Large Scale Production Molds

Abstract

A mold for molding large articles is provided, the mold including at least one molding surface for receiving a material to be molded, the mold including at least one polyarylsulfone polymer selected from poly(ethersulfone) and poly(biphenylsulfone), at least one poly(etherimide), and a reinforcing carbon filler. The mold has excellent mechanical properties and heat resistance.

Description

[Technical field]

[0001] REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Patent Application No. 63 / 322727, filed March 23, 2022, and European Patent Application Publication No. 22171948.7, filed May 6, 2022, the entire contents of each of which are incorporated herein by reference for all purposes.

[0002] The present invention relates to moulds for moulding large sized articles from plastic materials, such as composite materials containing continuous fibres. [Background technology]

[0003] The present invention relates to moulds for moulding large sized articles from plastic materials.

[0004] Molds for manufacturing large-sized objects are often made of metal. Replacing metal with lighter plastic materials would provide several advantages in terms of overall cost and ease of manufacture. However, some obstacles exist, such as the heat resistance and mechanical resistance of the mold itself. In fact, molding plastic or composite materials involves subjecting the mold to cycles of heating and cooling, either by heating the mold itself or by contacting the mold with molten plastic material. This has the disadvantage that deformations of the mold's shape and changes in its dimensions occur during the subsequent cooling, which results in a loss of repeatability of the molding.

[0005] Therefore, there remains a need for molds made of plastic materials suitable for molding large sized articles having good thermal and mechanical resistance and low warpage. Summary of the Invention

[0006] It has now been discovered that certain compositions comprising at least one polyarylsulfone selected from poly(ethersulfone) or poly(biphenylsulfone), at least one poly(etherimide), and a reinforcing carbon filler provide molds having large dimensions that are exceptionally resistant to warping.

[0007] A first object of the present invention is therefore a mold for molding an article, comprising at least one molding surface for receiving a material to be molded, the mold comprising at least one polyarylsulfone polymer selected from poly(ethersulfone) and poly(biphenylsulfone), at least one poly(etherimide), and a reinforcing carbon filler.

[0008] The mold of the present invention has mechanical properties such as impact strength, tensile strength, and tensile modulus, as well as high heat distortion temperature to meet the needs of the application.

[0009] A second object of the invention is a method for producing moulds using fusion manufacturing techniques, including injection moulding, compression moulding as well as fused additive manufacturing techniques, including both filament-based methods (Fused Filament Fabrication, FFF) and large format fused additive manufacturing by direct extrusion.

[0010] A further object of the invention is a method for producing a molded article using the mold of the invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] In this application: Any description, even if made in relation to a particular embodiment, is applicable to and interchangeable with other embodiments of the present disclosure; Where an element or component is referred to as being included in and / or selected from a list of enumerated elements or components, it is to be understood that in the relevant embodiments expressly contemplated herein, the element or component may be any one of the individually enumerated elements or components, or may be selected from a group consisting of any two or more of the explicitly enumerated elements or components, and that any element or component enumerated in a list of elements or components may be omitted from such list; Any recitation herein of numerical ranges by endpoints includes all numbers subsumed within the recited range, as well as the endpoints of the range, and equivalents thereof.

[0012] A first object of the invention is a mould for moulding an article, said mould comprising at least one moulding surface for receiving a material to be moulded, said moulding surface having a length of at least 1.0 m in at least one direction, said mould comprising: 0.5 to 40.0 weight percent of at least one poly(etherimide) polymer; 0.0 to 70.0 weight percent of at least one poly(biphenyl sulfone) polymer; 0.0 to 70.0 wt. % of at least one poly(ether sulfone) polymer; 5.0-50.0 wt. % of at least one reinforcing carbon filler, preferably a carbon fiber filler; The composition (C) contains 10.0≦(X PPSU +X PES ) ≦ 94.5 and X PPSU and X PES are not zero at the same time, and X PPSU is the weight percent of the at least one poly(biphenyl sulfone) polymer in composition (C), and X PES is the weight percent of the at least one poly(ether sulfone) polymer in composition (C).

[0013] As used herein, all weight percentages (wt %) are based on the total weight of the composition, unless expressly indicated otherwise.

[0014] The molding surface of the mould of the invention typically has a length in at least one direction of at least 1.5 m, or even at least 2.0 m, and / or up to 30 m, or even up to 50 m. The molding surface may have a length in at least one direction of from 1.0 to 30.0 m, or even from 1.5 to 25.0 m, or even from 3.0 to 20.0 m.

[0015] The molding surface of the mould of the present invention may have a length in at least two directions of at least 1.0 m, or even at least 1.5 m, or even at least 2.0 m or more.

[0016] In a particular embodiment, the forming surface has a length in two directions of 1.0 to 30.0 m, or even 1.5 to 20.0 m.

[0017] The molding surface is usually contoured to the same shape as the article to be molded. It may be convex or concave. The mold may include inserts as required for the article to be molded therein. In certain embodiments, the mold may include multiple molding surfaces, for example, arranged to form a closed continuous surface.

[0018] The molds of the invention comprise a composition (C) which is described in detail below. Typically, the molding surface of the molds of the invention comprises composition (C). Preferably, the molds are made from composition (C).

[0019] Composition (C) The composition (C) is 0.5 to 40.0% by weight of at least one poly(etherimide) polymer [polymer PEI]; 0.0 to 70.0% by weight of at least one poly(biphenylsulfone) polymer [polymer PPSU]; 0.0 to 70.0% by weight of at least one poly(ether sulfone) polymer [polymer PES]; 5.0-50.0 wt. % of at least one reinforcing carbon filler; Including, 10.0≦(X PPSU +X PES )≦94.5, and X PPSU and X PES are not zero at the same time, and X PPSU is the weight percent of the at least one poly(biphenyl sulfone) polymer in composition (C), and X PES is the weight percent of the at least one poly(ether sulfone) polymer in composition (C).

[0020] For the avoidance of doubt, X PPSU If =0 then X PES ≠ 0 and X PES If =0 then X PPSU ≠0.

[0021] 0.5 to 40.0% by weight of at least one polymer PEI, 0.0 to 70.0% by weight of at least one polymer PPSU, 30.0 to 70.0% by weight of at least one polymer PES, 5.0 to 50.0 wt. % of at least one reinforcing carbon filler; A composition (C) containing

[0022] In a first embodiment of the present invention, the composition (C) does not contain polymer PPSU, i.e., 0.0% by weight of polymer PPSU or X PPSU = 0. In such an embodiment, composition (C) comprises 0.5 to 40.0% by weight of at least one polymer PEI, 40.0 to 70.0% by weight of at least one polymer PES, 5.0 to 50.0 wt. % of at least one reinforcing carbon filler; Includes.

[0023] In such embodiments, the amount of polymeric PES may be at least 45.0% by weight, or even 50.0% by weight, based on the total weight of the composition.

[0024] Advantageous results have been obtained with a composition (C) comprising 3.0 to 15.0% by weight of at least one polymer PEI, 50.0 to 70.0% by weight of at least one polymer PES and 15.0 to 50.0% by weight of at least one reinforcing carbon filler.

[0025] In another embodiment of the present invention, composition (C) does not contain polymer PES, i.e., 0.0% by weight of polymer PES or X. PES = 0. In such an embodiment, composition (C) comprises 0.5 to 40.0% by weight of at least one polymer PEI, 30.0 to 65.0% by weight of at least one polymer PPSU, 5.0 to 50.0 wt. % of at least one reinforcing carbon filler; Includes.

[0026] In such embodiments, the amount of polymeric PPSU may be at least 35.0 wt. %, based on the total weight of the composition.

[0027] Advantageous results have been obtained with a composition (C) comprising 5.0-40.0% by weight of at least one polymer PEI, 35.0-65.0% by weight of at least one polymer PPSU and 15.0-50.0% by weight of at least one reinforcing carbon filler.

[0028] In a further embodiment, composition (C) comprises 0.5 to 40.0% by weight of at least one polymer PEI, 5.0 to 70.0% by weight of at least one polymer PPSU, 30.0 to 70.0% by weight of at least one polymer PES, 5.0 to 50.0 wt. % of at least one reinforcing carbon filler; Includes.

[0029] Advantageous results have been obtained with a composition (C) comprising 5.0 to 20.0% by weight of at least one polymer PEI, 30.0 to 70.0% by weight of at least one polymer PES, 5.0 to 20.0% by weight of at least one polymer PPSU and 15.0 to 50.0% by weight of at least one reinforcing carbon filler, based on the total weight of the composition.

[0030] Composition (C) typically contains at least 2.0% by weight, preferably at least 5.0% by weight, of polymeric PEI. The amount of polymeric PEI is usually not more than 35.0% by weight, based on the total weight of the composition.

[0031] Composition (C) typically comprises at least 10.0% by weight, preferably at least 15.0% by weight, of at least one reinforcing carbon filler. The amount of reinforcing carbon filler usually does not exceed 45.0% by weight. Good results in terms of reinforcing properties are usually obtained with an amount of reinforcing carbon filler ranging from 15.0 to 45.0% by weight, or even from 20.0 to 45.0% by weight.

[0032] PEI Polymer For purposes of the present invention, a poly(etherimide) polymer, i.e., the polymer PEI, is defined as a polymer having a repeating unit (R PEI is intended to mean any polymer in which more than 50 mole percent of the repeat units (A) contain at least one aromatic ring, at least one imide group as such and / or in its amic acid form, and at least one ether group [repeating units (A)].

[0033] The repeating unit (A) may optionally further contain at least one amide group that is not included in the amic acid form of the imide group.

[0034] The repeating units (A) are advantageously represented by the following formulae (I), (II), (III), (IV), and (V): [ka] and mixtures thereof, where Ar is a tetravalent aromatic moiety selected from the group consisting of substituted or unsubstituted, saturated, unsaturated, or aromatic monocyclic and polycyclic groups having 5 to 50 carbon atoms; Ar''' is a trivalent aromatic moiety selected from the group consisting of substituted or unsubstituted, saturated, unsaturated or aromatic monocyclic and polycyclic groups having 5 to 50 carbon atoms; R is a substituted or unsubstituted divalent organic group, more specifically, (a) an aromatic hydrocarbon group having 6 to 20 carbon atoms and a halogenated derivative thereof; (b) a linear or branched alkylene group having 2 to 20 carbon atoms; (c) a cycloalkylene group having 3 to 20 carbon atoms, and (d) a divalent group of the general formula (IV): [ka] (wherein Y is an alkylene having 1 to 6 carbon atoms, particularly -C(CH)- and -C n H 2n - (n is an integer of 1 to 6); perfluoroalkylene having 1 to 6 carbon atoms, particularly -C(CF3)2- and -C n F 2n - (n is an integer from 1 to 6); cycloalkylene of 4 to 8 carbon atoms; alkylidene of 1 to 6 carbon atoms; cycloalkylidene of 4 to 8 carbon atoms; -O-; -S-; -C(O)-; -SO2-; -SO-; R' is selected from the group consisting of hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium; i and j are the same or different and are independently 0, 1, 2, 3, or 4). is selected from the group consisting of provided that at least one of Ar, Ar''', and R contains at least one ether group present in the polymer chain backbone.

[0035] Preferably, Ar is of the formula: [ka] and In these formulas, X is a divalent moiety having a divalent bond at the 3,3', 3,4', 4,3'', or 4,4' positions and is an alkylene of 1 to 6 carbon atoms, particularly -C(CH) and -C n H 2n - (n is an integer from 1 to 6); perfluoroalkylene having 1 to 6 carbon atoms, particularly -C(CF3)2 and -C n F 2n - (n is an integer from 1 to 6); cycloalkylene of 4 to 8 carbon atoms; alkylidene of 1 to 6 carbon atoms; cycloalkylidene of 4 to 8 carbon atoms; -O-; -S-; -C(O)-; -SO2-; -SO-, or X is a group of formula O-Ar"-O, where Ar" is selected from the group consisting of the following formulae (VII) to (XIII): [ka] and mixtures thereof; R and R' are the same or different and are independently selected from the group consisting of hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkylsulfonate, alkali or alkaline earth metal phosphonate, alkylphosphonate, amine, and quaternary ammonium; j, k, l, n, and m are the same or different and are independently 0, 1, 2, 3, or 4; W is an alkylene of 1 to 6 carbon atoms, particularly -C(CH3)2 and -C n H 2n - (n is an integer from 1 to 6); perfluoroalkylene having 1 to 6 carbon atoms, particularly -C(CF3)2 and -C n F 2n-(n is an integer from 1 to 6); cycloalkylene of 4 to 8 carbon atoms; alkylidene of 1 to 6 carbon atoms; cycloalkylidene of 4 to 8 carbon atoms; -O-; -S-; -C(O)-; -SO2-; and -SO-.

[0036] Preferably, Ar''' is of the formula: [ka] and X has the same meaning as defined above.

[0037] In a preferred specific embodiment, the repeating unit (A) comprises a unit of formula (XIV) in imide form, corresponding units of formula (XV) and of formula (XVI) in amic acid form: [ka] and mixtures thereof; In these formulas: → means isomerism such that in any repeat unit the group pointed to by the arrow may be present either as shown or in interchangeable positions; Ar″ is a group represented by the following formulae (VII) to (XIII): [ka] is selected from the group consisting of: In these formulas, R and R' are the same or different and are independently selected from the group consisting of hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium; j, k, l, n and m are the same or different and are independently 0, 1, 2, 3 or 4; W is an alkylene of 1 to 6 carbon atoms, particularly -C(CH3)2 and -C n H2n - (n is an integer from 1 to 6); perfluoroalkylene having 1 to 6 carbon atoms, particularly -C(CF3)2 and -C n F 2n -(n is an integer from 1 to 6); cycloalkylene of 4 to 8 carbon atoms; alkylidene of 1 to 6 carbon atoms; cycloalkylidene of 4 to 8 carbon atoms; -O-; -S-; -C(O)-; -SO2-; and -SO-; E is -C n H 2n - (n is an integer from 1 to 6), divalent radicals of general formula (VI) as defined above, and those according to formulae (XVII) to (XXII): [ka] wherein R' is selected from the group consisting of hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali metal or alkaline earth metal sulfonate, alkyl sulfonate, alkali metal or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium; and o, p and q are the same or different from one another and are independently 0, 1, 2, 3 or 4. is selected from the group consisting of:

[0038] Preferably, E is selected from the group consisting of those according to formulae (XVII) to (XIX) as defined above, more preferably E is selected from the group consisting of unsubstituted m-phenylene and unsubstituted p-phenylene, and mixtures thereof.

[0039] Preferably, Ar″ is of general formula (XIII) as defined above, more preferably, Ar″ is [ka] It is.

[0040] The polymer PEI in which the repeating unit (A) is a repeating unit of formula (XIV) as defined above in its pure form, in its imide form and / or in its amic acid form [formulae (XV) and (XVI)] has the formula: [ka] (wherein Ar″ is as previously defined herein). with any aromatic bis(ether anhydride) of the formula: H2N-E-NH2 (XXIV) where E is as previously defined. The compounds can be prepared by any of the methods known to those skilled in the art, including reaction with a diamino compound of formula (I).

[0041] Alternatively, these poly(etherimide) polymers can be prepared by melt polymerizing any dianhydride of formula (XXIII) and any diamino compound of formula (XXIV) while simultaneously heating and mixing the mixture of these ingredients at an elevated temperature.

[0042] The aromatic bis(ether anhydride) of formula (XXIII) may, for example, be 2,2-Bis[4-(2,3-dicarboxyphenoxy)phenyl]propane dianhydride; 4,4'-Bis(2,3-dicarboxyphenoxy)diphenyl ether dianhydride; 1,3-Bis(2,3-dicarboxyphenoxy)benzene dianhydride; 4,4'-Bis(2,3-dicarboxyphenoxy)diphenyl sulfide dianhydride; 1,4-Bis(2,3-dicarboxyphenoxy)benzene dianhydride; 4,4'-Bis(2,3-dicarboxyphenoxy)benzophenone dianhydride; 4,4'-Bis(2,3-dicarboxyphenoxy)diphenylsulfone dianhydride; 2,2-Bis[4(3,4-dicarboxyphenoxy)phenyl]propane dianhydride; 4,4'-Bis(3,4-dicarboxyphenoxy)diphenyl ether dianhydride; 4,4'-Bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride; 1,3-Bis(3,4-dicarboxyphenoxy)benzene dianhydride; 1,4-Bis(3,4-dicarboxyphenoxy)benzene dianhydride; 4,4'-Bis(3,4-dicarboxyphenoxy)benzophenone dianhydride; Included are 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl-2,2-propane dianhydride, and the like, and mixtures of such dianhydrides.

[0043] The organic diamine of formula (XXIV) includes, for example, m-phenylenediamine, p-phenylenediamine, 2,2-bis(p-aminophenyl)propane, 4,4'-diaminodiphenyl-methane, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, and mixtures thereof. In a preferred embodiment, the organic diamine of formula (XXIV) is selected from the group selected from m-phenylenediamine and p-phenylenediamine, and mixtures thereof.

[0044] In the most preferred embodiment, the repeating units (A) are those of formula (XXV) in imide form, their corresponding amic acid forms of formula (XXVI) and formula (XXVII): [ka] (In formulae (XXVI) and (XXVII), → denotes isomerism such that in any repeat unit, the two groups pointed to by the arrows from the same aromatic ring may be present as shown or in interchanged positions.) and mixtures thereof.

[0045] In another most preferred embodiment, the repeating units (A) are those of formula (XXVIII) in imide form, their corresponding amic acid forms of formulae (XXIX) and (XXX): [ka] (In formulae (XXIX) and (XXX), → denotes isomerism such that in any repeat unit, the two groups pointed to by the arrows from the same aromatic ring may be present as shown or in interchanged positions.) and mixtures thereof.

[0046] Preferably, greater than 75 mol % of the repeat units of the polymeric PEI are repeat units (A), more preferably greater than 90 mol %. Even more preferably, essentially all, if not all, of the repeat units of the PEI are repeat units (A).

[0047] In a preferred embodiment of the invention, more than 75 mol %, more preferably more than 90 mol %, more preferably more than 99 mol %, and even more preferably all, of the repeat units of the PEI are repeat units selected from the group consisting of those in imide form of formula (XXV), those in their corresponding amic acid form of formula (XXVI) and (XXVII), and mixtures thereof.

[0048] In another preferred embodiment of the invention, more than 75 mol %, more preferably more than 90 mol %, more preferably more than 99 mol %, and even more preferably all of the repeat units of the polymer PEI are repeat units selected from the group consisting of those in imide form of formula (XXVIII), those in their corresponding amic acid form of formula (XXIX) and (XXX), and mixtures thereof.

[0049] A suitable polymer, PEI, is commercially available from Sabic Innovative Plastics as ULTEM® poly(etherimide) polymer.

[0050] The composition may contain only one type of polymer, PEI, or it may contain a mixture of two or more types of polymer, PEI.

[0051] Typically, the polymeric PEI useful in the present invention has a melt flow rate (MFR) in the range of 0.1 to 40.0 grams per 10 minutes, as measured according to ASTM D1238 at 337° C. under a load of 6.6 kg, preferably in the range of 4 to 25 grams per 10 minutes, as measured according to ASTM D1238 at 337° C. under a load of 6.6 kg.

[0052] In certain embodiments, the polymeric PEI advantageously has a weight average molecular weight (Mw) of 10,000 to 150,000 grams per mole (g / mol) as measured by gel permeation chromatography using polystyrene standards. Such polymeric PEI typically has an intrinsic viscosity measured in m-cresol at 25° C. of greater than 0.2 deciliters per gram (dl / g), advantageously 0.35 to 0.7 dl / g.

[0053] Polymer PPSU The composition comprises at least one polymeric PPSU. As used herein, the polymeric PPSU is defined as a polymer having a repeating unit (R PPSU ), where the mole percent is the repeat unit in the polymer: [ka] The total number of moles is the basis.

[0054] According to one embodiment of the present disclosure, at least 60 mol%, at least 70 mol%, at least 80 mol%, at least 90 mol%, at least 95 mol%, at least 99 mol%, or all of the repeat units in the PPSU are repeat units of formula (B) (R PPSU ).

[0055] PPSU can be prepared by known methods and is available as RADEL® PPSU from Solvay Specialty Polymers USA, LLC, among others.

[0056] The PPSU polymer advantageously has a melt flow rate (MFR) of 5 g / 10 min or more at 365° C. and 5.0 kg load, preferably 10 g / 10 min or more at 365° C. and 5.0 kg load, more preferably 14 g / 10 min or more at 365° C. and 5.0 kg load, as measured according to ASTM method D1238.

[0057] The upper limit for the melt flow rate of the PPSU polymer is usually a maximum of 100 g / 10 min, preferably a maximum of 60 g / 10 min, more preferably a maximum of 40 g / 10 min.

[0058] The weight average molecular weight of the PPSU polymer can be from 20,000 to 100,000 grams per mole (g / mol) as determined by gel permeation chromatography according to ASTM D5296 using methylene chloride as the mobile phase and polystyrene standards. In some embodiments, the weight average molecular weight of the PPSU polymer can be from 40,000 to 80,000 grams per mole (g / mol). In another embodiment, the PPSU polymer has a weight average molecular weight (Mw) in the range of 48,000 to 52,000 g / mol.

[0059] Polymer PES As used herein, poly(ether sulfone), the polymer PES, has at least 50 mol % of its repeat units of the formula (D): [ka] "A" refers to any polymer having repeating units of the formula:

[0060] Preferably, at least 60 mol %, 70 mol %, 80 mol %, 90 mol %, 95 mol %, 99 mol %, and most preferably all, of the repeat units in the PES are repeat units of formula (D).

[0061] PES can be prepared by known methods and is notably available as VERADEL® PESU from Solvay Specialty Polymers USA, LLC.

[0062] The PES polymer advantageously has a melt flow rate (MFR) of at least 10 g / 10 min, measured according to ASTM D1238 using a temperature of 380° C. and a load of 2.17 kg. The MFR is more preferably greater than 15 g / 10 min, and most preferably greater than 20 g / 10 min. The MFR is usually up to 100 g / 10 min, preferably up to 80 g / 10 min, and most preferably up to 60 g / 10 min.

[0063] Reinforcing carbon filler Composition (C) contains at least one reinforcing carbon filler, preferably a carbon fiber filler.

[0064] For purposes of the present invention, the term "carbon fiber filler" is intended to include graphitized, partially graphitized, and non-graphitized carbon-based reinforcing fibers or mixtures thereof.

[0065] The term "graphitized" is intended to mean carbon fibers obtained by high-temperature pyrolysis (above 2000° C.) of carbon fibers, in which the carbon atoms are arranged similarly to the graphite structure.

[0066] The carbon fibers useful in the present invention can be advantageously obtained by heat treatment and pyrolysis of different polymer precursors, such as, for example, rayon, polyacrylonitrile (PAN), aromatic polyamides or phenolic resins; they can also be obtained from pitch materials.

[0067] The carbon fibers useful in the present invention are preferably selected from the group consisting of PAN-based carbon fibers (PAN-CF), pitch-based carbon fibers, graphitized pitch-based carbon fibers, and mixtures thereof.

[0068] The PAN-based carbon fibers (PAN-CF) advantageously have a diameter of 3 to 20 μm, preferably 4 to 15 μm, more preferably 5 to 10 μm, most preferably 6 to 8 μm. Good results have been obtained with PAN-based carbon fibers (PAN-CF) having a diameter of 7 μm.

[0069] The PAN-CF may be of any length. Generally, the length of the PAN-CF is at least 50 μm.

[0070] Graphitized pitch-based carbon fibers containing at least about 50% by weight graphitic carbon, greater than about 75% by weight graphitic carbon, and up to substantially 100% graphitic carbon, are readily available from commercial sources. Highly graphitic carbon fibers particularly suitable for use in the practice of the present invention can be further characterized as highly conductive, and typically such fibers are used having an elastic modulus of about 550 to about 830 GPa. In a particular embodiment, the highly graphitic carbon fibers have an elastic modulus of about 590 to about 830 GPa, and in another particular embodiment, about 690 to about 793 GPa.

[0071] The pitch-based CF advantageously has a diameter of 5 to 20 μm, preferably 7 to 15 μm and more preferably 8 to 12 μm.

[0072] The pitch-based CF may be of any length, preferably having a length of at least 50 μm.

[0073] Additives The composition may further include optional additives such as, but not limited to, antioxidants (e.g., ultraviolet light stabilizers and heat stabilizers), processing aids, nucleating agents, lubricants, flame retardants, smoke suppressants, antistatic agents, antiblocking agents, colorants, pigments, and the like.

[0074] In some embodiments, antioxidants can be particularly desirable additives. Antioxidants can improve the thermal and photostability of the composition. For example, antioxidants that are thermal stabilizers can improve the thermal stability of the composite during manufacturing (or in high temperature application settings), for example, by helping to prevent polymer degradation while allowing the polymer to be processable at higher temperatures.

[0075] When present, the additives are typically included in the composition in an amount not exceeding 10.0% by weight, or even not exceeding 8% by weight, relative to the total weight of the composition. The additives are usually present in an amount of at least 0.5% by weight, for example at least 1.0% by weight, relative to the total weight of the composition.

[0076] Composition (C) can be prepared by melt-kneading the powder mixture of polymer and filler. Conventional melt-kneading equipment can be used, such as co-rotating and counter-rotating extruders, single screw extruders, co-kneaders, disk pack processors and various other types of extrusion equipment. Preferably, extruders can be used, more preferably twin screw extruders.

[0077] It is advantageously possible to obtain strand extrudates of the composition (C) of the invention, which can be chopped into pellets or beads and then further used for the manufacture of the moulds of the invention.

[0078] A further object of the present invention is a method for producing the mould according to the first object of the present invention. To produce the mould of the present invention, any method suitable for producing three-dimensional articles having a length of at least 1.0 m in at least one direction from a polymer composition can be used.

[0079] Suitable techniques include, for example, rotational molding or injection molding.

[0080] In a preferred embodiment of the invention, the molds of the invention are manufactured by additive manufacturing techniques, preferably fused additive manufacturing techniques, including both filament-based methods (Fused Filament Fabrication, FFF) and large-format fused additive manufacturing by direct extrusion.

[0081] It is therefore a further object of the present invention to Providing a component material comprising the composition (C) detailed above; and Depositing layers of a three-dimensional object from part material; The method for producing the mold of the present invention includes the steps of:

[0082] The expression "part material" refers herein to a blend of materials, in particular polymer-based compounds, intended to form at least a part of a three-dimensional object. Part materials are used as raw materials used for the manufacture of a three-dimensional object according to the present disclosure.

[0083] The component material may be in the form of filaments or particulates.

[0084] The expression "filament" refers to a thread-like body or fiber formed from a material or blend of materials, in particular composition (C). The expression "particulate" refers to a particle having a size comprised between 1 and 200 μm, for example between 10 and 100 μm or between 20 and 80 μm. The particulate can be prepared, for example, by feeding composition (C) through a blade, roll or auger pump print head.

[0085] According to one embodiment, a method for producing a three-dimensional object using an additive manufacturing system includes a step of extruding part material. This step may occur, for example, when printing or depositing strips or layers of part material. The method for producing a 3D object using an extrusion-based additive manufacturing system is also known as Fused Filament Fabrication (FFF).

[0086] Another fused additive manufacturing technique uses direct extrusion for strand-by-strand and layer-by-layer formation of the manufactured parts without the use of pre-manufactured filaments. This technique, which often uses vertically oriented extruders, is referred to in the art as "large area additive manufacturing" (BAAM). It is a more practical technique for additive manufacturing of parts larger than 1.0 m in at least one direction, such as the molds that are the subject of this invention.

[0087] A further object of the invention is a method for producing an article comprising molding a material on the molding surface of the mold of the invention. Any known technique can be used to mold a material on the molding surface of the mold, including coating, extrusion coating, or deposition of individual layers of material.

[0088] The above embodiments are intended to be illustrative and not limiting. Additional embodiments are within the concept of the present invention. In addition, while the present invention has been described with reference to specific embodiments, those skilled in the art will recognize that changes in form and detail may be made without departing from the spirit and scope of the present invention. EXAMPLES

[0089] The formulations and test data presented in this example document illustrate the practice of the present invention and demonstrate the unexpected advantages and utility of the present invention. The examples are intended to illustrate the present invention through selected embodiments and are not intended to imply any limitation on the broad scope and generality of the present invention.

[0090] Starting materials used Poly(biphenyl sulfone): (PPSU) grade Radel® R-5600NT, available from Solvay Specialty Polymers. This grade has a melt flow rate of 31-40 g / 10 min, measured according to ASTM D1238 at 365° C. and 5.0 kg load.

[0091] Poly(ethersulfone) (PES) grade Veradel® 3300, also available from Solvay Specialty Polymers, has a melt flow rate of 25-35 g / 10 min when measured according to ASTM D1238 at 380° C. with a load of 2.16 kg.

[0092] Poly(etherimide) (PEI), a high melt flow rate grade available as Ultem® 1010 from Sabic Innovative Plastics.

[0093] The carbon fiber reinforcement used was chopped carbon fiber sold by Teijin Limited as Tenax® A P742.

[0094] Other additives included zinc oxide grade Activ® R-609 sourced from Lanxess Corporation.

[0095] Preparation of Formulations The example formulations were prepared by first tumble blending the zinc oxide with pellets or powder of the polymers that make up the composition in the desired composition ratio for about 20 minutes, followed by melt kneading using a 26 mm diameter Coperion ZSK-26 co-rotating partially intermeshing twin screw extruder with an L / D ratio of 48:1. The extruder had 12 barrel sections, with barrel sections 2 through 11 heated to a set temperature of 350° C. The die section was also set at 350° C.

[0096] The polymer and zinc oxide preblends were fed into barrel section 1 using a gravimetric feeder at nominal throughput rates of 7.9-12.7 kg / hr, and the carbon fiber reinforcement was fed into the extruder in barrel section 7 at the corresponding throughput rate to achieve a carbon fiber loading level of 30 wt% in all finished compounds. The extruder was operated at a screw speed of approximately 200 rpm, and a vacuum was applied in barrel section 10 during compounding to strip out moisture and any possible residual volatiles from the compounds. A single hole die was used for all compounds, and the molten polymer strands exiting the die were cooled in a water trough and then cut in a pelletizer to form pellets approximately 3.0 mm long and 2.7 mm in diameter. Comparative examples consisting of only one polymer in the formulation were also prepared by feeding the polymer or polymer / zinc oxide mixture in barrel section 1 and the carbon fiber in barrel section 7 under the same conditions as above.

[0097] Injection molding was used to produce test specimens for measuring mechanical properties and heat distortion temperature. Twenty-five tensile and twenty-five flexural specimens were made from each composition. The tensile specimens were Type I ASTM tensile bars with a thickness of 3.2 mm (0.125 inch) conforming to ASTM standard D638, and the flexural specimens had dimensions of 127 mm x 12.7 mm x 3.2 mm. The mechanical specimens were injection molded using the following approximate set temperature conditions conforming to supplier recommended injection molding guidelines for various polymers: rear barrel section: 680°F (360°C), mid barrel section: 690°F (365°C); front barrel section: 700°F (371°C); nozzle: 700°F (371°C); mold: 330°F (165°C);

[0098] test The following ASTM test methods were used in evaluating all compositions: D638: Tensile properties D790: Bending properties D256: Notched Izod impact resistance D4812: Unnotched Izod impact resistance D648: Heat distortion temperature at 1.82 MPa

[0099] All tests were performed on the as-molded test parts except for heat distortion temperature, which was performed on specimens annealed using annealing conditions of 200°C for 1 hour in a forced air oven.

[0100] Table 1 shows all the formulations of Examples 1 to 5 and Comparative Examples 1 to 3 and the corresponding mechanical evaluation results.

[0101] [Table 1]

[0102] The data show that the compositions of Examples 1-5 exhibit an excellent balance of strength, modulus, impact resistance, and heat distortion temperature. These improved properties are expected to extend to the long term properties of the molds of the invention, such as fatigue resistance and creep rupture resistance. The high heat distortion temperatures of the compositions of Examples 1-5 combined with their excellent mechanical properties make them particularly suitable for use in molds for molding thermoplastic composites, where processing temperatures can reach as high as 200°C.

Claims

1. 1. A mold for molding an article, said mold including at least one molding surface for receiving a material to be molded, said molding surface having a length of at least 1.0 m in at least one direction, said mold comprising: 0.5 to 40.0 wt. % of at least one poly(etherimide) polymer; 0.0 to 70.0 wt. % of at least one poly(biphenyl sulfone) polymer; 0.0 to 70.0 wt. % of at least one poly(ether sulfone) polymer; 5.0 to 50.0 wt. % of at least one reinforcing carbon filler, preferably a carbon fiber filler; The composition (C) contains 10.0≦(X ＰＰＳＵ +X ＰＥＳ )≦94.5, and X ＰＰＳＵ and X ＰＥＳ are not zero at the same time, and X ＰＰＳＵ is the weight percent of the at least one poly(biphenyl sulfone) polymer in composition (C), and X ＰＥＳ is the weight percent of the at least one poly(ether sulfone) polymer in composition (C); template.

2. 10. The mold of claim 1, wherein the molding surface has a length of at least 1.0 m and / or up to 50.0 m in at least two directions.

3. The composition (C) is 0.5 to 40.0 wt. % of at least one poly(etherimide) polymer; 0.0 to 70.0 wt. % of at least one poly(biphenyl sulfone) polymer; 30.0 to 70.0 wt. % of at least one poly(ether sulfone) polymer; 5.0 to 50.0 wt. % of at least one reinforcing carbon filler, preferably a carbon fiber filler; The mold of claim 1 , comprising:

4. The composition (C) is 0.5 to 40.0 wt. % of at least one poly(etherimide) polymer; 10.0 to 70.0 wt. % of at least one poly(biphenyl sulfone) polymer; 0.0 to 70.0 wt. % of at least one poly(ether sulfone) polymer; 5.0 to 50.0 wt. % of at least one reinforcing carbon filler, preferably a carbon fiber filler; The mold of claim 1 , comprising:

5. 2. The mold of claim 1, wherein composition (C) comprises 5.0 to 35.0 wt. % of at least one poly(etherimide) polymer and / or 15.0 to 45.0 wt. % of at least one reinforcing carbon fiber filler.

6. The at least one poly(etherimide) polymer may be selected from the group consisting of the imide form of formula (XXV), the corresponding amic acid form of formula (XXVI) and the corresponding amic acid form of formula (XXVII): 【Chemistry 1】 (In formulas (XXVI) and (XXVII), → denotes isomerism such that in any repeat unit, the two groups pointed to by the arrows from the same aromatic ring may be present as shown or in interchanged positions.) 2. The mold of claim 1, comprising more than 50 mole %, preferably more than 90 mole %, of repeat units selected from: and mixtures thereof, based on the total number of moles of repeat units in the polymer.

7. The at least one poly(biphenyl sulfone) polymer comprises repeating units of formula (B): 【Chemistry 2】 2. The mold of claim 1, comprising at least 50 mol %, preferably at least 90 mol %, of:

8. The at least one poly(ether sulfone) polymer comprises repeating units of formula (D): 【Transformation 3】 2. The mold of claim 1, comprising at least 50 mol %, preferably at least 90 mol %, of:

9. 2. The mold of claim 1, wherein the carbon fiber filler is selected from the group consisting of PAN-based carbon fiber (PAN-CF), pitch-based carbon fiber, graphitized pitch-based carbon fiber, and mixtures thereof.

10. A method for producing the mold according to any one of claims 1 to 9, comprising: Providing a component material comprising the composition (C) according to any one of claims 1 to 9; and depositing a layer of the three-dimensional object from the part material; A method comprising:

11. The method of claim 10 , wherein the component material is in the form of filaments or microparticles.

12. The method of claim 10 , wherein the step of depositing a layer comprises extruding the part material.

13. A method of making an article, comprising molding a material on at least one molding surface of a mold according to any one of claims 1 to 9.

14. 0.5 to 40.0 wt. % of at least one poly(etherimide) polymer; 0.0 to 70.0 wt. % of at least one poly(biphenyl sulfone) polymer; 30.0 to 70.0 wt. % of at least one poly(ether sulfone) polymer; 5.0 to 50.0 wt. % of at least one reinforcing carbon filler, preferably a carbon fiber filler; A composition (C) comprising:

15. The at least one poly(etherimide) polymer may be selected from the group consisting of the imide form of formula (XXV), the corresponding amic acid form of formula (XXVI) and the corresponding amic acid form of formula (XXVII): 【Chemistry 4】 (In formulae (XXVI) and (XXVII), → denotes isomerism such that in any repeat unit, the two groups pointed to by the arrows from the same aromatic ring may be present as shown or in interchanged positions.) and mixtures thereof, based on the total number of moles of repeat units in the polymer.

16. The at least one poly(biphenyl sulfone) polymer comprises repeating units of formula (B): 【Transformation 5】 15. The composition (C) of claim 14, comprising at least 50 mol %, preferably at least 90 mol %, of the formula (I), said mol % being based on the total number of moles of repeat units in said polymer.

17. The at least one poly(ether sulfone) polymer comprises repeating units of formula (D): 【Transformation 6】 15. The composition (C) of claim 14, comprising at least 50 mol %, preferably at least 90 mol %, of the formula (I), said mol % being based on the total number of moles of repeat units in said polymer.

18. 15. The composition (C) of claim 14, wherein the carbon fiber filler is selected from the group consisting of PAN-based carbon fiber (PAN-CF), pitch-based carbon fiber, graphitized pitch-based carbon fiber, and mixtures thereof.