[go: up one dir, main page]

WO2018175384A1 - Compositions de polyamide cristallines poreuses - Google Patents

Compositions de polyamide cristallines poreuses Download PDF

Info

Publication number
WO2018175384A1
WO2018175384A1 PCT/US2018/023268 US2018023268W WO2018175384A1 WO 2018175384 A1 WO2018175384 A1 WO 2018175384A1 US 2018023268 W US2018023268 W US 2018023268W WO 2018175384 A1 WO2018175384 A1 WO 2018175384A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyamide
polyamide composition
solvent
monomer
monomer mixture
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.)
Ceased
Application number
PCT/US2018/023268
Other languages
English (en)
Inventor
Alan James Lesser
Md Arifur RAHMAN
Philippe Desbois
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
University of Massachusetts Boston
University of Massachusetts Amherst
Original Assignee
BASF SE
University of Massachusetts Boston
University of Massachusetts Amherst
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, University of Massachusetts Boston, University of Massachusetts Amherst filed Critical BASF SE
Publication of WO2018175384A1 publication Critical patent/WO2018175384A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

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
    • 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
    • C08G69/16—Preparatory processes
    • C08G69/18—Anionic polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
    • C08J2201/05—Elimination by evaporation or heat degradation of a liquid phase
    • C08J2201/0502—Elimination by evaporation or heat degradation of a liquid phase the liquid phase being organic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/02—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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
    • C08J9/286—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum the liquid phase being a solvent for the monomers but not for the resulting macromolecular composition, i.e. macroporous or macroreticular polymers

Definitions

  • polyamides such as polyamide 6, can be synthesized by hydrolysis or by anionic ring opening polymerization.
  • the hydrolytic polymerization process is more industrially viable, because it is easier to control and better adapted for large-scale operation.
  • Anionically polymerized polyamides though have an improved crystallinity as compared to hydrolytically polymerized polyamides.
  • the crystallinity of anionically polymerized polyamide 6 is about 40%, which is significantly greater than the crystallinity of hydrolytic polyamide 6.
  • anionically polymerized polyamide 6 can be synthesized at a temperature closer to its crystallization temperature, whereas hydrolytic polyamide 6 is synthesized above its melting point.
  • anionically polymerized polyamide 6 exhibits a reduced water uptake, a better toughness, and improved impact resistance over hydrolytic polyamide 6.
  • a polyamide having an increased crystallinity is desired as such a polyamide could result in a polyamide composition with a reduced amount of water uptake.
  • a polyamide composition comprises an anionically polymerized polyamide; wherein the polyamide composition has a crystallinity of greater than or equal to 45 wt% as determined by DSC; and a porosity of greater than or equal to 10 vol% as determined based on the density of the polyamide composition.
  • a method of making any one or more of the preceding polyamide compositions comprises anionically polymerizing a monomer mixture comprising a cyclic lactam monomer, a solvent in which the cyclic lactam monomer is soluble, a catalyst, and an activator to form the anionically polymerized polyamide.
  • FIG. 1 is a scanning electron microscopy image of the polyamide composition of Example 4.
  • FIG. 2 is a graphical illustration of the temperature with time of the polymerization of the polyamide of Example 1 ;
  • FIG. 3 is a graphical illustration of the temperature with time of the polymerization of the polyamide of Example 4.
  • FIG. 4 is a graphical illustration of the stress versus strain of Examples 1, 4, 7, and 8;
  • FIG. 5 is a graphical illustration of the moisture update with time of the polyamide compositions of Examples 1 and 4.
  • the process comprises anionically polymerizing a monomer mixture comprising a cyclic lactam monomer, a solvent in which the cyclic lactam monomer is soluble, a catalyst, and an activator to form the anionically polymerized polyamide.
  • a monomer mixture comprising a cyclic lactam monomer, a solvent in which the cyclic lactam monomer is soluble, a catalyst, and an activator to form the anionically polymerized polyamide.
  • the solvent does not initially boil off during the polymerization and can be present to reduce the exotherm, ultimately resulting in the polymerization temperature being maintained below the crystallization temperature. Therefore, crystalline polyamide is formed throughout the polymerization reaction, resulting in a polyamide composition with increased crystallinity.
  • the boiling point of the solution also decreases and the solvent can begin to boil off under the right conditions. Any residual solvent present after the polymerization can be further evaporated.
  • the type and amount of solvent can have a dramatic effect on the resultant morphology of the polyamide composition.
  • the polyamide composition can have a closed pore structure, an open pore structure, both open pores and closed pores, or an aggregate pore structure if the initial solvent concentration is high.
  • a spherulitic morphology was observed to create the open pore structures and the aggregate pore structures.
  • the spherulitic formation arises from a reduction of the exotherm that results not only in a reduction in the polymerization temperature, but also slows down the polymerization kinetics of the cyclic lactam monomer.
  • the resulting polyamide composition therefore has a hierarchical morphological structure comprising spherulitic structures having a lamella length scale of only a few micrometers or less, forming the overall spherulite having a length scale in the 10s of micrometers. For example, FIG.
  • FIG. 1 is an SEM image of an example of a polyamide composition having a spherulite morphology with an open pore structure that can arise from the present polymerization.
  • FIG.1 shows spherulites having an overall length scale on the order of 10s of micrometers comprising lamella having a length scale of only a few micrometers. This hierarchical morphology can result in one or both of a lotus leaf effect and an ultrahydrophobic surface.
  • the polyamide composition comprises an anionically polymerized polyamide.
  • the anionically polymerized polyamide can have a weight average molecular weight of 2,000 to 100,000 Daltons (Da), or 5,000 to 50,000 Daltons as measured by gel permeation chromatography based on polystyrene standards.
  • the polyamide composition can have a crystallinity of greater than or equal to 45 weight percent (wt%), or greater than or equal to 50 wt%, or 45 to 75 wt% as determined by differential scanning calorimetry (DSC).
  • a polyamide composition having a size of 4.5 ⁇ 0.1 milligram (mg) is sealed in a closed hermetic aluminum pan and heated at a heating rate of 10 degrees Celsius per minute (°C/min) over a temperature range of -20 to 250 degrees Celsius (°C).
  • the weight percent crystallinity (X c ) is then determined by dividing the change in enthalpy of the polyamide composition measure from the DSC scan (AH m ) by the change in enthalpy of a 100 wt% crystalline sample of the same polyamide (AH C ) as shown in Equation (I).
  • the polyamide composition can have a porosity of greater than or equal to 10 volume percent (vol%), or 10 to 50 vol% as determined using a density method as defined by Equation (II).
  • Equation (II) the bulk density pbuik is calculated by dividing the weight of the polyamide composition by the volume of polyamide composition and p po iyamide is the density of the polyamide.
  • the polyamide composition can have a reduced water uptake as compared to a corresponding polyamide formed in the absence of a solvent.
  • the polyamide composition can have a water uptake of less than or equal to 6 wt%, or less than or equal to 5 wt%, or 1 to 6 wt%.
  • water vapor permeability of polymers depends on their phase morphology and the diffusion of water molecules can be facilitated by the free volume of an amorphous phase in polymers. However, the crystalline phase, being ordered and tightly packed, can hinder the diffusion of water molecules.
  • Polyamide compositions though, in spite of being semicrystalline, can exhibit high moisture absorption due to the presence of hydrogen bonded amide groups.
  • W f ⁇ 100% (III)
  • W is the initial (dry) weight of the sample and Wf is the final weight of the sample measured at a time, t, once a final weight is achieved.
  • a method of making the composition can comprise anionically polymerizing a monomer mixture comprising a cyclic lactam monomer and a solvent to form the anionically polymerized polyamide.
  • the monomer mixture can further comprise a catalyst and an initiator.
  • the solvent can be a solvent in which the cyclic lactam monomer is soluble.
  • the polymerizing can comprise melt polymerizing at a temperature of greater than or equal to the melting temperature of the cyclic lactam monomer and below the melting point of the polymerizing polyamide. For example, the melt polymerizing can occur at a temperature of 25 to 70 °C, or 80 to 220 °C, or 100 to 200 °C, or 145 to 165 °C.
  • the melt polymerizing can occur at a temperature of less than or equal to 190 °C.
  • the melt polymerizing can occur at a temperature of 100 to 220 °C, or 145 to 165 °C.
  • the cyclic lactam monomer can comprise greater than or equal to 3 carbon atoms, or 3 to 14, or 5 to 10 carbon atoms in the lactam ring.
  • the cyclic lactam monomer can comprise ⁇ -propiolactam (also known as 2-azetidinone), ⁇ -butyrolactam (also known as 2- pyrrolidone), ⁇ -valerolactam (also known as 2-piperidine), ⁇ -caprolactam, enantholactam, caprylolactam, laurolactam, ⁇ , ⁇ -dimethylpropiolactam, ⁇ , ⁇ -dimethylpropiolactam, amylolactam, or a combination comprising at least one of the foregoing.
  • the cyclic lactam monomer can comprise an alkyl substituted cyclic lactam, an aryl substituted cyclic lactam, or a combination comprising at least one of the foregoing.
  • the cyclic lactam monomer can comprise ⁇ -caprolactam.
  • the cyclic lactam monomer can comprise a combination comprising at least one of the foregoing cyclic lactam monomers.
  • the polymerizing occurs in the presence of a solvent and the cyclic lactam monomer can be soluble in the solvent.
  • the cyclic lactam monomer can be considered soluble in the solvent if greater than or equal to 100 mg of the cyclic lactam monomer can be dissolved in 1 milliliter (mL) of solvent at 23 °C.
  • the solvent can comprise methyl tert-butyl ether, isopropyl ether, diphenyl ether, biphenyl, an alkanol (such as methanol, ethanol, 1-propanol, 2-propanol, n-butanol, isobutanol, and tert-butanol), a polyol (such as diethylene glycol and tetraethylene glycol), an aromatic hydrocarbon (such as benzene, toluene, xylene (such as meta-xylene, ortho-xylene, and para-xylene)), a carboxylate (such as a carboxylic acid having 1 to 8 carbon atoms), an alkyl- substituted lactam (such as N-methylpyrrolidone, N-methylcaprolactam, and N-ethylcaprolactam), or a combination comprising at least one of the foregoing.
  • an alkanol such as methanol, ethanol, 1-propano
  • the solvent can comprise xylene, specifically, meta-xylene.
  • the solvent can comprise n-nonane, a-pinene, n-decane, or a combination comprising at least one of the foregoing.
  • the solvent can comprise a combination comprising at least one of the foregoing solvents.
  • the solvent can have a boiling point that is less than the polymerization temperature, or less than or equal to the polymerization temperature minus 5 °C.
  • the solvent can comprise m-xylene having a boiling point of 140 °C
  • the cyclic lactam monomer can comprise ⁇ -caprolactam
  • the polymerization temperature can be 150 °C.
  • the solvent can have a boiling point that is greater than or equal to the polymerization temperature, or greater than or equal to the polymerization temperature plus 5 °C. Using a solvent having a boiling point that is greater than the polymerization temperature can result in the formation of closed pores in the resultant polyamide composition.
  • the monomer mixture can comprise 2 to 50 wt%, or 10 to 40 wt% of the solvent based on the total weight of the monomer mixture. If the monomer mixture comprises greater than 0 to 15 wt% of the solvent, then the polyamide composition can have a closed pore structure. If the monomer mixture comprises greater than 15 to 25 wt% of the solvent, then the polyamide composition can have a mixed pore structure comprising both open and closed pores. If the monomer mixture comprises greater than 25 to 35 wt% of the solvent, then the polyamide composition can have an open pore structure. If the monomer mixture comprises greater than 45 wt% of the solvent, then the polyamide composition can have an aggregate pore structure.
  • a closed pore structure can refer to a polyamide composition, where the pores are not connected to each other.
  • An open pore structure can refer to a polyamide composition having an interconnected pore structure. The open pore structure can allow for near complete or complete removal of the solvent from the polyamide composition (for example, 95 to 100 wt% of the initial solvent can be removed from the polyamide composition).
  • a mixed pore structure can refer to a polyamide composition having both open and closed pores.
  • the aggregate pore structure can refer to a polyamide composition having pores of multiple length scales, for example, on the micrometer length scale (such as 5 to 100 micrometers) as well as on the millimeter length scale (such as 0.2 to 2 millimeters).
  • the monomer mixture can comprise a catalyst.
  • the catalyst can comprise an iminium salt that can be prepared by reacting a base with a lactam such as the cyclic lactam monomer.
  • a lactam such as the cyclic lactam monomer.
  • the cyclic lactam monomer to be polymerized can be used for the preparation of the catalyst; but the catalyst can likewise be prepared from a different lactam.
  • the iminium salt can be prepared by reacting the lactam with a metal compound.
  • the metal compound can comprise a metal, a basic derivative of the metal, or a combination comprising at least one of the foregoing.
  • the metal can comprise an alkali metal (such as sodium and potassium), an alkaline earth metal (such as magnesium), aluminum, or a combination comprising at least one of the foregoing.
  • the basic derivative of the metal can comprise a hydroxide, an alkoxide, a hydride, an aryl, an amide, an organic acid salt, or a combination comprising at least one of the foregoing.
  • the basic derivative of the metal can comprise sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, lithium hydride, sodium hydride, sodium methylate, sodium ethylate, sodium phenolate, sodium beta-naphtholate, sodamide, sodium stearate, lithium aluminium hydride, aluminium propylate, or a combination comprising at least one of the foregoing.
  • the catalyst can comprise sodium caprolactamate, such as CIO commercially available from BASF SE of Ludwigshafen, Germany.
  • the iminium salt can be prepared by adding the metal compound to the cyclic lactam monomer; or by first adding the metal compound to a portion of the cyclic lactam monomer and then adding the iminium salt to the remaining cyclic lactam monomer.
  • the lactam can be as anhydrous as the metal compound.
  • the catalyst can be present in an amount of 0.1 to 10 mole percent (mol%), or 0.1 to 5 mol% based on the total moles of the lactam and catalyst.
  • the catalyst can be present in an amount of 1 to 6 wt% based on a total weight of the monomer, activator, and catalyst. The more catalyst added, the lower the molecular weight of the resultant polyamide.
  • the time used for the preparation of the catalyst depends upon the properties of the compounds employed, the quantity added, and the temperature chosen, and can generally be from a few seconds to several hours (hrs).
  • the iminium salt can be prepared by reacting the lactam with the metal compound by heating at a temperature of 25 to 220 °C.
  • the monomer mixture can comprise an activator (also referred to as a co- catalyst).
  • the activator can comprise any compound that, in addition to the catalyst, brings about polymerization of the cyclic lactam monomer.
  • the activator can comprise a carbodiimide (such as ⁇ , ⁇ '- diisopropyl carbodiimide, N,N'-di-(o-tolyl)-carbodiimide, ⁇ , ⁇ '- dicyclohexyl carbodiimide, 2,2',6,6'-tetraisopropyl diphenyl carbodiimide, or poly-(2,2- diisopropyl)-p-phenylene carbodiimide), a blocked or unblocked isocyanate (such as diphenyl methane diisocyanate, hexamethylene diisocyanate, toluol diisocyanate, isophorone diisocyanate, m-xylidene diisocyanate,
  • the activator can comprise a multifunctional activator (such as poly(hexamethylene diisocyanate, poly[(phenyl isocyanate)-co- formaldehyde], methyl isocyanate bound to polystyrene, 1-adamentyl isocyanate, or a combination comprising at least one of the foregoing.
  • the activator can comprise a combination comprising at least one of the foregoing activators.
  • the activator can be present in an amount of 0.1 to 5 mol% based on the total moles of the cyclic lactam monomer.
  • the activator can be present in an amount of 1 to 4 wt% based on a total weight of the monomer, activator, and catalyst.
  • a molar ratio of the catalyst to the activator can be 0.5 to 2, or 0.8 to 1.2.
  • the activator can be added before, during, or after adding the catalyst.
  • the activator can be dissolved in a portion of the cyclic lactam monomer and the dissolved activator can be added as an activator mixture.
  • the catalyst can be dissolved in a portion of the cyclic lactam monomer and the dissolved catalyst can be added as a catalyst mixture.
  • the polymerization can be performed in an inert environment.
  • an inert gas such as nitrogen, argon, and a noble gas
  • nitrogen, argon, and a noble gas can be introduced onto the surface of the reaction mixture during the polymerization to prevent oxidation.
  • the polymerization can comprise polymerizing the reaction mixture in a batch reactor.
  • the polymerization can comprise mixing the solvent and the cyclic lactam monomer with one of the catalyst and the activator to form a monomer mixture, increasing the temperature of the monomer mixture to a polymerization temperature, and adding the other of the catalyst and the activator to initiate polymerization and form the polyamide composition.
  • the polyamide composition can be dried, for example, by heating to remove any remaining solvent.
  • reaction injection molding can be useful in rapidly preparing cast articles of varying size and shape directly from the cyclic lactam monomer.
  • reaction injection molding can have advantages when used in the manufacture of large molded articles, because reaction injection molding or similar processes use high temperatures and high pressures for their operations. Therefore, simpler and lighter weight molds can be employed and faster cycles can often be obtained in the manufacture of large shaped articles.
  • the reaction injection molding can comprise injecting a single mixture comprising the cyclic lactam monomer, the solvent, the catalyst, and the activator into a mold; two or more mixtures can be mixed just prior to the injection molding; or the two or more mixtures can be simultaneously added to the mold during the injection molding.
  • a first mixture comprising the cyclic lactam monomer, the solvent, and one of the catalyst and the activator can be mixed with a second mixture comprising the other of the catalyst and the activator just prior to the injection molding and the combined mixture can be injected into a mold to form the article.
  • the polyamide composition can be ground up to form a high crystallinity powder.
  • the high crystallinity powder can be used as an extrusion additive.
  • the high crystallinity powder can be added as an extrusion additive in order to reduce the viscosity of the polymer melt. If the extrusion time is greater than the time is would take for the polyamide crystals to melt and to reach their entanglement density, then the resultant extrudate could have improved properties.
  • the high crystallinity powder could also be used in three dimensional (3D) printing applications.
  • Using the high crystallinity powder could be advantageous as the polymer segments in the crystalline regions of the high crystallinity powder are inherently disentangled and, upon melting, the polymer chains are also initially disentangled. Therefore, the initial viscosity of the melt will be low, but the driving force for the polymer chains to reach its equilibrium entanglement density will be high, which could ultimately result in a faster, sintering polymer.
  • the high crystallinity powder has a high fraction of crystallinity, upon melting, the high crystallinity powder will inherently expand during the melting, which can potentially reduce void formation during printing.
  • the polyamide composition can further comprise a second polymer.
  • the second polymer can be present during the polymerization of the cyclic lactam monomer.
  • the second polymer can be at least partially soluble in the cyclic lactam monomer.
  • the second polymer can comprise a polyacetal, a polyolefin, a polyacrylic, a polycarbonate, a polystyrene, a polyester, a second polyamides, a polyamideimide, a polyarylate, a polyarylsulfone, a polyethersulfone, a polyphenylene sulfide, a polyvinyl chloride, a polysulfone, a polyimide, a polyetherimide, a polyfluoroethylene, a
  • polyetherketone a poly(ether ether ketone), a poly(ether ketone ketone), a polybenzoxazole, a polyphthalide, a polyacetal, a poly anhydride, a polyvinyl ether, a polyvinyl thioether, a polyvinyl alcohol, a polyvinyl ketone, a polyvinyl halide, a polyvinyl nitrile, a polyvinyl ester, a polysulfonate, a polysulfide, a polythioester, a polysulfone, a polysulfonamide, a polyurea, a polyphosphazene, a polysilazane, or a combination comprising at least one of the foregoing.
  • the second polymer can comprise a polystyrene, a polyphenylene oxide, a poly(ether ether sulfone), a poly( ether imide), a polysiloxane, or a combination comprising at least one of the foregoing.
  • the polyamide composition can comprise a copolymerized siloxane that is polymerized simultaneously with the polyamide.
  • the copolymerized siloxane can be derived from octaphenylcyclotetrasiloxane.
  • the polyamide composition can comprise an additive.
  • the additive can comprise a filler, an antioxidant, a blowing agent, a plasticizer, a colorant, or a combination comprising at least one of the foregoing.
  • the additive can comprise eicosane, triacontane, a paraffin wax, or a combination comprising at least one of the foregoing.
  • An article can comprise the polyamide composition.
  • the article can be a filter.
  • WAXS Wide angle x-ray scattering
  • the porosity of the polyamide compositions was determined using a density method as defined by Equation (II).
  • Compression testing on the polyamide compositions was carried out using a mechanical testing machine (Instron) on samples having a dimension of 15x 15 millimeters (mm) at a speed of 2 millimeters per minute (mm/min) at room temperature (about 23 °C).
  • Example 1 anionic polymerization of ⁇ -caprolactam was carried out in a 20 mL glass vial under atmospheric pressure.
  • the monomer mixture comprising ⁇ -caprolactam and the C20 activator, was melt mixed at a temperature of 150 °C under constant stirring.
  • the polymerization was initiated upon addition of the CIO catalyst, where the monomer mixture comprised 94 wt% of the ⁇ -caprolactam, 2 wt% of the C20 activator, 4 wt% of the CIO catalyst; all based on the total weight of the monomer mixture.
  • Example 2-6 anionic polymerization of ⁇ -caprolactam was carried out in accordance with Example 1, except that an amount of m-xylene was added to the monomer mixture.
  • Example 2-6 the same amounts of the ⁇ -caprolactam, the C20 activator, and the CIO catalyst as used in Example 1 were used and an amount of m-xylene was added such that the resultant monomer mixture comprised a wt% m-xylene based on the total weight of the monomer mixture as shown in Table 1.
  • Example 1 The morphology of the polyamide compositions of Examples 1-6 was studied using scanning electron microscopy (SEM) and the morphology type is shown in Table 1.
  • Table 1 shows that there is no pore structure of Example 1 ; a closed pore structure in Example 2; a mixed pore structure in Example 3 having both open and closed pores; an open pore structure in Example 4; and aggregate structures of spherulitic domains formed in both Examples 5 and 6.
  • Table 1 shows that adding 10 wt% of solvent still results in the desired increase in crystallinity, but is not enough to form interconnected pores through the sample. Increasing the solvent concentration to greater than 10 wt% results in the formation of interconnected, open pores through the polyamide composition.
  • FIG. 1 shows an SEM image of the polyamide composition of Example 4.
  • FIG. 1 shows that the composition has a spherulitic morphology, where the individual spherulites have a length scale of about 10 micrometers.
  • FIG. 1 further shows that the multiple spherulites can comprise submicron sized fibrillated domains, see the connected spherulites in the boxed portion of the image.
  • FIG. 2 illustrates that at the polymerization temperature of 150 °C, an exotherm of about 20 °C is produced.
  • the crystallization temperature of polyamide 6 is at about 150 °C, the polymer produced during the exotherm is primarily in the amorphous phase.
  • FIG. 3 illustrates that the presence of the solvent is capable of reducing the exotherm such that the reaction temperature is maintained below 150 °C. Without being bound by theory, it is believed that the polymerization forms an increased amount of crystalline polyamide by maintaining the reaction temperature below the crystallization temperature of 150 °C.
  • Examples 7-12 were prepared in accordance with Example 4, except that the solvent was varied. In Examples 7-9, solvents having a boiling point less than the
  • Examples 10-12 solvents having a boiling point greater than or equal to the polymerization temperature were used. Examples 7-9 all showed an open pore structure, whereas Examples 10-12 all resulted in closed pore structure.
  • Tables 1 and 2 show that the polyamide compositions prepared in the presence of the solvent all have higher melting temperatures and increased crystallinity, exhibiting a 50 to 60% increase relative to the polyamide composition of Example 1.
  • Moisture absorption tests of the polyamide compositions of Examples 1 and 4 were performed by putting the compositions in a closed desiccator with 100 mL of water.
  • the closed desiccator had a relative humidity of 65% and a temperature of 70 °C.
  • the compositions were periodically weighed over two weeks to measure the moisture uptake (Wu) by using Equation (IV).
  • Equation (IV) W, is the initial (dry) weight of the sample and W t is the weight of the sample measured at a time, t.
  • the moisture uptake is shown in FIG. 5.
  • FIG. 5 shows that the water uptake of Example 1 reaches its maximum moisture uptake (-7%) in 96 hours and reaches a plateau at 144 hours.
  • FIG. 5 shows a significant reduction in water uptake of Example 4, where Example 4 exhibits a reduction in moisture uptake by more than 40% relative to that of Example 1.
  • the lower moisture absorption in Example 4 can be attributed to their higher crystallinity, which is about 50% higher than that of Example 1.
  • Example 15 Filtration using a porous polyamide composition
  • Embodiment 1 A polyamide composition, comprising: an anionically polymerized polyamide; wherein the polyamide composition has a crystallinity of greater than or equal to 45 wt% as determined by DSC; and a porosity of greater than or equal to 10 vol% as determined based on a density of the polyamide composition.
  • Embodiment 2 The polyamide composition of Embodiment 1, wherein the crystallinity is greater than or equal to 50 wt%.
  • Embodiment 3 The polyamide composition of Embodiment 1, wherein the crystallinity is 45 to 75 wt%.
  • Embodiment 4 The polyamide composition of any one or more of the preceding embodiments, wherein the porosity is 10 to 50 vol%.
  • Embodiment 5 The polyamide composition of any one or more of the preceding embodiments, wherein the polyamide composition has an open pore structure.
  • the polyamide composition has an interconnected pore structure.
  • Embodiment 6 The polyamide composition of any one or more of the preceding embodiments, wherein the polyamide composition has a water uptake of less than or equal to 5 wt%.
  • the water uptake can be the weight percent increase based on the initial water free weight of the polyamide composition.
  • Embodiment 7 The polyamide composition of any one or more of the preceding embodiments, wherein the anionically polymerized polyamide has a weight average molecular weight of 2,000 to 100,000 Da as measured by gel permeation
  • Embodiment 8 The polyamide composition of any one or more of the preceding embodiments, wherein the anionically polymerized polyamide has a weight average molecular weight of 5,000 to 50,000 Da as measured by gel permeation
  • Embodiment 9 The polyamide composition of any one or more of the preceding embodiments, wherein the anionically polymerized polyamide is derived from a cyclic lactam monomer comprising ⁇ -propiolactam, ⁇ -butyrolactam, ⁇ -valerolactam, ⁇ - caprolactam, enantholactam, caprylolactam, laurolactam, ⁇ , ⁇ -dimethylpropiolactam, ⁇ , ⁇ - dimethylpropiolactam, amylolactam, or a combination comprising at least one of the foregoing.
  • a cyclic lactam monomer comprising ⁇ -propiolactam, ⁇ -butyrolactam, ⁇ -valerolactam, ⁇ - caprolactam, enantholactam, caprylolactam, laurolactam, ⁇ , ⁇ -dimethylpropiolactam, ⁇ , ⁇ - dimethylpropiolactam, amylol
  • Embodiment 10 The polyamide composition of any one or more of the preceding embodiments, wherein the anionically polymerized polyamide is derived from a cyclic lactam monomer comprising ⁇ -caprolactam.
  • Embodiment 1 1 The polyamide composition of any one or more of the preceding embodiments, wherein the polyamide composition further comprises an additive, a second polymer different from the anionically polymerized polyamide, or a combination comprising at least one of the foregoing.
  • Embodiment 12 A method of making any one or more of the preceding polyamide compositions, comprising: anionically polymerizing a monomer mixture comprising a cyclic lactam monomer, a solvent in which the cyclic lactam monomer is soluble, a catalyst, and an activator to form the anionically polymerized polyamide.
  • Embodiment 13 The method of Embodiment 12, wherein the cyclic lactam monomer comprises ⁇ -propiolactam, ⁇ -butyrolactam, ⁇ -valerolactam, ⁇ -caprolactam, enantholactam, caprylolactam, laurolactam, ⁇ , ⁇ -dimethylpropiolactam, ⁇ , ⁇ - dimethylpropiolactam, amylolactam, or a combination comprising at least one of the foregoing.
  • the cyclic lactam monomer comprises ⁇ -propiolactam, ⁇ -butyrolactam, ⁇ -valerolactam, ⁇ -caprolactam, enantholactam, caprylolactam, laurolactam, ⁇ , ⁇ -dimethylpropiolactam, ⁇ , ⁇ - dimethylpropiolactam, amylolactam, or a combination comprising at least one of the foregoing.
  • Embodiment 14 The method of Embodiment 12, wherein the cyclic lactam monomer comprises ⁇ -caprolactam.
  • Embodiment 15 The method of any one or more of Embodiments 12 to 14, wherein greater than or equal to 100 mg of the cyclic lactam monomer can be dissolved in 1 milliliter of solvent at 23 °C.
  • Embodiment 16 The method of any one or more of Embodiments 12 to 15, wherein the solvent comprises methyl tert-butyl ether, isopropyl ether, an alkanol, a polyol, an aromatic hydrocarbon, a carboxylate, diphenyl ether, biphenyl, an alkyl-substituted lactam, n-nonane, a-pinene, n-decane, or a combination comprising at least one of the foregoing.
  • the solvent comprises methyl tert-butyl ether, isopropyl ether, an alkanol, a polyol, an aromatic hydrocarbon, a carboxylate, diphenyl ether, biphenyl, an alkyl-substituted lactam, n-nonane, a-pinene, n-decane, or a combination comprising at least one of the foregoing.
  • Embodiment 17 The method of any one or more of Embodiments 12 to 16, wherein the solvent comprises benzene, toluene, meta-xylene, ortho-xylene, para-xylene, or a combination comprising at least one of the foregoing.
  • Embodiment 18 The method of any one or more of Embodiments 12 to 17, wherein the anionically polymerizing occurs at a polymerization temperature and wherein the solvent has a boiling point that is less than a polymerization temperature.
  • Embodiment 19 The method of any one or more of Embodiments 12 to 18, wherein the anionically polymerizing occurs at a polymerization temperature and wherein the solvent has a boiling point that is less than or equal to the polymerization temperature minus 5 °C.
  • Embodiment 20 The method of any one or more of Embodiments 12 to 19, wherein the monomer mixture comprises 2 to 50 wt% of the solvent based on the total weight of the monomer mixture.
  • Embodiment 21 The method of Embodiment 20, wherein the monomer mixture comprises 10 to 40 wt% of the solvent based on the total weight of the monomer mixture.
  • Embodiment 22 The method of any one or more of Embodiments 12 to 21, wherein the monomer mixture comprises 1 to 6 wt% of the catalyst based on the total weight of the monomer mixture.
  • Embodiment 23 The method of any one or more of Embodiments 12 to 22, wherein the monomer mixture comprises 1 to 4 wt% of the activator based on the total weight of the monomer mixture.
  • Embodiment 24 The method of any one or more of Embodiments 12 to 23, wherein the anionically polymerizing comprises reaction injection molding.
  • Embodiment 25 The method of any one or more of Embodiments 12 to 24, further comprising forming a powder from the polyamide composition.
  • Embodiment 26 A powder comprising the polyamide composition of any one or more of the preceding embodiments.
  • Embodiment 27 A method comprising, 3D printing the powder of
  • Embodiment 28 A method comprising, extruding a melt comprising a thermoplastic polymer and the powder of Embodiment 26.
  • Embodiment 29 An article comprising the polyamide composition of any one or more of Embodiments 1 to 24.
  • Embodiment 30 The article of Embodiment 29, wherein the article is a filter.
  • the disclosure can alternately comprise, consist of, or consist essentially of, any appropriate components herein disclosed.
  • the disclosure can additionally, or alternatively, be formulated so as to be devoid, or substantially free, of any components, materials, ingredients, adjuvants or species used in the prior art compositions or that are otherwise not necessary to the achievement of the function and/or objectives of the present disclosure.
  • the terms “a” and “an” do not denote a limitation of quantity, but rather denote the presence of at least one of the referenced item.
  • the term “or” means “and/or” unless clearly indicated otherwise by context.
  • the term “combination” is inclusive of blends, mixtures, alloys, reaction products, and the like.
  • compositions, methods, and articles can alternatively comprise, consist of, or consist essentially of, any ingredients, steps, or components herein disclosed.
  • the compositions, methods, and articles can additionally, or alternatively, be formulated, conducted, or manufactured so as to be devoid, or substantially free, of any ingredients, steps, or components not necessary to the achievement of the function or objectives of the present claims.
  • test standards are the most recent standard in effect as of the filing date of this application, or, if priority is claimed, the filing date of the earliest priority application in which the test standard appears.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyamides (AREA)

Abstract

Conformément à un mode de réalisation, l'invention concerne une composition de polyamide, comprenant un polyamide polymérisé par voie anionique, la composition de polyamide ayant une cristallinité telle que déterminée par DSC supérieure ou égale à 45 % en poids, et une porosité telle que déterminée sur la base de la masse volumique de la composition de polyamide supérieure ou égale à 10 % en volume. Conformément à un autre mode de réalisation, l'invention concerne un procédé de fabrication de la composition de polyamide précitée, qui comprend la polymérisation par voie anionique d'un mélange à base de monomère comprenant un monomère lactame cyclique, un solvant dans lequel le monomère lactame cyclique est soluble, un catalyseur et un activateur pour former le polyamide polymérisé par voie anionique.
PCT/US2018/023268 2017-03-22 2018-03-20 Compositions de polyamide cristallines poreuses Ceased WO2018175384A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201762474803P 2017-03-22 2017-03-22
US62/474,803 2017-03-22

Publications (1)

Publication Number Publication Date
WO2018175384A1 true WO2018175384A1 (fr) 2018-09-27

Family

ID=63584686

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2018/023268 Ceased WO2018175384A1 (fr) 2017-03-22 2018-03-20 Compositions de polyamide cristallines poreuses

Country Status (1)

Country Link
WO (1) WO2018175384A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020221917A1 (fr) * 2019-05-01 2020-11-05 Novochem Green Additives B.V. Composition eutectique

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4520071A (en) * 1984-04-18 1985-05-28 Nitto Electric Industrial Co., Ltd. Spherical porous polyimide powder
US6291598B1 (en) * 1996-07-30 2001-09-18 Michael C. Williams Process for the production of a polymerized material and the product produced thereby
US20090061227A1 (en) * 2005-04-15 2009-03-05 Ube Industries, Ltd. Method for purifying porous polyamide fine powder

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4520071A (en) * 1984-04-18 1985-05-28 Nitto Electric Industrial Co., Ltd. Spherical porous polyimide powder
US6291598B1 (en) * 1996-07-30 2001-09-18 Michael C. Williams Process for the production of a polymerized material and the product produced thereby
US20090061227A1 (en) * 2005-04-15 2009-03-05 Ube Industries, Ltd. Method for purifying porous polyamide fine powder

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020221917A1 (fr) * 2019-05-01 2020-11-05 Novochem Green Additives B.V. Composition eutectique

Similar Documents

Publication Publication Date Title
KR101986985B1 (ko) 폴리아미드 제조에서의 폴리에틸렌이민의 용도
KR100355649B1 (ko) 폴리아마이드및당해폴리아마이드의제조방법및당해폴리아마이드를함유한조성물
US9486981B2 (en) Use of polyethyleneimines in the preparation of polyamides
Barhoumi et al. Polyamide from lactams by reactive rotational molding via anionic ring-opening polymerization: Optimization of processing parameters.
KR20180054708A (ko) 락탐의 음이온 중합
HUE026999T2 (en) Preparations containing N-acetylcaprolactam, their preparation and use for the production of polyamide castings
HUP0201912A2 (en) Method for condensing oligo- and/or polyamides at least a compound with carbonate groups as additive and a producing process using this additive and additiv for producing oligo- and/or (co)polyamides and using this for compounding paipc mixture
Rahman et al. High crystalline, porous polyamide 6 by anionic polymerization
JP2013064420A (ja) 摺動部材
CA2993247A1 (fr) Compositions de resistance aux chocs modifiee, procedes pour les fabriquer et articles les comprenant
WO2018175384A1 (fr) Compositions de polyamide cristallines poreuses
JP6433891B2 (ja) 注型ポリアミドを製造するための触媒、それらを製造するためのプロセス、およびそれらの使用
KR20180006434A (ko) 카프로락탐 제제
JP3796479B2 (ja) コポリアミド及びコポリアミドをベースとする組成物
WO2018175386A1 (fr) Compositions polyamide comprenant un polymère thermoplastique
KR20150139923A (ko) 술폰화 폴리아릴 술폰을 함유하는 중합가능한 락탐 조성물
KR102262508B1 (ko) 음이온 개환 공중합에 의한 폴리아마이드 제조방법 및 이에 제조된 폴리아마이드
JP7657593B2 (ja) アマイド系－分子量調節剤を含むポリアマイド製造方法及びそれにより製造されたポリアマイド
KR102041358B1 (ko) 락탐을 포함하는 조성물
CN103582628B (zh) 用于生产铸型聚酰胺的新型组合物
KR102204083B1 (ko) 폴리아미드 수지의 제조방법
KR102508974B1 (ko) 신규한 폴리아미드 합성용 활성화제 및 그로부터 제조된 폴리아미드
Rusu et al. Biodegradable anionic poly (esteramide) s. Physico-mechanical properties
JP3067861B2 (ja) ポリエステルグラフト化ポリアミドおよびその製造法
KR20200049903A (ko) 중축합에 의해 폴리아미드를 제조하는 방법

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18770514

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18770514

Country of ref document: EP

Kind code of ref document: A1