copolymer and the filler.
  • particulate fillers for example, having an average particle size as little as 10 nm, 1 ⁇ m, or 8 ⁇ m, or as great as 15 ⁇ m, 100 ⁇ m, or 500 ⁇ m, or may be between any pair of the forgoing values, such as between 10 nm and 15 ⁇ m, 8 ⁇ m and 15 ⁇ m, and 8 ⁇ m and 500 ⁇ m, based on the total weight of the polyamide 6/66 copolymer and the filler.
  • additives may include pigments, lubricants, heat stabilizers, anti-wear additives, ultraviolet (UV) stabilizers, flexibilizers, nucleating additives, fire retardants, antioxidants, antistatic additives, and other suitable additives.
  • heat stabilizers include copper iodide, potassium iodide, potassium bromide, sodium iodide, potassium chloride, other copper halides, and other metallic halides.
  • Exemplary lubricants include ethylene bis stearamide ( "EBS" ) , other organic amides, aluminum stearate, zinc stearate, calcium stearate, other metallic stearates, and other metallic fatty acids.
  • Exemplary anti-wear additives include perfluoropolyether, polytetrafluoroethylene, functional and non-functional polydimethylsiloxane, graphite, molybdenum disulfide, and silicone oil.
  • Exemplary UV stabilizers may include a hindered amine light stabilizer ( “HALS” ) , such as N, N'-Bis-2, 2, 6, 6-tetramethyl-4-piperidinyl-1, 3-benzene dicarboxamide, for example.
  • Exemplary flexibilizers may include polyolefins and polystyrene flexibilizers, such as polyolefin elastomers, for example.
  • Exemplary nucleating additives may include small size talcum powder, silicon dioxide powder, aluminium oxide powder and montmorillonoid powder.
  • Exemplary fire retardants may include tripolycyanamide, antimonous oxide, zinc borate, and brominated flame retardant, such as decabromodiphenyl ether and decabromodiphenyl ethane, for example; and may also include phosphorus flame retardants, such as red phosphorus, for example.
  • Exemplary antioxidants include amine antioxidants, such as diphenylamine, p-phenylenediamine, and dihydro-quinoline; and may also include hindered phenol antioxidants, such as 2, 6-di-tert-butyl-4-methylphenol and pentaerythrotol, for example.
  • Exemplary antistatic additives include alkyl sulfonic acid alkali metal salt and aminodithioformic acid alkali metal salt, for example.
  • a finished part formed from the present polyamide 6/66 copolymer base resin composition has a relatively high flexural modulus.
  • the flexural modulus may be measured according to ASTM D 790 in some embodiments.
  • the measured storage modulus may be as little as 536 MPa, 1887 MPa, 2481 MPa, as high as 8000 MPa, 12000 MPa, 15000 MPa, or within any range defined by any two of the foregoing values, such as 536 MPa to 8000 MPa, or 2481 MPa to 15000 MPa, for example.
  • the claimed polyamide 6/66 copolymer has lower warpage compared with polyamide 6 and polyamide 66 homopolymers. Warpage was measured according to the following method. Pellets are pre-dried@80°C for 6h before injection molding. Molding plates with a size of 100*100*2 mm are used and the general injection molding parameters are as follows: injection temperature 280°C, molding temperature 100°C. Fix one side of the plates to a flat and smooth desktop, measure the distance between the other side of the plate and the desktop. Testing conditions 23°C and 50%relative humidity. 10 plates were tested for each sample, and an average value is calculated and recorded.
  • the measured warpage may be as little as 3.0 mm, 3.5 mm, 4.0 mm, as high as 5.0 mm, 5.5 mm, 6.0 mm, or within any range defined by any two of the foregoing values, such as 3.0 mm to 4.0 mm, or 3.5 mm to 5.5 mm, for example.
  • a finished part formed from the present polyamide 6/66 copolymer base resin composition has much higher wet condition toughness compared with that of a polyamide 6 homopolymer.
  • the wet condition toughness may be determined according to ASTM D-256. At 23°C, the measured wet condition toughness may be as little as 180 MPa, 200 MPa, 250 MPa, as high as 350 MPa, 450 MPa, 500 MPa, or within any range defined by any two of the foregoing values, such as 180 MPa to 500 MPa, or 200 MPa to 450 MPa, for example.
  • the measured wet condition toughness may be as little as 40 MPa, 50 MPa, 60 MPa, as high as 150 MPa, 200 MPa, 250 MPa, or within any range defined by any two of the foregoing values, such as 40 MPa to 250 MPa, or 60 MPa to 200 MPa, for example.
  • the measured wet condition toughness may be as little as 30 MPa, 40 MPa, 50 MPa, as high as 100 MPa, 150 MPa, 200 MPa, or within any range defined by any two of the foregoing values, such as 30 MPa to 200 MPa, or 50 MPa to 150 MPa, for example.
  • a finished part formed from the present polyamide 6/66 copolymer base resin composition has much higher dry condition toughness compared with that of a polyamide 6 homopolymer.
  • the dry condition toughness may be determined according to ASTM D-256. At 23°C, the measured dry condition toughness may be as little as 30 MPa, 40 MPa, 50 MPa, as high as 100 MPa, 150 MPa, 250 MPa, or within any range defined by any two of the foregoing values, such as 30 MPa to 250 MPa, or 40 MPa to 150 MPa, for example.
  • the measured dry condition toughness may be as little as 30 MPa, 40 MPa, 50 MPa, as high as 90 MPa, 120 MPa, 180 MPa, or within any range defined by any two of the foregoing values, such as 30 MPa to 180 MPa, or 40 MPa to 120 MPa, for example.
  • the measured dry condition toughness may be as little as 25 MPa, 30 MPa, 40 MPa, as high as 90 MPa, 120 MPa, 180 MPa, or within any range defined by any two of the foregoing values, such as 20 MPa to 180 MPa, or 40 MPa to 120 MPa, for example.
  • the present polyamide 6/66 copolymers have lower shrinkage than polyamide 6 homopolymers.
  • the shrinkage may be determined according to ASTM D-955.
  • the measured initial shrinkage vertical to the flow direction may be as little as 0.45%, 0.51%, 0.55%, as high as 0.80%, 0.90%, 1.2%, or within any range defined by any two of the foregoing values, such as 0.45%to 1.2%, or as 0.55%to 0.90%, for example.
  • the measured 48 hours shrinkage vertical to the flow direction may be as little as 0.51%, 0.55%, 0.60%, as high as 0.90%, 1.0%, 1.3%, or within any range defined by any two of the foregoing values, such as 0.51%to 1.3%, or as 0.55%to 0.90%, for example.
  • the measured initial shrinkage parallel to the flow direction may be as little as 0.12%, 0.20%, 0.25%, as high as 0.80%, 0.90%, 1.0%, or within any range defined by any two of the foregoing values, such as 0.12%to 1.0%, or as 0.20%to 0.90%, for example.
  • the measured 48 hours shrinkage parallel to the flow direction may be as little as 0.15%, 0.27%, 0.32%, as high as 0.80%, 1.0%, 1.1%, or within any range defined by any two of the foregoing values, such as 0.15%to 1.1%, or as 0.27%to 1.0%, for example.
  • Finished articles made from polyamide 6/66 copolymer both form the neat polymer and with a reinforcement component, also show better smooth surface finish than corresponding finished articles made from polyamide 6 homopolymer.
  • Exemplary formulations were tested using differential scanning calorimetry to determine melt point temperature (T m ) and crystallization temperature (T c ) in accordance with ASTM D3418 and isothermal crystallization time (t 1/2 ) in accordance with ASTM E2070.
  • the log crystallization rate of various compositions was determined as a function of temperature. Solid lines indicate experimental data, while dashed lines indicate extrapolated values for crystallization rate based on the Sestak Berggren equation. As shown in the upper curve of Fig. 1, the crystallization rate of PA 6 homopolymer is relatively high.
  • the middle curve of Fig. 1 shows the crystallization rate of a physical blend of 70 mol. %PA 6 homopolymer having a melting point of 220°C, relative viscosity 4.0 with 30 mol. %of a PA 6/66 copolymer having a melting point of 193°C and relative viscosity of 4.0.
  • the PA 6/66 copolymer contains about 82 mol. %PA 6 and 18 mol. %PA 66, and the 30: 70 blend overall is estimated to contain about 5.4 mol. %of the PA 66 material.
  • the addition of the PA 66 reduces the crystallization rate of the blend compared to that of the PA 6 monomer.
  • the lower curve of Fig. 1 further shows the crystallization rate of a copolymer formed from a copolymerized mixture of 94 mol. %caprolactam and 6 mol. %AH salt.
  • the 6 mol. %copolymer formed from the caprolactam and AH salt had a lower crystallization rate than the 30: 70 blend of the middle curve.
  • Polyamide compositions containing various amounts of caprolactam and AH salt were produced in pellet form. Pellets of each composition were produced with according to the molar percent of caprolactam and AH salt shown in Table 1 below. For each sample, the polyamide composition was produced in a continuous process from the caprolactam and AH salt monomers. The temperature for each stage was set to 260°C with a flow rate of around 7000 lb/hr.
  • Thermal analysis was performed on a 6 mg sample of each composition by using a TA Q series differential scanning calorimeter (DSC) at a heating rate of 10°C/min to 265°C, followed by rapid cooling to 170°C and holding for 30 minutes.
  • the T m , T c , and t 1/2 for each sample are provided in Table 1.
  • Polyamide compositions containing various amounts of caprolactam and AH salt were produced in pellet form. Pellets of each composition were produced with according to the molar percent of caprolactam and AH salt shown in Table 2.
  • Cast films were prepared from pellets of each composition using a Haake single screw extruder (Zone temperature: 240 ⁇ 260°C, roll temperature: 25°C, screw rpm: 75, melt temperature: 250°C) .
  • comparative films were produced from a dry blended mixture of 70 wt. %PA6 and 30 wt. %PA 6/66 pellets.
  • the PA 6 pellets were B40 polyamide and the PA 6/66 pellets were C40 L polyamide, each available from BASF.
  • the comparative pellets were similar in PA 6 and PA 66 concentration to the 94/6 concentration of Ex. 2B.
  • Thermal analysis was performed on a 6 mg sample of each composition by using a TA Q series differential scanning calorimeter (DSC) at a heating rate of 10°C/min to 265°C, followed by rapid cooling to 170°C and holding for 30 minutes.
  • the T m , T c , and t 1/2 for each sample are provided in Table 2.
  • Examples 2A-2E which were formed from the wholly compounded PA compositions, had a lower crystallization temperature (T c ) and longer isothermal crystallization time than the pellet blend of Comp. Ex. 2.
  • Ex. 2B and Comp. Ex. 2 each contained about 94 mol. %caprolactam and 6 mol. %AH salt.
  • the Ex. 2B sample provided a decrease of nearly 20°C and a substantial increase in isothermal crystallization time compared to Comp. Ex. 2.
  • Examples 3A-3D which were formed from the wholly compounded PA compositions, had a lower melt temperature (T m ) and crystallization temperature (T c ) than the pellet blend of Comp. Ex. 3 as shown in Fig. 5A.
  • Ex. 3B and Comp. Ex. 3 each contained about 94 mol. %caprolactam and 6 mol. %AH salt.
  • the Ex. 3B sample provided a decrease of nearly 20°C (Fig. 2A) and a substantial increase in isothermal crystallization time (Fig. 2B) compared to Comp. Ex. 3.
  • Polyamide compositions containing various amounts of caprolactam and AH salt were produced in pellet form.
  • Samples for nuclear magnetic resonance (NMR) spectroscopy were prepared in 5 mm NMR tubes. Each sample weighed approximately 25 mg and was dissolved in 1 mL deuterated H 2 SO 4 to get a clear solution. The solution was locked externally with either a 0.2 mL solution of CDCl 3 or a 0.2 mL solution of CD 3 COCD 3 and spectra were recorded on a 100 MHz ( 13 C) NMR instrument. The 13 C Quantitative NMR spectra were acquired using a program (e.g., Bruker pulse program) .
  • a program e.g., Bruker pulse program
  • Quantitative 13 C spectra were acquired on a Bruker AV-III 400MHz NMR Spectrometer operating at 100.62 MHz, the spectral width was 24 kHz, the relaxation delay was 5 seconds, and inverse gated decoupling was used to eliminate the nuclear Overhauser effect. A total of 8000 scans were acquired.
  • compositions, the sequence distributions, and the degree of randomness were calculated (with Formulas I and II as shown below) from the intensities of carbonyl peaks in the spectra as shown in Fig. 3.
  • Comp. Ex. 3 has an additional peak at point 4 indicating the presence of additional polyamide 6, 6, -polyamide 6, 6 block. Furthermore, as shown in Fig. 4 and in Table 4 below, as compared to Comp. Ex. 3, the degree of randomness clearly increases with Examples 3A-3D, though there may be some slight inaccuracies in these measured results. As such, Ex. 3A-3D yield more random copolymers than melt blending in a single screw extruder. Also, Ex. 3A and 3B have lower nylon 6, 6 content and polyamide 6-polyamide 66 and polyamide 66-polyamide 6 bonding as compared to Comp. Ex. 3.
  • compositions of films formed from compositions having varying levels of monomers having varying levels of monomers
  • PA6/66 copolymer with 7%PA66 means the synthesized polyamide 6/66 copolymer with 7 mol%polyamide 6.
  • PA6+7%PA66 means physical melt blending of 93 wt. %polyamide 6 and 7 wt. %polyamide 66 via compounding.
  • PA6+20%PA66 means physical melt blending of 80 wt. %polyamide 6 and 20 wt. %polyamide 66 via compounding.
  • PA6 means polyamide 6 homopolymer.
  • Shrinkage is given in Fig. 6. “Ws” means shrinkage vertical to the flow direction, and “Ls” means shrinkage parallel to the flow direction.
  • 30 wt. %glass fiber filled PA6/66 copolymer with 7%PA66 shows lowest shrinkage among the tested samples. Lower shrinkage will facilitate lower warpage.
  • the 30 wt. %glass fiber filled PA6+7wt. %PA66 blend has similar shrinkage as the claimed PA6/66 copolymer with 7 mol%PA66, while much higher warpage. Warpage will be influenced by crystallization time, crystal size, shrinkage and processing, wherein samples having similar shrinkage may have different warpage behavior.
  • Crystalline degree, or crystallization is given in Table 6 using the following equation to calculate the crystalline degree:
  • Crystalline enthalpy is acquired by dynamic differential scanning calorimeter (DSC) .
  • the dynamic DSC analysis was performed on a 6 mg sample of each composition at a heating rate of 10°C/min to 280°C, followed by 10°C/min cooling from 280°C to 25°C and then heating to 280°C at a heating rate of 10°C/min.
  • Crystalline enthalpy is the heat released during the cooling process.
  • Standard enthalpy of PA6 is 230J/g, very similar with PA66 (226J/g) .
  • 15 wt%glass fiber filled PA6/66 copolymer with 7%PA66 also shows similar notched izod impact strength with 15 wt%glass fiber filled PA6 at 23, -20 and -40°C.
  • 30 wt%glass fiber filled PA6/66 copolymer with 7%PA66 shows 19.2%higher notched izod impact strength than 30 wt%glass fiber filled PA6 at 23°C, 10%higher at -20 and -40°C.
  • polyamide 6 and polyamide 6/66 copolymer are seldom used in a form of neat resin, a 30 wt. %filled formulation may be considered as a generally used formulation.
  • polyamide 6/66 has an advantage in dry condition toughness compared with polyamide 6.
  • Table 8 gives the formulation for wet condition notched izod impact strength study.
  • the sample “PA6/66 copolymer with 7%PA66” , “PA6” , “PA6+7%PA66” and “PA6+20%PA66” have the same composition as that provided in Table 5.
  • PA66 means polyamide 66 homopolymer. Compositions of the base resin at 0 wt., 15 wt. %and 30 wt. %glass fiber filled are used for wet condition toughness testing.
  • Notched izod impact strength at wet condition is given in Table 9.
  • PA6/66 copolymer with 7%PA66 neat resin shows significantly higher notched izod impact strength than the other tested neat resin at 23°C.
  • 15 wt%and 30 wt%glass fiber filled PA6/66 copolymer with 7%PA66 also shows obviously higher notched izod impact strength than the other tested 15 wt%and 30 wt%glass fiber filled formulation at 23°C. This should be mainly caused by the lower crystalline degree of PA6/66 copolymer with 7%PA66 than the other tested formulations.
  • PA66 has the lowest notched izod impact strength compared with the other samples. This may be due to the different water content in PA66 and/or different water absorption rate.
  • Notched izod impact strength of PA6/66 copolymer with 7%PA66 neat resin is similar with PA6 neat resin and lower than PA66, PA6+7%PA66 and PA6+20%PA66 neat resin, at -20°C and -40°C.
  • Notched izod impact strength of 15 wt%glass fiber filled PA6/66 copolymer with 7 mol%PA66 is similar with the other tested 15 wt%glass fiber filled formulation, at -20°C and -40°C.
  • Notched izod impact strength of 30 wt%glass fiber filled PA6/66 copolymer with 7 mol%PA66 is similar to 30 wt%glass fiber filled PA6+7%PA66 and PA6+20%PA66 and higher than 30 wt%glass fiber filled PA6 and PA66, at -20°C and -40°C.
  • Table 10A and 10B give the mechanical strength of neat resin and 30 wt%glass fiber filled PA6, PA66, PA6/66 copolymer with 7%PA66, PA6+7%PA66 and PA6+20%PA66 at dry condition.
  • PA6/66 copolymer with 7 mol%PA66 shows lower mechanical strength than PA6, PA66, PA6+7%PA66 and PA6+20%PA66 at dry condition.
  • 30 wt%glass fiber filled PA6/66 copolymer with 7%PA66 also shows lower mechanical strength than the 30 wt%glass fiber filled PA6, PA66, PA6+7%PA66 and PA6+20%PA66 at dry condition, but the gap is smaller than the neat resin data.
  • Relatively high crystalline degree of PA6 and PA66 contributes to the high mechanical strength, once filling glass fiber, the influence of crystalline degree on mechanical strength will be weakened, so the gap is smaller when filling 30 wt%glass fiber compared with neat resin.
  • Tables 11A and 11B provide the mechanical strength of unreinforced resin and 30 wt%glass fiber filled PA6, PA66, PA6/66 copolymer with 7%PA66, PA6+7%PA66 and PA6+20%PA666/66 at wet condition.
  • PA6/66 copolymer with 7 mol%PA66 resin shows lower mechanical strength than PA6, PA66, PA6+7%PA66 and PA6+20%PA66 at wet condition, PA66 neat resin shows the best mechanical strength.
  • 30 wt%glass fiber filled PA6/66 copolymer with 7%PA66 also has lower mechanical strength than the 30 wt%glass fiber PA6, PA66, PA6+7%PA66 and PA6+20%PA66 at dry condition, but the gap is smaller than the neat resin data.
  • Tables 12A and 12B give the initial, 24 hours and 48 hours shrinkage of unreinforced resin and 30 wt%glass fiber filled PA6, PA66, PA6/66 copolymer with 7 mol%PA66, PA6+7%PA66 and PA6+20%PA66.
  • PA6/66 copolymer with 7 mol%PA66 neat resin shows lower shrinkage than PA66 and PA6+20%PA66 neat resin, similar shrinkage with PA6 and PA6+20%PA66 neat resin.
  • 30 wt%glass fiber filled PA6/66 copolymer shows lowest shrinkage among the tested samples, mainly attributes to the lowest crystalline degree. PA66 shows the highest shrinkage among the tested samples.

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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)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyamides (AREA)

Abstract

L'invention concerne des résines à base de polyamide présentant une dynamique de cristallisation améliorée et destinée à la production de compositions renforcées à base de polyamide présentant des propriétés améliorées de surface, de rétrécissement, de gauchissement et mécaniques telles que la ténacité. Les résines à base de polyamide sont des copolymères de polyamide 6 et de polyamide 66, formés de rapports qui sont adaptés pour réduire le taux de cristallisation et le degré final de cristallisation lorsqu'ils sont utilisés dans un traitement de fusion pour produire des articles garnis de verre. Les copolymères présentent une dynamique améliorée de morphologie de polyamide qui leur confère des propriétés finales améliorées dans des articles moulés renforcés, telles qu'une finition améliorée de surface, une ténacité/résistance aux chocs améliorée, un gauchissement réduit et des propriétés de rétrécissement plus symétriques.
PCT/CN2017/074718 2017-02-24 2017-02-24 Résine à base de polyamide améliorée destinée à des formulations élaborées de matières plastiques WO2018152761A1 (fr)

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PCT/CN2017/074718 WO2018152761A1 (fr) 2017-02-24 2017-02-24 Résine à base de polyamide améliorée destinée à des formulations élaborées de matières plastiques
PCT/CN2017/100107 WO2018153048A1 (fr) 2017-02-24 2017-09-01 Résine polyamide de base améliorée destinée à des formulations de plastiques techniques
TW107106225A TW201837079A (zh) 2017-02-24 2018-02-23 用於工程塑膠調配物之增強聚醯胺基礎樹脂
US15/903,185 US20180244918A1 (en) 2017-02-24 2018-02-23 Enhanced polyamide base resin for engineering plastics formulations

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1559741A1 (fr) * 2004-01-30 2005-08-03 Mitsubishi Engineering-Plastics Corporation Film termorétractable à base de polyamides aliphatiques
CN102108208A (zh) * 2009-12-29 2011-06-29 合肥杰事杰新材料有限公司 一种高强度阻燃聚酰胺复合材料及制备方法
EP2457952A1 (fr) * 2010-11-30 2012-05-30 LANXESS Deutschland GmbH Réservoir de gaz
CN103724992A (zh) * 2012-10-10 2014-04-16 朗盛德国有限责任公司 模制组合物、生产产品的方法、基于乙烯和丁烯共聚物的应用及由其可获得的产品

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DE19546417B4 (de) * 1995-12-12 2005-12-22 Karl-Heinz Wiltzer Verfahren und Vorrichtung zur vereinheitlichten, kontinuierlichen Herstellung von Polyamiden
EP1574547A1 (fr) * 2004-03-09 2005-09-14 Mitsubishi Engineering-Plastics Corporation Composition de polyamide ignifugée et objets moulés par extrusion à partir de celle-ci.

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1559741A1 (fr) * 2004-01-30 2005-08-03 Mitsubishi Engineering-Plastics Corporation Film termorétractable à base de polyamides aliphatiques
CN102108208A (zh) * 2009-12-29 2011-06-29 合肥杰事杰新材料有限公司 一种高强度阻燃聚酰胺复合材料及制备方法
EP2457952A1 (fr) * 2010-11-30 2012-05-30 LANXESS Deutschland GmbH Réservoir de gaz
CN103724992A (zh) * 2012-10-10 2014-04-16 朗盛德国有限责任公司 模制组合物、生产产品的方法、基于乙烯和丁烯共聚物的应用及由其可获得的产品

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