KR20180088686A - Lamination process for improved interlayer adhesion of polyetherimide blend - Google Patents

Abstract

The present disclosure provides a method of making an article through a lamination process, the method comprising depositing at least first and second amounts of a molten thermoplastic composition such that at least a portion of the first amount is deposited on at least a portion of the second amount And fusing to form a fused region of the article. The thermoplastic composition may comprise at least first and second assemblies of polyetherimide, wherein the first and second assemblies have, when measured by gel permeation chromatography (GPC) on a polystyrene standard, for example, , Up to about 100 kDa.

Description

Lamination process for improved interlayer adhesion of polyetherimide blend

This disclosure relates to the field of lamination and the field of polymer blends.

Articles formed through layer-by-layer processing can exhibit excellent resolution, durability, and strength. These articles of manufacture can be used in a variety of applications including molds for final products as well as prototypes and end products. However, for parts produced by lamination processing, such as fused deposition modeling (FDM), weak interlaminar adhesion due to limited bonding between subsequent layers of the structure may result in structural orientation (also known as z-direction) It is possible to reduce the strength of the printed parts even in the direction.

As the use of the lamination process increases, there is a need in the art for a lamination process that can produce parts with improved interlayer adhesion to achieve better aesthetic quality and structural properties. There is also a need for a composition that enables such an improved lamination process.

summary

In order to meet this long-felt need, the present disclosure provides a method of forming an article, the method comprising depositing at least first and second amounts of a molten thermoplastic composition such that at least a portion of the first amount Wherein the thermoplastic composition comprises at least first and second populations of a polyetherimide, wherein the first and second populations of the polyetherimide are at least partially fused to at least a portion of the polyetherimide, The aggregates differ in weight average molecular weight up to about 100 kDa when measured by gel permeation chromatography (GPC) on polystyrene standards.

The disclosure also provides an article comprising at least a first and a second amount of thermoplastic composition fused with the fused region, wherein the thermoplastic composition comprises at least a first and a second aggregate of polyetherimides , Said at least two aggregates differing in weight average molecular weight up to about 100 kDa as measured by GPC for polystyrene standards.

A method of forming an article is further provided wherein the method comprises providing a plurality of portions of a molten thermoplastic composition comprising at least a first and a second aggregate of polyetherimides different in weight average molecular weight as measured by GPC to polystyrene standards Wherein the deposition is performed such that at least a portion of the plurality of portions of the thermoplastic composition are fused together to form the article.

The present disclosure also provides a method of forming an article comprising depositing at least first and second amounts of a molten thermoplastic composition comprising a polyetherimide such that at least a portion of the first amount is a second amount Wherein the thermoplastic composition comprises a plurality of polyetherimide polymer chains, wherein the polyetherimide polymer chain comprises at most 50% or less of the chain weight of the polyetherimide of the thermoplastic composition (up to the lower 50%) comprises a polyetherimide polymer chain having a molecular weight of from about 40 kDa to about 2 kDa.

A method of forming an article is provided wherein the method comprises depositing at least first and second amounts of a molten thermoplastic composition comprising a polyetherimide such that at least a portion of the first amount is present in at least a portion of the second amount Wherein the thermoplastic composition comprises a plurality of polyetherimide polymer chains, wherein the thermoplastic composition comprises a plurality of polyetherimide polymer chains, wherein the thermoplastic composition comprises a plurality of polyetherimide polymer chains And up to the upper 99.9% of the chain weight of the polyetherimide of the thermoplastic composition comprises a polyetherimide polymer chain having a molecular weight of from about 40 kDa to about 120 kDa.

There is further provided an article comprising at least a first and a second amount of a thermoplastic composition fused together in a fused region, the thermoplastic composition comprising a plurality of polyetherimide polymer chains, wherein (a) the thermoplastic composition comprises Wherein up to 50% of the chain weight of the polyetherimide comprises a polyetherimide polymer chain having a molecular weight of from about 40 kDa to about 2 kDa, (b) up to 80% of the chain weight of the polyetherimide of the thermoplastic composition is about A polyetherimide polymer chain having a molecular weight of from about 40 kDa to about 120 kDa; Or (a) and (b).

The present disclosure may be more readily understood by reference to the following detailed description taken in conjunction with the accompanying drawings and embodiments forming part of this disclosure. It is to be understood that the disclosure is not limited to the specific devices, methods, applications, conditions, or parameters described and / or shown herein, and the terminology used herein is for the purpose of describing particular embodiments only as examples, And are not intended to limit the scope of the disclosed subject matter. Also, as used in the specification including the appended claims, the singular forms "a," "an," and "the" include plural and, unless the context clearly dictates otherwise, A reference to at least includes that particular value.

As used herein, the term "plurality" means more than one. When a range of values is expressed, another embodiment includes from one particular value and / or to another particular value. Similarly, it will be understood that when a value is approximated by the use of the preceding "about ", a particular value forms another embodiment. All ranges are inclusive and combinable. The weight percentage is 100 wt. % ≪ / RTI > by weight. If a standard is mentioned and there is no date associated with that standard, it should be understood that the standard is the most recent standard available at the filing date of the present application.

It should be appreciated that for clarity, certain features of the disclosed subject matter described herein in the context of separate implementations may be provided in combination in a single embodiment. Conversely, for brevity, various features of the disclosed subject matter described in the context of a single embodiment may be provided individually or in any subcombination. Also, references to values referred to in the scope include each and every value within that range. Any document cited herein is incorporated herein by reference in its entirety for any and all purposes.

A variety of thermoplastics are used in the lamination process. Polyetherimide (PEI) blends are particularly suitable because they provide high thermal, strength, and chemical resistance to many injection molding and lamination (3D printing) applications. However, in processes such as fused deposition modeling (FDM), poor adhesion between layers of deposited material can reduce the strength of the printed portion in all directions, especially in the printing direction. The described adjustments to the melt flow and / or the molecular weight of the PEI blend result in improved interlayer adhesion (also known as z-strength) and improved printed part performance, including mechanical, thermal, and flame characteristics.

In some embodiments of the method, the plurality of layers are patterned in a predetermined pattern by a lamination process. The "plurality" as used in the context of lamination includes two or more layers. The maximum number of layers may vary and may be determined by considerations such as, for example, the size of the article being manufactured, the technology used, the capabilities of the equipment used, and the level of detail desired in the final article . For example, 5 to 100,000 layers may be formed, or 50 to 50,000 layers may be formed.

The fused layer of the printed article may be any thickness suitable for the FDM process. The plurality of layers may each be on average, preferably at least 50 microns thick, more preferably at least 80 microns thick, and even more preferably at least 100 microns thick. In a preferred embodiment, the plurality of sintered layers each have an average thickness of preferably less than 500 microns (microns), more preferably less than 300 microns (microns) thicker, and even more preferably less than 200 microns ).

Thus, the layer may be, for example, 50-500, 80-300, or 100-200 micrometers (microns) thick. Of course, the articles produced through the filament-based deposition process may have the same or different layer thickness than those described above.

In existing lamination processes, adhesion may be weakest in the structure direction (z-direction) due to incomplete bonding between subsequent layers of the structure. Secondary operations such as coating, curing (radiation or heat), painting, sanding, or heating may improve the structural properties and / or aesthetics of the printed part. However, these tasks can add time and cost to the production process in some cases.

Proper melt flow control or reduction in glass transition temperature can help to mitigate internal stress and help the extruded material remain molten for long periods of time, thus increasing bonding with previously deposited materials and, Thereby enhancing adhesion between layers.

The melt flow adjustment can be accomplished by a change in polymer molecular weight, a flow enhancing additive, or a combination of these methods. The mechanical properties of the polymer also contribute to the strength of the printed part, and must be considered when developing materials with improved z-strength.

The polyetherimide compositions may include various additives commonly incorporated into polymeric compositions of this type, provided that the additives are chosen so as not to negatively affect the desired properties of the composition. Exemplary additives include, but are not limited to, catalysts, impact modifiers, antioxidants, heat stabilizers, light stabilizers, UV absorbing additives, quenchers, plasticizers, lubricants, mold release agents, antistatic agents, visual effects additives such as dyes, Radiation stabilizers. Combinations of additives may be used, examples of which are combinations of thermal stabilizers, mold release agents, and optionally ultraviolet light stabilizers. In general, the additives are used in amounts generally known to be effective. The aforementioned additives are generally present in an amount of 0.005 to 20 wt%, specifically 0.01 to 10 wt%, based on the total weight of the composition. Alternatively, in some embodiments, the composition does not contain a significant amount of additive, and in some situations, there is no detectable amount of additive, i. E., The additive is substantially absent or absent from the composition. Thus, the additives described above may be present in an amount of from 0 to 20 wt%, 19 wt% to 18 wt%, 17 wt%, 16 wt%, 15 wt%, 14 wt%, 13 wt%, 12 wt% , 11 wt%, 10 wt%, 9 wt%, 8 wt%, 7 wt%, 6 wt%, 5 wt%, 4 wt%, 3 wt%, 2 wt%, 1 wt%, and 0.0001 wt% It can be present in less than the selected amount. In another embodiment, a notable amount of a heat stabilizer, a mold release agent, and optional additives other than ultraviolet light stabilizers is not present in the composition. In another embodiment, the detectable amount of the heat stabilizer, the mold release agent, and optionally any additives other than ultraviolet light stabilizers is not present in the composition.

Suitable antioxidants may be compounds such as phosphites, phosphonites and hindered phenols or mixtures thereof. Phosphorus-containing stabilizers, including triaryl phosphites and aryl phosphonates, are useful additives. Double functional phosphorus containing compounds can not also be seeded. Preferred stabilizers may have a molecular weight of 300 or greater. Some exemplary compounds include tris-di-tert-butylphenyl phosphite (available from Ciba Chemical Co.) as IRGAFOS ^TM 168 and bis (2,4-dicumylphenyl) pentaerythritol diphosphite as DOVERPHOS ^TM S- (Commercially available from Dover Chemical Co.).

Examples of phosphites and phosphonites include: triphenyl phosphite, diphenyl alkyl phosphite, phenyl dialkyl phosphite, tris (nonylphenyl) phosphite, triruryl phosphite, trioctadecyl phosphite (2,4-di-tert-butylphenyl) phosphite, diisodecylpentaerythritol diphosphite, bis (2,4-di-tert- butylphenyl) pentaerythritol (2,6-di-tert-butyl-4-methylphenyl) -pentaerythritol diphosphite, diisodecyloxy pentaerythritol diphosphite, bis (2,4- 6-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tris (butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis (2,4- -Butyl-phenyl) 4,4'-biphenylene diphosphonite, bis (2,4-di-t (2,4-di-tert-butyl-6-methylphenyl) ethylphosphite, 2,2 ', 2 "-nitrilo [triethyltris (3, 3'5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl) phosphite], 2-ethylhexyl (3,3 ', 5,5'- butyl-1,1'-biphenyl-2,2'-diyl) phosphite and 5-butyl-5-ethyl- 2- (2,4,6-tri-tert- butylphenoxy) 3,2-dioxaphosphorane.

Combinations comprising more than one organogein compound are contemplated. When used together, the organo-phosphorus compound may be of the same type or of a different type. For example, the combination may comprise two phosphites, or the combination may comprise phosphites and phosphonites. In some embodiments, a phosphorus-containing stabilizer having a molecular weight of 300 or greater is useful. Phosphorus-containing stabilizers, such as aryl phosphites, are generally present in the composition in an amount of 0.005 to 3 wt%, particularly 0.01 to 1.0 wt%, based on the total weight of the composition.

Hindered phenols may also be used as antioxidants, examples of which are alkylated monophenols, and alkylated bisphenols or polyphenols. Exemplary alkylated monophenols include: 2,6-di-tert-butyl-4-methylphenol; 2-tert-butyl-4,6-dimethylphenol; 2,6-di-tert-butyl-4-ethylphenol; 2,6-di-tert-butyl-4-n-butylphenol; 2,6-di-tert-butyl-4-isobutylphenol; 2,6-dicyclopentyl-4-methylphenol; 2- (alpha-methylcyclohexyl) -4,6-dimethylphenol; 2,6-dioctadecyl-4-methylphenol; 2,4,6-tricyclohexylphenol; 2,6-di-tert-butyl-4-methoxymethylphenol; Nonylphenols whose side chain is linear or branched, for example 2,6-di-nonyl-4-methylphenol; 2,4-dimethyl-6- (1'-methylundec-1'-yl) phenol; 2,4-dimethyl-6- (1'-methylheptadec-1'-yl) phenol; 2,4-dimethyl-6- (1'-methyltridec-1'-yl) phenol and mixtures thereof. Exemplary alkylidene bisphenols include: 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 2,2'-methylenebis (6-tert- , 2,2'-methylenebis [4-methyl-6- (alpha-methylcyclohexyl) -phenol] Methylenebis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis (4,6-di- Butylphenol), 2,2'-ethylidenebis (6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis [6- , 2'-methylenebis [6- (alpha, alpha-dimethylbenzyl) -4-nonylphenol], 4,4'- methylenebis- (2,6- Butene, 2,6-bis (3-tert-butyl-2-methylphenol), 1,1-bis (5-tert- Methyl-2-hydroxybenzyl) -4-methylphenol, 1,1,3-tris (5-tert- butyl- -Butyl-4-hydro (3'-tert-butyl-4'-hydroxyphenyl) butyrate], bis (3-methyl-phenyl) -3-n-dodecylmercaptobutane-, ethylene glycol bis methyl-phenyl) dicyclopentadiene, bis [2- (3'-tert-butyl-2'-hydroxy-5'- methylbenzyl) -6-tert- Butyl-4-methylphenyl] terephthalate, 1,1-bis- (3,5-dimethyl-2-hydroxyphenyl) butane, 2,2- (5-tert-butyl-4-hydroxy-2-methylphenyl) -4-n-dodecyl mercaptobutane-, 1,1,5,5-tetra- 5-tert-butyl-4-hydroxy-2-methylphenyl) pentane and mixtures thereof.

The hindered phenolic compound may have a molecular weight of at least 300 g / mole. The high molecular weight can help to maintain the hindered phenolic moiety in the polymer being melted at high processing temperatures, for example, above 300 < 0 > C. The hindered phenolic stabilizer is generally present in the composition in an amount of 0.005 to 2 wt%, specifically 0.01 to 1.0 wt%, based on the total weight of the composition.

Examples of mold release agents include both aliphatic and aromatic carboxylic acids and their alkyl esters, such as stearic acid, behenic acid, pentaerythritol tetrastearate, glycerin tristearate, and ethylene glycol distearate. Polyolefins such as high density polyethylene, linear low density polyethylene, low density polyethylene, and similar polyolefin homopolymers and copolymers can also be used as mold release agents. The mold release agent is typically present in the composition in an amount of 0.05 to 10 wt%, specifically 0.1 to 5 wt%, based on the total weight of the composition. A preferred mold release agent will have a high molecular weight, typically greater than 300, to prevent loss of the release agent from the molten polymer mixture during the melt process.

In particular, selective polyolefins may be added to modify the chemical resistance characteristics and mold release characteristics of the composition. Homopolymers such as polyethylene, polypropylene, polybutene can be used individually or in combination. The polyethylene may be added as high density polyethylene (HDPE), low density polyethylene (LDPE), or branched polyethylene. The polyolefin may also contain a compound comprising at least one of the foregoing, as well as acidic compounds containing carboxylic acid radicals such as maleic acid or a compound containing citric acid or an anhydride thereof, acrylic acid radicals such as acrylic acid esters, May be used together in copolymer form. When present, polyolefins, especially HDPET, can be used in amounts of from greater than 0 to 10 wt%, specifically from 0.1 to 8 wt%, more specifically from 0.5 to 5 wt%, based on the total weight of the composition.

Colorants such as pigments and / or dye additives may also optionally be present. Useful pigments may include, for example, the following: inorganic pigments such as metal oxides and mixed metal oxides such as zinc oxide, titanium dioxide, iron oxides, and the like; Sulfides such as zinc sulfide, etc .; Aluminate; Sodium sulfo-silicate sulfate, chromate, etc .; Carbon black; Zinc ferrite; Ultra marine blue; Organic pigments such as azo pigments, di-azo, quinacridone, perylene, naphthalene tetracarboxylic acid, flavanthrone, isoindolinone, tetrachloroisoindolinone, anthraquinone, entrone, dioxazine, phthalocyanine, lake; Pigment Red 101, Pigment Red 122, Pigment Red 149, Pigment Red 177, Pigment Red 179, Pigment Red 202, Pigment Violet 29, Pigment Blue 15, Pigment Blue 60, Pigment Yellow 119, Pigment Yellow 147, Pigment Yellow 150, and Pigment Brown 24; Or at least one of the foregoing pigments. The pigment is generally used in an amount of 0 to 10 wt%, specifically 0 to 5 wt%, based on the total weight of the composition. In some instances, if improved impact is desired, the pigment, such as titanium dioxide, may have an average particle size of less than 5 microns.

Exemplary Implementation Example

A qualitative bonding method was used to predict the interlayer adhesion of various PEI resin grades during the 3D printing process. Exemplary PEI pellets were injection molded into flame rods with a thickness of 1 mm, and two rods of the same material were clamped together and placed in an oven at a temperature 3-5 degrees higher than the glass transition temperature of the polymer. After cooling, the adhesive force is weak against the bar which is easily pulled down, characterized by a medium to a bar that can be pulled into a welded but undamaged condition, and a strong to a bar that can not be pulled off without being fully welded and broken .

Table 1 below provides exemplary adhesion results for various exemplary PEI grades (considered as a particularly suitable PEI material by ULTEM? Of SABIC) after 15 minutes at 220 占 폚. The molecular weight is lowered for PEI 1 (MW = 57 kDa), PEI 2 (MW = 49 kDa), and PEI 3 (MW = 33 kDa) (all weight average molecular weights determined by GPC for polystyrene standards, M _w values) As the flow increased, the adhesion between the rods became stronger. Without being bound by any particular theory, these results demonstrate that at least some relatively low molecular weight materials (and consequently the higher flow materials) are superior to the relatively higher molecular weight materials in the 3D printed portions, It is possible to have an adhesive force.

Table 1 provides nested shear adhesion test data for an exemplary PEI rod:

The adhesive strength results in Table 1 were confirmed by the superposition shear method to measure the breaking strength. The failure mode (Figure 1) represents the bond strength between the layers.

Most of the PEI 1 samples were broken by shear (rod breakage without breakage, type 1 failure) or partial shear and breakage (type 2) at the overlap between the bars. On the other hand, the PEI 2 and PEI 3 samples are broken by fracture (Type 3) at one end of the overlap, suggesting adhesion between the stronger layers.

Again without being bound by any particular theory, these results confirm that the layer-to-bed adhesion is superior to the lower molecular weight (higher flow) materials. Also, without being bound by any particular theory, breakage can also be accounted for by the lower embrittlement of lower molecular weight grades, especially PEI 3. A further test (Figure 2) showed a slight decrease in breakdown force against PEI 2 compared to PEI 1 and showed a more significant reduction for PEI 3 as compared to the higher MW PEI 1.

Table 2 (below) provides additional properties of some exemplary PEI 1 and PEI 3 blends

The molecular weight is linearly related to the blend ratio of the two grades. Thus, in compounding the low-molecular weight and high-molecular weight components, the polydispersity (D) of the compounded samples was higher than in the individual components. The glass transition temperature decreased with decreasing molecular weight over the studied range.

In a further evaluation, four experimental blends were injection molded into 3.2mm standard ASTM parts on a 180T molding machine with a flat barrel zone temperature profile at 680F. The parts were tested for bending, tensile and impact properties.

Table 3 below provides tensile properties data of the injection molded, exemplary PEI blends.

The tensile modulus and tensile strength and yield elongation were essentially the same between all samples. There was no tendency to be perceived by the tensile fracture elongation.

Table 4 provides the flexural characteristic data for several injection-molded PEI blends:

As shown in the above table, as the relative amount of lower molecular weight PEI was increased, flexural modulus and flexural stress were increased.

Table 5 provides exemplary impact property data for several injection molded PEI blends:

As shown above, the reduced impact strength was seen in PEI blend 4 in the MAI test because the total energy is lower than the other three samples at both temperatures. PEI blend 4 is also the only sample with 0% ductile fracture at 100 ° C.

The notch Izod impact results at 23 [deg.] C did not show a clear trend. The reverse notch Izod impact test at 23 ° C showed an increase in impact strength as the proportion of the higher molecular weight PEI increased.

In summary, increasing the relative ratio of low-MW PEI in the composition served to enhance interlayer adhesion in the lamination process. The increased interlayer adhesion did not sacrifice a wide range of mechanical properties.

The following aspects of the present disclosure are merely illustrative and do not limit the scope of the disclosure or appended claims.

A method of forming an article, the method comprising depositing at least first and second amounts of a molten thermoplastic composition such that at least a portion of the first amount is fused to at least a portion of the second amount to form a fused Wherein the thermoplastic composition comprises at least a first and a second assembly (or PEI) of a polyetherimide, wherein the first and second assemblies are selected from the group consisting of gel permeation chromatography (GPC), the weight average molecular weight differs up to about 100 kDa.

Suitable polyetherimides are described, for example , in U.S. Published Patent Application No. 2014/0228462, the entirety of which is incorporated herein by reference.

Polyetherimides ("PEIs") are amorphous, transparent, high performance polymers having a glass transition temperature ("Tg") of greater than 180 ° C. PEI additionally has high strength, heat resistance, and modulus, and wide chemical resistance. The high reliability and safety benefits provided by the polyetherimide from its optical clarity, toughness, and heat resistance can be useful in medical applications.

The polyetherimide may comprise a polyetherimide homopolymer (e.g., polyetherimide sulfone) and a polyetherimide copolymer. The polyetherimide may be selected from (i) a polyetherimide homopolymer, for example, a polyetherimide, (ii) a polyetherimide co-polymer, and (iii) combinations thereof. Polyether imide, and a known polymer is sold by ULTEM EXTEM ^{TM TM, TM} and SILTEM be underground SABIC Innovative Plastics.

The polyetherimide can be represented by formula (1): < EMI ID =

Where a is greater than 1, such as from 10 to 1,000 or more, or, more specifically, from 10 to 500.

The group V in formula (1) is a quaternary linker containing a combination of an ether group ("polyetherimide" as used herein) or an ether group and an arylene sulfonoxy group ("polyetherimide sulfone"). Such linkers include, but are not limited to: (a) substituted or unsubstituted, saturated, unsaturated or aromatic monocyclic and polycyclic groups having 5 to 50 carbon atoms, which include ether groups, aryl Or a combination of an ether group and an arylenesulfone group); And (b) a substituted or unsubstituted, linear or branched, saturated or unsaturated alkyl group which has 1 to 30 carbon atoms and is optionally substituted by a combination of an ether group or an ether group, an arylene group, Lt; / RTI > Or a combination comprising at least one of the foregoing. Suitable further substitutions include, but are not limited to, ether, amide, ester, and combinations comprising at least one of the foregoing.

The R groups in formula (1) include, but are not limited to, substituted or unsubstituted divalent organic groups such as: (a) aromatic hydrocarbon groups having 6 to 20 carbon atoms and halogenated derivatives thereof; (b) a straight or branched alkylene group having 2 to 20 carbon atoms; (c) a cycloalkylene group having 3 to 20 carbon atoms, or (d) a divalent group of formula (2)

Wherein Q1 is a divalent moiety such as -O-, -S-, -C (O) -, -SO2-, -SO-, -CyH2y- (where y is an integer of 1 to 5) Halogenated derivatives (including perfluoroalkylene groups).

Linker V may include, but is not limited to, a tetravalent aromatic group of formula (3):

Wherein W is -O-, -SO2-, or a group of the formula -OZO- wherein the divalent bond of the -O- or -OZO- group is 3,3 ', 3,4', 4,3 ', or 4 , 4 'position, and Z is, but not limited to, a divalent group of formula (4)):

Wherein Q is, but not limited to, -O-, -S-, -C (O ), -SO 2 -, -SO-, -C y H 2y - (y being an integer from 1 to 5), and their halogenated (Including a perfluoroalkylene group). The term " monovalent moiety "

The polyetherimide may comprise more than one, specifically 10 to 1,000, or more specifically 10 to 500 structural units of formula (5)

Wherein T is -O- or -OZO-, wherein the divalent bond of the -O- or -OZO- group is at the 3,3 ', 3,4', 4,3 ', or 4,4' position Z is a divalent group of formula (3) as defined above in formula (3); and R is a divalent group of formula (2) as defined above.

In some embodiments, the thermoplastic composition comprises a double-, triple- or other multi-rod distribution of polyetherimides, for example a bee-shaped distribution of a polyetherimide polymer. The manner of distribution can be identical to each other, for example half of the composition comprises PEI of MW ₁ and the other half of the composition comprises PEI of MW ₂ . The width of the distribution can be such that between 1% and 99% of the PEI is within 10% of the weight average molecular weight for that mode.

The first and second assemblies may include, for example , about 1 to about 90 kDa, or about 15 to about 85 kDa, or about 20 to about 80 kDa, or about 25 to about 75 kDa, or about 30 to about 65 kDa , Or about 35 to about 60 kDa, or about 40 to about 65 kDa, or about 45 to about 60 kDa, or about 50 to about 55 kDa. Different aggregates in molecular weight from about 10 to about 25 kDa (e.g., from about 15 kDa to about 24 kDa) are considered particularly suitable.

Deposition can be achieved, for example, by filament deposition, dripping, and the like. The composition may be at a specific temperature prior to deposition. The article can be made by a layer from a thermoplastic material, such as, for example, strings or filaments of a pellet from a digital model by selectively distributing it through a nozzle or orifice. For example, an extruded material article can be made by piling a string of plastic filaments or pellets that are unwound from a coil or deposited from an extrusion head. These lamination techniques include fused deposition modeling and fused filament weaving as well as other material extrusion techniques as defined in ASTM F2792-12a.

Embodiment 2. The method of embodiment 1, wherein the thermoplastic composition comprises at least one polyetherimide oligomer. Polyetherimides (PEI) are considered to be particularly suitable thermoplastics. Ultem ^TM PEI (SABIC) is considered particularly suitable, but other PEI compositions may be used.

Embodiment 3. The method of either of modes 1 or 2, wherein the first and second assemblies have different weight average molecular weights from about 2 kDa to about 50 kDa as measured by GPC for polystyrene standards.

Embodiment 4. The method of any one of modes 1 to 3, wherein the weight ratio of the first aggregate of polyetherimide to the second aggregate of polyetherimide is from about 100: 1 to about 1: 100. The ratio can also be from about 95: 5 to about 5:95, or from about 90:10 to about 10:90, or from about 85:15 to about 15:85, or from about 80:20 to about 20:80, : 70 to about 70:30, or about 35:65 to about 65:35, or about 60:40 to about 40:60, or about 55:45 to about 45:55, or about 50:50.

5. The method of embodiment 4, wherein the weight ratio of the first aggregate of polyetherimide to the second aggregate of polyetherimide is from 10: 1 to 1:10.

6. The method according to any one of modes 1 to 5, wherein the deposition is performed according to a preset pattern. The preset pattern can be determined from a three-dimensional digital representation of the desired article as is known in the art. As an example, a user may generate a digital representation of a desired article by performing a 3-D scan of the article. The user can also construct a 3-D representation of the original article based on the user's own needs. For example, a user may configure a 3-D representation of the casing based on the dimensions of the item to be placed in the casing.

7. An article, comprising at least first and second amounts of a thermoplastic composition fused together with a fused region, wherein the thermoplastic composition comprises at least a first and a second aggregate of polyetherimides, the at least two Or more aggregates differ in weight average molecular weight up to about 100 kDa when measured by GPC for polystyrene standards.

The fused region may be the interface between the first and second layers. The article may comprise one, two, or more fused regions. The fused region may overlap between the first and second amounts of the thermoplastic composition. The overlap region may be square or otherwise polygonal in shape. The fusion may be in an individual position, but may also be in a line, a seam, or some other continuous shape. The two quantities may be fused along the entirety of their overlap, but may also be fused in separate, discrete regions along the overlap.

The two quantities can be arranged such that fusion occurs in conjunction with the deposition of the second quantity. The user may also be able to adjust the temperature of the chamber after deposition (e. G., Via an infrared source, through a microwave source, through forced ventilation, through convection, or through other sources known to those skilled in the art Additional energy can be applied).

Embodiment 8. The article of embodiment 7 wherein said first and second assemblies differ in weight average molecular weight from about 2 kDa to about 60 kDa as determined by GPC for polystyrene standards. The first and second assemblies may comprise, for example, about 10 to about 90 kDa, or about 15 to about 85 kDa, or about 20 to about 80 kDa, or about 25 to about 75 kDa, or about 30 to about 65 kDa , Or about 35 to about 60 kDa, or about 40 to about 65 kDa, or about 45 to about 60 kDa, or about 50 to about 55 kDa. Different aggregates in molecular weight from about 10 to about 25 kDa (e.g., from about 15 kDa to about 24 kDa) are considered particularly suitable.

Modal 9. The article of embodiment 8, wherein the article comprises a polyetherimide oligomer. As described elsewhere herein, Ultem ^TM is considered particularly suitable. Pure PEI or PEI blended with other materials is considered appropriate.

Embodiment 10. The article of any of items 7 to 9, wherein at least one of the first and second amounts is characterized as a layer. As used herein, a "layer" is a convenience term that includes any regular or irregular shape having at least a predetermined thickness. In some implementations, two dimensions of size and placement form are contemplated, and in some embodiments, the size and shape of all three dimensions of the layer are predetermined.

The thickness of each layer can vary greatly depending on the method of lamination and the particle size. The thickness of each layer formed in some embodiments is different from previous or subsequent layers. In some embodiments, the thickness of each layer is the same. The thickness of each layer formed in some embodiments is between 50 microns (microns) and 500 microns (microns).

Embodiment 11. The article of any of embodiments 7 to 10 wherein the weight ratio of the first aggregate of polyetherimide to the second aggregate of polyetherimide is from 100: 1 to 1: 100. The ratio can also be from about 95: 5 to about 5:95, or from about 90:10 to about 10:90, or from about 85:15 to about 15:85, or from about 80:20 to about 20:80, : 70 to about 70:30, or about 35:65 to about 65:35, or about 60:40 to about 40:60, or about 55:45 to about 45:55, or about 50:50.

Embodiment 12. The article of embodiment 11 wherein the weight ratio of the first aggregate of polyetherimide to the second aggregate of polyetherimide is from 10: 1 to 1:10.

13. The article of any of embodiments 7-12 wherein the article is an aircraft component, a medical device, a tray, a container, a laboratory tool, a food- or beverage-service article, an automotive component, a construction article, a medical implant, , Ornaments, or any combination thereof.

Some exemplary applications include, but are not limited to, feeding, medical, lighting, lenses, glasses, windows, enclosures, safety screens, cooking utensils, medical devices, trays, plates, handles, helmets, Including those molded into enclosures, engine parts, automotive engine parts, lighting sockets and reflectors, electric motor parts, power distribution equipment, telecommunications equipment, computers, and coupling device connectors. Other articles include, for example, hollow fibers, hollow tubes, fibers, sheets, films, multilayer sheets, multilayer films, molded parts, extruded profiles, coated parts, foams, windows, shelves, wall panels, Lighting panel, duster, shade, partition, lens, skylight, lighting device, reflector, ducting, cable tray, conduit, pipe, cable tie, wire coating, electrical connector, air handling device, ventilator, louver, insulation, lid A door, a hinge, a handle, a sink, a mirror housing, a mirror, a toilet seat, a hanger, a coat hook, a shelf, a ladder, a railing, a step, a cart, a tray, a cooking appliance, And combinations thereof.

Embodiment 14. The article of any one of embodiments 7-13 wherein the thermoplastic composition has a Tg in the range of about 175 to about 235 DEG C as measured by DSC. The composition may also have a Tg (measured as described) ranging from about 215 ° C to about 221 ° C.

15. The article of any one of embodiments 7-14, wherein the article exhibits at least one of interlayer adhesion, tensile modulus, flexural modulus, and elongation at break, which are comparable to corresponding articles formed from a single aggregate of polyetherimide It is an improvement.

Embodiment 16. A method of forming an article, the method comprising: providing a plurality of portions of a molten thermoplastic composition comprising at least a first and a second aggregate of polyetherimides different in weight average molecular weight as measured by GPC for a polystyrene standard Wherein the deposition is performed such that at least a portion of the plurality of portions of the thermoplastic composition are fused together to form the article.

Suitable polyetherimide compositions are described elsewhere herein. As described elsewhere herein, the aggregate can be, for example, from about 1 to about 90 kDa, or from about 15 to about 85 kDa, or from about 20 to about 80 kDa, or from about 25 to about 75 kDa, Or about 65 kDa, or about 35 to about 60 kDa, or about 40 to about 65 kDa, or about 45 to about 60 kDa, or about 50 to about 55 kDa. Aggregates having different molecular weights from about 10 to about 25 kDa (e.g., from about 15 kDa to about 24 kDa) are considered particularly suitable.

Embodiment 17. The method of embodiment 16, wherein the thermoplastic composition may be deposited from a dispenser region (e.g., a nozzle) having a temperature of from about 300 to about 400 占 폚. The temperature may be from about 330 to about 370 ° C, or even from about 340 to about 360 ° C.

Embodiment 18. The method of any one of modes 16-17, wherein the assembly of the lowest molecular weight polyetherimide has a weight average molecular weight of about 10 kDa to about 50 kDa.

19. The method of any one of modes 16-18, wherein the thermoplastic composition has a Tg in the range of from about 190 to about 230 DEG C, or from about 200 to about 220 DEG C, or even about 210 DEG C, as measured by DSC.

Embodiment 20. The method of any one of embodiments 16-19 wherein the weight ratio of the first aggregate of polyetherimide to the second aggregate of polyetherimide is 100: 1 to 1: 100. The ratio can also be from about 95: 5 to about 5:95, or from about 90:10 to about 10:90, or from about 85:15 to about 15:85, or from about 80:20 to about 20:80, : 70 to about 70:30, or about 35:65 to about 65:35, or about 60:40 to about 40:60, or about 55:45 to about 45:55, or about 50:50.

Embodiment 21. The article or method of any of embodiments 1-21, wherein the thermoplastic composition comprises a multi-rod (multi-rod) distribution of weight average molecular weight. Thus, the distribution suitably includes two or more schemes.

Embodiment 22. The article or method of embodiment 21, wherein the multi-dimensional distribution comprises a bee-shaped distribution.

Embodiment 23. The article or method of embodiment 21, wherein the multiple distribution comprises a bee-shaped distribution.

24. The article or method of embodiment 21 wherein the at least two modes are from about 2 to about 70 kDa, or from about 5 to about 60 kDa, or from about 7 to about 47 kDa, or from about 9 to about 39 kDa, 11 to about 33 kDa, or about 13 to about 29 kDa, or about 15 to about 26 kDa, or about 15 to about 21 kDa, or about 17 to about 19 kDa.

Embodiment 25. The article or method of embodiment 21, wherein the minimum mode has a weight average molecular weight of from about 20 to about 40 kDa. The lowest mode of about 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 21, 32, 33, 34, 35, 36, 37, 38, and 39 kDa All are considered appropriate.

Embodiment 26. The article or method of embodiment 21, wherein the peak mode has a weight average molecular weight of from about 35 to about 70 kDa. About 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60 , 61, 62, 63, 64, 65, 66, 67, 68, and 69 kDa (and all intermediate values) are considered to be suitable.

27. A method of forming an article, comprising: depositing at least first and second amounts (e.g., layers, lands) of a molten thermoplastic composition comprising a polyetherimide to form at least a portion And fusing to at least a portion of the second volume to form a fused region of the article. As described elsewhere herein, the amount of fusion of the present compositions can be achieved by heating, pressure, and the like.

28. The method of embodiment 27 wherein the thermoplastic composition comprises a plurality of polyetherimide polymer chains wherein up to 50% of the chain weight of the polyetherimide of the thermoplastic composition is from about 40 kDa to about 8 kDa, A weight average molecular weight of about 3 kDa, or even about 2 kDa, or even about 50 times the weight of a PEI monomer unit.

 "Chain weight" means the weight average molecular weight of a given chain. For example, in a sample of chains having weight average molecular weights of 10 kDa, 15 kDa, 20 kDa, 70 kDa, 75 kDa, and 80 kDa, up to 50% Etherimide chain.

 "Up to the lower x%" means the xth percentile or less. For example, "up to 25%" means less than 25%.

29. The method of embodiment 28 wherein the thermoplastic composition comprises a plurality of polyetherimide polymer chains wherein up to 40% of the chain weight of the polyetherimide of the thermoplastic composition has a molecular weight from about 40 kDa to about 15 kDa Lt; RTI ID = 0.0 > polyetherimide < / RTI > polymer chains.

30. The method of embodiment 29 wherein the thermoplastic composition comprises a plurality of polyetherimide polymer chains wherein up to 30% of the chain weight of the polyetherimide of the thermoplastic composition has a molecular weight from about 40 kDa to about 15 kDa Lt; RTI ID = 0.0 > polyetherimide < / RTI > polymer chains.

31. The method of embodiment 30 wherein the thermoplastic composition comprises a plurality of polyetherimide polymer chains wherein up to 20% of the chain weight of the polyetherimide of the thermoplastic composition has a molecular weight from about 40 kDa to about 15 kDa Lt; RTI ID = 0.0 > polyetherimide < / RTI > polymer chains.

32. The method of embodiment 31 wherein the thermoplastic composition comprises a plurality of polyetherimide polymer chains wherein up to 10% of the chain weight of the polyetherimide of the thermoplastic composition has a molecular weight of from about 40 kDa to about 15 kDa Lt; RTI ID = 0.0 > polyetherimide < / RTI > polymer chains.

33. The method of embodiment 27 wherein the thermoplastic composition comprises a plurality of polyetherimide polymer chains wherein up to 99.9% of the chain weight of the polyetherimide of the thermoplastic composition is from about 40 kDa to about 120 kDa, kDa to about 110 kDa, or from about 60 kDa to about 100 kDa, or from about 70 kDa to about 90 kDa, or even about 80 kDa.

 "Up to the upper x%" means from the [100-x] th percentile to the 100 th percentile. For example, in a sample of chains having molecular weights of 10 kDa, 15 kDa, 20 kDa, 70 kDa, and 80 kDa, the sample up to 80% by chain weight comprises a polyetherimide chain having a molecular weight of 15 kDa or greater do.

34. The method of embodiment 33 wherein the thermoplastic composition comprises a plurality of polyetherimide polymer chains wherein up to 70% of the chain weight of the polyetherimide of the thermoplastic composition is from about 40 kDa to about 120 kDa, kDa to about 110 kDa, or from about 60 kDa to about 100 kDa, or from about 70 kDa to about 90 kDa, or even about 80 kDa.

35. The method of embodiment 34 wherein the thermoplastic composition comprises a plurality of polyetherimide polymer chains wherein up to 60% of the chain weight of the polyetherimide of the thermoplastic composition is from about 40 kDa to about 120 kDa, kDa to about 110 kDa, or from about 60 kDa to about 100 kDa, or from about 70 kDa to about 90 kDa, or even about 80 kDa.

36. The method of embodiment 35 wherein the thermoplastic composition comprises a plurality of polyetherimide polymer chains wherein up to 50% of the chain weight of the polyetherimide of the thermoplastic composition is from about 40 kDa to about 120 kDa, kDa to about 110 kDa, or from about 60 kDa to about 100 kDa, or from about 70 kDa to about 90 kDa, or even about 80 kDa.

37. The method of embodiment 35 wherein the thermoplastic composition comprises a plurality of polyetherimide polymer chains wherein up to 40% of the chain weight of the polyetherimide of the thermoplastic composition is from about 40 kDa to about 120 kDa, kDa to about 110 kDa, or from about 60 kDa to about 100 kDa, or from about 70 kDa to about 90 kDa, or even about 80 kDa.

38. The method of embodiment 37 wherein the thermoplastic composition comprises a plurality of polyetherimide polymer chains wherein up to 30% of the chain weight of the polyetherimide of the thermoplastic composition is from about 40 kDa to about 120 kDa, kDa to about 110 kDa, or from about 60 kDa to about 100 kDa, or from about 70 kDa to about 90 kDa, or even about 80 kDa.

39. The method of embodiment 38 wherein the thermoplastic composition comprises a plurality of polyetherimide polymer chains wherein up to 20% of the chain weight of the polyetherimide of the thermoplastic composition is from about 40 kDa to about 120 kDa, kDa to about 110 kDa, or from about 60 kDa to about 100 kDa, or from about 70 kDa to about 90 kDa, or even about 80 kDa.

40. The method of embodiment 39 wherein the thermoplastic composition comprises a plurality of polyetherimide polymer chains wherein up to 10% of the chain weight of the polyetherimide of the thermoplastic composition is from about 40 kDa to about 120 kDa, kDa to about 110 kDa, or from about 60 kDa to about 100 kDa, or from about 70 kDa to about 90 kDa, or even about 80 kDa.

It should be understood that the thermoplastic composition essentially comprises any distribution of polyetherimide chains. The distribution may be a single-rod type, a beep type, a three-point type, or otherwise multiple types. The distribution can be symmetrical (e.g., traditional bell curve) or even distorted. While a honeycomb distribution of polyetherimide chains of different weights is particularly suitable, a mono- or multi-ply distribution is also suitable.

The aggregate of polyetherimides can also be defined in terms of average values. For example, the aggregate of polyetherimides in the thermoplastic composition may have a maximum of 50%, up to 40%, up to 30%, up to 20%, or even up to 10% up to about 50 kDa in the number of polyetherimide chains in the sample To about 15 kDa. ≪ / RTI > Similarly, the aggregate of polyetherimide in the thermoplastic composition can have a maximum of about 50%, up to 40%, up to 30%, up to 20%, or even up to 10% up to about 40 kDa in the number of polyetherimide chains in the sample About 120 kDa, or about 50 kDa to about 110 kDa, or about 60 kDa to about 100 kDa, or about 70 kDa to about 90 kDa, or even about 80 kDa.

41. An article, comprising at least a first and a second amount of a thermoplastic composition fused together with a fused region, wherein the thermoplastic composition comprises a plurality of polyetherimide polymer chains, wherein the thermoplastic composition comprises: (a) Up to 50% of the chain weight of the etherimide comprises a polyetherimide polymer chain having a molecular weight of from about 40 kDa to about 2 kDa; (b) a polyetherimide polymer chain having a molecular weight of from about 40 kDa to about 120 kDa up to 80% of the chain weight of the polyetherimide of the thermoplastic composition; Or (a) and (b).

42. The article of embodiment 41 wherein up to 50% of the chain weight of the polyetherimide of the thermoplastic composition comprises a polyetherimide polymer chain having a molecular weight of from about 40 kDa to about 2 kDa.

43. The article of embodiment 41 wherein up to 30% of the chain weight of the polyetherimide of the thermoplastic composition comprises a polyetherimide polymer chain having a molecular weight of from about 40 kDa to about 2 kDa.

44. The article of embodiment 41 wherein up to 20% of the chain weight of the polyetherimide of the thermoplastic composition comprises a polyetherimide polymer chain having a molecular weight of from about 40 kDa to about 2 kDa.

45. The article of embodiment 42 wherein up to 50% of the chain weight of the polyetherimide of the thermoplastic composition comprises a polyetherimide polymer chain having a molecular weight from about 30 kDa to about 20 kDa.

46. The article of embodiment 41 wherein up to 80% of the chain weight of the polyetherimide of the thermoplastic composition comprises a polyetherimide polymer chain having a molecular weight of from about 40 kDa to about 120 kDa.

47. The article of embodiment 46 wherein up to 60% of the chain weight of the polyetherimide of the thermoplastic composition comprises a polyetherimide polymer chain having a molecular weight of from about 40 kDa to about 120 kDa.

48. The article of embodiment 47 wherein up to 50% of the chain weight of the polyetherimide of the thermoplastic composition comprises a polyetherimide polymer chain having a molecular weight of from about 40 kDa to about 120 kDa.

49. The article of embodiment 48 wherein up to 30% of the chain weight of the polyetherimide of the thermoplastic composition comprises a polyetherimide polymer chain having a molecular weight of from about 40 kDa to about 120 kDa.

Embodiment 50: An article of any one of embodiments 41 to 49, wherein the article is an aircraft part, a medical device, a tray, a container, a laboratory tool, a food or beverage-service article, an automotive part, a construction article, a medical implant, , Ornaments, or any combination thereof.

As a further non-limiting example, an article according to the present disclosure may be used in a variety of applications including, for example, computer and office equipment housings such as monitor housings, portable electronic device housings such as cellular phone housings, A home appliance, a roof, a greenhouse, a solarium, a swimming pool enclosure, a thin walled article such as a housing for an electronic device, and the like. Further examples of articles that may be formed from the present compositions include electrical components such as relays and enclosures, appliances such as laptops, desktops, docking stations, personal digital assistants (PDAs), digital cameras, desktop enclosures and components, For example, components for a base station terminal. Further examples of articles that can be formed from the present compositions include light guides, light guiding panels, lenses, covers, sheets, films, and the like, such as LED lenses, LED covers, and the like.

The thermoplastic composition of the article may also have a Tg in the range of from about 175 to about 235 DEG C, as measured by DSC. The composition may also have a Tg (measured as described) ranging from about 215 [deg.] C to about 221 [deg.] C.

51. A method of forming an article comprising depositing at least first and second amounts of a molten thermoplastic composition comprising a polyetherimide such that at least a portion of the first amount is fused to at least a portion of the second amount, Wherein the thermoplastic composition comprises a plurality of polyetherimide polymer chains, wherein the thermoplastic composition comprises a plurality of polyetherimide polymer chains, wherein the polyetherimide polymer chain of the thermoplastic composition comprises a plurality of polyetherimide polymer chains, Up to 99.9% of the chain weight of the mid-chain comprises a polyetherimide polymer chain having a molecular weight of from about 40 kDa to about 120 kDa.

In such articles, the chain weight of the polyetherimide of the thermoplastic composition may be up to about 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, , 10, or even up to about 5%, of a polyetherimide polymer chain having a molecular weight of from about 40 kDa to about 120 kDa, wherein the remainder of the polyetherimide polymer chain is less than about 40 kDa, Suitably between about 2 kDa and all intermediate values, for example from about 30 kDa to about 5 kDa, from about 25 kDa to about 10 kDa, and all intermediate values.

52. An article formed by lamination, said article comprising: at least first and second portions of a molten thermoplastic composition comprising a polyetherimide, wherein at least a portion of the first amount is present in at least a portion of the second amount Wherein the thermoplastic composition comprises a plurality of polyetherimide polymer chains, wherein up to 50% of the chain weight of the polyetherimide of the thermoplastic composition is less than about 50% of the chain weight of the polyetherimide of the thermoplastic composition, And a polyetherimide polymer chain having a molecular weight of from about 40 kDa to about 2 kDa.

In such articles, a maximum of about 45, 40, 35, 30, 25, 20, 15, 10, 5, 4, 3, 2, or even about 1% of the chain weight of the polyetherimide of the thermoplastic composition And a polyetherimide polymer chain having a molecular weight of from about 40 kDa to about 2 kDa.

As disclosed herein, it should be understood that the distribution of the double-, triple-, or other multiples of molecular weight is not a requirement. As an example, a unipolar (e.g., polydisperse) distribution of molecular weight is also suitable. In some embodiments of the disclosed technique (both unipolar and multibond) where there is a so-called light PEI of from about 2 to about 20 kDa, the presence of at least 1 wt% of such light PEI is considered appropriate, Is increased, the mechanical properties of the final composition may vary. Users of conventional technology will reach the optimal loading of lightweight PEI without difficulty to achieve the desired mechanical properties. As an example, for PEI 3 (described elsewhere herein), 10-15 wt% or more is considered suitable. The interlaminar adhesion can be improved to a relatively high level of lightweight PEI, but other properties may deteriorate below the polymer entanglement molecular weight.

Thus, in a further aspect, the disclosure also provides a method, wherein the method deposits at least first and second amounts of molten thermoplastic composition such that at least a portion of the first amount is fused to at least a portion of the second amount, Thereby forming a fused region of the article. The thermoplastic composition suitably comprises a collection of polyetherimides and comprises up to 99.9% of the chain weight of the polyetherimide, a polyetherimide polymer chain having a molecular weight of from about 40 kDa to about 120 kDa, And a polyetherimide chain having a molecular weight of less than about 40 kDa.

Claims (20)

A method of forming an article,
Depositing at least first and second amounts of the molten thermoplastic composition such that at least a portion of the first amount is fused to at least a portion of the second amount to form a fused region of the article,
Wherein the thermoplastic composition comprises at least first and second populations of polyetherimide and wherein the first and second assemblies have a maximum of about < RTI ID = 0.0 > about <Lt; RTI ID = 0.0 > 100 kDa. ≪ / RTI > The method of claim 1, wherein the thermoplastic composition comprises at least one polyetherimide oligomer. The method of claim 1 or 2, wherein the first and second aggregates differ in weight average molecular weight from about 2 kDa to about 60 kDa as measured by GPC for polystyrene standards. The method according to any one of claims 1 to 3, wherein the weight ratio of the first aggregate of polyetherimide to the second aggregate of polyetherimide is from 100: 1 to 1: 100. The method of claim 1, wherein the weight ratio of the first aggregate of polyetherimide to the second aggregate of polyetherimide is from 10: 1 to 1:10. The method according to any one of claims 1 to 5, wherein the deposition is performed according to a preset pattern. As an article,
At least first and second amounts of the thermoplastic composition fused with the fused region,
Wherein the thermoplastic composition comprises at least a first and a second aggregate of polyetherimides and wherein the at least two aggregates have a weight up to about 100 kDa as measured by gel permeation chromatography (GPC) on polystyrene standards Different in average molecular weight. 8. The article of claim 7, wherein the first and second assemblies differ in weight average molecular weight from about 2 kDa to about 60 kDa as measured by GPC for polystyrene standards. 9. The article of claim 8, wherein the article comprises a polyetherimide oligomer. The article of any one of claims 7 to 9, wherein at least one of the first and second amounts is characterized as a layer. The article of any one of claims 7 to 10, wherein the weight ratio of the first aggregate of polyetherimide to the second aggregate of polyetherimide is from 100: 1 to 1: 100. 12. The article of claim 11, wherein the weight ratio of the first aggregate of polyetherimide to the second aggregate of polyetherimide is from 10: 1 to 1:10. The article of any one of claims 7 to 12, wherein the article is an aircraft component, a medical device, a tray, a container, a laboratory tool, a food or beverage-service article, an automotive component, a construction article, a medical implant, a housing, , ≪ / RTI > or any combination thereof. The article of any one of claims 7 to 13 wherein the thermoplastic composition has a Tg in the range of from about 175 to about 235 ° C as measured by DSC. The article of any one of claims 7 to 14, wherein the article exhibits at least one of interlayer adhesion, tensile modulus, flexural modulus, and elongation at break, which are improved compared to corresponding articles formed from a single assembly of polyetherimide Goods. A method of forming an article,
Depositing a plurality of portions of a molten thermoplastic composition comprising at least a first and a second aggregate of polyetherimides different in weight average molecular weight as measured by gel permeation chromatography (GPC) on a polystyrene standard, ,
Wherein the deposition is performed such that at least some of the plurality of portions of the thermoplastic composition are fused together to form the article. A method of forming an article comprising depositing at least first and second amounts of a molten thermoplastic composition comprising a polyetherimide such that at least a portion of a first amount is fused to at least a portion of a second amount to form a fused Wherein the thermoplastic composition comprises a plurality of polyetherimide polymer chains wherein up to the lower 50% of the chain weight of the polyetherimide of the thermoplastic composition is less than 50% And a polyetherimide polymer chain having a molecular weight of from about 40 kDa to about 2 kDa. A method of forming an article comprising depositing at least first and second amounts of a molten thermoplastic composition comprising a polyetherimide such that at least a portion of a first amount is fused to at least a portion of a second amount to form a fused Wherein the thermoplastic composition comprises a plurality of polyetherimide polymer chains, wherein the thermoplastic composition comprises a plurality of polyetherimide polymer chains, wherein the chain of polyetherimides of the thermoplastic composition Wherein up to the upper 99.9% of the weight comprises a polyetherimide polymer chain having a molecular weight of from about 40 kDa to about 120 kDa. An article comprising at least first and second amounts of a thermoplastic composition that are fused together in a fused region, wherein the thermoplastic composition comprises a plurality of polyetherimide polymer chains, wherein (a) the chain of polyetherimides of the thermoplastic composition (B) up to about 80% of the chain weight of the polyetherimide of the thermoplastic composition is from about 40 kDa to about 2 kDa, and wherein the polyetherimide polymer chain has a molecular weight of from about 40 kDa to about 2 kDa, A polyetherimide polymer chain having a molecular weight of 120 kDa; Or (a) and (b). 20. The article of claim 19, wherein up to 50% of the chain weight of the polyetherimide of the thermoplastic composition comprises a polyetherimide polymer chain having a molecular weight of from about 40 kDa to about 2 kDa.