HUT72760A - Apparatus and process for producing thermoplastic products having oriented components, and the product - Google Patents

Description

COPIES

inventors:

SUWANDA, Dedo [CA] address: 59 Falcon Street, Toronto, Ontario M4S 2P4 Canada, CA

PABEDINSKAS, Arunas, A. [CA] Address: 12 Laurel Avenue, Etobicoke, Ontario M9B 4S8 Canada, CA

ZHOU, Vincent, Weixing [CA] at Apartment 1619, 30 Charles Street West

Toronto, Ontario M4Y 1R5 Canada, CA

WOODHAMS, Raymond, T. [CA] at 33 The Palisades,

Toronto, Ontario M6S 2W9 Canada, CA

Date of announcement: PCT notification number:

PCT Publication Number:

August 22, 1994 PCT / CA94 / 00457 WO 95/05932

Announcements based on EU priorities:

Country: United States of America, US Date: 23 August 1993

On the Act: 08 / 110,688

Country: United States of America, US

Date: November 12, 1993

Acts by: 08 / 150,877

The present invention relates to a process for the continuous production of thermoplastic products having oriented components. The thermoplastic mixture may contain a filler. Preferably, the filler is characterized by a high aspect ratio (length per diameter). The filler material may be an inorganic filler such as mica sponge talcum, glass and carbon fiber short fibers or organic cellulose materials which are wood / forest by-products or agricultural by-products. Plastics such as polyolefins, vinyls, styrenes, polyesters and polycarbonates can be used. The process can be used to produce both foamed products made in one piece and substantially solid products which may have different shapes, having a bending strength and modulus of 2 to 10 times greater than those of conventionally manufactured products made of the same plastic / polymer material (foamed and foamed). nemhabosított). The process product may contain up to 75% filler content. The product, which is made by an extrusion process that orientates the thermoplastic polymer and filler, if present, is in the longitudinal direction during extrusion and prevents the relaxation of the thermoplastic polymer, thereby retaining the reported orientation. In connection with a single foam core embodiment, the tool structure is designed to allow the orientation of the polymer molecules and filler particles, if present, to provide an oriented layer | create; to create a cavity in the thermoplastic mixture; ii) foaming the thermoplastic mixture into the cavity under the effect of the blowing agent; and cooling the thermoplastic mixture to form a co-produced foamed product.

Typical Figure 2.

-21996 FEB>

Representative: SWORKS Workshop for Intellectuals and Property BT 1134 Budapest, Dévai u. 22-26 / B patent attorney: Tamás Mester Service invention

Thermoplastic products with process oriented components

Applicant: and the apparatus and product for this purpose - Patent Application of the Invention SRP INDUSTRIES LTD, (CA / CA) address: l Valleywood Drive, Unit 1, Markham, Ontario L3R 5L9, Canada, CA inventors: SUWANDA, Dedo [CA] address: 59 Falcon Street, Toronto, Ontario M4S 2P4 Canada, CA PABEDINSKAS, Arunas, A. [CA] Address: 12 Laurel Avenue, Etobicoke, Ontario M9B 4S8 Canada, CA ZHOU, Vincent, Weixing [CA ] address: Apartment 1619 30 Charles Street West Toronto, Ontario M4Y 1R5 Canada, CA WOODHAMS, Raymond, T [CA] at 33 The Palisades, Toronto, Ontario M6S 2W9 Canada, CA

- 1 Date of notification: 22 August 1994

Priority Submissions:

Country: United States of America, US

Date: August 23, 1993

On the Act: 08 / 110,688

Country: United States of America, US

Date: November 12, 1993

Acts by: 08 / 150,877

PCT Application No. PCT / CA94 / 00457

PCT Publication No. WO 95/05932

The present invention relates to a method and apparatus for producing thermoplastic mixtures. More specifically, it relates to the production of thermoplastic mixtures having longitudinal orientation polymer molecules. The products produced by this process may be solid or have hollow or integral foamed cores.

Thermoplastic polymers have been widely used for years. However, a disadvantage of thermoplastic, extruded polymers is that they have poor mechanical properties, such as their load bearing capacity, compared to materials such as wood or metal. These poorer mechanical properties narrow the range of applications in which most thermoplastic polymers can be used.

Many efforts were made to develop polymers with improved mechanical properties. While these poliemers, which are generally referred to as engineering polymers, have better mechanical properties than those referred to as commercial thermoplastic polymers (polyethylene, polypropylene, polystyrene, polyvinyl chloride), however, changes in mechanical properties typically result in higher prices.

Alternatively, various means have been proposed to improve the mechanical properties of commercial thermoplastic polymers. One of the most common methods is to provide a reinforcing filler to the thermoplastic polymers. Materials that are typically used as reinforcing fillers have a significantly larger aspect ratio (i.e., length to effective diameter), such as fibers or thin plates, and have properties such as stiffness greater than thermoplastic. polymer. As a result of the reinforcing effect of the filler, the resulting composite material typically has a significantly superior mechanical property compared to a pure thermoplastic polymer. Reinforcing fillers may be made of glass, carbon, metal ceramics, or naturally occurring, such as cellulose fibers, asbestos, mica or talc. A wide variety of polymers are available commercially, which contain different fibrous or mineral fillers.

Another way to increase the mechanical properties of thermoplastic polymers is to direct a significant portion of the polymer molecules in the same direction or orientation. Thus, we utilize the strong carbon-carbon backbone of the polymers where it is present. The orientation of the polymer molecules increases the rigidity and strength of the resulting product. Various methods have been proposed which increase the mechanical properties of thermoplastic polymers by orientation. In the filament, the polymer fibers are pulled after leaving the tool, and consequently the polymer molecules are oriented in the direction of the pull. In the case of film blowing, two-axis orientation (both parallel and perpendicular to the machine direction) is achieved under high pressure air by stretching an annular extrudate. Expansion of the extrudate results in circumferential and axial stretching. In both processes, the resulting product has dimensions that allow for rapid cooling that retains the orientation it has been given. For larger sections, the ability to cool the gauge to maintain the orientation to be communicated is substantially more difficult, especially since conventional extrusion processes generally employ temperatures that are well above the melting or softening point of the thermoplastic polymer.

Another method is disclosed in U.S. Patent No. 4,734,240, issued to Chung and his associates on March 29, 1988, which is limited to a method for extruding polymers, which polymers have an anisotropic melt phase as shown in the title and claims. An important element of this process is that during the cooling step, the extrudate will be ca. It is subjected to 1.5: 1 to 10: 1 peeling. It is well known that, in order to reach the tensile stress, the pulling tension should be applied or the extrudate should be pulled.

A solution to the problem of sufficient cooling is solid phase extrusion, in which the orientation of the polymer molecules occurs under the melting point or softening point of the thermoplastic polymer. For example, UK 2 207 436 (Ward et al., 1989) describes a process for orientation of linear polyethylene molecules by extrusion in solid phase. This solid phase deformation process occurs in a hydraulic tool extruder and ranges from 150 MPa to 250 MPa (22,000 to 36,000 psi). ) to overthrow the polyethylene through the die under the melting point of polyethylene. However, the press

-3extruding is a slow and non-continuous process that puts a lot of pressure and is uneconomical for most commercial applications.

In accordance with the present invention, it has been found that all molecular weight thermoelastic polymers can be continuously extruded to produce different profiles having substantial orientation. This increases the strength and modulus of the resulting product compared to the conventional extrusion process. In addition, the extrusion process of this invention can orient both thermoplastic polymer molecules and filler particles that may be present in the same direction during extrusion and substantially prevent relaxation of the reported orientation.

Summary of the Invention:

The present invention provides a process for the continuous production of thermoplastic products having oriented components. The process includes the steps of providing a thermoplastic mixture comprising a thermoplastic polymer. The thermoplastic mixture is brought to a predetermined temperature range that is just above and includes the softening point of the thermoplastic mixture by which a molten thermoplastic mixture is produced. The molten thermoplastic mixture is passed through the tool, the thermoplastic mixture is subjected to a converging stream through the tool to provide longitudinal orientation to at least a portion of the thermoplastic polymer. The thermoplastic mixture is cooled after the longitudinal orientation is communicated below the softening temperature to preserve the orientation indicated and to solidify the thermoplastic mixture. The products may be concave or hollow.

Another aspect of the invention is to provide a process for the continuous manufacture of a thermoplastic product having oriented components and a foamed core. .The process includes the steps of providing a thermoplastic mixture, including a thermoplastic polymer and a blowing agent (additive). The thermoplastic mixture is brought to a predetermined range of temperature, which is just above the softening point of the thermoplastic mixture, and is produced by a molten thermoplastic mixture. The molten thermoplastic mixture is passed through the tool and an internal cavity is formed therein. The thermoplastic mixture is subjected to a converging stream through the tool to provide longitudinal orientation with at least a portion of the thermoplastic polymer. The disclosed longitudinal orientation is retained in the outer layer of the thermoplastic polymer and therefore forms an oriented outer skin layer. The thermoplastic mixture is foamed into the cavity. The thermoplastic mixture is cooled below the softening point of the thermoplastic mixture to solidify the thermoplastic mixture. By producing the products according to this aspect of the invention, uniform foam sections are obtained which consist of a solid oriented outer layer and a foamed core.

In another aspect of the invention, there is provided a device for producing a thermoplastic product having oriented components of a thermoplastic mixture having a thermoplastic polymer. The device comprises a device for bringing the thermoplastic mixture into a predetermined temperature range that is just above or below the softening point of the thermoplastic mixture. It is downstream of it. a tool having internal walls, an inlet, an output and a channel between the input and the output, the diameter of the inlet is larger than the output, some of the inner walls are cohesive and a convergent gateway is defined in which the thermoplastic mixture is in use in use it flows under the tool to communicate the longitudinal orientation with at least a portion of the polymer molecules. The device also comprises a pressure means for pushing the heated thermoplastic mixture through the tool and a cooling means downstream of the constricted channelway for cooling the thermoplastic mixture. Optionally, the device may include a mandrel disposed in the die and wherein the mandrel causes a cavity to be formed in the thermoplastic mixture.

Another aspect of the present invention is to provide a thermoplastic product comprising a thermoplastic composition comprising a thermoplastic polymer having a rigid solid outer layer having an outer layer longitudinally oriented polymer and a uniformly low density foamed interior.

A brief description of the drawings:

The process of this invention is illustrated by means of examples, where reference is made to the accompanying drawings, in which:

Figure 1 is a view of a device for manufacturing thermoplastic products in accordance with the present invention;

Fig. 2 is a detailed enlarged sectional view of a portion of the apparatus, which comprises part 2 of Fig. 1, which is configured to produce solid products;

Figure 3 is a detailed enlarged sectional view of a portion of the device, which comprises part 2 of Figure 1 configured to produce hollow and co-manufactured foam products;

Figure 4: Section 4-4 of Figure 3

Fig. 5 is a cross-sectional view of the circular symmetrical hollow section which can be produced by the assembly shown in Fig. 3;

Fig. 6 is a cross-sectional view of a single-piece, circularly symmetrical gauge section, with a gauge-oriented solid outer skin layer which can be produced by the assembly of Fig. 3.

Detailed Description of the Invention:

In the present process, the thermoplastic mixture is continuously extruded from an extruder through a tool assembly comprising a connecting piece, a container, a tool and a calibration device and a mandrel for hollow and one-piece molded foam products. First, the container is used to homogenize the mass temperature of the thermoplastic mixture, secondly, to ensure uniform distribution of the lubricant before entering the die, which lubricant is a lubricant. it can be injected between the inner walls of the tool and the thermoplastic mixture. The thermoplastic mixture first passes through the coupling piece and the reservoir due to the conveyor movement of the extruder screw and is then pushed through the converging tool. The lubricant is used to promote stretch flow and reduce shear flow through the tool. The tool is designed to provide longitudinal orientation with polymer molecules and, if present, filler particles. The process conditions are selected to facilitate orientation in the tool and then retain the orientation indicated and consolidate the resultant product. Vacuum calibration devices or gauges, punches, caterpillar pullers, and other flow control devices known to be used in the downstream of the calibration means to further improve product quality and increase productivity. The term "thermoplastic mixture" is understood to mean a mixture of thermoplastic polymer and additives such as dyes, stabilizers, flame retardants, lubricants, pharmaceutical auxiliaries and the like. In addition, the thermoplastic mixture may or may not contain fillers, in particular reinforcing fillers, surfactants, and physical and / or chemical blowing agents. Embodiments of the construction for the manufacture of solid, hollow or single-molded thermoplastic products having a degree of longitudinal molecular orientation and, if present, filler with filler dispensing, starting with the process disclosed below for discussing and preparing the raw materials used, which have a high modulus materials can be used to produce products.

Equipment and method for producing solid products:

Referring to FIGS. 1 and 2, there is illustrated an embodiment of a structure 10 for the manufacture of solid, high modulus thermoplastic products using the method of the present invention. The structure consists of a series of 12 extruders, 14 tool assemblies, 16 coolers, 18 drawers and 20 cutting blades. The extruder 12, which may be one of a wide variety of different types, may be known as single or twin screw extruders used to melt and transport the thermoplastic. a passage through the passage 17 into the tool as described in detail in FIG.

Figure 6. The process conditions in the extruder 12 are selected to ensure the melting of the thermoplastic mixture.

Figure 2 shows a longitudinal section of the tool assembly 14 configured to produce solid or non-foamed oriented thermoplastic circular symmetric sections according to the present invention. It will be appreciated by those skilled in the art that the non-foamed term refers to substantially solid products. It is clear that, depending on the material, natural blowing agents (such as water) may be present which cause some degree of foaming. It is also clear that this method can be used to produce a profile profile of all kinds with a profile having a constant cross-section, provided that the tool assembly 14 is configured to produce the desired profile. The tool assembly 14 further comprises a connecting piece 30 connected to the extruder tube 24 of the extruder. with a crusher plate located between the end of 24 tubes and the connection piece 30. The tool assembly 14 comprises 40 containers downstream of the upper end of the flow, connected to the connector 30, a tool 60, a tool 100 (calibration device). The conveyor activity of the 26 extruder screws in the extrusion tube 24 pushes the molten thermoplastic mixture into the connection piece 30 on the crusher 28. The shape of the connection piece 30 is designed to be attached to the upper flow 32 by the known means for the extruder tube 24 by a gradual transition from the upstream section 32 to the downstream or outlet portion 34 of the connecting piece 30 which fits into the upstream inlet portion of the container section 40 . The connection piece 30 and container 40 may be constructed as a section in some cases.

One or more channels 52 are provided on the side of the container 40 through which the lubricant can be injected between the container wall and the thermoplastic mixture. 52 is advantageously shaped, sized and arranged in space to ensure that the lubricant is evenly distributed around the inner wall of the container 40, thereby providing an equal access to the exterior of the thermoplastic mixture as it is passed through the channel 17. The thermoplastic mixture may also contain a lubricant added to the mixture prior to extrusion. As shown in Figure 1, the lubricant which may be injected through a device 56, which may be a metering pump, a syringe pump, a toothed syringe, or any other known device that can continuously deliver the required amount of lubricant at a sufficiently high pressure to overcome the internal pressure of the container. The lubricant is used to promote longitudinal flow and to reduce cross-flow through the tool 60. Injection lubricants may include silicone oils, liquid paraffin, glycerol, fatty amides and other liquid lubricants.

the length of the container is chosen so that there is sufficient time for the lubricant to uniformly settle around the outer circumference of the thermoplastic mixture.

In addition, the container 40 must be long enough to ensure that the thermoplastic mixture enters the die 60 at the desired temperature and that the temperature of the mixture is as uniform as possible along its cross-section.

The design of the tool 60 is essential for the success of the process. First, the output section of the tool 60 must correspond to the profile of the desired profile. Second, the tool profile should be carefully designed with regard to the degree of molecular orientation resulting from the result and the degree of filler orientation (if filler is present), the extruding power, and the appearance of the product surface. In order to promote the orientation of the polymer molecules and filler particles (if filler is present) in the flow direction, it is desirable to pressurize the thermoplastic mixture on the cohesive profile tool so that the tool will indicate the permanent deformation with the molten mixture. The tool 60 is shaped to provide a converging flow of the molten mixture. It will be appreciated that container 40 and tool 60 may in some cases be constructed as a section.

The drag ratio of the tool, defined by the ratio of the tool inlet and outlet cross-sectional areas, should be large enough so that the resulting longitudinal flow is sufficient to orient the polymer molecules and filler particles (if a filler is present) in the product. too high, the pressure drop along the die will be unacceptably high and errors may occur on the extrudate surface due to melt fracture. Tensile ratios are typical from 3: 1 to 15: 1, but higher tensile ratios may be possible with certain thermoplastic mixtures, provided there are appropriate process conditions. In addition, higher tensile ratios are typically expected for a greater degree of orientation in the product than minor tensile ratios for the same thermoplastic mixture.

The contour of the tool is mathematically correlated with the viscoelastic deformation of the molten thermoplastic mixture as a function of the velocity or longitudinal tension of the tool-holding zone. Studies have shown that constant longitudinal specific elongation is usually effective. The longitudinal deformation rate is defined by the rate of change in length per unit length, and as a result, the longitudinal deformation rate is a function of the volumetric flow rate of the thermoplastic mixture through the tool. outside, parabolic or conical profiles are sufficient. However, in order to increase the maximum acceptable flow rate of the thermoplastic mixture through the tool, the cohesive angles should be small so that the resulting deformation rate can be increased by

-8 do not exceed the deformation rate that can be associated with the melt fracture (i.e., poor extrudate surface quality). Thus, the maximum acceptable flow rate of the thermoplastic mixture through the tool is determined by the profile separation and the molecular weight of the polymer resin, the type and concentration of the filler, and the inlet temperature of the tool and the thermoplastic mixture.

External lubricants that can be injected into the container 40 or added to the thermoplastic mixture will aid in longitudinal deformation in the tool 60 by reducing the friction between the mixture and the inner surface 94 of the tool 60. Improving the lubricity of the inner surfaces 94 of the tool 60 is possible by high polishing or by applying coatings that increase lubricity, also helping to minimize friction.

The last element of the tool assembly 14 is a calibration device 100 having the same cross-section as the outlet portion of the tool 60 and consequently as the desired profile of the product. The main function of the calibration device 100 is to ensure the product's dimensional stability and to provide the cooling required to maintain the orientation of the polymer molecules and (if filler is present) the filler in the thermoplastic mixture. The length of the calibration device 100 is selected so that the thermoplastic mixture has sufficient cooling to maintain the orientation indicated. The temperature of the calibration device 100 is important in determining the length of the calibration device. Alternative embodiments of the apparatus 10 may include more than one temperature control zone for the calibration device and may include a calibration device consisting of a plurality of sections to achieve a temperature profile that permits gradual or programmed cooling of the thermoplastic mixture. in detail below. It will be appreciated that the tool 60 and the calibration device 100 may be constructed as a section in some cases.

For the extrusion tube 24 and the tool assembly 14 (connector 30, container 40, tool 60 and calibration device 100), the temperature settings must be carefully selected. For example, the temperature of the extruder tube 24 of the extruder must be chosen high enough to melt the thermoplastic mixture and to avoid the violet lines or grooves visible in the product due to the crushing plate 28 The temperature in the extruder tube 24 is also carefully checked to prevent excessive twisting. However, if the resultant temperature of the thermoplastic mixture is too high, the container 40 may be too short to ensure cross-sectional uniformity of the mixture temperature. The temperature of the tool 60 should be high enough to facilitate orientation, but low enough to prevent polymer molecules and filler

-9 particles (if present) to relax from the oriented state. Typically, the tool temperature is 0-10 ° C above the melting point (softening point) for semi-crystalline polymers and 10-60 ° C above the transition temperature of the glass (i.e. above the softening point temperature) for the amorphous polymers. The temperature of the calibration device 100 is chosen so that the thermoplastic mixture is sufficiently cooled to preserve the orientation and to substantially solidify the product. Therefore, the temperature of the calibration device 100 should be below the softening point of the thermoplastic mixture

Referring again to FIG. 1, etxrudate, leaving tool assembly 14, can be passed through a coolant 16, as shown in FIG. 1, for further cooling of the extrudate to facilitate the handling of the finished product. The cooler 16 can also be used to wash off the remaining lubricant. After passing through the cooling bath 16, the caterpillar 18 pulling device can be used to pull out the extrudate. The resulting tension can help the extrusion process by preventing deformation of the extrudate due to bending which may occur downstream of the tool assembly downstream. Finally, a line saw 20 can be used to cut the finished product to the desired length.

Equipment and method for producing hollow products:

Figure 3 shows a longitudinal sectional view of the tool assembly 14 'which is designed to produce hollow thermoplastic ring-shaped products using the method of the present invention. It will be appreciated that it is possible to produce hollow articles of any profile having a constant cross-section, provided that the tool assembly 14 'is configured to produce the desired profile. The most significant difference between the tool assembly 14 'shown in Figure 3 and the tool assembly 14 shown in Figure 2 is the presence of a pin 46 which is required to produce hollow products. All other elements in the tool assemblies 14 'and 14 are the same. 46, at the upper end 49 of the spike is secured with a primary pin fastener 42 disposed between the connection piece 30 and the container 40. The cross-section of the pin 42 is illustrated in FIG. 4 and has three fasteners 44 with a pin 46 engaged. The number and positioning of the fasteners 44 is selected to provide a suitable fastening to the mandrel 46 without significantly obstructing the flow of the thermoplastic mixture until the shape of the fasteners 44 is selected to facilitate the flow of the thermoplastic mixture around the fasteners 44. At the center of one or more fasteners 44 is a channel 50 through which the lubricant can be injected between the mandrel 46 and the thermoplastic mixture. This can be done by similar means as shown in FIG

- It is written above. It will be appreciated that a pin 46 and a pin 42 may be constructed as one or more sections.

A second spike attachment section 62 is disposed between the container 40 and the tool 60. The cross-section of the spigot 62 is similar to the spigot 42 shown in Figure 4, but in this case, the spike 46 is not secured to the fastening section 62 so that the assembly 14 'is easily disassembled for maintenance. As before, the number and positioning of the fasteners within the spigot 62 is chosen to provide a suitable fastening for the spike without significantly obstructing the flow of the thermoplastic mixture, while the fasteners are designed and dimensioned to provide a thermoplastic mixture. streamlined flow around the fasteners. A second pin fastening section may or may not be required depending on the size and length of the pin.

All the considerations that need to be made to produce compact products when designing the 14 tool assemblies should be made when designing the 14 'tool kit for the production of hollow products. For example, the length of the container 40 and calibration device (s) 100, the shape of the tool 60, the temperature setting of the tool assembly 14 and the extruder 12, etc., are chosen to take into account the degree of orientation, extruding power, and surface appearance of the extrudate as described above. a. In the production of hollow products, the choice of shape / size and length of the mandrel 46 is of considerable importance. The cross-section of the mandrel 46 together with the cross-section of the tool 60 and the cross-section of the calibration means 100 determines the shape and the wall thickness of the product. The length of the mandrel 46 is selected to provide dimensional stability to the inner circumference of the resulting hollow profile. It may also be desirable to whisk and / or cool the mandrel by any suitable known means. The process conditions, including temperature settings for the mandrel when cooling and / or heating are used, are selected to facilitate the orientation of the thermoplastic mixture in the cohesive tool and to subsequently maintain the orientation indicated and to substantially consolidate the resulting hollow product.

Fig. 5 is a cross-sectional view of a circular hollow section, which hollow circular sections are formed in the tool assembly 10 using the present method. The wall thickness of the hollow section 124 is determined by the design details of the tool assembly 14 '.

Equipment and method for producing single-piece foamed products:

The apparatus 10 illustrated in Figure 1, using the tool assembly 14 'depicted in Figure 3, can also be used to produce single-piece circular foam products having a solid skin and a foam core.

- 11 is. It is understood that the production of foamed products of all cross-sections made in one piece is possible if the cross-section is of a constant size, provided that the tool assembly 14 'is configured to produce the desired profile In this case, 12 extruders are used to melt and transport the thermoplastic mixture. via the tool assembly 14 ', as shown in FIG. 3, which comprises a thermoplastic blowing agent blowing agent, is also used to initiate foaming, which is required for the production of the foamed core, the activation of the blowing agents and the necessary pressure required for the process. The process conditions of the extruder 12 are selected to melt the thermoplastic mixture and to activate and disperse the blowing agents in a substantially homogeneous manner. It will be appreciated that the blowing agents in this case refer either to physical or chemical blowing agents or to a combination of the two

The design of the tool assembly, which is necessary for the production of the foamed products made in one, is similar to the design of the tool assembly 14 'used for the production of hollow products. As described above, a lubricant is injected between the surface 41 of the inner wall 41 of the mandrel 46 and the container 40 to facilitate longitudinal flow and reduce shear flow through the annular tool 60. In the tool assembly 14 ', the difference in the production of hollow products and the manufacture of products made in one is in the design and function of the pin 46. In the production of hollow products, the function of the pin 46 is to determine the inner circumference of the resulting extrudate and is accordingly designed. In the production of foamed products made in one, the function of the mandrel 46 is to form a cavity in the thermoplastic mixture into which the mixture can expand to form one foamed foam made of foam.

Thus, the cross-section of the spike 46 is selected to facilitate the formation of a foam core, which is substantially homogeneous in both density and cell size. Similarly, the gap 90 has an important thickness between the outer wall 92 of the mandrel 46 and the inner wall 94 of the tool 60. If the gap 90 is too small and the tool temperature is low enough, the thermoplastic mixture can completely solidify in the gap before any foaming occurs, resulting in a hollow product instead of the foamed product made together. A too small gap also undesirably leads to a high pressure drop along the tool 60, while a large gap of needles does not reach the required high pressure drop, so substantially all the foaming occurs after the end portion 47 of the mandrel. The length of the spike 46 is also important in determining where the foaming occurs and as a result, its length will determine the thickness of the oriented solid skin as well as the properties of the foam core. In order to pass the desired thickness of the skin layer and degree of agglomeration, the length of the mandrel 46 extends downwardly on a plurality of strands in the downward direction of the converging portion of the tool 60. In addition, the tool assembly 14 'is designed to provide the required high pressure along the tool assembly 14', so that substantially all of the foaming occurs only after the end portion 47 of the spike 46.

In this process, the main function of the calibration device 100 is to assure the dimensional stability of the product and to provide the necessary cooling for what is needed to maintain the orientation of the polymer molecules and (if present) filler particles in the solid skin. The calibration device 100 also prevents foaming due to deformation of the gauge. The length of the calibration device 100 is chosen such that the oriented skin layer is sufficiently solidified and that the foaming is complete. The temperature profile of the calibration device 100 is therefore important in determining the length of the calibration device.

The temperature setting of the extruder tube 24 and the tool assembly 14 '(connection piece 30, container 40, pin 46, tool 60 and calibration device 100) must be carefully selected to produce foamed products made in one. For example, the temperature of the extruder tube 24 should be set high enough to melt the thermoplastic mixture and to avoid violent lines and grooves due to the crushing plate 28. The temperature of the tool 60 should be high enough to allow orientation, but low enough to substantially prevent relaxation of oriented polymer molecules and (if present) filler particles from their oriented state on the outside of the product being formed. The temperature of the calibration device 100 is chosen such that the thermoplastic mixture is sufficiently cooled to form an orientated solid skin layer without significantly obstructing the formation of the foam core. In addition, it may be desirable to heat the tip of the mandrel 46 with any known suitable means to maintain the internal temperature of the thermoplastic mixture to facilitate the formation of the foam core, such as the temperature of the thermoplastic mixture (determined by the temperature of the extruder and container 40). the temperature of the tool 60, the mandrel 46 and the calibration device 100 and the length of the mandrel 46 together determine the thickness of the extrudate oriented solid skin layer. Similarly, the drag ratio, the tool profile 60, the amount and type of lubricant that is injected, the mass temperature of the mixture, and the tool temperature of 60 determine the degree of orientation of the oriented outer skin. The density of the resulting foam core is the composition of the thermoplastic mixture, the concentration and type of blowing agent. (physical and / or chemical), the temperature of the material to be foamed, the length and shape of the mandrel 46 and the thickness of the oriented solid skin.

13 Referring to FIG. 6, a circular profile of a foam profile is provided which can be produced by the present method. The product contains 120 foam seeds and an outer solid surface or skin 122 As described above, the thickness of the oriented solid skin 122, the thermoplastic polymer molecules and (if present) the degree of orientation of the filler in the solid skin, the surface appearance of the product, and finally the density of the foam core 120 and the cell size from the design details of the tool assembly 14 '(in particular the design details of the tool 60 and the pin 46), the process! conditions (such as the temperature profile of the various components of the extruder 12 and the temperature profiles of the tool assembly 14 '), the type and amount of the lubricant, the extrusion performance of the process, and finally the formulation of the thermoplastic mixture, including the selection of the foaming agents. thickness and density of solid 122 and foam 120 core

The properties of the foam products produced in one process, which are made according to the process of the present invention, are desirable in comparison with the properties of the conventional one-piece foam in many respects. First, the foam products produced in the same process, which are made according to the process of the present invention, have higher bending strength and modulus (typically 2 to 10 times that of conventional co-manufactured foam products). These repairs are the result of the presence of solid polymer molecules in the oriented polymer molecules and, if present, the filler particles, so that maximizing the effectiveness of the concept of the foamed product produced in one is limited, since the strength and stiffness of the foamed products produced in one are limited by the strength of the solid skin and stiffness, which solid skin surrounds the foam core. Secondly, the foamed products produced in accordance with the process of the present invention have a thicker skin allowing them to be nailed or screwed without damage, in contrast to typical one-piece foamed products that cannot be nailed or screwed because the solid skin is thin and the foamed core is brittle. Thirdly, the products produced by the process of the present invention may contain higher concentrations of fillers (in some cases up to 80% by weight) than the typical foam products containing very little filler (less than 30% by weight) if used at all. In addition, to reduce material costs, the increased filler content also contributes to improved mechanical properties when used as a reinforcing filler

Recipe and preparation of thermoplastic mixtures:

The polymer component of the thermoplastic mixture may comprise a thermoplastic polymer which is made of polyolefins (polyethylenes, polypropylene and copolymers thereof), homopolymers and copolymers of vinyl chloride, containing styrene.

- 14 (polystyrenes, ABS and styrene / malein anhydride copolymers), polyesters, polyamides, polycarbonates and the like Furthermore, this method excludes thermosetting plastics such as phenolic, urea, brothaldehyde resins, epoxy resins and the like. The process can be accomplished with intact or recycled (waste) thermoplastic polymers (plastics). While the process is feasible with blended (recycled) recycled plastics, the quality of the resulting extruded products depends to a large extent on the composition of the submerged material, more specifically on the type and concentration of the various polymers. For economic reasons, granular (chipped) plastics from bottles or films (prior to granulation). ) are preferred, since the granulation can significantly increase the cost of the resulting material.

By choosing between the different qualities of a polymer, the average molecular weight of the particular quality may have a significant effect on the degree of orientation achieved by the process of the present invention Typically, for a given polymer, the qualities in which the average molecular weight is smaller, lose their orientation faster due to relaxation than the higher average molecular weight grades. Thus, higher molecular weight grades of a particular polymer are preferred to help maintain the highest degree of orientation reported by the converging tool. In addition, higher molecular weight grades can typically be extruded at a higher rate of deformation in the cohesive tool and therefore processed at a higher flow rate. However, the choice of polymer molecular weight is limited depending on the ability of the polymer to be mixed with a reinforcing filler. Therefore, a compromise is usually needed between the degrees of relaxation and orientation between the ease of processing and the ease of mixing. Hence, the greatest molecular weight is consistently advantageous with the ease of mixing under normal conditions.

The filler component of the thermoplastic mixture may contain materials that are typically used as reinforcing fillers. A filler is typically considered to be a reinforcing filler when its aspect ratio, defined as the ratio of the length to the effective diameter, is substantially greater than one. Inorganic reinforcing fillers include glass fibers, carbon fibers, metal fibers, ceramic fibers, asbestos, talc, mica, and the like. Organic materials can also be used as reinforcing fillers. For example, it is possible to use fibers made with a polymer with a higher softening point as the polymer of the thermoplastic mixture, such as nylon or polyester fibers with polyethylene. The filler concentration may vary, but mixing the filler material and polymer may be high

- 15 filler concentrations (above 70% by weight) in different filler and polymer combinations.

Cellulose fibers or particles containing substantially cellulose fibers can also be used as reinforcing filler. However, cellulose has a steep tendency to decompose at temperatures above 220 ° C, and therefore polymers that have to be processed at temperatures above this are necessarily excluded when using cellulose-based fillers, so that most of the so-called engineering polymers can not be used in the process of the present invention with cellulose fibers, as a filler because their softening temperatures are too high Cellulose fibers can be obtained from wood / forest by-products and waste, such as wood or wood, drill dust, paper (newsprint, postcards, cardboard), wood pulp (chemical, chemical-mechanical, mechanical, bleached or unbleached) ) and agricultural by-products such as rice flakes, wheat straws, corn flakes, cocoa shells, shells of various nuts and the like, having essential cellulose components. Techniques that produce fine but free-flowing cellulose fillers that are readily applicable to the process of this invention are well known. Thus, the supply of cellulose fillers is almost unlimited, which offers economic benefits. For example, short cellulose fibers can be advantageously used in the process of the present invention which otherwise have no commercial value, such as the fine fraction from pulp. In addition, studies have shown that a thermoplastic mixture containing a cellulose filler can be recycled many times without significant deterioration of the mechanical properties in the resulting product. This remarkable durability is related to the elasticity and toughness of the cellulose fibers, which are resistant to further fractures during recycling. .

The preparation of the thermoplastic mixture may require the use of dispersant / surface treatment agents to disperse and compatible nonpolar polymers with highly polar fillers such as cellulose. These surfactants are particularly wettable to the surfaces of the filler particles (thereby increasing the degree of dispersion) and provide increased adhesion (coupling) between the surfaces of the filler particles and polymers. It has been found useful to use carboxylated polyolefins as dispersing / surface-treating agents with polyolefin polymers. usually one to five percent by weight of the thermoplastic mixture. The optimum amount

- 16 easy to define experiment. Other mixtures, such as fatty acids, titanates, zirconates, silanes and the like, may be used as a compatible / dispersing agent.

In order to produce a thermoplastic mixture comprising a reinforcing filler, a measured amount of filler is first mixed with a suitable polymer, with a suitable compatible / dispersant (if necessary) and other additives such as dyes, stabilizers, flame retardants and the like, which may be used. to Improve Product Properties The blend is subjected to intensive mixing and then in a two screw extruder, a thermokinetic mixer such as a Gelimat mixer (Draiswerke), or a K-mixer (Synergisics) or a similar mixer. Thermokinetic mixers are particularly effective in preparing high filler contents of thermoplastic mixtures, as it has been found to effectively disperse the filler in the mixture. In addition, it is desirable to use thermokinetic mixers for the preparation of thermoplastic mixtures containing cellulose. The high intensity mixing of thermokinetic mixers not only reduces unacceptably high cellulose particles, but also separates loosely bonded cellulose fibers, thereby increasing the capacity of the cellulose filler enhancer.

When a foamed article is produced with the apparatus 10 shown in Figure 1, the choice of blowing agent depends on a number of factors, including the conditions of extrusion, the type of resin, and the cost of the blowing agent. The foaming agents are generally categorized as chemical or physical blowing agents. Chemical foaming agents disintegrate when heated to develop gases that can foam the thermoplastic mixture. Common chemical foaming agents include sodium bicarbonate which decomposes to develop carbon dioxide and azodicarbonamide and decomposes to produce nitrogen. Physical blowing agents are typically compounds which are greased or volatile at the processing temperature and can produce the required pressure to foam the thermoplastic mixture. Water, carbon dioxide, nitrogen and chlorofluorocarbons are commonly used as physical blowing agents and can be blended with the blend before being extruded or injected directly into the tube or extruder. While chemical foaming agents are more expensive than physical blowing agents, they generally produce a finer cell structure in the foamed product, which is often desirable. Consequently, a combination of physical and chemical foaming agents is used to achieve the desired cell structure while reducing the cost of the blowing agent.

When cellulose filler is used, the water absorbed by the cellulose may be sufficient to provide the desired degree of foaming required by the process so that no further blowing agent is required. For example, under normal conditions, wood fibers may contain water up to 10%, depending on air humidity. Water absorbed by cellulose fibers evaporates during mixing

- 17de remains sufficient to foam the thermoplastic mixture. In addition, the thermoplastic mixture can absorb water during the mixing process if, for example, an underwater granulator is used. However, the use of water as a foaming agent is limited by the fact that the polycondensation polymers such as polyesters and polycarbonates are depolymerized at the processing temperature already a few millionth of a part in the presence of water. Thus, the use of water as a blowing agent for these polymers is not recommended.

Examples:

The following non-limiting examples will illustrate the method of manufacturing according to the method of the present invention with the apparatus according to the present invention, the embodiment of which is shown in Figs. Figure 1B is shown.

The bending characteristics were measured according to ATSM D-790. For circular patterned products, we modified the sieve according to ASTM D-4476 to accommodate the curvature of the test samples. The measurement of fracture strength was in accordance with the ASTM D-256 Izod test.

A number of substantially non-oriented solid samples (with and without filler) produced by injection molding are shown in Table 1 in comparison with the characteristics of different orientated patterns.

The following notations are used in the examples:

polymers: HIPS high impact polystyrene, MI = 13.5 MB recycled high density polyethylene milk bottle MC recycled mixed colored high density polyethylene MIPS medium impact polystyrene, MI = 19 PE1 high-density polyethylene molded with blast, MI = 0.4 PE2 injection molded high density polyethylene, MI = 5 PP polypropylene, MI = 0.8 PVC polyvinyl chloride, K = 58 Cellulose-containing fillers: CS corn bast DIN inkjet paper GC ground cardboard GN ground newsprint GWP ground wooden pulp RH rice husks

SD TMP WF sawdust thermomechanical pulp wood flour

WS wheat straw

Compatible:

IR ionomer resin

MPE maleate polyethylene

MPP maleate polypropylene

RPS reactive polystyrene

SMA styrene maleate anhydride

Example 1:

This example describes the production of a 0.33 inch diameter, symmetric solid polypropylene product:

(a) The thermoplastic mixture used in this example comprises polypropylene of extrusion quality (Profax 6631, MI = 1, Himon), 1% by weight of silicone oil (Dow Corning 200, 12,500 cs, Dow Corning) was added as a lubricant to the mixture.

(b) The apparatus used in this example is a single screw, 0.75 inch extruder (length / diameter ratio 24: 1), equipped with a tool assembly of suitable size, suitable for producing a solid round section with a diameter of 0.33 inches. The tank and the tool were constructed as a 0.75 inch and 0.33 inch inlet and outlet sections. Calibration tool approx. 7 inches long. The drag ratio of the tool assembly is 5: 1.

(c) The process conditions are as follows:

Adjusting the temperature control zones of the extruder tube (from the direction of the upper end to the lower flow end): 155, 170, 175 ° C.

Setting the temperature control zones of the tool assembly (connection piece, tank / tool, calibration tool): 165, 140, 90 ° C.

Rotation speed of the extruder screw: 8 rpm.

(d) Outer diameter of the circular symmetrical solid sample: 0.33 inch The mechanical properties of the sample are shown in Table 2 below.

example:

This example describes the preparation of a circular solid polystyrene with a diameter of 0.33 inches.

(a) The thermoplastic mixture used in this example comprises polypropylene of extrusion quality (Crystal polystyrene 202, MI = 3.0, Huntsman Chemical Corp), 1

- 19% by weight of silicone oil (Dow Corning 200, 12,500 cs, Dow Corning) was added as a lubricant (b) The apparatus was the same as in Example 1.

(c) The process conditions are as follows:

Adjusting the temperature control zones of the extruder tube (from the direction of the upper end to the lower flow end): 155, 180, 180 ° C.

Setting the temperature control zones of the tool assembly (connection piece, tank / tool, calibration tool): 160, 140, 90 ° C.

Rotation speed of the extruder screw: 6 rpm.

(d) The outer diameter of the circular symmetrical solid sample is 0.33 inches. The mechanical properties of the sample are shown in Table 2.

Example 3:

This example describes the production of a circular symmetric solid polyethylene, 1 inch diameter product.

(a) The thermoplastic mixture used in this example comprises high-density polyethylene of cast-grade quality (Sclair 58a, M1 = 0.4, Du Pont).

(b) The apparatus in this example was a single-screw 2.5-inch extruder (length / diameter ratio 24 I), equipped with a tool assembly of suitable size to produce a circular metric 1 inch diameter gauge. The container is 2 inches in diameter and 12 inches long. The calibration device consists of two sections, each with a 10-inch long, separate temperature control system that provides air cooling. The drag ratio of the tool assembly was 4: 1 (c) The process conditions were as follows:

Adjusting the temperature control zones of the extruder tube (from the direction of the upper end to the lower flow end): 135, 140, 141, 142 ° C.

Setting the temperature control zones of the tool assembly (connection piece, tank / tool, calibration tools): 140, 138, 136, 125, 90 ° C.

Rotation speed of the extruder screw: 20 rpm.

Lubrication: 200 cc silicone oil (Dow Corning) injected into two containers at 20 ml per hour.

Productivity is 24 inches per minute.

(d) The outer diameter of the circular symmetrical solid samples is 1.0 inches. The mechanical properties of the sample are shown in Table 1.

Example 4:

This example describes the production of various products of circular symmetrical solid polyethylene filled with cellulose as filler with a diameter of 0.33 inches.

-20 • · (a) The thermoplastic mixture used in this example comprises high-grade, high-density polyethylene (Sclair 58a, MI = 0.4, Du Pont) for the 4% by weight surface treatment material (Fusabond MB 226D, Du Pont) referring to the cellulose filler, to the concentrations of several cellulose fillers. The cellulose fillers used were:

crop-mechanical pulp (TMP), ground wood pulp (GWP), de-inked newsprint (DIN), minced newsprint (GN), wood flour (WF), ground cardboard (GC), ground corn bast (CS), ground wheat straw (WS) and ground rice flakes (RH). Typically, 1% by weight of silicone oil (Dow Coming 200, 12,500 cs, Dow Corning) was added as a lubricant. The type and concentration of filler for the various mixtures are shown in Table 3 (b) The apparatus in this example is the same as in Example 1.

(c) The representative procedural conditions were for each mixture:

Adjusting the temperature control zones of the extruder tube (from the direction of the upper end to the lower flow end): 135, 165, 150 ° C.

Setting the temperature control zones of the tool assembly (connection piece, tank / tool, calibration tool): 145, 140, 120 ° C.

Rotation speed of the extruder screw: 20 rpm.

(d) The outer diameter of the circular symmetrical solid samples is 0.33 inches. The mechanical properties of the different samples are shown in Table 3.

Example 5:

This example describes the production of various products of circular symmetrical solid polyethylene filled with cellulose as filler with a diameter of 0.33 inches.

(a) The thermoplastic mixture used in this example comprises 50 parts by weight of different grades of polyethylene, 4% by weight of the cellulose filler is maleate polyethylene (Fusabond MB 226D, Du Pont) as a surfactant and 50 parts by weight of thermomechanical pulp or dotted newsprint. The following polyethylenes were used in injection molding grade polyethylene (Sclair 2907, MI = 5, Du Pont), recycled high density polyethylene milk bottles and recycled (post-consumer) mixed color high density polyethylene. The type of polymer and the type of filler are shown in Table 4 for different blends. Typically, 1% by weight of silicone oil (Dow Corning 200, 12,500 cs, Dow Corning) was added as a lubricant.

(b) The apparatus in this example is the same as in Example 1.

(c) Representative process conditions were similar to those used in Example 4 for each mixture.

-21 (d) The outer diameter of the circular symmetrical solid samples is 0.33 inches. The mechanical properties of the different samples are shown in Table 4.

example:

This example describes the preparation of a 0.33 inch diameter polypropylene product filled with solid, circular symmetric cellulose:

(a) The thermoplastic mixture used in this example comprises 50% by weight of polypropylene of extrusion quality (Profax 6631, MI = 1, Himont), 4% by weight of maleate polypropylene (Epolene E-43, MW = 4500, Eastman Chemicals) and 50% of cellulose filler. Part of the type and concentration of the filler in the mechanical and mechanical pulp The type and concentration of filler for many mixtures are shown in Table 4, 1% by weight of silicone oil (Dow Corning 200, 12,500 cs, Dow Corning) as a lubricant (b) The apparatus used in this example was the same, as used in the 1st half.

(c) The representative process conditions for each mixture were as follows:

Adjusting the temperature control zones of the extruder tube (from the direction of the upper end of the flow towards the lower flow end): 165, 190, 180 ° C.

Setting the temperature control zones of tool assembly (connection piece, tank / tool, calibration tool): 180, 165, 130 ° C.

Rotation speed of the extruder screw: 20 rpm.

(d) The outer diameter of the circular symmetrical solid samples is 0.33 inches. The mechanical properties of the different samples are shown in Table 4.

Example 7:

This example describes the preparation of various solid, cellulose-filled polyvinyl chloride products having a diameter of 0.33 inches:

(a) The thermoplastic mixture used in this example comprises 70% by weight of rigid polyvinyl chloride (K = 58), suitable stabilizers and processing aids and 30 parts of wood flour. 1% by weight of silicone oil (Dow Corning 200, 12,500 cs, Dow Corning) was added as a lubricant to the mixture.

(b) The apparatus used in this example is the same as that used in Example 1 for each mixture.

(c) The process conditions are as follows:

Adjustment of the temperature control zones of the extruder tube (from the direction of the upper end to the lower flow end): 140, 190, 180 ° C.

Setting the temperature control zones of the tool assembly (connection piece, tank / tool, calibration tool): 170, 150, 105 ° C.

Rotation speed of the extruder screw: 6 rpm

- 22 (d) The outer diameter of the circular symmetrical solid samples is 0.33 inches. The mechanical properties of the sample are shown in Table 4.

Example 8:

This example describes the production of various solid, cellulose-filled polystyrene products with a diameter of 0.33 inches:

(a) The thermoplastic mixture used in this example comprises either a medium or high impact polystyrene (MI = 19) as a polymer component, a yield-mechanical pulp or a wood flour as a filler and a reactive polystyrene or styrene maleic anhydride in a 4% by weight of cellulose filler. and the concentrations for the various mixtures are shown in Table 5. 1% by weight of silicone oil (Dow Corning 200, 12,500 cs, Dow Coming) was added as a lubricant.

(b) The apparatus used in this example is the same as that used in Example 1 (c) Process conditions are for each of the following mixtures:

Adjusting the temperature control zones of the extruder tube (from the direction of the upper end to the lower flow end): 100, 160, 145 ° C.

Setting the temperature control zones for tool assembly (connection piece, tank / tool, calibration tool): 130, 120, 110 ° C.

Rotation speed of the extruder screw: 6 rpm.

(d) External diameter of circular symmetrical solid samples: 0.33 inch The mechanical properties of the samples are shown in Table 5

Example 9:

This example describes the production of various solid polyethylene products with a diameter of 0.33 inches:

(a) The thermoplastic mixture used in this example contains high density high density polyethylene (Sclair 58a, MI = 0.4, Du Pont), mica (Mica White 200, average particle size = 35 micron, LV Lomas) and ionomer resin. (Surly 9950, MI =

5.5, Du Pont) as a compatible substance The polymer type and filler type and concentrations for the various mixtures are shown in Table 6, 1% by weight of silicone oil (Dow Corning 200, 12,500 cs, Dow Corning) was added as a lubricant.

(b) The apparatus used in this example is identical to that used in Example 1.

(c) The procedural conditions for each of the mixtures were as follows:

Adjusting the temperature control zones of the extruder tube (from the direction of the upper end to the lower flow end): 135, 155, 155 ° C.

-23 Setting the temperature control zones of the tool assembly (connection piece, tank / tool, calibration tool): 145, 140, 120 ° C.

Rotation speed of the extruder screw: 10 rpm.

(d) External diameter of the circular symmetrical solid sample: 0.33 inch The mechanical properties of the samples are shown in Table 6

Example 10:

This example describes the production of solid, polyethylene polyethylene products packed with solid powder, circularly symmetrical:

(a) The thermoplastic mixture used in this example comprises 50% by weight of high density polyethylene (Sclair 58a, MI = 0.4, Du Pont), 50 parts of sawdust and 4 parts of maleate polyethylene (Fusabond MB 226D, MI = 2, Du Pont) .

(b) The apparatus used in this example is identical to that used in Example 3.

(c) The process conditions are as follows:

Adjusting the temperature control zones of the extruder tube (from the direction of the upper end to the lower flow end): 140, 142, 145, 148 ° C.

Setting the temperature control zones of the tool assembly (connection piece, tank, tool, calibration means): 144, 140, 136, 100, 50 ° C.

Rotation speed of the extruder screw: 14 rpm.

Lubrication: 200 cc silicone oil (Dow Corning) injected into two injection openings into the container, injected with 1 ml / h current.

Extrusion speed: 20 inch / min (d) The outer diameter of the circular symmetrical solid sample is 1.0 inch. The mechanical properties of the samples are shown in Table 7.

example:

This example describes the production of hollow, perforated polyethylene products with a hollow powder having a diameter of 1 inch:

(a) The same thermoplastic mixture was used as in Example 10.

(b) The apparatus in this example was a single-screw 2.5-inch extruder (length / diameter ratio 24 1), equipped with a tool assembly of appropriate size to produce a circular symmetrical 1-inch diameter gauge. The container is 2 inches in diameter and 12 inches long. The calibration tool consists of two sections, each of 10 inches long, with a separate temperature control system that provides air heating The tool assembly was equipped with a circular symmetrical 0.7 inch diameter spanner extending to 8 inches at the end of the tool The tooling ratio was 7: 1 (c) A process conditions include:

-24Configuration of the temperature control zones of the extruder tube (from the direction of the upper end to the lower end): 140, 145, 148, 151 ° C.

Adjusting the temperature control zones of the tool assembly (connection piece, spike, fastener, container, tool, paddle tool): 149, 146, 142, 135, 124, 63 ° C.

The rotation speed of the extruder screw is 6 rpm.

Lubrication: 200 cc silicone oil (Dow Coming) injected into two injection holes, injected with 2 ml / hour.

Extrusion speed: 16in / min.

(d) The outer diameter of the circular symmetrical solid samples was 1.0 inch. The mechanical properties of the samples are shown in Table 7.

Example 12:

This example describes the production of co-produced polyethylene foam products with a 1-inch diameter polyethylene powder filled:

(a) The same thermoplastic mixture was used as in Example 10. The combination of water (moisture in the mixture) and calcium bicarbonate was used as a blowing agent (about 2 weight percent water, 1 part calcium bicarbonate).

(b) The apparatus in this example was a single-screw 2.5-inch extruder (length / diameter ratio of 24: 1), equipped with a suitable tool assembly to produce a circularly symmetrical foamed 1-inch diameter gauge. The tank is 2 mch in diameter and 12 inches long. The calibration tool consists of two sections, each with a 10 inch long, separate temperature control system that provides air cooling. The tool assembly was equipped with a circular symmetrical 0.7 inch diameter spike extending 2.5 inches at the end of the tool.

(c) The process conditions are as follows:

Adjusting the temperature control zones of the extruder tube (from the direction of the upper end to the lower flow end): 135, 142, 144, 146 ° C.

Setting the temperature control zones of the tool assembly (connection piece, spike, fastener, container, tool, calibration means): 140, 135, 124, 122, 100, 44 ° C.

The rotation speed of the extruder screw is 15 rpm.

Lubrication: 200 cc silicone oil (Dow Coming) injected into two injection holes, injected with 1 ml / h current.

Etxruding speed: 20 inch / min.

(d) The outer diameter of the circularly symmetrical foam samples is 1 inch, their rigid glossy skin and their cellular internal structure. The mechanical properties of the samples are shown in Table 7.

Example 13:

-25This example describes the production of 1.5 χ 2.5 inch polyethylene products filled with perforated powder with rectangular profile:

(a) The same thermoplastic mixture was used as in Example 10.

(b) The apparatus in this example was a single-screw 2.5-inch extruder (length / diameter ratio 24 I), equipped with a suitable tool assembly to produce a 1.5 * 2.5 inch solid rectangular profile The container consisted of two sections each 7, 5 inches long and 3 in 5 inches, with separate temperature control for the two sections. The calibration tool also consists of two sections, each with a 10 inch long, separate temperature control system that provides air cooling. The tensile ratio of the tool assembly was 4: 1.

(c) The terms of payment are as follows:

Adjusting the temperature control zones of the extruder tube (from the direction of the upper end to the lower flow end): 140, 142, 143, 146 ° C.

Setting the temperature control zones of the tool assembly (connection piece, tanks, tool, calibration means): 144, 142, 138, 136, 115, 80 ° C.

The rotation speed of the extruder screw is 6 rpm.

Lubrication 200 cc silicone oil (Dow Coming) injected on two injection holes into the first container injected at 16 ml / h.

Etxruding speed: 3.25 inch / min.

(d) Rectangular patterns were produced with 1.5 χ 2.5 inches. The mechanical properties of the sample are shown in Table 8.

Example 14:

This example describes the production of hollow, rectangular sectioned 1.5 x 2.5 inch polyethylene products filled with boring powder:

(a) The same thermoplastic mixture was used as in Example 10.

(b) The apparatus in this example was a single-screw 2.5-inch extruder (length / diameter ratio 24: 1), equipped with a suitable tool assembly to produce a 1.5 ^x 2.5-inch rectangular profile The container is 9 inches long and 3> 5 inch inside size. The vibration device also consists of two sections, each 10 inch long, with a separate temperature control system that provides air cooling The tool assembly has a rectangular section with a 0.96 inch * 1.96 inch spike that extends to 8 inches at the end of the tool. : 1 was (c) The process! conditions are:

Adjustment of the temperature control zones of the extruder tube (from the direction of the upper end to the lower flow end): 139, 141, 142, 144 ° C.

Setting the temperature control zones of the tool assembly (connection piece, tank, tool, calibration means): 140, 127, 136, 100, 70 ° C.

-26 • * · ·

The rotation speed of the extruder screw is 8 rpm.

Lubrication. 200 cc silicone oil (Dow Coming) injected through two injection holes into the first container injected with 10 ml / h of current.

Etching rate: 4 inches per minute.

(d) Hollow sections with rectangular sections were produced with 1.5 χ 2.5 inch sides, 0.27 inch wall thickness. The mechanical properties of the samples are shown in Table 8.

Example 15:

This example describes the production of polyurethane products made of powdered, co-manufactured, foam, rectangular, 1.5 χ 2.5 inches:

(a) The same thermoplastic mixture was used as in Example 10.

Water was used as a blowing agent and the moisture content of the thermoplastic mixture was carefully adjusted to 4%.

(b) The apparatus in this example was a single-screw 2.5-inch extruder (length / diameter ratio of 24: 1), equipped with a tool assembly of appropriate size to produce a 1.5 χ 2.5 inch rectangle for the production of a co-produced foam profile. The tank consists of two stages, each one

7.5 inches long and 3 inches ^x 5 inches with internal temperature control. The calibration tool also consists of two sections, each with a 10 inch long, separate temperature control system that provides air cooling. The tool assembly was equipped with a rectangular cross-section with a 0.96 inch <1.96 inch spike, approx. The length of the tool set is 7: 1 (c) The process conditions are as follows:

Adjusting the temperature control zones of the extruder tube (from the direction of the upper end to the lower flow end): 140, 141, 143, 143 ° C.

Setting the temperature control zones of the tool assembly (connection piece, tanks, tool, calibration tools): 143, 138, 135, 133, 110, 70 ° C

The rotation speed of the extruder screw is 8 rpm.

Lubrication: 200 cc silicone oil (Dow Coming) injected into two injection holes into the first container injected with 24 ml / h of current.

Etxruding speed is 3.2 inches / min.

(d) Samples of rectangular sections made in one piece were produced with 1.5 ^x 2.5 inch pages, rigid, glossy skin and cellular internal structure. The mechanical properties of the samples are shown in Table 8.

Table 1. Mechanical properties of injection molded samples

Mixture Filler Izod Bending Properties

content (weight%) effect (kJ / m2) strength (MPa) Modules (GPa) PE2 - 100 20 0.9 PE2 / TMP / MPE 25 78 55 2.0 1 - - 35 1.5 PP 25 23 75 2.6 PP / TMP / MPP ₂ - - 76 3.1

PS

The thermoplastic mixture contains 50% by weight injection molding grade high density polyethylene, 50% thermomechanical pulp and 4 parts maleate polyethylene (Fusabond MB226D, MI = 2, DuPont)

2. The thermoplastic mixture consists of 50 weight percent polypropylene (Profax 6631, MI = 2, Himont), 50 percent thermo-pulp and 4 percent maleate polypropylene (Epolene E-43, MW = 4500, Eastman Chemicals).

Table 2 Bending modulus of various solid, non-filled samples

Mixture Modulus (GPa) PE ¹ "'· * PP ² 2.8 PS ² 4.0

1.0 inch diameter pattern

0.33 inch diameter pattern

-28 • · ·

Table 3: Mechanical properties of solid cellulose-filled polyethylene samples

Mixture' Filler content (weight%) Izod effect (kJ / m2) Bending properties strength (MPa) Modules (GPa) PE1 / TMP / MPE 30 13.0 99.7 3.97 PE1 / TMP / MPE 40 12.7 100.4 4.15 PE1 / TMP / MPE 50 10.2 105.3 4.60 PE1 / TMP / MPE 60 7.2 94.7 4.87 PE1 / GWP / MPE 50 9.1 94.6 4.35 PE1 / DIN / MPE 50 13.6 101.3 4.20 PE1 / GN / MPE 50 14.6 114.7 4.60 PE1 / WF / MPE 50 11.8 93.4 4.10 PE1 / WF / MPE 70 9.3 85.9 4.93 PE1 / GC / MPE 40 15.1 99.7 4.61 PE1 / GC / MPE 50 14.6 101.2 4.34 PE1 / CS / MPE 50 10.3 103.7 4.9 PE1 / RH / MPE 50 13.2 101.9 4.7 PE1 / RH / MPE 60 10.1 90.6 4.8 PE1 / RH / MPE 70 8.9 86.8 4.5

1. Each mixture contains 4% by weight of surfactant (s) based on the filler

Table 4: Mechanical properties of various solid, cellulose-filled samples

Mixture Filler content Izod effect Bending properties strength modulus -29-

• · · · · · · · · · · · · · · · · · · · · ···

(weight%) (KJ / m2) (MPa) (GPa) PE2 / TMP / MPE 50 H, 8 101.5 4.55 MB / DIN / MPE 50 13.8 97.1 4.53 MC / DIN / MPE 50 12.8 86.5 3.78 MC / TMP / MPE 50 13.7 92.7 3.91 PP / TMP / MPP 50 11.1 104.5 4.0 PP / DIN / MPP 50 7.5 85.9 4.0 PVC / WF 30 3.7 59.0 3.60

Table: Mechanical properties of solid, cellulose filled polystyrene samples

Mixture ¹

Filler content (weight%)

Izod effect (kJ / m2)

Bending Properties Strength (MPa) Modules (GPa)

MIPS / TMP

5.5

52.4

3.1

MIPS / TMP / RPS

5.3

56.4

3.4

MIPS / TMP / RPS

4.2

64.6

4.0

HIPS / TMP / RPS

4.2

61.9

3.6

MIPS / WF / RPS

3.9

62.0

4.9

MIPS / WF / RPS

3.4

60.3

5.1

MIPS / WF / RPS

2.7

55.4

5.6

Claims (2)

MIPS / WF / SMA 3.3 54.0 6.2 1/2 ♦ «· • · · · WORKS hl. 11'34 Bp, Dévai u. 22-2C Master Tamás Patent Attorney A method of continuously producing a thermoplastic product comprising a thermoplastic mixture having oriented components and providing a thermoplastic mixture comprising the steps of providing a thermoplastic mixture comprising a thermoplastic mixture, the thermoplastic mixture being brought to a temperature in an effective range; which is just above the softening point of the thermoplastic mixture and contains the softening point by which a molten thermoplastic mixture is produced, the molten thermoplastic mixture is pushed through the tool, under which the thermoplastic mixture is subjected to the converging flow to communicate the longitudinal orientation of at least the thermoplastic. comprising a portion of the polymer and exterior dimensions, characterized in that (a) the thermoplastic mixture is pushed through the tool and downstream downwardly connected; cooling zone to cool the thermoplastic mixture having its longitudinal orientation, at a temperature below the softening point temperature of the thermoplastic mixture, and maintaining the orientation therein and solidifying the thermoplastic mixture, and (b) introducing the thermoplastic mixture into the cooling zone to retain the outer dimensions of the thermoplastic mixture. A method according to claim 1, wherein the thermoplastic mixture is subjected to the cohesive flow through the tool, characterized in that it provides a declining longitudinal deformation rate that does not exceed the deformation rate associated with the melt fracture. The method according to claim 1, wherein the thermoplastic mixture is subjected to the cohesive flow through the tool, characterized in that it provides a substantially constant longitudinal deformation rate which does not exceed the deformation rate associated with the melt fracture. - 33 ··· · * · »·« ·· ·· * · · ··· A method according to any one of claims 1,2 or 3, characterized in that the thermoplastic mixture comprises a filler with which it is directly mixed. Method according to claim 4, characterized in that the side portion of the filler is greater than one. Method according to claim 5, characterized in that the cohesive flow through the tool communicates the longitudinal orientation with at least part of the filler Process according to claim 4 or 5, characterized in that the filler is selected from the group consisting of cellulose-containing fibers, cellulose particles, mica flakes, talcumflies, asbestos fibers, glass fibers, metal fibers and carbon fibers. Process according to any one of claims 4, 5, 6 or 7, characterized in that the thermoplastic mixture has a proportion of up to 75% by weight of filler. 9. Procedure in FIGS. The thermoplastic mixture according to any one of claims 1 to 3, wherein the thermoplastic mixture is subjected to the cohesive flow through the tool, characterized in that it provides a declining longitudinal deformation rate which does not exceed the rate of change of shape associated with the melt fracture. 10. Methods 4-8. The thermoplastic mixture according to any one of claims 1 to 3, wherein the thermoplastic mixture is subjected to a cohesive flow through the tool, characterized in that it provides a substantially constant longitudinal deformation rate that does not exceed the deformation rate associated with the melt fracture. A method according to any one of the preceding claims, comprising forming an internal cavity in the thermoplastic mixture as it passes through said tool, creating a hollow profile and thereby solidifying the hollow profile during cooling. - 34 • « A method of continuously producing a thermoplastic product comprising a thermoplastic mixture having oriented components and a foamed core comprising steps for providing a thermoplastic mixture comprising a thermoplastic polymer and a blowing agent, bringing the thermoplastic mixture to a temperature that is within an effective temperature range. just above the softening point of the thermoplastic mixture and containing the softening point by which a molten thermoplastic mixture is produced, the molten thermoplastic mixture is pushed through the tool to form an inner cavity and pass through the thermoplastic mixture through the cooling zone, where cooling the thermoplastic mixture below the softening point temperature of the thermoplastic mixture to solidify its outer layer and form a skin layer and foil the thermoplastic mixture characterized in that (a) the molten thermoplastic mixture is pushed through the die and downstream of the connecting cooling zone, where the thermoplastic mixture is pressed through the tool, an internal cavity is formed therein, and the thermoplastic mixture is subjected to a converging flow of the converging stream through the tool and communicating the longitudinal orientation to at least a portion of the thermoplastic polymer; and (b) maintaining said longitudinal orientation in the outer layer of the thermoplastic mixture, thereby forming said skin as an orientated skin, and (c) introducing said thermoplastic mixture into said cooling zone to maintain the outer dimensions of the thermoplastic mixture. A method according to claim 12, wherein the thermoplastic mixture is subjected to the cohesive flow through the tool, characterized in that it provides a declining longitudinal deformation rate which does not exceed the rate of change of shape associated with the melt fracture. The method of claim 12, wherein the thermoplastic mixture is subjected to the cohesive flow through the die, characterized in that it provides a substantially constant longitudinal deformation rate that does not exceed the deformation rate associated with the melt fracture. A method according to any one of claims 12, 13 or 14, wherein the thermoplastic mixture comprises a filler which is directly mixed with it. · 35 * · · · · • 4 ** · «· · * · · · · · ··· Method according to claim 15, characterized in that the side portion of the filler is greater than one. Method according to claim 15 or 16, characterized in that the cohesive flow through the tool communicates the longitudinal orientation with at least a portion of the filler. Process according to any one of claims 15, 16 or 17, characterized in that the filler is selected from the group consisting of cellulose-containing fibers, cellulose particles, mica flakes, talcumflies, asbestos fibers, glass fibers, metal fibers and carbon fibers. Process according to any one of claims 15 to 18, characterized in that the thermoplastic mixture comprises up to 75% by weight of filler. A method according to any one of claims 15 to 18, characterized in that the thermoplastic mixture is subjected to the cohesive flow through the tool, which indicates a decreasing longitudinal deformation rate which does not exceed the deformation rate associated with the melt fracture. 21. Methods 15-18. The thermoplastic mixture according to any one of claims 1 to 3, characterized in that the thermoplastic mixture is subjected to the cohesive flow through the tool which communicates the substantially constant longitudinal deformation rate which does not exceed the deformation rate associated with the melt fracture. An apparatus for producing a thermoplastic product comprising orientated components of a thermoplastic mixture comprising a thermoplastic polymer comprising means for bringing the thermoplastic mixture to an effective temperature range which is just above the softening point of the thermoplastic mixture and includes a tool ( 60) having internal walls, inlets and outlets, a passage path that passes between the inlet and outlet, the input area is greater than the output, some of the internal walls converge and define a converging passage and a cooling means for cooling the thermoplastic mixture, characterized in that -36 • <* · ·· «« · · · · · · · · · ··· · «··· • forcing the thermoplastic mixture through the tool and the cooling means, wherein the thermoplastic mixture is subjected to a converging flow through the tool and longitudinal orientation is provided with at least a portion of the thermoplastic polymer; for the passage, wherein the cooling means has a calibration device having an internal wall channel, the inner wall is configured to have the same cross-sectional profile as the tool outlet and by which the stated longitudinal orientation is preserved. Apparatus according to claim 22, characterized in that the drag ratio of the tool is defined by the ratio of the cross-sectional areas of the inlet and outlet and wherein the tensile ratio is between 3: 1 and 15: 1. Apparatus according to claim 23, characterized in that the converging passage has a substantially hyperbolic gauge Apparatus according to any one of claims 22 to 24, characterized in that the compression means comprises a standard screw type extruder. 26. Apparatus according to Figs. The container according to any one of claims 1 to 4, characterized in that the device for bringing the thermoplastic mixture to a temperature in an effective temperature range which is just above the softening point of the thermoplastic mixture and comprises the softening point is the container (40) connected to the tool. (60). Apparatus according to any one of claims 22 to 26, characterized in that the cooling means comprises a calibration device having an inner wall defining a channel, the calibration means being disposed on the tool (60), the inner wall being configured to be the same its cross-sectional profile as the tool output. 28. Apparatus according to Figs. Claims according to any one of claims 1 to 4, characterized in that the tool further comprises a mandrel which is contained therein and extends over the cohesive passage in which the mandrel (46) forms a cavity in the thermoplastic mixture when in use. -37 «« «· ···· · · *« r · · · · · · ··· · V ·· * «·« · ··· ···· · ♦ · An apparatus as claimed in claim 28, wherein the distance, characterized in that the spike (46) extends downwardly through the converging passage, is selected such that the thermoplastic mixture is sufficiently cooled down before reaching the end of the mandrel, and the cavity that was formed in it is preserved. The apparatus of claim 28, wherein the distance by which the mandrel (46) extends downwardly through the converging passage is selected so that the longitudinal orientation of at least a portion of the thermoplastic polymer is retained in the outer layer of the thermoplastic mixture and the thermoplastic. the blend is foamed into the cavity and forms a concave section with a foamed inner core 31. The thermoplastic product of the method of claim 1, wherein at least a portion of the thermoplastic polymer has a longitudinal orientation. 32. A thermoplastic product according to the method of claim 5, wherein the at least a portion of the filling material of the thermoplastic polymer and the thermoplastic mixture has a longitudinal orientation. A thermoplastic product comprising a thermoplastic mixture comprising a thermoplastic polymer having a rigid, solid outer layer having a longitudinal oriented polymer and a product having a low density foamed interior. The thermoplastic product of claim 33, wherein the thermoplastic mixture comprises a filler directly mixed with the filler material in the solid outer layer oriented longitudinally with the longitudinally oriented thermoplastic polymer. 35. The thermoplastic product of claim 34, wherein said filler has a greater than one aspect ratio. 36. The thermoplastic product is shown in Figures 33-34. Claims according to any one of the preceding claims, characterized in that the filler is selected from the group consisting of cellulose-containing fibers, cellulose-containing particles, mica, talc fibers, asbestos, glass fibers, metal fibers and carbon fibers. -38 ···· ♦ · · · · · · · · · · · · ··· · «· · · · · · · · · · ···· · ·« 37. Thermoplastic product 33-36. The thermoplastic composition according to any one of claims 1 to 3, wherein the thermoplastic mixture comprises up to 75% by weight of filling material. Thermoplastic product 33-37. The thermoplastic polymer is selected from the group consisting of polyethylene, polypropylene, polystyrene, polyvinyl and ethylene copolymer. U i. . SWORKS BT. 1134 Bp, Dévai u. 22-26 / b MESTER TAMÁS patent attorney 1. The thermoplastic mixture comprises 50% by weight injection molding grade high density polyethylene (Sclair 58A, MI = 0.4, DuPont), 50% sawdust and 4 parts maleate polyethylene (Fusabond MB226D, MI 2, DuPont). 2. The density of the material, which forms the solid wall of the profile. 1.16 ² 9.76 PE / SD / MPE ¹ Made of foamed one 0.61 4.94 PE / SD / MPE ¹ He made it together 0.70 5.73 foamed 6.31 PE / SD / MPE ¹ Made of foamed one 0.82 Spruce - 0.42 7.12 White Pine - 0.44 9.46 1.16 9.11 PE / SD / MPE ¹ Hollow 1. The thermoplastic mixture comprises 50% by weight injection molding grade high density polyethylene (Sclair 58A, MI = 0.4, DuPont), 50% quartz powder and 4 parts maleate polyethylene (Fusabond MB226D, MI = 2, DuPont) 2. The density of the material, which forms the solid wall of the profile. Table 8: Mechanical properties of various polyethylene samples filled with 1.5 * 2.5 cellulose Mass / matter Product type Density (g / cm3) Bending Modules (GPa) PE / SD / MPE ¹ Solid 1.15 ² 8.1 PE / SD / MPE ¹ He made it together 0.57 4.0 foamed 1.15 4.9 PE / SD / MPE ¹ Hollow 1. The average particle size of the mica (Mica White 200, L.V. Lomas) is 35 microns and its length is approx. 5th Lonomer 2 (Surlyn 9970, DuPont) was used as a surfactant. Table 7. Mechanical properties of different 1-inch cellulose-filled polyethylene samples Mixture Product type Density (g / cm3) Bending Modules (GPa) PE / SD / MPE ¹ Solid 1. The thermoplastic mixture comprises 4% by weight of surfactants based on the filler (if added). Table 6: Mechanical properties of solid polyethylene patterns filled with mica Mixture Filler ¹ Content (Weight%) Surfactant content (% by weight of filler) Bending Properties Strength (MPa) Modules (GPa) PE1 / Mica / 1R 4.3 PEI / Mica / IR 4.8 PE1 / Mica / 1R 108 7.1 PEI / Mica / IR 7.6 -30 • · PEl / Mica / IR 70 100.0 7.2 ·· ♦ 2/2