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    • 专利摘要:
    The invention relates to a profile made from a reinforced polyvinyl chloride polymer comprising per 100 parts by weight of polyvinyl chloride (PVC) at least 40 parts by weight, preferably 60 parts by weight, more preferably 80 parts by weight of a naturally occurring mineral filler, and PVC with K value 50- 68.
    公开号:BE1018320A3
    申请号:E2009/0670
    申请日:2009-10-30
    公开日:2010-08-03
    发明作者:Raf Bussels
    申请人:Tessenderlo Chemie N V S A；
    IPC主号:
    专利说明:

    PVC profiles with a high content of mineral filler and their use
    Technical field
    The invention relates to PVC profiles with a high content of naturally occurring mineral filler and their use.
    Background
    Polyvinyl chloride polymer (PVC) is a plastic that, due to its versatile physical and chemical properties, is used in all kinds of industries. There is a demand for reinforced PVC because bending or expanding / shrinking a PVC profile is undesirable in various applications.
    EP 0085778 states that the best reinforcement materials are generally fiber structures. The use of alternative reinforcing fibers, synthetic fibers (aramid or carbon fibers), mineral fibers (glass fibers)) or natural fibers (flax, wood) leads to a considerable increase in raw material costs, which makes a PVC profile unattractively expensive. These fillers should also be avoided for health reasons, for example because of the exposure risk associated with inhaling glass fibers. A disadvantage of natural fibers, such as flax or wood, is their varying composition and therefore fluctuating quality. They are moisture sensitive and mold and rot even when they are processed in a PVC device such as a profile. An additional disadvantage of synthetic, mineral or natural fibers is that they make the processing of PVC considerably more difficult.
    In US2007 / 0078191, PVC was reinforced by means of increased amounts of fiberglass. The use of large amounts of glass fiber is disadvantageous. The abrasive glass fibers abrade and damage metal machine parts. As a result, frequent repairs and replacements must be made. Damaging the mold for the production of PVC profiles causes loss of shape retention and increased rejection percentages.
    Glass fiber reinforced profiles produced via a pultrusion technique, whereby thermosetting polymer and reinforcing fiber are formed into a profile, have the disadvantage that the adhesion between the fiber and the polymer is often insufficient, and that adhesives are necessary. The material cannot be recycled. The raw material and equipment costs are high.
    Thus, there is a need for new PVC profiles. The present invention has for its object to at least partially solve the above problems.
    Summary
    The invention provides for this purpose PVC profiles with a high content of a naturally occurring mineral filler and the description of their use.
    In a first aspect, the invention relates to profiles made from a reinforced polyvinyl chloride polymer comprising per 100 parts by weight of polyvinyl chloride (PVC) at least 40 parts by weight, preferably 60 parts by weight, more preferably 80 parts by weight of a naturally occurring mineral filler, and PVC with K- value 50-68.
    In a further aspect the invention relates to a method for manufacturing a profile according to the invention.
    In a third aspect, the invention provides a granulate or profile obtained by a method according to the invention.
    In a final aspect, possible uses of PVC profiles according to the invention are described.
    In order to better show the characteristics of the invention, a few preferred embodiments are described below as an example without any limiting character.
    Description of the invention
    As used further in this text, the singular forms "one," "the," "the," include both the singular and the plural unless the context is clearly different.
    The terms "include", "includes" as used further are synonymous with "inclusive," include "or" contain, "contain" and are inclusive or open and do not exclude additional, unnamed members, elements or method steps.
    The terms "include", "includes" include the term "include".
    The enumeration of numerical values of Tfand of numerical ranges includes all values and fractions in these ranges, as well as the cited end points.
    The term "about" as used when referring to a measurable value such as a parameter, a quantity, a duration, and so on, is intended to encompass variations of +/- 10% or less, preferably +/- 5% or less, more preferably +/- 1% or less, and even more preferably +/- 0.1% or less, from and from the specified value, as far as the variations apply to function in the disclosed invention. It is to be understood that the value to which the term "approximately" refers per se has also been disclosed.
    All documents quoted in the current specification are fully incorporated herein by reference.
    Unless defined otherwise, all terms disclosed in the invention, including technical and scientific terms, have the meaning that those skilled in the art usually understand. As a further guide, definitions are included for further explanation of terms used in the description of the invention.
    It is generally assumed that in order to obtain reinforced PVC, fiber materials must be used as reinforcement material. In the present invention, the term "fiber materials" is understood to mean glass fibers, aramid fibers, carbon fibers and / or combinations thereof. To increase a reinforcement level, the amounts of reinforcement material are increased. However, with large amounts of reinforcing material mixing problems occur, compositions are no longer sufficiently homogeneous and PVC profiles exhibit bulging fiber materials on their surface.
    The inventors have succeeded in making reinforced PVC profiles based solely on naturally occurring mineral fillers.
    The term "naturally occurring mineral filler" is understood to mean a filler that can be found as such in nature and that can be used with the exception of grinding without the use of a synthesis process. The designation mineral indicates that it is an element or chemical compound that is usually crystalline and that was formed as a result of geological processes. Glass fibers are excluded by the definition as they require a synthesis step starting from SiO2. Wood fibers are not mineral.
    In the present invention, the term "naturally occurring mineral filler" is understood to mean in particular wollastonite, vermiculite, talc, mica and / or combinations thereof. In a preferred embodiment of the invention, the naturally occurring mineral filler is selected from a group comprising wollastonite, vermiculite, talc, mica and / or combinations thereof. In a preferred embodiment of the invention, the naturally occurring mineral filler in a profile is talc and / or mica. The use of a naturally occurring mineral filler can improve the modulus or stiffness and the linear thermal expansion coefficient of an end product. If a rigid profile is desired, mica is preferred. If a profile is desired with a reduced linear thermal expansion coefficient, talc is preferred.
    They were not hindered by mixing problems. The highly filled PVC profiles were of good quality. In the present invention, the term "highly filled" is understood to mean a high content of naturally occurring mineral filler. A PVC profile is highly filled when at least 25 parts by weight of a naturally occurring mineral filler are used per 100 parts by weight of polyvinyl chloride. This is also expressed with the term "phr", which stands for "parts per hundred resin".
    In a preferred embodiment, the profiles are made from a reinforced polyvinyl chloride polymer comprising per 100 parts by weight of polyvinyl chloride (PVC) at least 40, preferably at least 60 parts by weight of a naturally occurring mineral filler. More preferably, PVC profiles comprise at least 80 parts by weight, most preferably at least 100 parts by weight, of a naturally occurring mineral filler. Being able to replace large quantities of fiber materials with a naturally occurring mineral filler has the advantage that the price of PVC profiles can be reduced. Not only through savings on raw material costs, but also through saving on repair and replacement costs, and reducing the percentage of rejected products. When using large quantities of fibers, adhesion problems often occur and large quantities of adhesives must be used. The invention has the advantage that no adhesives need to be added. The PVC profiles have a smooth surface.
    In a preferred embodiment, PVC is used with a K value between 50 and 68. The "K value" of a polymer is a measure of the molecular weight and is based on the inherent viscosity. A K value between 50 and 68 corresponds to a weight average molecular weight of approximately 40000-100000 g / mol. In a more preferred embodiment, the polyvinyl chloride polymer has a K value between 60 and 68. In a most preferred embodiment of the invention, the PVC has a K value between 64 and 68. A K value of 65 is advantageous for good processability. and mechanical properties. PVC is commercially available in the form of powder. The PVC can be used in the form of regenerate (scrap). The term "regenerate (scrap)" as used in the present invention is understood to mean recyclable PVC-based materials from the starting or stopping of extrusion lines, or PVC-based material outside of specification. In a preferred form, a method comprises extruding a formulation comprising at least 10% by weight of regenerate.
    The invention thus provides profiles of PVC, characterized in that per 100 parts by weight of PVC at least 40 parts by weight, preferably at least 60 parts by weight, more preferably at least 80 parts by weight, most preferably at least 100 parts by weight of a naturally occurring mineral filler are used ; and the PVC has a K value preferably between 50 and 68, more preferably between 60 and 68, most preferably between 64 and 68, and typically around 65. In a preferred form of the invention, profiles are made of reinforced polyvinyl chloride polymer with a K value between 64 and 68.
    In a preferred embodiment, the naturally occurring mineral filler is talc and / or mica. Talc is a hydrated magnesium silicate, with the chemical structural formula Mg3Si40io (OH) 2. For use, it is ground to powder with an average grain size between 0.5 µm and 20 µm which are commercially available. Mica is preferably of the muscovite type, this is a phyllosilicate mineral, with the chemical structural formula KAI2 (AISi3O10) (OH, F) 2. For use, it is ground to powder with an average grain size between 0.5 µm and 40 µm. It is commercially available. This feature has the advantage that the PVC profiles have improved fire-resistant properties, a reduced thermal expansion, and a higher rigidity. This is an interesting feature for use in building components. The invention thus provides profiles from PVC, characterized in that the naturally occurring mineral filler is talc and / or mica. In a preferred form of the invention, the naturally occurring mineral filler is talc and / or mica with an average grain size d50 of between 0.5 and 40 µm.
    In a preferred embodiment of the invention, the naturally occurring mineral filler is talc and / or mica with an average grain size between 0.5 and 5 µm. In a more preferred embodiment, the naturally occurring mineral filler is talc and / or mica with an average grain size between 0.5 and 3 µm for talc and between 30 and 35 µm for mica. Preferably, the granules are elongated in shape and are platelets. The average grain size d50 of a naturally occurring mineral filler can be determined by measurement techniques known to those skilled in the art. For example, using the method described in ISO 13320.
    Due to the large amounts of naturally occurring mineral filler, PVC profiles according to embodiments of the invention are less flexible and not easily breakable. In a preferred embodiment, a profile has an elastic modulus of preferably at least 5 GPa. In a more preferred embodiment, the elastic modulus is at least 8 GPa. In a most preferred embodiment, the elastic modulus is at least 10 GPa. The term "flexural modulus" indicates the modulus of elasticity under deflection, also defined as the ratio of flexural stress divided by flexural strain. The flexural modulus of a material can be measured by techniques well known to those skilled in the art, for example according to ISO 178.
    This feature has the advantage that the PVC profiles can be used in applications where profiles must have large dimensions. Because of their stiffness, they will bend less easily. This is useful in applications where metal reinforcements are currently being applied. This is the case, for example, with profiles in sliding doors and windows. The invention thus provides PVC profiles, characterized in that an elastic modulus of preferably at least 5 GPa, more preferably at least 8 GPa, most preferably at least 10 GPa.
    In a preferred embodiment, a profile has a thermal expansion coefficient lower than 25 x 10 6 mm / mm / K. In a more preferred embodiment, a profile has a thermal expansion coefficient lower than 20 x 10 6 mm / mm / K. In a most preferred embodiment, a profile has a thermal expansion coefficient of less than 15 x 10 -6 mm / mm / K.
    The term "linear thermal expansion coefficient", also abbreviated as CLTE, describes how much a material will expand for each increment in temperature change, as represented by formula:
    where d1 = the change in length of the material in the measuring direction, I0 = initial length of the material in the measuring direction, dT = change in temperature over the interval d1 over which measurement is made.
    Linear thermal expansion coefficients can be measured by techniques known to those skilled in the art. For example, linear thermal expansion coefficients can be determined by means of a silica dilatometer according to ASTM D 696 or ISO 11359.
    This feature has the advantage that the profiles are less susceptible to shrinking and expansion under the influence of temperature. This is advantageous in applications where PVC profiles are exposed to weather conditions, for example in windows, external doors and gates, cladding of facades, terrace floors. They are suitable for replacing reinforcement elements made of steel (CLTE = 13 x 10 "6 mm / mm / K) or aluminum (CLTE = 22 x 10" 6 mm / mm / K). Thus, the invention provides PVC profiles, preferably with a thermal expansion coefficient lower than 25 x 10 -6 mm / mm / K, more preferably lower than 20 x 10 -6 mm / mm / K, most preferably lower than 15 x 10 -6 mm / mm / K.
    In a preferred embodiment, a profile is provided with cavities. Profiles so provided with chambers are light and easily transportable.
    In a preferred embodiment, a profile was created with a raw material obtained by two mixing steps; each mixing step involves mixing PVC with a naturally occurring mineral filler and a temperature treatment. Eligible mixing steps are traditional preparation steps such as compounding, granulating, extruding, injection molding. More information about these preparations can be found in manuals such as, for example, PVC Handbook, Eds. Charles E. Wilkes, James W. Summers, and Charles A. Daniels, Published by Hanser Gardner, 2005. The advantage of this preparation is that the homogeneity of a formulation is preserved, so that problems such as demixing and loss of quality are reduced. The invention thus provides profiles, characterized in that the raw material for the profile is obtained by means of two mixing steps for mixing the PVC with naturally occurring mineral fillers. Preferably the naturally occurring mineral filler is talc and / or mica. More preferably, the naturally occurring mineral filler is talc with an average grain size d50 of between 0.5 and 40 µm.
    In a preferred embodiment, a preparation comprises a first mixing step a) in which a pre-reinforced polymer is formed by mixing an amount A of a naturally occurring mineral filler with PVC at a temperature lower than the melting temperature of PVC. Unlike other plastics, polyvinyl chloride does not have one specific melting temperature, but rather a melting range ranging from 130 ° C to 240 ° C. By "temperature lower than the melting temperature" of a polyvinyl chloride polymer, a temperature lower than 130 ° C is meant.
    The pre-reinforced polymer obtained in step a) is mixed in a second mixing step b) with an amount B of a naturally occurring mineral filler at a temperature higher than 180 ° C. The temperature higher than 180 ° C is preferably 185 ° C, more preferably 190 ° C, even more preferably 195 ° C, most preferably 200 ° C. In a preferred embodiment, a PVC profile is obtained by extruding in step b) at a temperature of preferably 185 ° C, more preferably 190 ° C, even more preferably 195 ° C, most preferably 200 ° C. The filler used in step a) may differ from that used in step b). The advantage of this preparation is that the amount of filler in a formulation can be increased without the processability being compromised. The resulting profiles are of good quality. For example, the profiles have a smooth and homogeneous surface, with no protruding filler parts on their surface. The invention thus provides profiles characterized in that in their preparation, in a first mixing step, an amount A of the naturally occurring mineral filler is mixed with PVC at a temperature lower than the melting temperature of the PVC; and that in a second mixing step an amount B of the naturally occurring mineral filler is mixed with the first mixture at a temperature higher than 180 ° C.
    In a preferred form, a method for obtaining a profile according to the invention comprises the following steps: a) preparing a pre-reinforced polymer by blending a polyvinyl chloride polymer with an amount A of a naturally occurring mineral filler at a temperature lower than the melting temperature of the polyvinyl chloride polymer; and b) mixing the pre-reinforced polymer obtained under a) with an amount B of a naturally occurring mineral filler at a temperature higher than 180 ° C into a reinforced Polyvinyl chloride polymer, c) optionally granulating the reinforced Polyvinyl chloride polymer obtained in step b), d) pressing the reinforced polyvinyl chloride polymer obtained in step b) or the granulate obtained in step c) through a mold to obtain the profile.
    In a preferred form of the above process, the amount of A of a naturally occurring mineral filler is between 0-2 phr, between 2-25 phr or between 25-40 per hundred parts of Polyvinyl chloride polymer (phr). In a production environment where the processing equipment is close to the mixer, an amount of A between 25-40 phr is advantageous, since there is little transport and therefore little risk of demixing. For situations with an average transport requirement, an amount of A between 2-25 phr is an advantage. With excellent dosing systems, the amount of A can be reduced to 0-2 phr. In a preferred embodiment, a highly filled compound is formed in the first step by using at least 25 parts by weight of naturally occurring mineral filler.
    The ratio of an amount of A of a filler to an amount of B of a filler is at least 0.1, preferably at least 0.2, more preferably at least 0.25, most preferably at least 0.3. If this ratio is used in the preparation of a feed from an extruder, it will show an almost optimum flow and compressibility. This is unexpected since it is known that highly filled compositions are difficult to flow through the fill opening in a cylinder of an extruder and do not flow fast enough to properly fill the first passages of a screw. This leads to incomplete mixing and poor quality of the end product. It is also known that a highly filled composition has a very high compressibility. A screw of an extruder can therefore compact the feed to a limited extent, insufficient to generate the required friction to melt the material. As a result, a powder or only sintered product comes out of the extruder, and no good melt. The invention thus provides PVC profiles, characterized in that the ratio of the amount of A to the amount of B is preferably at least 0.2, more preferably at least 0.25, most preferably at least 0.3.
    In a preferred embodiment, the total amount of filler is in weight%, up to 70% of the reinforced polyvinyl chloride polymer. The usability of larger quantities of filler offers more possibilities for controlling product properties, for example the reduction of the linear thermal expansion coefficient.
    In a preferred embodiment, the total number of parts filler (A + B) is opposite the number of parts Polyvinyl chloride polymer, preferably between 0.4 and 2.5, more preferably between 0.6 and 1.5, most preferably between 0.8 and 1.2. In a preferred embodiment, the total amount of naturally occurring mineral filler (A + B) is opposed to the amount of Polyvinyl chloride polymer, preferably between 0.4 (about 30% by weight amount of naturally occurring mineral filler / 70% by weight PVC) and 2.5 ( about 70% by weight amount of naturally occurring mineral filler / 30% by weight PVC), more preferably between 0.6 and 1.5, most preferably between 0.8 and 1.2. This ratio has the advantage that sufficient polymer is present in comparison with naturally occurring mineral filler for good melting and mixing in an extruder, resulting in a homogeneous mixture.
    In a preferred embodiment, the total amount of naturally occurring mineral filler (A + B) is opposed to the amount of polyvinyl chloride polymer in a method for the preparation of a device according to the invention, preferably between 0.4 and 2.5, more preferably between 0.6 and 1.5, most preferably between 0.8 and 1.2.
    In a preferred embodiment, a PVC profile comprises at least one auxiliary substance selected from a group comprising heat stabilizers, lubricants, processing aids, impact fasteners, foaming agents, light stabilizers, colorants. In a preferred embodiment according to the invention, the excipients in a formulation consist of a heat stabilizer, a lubricant and a processing excipient. No further additives are required.
    In a preferred embodiment, a heat stabilizer is selected from a group of CaZn, Ca-organic, Sn, or Pb stabilizers. Type CaZn refers to calcium-zinc systems based on fatty acid salts of calcium and zinc in combination with cost stabilizers. Type Ca organic means stabilizers based on fatty acid salts of calcium in combination with cost stabilizers. Type Sn means stabilizers based on organotin compounds. Type Pb refers to stabilizers based on (in) organic lead salts. A heat stabilizer causes the dehydrochlorination process of Polyvinyl chloride to be delayed and prevents Polyvinyl chloride from burning during a heat treatment such as extruding. In a more preferred embodiment, the heat stabilizer comprises CaZn or Ca-organic stabilizers, while for use in North America there is a preference for Sn stabilizers. The reasons for this are historical. North America has always preferred Sn, while Europe has always preferred Pb stabilizers. As Pb stabilizers will disappear (at the latest in 2015), the preference in Europe is now for CaZn and Ca-organic.
    In another embodiment of the invention, the heat stabilizer is a blocked thiol type heat stabilizer. By the term "blocked thiol type" heat stabilizer is meant a thiol of formula B-S-R wherein B and R represent an organic portion. Blocked thiols and organic-based heat stabilizers are interchangeable as terms. An organic-based heat stabilizer comprises a zinc salt, and at least one sulfur compound selected from the group consisting of a free mercaptan, a zinc mercaptide, and a latent mercaptan. Preferably, an organic-based heat stabilizer is an organic-based composition comprising at least one organic-based heat stabilizer component, and at least one stabilizer modifying compound selected from the group comprising a liquid calcium soap and 1,3,5-tris (2- hydroxyethyl cyanuric acid; wherein the organic-based heat stabilizer component comprises a zinc salt and at least one sulfur compound selected from the group consisting of a free mercaptan, a zinc mercaptide, and a latent mercaptan; and wherein the liquid calcium salt is a solution of a calcium salt that is liquid at 105 ° C and free from other metal salts.
    Use of a blocked thiol type stabilizer system is advantageous since it is substantially free of heavy metals and harmful bisphenol A co-stabilizer. It is a more environmentally friendly type of stabilizer. An additional advantage is that this type of stabilizer is a recycling booster. PVC stabilized with a blocked thiol-type stabilizer is compatible with other stabilization systems such as the CaZn, Ca-organic or Sn-type stabilizers. It can be safely combined with recycled PVC. It delivers good color stability to PVC profiles. In a preferred form of the invention, a profile comprises up to 10% by weight of recycled PVC; preferably up to 25% by weight recycled PVC, comprising a blocked thiol type stabilizer.
    In a preferred embodiment, the total amount of stabilizers in a formulation is preferably between 1 to 4% by weight, more preferably between 2 and 4% by weight, most preferably between 3 and 4% by weight. In a more preferred embodiment of the invention, the total amount of stabilizers in a formulation is a maximum of 1.5% by weight when using stabilizers of the Sn type, 5% by weight when using stabilizers of the Pb type, 2-4% by weight when using Ca / Zn or Ca-organic stabilizers, 4% by weight when a blocked thiol type is used.
    In a preferred embodiment of the invention, a method further comprises the step of: adding a thermal stabilizer in an amount between 0 and 5% by weight; preferably between 1 and 4% by weight; wherein the thermal stabilizer is preferably a blocked thiol type stabilizer.
    An auxiliary substance can also be a lubricant, for example to promote the flow of a polymer melt through a processing device such as an extruder. In a preferred embodiment, a lubricant is selected from a group comprising polyethylene waxes, oxidized polyethylene waxes, paraffin waxes, fatty acid ester waxes (e.g. distearyl phthalate), salts of fatty acids (e.g. calcium stearate), fatty acids, fatty acid alcohols, amine waxes and / or combinations thereof. In a preferred embodiment, the total amount of lubricant in a formulation is preferably between 0 and 2% by weight, more preferably between 1 and 2% by weight, most preferably between 1.5 and 2% by weight.
    In a preferred embodiment, a processing aid is selected from a group comprising methacrylate copolymers, acrylate copolymers, methacrylate terpolymers, acrylate terpolymers and / or a combination thereof. In a preferred embodiment, the total amount of processing aid in a formulation is preferably between 0 and 15% by weight, more preferably between 5 and 15% by weight, most preferably between 10 and 15% by weight. This use, for example, supports the processability of a polymer by promoting fusion, improves melt strength, changes surface properties, ensures better release of a formulation of metal parts.
    In addition to polyvinyl chloride polymer and naturally occurring mineral filler, a formulation may also comprise one or more excipients. In an embodiment of the invention, a method comprises the step of adding a processing aid is used in an amount between 0 and 15% by weight; preferably between 5 and 15% by weight.
    To improve the impact resistance of an end product, an impact protector can be added to a formulation. In a preferred embodiment of the invention, the total amount of impact fasteners is preferably between 0 and 5% by weight, more preferably between 1 and 5% by weight, most preferably between 2 and 5%.
    A light stabilizer can be added to inhibit the degradation of PVC by the influence of light. In a preferred embodiment, a light stabilizer is selected from a group comprising a stabilizer of the titanium dioxide type, the benzotriazole type, the 2-hydroxybenzophenone type, and / or combinations thereof. In a more preferred embodiment of the invention, titanium dioxide is used. In a most preferred embodiment, the total amount of light stabilizers in a formulation is preferably between 0 and 10, more preferably between 2 and 8, most preferably between 4 and 6% by weight.
    A profile according to the invention can be provided with a covering layer or cap. The coating material is selected from a group comprising poly ((meth) acrylate), poly (butyl acrylate-styrene-acrylonitrile), polyvinylidene fluoride, polyvinyl fluoride, poly (styrene-acrylonitrile), a light-resistant polyvinyl chloride material and / or a combination thereof. In a preferred embodiment of the invention, the total amount of coating additive in a formulation is preferably between 0 and 6% by weight, more preferably between 0 and 4% by weight, most preferably between 0 and 2% by weight.
    If the end application becomes a visible part, in other words if no cover layer (cap) will be extruded over a profile, a PVC profile can be colored with a dye. In a preferred embodiment, a colorant is selected from a group comprising a metal salt, metal oxide, mixed metal oxide and / or combinations thereof. In a more preferred embodiment, a mixed metal oxide is used. This shows the best aging behavior. In a preferred embodiment, the total amount of colorants in a formulation is preferably between 0 and 5% by weight, more preferably between 1 and 4% by weight, most preferably between 2 and 3% by weight.
    In an additional aspect, the invention provides a reinforced polyvinyl chloride polymer based on a formulation comprising: - polyvinyl chloride polymer in an amount that is preferably between 30 and 70, more preferably between 35 and 70, most preferably between 40 and 70 weight. % of the formulation; - a naturally occurring mineral filler in an amount that is preferably between 30 and 70% by weight, more preferably between 35 and 70% by weight, most preferably between 40 and 70% by weight of the formulation.
    In a preferred form of the invention, a reinforced polyvinyl chloride polymer is based on a formulation comprising: - Polyvinyl chloride polymer in an amount of at least 30 weight%, preferably at least 35 weight%, more preferably at least 40 weight%, most preferably preferably at least 45% by weight of the formulation; - a naturally occurring mineral filler in an amount of at least 30% by weight, preferably at least 35% by weight, more preferably at least 40% by weight, most preferably at least 45% by weight of the formulation.
    In a preferred form of the invention, a reinforced polyvinyl chloride polymer is based on a formulation comprising: - Polyvinyl chloride polymer in an amount of at least 30% by weight, preferably at least 35% by weight, more preferably at least 40% by weight, most preferably at least at least 45% by weight of the formulation: - a naturally occurring mineral filler in an amount of at least 30% by weight, preferably at least 35% by weight, more preferably at least 40% by weight, most preferably at least 45% by weight of the formulation; wherein the naturally occurring mineral filler is talc and / or mica, preferably talc.
    A polyvinyl chloride polymer based on a formulation according to a preferred embodiment of the invention contains increased filler levels. These highly filled polyvinyl chloride polymers are heavier reinforced, have increased fire retardant properties, increased toughness, increased rigidity.
    In a further aspect, the invention provides a granulate or profile obtained by a method as previously described. In a further aspect of the invention, uses of the PVC profiles are provided.
    The profiles according to an embodiment of the invention are preferably used as reinforcing element. Reinforcement elements find application as reinforcement of large-sized PVC profiles, for example in sliding windows, window frames, doors, gates, fencing, or other fences. Reinforcement elements made of steel or aluminum are typically used for this. A reinforcing element according to an embodiment of the invention can be a profile, one or more strips or co-extrudate. In the first case, for the production of a reinforced PVC profile, a PVC profile with chamber and a reinforcing element are created. The reinforcement element is slid into the chamber. It can be fixed, for example with screws or glue. The reinforcement element can also be integrated into a PVC profile during the production of the PVC profile itself, preferably by (co-) extrusion. A part of the profile will here consist of a profile according to the invention, for example by (co-) extrusion. A (co-) extrudate can take the form of one or more strips. The use of a reinforcement element according to the invention, as a replacement for a reinforcement element of metal, has the advantage that an improved insulation value is obtained. A good conductive material such as metal is after all replaced by a less conductive material. This can be important in windows or other building materials, in order to be able to meet stricter insulation standards. The use of a reinforcement element made of PVC also has the advantage that a lighter construction is obtained without losing strength. This makes easier manipulation and placement possible. The invention thus provides for a use of a profile according to a preferred embodiment, as a reinforcing element, preferably in a window frame or fence.
    PVC profiles according to a preferred form of the invention find application in the covering of floors. It is sturdy, light and well-insulated material. PVC profiles according to a preferred form of the invention are recyclable.
    PVC profiles according to a preferred form of the invention have good processability. They can be machined with standard joiner's tools such as a drill or a saw. They can be nailed or nailed without the profile cracking or splintering. A profile according to a preferred form of the invention can serve as the basis for hinges and locks (the fitting). To this end, the invention provides for the use of a profile as the basis for a suspended structure or closing device such as a fitting. In another preferred form, the invention provides for the use of a profile according to the invention, wherein the profile is fixed with nails or screws.
    It is self-evident that the description of this invention within its scope may relate to alternative embodiments. The invention is illustrated by the following non-limitative examples.
    PVC Profiles Examples 1-8
    Profiles according to a preferred form of the invention may be based on compositions as shown in Table 1. The term "phr" as used in this invention is understood to mean "parts per hundred resin". The use of this unit is based on 100 parts of polyvinyl chloride polymer and the amount of other ingredients is expressed with respect to this 100 parts of polyvinyl chloride polymer.
    For the preparation of a batch quantity of 100 kg, the following quantities were introduced into a Periplast brand hot mixer with a tank volume of 250 liters: 100 parts Polyvinyl chloride polymer, 3.5 parts CaZn stabilizer or 1.5 parts Sn stabilizer or 4.0 parts of a blocked thiol type stabilizer, 1.9 parts of lubricants, 8 or 10 parts of processing aid, 5 or 6 parts of impact stabilizer and 25 parts of talc, mica or fiberglass. The ingredients were mixed by means of a stirrer with tip speed 38 m / s. The jacket temperature was 80 ° C. Upon reaching a temperature of 120 ° C, the mixture was overflowed. The mixture was placed in a Periplast brand cold mixer with a tub volume of 800 liters. The mixture was stirred at a tip speed of 6 m / s. The jacket temperature was set to 10 ° C to cool the mixture. The mixture was cooled until an overflow temperature of 40 ° C was reached.
    Table 1: Compositions for making PVC profiles according to the invention (Example 1-7) and according to the state of the art (Example 8)
    j
    Example 9-11
    The thus obtained pre-reinforced polymer was introduced into a metering unit of a counter-rotating parallel double-screw extruder of the Bandera brand and processed into granules or directly into a profile using a mold.
    A typical method for granulation is shown in Table 2. A total of 100 phr naturally occurring mineral filler was used; 25 phr in a first and 75 phr in a second process step. From a first dosing unit filled with a compound containing 25 phr naturally occurring mineral filler and a second dosing unit filled with naturally occurring mineral filler, product streams were fed to a reciprocating single screw extruder of the Buss PR-46 brand, with a flow rate of respectively 26 and 14 kg per hour. Each product stream was applied to the screw of the extruder via a separate filling opening. The kneader and extruder had the properties as shown in Table 2.
    Table 2: example of a typical granulation process

    (*) 11D - 11x screw diameter, 6D = 6x screw diameter, rpm = rotations per minute
    A typical example of a profile extrusion from granulate (example 10) and a direct profile extrusion (example 11) are shown in Table 3.
    Table 3: Typical example of a profile extrusion from granulate and a direct profile extrusion.

    (*) 20D = 20x screw diameter, rpm = rotations per minute
    Example 12
    As an additional example, the inventors have prepared a formulation as described by Example 12. To prepare a 100 kg batch, the ingredients and amounts were used as illustrated in Table 4. The amounts are expressed in weight percentages of the formulation.
    Polyvinyl chloride polymer with K-value 65, titanium dioxide, tin-based stabilizer, lubricants and auxiliary processing substances were loaded in a warm mixer at room temperature. These ingredients were mixed using a stirrer with a tip speed of 38 m / s. Upon reaching 80 ° C in the mixture, a first amount of talc was added to the heat mixer and stirred continuously. Upon reaching a temperature of 120 ° C, the mixture was transferred to a cold mixer. The mixture was stirred at a tip speed of 6 m / s. The jacket temperature was set to 15 ° C to cool the mixture. The mixture was cooled until an overflow temperature of 40 ° C was reached.
    The compound thus obtained was transported by means of transport lines to a mixing station (hopper + feed). A first hopper was loaded with the compound in the mixing station. A second hopper from the mixing station was loaded with PVC regenerate from a window profile. The amount of PVC regenerate as indicated in Table 3 was mixed with the compound in the mixing station. From the mixing station the mixture thus obtained was transported by means of a line to the main hopper or the granulation extruder. The used extruder was a counter-rotating parallel twin-screw extruder of the Krauss-Maffei KMD90 type.
    Table 4: Composition for producing PVC profiles (Example 12)
    The main dosing installation consisted of a hopper and feed. The feed was connected to an input on the extruder. The mixture was loaded in the hopper. From this funnel the material flowed to the screws of the granulation extruder. The remaining part (amount B) of the talc was added via a second dosing installation (hopper + feed) on the extruder. The foaming agent and the coloring agent were added online via two additional dosing installations. All material flows came together on the screws. The conditions used for the granulation extruder are shown in Table 5.
    On the extruder screws, the material was melted to above the melting temperature of PVC and intensive mixing took place. The granulation extruder was equipped with a mold. The melt flow was pressed through the mold. Upon leaving, thin strands were formed with a diameter of approximately 3 mm. The wires were shortened by means of a rotating knife to pieces with a length of approximately 1 to 3 mm. The resulting granulate was blown to a drying and cooling speed, cooled and brought into big bags or a storage tank. The granulate was suitable for further use.
    Table 5: Operational conditions used in a granulation extruder for the preparation of granules based on a compound as illustrated by example 10.

    The resulting granulate was transported to a profile extruder. The extruder used is a counter-rotating conical twin-screw extruder of the Krauss-Maffei KMD60 type. The granulate was loaded into the extruder dosing station. The dosing station was connected to the input of the extruder. The granulate flowed from this dosing station onto the screws of the extruder. On the screws of the granulate, it was heated, melted and transported to a mold. The conditions used in the extruder for the preparation of the profile are shown in Table 6.
    Table 6: Operational conditions used in an extruder for the preparation of profile based on a compound as illustrated by example 12.
    The mold that was used had the shape and size of the desired profile. The melt was pushed through the mold and assumed the shape imposed by the mold. The melt was sent to a calibration and cooling installation, where the melt was brought to the final dimensions and cooled.
    The thus obtained reinforcement profile was cut to the desired length in order to obtain reinforcement elements. These elements were introduced into a room of a window profile. The reinforced window profiles thus obtained were assembled window frames, according to techniques known to those skilled in the art.
    Properties PVC profiles
    Properties of PVC profiles based on a composition from Table 1 and according to a method from Table 3 are shown in Table 7. The results obtained by the use of naturally occurring mineral fillers (examples 1-7) are comparable with the results obtained with fiberglass (example 8). For comparison, a PVC without reinforcing filler has a flexural modulus of 2.7 GPa and a linear thermal expansion coefficient (CLTE) of 52 x 1CT6 mm / mmK.
    Table 7: Properties of PVC profiles according to the invention (examples 1-7 and 11) and according to the state of the art (example 8)
    权利要求:
    Claims (18)
    [1]
    A profile made from a reinforced polyvinyl chloride polymer comprising per 100 parts by weight of polyvinyl chloride (PVC) at least 40 parts by weight, preferably 60 parts by weight, more preferably 80 parts by weight of a naturally occurring mineral filler, and PVC with a K value of 50-68.
    [2]
    Profile according to claim 1, characterized in that the naturally occurring mineral filler is selected from a group comprising wollastonite, vermiculite, talc, mica and / or combinations thereof.
    [3]
    Profile according to claim 1 or 2, characterized in that the naturally occurring mineral filler is talc and / or mica.
    [4]
    Profile according to any one of claims 1-3, characterized in that the PVC has a K value between 64 and 68.
    [5]
    Profile according to any one of claims 1-4, characterized in that the naturally occurring mineral filler has an average grain size d50 of between 0.5 and 50 µm; preferably talc has an average grain size d50 between 0.5 and 5 µm and mica has an average grain size d50 between 30 and 35 µm.
    [6]
    Profile according to any of claims 1-5, with an elastic modulus of at least 5 GPA, preferably at least 10 GPa.
    [7]
    Profile according to any of claims 1-6, with a linear thermal expansion coefficient (CLTE) lower than 25 x 10 -6 mm / mm / K, preferably lower than 15 x ICT6 mm / mm / K.
    [8]
    8. Profile as claimed in any of the claims 1-7, wherein the profile is provided with hollow spaces.
    [9]
    A method for manufacturing a profile according to any one of claims 1-8, comprising the steps of: a) preparing a pre-reinforced polymer by blending a polyvinyl chloride polymer with an amount A of a naturally occurring mineral filler at a temperature lower than the melting temperature of the Polyvinyl chloride polymer; and b) mixing the pre-reinforced polymer obtained under a) with an amount B of a naturally occurring mineral filler at a temperature higher than 180 ° C into a reinforced Polyvinyl chloride polymer, c) optionally granulating the reinforced Polyvinyl chloride polymer obtained in step b), d) pressing the reinforced polyvinyl chloride polymer obtained in step b) or the granulate obtained in step c) through a mold to obtain the profile.
    [10]
    Method according to claim 9, characterized in that the amount of A of a naturally occurring mineral filler is between 0-2 phr, between 2-25 phr or between 25-40 phr.
    [11]
    A method according to claim 9 or 10, characterized in that the ratio of the amount of A over the amount of B is at least 0.1, preferably at least 0.2, more preferably at least 0.25, most preferably at least 0.3.
    [12]
    A method according to any one of the preceding claims 9-11, characterized in that the total amount of naturally occurring mineral filler (A + B) versus the amount of polyvinyl chloride polymer is preferably between 0.4 and 2.5, more preferably between 0.6 and 1.5, most preferably between 0.8 and 1.2.
    [13]
    A method according to any of the preceding claims 9-12, characterized in that the method comprises the step of: adding a processing aid is used in an amount between 0 and 15% by weight; preferably between 5 and 15% by weight.
    [14]
    A method according to any of the preceding claims 9-13, characterized in that the method comprises the step of: adding a thermal stabilizer in an amount between 0 and 5% by weight; preferably between 1 and 4% by weight; wherein the thermal stabilizer is preferably a blocked thiol type stabilizer.
    [15]
    A granulate or profile obtained by a method according to any of the claims 9-14 above.
    [16]
    Use of a profile according to any of the claims 1-8 or claim 15 above, as a reinforcing element, preferably in a window frame or fence.
    [17]
    17. Use of a profile according to claim 16, wherein the reinforcement element is the basis for a suspended structure or latch such as a fitting.
    [18]
    Use of a profile according to any of the claims 1-8 or claim 15 above, wherein the profile is fixed with nails or screws.
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    同族专利:
    公开号 | 公开日
    BE1018451A3|2010-12-07|
    EP2346933B1|2016-06-29|
    EP2346933A1|2011-07-27|
    US20110207870A1|2011-08-25|
    WO2010049532A1|2010-05-06|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US11020408P| true| 2008-10-31|2008-10-31|
    BE2008/0593A|BE1018451A3|2008-10-31|2008-10-31|PVC PROFILES WITH HIGH CONTENT OF MINERAL FILLER AND THEIR USE.|
    BE200800593|2008-10-31|
    US11020408|2008-10-31|
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