Thermoplastic composition, method for preparing the same, and articles prepared therefrom

Abstract

A thermoplastic composition comprising: 25 to 95 weight percent of a poly(etherimide); 5 to 70 weight percent of a polymer different from the poly(etherimide), the polymer being partially miscible with the poly(etherimide); and 1 to 15 weight percent of a mineral filler having an average particle size of 0.1 to 10 microns; wherein the weight percents are based on the total weight of the composition. The thermoplastic composition can be prepared by melt mixing the components of the composition. The present invention also describes an article comprising the composition.

Description

[0001] Citations of Related Applications

[0002] This application claims priority to and the benefit of U.S. Provisional Application No. 62 / 896,808, filed September 6, 2012, the contents of which are incorporated herein by reference in their entirety. Background Art

[0003] Polyetherimide ("PEI") is an amorphous, transparent, high-performance polymer having a glass transition temperature ("Tg") greater than 180°C. PEI further has high strength, heat resistance, and modulus as well as a wide range of chemical resistance, and is therefore widely used in a variety of applications such as automotive, telecommunications, aerospace, electrical / electronics, transportation, and healthcare. Compositions comprising poly(etherimide)s typically exhibit high temperature resistance, high stiffness, and high strength. However, the impact properties of poly(etherimide) compositions are relatively poor.

[0004]

[0006] Thus, there remains a need in the art for poly(etherimide) compositions that can maintain desirable high thermal and mechanical properties while also exhibiting improved impact properties. Summary of the invention

[0005] A thermoplastic composition comprising: 25 to 95 weight percent of a poly(etherimide); 5 to 70 weight percent of a polymer different from the poly(etherimide) and partially miscible with the poly(etherimide); and 1 to 15 weight percent of a mineral filler having an average particle size of 0.1 to 10 microns; wherein the weight percents are based on the total weight of the composition.

[0006] In another aspect, a method of preparing a thermoplastic composition includes melt mixing components of the composition.

[0007] Articles comprising the thermoplastic composition are also described.

[0008] The above described and other features are exemplified by the following figures and detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0009] The following figures represent exemplary embodiments.

[0010] Figure 1 Scanning electron microscope (SEM) images of (a) the composition according to Comparative Example 1 and (b) the composition according to Comparative Example 2 are shown.

[0011] Figure 2 Scanning electron microscope (SEM) images of (a) the composition according to Comparative Example 3, (b) the composition according to Example 1, and (c) the composition according to Example 2 are shown.

[0012] Figure 3 Scanning electron microscope (SEM) images of (a) the composition according to Comparative Example 4, (b) the composition according to Example 3, and (c) the composition according to Example 4 are shown.

[0013] Figure 4 Scanning electron microscope (SEM) images of (a) the composition according to Comparative Example 5 and (b) the composition according to Comparative Example 6 are shown. DETAILED DESCRIPTION

[0014] The present inventors have unexpectedly discovered that the addition of specific fillers (also referred to herein as "microfillers") to thermoplastic compositions comprising a poly(etherimide) and a polymer that is not completely miscible (i.e., partially miscible) with the poly(etherimide) can significantly improve the impact properties of the composition while maintaining the desired thermal properties of the composition.

[0015] Thus, one aspect of the present disclosure is a thermoplastic composition. The composition comprises a poly(etherimide). The poly(etherimide) comprises greater than 1, for example 2 to 1000, or 5 to 500, or 10 to 100 structural units of formula (1):

[0016]

[0017] wherein each R is independently the same or different and is a substituted or unsubstituted divalent organic group, such as a substituted or unsubstituted C 6-20 Aromatic hydrocarbon, substituted or unsubstituted straight chain or branched C 4-20 Alkylene, substituted or unsubstituted C 3-8 Cycloalkylene, in particular a halogenated derivative of any of the foregoing. In one aspect, R is a divalent group of one or more of the following formula (2):

[0018]

[0019] Among them, Q 1 Is -O-, -S-, -C(O)-, -SO 2 -、-SO-、-P(R a )(=O)-, where R a It is C 1-8 Alkyl or C 6-12 Aryl, -C y H 2y -(wherein y is an integer from 1 to 5) or a halogenated derivative thereof (which includes a perfluoroalkylene group), or -(C 6 H 10 ) z- (wherein z is an integer from 1 to 4). In one aspect, R is m-phenylene, p-phenylene, or arylene sulfone, especially bis(4,4'-phenylene)sulfone, bis(3,4'-phenylene)sulfone, bis(3,3'-phenylene)sulfone, or a combination thereof. In one aspect, at least 10 mole percent or at least 50 mole percent of the R groups contain sulfone groups, and in other aspects, no R groups contain sulfone groups.

[0020] Further in formula (1), T is -O- or a group of the formula -OZO-, wherein the divalent bond of the -O- or -OZO- group is at the 3,3', 3,4', 4,3' or 4,4' position, and Z is optionally composed of 1 to 6 C 1-8 Alkyl, 1 to 8 halogen atoms, or a combination thereof substituted aromatic C 6-24 A monocyclic or polycyclic moiety, provided that the valence of Z is not exceeded. Exemplary groups Z include groups of formula (3):

[0021]

[0022] Among them, R a and R b are each independently the same or different and are, for example, a halogen atom or a monovalent C 1-6 alkyl; p and q are each independently an integer from 0 to 4; c is from 0 to 4; and X a It is a bridging group connecting hydroxy-substituted aromatic groups, where each C 6 The bridging group and hydroxyl substituent of the arylene group are on the C 6 The arylene groups are arranged in ortho, meta or para (especially para) positions to each other. a Can be a single bond, -O-, -S-, -S(O)-, -S(O) 2 -, -C(O)-, or C 1-18 Organic bridging group. 1-18 The organic bridging group may be cyclic or acyclic, aromatic or non-aromatic, and may further contain heteroatoms such as halogens, oxygen, nitrogen, sulfur, silicon, or phosphorus. 1-18 The organic group is such that the C 6 The arylene groups are each bonded to a common alkylidene carbon or to a C 1-18 Different carbon atoms of the organic bridging group. A specific example of the group Z is a divalent group of formula (3a):

[0023]

[0024] Wherein, Q is -O-, -S-, -C(O)-, -SO 2 -、-SO-、-P(R a )(=O)-, where Ra It is C 1-8 Alkyl or C 6-12 Aryl, or -C y H 2y - (wherein y is an integer from 1 to 5) or a halogenated derivative thereof (including perfluoroalkylene). In one aspect, Z is derived from bisphenol A, such that Q in formula (3a) is 2,2-isopropylidene.

[0025] In one aspect, in formula (1), R is m-phenylene, p-phenylene, or a combination thereof, and T is -OZO-, wherein Z is a divalent group of formula (3a). Alternatively, R is m-phenylene, p-phenylene, or a combination thereof, and T is -OZO-, wherein Z is a divalent group of formula (3a) and Q is 2,2-isopropylidene. Such materials can be obtained from SABIC under the trade name ULTEM. Alternatively, the poly(etherimide) can be a copolymer comprising additional structural poly(etherimide) units of formula (1), wherein at least 50 mole percent (mol%) of the R groups are bis(4,4′-phenylene)sulfone, bis(3,4′-phenylene)sulfone, bis(3,3′-phenylene)sulfone, or a combination thereof, and the remaining R groups are p-phenylene, m-phenylene, or a combination thereof; and Z is 2,2-(4-phenylene)isopropylidene, i.e., a bisphenol A moiety, an example of which is commercially available from SABIC under the trade name EXTEM.

[0026] In one aspect, the poly(etherimide) is a copolymer optionally comprising imide units of another structure other than poly(etherimide) units, for example, imide units of formula (4):

[0027]

[0028] wherein R is as described in formula (1), and each V is the same or different and is a substituted or unsubstituted C 6-20 Aromatic hydrocarbon groups, such as the tetravalent linking group of the formula:

[0029]

[0030] Wherein W is a single bond, -O-, -S-, -C(O)-, -SO 2 -、-SO-、C 1-18 Alkylene, -P(R a )(=O)-(where R a It is C 1-8 Alkyl or C 6-12 Aryl), or -C y H 2y- (wherein y is an integer from 1 to 5) or a halogenated derivative thereof (which includes perfluoroalkylene). These additional structural imide units preferably comprise less than 20 mol% of the total number of units, and more preferably may be present in an amount of 0 to 10 mol% of the total number of units, or 0 to 5 mol% of the total number of units, or 0 to 2 mol% of the total number of units. In one aspect, no additional imide units are present in the poly(etherimide).

[0031] The poly(etherimides) may be prepared by any method known to those skilled in the art, including the reaction of an aromatic bis(ether anhydride) of formula (5) or a chemical equivalent thereof with an organic diamine of formula (6):

[0032] H 2 NR-NH 2 (6).

[0033] wherein T and R are as defined above. Copolymers of poly(etherimide)s can be prepared using a combination of an aromatic bis(ether anhydride) of formula (5) and another bis(anhydride) other than a bis(ether anhydride) (e.g., pyromellitic dianhydride or bis(3,4-dicarboxyphenyl)sulfone dianhydride).

[0034] Illustrative examples of aromatic bis(ether anhydrides) include 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride (also known as bisphenol A dianhydride or BPADA), 3,3-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; 4,4'-bis(3,4-dicarboxyphenoxy)benzophenone dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfone dianhydride; 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl ether dianhydride; 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl sulfide dianhydride; diphenyl dianhydride; 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl-2,2-propane dianhydride; 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl ether dianhydride; 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride; 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)benzophenone dianhydride; 4,4'-(hexafluoroisopropylidene)diphthalic anhydride; and 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl sulfone dianhydride. Combinations of different aromatic bis(ether anhydrides) may be used.

[0035] Examples of the organic diamines include 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,12-dodecanediamine, 1,18-octadecanediamine, 3-methylheptanediamine, 4,4-dimethylheptanediamine, 4-methylnonanediamine, 5-methylnonanediamine, 2,5-dimethylhexanediamine, 2 ,5-dimethylheptyldiamine, 2,2-dimethylpropylenediamine, N-methyl-bis(3-aminopropyl)amine, 3-methoxyhexanediamine, 1,2-bis(3-aminopropoxy)ethane, bis(3-aminopropyl)sulfide, 1,4-cyclohexanediamine, bis-(4-aminocyclohexyl)methane, meta-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, meta-phenylenediamine, p-Xylylenediamine, 2-methyl-4,6-diethyl-1,3-phenylene-diamine, 5-methyl-4,6-diethyl-1,3-phenylene-diamine, benzidine, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 1,5-diaminonaphthalene, bis(4-aminophenyl)methane, bis(2-chloro-4-amino-3,5-diethylphenyl)methane, bis(4-aminophenyl)propane, 2,4-bis(p-amino-tert-butyl)toluene, bis(p-amino-tert-butylphenyl)ether, bis(p-methyl-o-aminophenyl)benzene, bis(p-methyl-o-aminopentyl)benzene, 1,3-diamino-4-isopropylbenzene, bis(4-aminophenyl)sulfide, bis-(4-aminophenyl)sulfone (also known as 4,4'-diaminodiphenylsulfone (DDS)) and bis(4-aminophenyl)ether. Any regioisomer of the foregoing compounds may be used. Any of the aforementioned C 1-4 Alkylated or poly(C 1-4 ) alkylated derivatives, such as polymethylated 1,6-hexanediamine. Combinations of these compounds may also be used. In one aspect, the organic diamine is m-phenylenediamine, p-phenylenediamine, 4,4′-diaminodiphenyl sulfone, 3,4′-diaminodiphenyl sulfone, 3,3′-diaminodiphenyl sulfone, or a combination thereof.

[0036] The poly(etherimide) may also comprise a poly(siloxane-etherimide) copolymer comprising a poly(etherimide) unit of formula (1) and a siloxane block of formula (7):

[0037]

[0038] wherein E has an average value of 2 to 100, 2 to 31, 5 to 75, 5 to 60, 5 to 15, or 15 to 40, and each R' is independently C 1-13 For example, each R' can be independently C 1-13 Alkyl, C 1-13 Alkoxy, C 2-13 Alkenyl, C2-13 Alkenyloxy, C 3-6 Cycloalkyl, C 3-6 Cycloalkoxy, C 6-14 Aryl, C 6-10 Aryloxy, C 7-13 Aralkyl, C 7-13 Aralkyloxy, C 7-13 Alkyl or C 7-13 The above groups can be completely or partially halogenated with fluorine, chlorine, bromine, or iodine or a combination thereof. In one aspect, bromine or chlorine is absent, and in one aspect, halogen is absent. Combinations of the foregoing R groups can be used in the same copolymer. In one aspect, the polysiloxane block contains R' groups with a minimum hydrocarbon content. In one aspect, the R' group with a minimum hydrocarbon content is methyl.

[0039] The poly(siloxane-etherimide) can be formed by polymerizing a bis(ether anhydride) of formula (5) and a diamine component comprising an organic diamine (6) or a combination of aromatic diamines as described above, and a polysiloxane diamine of formula (8):

[0040]

[0041] Wherein, R' and E are as described in formula (7), and R 4 Each is independently C 2 -C 20 Hydrocarbons, especially C 2 -C 20 In one aspect, R 4 It is C 2 -C 20 Alkylene, especially C 2 -C 10 The alkylene group is such as propylene, and E has an average value of 5 to 100, 5 to 75, 5 to 60, 5 to 15, or 15 to 40. The procedures for preparing the polysiloxane diamines of formula (8) are well known in the art.

[0042] In some poly(siloxane-etherimides), the diamine component may comprise 10 to 90 mole percent (mol%), or 20 to 50 mol%, or 25 to 40 mol% of a polysiloxane diamine (8) and 10 to 90 mol%, or 50 to 80 mol%, or 60 to 75 mol% of a diamine (6), for example, as described in U.S. Pat. No. 4,404,350. The diamine components may be physically mixed prior to reaction with the dianhydride to form a substantially random copolymer. Alternatively, block or alternating copolymers may be formed by selective reaction of (6) and (8) with an aromatic bis(ether anhydride) (5) to prepare polyimide blocks that are subsequently reacted together. Thus, the poly(siloxane-imide) copolymer may be a block, random, or graft copolymer. In one aspect, the copolymer is a block copolymer.

[0043] Examples of specific poly(siloxane-etherimides) are described in U.S. Pat. Nos. 4,404,350, 4,808,686, and 4,690,997. In one aspect, the poly(siloxane-etherimide) has units of formula (9):

[0044]

[0045] Wherein, R' and E of siloxane are the same as those in formula (7), R and Z of imide are the same as those in formula (1), and R 4 As in formula (8), and n is an integer from 5 to 100. In the poly(siloxane-etherimide) aspect, R of the etherimide is phenylene, Z is the residue of bisphenol A, and R 4 is n-propylene, E is 2 to 50, 5 to 30, or 10 to 40, n is 5 to 100, and each R' of the siloxane is methyl.

[0046] The relative amounts of polysiloxane units and etherimide units in the poly(siloxane-etherimide) depend on the desired properties and are selected using the guidance provided herein. Specifically, as described above, the block or grafted poly(siloxane-etherimide) copolymer is selected to have a certain average value of E and is selected and used in an amount effective to provide the desired wt% of polysiloxane units in the composition. In one aspect, the poly(siloxane-etherimide) comprises 10 to 50 wt%, 10 to 40 wt%, or 20 to 35 wt% of polysiloxane units, based on the total weight of the poly(siloxane-etherimide).

[0047] The poly(etherimide) can have a melt index of 0.1 to 10 grams per minute (g / min) as measured by American Society for Testing Materials (ASTM) D1238 at 340 to 370° C. using a 6.7 kilogram (kg) weight. In one aspect, the poly(etherimide) has a weight average molecular weight (Mw) of 1,000 to 150,000 grams per mole (Dalton) as measured by gel permeation chromatography using polystyrene standards. In one aspect, the poly(etherimide) has a Mw of 10,000 to 80,000 Daltons. Such poly(etherimides) typically have an intrinsic viscosity of greater than 0.2 deciliters per gram (dl / g), or more specifically, 0.35 to 0.7 dl / g, as measured in m-cresol at 25° C.

[0048] In one aspect, the poly(etherimide) comprises repeating units derived from bisphenol A and m-phenylenediamine. In one aspect, the poly(etherimide) comprises a poly(etherimide-siloxane) copolymer.

[0049] The poly(etherimide) can be present in an amount of 25 to 95 weight percent, based on the total weight of the composition. Within this range, the poly(etherimide) can be present in an amount of 50 to 95 weight percent, or 75 to 95 weight percent, or 80 to 95 weight percent, or 85 to 95 weight percent. In one aspect, when the poly(etherimide) is a poly(etherimide)-polysiloxane copolymer, the poly(etherimide) can be present in an amount of 25 to 60 weight percent, or 25 to 50 weight percent, or 25 to 45 weight percent, or 35 to 45 weight percent.

[0050] In addition to the poly(etherimide), the composition further comprises a polymer different from the poly(etherimide), provided that it is partially miscible with the poly(etherimide). As used herein, the term "partially miscible" refers to a blend of a poly(etherimide) and a polymer different from the poly(etherimide) having more than one glass transition temperature (Tg) and exhibiting a multiphase morphology (e.g., observable by scanning electron microscopy (SEM)). Specifically, when blended, the partially miscible two polymers exhibit two separate glass transitions between the glass transitions of the respective components and have a phase rich in poly(etherimide) and a phase rich in "polymer 2", wherein "polymer 2" refers to a polymer different from the poly(etherimide). In contrast, a "miscible blend" describes a polymer blend having a single phase and a single glass transition temperature. Also in contrast, an "immiscible blend" describes a mixture of two or more polymers that cannot be uniformly mixed or blended to form a single phase. Thus, for example, by analyzing the glass transition behavior of blends of poly(etherimide) and polymers other than poly(etherimide) using differential scanning calorimetry (DSC), it can be determined whether the polymer other than poly(etherimide) meets the "partially miscible" criterion.

[0051] In one aspect, the polymer other than poly(etherimide) comprises a polyolefin, a poly(aryletherketone), or a combination thereof. In one aspect, the polymer other than poly(etherimide) can be a polyolefin, for example, poly(ethylene), and in particular a modified poly(ethylene) having improved compatibility with poly(etherimide). For example, the polymer other than poly(etherimide) can be an epoxy-functionalized poly(ethylene).

[0052] In one aspect, the polymer other than poly(etherimide) can be poly(aryletherketone). Poly(aryletherketone) is a class of aromatic poly(ketones) comprising repeating units of formula (10) and formula (11):

[0053] -Ar-O-(11).

[0054] Wherein, Ar is independently a substituted or unsubstituted, monocyclic or polycyclic aromatic group having 6-30 carbon atoms at each occurrence. Exemplary Ar groups include, but are not limited to, substituted or unsubstituted phenyl, tolyl, naphthyl and biphenyl. Unsubstituted phenyl is preferred.

[0055] In one aspect, the poly(aryletherketone) can be a poly(etheretherketone) comprising repeating units of formula (12):

[0056]

[0057] wherein Ar is as defined above, and Ar 1 and Ar 2 Each of Ar, Ar is independently a substituted or unsubstituted, monocyclic or polycyclic aromatic group having 6 to 30 carbon atoms at each occurrence. 1 and Ar 2 They may be the same or different from each other. 1 and Ar 2 In one aspect, two of Ar, Ar and Ar may be identical to each other, and the third may be different. 1 and Ar 2 is phenyl, preferably unsubstituted phenyl.

[0058] Poly(arylene ether ketones) are generally known, many examples of which are commercially available. Examples of commercially available aromatic poly(ketones) include those available under the trade name PEEK TM Those obtained from VICTREX.

[0059] The polymer other than the poly(etherimide) can be present in an amount of 5 to 70 weight percent, based on the total weight of the composition. Within this range, the polymer other than the poly(etherimide) can be present in an amount of 5 to 65 weight percent, or 5 to 50 weight percent, or 5 to 30 weight percent, or 5 to 25 weight percent, or 5 to 10 weight percent, or 20 to 70 weight percent, or 30 to 65 weight percent, or 45 to 65 weight percent. In one aspect, when the poly(etherimide) is a poly(etherimide-siloxane) copolymer, the polymer other than the poly(etherimide) can be present in an amount of 20 to 70 weight percent, or 30 to 65 weight percent, or 45 to 65 weight percent.

[0060] In addition to poly(etherimide) and polymers different from poly(etherimide), the thermoplastic composition further comprises a mineral filler. The mineral filler has an average particle size of 0.1 to 10 microns, or 0.1 to 7 microns, or 0.1 to 5 microns, or 0.1 to 2 microns, or 0.1 to 1 micron. An average particle size less than 3 microns is particularly preferred, such as 0.1 to 3 microns, or 0.1 to 2 microns, or 0.1 to 1 micron. The average particle size can be measured, for example, by a laser scattering method. The average particle size can also be referred to as a median particle size or "Dv50". The mineral filler can generally have any morphology, such as fibrous, modular, needle-shaped, lamellar, spherical or substantially spherical. Mineral fillers are also referred to as "microfillers" in this article.

[0061] In one aspect, the specific mineral filler suitable for use can include, for example, boehmite, kaolin or their combination. In a specific aspect, the mineral filler includes boehmite. In one aspect, the mineral filler can exclude talc (that is, talc can be excluded from the present composition). Without wishing to be bound by theory, it is possible that the defective area (which is a relatively large cavity) in the partially miscible polymer blend is filled with a filler with micron size to form more and smaller sized cavities, thereby contributing to impact improvement. Alternatively or additionally, it is possible that the mineral filler can serve as a physical compatibilizer with the poly (etherimide), with the poly (etherimide) partially miscible polymer or both to improve the compatibility of the two phases, thereby contributing to improving the impact properties of the resulting composition.

[0062] The mineral filler can be present in an amount of 1 to 15 weight percent based on the total weight of the composition. Within this range, the mineral filler can be present in an amount of 1 to 10 weight percent, or 2 to 9 weight percent, or 2 to 8 weight percent, or 3 to 8 weight percent, or 4 to 8 weight percent, or 5 to 7 weight percent.

[0063] In one aspect, the composition comprises 75 to 95 weight percent of a poly(etherimide); 5 to 10 weight percent of a polymer other than a poly(etherimide); and 1 to 10 weight percent of a mineral filler. The poly(etherimide) may comprise repeating units derived from bisphenol A dianhydride and meta-phenylenediamine, the polymer other than the poly(etherimide) may comprise a polyolefin, particularly a modified polyolefin, and the mineral filler may comprise kaolin, boehmite, or a combination thereof.

[0064] In one aspect, the composition comprises 25 to 45 weight percent of a poly(etherimide); 45 to 65 weight percent of a polymer other than a poly(etherimide); and 1 to 10 weight percent of a mineral filler. The poly(etherimide) can be a poly(etherimide-siloxane) copolymer; the polymer other than the poly(etherimide) comprises a poly(aryletherketone); and the mineral filler comprises clay, boehmite, or a combination thereof.

[0065] In one aspect, the composition may optionally further comprise an additive. The additive may be selected to achieve the desired performance, provided that the additive is also selected to not significantly adversely affect the desired performance of the composition. Any additive may be mixed at a suitable time during the mixing of the components used to form the composition. Exemplary additives may include, for example, antioxidants, heat stabilizers, water stabilizers, metal passivators, UV stabilizers, processing aids, colorants, or combinations thereof. Additives are used in a known effective amount. For example, the total amount of any additive (except any impact modifier or reinforcing agent) may be greater than 0 to 5 weight percents, or 0.001 to 5 weight percents, or 0.01 to 5 weight percents, each based on the gross weight of the composition.

[0066] The composition can optionally exclude or minimize any component that is not clearly disclosed herein. For example, in one aspect, the composition can include any polymer except poly(etherimide) less than 5 weight percent or less than 1 weight percent, and a polymer miscible with the poly(etherimide) portion. In one aspect, the composition can exclude any polymer except poly(etherimide), and a polymer miscible with the poly(etherimide) portion. For example, the composition can exclude poly(ester). In one aspect, the composition can exclude polymer impact modifiers, including those derived from alkenyl aromatic compounds and conjugated dienes (including hydrogenated and unhydrogenated derivatives), and rubber-modified polystyrene, etc. Commonly used polymer impact modifiers are not easy to process at high temperatures (such as those required for processing poly(etherimide) compositions). The degradation of such impact modifiers during processing can lead to the reduced high thermal properties of the resulting composition. In one aspect, the composition can exclude a compatibilizer except a mineral filler.

[0067] The thermoplastic composition can exhibit one or more advantageous properties. In particular, the composition can advantageously exhibit improved impact strength. For example, the thermoplastic composition can exhibit a notched Izod impact strength greater than 50 MPa, or greater than 75 MPa, as determined according to ASTM D256. The thermoplastic composition can exhibit a notched Izod impact strength that is at least 20%, or at least 50%, or at least 100% higher than the notched Izod impact strength of the same composition without the mineral filler.

[0068] In a preferred aspect, the thermoplastic composition comprises: 25 to 95 weight percent, preferably, a poly(etherimide); 5 to 70 weight percent of a polymer other than a poly(etherimide), wherein the polymer is a polyolefin, a poly(aryletherketone), or a combination thereof, preferably wherein the polymer is an epoxy-functionalized poly(ethylene), a poly(etheretherketone), or a combination thereof that is partially miscible with the poly(etherimide); and 1 to 15 weight percent of a mineral filler, preferably boehmite, kaolin, or a combination thereof, more preferably boehmite, the mineral filler having an average particle size of 0.1 to 5 microns, 0.1 to 3 microns, or 0.1 to 2 microns, or 0.1 to 1 micron; wherein the weight percents are based on the total weight of the composition, and a molded sample of the thermoplastic composition exhibits a particle size of 0.1 to 5 microns, 0.1 to 3 microns, or 0.1 to 2 microns, or 0.1 to 1 micron according to ASTM D 1478. A notched Izod impact strength of greater than 50 MPa, or greater than 75 MPa, as determined by D256, such as a notched Izod impact strength that is at least 20%, or at least 50%, or at least 100% greater than the notched Izod impact strength of the same composition without the mineral filler. In this aspect, the composition does not include a polymeric impact modifier.

[0069] The poly(etherimide) preferably comprises repeating units derived from bisphenol A and meta-phenylenediamine, or is a poly(etherimide-siloxane) copolymer. Still more preferably, the thermoplastic composition comprises 75 to 95 weight percent poly(etherimide); 5 to 10 weight percent polymer other than poly(etherimide); and 1 to 10 weight percent mineral filler, or the thermoplastic composition comprises 25 to 45 weight percent poly(etherimide); 45 to 65 weight percent polymer other than poly(etherimide); and 1 to 10 weight percent mineral filler.

[0070] The composition can be prepared by commonly known methods. For example, the composition can be prepared by melt mixing the components of the composition. The composition can be further molded into a useful shape to form an article by a variety of techniques such as injection molding, extrusion, rotational molding, blow molding and thermoforming.

[0071] The improved impact and other desirable properties of these compositions make them useful in many applications, such as safety equipment (e.g., protective gear and helmets), housings for various devices, such as medical devices, analytical equipment, and electronic devices (e.g., computers, tablets, cell phones and other wearable devices), and interior parts for transportation and mass transportation (e.g., cars, trains, buses, ships and airplanes).

[0072] The present disclosure is further illustrated by the following examples, which are non-limiting.

[0073] Example

[0074] The materials used in the following examples are described in Table 1.

[0075] Table 1

[0076]

[0077] The compositions of the following examples were prepared by compounding on a twin screw extruder. The polymers and additives were blended together and fed through a main feeder. The strands of these compositions were cut into pellets and then dried for molding and physical testing. Table 2 shows the compounding summary used.

[0078] Table 2

[0079] parameter unit Settings Zone 1 Temperature ℃ 50 Zone 2 Temperature ℃ 150-200 Zone 3 Temperature ℃ 300-320 Zone 4 Temperature ℃ 320-360 Zone 5 Temperature ℃ 340-370 Zone 6 Temperature ℃ 340-370 Zone 7 Temperature ℃ 340-370 Zone 8 Temperature ℃ 340-370 Zone 9 Temperature ℃ 340-370 Zone 10 Temperature ℃ 340-370 Zone 11 Temperature ℃ 340-370 Die temperature ℃ 340-370 Screw speed rpm 400 Production kg / h 20-30

[0080] Table 3 shows the injection molding outline used to mold parts suitable for physical testing.

[0081] Table 3

[0082] parameter unit Settings Condition: Pre-drying time Hour 4-6 Conditions: Pre-drying temperature ℃ 135-150 Hopper temperature ℃ 70 Zone 1 Temperature ℃ 320-360 Zone 2 Temperature ℃ 340-370 Zone 3 Temperature ℃ 345-380 Nozzle temperature ℃ 350-385 Mold temperature ℃ 140-180

[0083] The molding compositions were subjected to the following physical tests. The melt flow rate (MFR) was determined according to ASTM D1238, wherein the pellets were pre-dried at 150°C for 4 hours and the test was conducted at 337°C with a residence time of 300 seconds under a 6.7 kg load or at 367°C with a residence time of 300 seconds under a 6.7 kg load, as indicated in Table 4 below. Flexural properties were tested according to ASTM D790 with a span of 50 mm and a test speed of 1.27 mm / min. Impact strength (NII) was tested according to ASTM D256, wherein the test specimens were notched or unnotched, and the pendulum energy used for testing was 5 pound-force feet (lbf / ft). Heat deflection temperature (HDT) was determined according to ASTM D648, wherein the test specimens were 3.2 mm thick, and the stress used for testing was 1.82 MPa. Tensile properties were tested according to ASTM D638 using a test speed of 50 mm / min. Glass transition temperatures (Tg) are reported in °C and were determined using differential scanning calorimetry.

[0084] The compositions and test results are shown in Table 4. The amount of each component of the composition is provided in weight percent, based on the total weight of the composition.

[0085] Table 4

[0086]

[0087] *NB=Not Broken

[0088] As shown in Table 4, Comparative Examples 1 and 2 are compositions comprising PEI and PET with and without microfillers. PEI and PET are completely miscible, as shown in Figure 1 As can be seen in the scanning electron microscope (SEM) images of ((a) shows the SEM image for CE1 and (b) shows the SEM image for CE2), these images do not show any obvious phase separation. By adding fillers (e.g., boehmite), there is no significant effect on the impact properties of the composition.

[0089] Comparative Example 3 and Inventive Examples 1 to 4 are compositions comprising PEI and epoxy olefin copolymers, with and without microfillers. The PEI / polyolefin blends are partially miscible, as in Figure 2 As shown in Table 4, without wishing to be bound by theory, it is believed that the addition of microfillers as compatibilizers significantly improves the impact properties of the composition while not affecting thermal properties such as HDT. Figure 2 (b)-(c) show the SEM images of Examples 1-2, respectively.

[0090] Comparative Examples 5 and 6 are compositions comprising PEI and LCP with and without microfillers. PEI and LCP are completely immiscible, as shown in Figure 4 As shown in Table 4, the addition of microfillers did not improve the impact properties of the composition compared to the composition without microfillers.

[0091] Table 4 also shows compositions comprising PEI-Si and PEEK (Comparative Example 4 and Examples 3-4). Figure 3 As can be seen from the SEM image of (a), Comparative Example 4 does not contain a microfiller and is not a fully miscible composition. After adding the microfilter to Examples 3 and 4, it can be seen that the impact properties are significantly improved without sacrificing any thermal properties, especially for the compositions containing boehmite as a microfiller. Figure 3 (b) and 3(c) show SEM images of Examples 3 and 4.

[0092] Thus, the present inventors have unexpectedly discovered that the addition of specific fillers to compositions comprising partially miscible polymer components can provide improved impact strength without substantially adversely affecting other physical properties of the composition. Thus, the compositions of the present invention achieve significant improvements.

[0093] The present disclosure further encompasses the following aspects.

[0094] Aspect 1: A thermoplastic composition comprising: 25 to 95 weight percent of a poly(etherimide); 5 to 70 weight percent of a polymer other than the poly(etherimide) partially miscible with the poly(etherimide); and 1 to 15 weight percent of a mineral filler having an average particle size of 0.1 to 10 microns, or 0.1 to 7 microns, or 0.1 to 5 microns, or 0.1 to 2 microns, or 0.1 to 1 micron; wherein the weight percents are based on the total weight of the composition.

[0095] Aspect 2: The thermoplastic composition according to aspect 1, wherein the thermoplastic composition exhibits a notched Izod impact strength greater than 50 MPa, or greater than 75 MPa, as determined according to ASTM D256.

[0096] Aspect 3: The thermoplastic composition according to aspect 1 or 2, wherein the thermoplastic composition exhibits a notched Izod impact strength that is at least 20%, or at least 50%, or at least 100% greater than the notched Izod impact strength of the same composition without the mineral filler.

[0097] Aspect 4: The thermoplastic composition of any one of aspects 1 to 3, wherein the composition does not contain a polymeric impact modifier.

[0098] Aspect 5: The thermoplastic composition of any one of aspects 1 to 4, wherein the poly(etherimide) comprises repeating units derived from bisphenol A and meta-phenylenediamine.

[0099] Aspect 6: The thermoplastic composition of any one of Aspects 1 to 5, wherein the poly(etherimide) comprises a poly(etherimide-siloxane) copolymer.

[0100] Aspect 7: The thermoplastic composition according to any one of aspects 1 to 6, wherein the polymer other than the poly(etherimide) comprises a polyolefin, a poly(aryletherketone), or a combination thereof, preferably an epoxy-functionalized poly(ethylene), a poly(etheretherketone), or a combination thereof.

[0101] Aspect 8: The thermoplastic composition according to any one of aspects 1 to 7, wherein the mineral filler comprises boehmite, kaolin, or a combination thereof, preferably boehmite.

[0102] Aspect 9: The thermoplastic composition according to aspect 1, comprising: 75 to 95 weight percent of the poly(etherimide); 5 to 10 weight percent of the polymer other than the poly(etherimide); and 1 to 10 weight percent of the mineral filler.

[0103] Aspect 10: The thermoplastic composition of aspect 9, wherein the poly(etherimide) comprises repeating units derived from bisphenol A dianhydride and meta-phenylenediamine; the polymer other than the poly(etherimide) comprises a polyolefin; and the mineral filler comprises clay, boehmite, or a combination thereof.

[0104] Aspect 11: The thermoplastic composition according to aspect 1, comprising: 25 to 45 weight percent of the poly(etherimide); 45 to 65 weight percent of the polymer other than the poly(etherimide); and 1 to 10 weight percent of the mineral filler.

[0105] Aspect 12: The thermoplastic composition of aspect 11, wherein the poly(etherimide) is a poly(etherimide-siloxane) copolymer; the polymer different from the poly(etherimide) comprises a poly(aryletherketone); and the mineral filler comprises clay, boehmite, or a combination thereof.

[0106] Aspect 13: The thermoplastic composition according to any one of Aspects 1 to 12, wherein the thermoplastic composition further comprises an additive, preferably an antioxidant, a heat stabilizer, a water stabilizer, a metal deactivator, a UV stabilizer, a processing aid, a colorant or a combination thereof, preferably wherein the additive is present in an amount greater than 0 to 5 weight percent.

[0107] Aspect 14: A method of preparing the thermoplastic composition of any of Aspects 1 to 13, the method comprising melt mixing the components of the composition.

[0108] Aspect 15: An article comprising the composition according to any one of aspects 1 to 13.

[0109] Alternatively, the compositions, methods and articles may comprise, consist of or consist essentially of any suitable material, step or component disclosed herein. The compositions, methods and articles may additionally or alternatively be formulated so as to be free of or essentially free of any material (or species), step or component that is otherwise not necessary to achieve the function or purpose of the compositions, methods and articles.

[0110] All ranges disclosed herein include endpoints, and endpoints can be combined independently of each other. "Combination" includes blends, mixtures, alloys, reaction products, etc. The terms "first", "second", etc. do not represent any order, quantity, or importance, but are used to distinguish one element from another. Unless otherwise specified herein or clearly contradictory to the context, the terms "one" and "a kind of" and "the" do not represent the limitation of quantity, but are interpreted as covering the singular and plural. Unless otherwise clearly stated, "or" refers to "and / or". Throughout the specification, mentioning "some aspects", "an aspect", etc. refers to that the specific elements described in conjunction with the aspect are included in at least one aspect described herein, and may or may not be present in other aspects. The term "their combination" as used in this article includes one or more listed elements, and is open, allowing one or more unnamed similar elements to exist. In addition, it should be understood that the described elements can be combined in any suitable manner in various aspects.

[0111] Unless otherwise specified herein, all test standards are the most current standards in effect as of the filing date of this application or, if priority is claimed, as of the filing date of the earliest priority application in which the test standards appear.

[0112] Unless otherwise defined, technical and scientific terms used herein have the same meanings as those commonly understood by those skilled in the art to which this application belongs. All cited patents, patent applications and other references are incorporated herein by reference in their entirety. However, if a term in this application contradicts or conflicts with a term incorporated in a reference, the term in this application takes precedence over the conflicting term incorporated in the reference.

[0113] Compounds are described using standard nomenclature. For example, any position not substituted by any specified group is understood to have its valency filled by a specified bond or hydrogen atom. A dash ("-") that is not between two letters or symbols is used to indicate the point of attachment of a substituent. For example, -CHO is attached through the carbon of the carbonyl group.

[0114] As used herein, the term "hydrocarbyl", whether used alone or as a prefix, suffix or fragment of another term, refers to a residue containing only carbon and hydrogen. The residue can be aliphatic or aromatic, straight chain, cyclic, bicyclic, branched, saturated or unsaturated. It can also contain a combination of aliphatic, aromatic, straight chain, cyclic, bicyclic, branched, saturated and unsaturated hydrocarbon parts. However, when the hydrocarbyl residue is described as being substituted, it can optionally contain heteroatoms on the carbon and hydrogen elements of the substituent residue. Therefore, when specifically described as substituted, the hydrocarbyl residue can also contain one or more carbonyls, amino, hydroxyl, etc., or it can contain heteroatoms in the main chain of the hydrocarbyl residue. The term "alkyl" refers to a branched or straight chain saturated aliphatic hydrocarbon group, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, sec-pentyl and n-hexyl and sec-hexyl. "Alkenyl" refers to a straight or branched monovalent hydrocarbon radical having at least one carbon-carbon double bond (e.g., vinyl (-HC=CH 2 "Alkoxy" refers to an alkyl group attached through an oxygen (i.e., alkyl-O-), such as methoxy, ethoxy, and sec-butoxy. "Alkylene" refers to a straight or branched chain saturated divalent aliphatic hydrocarbon group (e.g., methylene (-CH 2 -) or propylene (-(CH 2 ) 3 -)). "Cycloalkylene" refers to a divalent cyclic alkylene group, -C n H 2n-x , where x is the number of hydrogens substituted by cyclization. "Cycloalkenyl" refers to a monovalent group having one or more rings and one or more carbon-carbon double bonds in the ring, wherein all ring members are carbon (e.g., cyclopentyl and cyclohexyl). "Aryl" refers to an aromatic hydrocarbon group containing a specific number of carbon atoms, such as phenyl, trocon, indanyl or naphthyl. "Arylene" refers to a divalent aryl group. "Alkylidenearylene" refers to an arylene substituted by an alkyl group. "Arylalkylene" refers to an alkylene substituted by an aryl group (e.g., benzyl). The prefix "halogen" refers to a group or compound comprising one or more fluorine, chlorine, bromine or iodine substituents. There may be a combination of different halogen groups (e.g., bromine and fluorine), or there may be only chlorine groups. The prefix "hetero" refers to a compound or group including at least one ring member that is a heteroatom (e.g., 1, 2 or 3 heteroatoms), wherein the heteroatoms are each independently N, O, S, Si or P. "Substituted" means that the compound or group is substituted with at least one (e.g., 1, 2, 3 or 4) substituents, each of which may be independently C 1-9 Alkoxy, C 1-9 Haloalkoxy, nitro (-NO 2 ), cyano (-CN), C 1-6 Alkylsulfonyl (-S(=O) 2 -alkyl), C 6-12Arylsulfonyl (-S(=O) 2 -aryl), thiol (-SH), thiocyanate (-SCN), tosyl (CH 3 C 6 H 4 SO 2 -), C 3-12 Cycloalkyl, C 2-12 Alkenyl, C 5-12 Cycloalkenyl, C 6-12 Aryl, C 7-13 Arylalkylene, C 4-12 Heterocycloalkyl and C 3-12 A heteroaryl group replaces a hydrogen, provided that the normal valence of the substituted atom is not exceeded. The number of carbon atoms specified in the group does not include any substituents. For example, -CH 2 CH 2 CN is C substituted by nitrile 2 alkyl.

[0115] Although specific embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents that are not currently foreseeable or may not be foreseeable may occur to the applicant or other persons skilled in the art. Therefore, the appended claims as filed and as they may be amended are intended to cover all such alternatives, modifications, variations, improvements, and substantial equivalents.

Claims

1. A thermoplastic composition comprising: 25 to 86.7 weight percent of a poly(etherimide) comprising structural units of the following formula (1): Wherein each R is a substituted or unsubstituted C 6-20 Aromatic hydrocarbon group, substituted or unsubstituted straight chain or branched C 4-20 Alkylene, substituted or unsubstituted C 3-8 Cycloalkylene or their halogenated derivatives, and wherein each T is -O- or a group of the formula -OZO-, wherein the divalent bond of the -O- or -OZO- group is at the 3,3', 3,4', 4,3' or 4,4' position, and Z is optionally composed of 1 to 6 C 1-8 Alkyl, 1 to 8 halogen atoms or a combination thereof substituted aromatic C 6-24 a monocyclic or polycyclic moiety; 5 to 70 weight percent of a polymer other than the poly(etherimide), wherein the polymer other than the poly(etherimide) comprises a polyolefin, a poly(aryletherketone), or a combination thereof; and 1 to 15 weight percent of boehmite having an average particle size of 0.1 to 10 microns as determined by laser scattering, in, The weight percentages are based on the total weight of the composition, and Therein, blends of the poly(etherimide) and a polymer other than the poly(etherimide) show a multiphase morphology as observed by scanning electron microscopy.

2. The thermoplastic composition according to claim 1, wherein The thermoplastic composition exhibits a notched Izod impact strength greater than 50 J / m as determined according to ASTM D256.

3. The thermoplastic composition according to claim 1, wherein The thermoplastic composition exhibits a notched Izod impact strength that is at least 20% greater than the notched Izod impact strength of the same composition without the boehmite.

4. The thermoplastic composition according to claim 1, wherein The composition does not include a polymeric impact modifier, wherein the polymeric impact modifier is derived from an alkenyl aromatic compound and a conjugated diene or wherein the polymeric impact modifier is a rubber-modified polystyrene.

5. The thermoplastic composition according to claim 1, wherein The poly(etherimide) comprises repeating units derived from bisphenol A dianhydride and meta-phenylenediamine.

6. The thermoplastic composition according to claim 1, wherein The poly(etherimide) comprises a poly(etherimide-siloxane) copolymer.

7. The thermoplastic composition according to claim 1, wherein The polymer other than the poly(etherimide) comprises epoxy-functionalized poly(ethylene), poly(etheretherketone), or a combination thereof.

8. The thermoplastic composition according to claim 1, comprising: 75 to 86.7 weight percent of said poly(etherimide); 5 to 10 weight percent of said polymer other than said poly(etherimide); and 1 to 10 weight percent of said boehmite.

9. The thermoplastic composition according to claim 8, wherein The poly(etherimide) comprises repeating units derived from bisphenol A dianhydride and m-phenylenediamine; and The polymer other than the poly(etherimide) comprises a polyolefin.

10. The thermoplastic composition according to claim 1, comprising: 25 to 45 weight percent of said poly(etherimide); 45 to 65 weight percent of said polymer other than said poly(etherimide); and 1 to 10 weight percent of said boehmite.

11. The thermoplastic composition according to claim 10, wherein The poly(etherimide) is a poly(etherimide-siloxane) copolymer; and The polymer different from the poly(etherimide) comprises a poly(aryletherketone).

12. The thermoplastic composition according to claim 1, wherein The thermoplastic composition further comprises an additive.

13. A method of preparing a thermoplastic composition according to any one of claims 1 to 12, the method comprising melt mixing the components of the composition.

14. An article comprising the composition according to any one of claims 1 to 12.

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