• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention relates to a polyether-ether-ketone (PEEK) -based composition comprising polyether-ketone-ketone (PEKK), characterized in that the polyether-ketone-ketone (PEKK) comprises a mixture of terephthalic and isophthalic units, the mass percentage of terephthalic units with respect to the sum of the terephthalic and isophthalic units being between 55 and 85%, inclusive, and preferably between 55 and 70%, said composition comprising between 1 and 40%, including limits, preferably between 5 and 40%, and even more preferably between 10 and 30% by weight of PEKK with respect to the total mass of the composition.
    公开号:FR3027603A1
    申请号:FR1460158
    申请日:2014-10-22
    公开日:2016-04-29
    发明作者:Benoit Brule；Richard Audry；Jerome Pascal
    申请人:Arkema France SA；
    IPC主号:
    专利说明:

    [0001] The invention relates to the field of polyarylene ether ketones and more specifically to that of compositions based on polyether ether ketone (denoted PEEK in the rest of the description of the present invention. ). More particularly, the invention relates to a composition based on polyether-ether-ketone (PEEK) with improved properties and a method for improving at least one property of a composition based on PEEK. The composition according to the invention more particularly exhibits a slow crystallization rate and, on the other hand, better mechanical properties. BACKGROUND [0003] Polyarylene ether ketones (PAEK) are high performance materials with high thermomechanical properties. They consist of aromatic rings linked by an oxygen atom (ether) and / or by a carbonyl group (ketone). Their properties depend mainly on the ether / ketone ratio. In the abovementioned abbreviations, E denotes an ether function and K denotes a ketone function. In the rest of the document, these abbreviations will be used instead of the usual names to designate the compounds to which they relate. Polyarylene ether ketones are used for demanding applications in temperature and / or mechanical or chemical stresses. These polymers are found in fields as varied as aeronautics, offshore drilling, medical implants. They can be implemented by molding, extrusion, compression, spinning or laser sintering. In the family of PAEK, polyether-ether-ketone (PEEK) is particularly used in the context of the aforementioned applications. However, it has the disadvantage of crystallizing very quickly, which can generate significant internal stresses in the parts made of this material at the time of cooling. In some cases, such as PEEK coatings of metal parts, or in the case of massive PEEK parts, these internal stresses can lead to cracking of the material. A subsequent annealing step, followed by a slow cooling, is in general Ref: 0422-ARK52 necessary to eliminate, or at least reduce, these internal stresses. However, such a step is long and therefore implies a significant additional cost of the parts thus manufactured. In addition, in the particular case of laser sintering, the rapid kinetics of crystallization can cause deformation of the workpiece. Such deformation is also called curling. Therefore, in this case, the geometry of the part is not optimal. [0007] Finally, even if the PEEK already have good mechanical properties, it may be advantageous for certain applications to further improve the mechanical properties of objects obtained by different types of process, molding, injection, extrusion or laser sintering. . Thus, it may be advantageous to increase the stress at the threshold of plasticity in order to be able to work a material under greater stress, based on PEEK without irreversibly deforming it, but without degrading the other mechanical properties such as the elongation at break, for example. Indeed, an increase in the stress at the plasticity threshold classically reduces the value of the elongation at break of a material. However, for some applications, it may be important to maintain a ductile material with a high elongation at break. It is therefore generally necessary to find a compromise between the elongation at break and the threshold of plasticity, to have a plastic material having mechanical properties adapted to the application to which it is dedicated. US5 342 664 discloses a polymer alloy comprising between 60 and 98% by weight of a semi-crystalline PAEK and between 40 and 2% by weight of an amorphous PAEK. Such an alloy exhibits a higher elongation at break and a reduced viscosity compared to semi-crystalline PAEK alone. This document however remains silent on the crystallization speed which generates the problems of deformation of parts or requires a long and expensive post-annealing step to eliminate the internal stresses appearing in the part because of a kinetics of crystallization too fast. Nor does it mention the plasticity threshold of the alloy. The article entitled "Blends of two PAEK" published in the journal POLYMER, 1988, Vol.29, June, p. 1017-1020 describes the preparation of an alloy based on PEEK and Ref: 0422-ARK52 PEK, two polymers of the PAEK family which have the particularity of rapidly crystallizing both. This article studies the crystallization of the two compounds of the alloy and their behavior. On the other hand, this document does not study the speed of crystallization and its influence on the appearance of internal stresses and on the deformation of the pieces obtained, nor the mechanical properties of the alloy. The article entitled "Dynamic study of crystallization and melting-induced phase separation in PEEK / PEKK blends" American Chemical Society, 1997, 30, p.4544 - 4550, describes an alloy of PEEK and PEKK whose ratio T Between the terephthalic (T) and isophthalic (I) units is 30/70. This document shows that the incorporation of PEKK 30/70 into PEEK, in mass proportions equal to 50/50, makes it possible to slow the crystallization of PEEK because of an inter-diffusion of the two compounds of the alloy. . This document does not study the mechanical properties of such an alloy. TECHNICAL PROBLEM The object of the invention is therefore to remedy at least one of the disadvantages of the prior art. In particular, the object of the invention is to propose a composition based on PEEK whose at least one property is improved and a process for improving at least one property of such a composition based on PEEK, so as to allow the production of parts from such a composition which have a significant reduction in internal stresses so that one can overcome the additional post-annealing step, which are not deformed and which have mechanical properties increased. Brief description of the invention [0012] Surprisingly, it has been discovered that a polyether ether ketone (PEEK) composition comprising polyether ketone ketone (PEKK), characterized in that the polyether-ketone-ketone (PEKK) comprises a mixture of terephthalic and isophthalic units, the weight percentage of terephthalic units with respect to the sum of the terephthalic and isophthalic units being between 55% and 85%, inclusive, and preferably between 55% and 85%; % and 70%, said composition comprising between 1 and 40%, limits included, preferably between 5 and 40%, and even more preferably between 10 and 30% by weight of PEKK with respect to the total mass of the composition, Ref: 0422-ARK52 not only shows a slowing of the kinetics of crystallization compared to that of a pure PEEK, but also a gain on two generally antagonistic mechanical properties, since the stress has both the plasticity threshold and the elongation at break are increased compared to a pure PEEK. According to other optional features of the composition: - the PEEK can be replaced by PEK or PEKEKK, - the PEKK can be a mixture of PEKK, each PEKK having a mass percentage of terephthalic units in relation to the sum terephthalic and isophthalic units of between 55 and 85%, limits included, and preferably between 55 and 70%, the composition further comprises at least one filler and / or at least one additive, the mass proportion of PEEK in the composition ranging from 60 to 99%, limits included, preferably between 60 and 95%, and even more preferably between 70 and 90% relative to the total mass of the composition. The invention also relates to a process for improving at least one property of a composition based on PEEK, said process consisting in incorporating PEKK into said PEEK-based composition, said process being characterized by the PEKK comprises a mixture of terephthalic and isophthalic units, the mass percentage of terephthalic units with respect to the sum of the terephthalic and isophthalic units being between 55 and 85%, inclusive, and preferably between 55 and 70%, and in that the PEKK is incorporated in said composition in proportions of between 1 and 40%, including limits, preferably between 5 and 40%, and even more preferably between 10 and 30% by weight relative to the total mass. of the composition. The invention finally relates to an object manufactured by a technology selected from laser sintering, molding, injection or extrusion, from a composition as described above. Other advantages and features of the invention will appear on reading the following description given by way of illustrative and nonlimiting example, with reference to the appended figures which represent: Ref: 0422-ARK52 - Figure 1, the evolution of the heat flux of seven compositions based on PEEK as a function of temperature; - FIG. 2, the evolution of the crystallization rate of four compositions based on PEEK as a function of time. DESCRIPTION OF THE INVENTION [0017] The composition that is the subject of the invention is based on PEEK. The PEEK matrix constituting the composition can also be replaced by PEK or PEKEKK. In the abbreviations used, E denotes an ether function and K denotes a ketone function. The presence of PEKK, having terephthalic and isophthalic units, in the composition based on PEEK, makes it possible to slow down the kinetics of crystallization of the PEEK, and thus to limit the internal stresses that may cause cracking during the cooling of the material, and to obtain undeformed pieces whose geometry meets expectations. By terephthalic and isophthalic unit is meant the formula of terephthalic and isophthalic acids respectively. Preferably, the PEKK incorporated in the PEEK-based composition comprises a mass percentage of terephthalic units relative to the sum of the terephthalic and isophthalic units of between 55% and 85%, inclusive, and even more preferably between 55% and 70% and even more preferably, of the order of 60%. Such a PEKK with around 60% of terephthalic units is a very slow crystallization material, typically 20 minutes during isothermal crystallization at temperatures between 240 and 260 ° C, and having a glass transition temperature Tg of order of 160 ° C and a melting temperature of the order of 305 ° C. In particular, the variation of the proportions in terephthalic and isophthalic units of PEKK, in the range of proportions mentioned above, makes it possible to modulate the kinetics of crystallization of PEEK. The kinetics of crystallization will be studied either in anisotherm, that is to say during cooling via a temperature ramp, or in isotherm, that is to say that the crystallization rate will be monitored at a given temperature. In the case of the study of anisothermal crystallization, the lower the crystallization temperature, the slower the kinetics of Ref: 0422-ARK52 will be. It is therefore possible to obtain a range of compositions based on PEEK and PEKK, whose crystallization rate is known for each composition and adapted according to the subsequent application of said compositions. Preferably, the composition comprises between 60 and 99%, limits included, preferably between 60 and 95% and even more preferably between 70% and 90% by weight of PEEK relative to the total weight of the composition. composition and between 1 and 40%, limits included, preferably between 5 and 40%, and even more preferably between 10% and 30% by weight PEKK relative to the total mass of the composition. Such a composition advantageously makes it possible to improve two mechanical properties of PEEK, which are generally antagonistic. Indeed, the addition of PEKK having terephthalic and isophthalic units, in the proportions mentioned above, with a mass percentage of between 1 and 40%, preferably between 40% Set, and even more preferably between 10% and 30%. % with respect to the total mass of the composition, makes it possible to obtain a gain of between 5% and 15% of the plasticity threshold and an elongation at break improved by a factor of up to 3. [0023] composition may further comprise one or more additives or contain different compounds such as fillers, in particular mineral fillers such as carbon black, nanotubes, short fibers (glass or carbon), long fibers, crushed fibers or unmilled, stabilizing agents (light, in particular UV, and heat), flow-promoting agents such as silica, or optical brighteners, dyes, pigments, or a combination of these fillers and / or dditifs. The composition which has just been described consists of a matrix based on PEEK. In a variant, the PEEK matrix may be replaced by a PEK or PEKEKK matrix. In addition, the PEKK incorporated in the composition based on PEEK, or PEK or PEKEKK, may be a mixture of PEKK, provided that each PEKK has a mass percentage of terephthalic units relative to the sum of the terephthalic units. and isophthalic between 55 and 85%, preferably between 55 and 70% and even more preferably of the order of 60%. Ref: 0422-ARK52 [0026] The invention further relates to a method for improving at least one property of a PEEK-based composition, said method comprising incorporating PEKK into said PEEK-based composition. . The embedded PEKK comprises a mixture of terephthalic and isophthalic units, the mass percentage of terephthalic units with respect to the sum of the terephthalic and isophthalic units being between 55% and 85% and preferably between 55% and 70% and even more preferred, of the order of 60%. Advantageously, PEKK is incorporated in said composition in proportions of between 1 and 40%, preferably between 5 and 40%, and even more preferably between 10 and 30% by weight relative to the total mass of the composition. Such incorporation of PEKK in the composition based on PEEK not only modulates the kinetics of crystallization of PEEK, but also improve two mechanical properties of PEEK, which are generally antagonistic, namely the threshold of plasticity and elongation at break. The composition based on PEEK and PEKK as defined above can be prepared by any known method, to obtain a homogeneous mixture containing the composition according to the invention and optionally other additives, fillers. other polymers. Such a method may be chosen from the techniques of melt extrusion, compacting, or else kneading, using for example a roll kneader. More particularly, the composition according to the invention is prepared by melt blending of all its components, especially in a so-called live process. In the case of laser sintering, the composition may also be obtained by dry blending of powders. Advantageously, the composition can be obtained in the form of granules by compounding on a tool known to those skilled in the art, such as a twin screw extruder, a comalaxer, or an internal mixer. The composition thus prepared can then be transformed for subsequent use or processing known to those skilled in the art using tools such as an injection molding machine, an extruder, and the like. Ref: 0422-ARK52 [0033] The process for preparing the composition according to the invention can also use a twin-screw extruder feeding, without intermediate granulation, an injection molding machine or an extruder according to an implementation device known by the invention. skilled in the art. From the resulting composition which can be either granules or powders, it is possible to manufacture different objects by a laser sintering technique, or injection or extrusion for example. The following examples illustrate in a nonlimiting manner the scope of the invention: EXAMPLE 1 Compounding of Several Compositions Having Different Formulations Compounding is a process which makes it possible to mix by melting plastics and / or additives and / or fillers. To manufacture each composition, the raw materials, in the form of granules, are arranged in a twin-screw co-rotating extruder. The feeding zone of the extruder is heated to a temperature of the order of 300 ° C. The material mixing is done at a temperature of about 360 ° C, with a rotational speed of 300 rpm and a flow rate of 2.5 kg / h. The various compositions that have been compounded to be compared all include PEEK and PEKK in different mass proportions. The PEKK incorporated in the composition is a PEKK comprising terephthalic (T) and isophthalic (I) units, whose T / I ratio is equal to 60/40. Two different grades of PEKK were used. These two grades include the same proportions in terephthalic patterns. They differ from each other mainly by their viscosity. Thus, a first PEKK, referenced K1 in Table I below and marketed by Arkema under the trade name KEPSTAN® 6001, has a viscosity index of 0.95 dl / g, while the second PEKK, referenced K3 in the table below and marketed by Arkema under the trade name KEPSTAN ® 6003, has a Ref: 0422-ARK52 viscosity index of 0.82 dl / g. The viscosity number is measured according to ISO 307, in solution at 25 ° C. in 96% sulfuric acid. In these comparative examples, the mass proportions of PEKK in the composition vary between 10 and 30% of the total mass of the composition. The compositions based on PEEK and PEKK are intended to be compared with a control composition referenced CT, comprising only pure PEEK, sold by Victrex under the commercial reference Victrex 450G. The various compositions produced are grouped in Table I below. The amounts of the various constituents of the composition, that is PEEK and PEKK, are expressed as a percentage by weight relative to the total mass of the composition. CT Cl C2 C3 C4 C5 C6 PEEK 100% 90% 80% 70% 90% 80% 70% PEKK (K 1) 10% 20% 30% PEKK (K3) 10% 20% 30% Table I Example 2: Study of the kinetics of crystallization of the compositions obtained at the end of the compounding process of Example 1 [0042] A crystallization study was carried out on the PEEK control sample, referenced CT in Table I above and on the six samples of compositions referenced C1 to C6 in Table I above. The crystallization study is carried out by differential scanning calorimetry, denoted DSC. DSC, the English acronym "Differential Scanning Calorimetry", 20 is a thermal analysis technique for measuring differences in heat exchange between a sample to be analyzed and a reference. To carry out this crystallization study, the Q 2000 equipment of the company TA instruments was used. The study was conducted in anisothermic and isothermal crystallization. Ref: 0422-ARK52 Anisothermic Crystallization The protocol of the DSC in anisotherm, on the various samples CT, C1 to C6 resulting from example 1, consists initially in stabilizing the temperature at 20 ° C. The temperature is then increased progressively, with a ramp of 20 ° C. per minute up to 400 ° C., and is then progressively decreased down to 20 ° C., according to a reverse ramp of 20 ° C. per minute. The crystallization is studied during the cooling step. The heat flux is measured as a function of the temperature, and a curve representing the evolution of the heat flux as a function of the temperature is obtained for each composition studied. These curves are shown in FIG. 1. The crystallization temperature, denoted Tc and expressed in degrees Celsius, is then determined for each composition, projecting on the abscissa axis the maximum of the corresponding curve. This determination is made directly by the DSC equipment used. The crystallization temperatures Tc of each sample analyzed are grouped in Table II below. Composition Tc (° C) CT 291.3 Cl 289.1 C2 288.0 C3 286.6 C4 289.1 C5 287.7 C6 286.7 Table II [0048] The curve of the control composition CT (pure PEEK), not including PEKK, is the curve most This control composition has a highest crystallization temperature Tcc-r equal to 291.3 ° C. Ref: 0422-ARK52 [0049] These curves show that the higher the mass fraction of PEKK in the composition, the lower the crystallization temperature is, and therefore the more the crystallization is delayed. The addition of PEKK to the PEEK according to the invention thus makes it possible to delay the crystallization of the PEEK.
    [0002] Isothermal Crystallization An isothermal DSC was performed for a sample of control composition CT and a sample of compositions C1, C2 and C3, comprising respectively 10%, 20% and 30% by weight of PEKK. The isothermal DSC protocol comprises the following three steps: a first step consists first of all in stabilizing the temperature at 20 ° C, then a second step is to increase the temperature gradually, with a ramp of 20 ° C per minute, up to 400 ° C. Finally, the temperature is decreased from 400 ° C to 315 ° C, at a ramp of 20 ° C per minute, and then stabilized at 315 ° C for one hour. During the time of stabilization of the temperature at 315 ° C., the mass fraction of crystallized PEEK as a function of time t is measured. The measurements are performed on the compositions C1, C2 and C3 compared to the control composition CT. The four curves obtained are represented on the graph of FIG. 2. It follows from the curve corresponding to the control sample CT that the half-crystallization time is about 6 minutes. The half-crystallization time of a polymer is the time required for the crystallization of 50% of this polymer. On the curves of Figure 2, it is determined by placing itself at the value of 50% on the ordinate axis (`) / 0 of crystallized PEEK) and projecting this value on the abscissa axis (Time). The curve corresponding to the composition C3 is shifted to the right by about 4 minutes relative to the curve of the control composition CT. The half crystallization time on this curve is about 10 minutes. The curves corresponding to the compositions C1 and C2 are shifted to the right by about 3 minutes with respect to the curve of the control composition CT, the half-crystallization time of the composition Cl being approximately 9 minutes and that of the composition C2 being practically 10 minutes. Ref: 0422-ARK52 [0054] It follows from these curves that, surprisingly, the crystallization delay is not proportional to the level of PEKK incorporated in the composition. Contrary to what one could expect, the change of kinetics of crystallization is not linear as a function of the rate of incorporated PEKK. Therefore, it is preferred to incorporate a PEKK content of less than or equal to 40% by weight relative to the total weight of the composition in order to avoid the appearance of a demixing phenomenon in the composition. The addition of PEKK in a proportion of 1 to 40% by weight, preferably between 5 and 40% and even more preferably between 10 and 30% by weight relative to the total mass of the PEEK-based composition. according to the invention thus makes it possible to slow the crystallization of the PEEK, while avoiding a demixing phenomenon. EXAMPLE 3 Measurement of the Plasticity Threshold Stress and the Elongation at Break of Injected Parts Based on the Compositions Obtained after the Compounding Process of Example 1 [0056] In order to perform measurements of stress at the threshold of plasticity and elongation at break, specimens of samples were first made. For this, an injection molding machine is used. In this example, the injection press used is a Battenfeld 80T press. The feed temperature of the press is set at 350 ° C, the temperature of the injection nozzle 20 is set at 390 ° C and the mold temperature is set at 230 ° C. Specimens suitable for tensile tests of type 1BA according to ISO 527 are then obtained. For comparative tests for measuring stress at the plasticity threshold and elongation at break, two test pieces were made according to the ISO 25 527 1BA standard. A first specimen of the control composition CT is compared with a second specimen of the composition C3 of Example 1, comprising 30% by mass of PEKK. The stress measurements were carried out on each specimen by means of a tensile dynamometer, coupled to an optical extensometer for recording the stress curves as a function of the deformation of the specimens subjected to tensile stress. The dynamometer used for these Ref: 0422-ARK52 tests is more particularly a dynamometer of the company Zwick and marketed under the reference Zwick 1455. The measurements are carried out at 23 ° C., at a relative humidity of 50 ° / oHr and at a pulling speed of 25mm / min. The necessary traction force as a function of the elongation is then measured and the plastic threshold stress and elongation at break are determined. The results obtained are summarized in Table III below. Composition Threshold stress Plasticity elongation (MPa) rupture (`) / 0) CT 92.5 40 C3 101 100 Table III [0062] The addition of 30% by weight of PEKK in PEEK makes it possible to reduce the stress to the threshold plasticity of 92.5 MPa at 101 MPa, an increase of 7.5%. This addition also makes it possible to increase the elongation at break from 40% to 100%, an increase of a factor of 2.5. Thus, the incorporation of PEKK in a PEEK-based composition induces an increase in the stress at the plasticity threshold as well as an increase in elongation at break, and therefore an increase in two mechanical properties which are, in general, antagonistic. The composition according to the invention not only has the advantage of slowing down the crystallization kinetics of the PEEK, and thereby reducing the internal stresses in the material, thus avoiding the long and costly step of post-annealing, and obtain non-deformed parts to the desired optimum geometry, but it also has the advantage of possessing exceptional mechanical properties with a plasticity threshold gain and elongation at break that were up to now known to be antagonistic mechanical properties. Ref: 0422-ARK52
    权利要求:
    Claims (7)
    [0001]
    REVENDICATIONS1. Composition based on polyether ether ketone (PEEK) comprising polyether ketone ketone (PEKK), characterized in that the polyether ketone ketone (PEKK) comprises a mixture of terephthalic and isophthalic units, the mass percentage in units terephthalic content with respect to the sum of the terephthalic and isophthalic units being between 55 and 85 'Yo, inclusive, and preferably between 55 and 70%, said composition comprising between 1 and 40%, limits included, preferably between 5 and 40 %, and even more preferably between 10 and 30% by weight of PEKK relative to the total mass of the composition. 10
    [0002]
    2. Composition according to claim 1, characterized in that the PEEK is replaced by PEK or PEKEKK.
    [0003]
    3. Composition according to claim 1, characterized in that the PEKK may be a mixture of PEKK, each PEKK having a mass percentage of terephthalic units relative to the sum of the terephthalic and isophthalic units is between 55 and 85%, terminals included, and preferably between 55 and 70%.
    [0004]
    4. Composition according to claims 1 and 3, characterized in that it comprises at least one filler and / or at least one additive.
    [0005]
    5. Composition according to any one of claims 1, 3 or 4, characterized in that the mass proportion of PEEK in the composition is between 60 to 99%, limits included, preferably between 60 and 95%, and even more preferably between 70 and 90% relative to the total mass of the composition.
    [0006]
    A method of improving at least one property of a PEEK-based composition, said method comprising incorporating PEKK into said PEEK-based composition, said method being characterized in that the PEKK comprises a mixture of terephthalic and isophthalic units, the mass percentage of terephthalic units with respect to the sum of the terephthalic and isophthalic units being between 55 and 85%, inclusive, and preferably between 55 and 70%, and in that PEKK is incorporated in said composition in proportions between 1 and 40%, limits included, preferably between 5 and 40%, and even more preferably between 10 and 30% by weight relative to the total mass of the composition.
    [0007]
    7. Object manufactured by a technology selected from laser sintering, molding, injection or extrusion, from a composition according to one of claims 1 to 5. Ref: 0422-ARK52
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    KR20200049868A|2017-09-15|2020-05-08|알케마 인코포레이티드|Polyether ketone ketoneextrusion lamination manufacturing method and product|
    US11118053B2|2018-03-09|2021-09-14|Ticona Llc|Polyaryletherketone/polyarylene sulfide composition|
    EP3825345A1|2019-11-19|2021-05-26|Arkema France|Improved powder for additive manufacturing|
    WO2021249875A1|2020-06-11|2021-12-16|Solvay Specialty Polymers Usa, Llc|Fiber reinforced thermoplastic matrix composite material|
    WO2021249874A1|2020-06-11|2021-12-16|Solvay Specialty Polymers Usa, Llc|Blends of poly polymers|
    法律状态:
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1460158A|FR3027603B1|2014-10-22|2014-10-22|COMPOSITION BASED ON POLYARYLENE ETHER-KETONE WITH IMPROVED PROPERTIES|FR1460158A| FR3027603B1|2014-10-22|2014-10-22|COMPOSITION BASED ON POLYARYLENE ETHER-KETONE WITH IMPROVED PROPERTIES|
    BR112017007941-0A| BR112017007941B1|2014-10-22|2015-10-09|COMPOSITION BASED ON POLY, PROCESS FOR THE PREPARATION OF SUCH COMPOSITION, USE OF THE SAME AND OBJECT MANUFACTURED FROM THIS|
    CA2965371A| CA2965371C|2014-10-22|2015-10-09|Composition based on poly having improved properties|
    KR1020177013482A| KR101855054B1|2014-10-22|2015-10-09|Composition based on polyhaving improved properties|
    PCT/EP2015/073349| WO2016062558A1|2014-10-22|2015-10-09|Composition based on polyhaving improved properties|
    EP15189066.2A| EP3012297B2|2014-10-22|2015-10-09|Composition based on poly having improved properties|
    ES15775727T| ES2711305T3|2014-10-22|2015-10-09|Composition based on polythat has improved properties|
    US15/520,913| US10150866B2|2014-10-22|2015-10-09|Composition based on polyhaving improved properties|
    ES15189066.2T| ES2638654T3|2014-10-22|2015-10-09|Composition based on polythat has improved properties|
    CN201580062632.3A| CN107001787B|2014-10-22|2015-10-09|The composition based on poly-with improved property|
    MX2017005144A| MX2017005144A|2014-10-22|2015-10-09|Composition based on polyhaving improved properties.|
    RU2017115887A| RU2677666C2|2014-10-22|2015-10-09|Composition on basis of poly with improved properties|
    EP15775727.9A| EP3209729B1|2014-10-22|2015-10-09|Composition based on poly having improved properties|
    JP2017521508A| JP6505219B2|2014-10-22|2015-10-09|Composition based on polywith improved properties|
    US14/920,075| US9624371B2|2014-10-22|2015-10-22|Composition based on poly having improved properties|
    US16/204,290| US20190203044A1|2014-10-22|2018-11-29|Composition based on polyhaving improved properties|
    JP2019022785A| JP6823675B2|2014-10-22|2019-02-12|Composition based on polywith improved properties|
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