WO1989000918A2 - A method of producing microcellular foams and microcellular foams of semi-crystalline polymeric materials - Google Patents

A method of producing microcellular foams and microcellular foams of semi-crystalline polymeric materials Download PDF

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Publication number
WO1989000918A2
WO1989000918A2 PCT/US1988/002567 US8802567W WO8900918A2 WO 1989000918 A2 WO1989000918 A2 WO 1989000918A2 US 8802567 W US8802567 W US 8802567W WO 8900918 A2 WO8900918 A2 WO 8900918A2
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WO
WIPO (PCT)
Prior art keywords
microcellular
pressure
semi
polymeric material
temperature
Prior art date
Application number
PCT/US1988/002567
Other languages
French (fr)
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WO1989000918A3 (en
Inventor
Jonathan S. Colton
Nam P. Suh
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Massachusetts Institute Of Technology
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Filing date
Publication date
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Publication of WO1989000918A2 publication Critical patent/WO1989000918A2/en
Publication of WO1989000918A3 publication Critical patent/WO1989000918A3/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
    • B29B7/7404—Mixing devices specially adapted for foamable substances
    • B29B7/7409—Mixing devices specially adapted for foamable substances with supply of gas
    • B29B7/7428—Methodical aspects
    • 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
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/02—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles
    • B29C44/10—Applying counter-pressure during expanding
    • B29C44/105—Applying counter-pressure during expanding the counterpressure being exerted by a fluid
    • 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
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/3469—Cell or pore nucleation
    • B29C44/348—Cell or pore nucleation by regulating the temperature and/or the pressure, e.g. suppression of foaming until the pressure is rapidly decreased

Definitions

  • Microcellular foams have been made in the past by foaming amorphous polymeric materials such as polystyrene. This process involves cell nucleation at or near the glass transition temperature of the polymer material and is more thoroughly described in U.S. Patent 4,473,665 of Martini-Vvendensky, et al. This patent, however, does not teach foaming of semi-crystalline polymers such as polyethylene and polypropylene. Attempts to produce microcellular foamed articles from semi-crystalline polymers using the . method employed for amorphous polymers have proven to be failures. The three basic problems arising when icrocellularly foaming semi-crystalline polymers result from the polymers* icrostructure. They are as follows:
  • This invention pertains to closed cell micro ⁇ cellular foams of semi-crystalline polymeric materials and a method by which these microcellular foams are produced. More specifically, this invention per- tains to a method for producing closed cell micro ⁇ cellular foams from semi-crystalline polymeric materials comprising the steps of: a) saturating the semi-crystalline polymeric material at an elevated pressure and at a temperature at or above the melting temperature of the material with a uniform concentration of gas; b) shaping the polymeric material at an elevated pressure to substantially prevent cell nucleation within the material; c) reducing the pressure to supersaturate the polymeric material with gas and thereby produce a microcellular structure in said material, and d) lowering the temperature below the melting point of said polymeric material.
  • Polypropylene is used heavily in food container applications because it does not impart any flavor to the food contained within it, and because its thermal properties allow it to be filled with hot items.
  • a microcellular foam of this material would be ideal for food service applications due to its savings in raw materials (polypropylene) , its insulating ability, its strength and its inertness to flavors.
  • FIG. 1 is a schematic representation of a horizontal extrusion die system used in producing microcellular foam from a semi-crystalline polymeric material.
  • Figure 2 is a schematic representation of a vertical extrusion die system used in producing a microcellular foam from a semi-crystalline polymeric material.
  • Figure 3 is a schematic representation of an injection molding apparatus used in producing a microcellular foam from a semi-crystalline polymeric material.
  • This invention relates to microcellular foams of semi-crystalline polymers and a method for producing these foams.
  • the invention involves heating a semi-crystalline polymer to a temperature at or above its melting point.
  • a foaming gas is then supplied to diffuse into the molten polymer.
  • the polymer con- taining the diffused foaming gas is shaped, through extrusion, injection molding or other forming processes.
  • the polymeric body is subjected to a pressure reduction in the atmos ⁇ phere surrounding it which triggers the foaming process. Further cell growth is prevented by reducing the temperature to a point below the melting point of the polymeric material. This may be done, for example, by quenching the material with water.
  • Microcellular foam is a polymeric foam with cell sizes smaller than about 100 micrometers ( ⁇ m) and ideally in the range of about 5 to about 25 ⁇ m. These void diameters are found to be small enough to enhance or at least maintain the mechanical pro- perties of the parent polymer.
  • the crystalline domain of the material is a region in which the molecules have a regular and ordered arrangement. This may be contrasted to the amorphous domains in which the structure is more random and disordered. Due to the absence of polymers with an .absolute crystalline structure, the term semi-crystalline is used here, as in the art, to denote polymeric materials con ⁇ taining crystalline domains.
  • the glass transition temperature is distin ⁇ guished from the melting temperature as follows. Glasses are actually supercooled liquids of very high viscosity. The glass transition temperature is that temperature below which free rotations of the polymer molecules cease because of intermolecular forces. In this state, the material is glassy. Above the glass transition temperature, the polymer is rubbery. All polymers have a glass transition temperature. Semi-crystalline polymers also have a melting temperature above the glass transition temperature, above which the crystalline domains dissolve, leaving a fully amorphous material. Above the melting point, these polymers are viscous or viscoelastic materials.
  • FIG. 1 A schematic representation of a system for forming microcellular foams from crystalline polymers is shown in Figure 1.
  • An extruder 30, is loaded with polymer pellets 1. These pellets are heated to a temperature above their melting point and forced through the extrusion barrel 31 by a screw 32.
  • the molten polymer 10 is forced by the extrusion screw 32 into a horizontal extrusion die 20.
  • the die contains an aperture 22, through which gas at a high pressure can be pumped to allow interaction between the polymer 10 and the gas at the polymer/gas interface 40. At this interface 40, gas will dissolve into the molten polymer.
  • the polymer 10 then passes out of the die at exit 25, at which point foaming begins due to the reduced pressure on the polymer shape.
  • the material may then be quenched with cold water or other fluids to stop the foaming process.
  • the pressure can be increased prior to or during the reduction in temperature to further assist in preventing further cell growth.
  • Figure 2 is a schematic representation of a system similar to that depicted in Figure 1; however in Figure 2 the extrusion die 20' is in a vertical rather than a horizontal orientation.
  • the advantage of this orientation lies at the polymer/die seal 100.
  • This seal prevents the diffusion gas from escaping from the die 20* through the die exit 25'.
  • Gravitational force pulls the melted polymer 10 ' to the bottom of the die 20' thereby creating the seal 100 at a point anterior to the die exit 25'. This leads to a more uniform gas diffusion within the melted polymer 10'.
  • the operation of the system is similar to that depicted in Figure 1 and is described as follows.
  • An extruder 30' is loaded with polymer pellets 1*. These pellets are heated to a temperature above their melting point and forced through the extrusion barrel 31* by a screw 32'.
  • the molten polymer 10' is forced by the extrusion screw 32' into a verti ⁇ cally oriented extrusion die 20'.
  • the die contains an aperture 22', through which gas at a high pressure maybe pumped to allow interaction between the polymer 10 ' and the gas at the polymer gas interface 40'. At this interface 40', gas will dissolve into the molten polymer. Below this interface is the polymer/die seal 100 discussed previously.
  • the molten polymer 10' then passes out of the die at the die exit 25', at which point foaming begins due to the reduced pressure on the polymer shape.
  • the material may then be quenched with cold water or other fluids or an increase in pressure to stop the foaming process.
  • Figure 3 is a schematic representation of an injection molding system useful for producing microcellular foams from crystalline polymers.
  • the figure illustrates a number of known elements including an extruder 30'', extrusion barrel 31' ', extrusion screw 32", valve 44, nozzel 46, mold 48 and a clamping hydraulic pressure means 50.
  • the pressure in the mold 48 is maintained above the foaming pressure of the gas at melt temperatures for the given initial saturation.
  • the pressure is dropped and the part is allowed to foam.
  • a pressure substan ⁇ tially equal to that within the extrusion barrel 31" must be maintained within the mold cavity.
  • the pressure can be supplied by a moveable wall 52 under hydraulic pressure for simple part geometries.
  • the mold 48 When the nucleation temperature of the part is achieved the mold 48 is either expanded or cracked to allow the pressure to reach ambient pressure. The part will then expand as the polymer material foams to the final geometry.
  • Many currently existing injec ⁇ tion molding machines may be equipped with a move ⁇ able wall 52 to allow their use in this process.
  • gases can be used to supersaturate the polymeric material.
  • air noble gases (such as argon)
  • nitrogen or carbon dioxide can be used.
  • the pressure of the gas on the raw material should be high enough to provide uniform saturation.
  • Semicrystalline polymers, such as polyethylene and polypropylene, are ideal candidates for foaming due to their low cost and good physical properties. Satisfactory results have been obtained with gas saturation pressures between approximately 750 psig and 2500 psig for polypropylene. Saturation pressures below 750 psig have been found to result in unevenly saturated samples, resulting in uneven nucleation and bubble growth.
  • the foamed material resulting therefrom was found to contain a bubble density on the order of 10 bubbles per cubic centimeter with each bubble of 5 microns in dia ⁇ meter.
  • additives can be employed to enhance cell nucleation.
  • a material such as sodium benzoate can be added to enhance cell nucleation.
  • Foamed discs of semi-crystalline polymeric material were made by injection molding in the following manner.
  • a 2" diameter, 1/16" thick disc of the material to be foamed was placed in a pressure vessel and heated to a temperature above its melting point.
  • a temperature of approximately 173°C was found to be satisfactory.
  • the molten material was then saturated with 1500 psig of nitrogen for approximately 30 minutes.
  • the temperature of the material was then lowered and the pressure was released shortly thereafter. The drop in both temperature and pressure caused a spontaneous cell or bubble nucelation and growth within the material and resulted in a foamed part approximately 1/8" thick.
  • Himont copolymer 7823 polypropylene with 6.9% by weight ethylene
  • United States Steel copolymer polypropylene with 6.9% ethylene
  • Shell nucleated polypropylene 5524 Shell polypropylene 5384
  • Himont 101 polypropylene with 40% talc by weight
  • Microcellular foaming was most successful with the two copoly ers. This is likely the effect of two copolymer characteristics: a) a smaller dropoff of the temperature-viscosity relationship near the melting point, and, b) the existence of internal interfaces at which bubbles can nucleate.
  • the Shell nucleated polypropylene also foamed easily due to the large number of nucelation sites contained within the material.
  • the other Shell polypropylene did foam but not as easily as the others because its interfacial energy is not high enough to provide energy for foaming.
  • the talc-filled Himont was difficult to foam due to the very tight bonding between the talc particles and the polymer which interfered with foaming.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)

Abstract

A method for producing a microcellular foam from a semi-crystalline polymeric material. The material is heated to its melting point at an elevated pressure and then saturated with a uniform concentration of a gas. The pressure is then lowered causing bubble nucleation and growth within the material. The material is then quenched to prevent further foaming. Bubbles on the order of 5um in diameter are produced with a bubble density of approximately 1010 bubbles/cm3.

Description

A METHOD OF PRODUCING MICROCELLULAR FOAMS AND MICROCELLULAR 'FOAMS SEMI-CRYSTALLINE POLYMERIC MATERIALS
Background of the Invention
The ability to process polymers to desired shapes and sizes is one of the properties that makes polymers highly desirable for countless industrial and commercial applications. As with all materials, cost saving methods for processing and utilizing polymers are of key importance. One method for reducing the cost of a polymer article is through the use of blowing agents which produce a foam, thereby reducing the amount of polymer per unit volume. Unfortunately, conventional foamed polymers tend to exhibit a decrease in the mechanical prop- erties.
Microcellular foams have been made in the past by foaming amorphous polymeric materials such as polystyrene. This process involves cell nucleation at or near the glass transition temperature of the polymer material and is more thoroughly described in U.S. Patent 4,473,665 of Martini-Vvendensky, et al. This patent, however, does not teach foaming of semi-crystalline polymers such as polyethylene and polypropylene. Attempts to produce microcellular foamed articles from semi-crystalline polymers using the . method employed for amorphous polymers have proven to be failures. The three basic problems arising when icrocellularly foaming semi-crystalline polymers result from the polymers* icrostructure. They are as follows:
1) low gas solubility in the crystalline domains, 2) the requirement to foam near the melting temperature rather than near the glass transition temperature, and 3) the physical size and structure of the crystals. Taking the above characteristics of semi- crystalline polymers into account, it is apparent that conventional microcellular foaming techniques will fail to provide a desirable product when used on these polymer types.
Summary of the Invention
This invention pertains to closed cell micro¬ cellular foams of semi-crystalline polymeric materials and a method by which these microcellular foams are produced. More specifically, this invention per- tains to a method for producing closed cell micro¬ cellular foams from semi-crystalline polymeric materials comprising the steps of: a) saturating the semi-crystalline polymeric material at an elevated pressure and at a temperature at or above the melting temperature of the material with a uniform concentration of gas; b) shaping the polymeric material at an elevated pressure to substantially prevent cell nucleation within the material; c) reducing the pressure to supersaturate the polymeric material with gas and thereby produce a microcellular structure in said material, and d) lowering the temperature below the melting point of said polymeric material. The products produced by this process have essentially an infinite number of uses. However, one major use is expected to be in the food service industry. Polypropylene is used heavily in food container applications because it does not impart any flavor to the food contained within it, and because its thermal properties allow it to be filled with hot items. A microcellular foam of this material would be ideal for food service applications due to its savings in raw materials (polypropylene) , its insulating ability, its strength and its inertness to flavors.
Brief Description of the Drawings The features and advantages of the invention will now be described with more detail in con¬ junction with the accompanying drawings. These drawings are not necessarily complete in every detail, but instead are intended to illustrate the principles of the invention. For example, the dimensions and specific arrangement of various components of the apparatus may affect parameters of the process, such as the gas/polymer interface. Those skilled in the art will know, or be able to ascertain using no more than routine experimen¬ tation, the optimum arrangement of apparatus for each application taking specific materials and operating conditions into account. Figure 1 is a schematic representation of a horizontal extrusion die system used in producing microcellular foam from a semi-crystalline polymeric material.
Figure 2 is a schematic representation of a vertical extrusion die system used in producing a microcellular foam from a semi-crystalline polymeric material.
Figure 3 is a schematic representation of an injection molding apparatus used in producing a microcellular foam from a semi-crystalline polymeric material.
Detailed Description of the Invention
This invention relates to microcellular foams of semi-crystalline polymers and a method for producing these foams. In its most basic form, the invention involves heating a semi-crystalline polymer to a temperature at or above its melting point. A foaming gas is then supplied to diffuse into the molten polymer. Next, the polymer con- taining the diffused foaming gas is shaped, through extrusion, injection molding or other forming processes. After being shaped, the polymeric body is subjected to a pressure reduction in the atmos¬ phere surrounding it which triggers the foaming process. Further cell growth is prevented by reducing the temperature to a point below the melting point of the polymeric material. This may be done, for example, by quenching the material with water. Optionally, the pressure can be increased prior to or during the temperature reduction to assist in preventing further cell growth. Microcellular foam is a polymeric foam with cell sizes smaller than about 100 micrometers (μm) and ideally in the range of about 5 to about 25 μm. These void diameters are found to be small enough to enhance or at least maintain the mechanical pro- perties of the parent polymer.
While often referred to as crystalline polymers, materials such as polypropylene and polyethylene exist in states which are either amophous or semi-crystalline, depending upon the process used to produce them. Ignoring the amor¬ phous state, it is more accurate to term these materials semi-crystalline rather than crystalline since no material is entirely crystalline and free of amorphous domains. The crystalline domain of the material is a region in which the molecules have a regular and ordered arrangement. This may be contrasted to the amorphous domains in which the structure is more random and disordered. Due to the absence of polymers with an .absolute crystalline structure, the term semi-crystalline is used here, as in the art, to denote polymeric materials con¬ taining crystalline domains.
The glass transition temperature is distin¬ guished from the melting temperature as follows. Glasses are actually supercooled liquids of very high viscosity. The glass transition temperature is that temperature below which free rotations of the polymer molecules cease because of intermolecular forces. In this state, the material is glassy. Above the glass transition temperature, the polymer is rubbery. All polymers have a glass transition temperature. Semi-crystalline polymers also have a melting temperature above the glass transition temperature, above which the crystalline domains dissolve, leaving a fully amorphous material. Above the melting point, these polymers are viscous or viscoelastic materials.
A schematic representation of a system for forming microcellular foams from crystalline polymers is shown in Figure 1. An extruder 30, is loaded with polymer pellets 1. These pellets are heated to a temperature above their melting point and forced through the extrusion barrel 31 by a screw 32. The molten polymer 10 is forced by the extrusion screw 32 into a horizontal extrusion die 20. The die contains an aperture 22, through which gas at a high pressure can be pumped to allow interaction between the polymer 10 and the gas at the polymer/gas interface 40. At this interface 40, gas will dissolve into the molten polymer. The polymer 10 then passes out of the die at exit 25, at which point foaming begins due to the reduced pressure on the polymer shape. The material may then be quenched with cold water or other fluids to stop the foaming process. Optionally, the pressure can be increased prior to or during the reduction in temperature to further assist in preventing further cell growth.
Figure 2 is a schematic representation of a system similar to that depicted in Figure 1; however in Figure 2 the extrusion die 20' is in a vertical rather than a horizontal orientation. The advantage of this orientation lies at the polymer/die seal 100. This seal prevents the diffusion gas from escaping from the die 20* through the die exit 25'. Gravitational force pulls the melted polymer 10 ' to the bottom of the die 20' thereby creating the seal 100 at a point anterior to the die exit 25'. This leads to a more uniform gas diffusion within the melted polymer 10'. Otherwise, the operation of the system is similar to that depicted in Figure 1 and is described as follows.
An extruder 30', is loaded with polymer pellets 1*. These pellets are heated to a temperature above their melting point and forced through the extrusion barrel 31* by a screw 32'. The molten polymer 10' is forced by the extrusion screw 32' into a verti¬ cally oriented extrusion die 20'. The die contains an aperture 22', through which gas at a high pressure maybe pumped to allow interaction between the polymer 10 ' and the gas at the polymer gas interface 40'. At this interface 40', gas will dissolve into the molten polymer. Below this interface is the polymer/die seal 100 discussed previously. The molten polymer 10' then passes out of the die at the die exit 25', at which point foaming begins due to the reduced pressure on the polymer shape. The material may then be quenched with cold water or other fluids or an increase in pressure to stop the foaming process.
Figure 3 is a schematic representation of an injection molding system useful for producing microcellular foams from crystalline polymers. The figure illustrates a number of known elements including an extruder 30'', extrusion barrel 31' ', extrusion screw 32", valve 44, nozzel 46, mold 48 and a clamping hydraulic pressure means 50. The pressure in the mold 48 is maintained above the foaming pressure of the gas at melt temperatures for the given initial saturation. When the temperature of the molded part is lowered to the appropriate nucleation temperature, the pressure is dropped and the part is allowed to foam. To keep the melt from nucleating prior to shaping, a pressure substan¬ tially equal to that within the extrusion barrel 31" must be maintained within the mold cavity. The pressure can be supplied by a moveable wall 52 under hydraulic pressure for simple part geometries. When the nucleation temperature of the part is achieved the mold 48 is either expanded or cracked to allow the pressure to reach ambient pressure. The part will then expand as the polymer material foams to the final geometry. Many currently existing injec¬ tion molding machines may be equipped with a move¬ able wall 52 to allow their use in this process.
Various gases can be used to supersaturate the polymeric material. For example, air, noble gases (such as argon) , nitrogen or carbon dioxide can be used. The pressure of the gas on the raw material should be high enough to provide uniform saturation. Semicrystalline polymers, such as polyethylene and polypropylene, are ideal candidates for foaming due to their low cost and good physical properties. Satisfactory results have been obtained with gas saturation pressures between approximately 750 psig and 2500 psig for polypropylene. Saturation pressures below 750 psig have been found to result in unevenly saturated samples, resulting in uneven nucleation and bubble growth.
When the material was saturated by nitrogen at a pressure of 1500 psig, the foamed material resulting therefrom was found to contain a bubble density on the order of 10 bubbles per cubic centimeter with each bubble of 5 microns in dia¬ meter.
Optionally, additives can be employed to enhance cell nucleation. For example, a material such as sodium benzoate can be added to enhance cell nucleation.
Specific Examples
Foamed discs of semi-crystalline polymeric material were made by injection molding in the following manner. A 2" diameter, 1/16" thick disc of the material to be foamed was placed in a pressure vessel and heated to a temperature above its melting point. For the materials employed herein, a temperature of approximately 173°C was found to be satisfactory. The molten material was then saturated with 1500 psig of nitrogen for approximately 30 minutes. The temperature of the material was then lowered and the pressure was released shortly thereafter. The drop in both temperature and pressure caused a spontaneous cell or bubble nucelation and growth within the material and resulted in a foamed part approximately 1/8" thick.
The five following polymers were used with this method: Himont copolymer 7823 (polypropylene with 6.9% by weight ethylene) , United States Steel copolymer (polypropylene with 6.9% ethylene), Shell nucleated polypropylene 5524, Shell polypropylene 5384, and Himont 101 polypropylene (with 40% talc by weight) .
Microcellular foaming was most successful with the two copoly ers. This is likely the effect of two copolymer characteristics: a) a smaller dropoff of the temperature-viscosity relationship near the melting point, and, b) the existence of internal interfaces at which bubbles can nucleate. The Shell nucleated polypropylene also foamed easily due to the large number of nucelation sites contained within the material. The other Shell polypropylene did foam but not as easily as the others because its interfacial energy is not high enough to provide energy for foaming. Finally, the talc-filled Himont was difficult to foam due to the very tight bonding between the talc particles and the polymer which interfered with foaming.
Equivalents
Those skilled in the art will recognize, or be able to ascertain, using no more than routine experimentation, many equivalents to the specific embodiments of the invention described herein. For example, rather than allowing the foaming gas to diff se into the polymer melt in the die or injec¬ tion mold, this can be done in the extrusion barrel during the extrusion process. Such equivalents are intended to be encompassed by the following claims.

Claims

1. A method of producing a microcellular foam from a semi-crystalline polymeric material comprising: a) saturating the semi-crystalline polymeric material at an elevated pressure and at a temperature at or above the melting temperature of the material with a uniform concentration of gas; b) shaping the polymeric material at an elevated pressure to substantially prevent cell nucleation within the material; c) reducing the pressure to supersaturate the polymeric material with gas thereby causing nucleation and foaming and producing a microcellular structure in said polymeric material; and d) lowering the temperature below the melting point of said polymeric material.
2. The method of Claim 1 wherein the step of saturating the material at an elevated pressure further comprises saturating the material at a pressure between approximately 750 psig and 2500 psig.
3. The method of Claim 1 wherein the microcellular voids are on the order of about 1 to about 100 microns in diameter.
4. The method of Claim 1 wherein the microcellular voids are on the order of about 5 to about 25 microns in diameter.
5. The method of Claim 1 wherein the microcellular voids are approximately 10 microns in diameter.
6. The method of Claim 1 wherein the step of saturating the material at an elevated pressure with a uniform concentration of gas further comprises saturating the material with a uniform concentration of gas chosen from the group consisting of air, noble gases, nitrogen and carbon dioxide.
7. The method of Claim 1 wherein the step of reducing the temperature and pressure to a state where the material is supersaturated further comprises the steps of first reducing the temperature and then reducing the pressure.
8. The method of Claim 1 wherein the step of processing the material further comprises processing the material by die extrusion.
9. The method of Claim 1 wherein the step of processing the material further comprises processing the material by injection molding.
10. A closed cell, microcellular foam of a semi-crystalline polymeric material.
11. The material of Claim 10 wherein the polymeric material comprises a polymer of propylene.
12. The material of Claim 10 wherein the polymeric material comprises a polymer of ethylene.
13. The material of Claim 10 wherein the material contains microcelluar voids on the order of about 1 to about 10O microns in diameter.
14. The material of Claim 10 wherein the material contains microcellular voids on the order of about 5 to about 25 microns in diameter.
15. The material of Claim 10 wherein the microcellular voids are approximately 10 microns in diameter.
PCT/US1988/002567 1987-07-29 1988-07-28 A method of producing microcellular foams and microcellular foams of semi-crystalline polymeric materials WO1989000918A2 (en)

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US5182307A (en) * 1990-11-21 1993-01-26 Board Of Regents Of The University Of Washington Polyethylene terephthalate foams with integral crystalline skins
US5223545A (en) * 1992-02-03 1993-06-29 The Board Of Regents Of The University Of Washington Polyethylene terephthalate foams with integral crystalline skins
EP0580777A1 (en) 1991-04-05 1994-02-02 Massachusetts Institute Of Technology Supermicrocellular foamed materials
EP0692358A1 (en) * 1994-06-24 1996-01-17 Corell Resin Technology B.V. Method for manufacturing a plastic board and a board obtained with this method
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WO1998031521A2 (en) * 1997-01-16 1998-07-23 Trexel, Inc. Injection molding of microcellular material
WO1999000313A1 (en) * 1997-06-26 1999-01-07 Trexel, Inc. Microcellular food container and method for storing food in such a container
US6005013A (en) * 1995-08-14 1999-12-21 Massachusetts Institute Of Technology Gear throttle as a nucleation device in a continuous microcellular extrusion system
US6169122B1 (en) 1997-12-19 2001-01-02 Trexel, Inc. Microcellular articles and methods of their production
WO2001005569A1 (en) * 1999-07-16 2001-01-25 Wavin B.V. Method for forming an article comprising closed-cell microfoam from thermoplastic
US6231942B1 (en) 1998-01-21 2001-05-15 Trexel, Inc. Method and apparatus for microcellular polypropylene extrusion, and polypropylene articles produced thereby
US6235380B1 (en) 1997-07-24 2001-05-22 Trexel, Inc. Lamination of microcellular articles
US6284810B1 (en) 1996-08-27 2001-09-04 Trexel, Inc. Method and apparatus for microcellular polymer extrusion
US6322347B1 (en) 1999-04-02 2001-11-27 Trexel, Inc. Methods for manufacturing foam material including systems with pressure restriction element
WO2001094092A1 (en) * 2000-06-06 2001-12-13 Thermaflex International Holding B.V. A process for producing physically foamed polyolefin foams and insulation foams prepared therewith
EP1321271A2 (en) * 2000-02-07 2003-06-25 Guala Dispensing S.P.A. Closure for containers, in particular plug for bottles
US6706223B1 (en) 1997-12-19 2004-03-16 Trexel, Inc. Microcelluar extrusion/blow molding process and article made thereby
US6884380B2 (en) 2000-06-14 2005-04-26 Asahi Kasei Kabushiki Kaisha Method of injection molding of thermoplastic resin
US6884377B1 (en) 1996-08-27 2005-04-26 Trexel, Inc. Method and apparatus for microcellular polymer extrusion
US6884823B1 (en) 1997-01-16 2005-04-26 Trexel, Inc. Injection molding of polymeric material
WO2008046938A1 (en) * 2006-10-17 2008-04-24 Bernardo Del Carpio Conde Method and means for producing moulded pipes with a microcellular cranial structure
US7364677B2 (en) 2000-09-29 2008-04-29 Trexel, Inc. In-mold decorated articles and methods

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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EP2815879B1 (en) 2014-09-02 2024-10-09 Mondi AG Polyethylene coextrusion film

Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1504716A1 (en) * 1963-08-16 1969-09-25 Du Pont Ultra microcellular product and process for making the same
GB1196036A (en) * 1966-11-12 1970-06-24 Basf Ag Production of Expanded Olefin Polymer Moldings.
FR2047910A1 (en) * 1969-06-24 1971-03-19 Sekisui Chemical Co Ltd
DE1704478A1 (en) * 1967-06-06 1971-05-27 Basf Ag Process for the production of profiles from foam
DE1729052A1 (en) * 1966-09-23 1971-06-03 Stamicarbon Process for the production of multicellular molded bodies
FR2071992A1 (en) * 1969-12-22 1971-09-24 Mitsubishi Petrochemical Co Expanded polypropylene
US3793416A (en) * 1969-12-24 1974-02-19 Huels Chemische Werke Ag Process for injection molding foam synthetic resin materials involving introduction of the expansion agent into the metering zone between injection molding steps
FR2228596A1 (en) * 1973-05-08 1974-12-06 Basf Ag
DE2536305A1 (en) * 1974-09-30 1976-02-26 Bakelite Xylonite Ltd STRETCHED POLYOLE FILMS WITH A SUBSTANTIALLY EVEN CELL STRUCTURE AND PROCESS FOR THEIR PRODUCTION
US3975473A (en) * 1974-09-12 1976-08-17 Union Carbide Corporation Process for production of cellular thermoplastic bodies
DE1778373B2 (en) * 1967-04-24 1977-04-14 Mitsubishi Gas Chemical Co., Inc., Tokio PROCESS FOR THE MANUFACTURING OF SIGNIFICANTLY CLOSED-CELL, SHAPED FOAM PRODUCTS FROM OLEFIN POLYMERS
EP0041380A1 (en) * 1980-05-29 1981-12-09 Sekisui Kagaku Kogyo Kabushiki Kaisha Process for producing polyethylene foams
JPS58208328A (en) * 1982-05-31 1983-12-05 Asahi Chem Ind Co Ltd Novel cellular material
JPS59168038A (en) * 1983-03-16 1984-09-21 Asahi Chem Ind Co Ltd Highly expanded, high-density polyethylene foam
US4473665A (en) * 1982-07-30 1984-09-25 Massachusetts Institute Of Technology Microcellular closed cell foams and their method of manufacture
GB2140422A (en) * 1983-04-08 1984-11-28 Asahi Chemical Ind Preparation of foam particles of ethylenic resin and foam moldings prepared therefrom
US4676939A (en) * 1984-06-14 1987-06-30 Japan Styrene Paper Corporation Process for the production of expanded particles of a polypropylene resin

Patent Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1504716A1 (en) * 1963-08-16 1969-09-25 Du Pont Ultra microcellular product and process for making the same
DE1729052A1 (en) * 1966-09-23 1971-06-03 Stamicarbon Process for the production of multicellular molded bodies
GB1196036A (en) * 1966-11-12 1970-06-24 Basf Ag Production of Expanded Olefin Polymer Moldings.
DE1778373B2 (en) * 1967-04-24 1977-04-14 Mitsubishi Gas Chemical Co., Inc., Tokio PROCESS FOR THE MANUFACTURING OF SIGNIFICANTLY CLOSED-CELL, SHAPED FOAM PRODUCTS FROM OLEFIN POLYMERS
DE1704478A1 (en) * 1967-06-06 1971-05-27 Basf Ag Process for the production of profiles from foam
FR2047910A1 (en) * 1969-06-24 1971-03-19 Sekisui Chemical Co Ltd
FR2071992A1 (en) * 1969-12-22 1971-09-24 Mitsubishi Petrochemical Co Expanded polypropylene
US3793416A (en) * 1969-12-24 1974-02-19 Huels Chemische Werke Ag Process for injection molding foam synthetic resin materials involving introduction of the expansion agent into the metering zone between injection molding steps
FR2228596A1 (en) * 1973-05-08 1974-12-06 Basf Ag
US3975473A (en) * 1974-09-12 1976-08-17 Union Carbide Corporation Process for production of cellular thermoplastic bodies
DE2536305A1 (en) * 1974-09-30 1976-02-26 Bakelite Xylonite Ltd STRETCHED POLYOLE FILMS WITH A SUBSTANTIALLY EVEN CELL STRUCTURE AND PROCESS FOR THEIR PRODUCTION
EP0041380A1 (en) * 1980-05-29 1981-12-09 Sekisui Kagaku Kogyo Kabushiki Kaisha Process for producing polyethylene foams
JPS58208328A (en) * 1982-05-31 1983-12-05 Asahi Chem Ind Co Ltd Novel cellular material
US4473665A (en) * 1982-07-30 1984-09-25 Massachusetts Institute Of Technology Microcellular closed cell foams and their method of manufacture
JPS59168038A (en) * 1983-03-16 1984-09-21 Asahi Chem Ind Co Ltd Highly expanded, high-density polyethylene foam
GB2140422A (en) * 1983-04-08 1984-11-28 Asahi Chemical Ind Preparation of foam particles of ethylenic resin and foam moldings prepared therefrom
US4676939A (en) * 1984-06-14 1987-06-30 Japan Styrene Paper Corporation Process for the production of expanded particles of a polypropylene resin

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Patent Abstracts of Japan, Vol. 8, No. 52, (C-213), & JP,A,58 208 328 (05.12.1983) ASAHI KASEI KOGYA K.K. *
Patent Abstracts of Japan, Vol. 9, No. 21, (C-263), & JP,A,59 168 038 (21.09.1984) ASAHI KASEI KOGYO K.K. *

Cited By (38)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5182307A (en) * 1990-11-21 1993-01-26 Board Of Regents Of The University Of Washington Polyethylene terephthalate foams with integral crystalline skins
EP0580777A1 (en) 1991-04-05 1994-02-02 Massachusetts Institute Of Technology Supermicrocellular foamed materials
USRE37932E1 (en) 1991-04-05 2002-12-10 Massachusetts Institute Of Technology Supermicrocellular foamed materials
EP0580777B1 (en) * 1991-04-05 2002-02-13 Massachusetts Institute Of Technology Injection molding foamed materials
US5223545A (en) * 1992-02-03 1993-06-29 The Board Of Regents Of The University Of Washington Polyethylene terephthalate foams with integral crystalline skins
US6193916B1 (en) 1994-06-24 2001-02-27 Corell Resin Technology B.V. Method for manufacturing a plastic board
EP0692358A1 (en) * 1994-06-24 1996-01-17 Corell Resin Technology B.V. Method for manufacturing a plastic board and a board obtained with this method
NL9401055A (en) * 1994-06-24 1996-02-01 Corell Resin Technology Bv Method for fabricating a plastic lamina, and lamina obtained by said method
EP0753389A2 (en) * 1995-07-14 1997-01-15 MASCHINENFABRIK HENNECKE GmbH Method of making polyurethane foam articles
EP0753389A3 (en) * 1995-07-14 1997-12-03 Hennecke GmbH Method of making polyurethane foam articles
US5834527A (en) * 1995-07-14 1998-11-10 Maschinenfabrik Hennecke Gmbh Process for the manufacture of polyurethane foam moldings
US6005013A (en) * 1995-08-14 1999-12-21 Massachusetts Institute Of Technology Gear throttle as a nucleation device in a continuous microcellular extrusion system
US6884377B1 (en) 1996-08-27 2005-04-26 Trexel, Inc. Method and apparatus for microcellular polymer extrusion
US6284810B1 (en) 1996-08-27 2001-09-04 Trexel, Inc. Method and apparatus for microcellular polymer extrusion
US6884823B1 (en) 1997-01-16 2005-04-26 Trexel, Inc. Injection molding of polymeric material
US7361294B2 (en) 1997-01-16 2008-04-22 Trexel, Inc. Injection molding of polymeric material
WO1998031521A3 (en) * 1997-01-16 1999-01-28 Trexel Inc Injection molding of microcellular material
EP1264672A1 (en) * 1997-01-16 2002-12-11 Trexel, Inc. Injection molding of microcellular material
WO1998031521A2 (en) * 1997-01-16 1998-07-23 Trexel, Inc. Injection molding of microcellular material
AU742749B2 (en) * 1997-01-16 2002-01-10 Trexel, Inc. Injection molding of microcellular material
WO1999000313A1 (en) * 1997-06-26 1999-01-07 Trexel, Inc. Microcellular food container and method for storing food in such a container
US6235380B1 (en) 1997-07-24 2001-05-22 Trexel, Inc. Lamination of microcellular articles
US6294115B1 (en) 1997-12-19 2001-09-25 Trexel, Inc. Microcellular articles and methods of their production
US6706223B1 (en) 1997-12-19 2004-03-16 Trexel, Inc. Microcelluar extrusion/blow molding process and article made thereby
US6169122B1 (en) 1997-12-19 2001-01-02 Trexel, Inc. Microcellular articles and methods of their production
US6376059B1 (en) 1997-12-19 2002-04-23 Trexel, Inc. Polyethylene foams and methods of their production
US6231942B1 (en) 1998-01-21 2001-05-15 Trexel, Inc. Method and apparatus for microcellular polypropylene extrusion, and polypropylene articles produced thereby
US6579910B2 (en) * 1999-04-02 2003-06-17 Trexel, Inc. Methods for manufacturing foam material including systems with pressure restriction element
US6322347B1 (en) 1999-04-02 2001-11-27 Trexel, Inc. Methods for manufacturing foam material including systems with pressure restriction element
US7267534B2 (en) 1999-04-02 2007-09-11 Trexel, Inc. Methods for manufacturing foam material including systems with pressure restriction element
WO2001005569A1 (en) * 1999-07-16 2001-01-25 Wavin B.V. Method for forming an article comprising closed-cell microfoam from thermoplastic
EP1321271A3 (en) * 2000-02-07 2004-01-07 Guala Dispensing S.P.A. Closure for containers, in particular plug for bottles
EP1321271A2 (en) * 2000-02-07 2003-06-25 Guala Dispensing S.P.A. Closure for containers, in particular plug for bottles
WO2001094092A1 (en) * 2000-06-06 2001-12-13 Thermaflex International Holding B.V. A process for producing physically foamed polyolefin foams and insulation foams prepared therewith
US6884380B2 (en) 2000-06-14 2005-04-26 Asahi Kasei Kabushiki Kaisha Method of injection molding of thermoplastic resin
US7364677B2 (en) 2000-09-29 2008-04-29 Trexel, Inc. In-mold decorated articles and methods
WO2008046938A1 (en) * 2006-10-17 2008-04-24 Bernardo Del Carpio Conde Method and means for producing moulded pipes with a microcellular cranial structure
ES2301388A1 (en) * 2006-10-17 2008-06-16 Jose Fernando Lopez Diaz Method and means for producing moulded pipes with a microcellular cranial structure

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