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WO2018233793A1 - Mélanges polymères hydrophiles, pouvant être moulés, et leurs utilisations - Google Patents

Mélanges polymères hydrophiles, pouvant être moulés, et leurs utilisations Download PDF

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Publication number
WO2018233793A1
WO2018233793A1 PCT/DK2018/050162 DK2018050162W WO2018233793A1 WO 2018233793 A1 WO2018233793 A1 WO 2018233793A1 DK 2018050162 W DK2018050162 W DK 2018050162W WO 2018233793 A1 WO2018233793 A1 WO 2018233793A1
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Prior art keywords
pvp
polymer composition
molded
molding
compression
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Jacques JONSMAN
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Jonsman Innovation Aps
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Jonsman Innovation Aps
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Priority to EP18820701.3A priority Critical patent/EP3642022A4/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
    • C08L39/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
    • C08L39/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
    • C08L39/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
    • B29C71/02—Thermal after-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/003—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor characterised by the choice of material
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0092—Other properties hydrophilic

Definitions

  • the present invention relates to polymer blends with intrinsic hydrophilic properties, which are suitable for manufacturing thermoformed, compression-molded objects presenting hydrophilic external surfaces.
  • Hydrophilic properties means the device will interact better with water and the device thus performs its function better and is more reliable. Some applications even depend on the device being hydrophilic, for example for capillary filling of a device with water or a water based solution. Hydrophilic materials are of particular interest for medical devices, because these devices very often are in direct contact with biological samples such as blood and pharmaceutical solutions, wherein water is the main constituent.
  • hydrophilic means "water loving", and a water droplet placed on the surface of the hydrophilic material will spread over the surface, and capillary flow will occur in enclosed geometries.
  • the hydrophilic property of a material is determined by three surface tensions: 1) The surface tension between the solid material and air, 2) The surface tension between the solid material and water, and 3) The surface tension between water and air. For practical reasons this is very often condensed into the contact angle.
  • the contact angle is measured by placing a water droplet placed on the surface of the solid material being tested and observing the resulting angle that the water droplets presents between the water-air surface, and the solid material being tested, at the point where the droplet contacts the solid material. This is the standard definition of contact angle.
  • materials with contact angles above 90° are defined as being hydrophobic, meaning “water fearing”, and materials with contact angles less than 90° are defined as being hydrophilic. Materials with contact angles around 90° are considered neutral, meaning that they are neither hydrophilic nor hydrophobic.
  • Nylon 6 Polyamide 6, PA6 polycaprolactam
  • PET Polyethylene terephthalate
  • hydrophilic ranging from mildly hydrophilic to very hydrophilic. Some of these are listed in table 2 with their contact angles.
  • hydrophilic polymers have properties that make them unsuitable for molded devices.
  • the mentioned polymers are all water soluble, and devices made of these polymers will thus dissolve over time when in use. None of the polymers works well with injection molding, PPG is a liquid polymer at room temperature, PVA is a thermoset, and PVOH is very difficult to melt. PVP is prone to both crosslinking and degradation at elevated temperatures, and is therefore very difficult to injection mold and extrude.
  • the material must be thermoformable by standard processes such as injection molding and extrusion, and must be very hydrophilic directly from the molding machine without further processing.
  • PA6/PVP compounds Unfortunately, none of these PA6/PVP compounds has been found suitable in the thermoforming industry for replacing post- molding hydrophilic treatments. Accordingly, a need for improvements to PA6/PVP compound polymers for thermoforming remains .
  • Polyvinylpyrrolidone is used extensively in a number of different fields and applications: Food thickener (E1201), paint additive, glue, coating on pharmaceutical tablets, blood plasma substitute etc. Due to the wide range of use, PVP is technically specified by several different parameters. The most common way to describe a batch of PVP is by the Fikentscher' s K-value (c.f. e.g. US 4190718) . The K-value is calculated from the viscosity of a water solution containing PVP. The higher the viscosity the higher the K-value. A batch of PVP contain a range of molecular weights.
  • the molecular weight of PVP as determined within the accuracy of the Fikentscher' s K-value provides a sufficiently accurate molecular weight determination for the purposes of the present invention.
  • compound polymers of PA6 and PVP are blend compositions comprising a broad distribution of polymer lengths of both PA6 and PVP.
  • compression molding such as injection molding and extrusion, this is intended and further is advantageous.
  • Compound polymers having broader composition ranges are better suited for compression molding, as the flow properties of the compound polymers are better adjustable for use under different compression conditions.
  • a compound polymer or, alternatively, a blend polymer is intended to be a short term for the longer, but more accurate, expression: "A polymer composition comprising a polymer A, characterized by being present in the polymer composition in a first distribution of molecular weights, and at least one further polymer B, characterized by being present in the polymer composition in a second distribution of molecular weights.”
  • a polymer composition comprising a polymer A, characterized by being present in the polymer composition in a first distribution of molecular weights, and at least one further polymer B, characterized by being present in the polymer composition in a second distribution of molecular weights.
  • a polymer composition comprising polycaprolactam (PA6) and polyvinylpyrrolidone (PVP) with a Fikentscher' s K- value of K15 accordingly shall be understood to mean: "A polymer composition comprising polycaprolactam (PA6) , and polyvinylpyrrolidone (PVP) , the PVP present in the polymer composition with a distribution of molecular weights characterizable by a Fikentscher' s K-value of K15".
  • contact angles are static contact angles measured on planar surfaces as is well known in the art. It is further well known in the art, that surface structuring, e.g. by providing spikes and pinning points on the surface to be measured; will increase the measured static contact angles above their thermodynamic equilibrium values. Static contact angles disclosed herein were measured on surfaces that were planer within the accuracy of the mold. Within the accuracy of the present experiments, measured static contact angles are exact to within ⁇ 2°.
  • a polymer composition comprising from 10 w/w% to 35 w/w% polyvinylpyrrolidone (PVP) with a Fikentscher' s PC- value from K10 to K30; from 0 w/w% to 5 w/w% of at least one additive, and from 60 w/w% to 90 w/w% polycaprolactam (PA6) or polycaprolactone (PCL) for balance.
  • the polymer composition wherein the composition comprises from 25 to 30 w/w% PVP with a Fikentscher' s K-value from K10 to K30.
  • the polymer composition wherein the composition comprises PVP with a Fikentscher' s K-value from K10 to K17.
  • the polymer composition comprises from 60 w/w% to 90 w/w% polycaprolactam (PA6) for balance.
  • PA6 polycaprolactam
  • the polymer composition wherein the composition has been compounded at a compounding temperature at least 30°C above the glass transition temperature of PA6, preferably at least 50°C above the glass transition temperature of PA6.
  • the polymer composition wherein PVP and PA6 have been dried prior to compounding of said polymer composition wherein PVP and PA6 have been dried prior to compounding of said polymer composition .
  • the polymer composition wherein the drying temperature is raised at a rate not faster than 20°C per hour.
  • the polymer composition wherein said at least one additive is selected from fillers, binders, colorants, plasticizers, anti-oxidants , clarity enhancers, nucleation agents, UV-stabilizers, strength enhancers, or flow enhancers.
  • the polymer composition wherein said at least one additive is a blue colorant, preferably Solvent Blue 104, CAS No. 116-75-6.
  • a compression-molded plastics item having at least one outer surface after molding wherein said at least one outer surface after molding has a static contact angle to water at or below 45°.
  • the compression-molded plastics item wherein said at least one outer surface after molding has a static contact angle to water at or below 25°.
  • the compression-molded plastics item wherein said item is molded from a polymer composition according to any embodiments of the first aspect and embodiment .
  • the compression-molded plastics item wherein the plastics item has been heat-treated after molding for at least 10 minutes at from 120°C to 190°C, preferably from between 130°C and 170°C for 30 to 60 minutes.
  • Figure 1 Contact angle vs. the PVP concentration, for each grade of PVP and PA6 compound polymer.
  • Figure 2 Lowest consistently measured contact angle for each grade of PVP and PA6 compound polymer.
  • Figure 3 Minimum process temperature for the different PVP grades .
  • Figure 4 The color of the hydrophilic compound PA6/PVP material vs. how yellow the PVP is.
  • a polymer composition comprising from 10 w/w% to 35 w/w% polyvinylpyrrolidone (PVP) with a Fikentscher' s K-value from K10 to K30; from 0 w/w% to 5 w/w% of additives, and from 60 w/w% to 90 w/w% polycaprolactam (PA6) or polycaprolactone (PCL) for balance.
  • PVP polyvinylpyrrolidone
  • PA6 polycaprolactam
  • PCL polycaprolactone
  • the basic principle underlying the present invention is the modification of the surface properties of polycaprolactam (PA6) or polycaprolactone (PCL) by polyvinylpyrrolidone (PVP) , wherein PA6 or PCL constitute the balancing component to 100 w/w% of the polymer compositions of the present invention .
  • the preferred embodiments of the present invention relate to the use of from 60 w/w% to 90 w/w% polycaprolactam (PA6) for balance.
  • the concentration of polyvinylpyrrolidone (PVP) with a Fikentscher' s K-value from K10 to K30 must be from between 10 w/w% to 35 w/w% (weight per total weight of polymer composition) , preferably from between 15 w/w% to 34 w/w%, from between 20 w/w% to 33 w/w%, and even more preferably from between 25 w/w% to 30 w/w% . In some embodiments the concentration can be 27 w/w% .
  • PVP having an appropriate K-value PVP- grade will provide, when forming part of the herein disclosed polymer compositions, compression-molded plastics items having at least one outer surface after molding wherein the at least one outer surface after molding has a static contact angle to water at or below 45°.
  • polyvinyl ⁇ pyrrolidone (PVP) with a Fikentscher' s K-value from K10 to K30 must be used in the polymer compositions disclosed herein in order to provide compression-molded plastics items having at least one outer surface after molding wherein the at least one outer surface after molding has a contact angle to water less than 45°.
  • the PVP-grade is from between K10 to K27, from between K10 to K25, from between K12 to K20, preferably from between K12 to K17, and even more preferably from between K12 to K15.
  • PVP-grades between K12 to K17 are highly suitable for the present compositions as are further detailed in the below experiments, as these will provide optimized properties in terms of compounding, moldability and hydrophilicity, however, with appropriate after molding heat-treatment as detailed herein, also larger PVP-grades, such as e.g. K30, will provide very low contact angles, i.e. at or below 25°.
  • the PVP is composed of at least two or more of the following PVP grades, K10, K12, K15, K17, or K30.
  • PVP grades K10, K12, K15, K17, or K30.
  • polymer compositions for use in compression molding comprise a variety of additives that are added to influence other structural or chemical properties of the resulting molded items.
  • the polymer compositions disclosed herein may comprise from 0 w/w% to 5 w/w% of additives.
  • the amount of additives are at or below 3 w/w%, at or below 1 w/w%, or at or below 0.5 w/w% .
  • the additives are selected from fillers, binders, colorants, plasticizers, anti-oxidants , clarity enhancers, nucleation agents, UV-stabilizers, strength enhancers, or flow enhancers.
  • at least one additive is a blue colorant, preferably Solvent Blue 104, CAS No. 116-75-6.
  • the concentration of Solvent Blue 104 can suitably be 30 mg Solvent Blue 104 per kg compound polymer.
  • powdered titanium oxide is very suitable for producing white molded items, without influencing the hydrophilicity of the molded surfaces.
  • the polymer composition of according to any of the herein disclosed embodiments has been prepared by thermo-mechanical means, cf. e.g. Example 2.
  • the polymer compositions according to the invention are compounded at a compounding temperature at least 30°C above the glass transition temperature of PA6, preferably at least 50°C above the glass transition temperature of PA6.
  • PVP and PA6 have been dried prior to compounding of the polymer composition.
  • PVP is dried in dry air at a first drying temperature below 35°C, which is then raised to a maximum drying temperature of 100°C, optionally under vacuum.
  • the drying air has a water content at or below 100 ppm water.
  • the drying temperature is raised at a rate at or below 20°C/h, at or below 15°C/h, preferably at or below 10°C/h, or at or below 5°C/h.
  • a compression-molded plastics item having at least one outer surface after molding wherein the at least one outer surface has a static contact angle to water after molding at or below 45°.
  • the compression-molded item has been manufactured by injection molding or by extrusion.
  • the compression-molded item of the invention has a static contact angle to water after molding at or below 40°, preferable at or below 35°, more preferable at or below 30°, or even more preferable at or below 25°.
  • the static contact angle to water approaches the static contact angle to water of PVP itself .
  • the compression-molded plastics item is molded from a polymer composition according to any of the embodiments disclosed herein.
  • the compression-molded plastics item is molded from a polymer composition comprising polycaprolactam (PA6) .
  • the compression-molded plastics item of the invention is heat-treated after molding for at least 10 minutes at from 120°C to 190°C, preferably from between 130°C and 170°C for 30 to 60 minutes.
  • a blue colorant such as preferably Solvent Blue 104
  • post-molding yellowing will modify the blue color of the colorant and provide in a controlled manner a green color to the molded object.
  • the colorless to yellow tones of the compound material can then be prevented by changing to blue to green tones by adding a blue colorant to the compound, such as 30 mg/kg Solvent Blue 104.
  • a blue colorant such as 30 mg/kg Solvent Blue 104.
  • the present inventor has found 30 mg Solvent Blue 104 per kg compound polymer very suitable with a post-molding heat treatment for yellowing using 135°C at 25% RH (relative humidity) over a time up to three hours, for providing all color tones of Figure 4, depending on the time the heat treatment was stopped. Likewise, yellowing using 110°C at 10% RH (relative humidity) , over a time up to five hours, provided all color tones of Figure 4, again depending on the time the heat treatment was stopped.
  • increasing the concentration of the colorant will increase the post-molding treatment times to obtain a given green tone, and lowering the colorant concentration will decrease the post-molding treatment time to obtain the same given green tone.
  • small amounts, preferably below 1 w/w%, of PVP-grades above K17, such as e.g. K30 or K60, are added to the polymer compositions of the invention, as a colorant additive.
  • PVP-grades discolor more easily under influence of heat and humidity, the overall time to obtain a given color grade is reduced, however. If the higher-grade PVP concentration is kept low, the contact angle is not significantly influenced. Accordingly, there is herein disclosed a method of providing a compression-molded plastics item manufactured from any of the polymer compositions comprising PA6 and PVP disclosed herein with a controlled yellow color-grade, the method comprising :
  • the post-molding heat-treatment for yellowing is performed using 135°C at 25% RH (relative humidity) over a time up to three hours.
  • plastics item is molded from a polymer composition comprising a blue colorant, preferably comprising Solvent Blue 104, CAS No. 116-75-6, and even more preferably comprising Solvent Blue 104, CAS No. 116-75-6 in a concentration between 10 mg Solvent Blue 104 per kg polymer composition to 50 mg Solvent Blue 104 per kg polymer composition, preferably comprising Solvent Blue 104, CAS No. 116-75-6 in a concentration of 30 mg Solvent Blue 104 per kg polymer composition.
  • a blue colorant preferably comprising Solvent Blue 104, CAS No. 116-75-6, and even more preferably comprising Solvent Blue 104, CAS No. 116-75-6 in a concentration between 10 mg Solvent Blue 104 per kg polymer composition to 50 mg Solvent Blue 104 per kg polymer composition, preferably comprising Solvent Blue 104, CAS No. 116-75-6 in a concentration of 30 mg Solvent Blue 104 per kg polymer composition.
  • Example 1 Comparative compound polymers comprising PVP
  • PA6 and PVP were compounded, injection molded, and the resulting contact angles measured as static contact angle between water and the molded surfaces.
  • Compounding of the polymers were done according to normal procedures as are known in the art by preparing plastic formulations by mixing or/and blending polymers and additives in a hot molten state. The raw materials were automatically dosed usually through feeders/hoppers. This step was usually followed by extrusion compounding, wherein the hopper feed the inlet of the extrusion screw, thereby gradually transporting the polymers towards the extrusion die resulting in an extrudate. With the screw itself confined in a barrel comprising different zones that can be heated according to the polymer properties, temperatures could be varied during compounding. The extrudate, which in general looks like long plastic strands, are then cut into the desired pellet size by a granulator and are subsequently available for re-melting during compression molding.
  • PA6 polycaprolactone
  • the compounding must be done at a temperature where both polymers have a viscosity low enough to allow intermixing.
  • the compounded polymers were observed and measured for contact angle to water on all commercially available grades of PVP (K12, K15, K17, K30, K60, K90), in concentrations from 0 w/w% PVP to 35 w/w% PVP (weight of PVP per total weight of compound polymer) .
  • Figure 1 shows graphs of water contact angle vs. the PVP concentration in the molded compound. Data are included for PA6 compounded with PVP K12, K15, K17, K30, K60 and K90.
  • a molded PA6/PVP compound is most hydrophilic when the PVP concentration is 25% to 30%.
  • Low K-Values give more hydrophilic compounds, but K12, K15 and K17 give nearly the same results.
  • PVP- grades above K30, e.g. K90 and K60 reduce the contact angle too little to make a significant change in hydrophilicity .
  • any compounding of PA6 with PVP will result in a lowering of the contact angle of a surface molded from the compound polymer.
  • the PVP concentration is from 20 w/w% to 35 w/w%, even more pronounced from 25 w/w% to 30 w/w% .
  • PVP will lower the contact angle of PA6 for all polymer lengths of PVP, but as mentioned even at the optimum PVP concentration (25-30%), PVP-grades above K30, e.g. K90 and K60, reduce the contact angle too little to make a significant change in hydrophilicity .
  • Figure 2 shows the graph of the contact angle obtained at the optimum PVP concentration, for PVP-grades K12, K15, K17, K30, K60 and K90.
  • Low K-Values give more hydrophilic compounds, and further it can be observed that below a certain threshold between K-Values 17 and 30, the contact angle is not lowered further by lowering the K-Value. This indicates that the K-Value should be below a certain threshold (17-30) to give maximum reduction of the contact angle.
  • already K30 will provide lowest contact angles (39°), which are within the region of very hydrophilic surfaces for the purposes of the present invention.
  • the resulting molded objects are hydrophilic but not (significantly) hygroscopic.
  • the weight concentration of PVP in compound polymers suitable for molding hydrophilic surfaces must remain sufficiently low to avoid that the resulting molded surface from the compound polymer of PA6 and PVP becomes hygroscopic as well as hydrophilic.
  • Figure 3 shows the minimum process temperature for the different PVP grades (black curve) , and the standard compounding and molding process temperature range for PA6 (grey shading) .
  • Figure 3A shows equidistant data point spacing for clarity of viewing, whereas Figure 3B shows the same data linear in K-value.
  • the graphs in Figure 3 illustrate the thermal compatibility of PA6 and PVP with different K-Values.
  • the black curve is the preferred minimum compounding temperature for the PVP grade (50°C above the glass transition temperature) .
  • the grey shading is the preferred compounding and molding process temperature range for PA6, 210°C to 280°C. Compounding PA6 and PVP at the preferred temperature of at least 50°C above the glass transition temperature of the respective polymers thus require; that the compounding temperature is above the black curve and in the grey zone.
  • the minimum process temperature is therefore 210°C for all grades of PVP at the preferred compounding temperature of 50°C above the glass transition temperature.
  • PVP will degrade thermally. Above a specific degradation temperature, the PVP will discolor in orange or green tones, lose weight, crosslink the PVP polymer chains and produce small, undefined molecules from the degrading PVP. The result is a brittle and non-moldable material with discoloration, and having reduced and non- reproducible hydrophilic properties. Degradation of the PVP is unacceptable, and the process temperature for compounding must thus be below the degradation temperature.
  • red curve is the temperature where the PVP will start to degrade thermally. Degradation of the PVP is unacceptable, and the process temperature must thus be below the red curve but above the black curve.
  • PVP K12 and K15 degrades at a significantly higher temperature than PVP K17, K30, K60 and K90.
  • the mechanism behind this difference is unclear.
  • PVP K17, K30, K60 and K90 can be compounded with PA6, but only above the degradation temperature. Degradation of the PVP is thus inevitable for these polymers at the preferred compounding temperature.
  • Only PVP K12 and K15 have a non-degrading process window as indicated by the green bars in Figure 3 for the preferred compounding temperature of at least 50°C above the glass transition temperature of both PA6 and PVP.
  • PVP polymers of grades K17, K30, K60 and K90 can be compounded with PA6, but not without some degradation of the PVP at the preferred compounding temperature, but PVP K17 can be made part of the working range by lowering the compounding temperature to 30 °C above the glass transition temperature of PA6. This is not possible for PVP-grades above K17, as for these PVP-grades the minimum process temperature is always above the minimum degradation temperature of the respective PVP-grade.
  • the unexpected and highly beneficial effect is that it is possible to process (compound, extrude and mold) , PVP K12 and K15 with PA6 without any degradation of the PVP during the process. This results in molded and extruded parts or items being reproducibly highly hydrophilic, without crosslinking, discoloration or degradation.
  • Example 5 Leaching of PVP from compound PA6/PVP polymers
  • PVP is a water-soluble polymer
  • some of the PVP in the compound may leach into water when water is in permanent contact with a PVP-comprising material over prolonged times. Leaching of PVP into a contacting water solution is undesired because it will contaminate the solution, and will swell and deform the molded device.
  • Table 6 shows the dry weight loss of a molded device (PA6 + 25 w/w% PVP) after 60 days in contact with water.
  • PVP K12 is the lowest K-Value PVP grade currently available commercially. If PVP with lower K-Value were available, they would not be useful for compounding, although these would be as hydrophilic as PVP K12, K15 and K17, but would leach much faster than these grades. For this reason, the PVP-grades having a K-Value below 10 are less preferred embodiments of the invention.
  • Example 6 Heat-treating of molded devices
  • the contact angle is reduced the most by heat treating the molded device at temperatures of at least 120°C for at least 10 minutes, but preferably between 130°C and 170°C, for 30 to 60 minutes.
  • PA6 is mostly colorless but PVP may have a color ranging from very faintly yellow to dark yellow, cf. Figure 4, depending on residual water in the PVP.
  • the compound material thus may also have a yellow color tone.
  • the yellow tone is in general undesirable and therefore should be controlled and minimized, particularly if transparent molded items are desired.
  • PVP have two modes of interaction with H20, a relatively weak association and hydrolysis.
  • the weak association is what makes PVP water soluble, hygroscopic and hydrophilic.
  • the weakly associated water can be removed by drying at elevated temperature in dry air or vacuum.
  • Hydrolysis on the other hand, cause an irreversible chemical change in the PVP polymer, which cannot be reversed by drying.
  • the polymer chains remain intact and the hydrophilic sites are unaffected, but the chemical change causes the yellow color, and appears to be associated with unwanted oxidation of the pyrrolidone ring.
  • the primary properties of the polymer remain the same, but the material becomes yellow.
  • Hydrolysis require a combination of moisture and heat to occur. It was found that in PVP powder and in the compound polymer, no hydrolysis would occur below 120°C. Above 120°C, hydrolysis will occur progressively faster for higher temperatures. If no moisture is available hydrolysis cannot occur, and the polymer is stable at much higher temperatures. It was found that the yellow discoloration caused by hydrolysis could be prevented by drying both the PVP and PA6 raw materials before compounding, and keeping them dry during storage and compounding.
  • the present inventor has found that the PVP preferably should be dried in dry air having a water content preferably at or lower than 100 ppm, first at low temperatures, e.g. starting at room temperature, and then slowly increasing the temperature to a maximum 100°C. Vacuum can optionally be supplied in the drying process. Drying of PA6 can be done by traditional means.
  • FIG 4 is detailed the color of the hydrophilic compound material vs. how yellow the PVP is.
  • the PVP is colorless, and becomes progressively more yellow towards the right.
  • the top row is the compound material without colorant, and the bottom row is with Solvent Blue 104, CAS No. 116-75- 6, added to the compound.
  • Solvent Blue 104 CAS No. 116-75- 6, added to the compound.
  • the yellow tone of the PVP together with the blue color additive will provide the compound material with a green tone.
  • the yellow tone could be increased by a heat treatment in low humidity air.
  • the humidity in air will diffuse into the PVP powder and into the compound polymer pellets, and there cause more discoloration. If this is done in a controlled manner (temperature, relative humidity and time) , then the yellow color can be set to a standard yellow tone. Yellowing using 135°C at 25% RH (relative humidity) over a time up to three hours, provided all color tones of Figure 4, depending on the time the heat treatment was stopped. Likewise, yellowing using 110°C at 10% RH (relative humidity) , over a time up to five hours, provided all color tones of Figure 4, again depending on the time the heat treatment was stopped. Raising the temperature further is possible; however, the influence of the temperature on the hydrophilic properties of the molded surfaces then must be taken into account (cf . Example 6) .
  • Example 8 Polycaprolactone and PVP
  • PA6 polycaprolactam
  • PCL polycaprolactone
  • PCL and 1% w/w PPO resulted in molded objects with contact angles of 25.4°
  • compositions comprising PCL preferably comprise from 25 to 30 w/w% PVP with a Fikentscher' s K-value from K10 to K30.
  • the compositions preferably comprise PVP with a Fikentscher' s K-value from K10 to K17.
  • the polymers PA6 and PVP should preferably be dried prior to compounding, but in some embodiments, may be allowed to discolor in the presence of small amounts of water in the PVP to provide a controlled yellow color. 5. Optimally, receive heat treatment after molding for at least 10 minutes at 120°C, but preferably between 130°C and 170°C, for 30 to 60 minutes.

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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)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Casting Or Compression Moulding Of Plastics Or The Like (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)

Abstract

L'invention concerne un matériau polymère hydrophile qui est hydrophile directement après avoir été soumis à des procédés de thermoformage tels que le moulage par injection et l'extrusion. Le matériau selon l'invention est un matériau composite à base de polycaprolactame (PA6) ou de polycaprolactone (PCL) composé de polyvinylpyrrolidone (PVP), le polymère composite selon l'invention étant très hydrophile et étant thermoformable en fonction du type, de la qualité et de la concentration en polyvinylpyrrolidone (PVP), une importance moindre étant conférée au polymère d'équilibre.
PCT/DK2018/050162 2017-06-21 2018-06-21 Mélanges polymères hydrophiles, pouvant être moulés, et leurs utilisations Ceased WO2018233793A1 (fr)

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DKPA201700367A DK201700367A1 (en) 2017-06-21 2017-06-21 A hydrophilic polymeric material
DKPA201700367 2017-06-21

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WO2021023726A1 (fr) * 2019-08-05 2021-02-11 Basf Se Préparation de granules de polyvinylpyrrolidone réticulée hydrodispersables ne formant que peu ou pas de poussières
WO2021245069A1 (fr) 2020-06-03 2021-12-09 Mbh-International A/S Buse de lavement et dispositif de lavement comprenant ladite buse de lavement

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GB2108135A (en) * 1981-07-27 1983-05-11 Ethicon Inc Polyamide surgical device and method for producing the same
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CN101747624A (zh) * 2009-12-11 2010-06-23 杭州师范大学 吸湿性细旦/超细旦锦纶母粒、锦纶及其制备方法
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Publication number Priority date Publication date Assignee Title
WO2021023726A1 (fr) * 2019-08-05 2021-02-11 Basf Se Préparation de granules de polyvinylpyrrolidone réticulée hydrodispersables ne formant que peu ou pas de poussières
CN114174487A (zh) * 2019-08-05 2022-03-11 巴斯夫欧洲公司 低起尘或不起尘的水分散性交联聚乙烯吡咯烷酮颗粒的制剂
WO2021245069A1 (fr) 2020-06-03 2021-12-09 Mbh-International A/S Buse de lavement et dispositif de lavement comprenant ladite buse de lavement
EP4400129A2 (fr) 2020-06-03 2024-07-17 Qufora A/S Procédé de fabrication d'une buse de lavement, buse de lavement obtenue par ledit procédé et dispositif de lavement comprenant ladite buse de lavement
EP4400129A3 (fr) * 2020-06-03 2024-07-31 Qufora A/S Procédé de fabrication d'une buse de lavement, buse de lavement obtenue par ledit procédé et dispositif de lavement comprenant ladite buse de lavement

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EP3642022A1 (fr) 2020-04-29
DK201700367A1 (en) 2019-01-30

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