US20200115501A1 - Branched polyimide compositions, method of manufacture, and uses thereof - Google Patents

Branched polyimide compositions, method of manufacture, and uses thereof Download PDF

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US20200115501A1
US20200115501A1 US16/472,131 US201716472131A US2020115501A1 US 20200115501 A1 US20200115501 A1 US 20200115501A1 US 201716472131 A US201716472131 A US 201716472131A US 2020115501 A1 US2020115501 A1 US 2020115501A1
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branched
polyimide
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branched polyimide
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Roy Ray Odle
Thomas Link Guggenheim
Lioba Maria Kloppenburg
Timothy Edward Long
Joseph Michael DENNIS
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SHPP Global Technologies BV
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Definitions

  • Polyimides and in particular polyetherimides (PEIs), are amorphous, transparent, high performance polymers having a high glass transition temperature. Polyetherimides further have high strength, heat resistance, and modulus, and broad chemical resistance, and thus are widely used in applications as diverse as automotive, telecommunication, aerospace, electrical/electronics, transportation, and healthcare. Moreover, PEIs can be recycled, whereas some PIs are thermosets that cannot be recycled.
  • long-chain branches can influence the melt strength of the polymers, and can reduce the melt viscosity of higher molecular weight polymers for a given processing temperature.
  • long-chain branches can improve shear-thinning and extensional flow processing over linear analogues.
  • polyesters e.g., poly(ethylene terephthalate)
  • long-chain branches can improve melt strength and reduce the rate of crystallinity.
  • a branched polyimide has the formula
  • G is a group having a valence of t, present in an amount of 0.01 to 20 mol %, or 0.1 to 20 mol %, or 0.5 to 10 mol %, or 1.0 to 5 mol %, or 1.5 to 4 mol %, or 0.01 to 2 mol %
  • each Q is independently the same or different, and is a divalent C 1-60 hydrocarbon group
  • each M is independently the same or different, and is —O—, —C(O)—, —OC(O)—, —OC(O)O—, —NHC(O), —(O)CNH—, —S—, —S(O)—, or —S(O) 2 —
  • D is a phenylene
  • each V is independently the same or different, and is a tetravalent C 4-40 hydrocarbon group
  • each R is independently the same or different, and is a C 1-20 divalent hydrocarbon group
  • q is 0 or 1
  • m
  • a method for the manufacture of the branched polyimide includes reacting a polyamine of the formula
  • Another method for the manufacture of a branched polyetherimide includes reacting a polyamine of the formula
  • AM is an alkali metal, to provide the branched polyetherimide, wherein G, Q, M, D, R, V, Z, q, m, d, p, and t are as defined above.
  • a polyimide composition includes 1 to 99 wt %, or 10 to 90 wt %, or 0.1 to 20 wt %, or 0.5 to 10 wt %, or 1 to 5 wt % of a branched polyimide; and 91 to 1 wt %, or 90 to 10 wt %, or 99.9 to 80 wt %, or 99.5 to 90 wt %, or 99 to 95 wt % of the above branched polyimide and a second polyimide that is not the same as the branched polyimide, wherein each amount is based on the total weight of the branched polyimide and the polyimide.
  • a polymer composition includes the polyimide composition; and a second polymer that is not the same as the branched polyimide or the second polyimide.
  • An article includes the branched polyimide, the polyimide composition, or the polymer composition.
  • FIG. 1 is a chart showing dianhydrides according to an embodiment.
  • FIG. 2 is a chart showing diamines according to an embodiment.
  • FIG. 3 is a graph of average branch molecular weight (grams per mole (g/mol), Mb) versus mole percent (mol %) of tris((p-aminophenoxy)phenyl) ethane (TAPE) as measured by size exclusion chromatography-multiple angle light scattering (SEC-MALS) and 1 H NMR spectroscopy.
  • TAPE tris((p-aminophenoxy)phenyl) ethane
  • FIG. 4 is a graph of viscosity (pascal seconds (Pa s), ⁇ ) versus shear rate (radians per second (rad/s), ⁇ ) and shows a correlation between viscosity and shear rate.
  • FIG. 5 is a graph of molecular weight (g/mol) versus mole percent (% BA, TAPE) versus torque (Newton ⁇ meters, N ⁇ m).
  • FIG. 6 is a graph of molecular weight (g/mol) versus mole percent (% BA, TAPE) versus torque (N ⁇ m).
  • FIG. 7 shows photographs of a homogeneous polyetherimide with 1 wt % TAPE via a pre-dissolved amines method (left) and a homogenous polyetherimide with dark gel spots at 1.5 wt % TAPE prepared by without pre-dissolving in amines (right).
  • LCB-PIs long chain branched poly(imides)
  • LCB-PEIs polyetherimides
  • Careful consideration of the reaction conditions and molar ratios permits the use of higher molar ratios of the polyamines without forming an insoluble network during the synthetic steps.
  • LCB-PEIs prepared with 0.5 mole percent (mol %) of polyamine had comparable melt viscosities and processibility as compared to PEIs without the long-chain branching.
  • Such properties are especially useful in the manufacture of thin-wall parts, where high-flow properties, especially low melt viscosity under the high shear conditions are important in injection molding.
  • the LCB-PI and LCB-PEI can satisfy this criterion and fare better than the linear chained counterpart of the same molecular weight.
  • polymers display shear-thinning property being a non-Newtonian fluid.
  • An LCB-PI and LCB-PEI can shear thin faster (akin to any branched polymer over its linear counterpart), giving lower viscosity and subsequently higher flow rates with less processing demands. While the viscosity under shear can be lowered for linear PI or PEI by either increasing the temperature or using lower molecular weight polymers, such solutions can lead to degradation at high heat or lower impact properties of the molded materials, respectively.
  • the LCB-PI is a branched polyimide of formula (1) or (1′).
  • G is a group having a valence of t, present in an amount of 0.01 to 20 mol %, or 0.1 to 20 mol %, or 0.5 to 10 mol %, or 1.0 to 5 mol %, or 1.5 to 4 mol %, or 0.01 to 2 mol %, and q is 0 or 1, m is 0 or 1, d is 0 or 1, p is 1 or 2, t is 2 to 6, preferably 2 to 4.
  • t is 2, and G is —O—, —C(O)—, —OC(O)—, —(O)CO—, —NHC(O), —(O)CNH—, —S—, —S(O)—, —S(O) 2 —, or —P(R a )(O)— (wherein R a is a C 1-8 alkyl or C 6-12 aryl).
  • t is 3 and G is nitrogen, phosphorus, or P(O).
  • G is a C 1-60 hydrocarbon group having a valence of t.
  • G is —O— when m is 0, pentavalent P(O), a C 6-60 hydrocarbon having at least one aromatic group, for example a C 6-40 aromatic hydrocarbon group, a C 2-20 aliphatic group, a C 4-8 cycloaliphatic group, a C 3-12 heteroarylene, or a polymer moiety; or G is —O—, —S(O) 2 —, pentavalent P(O), a C 6-20 aromatic hydrocarbon group, a C 2-20 aliphatic group, or a C 4-8 cycloaliphatic group.
  • G is —O—, pentavalent P(O), or a C 6-50 hydrocarbon having at least one aromatic group.
  • G can be a saturated C 2-20 aliphatic group, C 3-12 heteroarylene or a polymeric moiety, for example an amino resin such as a urea-formaldehyde, a melamine-formaldehyde, or other resin having active amine groups.
  • each Q is independently the same or different, and is a divalent C 1-60 hydrocarbon group.
  • Q is a C 6-20 arylene, a C 1-20 alkylene, or a C 3-8 cycloalkylene.
  • Q is a C 6-20 arylene.
  • each M is independently the same or different, and is —O—, —C(O)—, —OC(O)—, —OC(O)O—, —NHC(O), —(O)CNH—, —S—, —S(O)—, —S(O) 2 —.
  • M is —O—, —C(O)—, —OC(O)—, —P(R a )—, or —P(O)R a —.
  • M is —O—, —C(O)—, —OC(O)—, —P(R a )—, or —P(O)R a — wherein R a is a C 1-8 alkyl or C 6-12 aryl.
  • each D is phenylene.
  • each D is the same or different, and is m-phenylene or p-phenylene.
  • each V is independently the same or different, and is a tetravalent C 4-40 hydrocarbon group.
  • V is a C 6-20 aromatic hydrocarbon group.
  • Exemplary aromatic hydrocarbon groups include any of those of the formulas (2)
  • W is —O—, —S—, —C(O)—, —SO 2 —, —SO—, —P(R a )( ⁇ O)— wherein R a is a 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 perfluoroalkylene groups), or a group of the formula —O—Z—O— as described in formula (1a) and (1a′) below.
  • each R is independently the same or different, and is a C 1-20 divalent hydrocarbon group.
  • each R can be the same or different, and is a divalent organic group, such as a C 6-20 aromatic hydrocarbon group or a halogenated derivative thereof, a straight or branched chain C 2-20 alkylene group or a halogenated derivative thereof, a C 3-8 cycloalkylene group or halogenated derivative thereof, in particular a divalent group of any of formulas (3)
  • Q 1 is —O—, —S—, —C(O)—, —SO 2 —, —SO—, —P(R a )( ⁇ O)— wherein R a is a 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 perfluoroalkylene groups), or —(C 6 H 10 ) z — wherein z is an integer from 1 to 4.
  • R is m-phenylene, p-phenylene, or a diarylene sulfone.
  • each n is independently the same or different, and is 1 to 1,000, preferably 2 to 500, or 3 to 100, provided that the total of all values of n is greater than 4, preferably greater than 10, more preferably greater than 20, or greater than 50, or greater than 100, or greater than 250, or 4 to 50, or 10 to 50, or 20 to 50, or 4 to 100, or 10 to 100, or 20 to 100.
  • the branched polyimide of formula (1) or (1′) can be a branched polyetherimide of formula (1a), preferably (1a′)
  • the group Z in —O—Z—O— of formula (1a) and (1a′) is a divalent organic group, and can be an aromatic C 6-24 monocyclic or polycyclic moiety optionally substituted with 1 to 6 C 1-8 alkyl groups, 1 to 8 halogen atoms, or a combination thereof, provided that the valence of Z is not exceeded.
  • Exemplary groups Z include groups derived from a dihydroxy compound of formula (4)
  • R a and R b can be the same or different and are a halogen atom or a monovalent C 1-6 alkyl group, for example; p′ and q′ are each independently integers of 0 to 4; c is 0 to 4; and X a is a bridging group connecting the hydroxy-substituted aromatic groups, where the bridging group and the hydroxy substituent of each C 6 arylene group are disposed ortho, meta, or para (preferably para) to each other on the C 6 arylene group.
  • the bridging group X a can be a single bond, —O—, —S—, —S(O)—, —S(O) 2 —, —C(O)—, or a C 1-18 organic bridging group.
  • the C 1-18 organic bridging group can be cyclic or acyclic, aromatic or non-aromatic, and can further comprise heteroatoms such as halogens, oxygen, nitrogen, sulfur, silicon, or phosphorous.
  • the C 1-18 organic group can be disposed such that the C 6 arylene groups connected thereto are each connected to a common alkylidene carbon or to different carbons of the C 1-18 organic bridging group.
  • a specific example of a group Z is a divalent group of formula (4a)
  • J is —O—, —S—, —C(O)—, —SO 2 —, —SO—, or —C y H 2y — wherein y is an integer from 1 to 5 or a halogenated derivative thereof (including a perfluoroalkylene group).
  • Z is a derived from bisphenol A, such that J in formula (4a) is 2,2-isopropylidene.
  • R is m-phenylene or p-phenylene, bis(4,4′-phenylene)sulfone, bis(3,4′-phenylene)sulfone, or bis(3,3′-phenylene)sulfone.
  • Z can be a divalent group of formula (4a).
  • R is m-phenylene or p-phenylene and Z is a divalent group of formula (4a) and J is 2,2-isopropylidene.
  • the branched polyimide can be a copolymer, for example a polyetherimide sulfone copolymer comprising structural units of formulas (1), (1′), (1a), or (1a′) wherein at least 50 mol % of the R groups are of formula (3) wherein Q 1 is —SO 2 — and the remaining R groups are independently p-phenylene or m-phenylene or a combination thereof; and Z is 2,2′-(4-phenylene)isopropylidene.
  • the branched polyetherimide copolymer optionally comprises additional structural imide units, for example imide units wherein V is of formula (2a) wherein R and V are as described in formula (2a), for example V is
  • W is a single bond, —O—, —S—, —C(O)—, —SO 2 —, —SO—, —P(R a )( ⁇ O)— wherein R a is a 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 groups).
  • These additional structural imide units can comprise less than 20 mol % of the total number of units, or 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 some embodiments, no additional imide units are present in the branched polyimides other than polyetherimide units.
  • the branched polyimides (which as indicated above include polyimides (1) and (1′) and the branched polyetherimides (1a) and (1a′)), can be prepared by methods known in the art, including a polycondensation or ether-forming polymerization. In any process, the appropriate amount of a polyamine of formula (8), preferably of formula (8′)
  • Exemplary polyamines (8) and (8′) can include any of formulas (8a)-(8t).
  • Z is a divalent C 1-600 hydrocarbon group, or a C 6-40 aromatic hydrocarbon group, a C 2-20 aliphatic group, or a C 4-8 cycloaliphatic group.
  • An exemplary method for the synthesis of the polyamine of formulas (8) and (8′) uses a two-step sequence as exemplified in Examples 1 and 2.
  • the first step is a nucleophilic aromatic substitution of a halogenated aromatic nitro compound (e.g., 1-chloro-4-nitrobenzene) with a polyphenol (e.g., 1,1,1-tris(4-hydroxyphenyl) ethane) that is converted to a polyphenoxide in-situ, providing a sufficiently nucleophilic oxygen to displace the activated halide.
  • a halogenated aromatic nitro compound e.g., 1-chloro-4-nitrobenzene
  • a polyphenol e.g., 1,1,1-tris(4-hydroxyphenyl) ethane
  • a polar aprotic solvent e.g., dimethylacetamide
  • a poly(nitrophenyl) compound e.g., 1,1,1-tris((p-nitrophenoxy)phenyl) ethane.
  • the second step is a reduction of the poly(nitrophenyl) compound to the polyamine of formula (10) using, for example, a palladium catalyst with a reducing agent, an iron-based catalyst, vasicine, zinc, samarium, and hydrazine.
  • the branched polyimide can be prepared by polycondensation, which includes an imidization of a dianhydride of formula (9) or formula (9a)
  • the polyamine (8), preferably (8′) can be present in the reaction in an amount of 0.01 to 20 mol %, or 0.1 to 20 mol %, or 0.5 to 10 mol %, or 1.0 to 5 mol %, or 1.5 to 4 mol %, or 0.01 to 2 mol % to achieve increased branching and increased PDI.
  • Exemplary dianhydrides include 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; 2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl]propane dianhydride; 4,4′-bis(2,3-dicarboxyphenoxy)diphenyl ether dianhydride; 4,4′-bis(2,3-dicarboxyphenoxy)diphenyl sulfide dianhydride; 4,4′-bis(2,3-dicarboxyphenoxy)benzophen
  • Still other specific dianhydrides include any of those as shown in FIG. 1 , wherein Y′ is —C(O)—, —C(CF 3 ) 2 —, —C(CH 3 ) 2 —, —SO 2 —, or —C ⁇ C—.
  • organic diamines include hexamethylenediamine, polymethylated 1,6-n-hexanediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, 1,12-dodecanediamine, 1,18-octadecanediamine, 3-methylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, 4-methylnonamethylenediamine, 5-methylnonamethylenediamine, 2,5-dimethylhexamethylenediamine, 2,5-dimethylheptamethylenediamine, 2, 2-dimethylpropylenediamine, N-methyl-bis (3-aminopropyl) amine, 3-methoxyhexamethylenediamine, 1,2-bis(3-aminopropoxy) ethane, bis(3-aminopropyl) sulfide, 1,4-cyclohexanediamine, bis-(4-aminocyclohe
  • the organic diamine is m-phenylenediamine, p-phenylenediamine, 4,4′-diaminodiphenyl sulfone, or a combination thereof.
  • Still other organic diamines can include any of those as shown in FIG. 2 , wherein A is —O—, —CH 2 —, —CH 2 CH 2 —, —SO 2 , —C(CF 3 ) 2 —, —S—, —S—S—, —CH ⁇ CH—, —C(O)—, —NH—, or —C(CH 3 ) 2 —; A 1 is —Cl, —OH, —OCH 3 , —CH 3 , or —CH 2 CH 3 ; A 2 is —CH 3 , —CF 3 , or —SO 3 H; A 3 is —CH 3 or —OH; and n′ is 1, 2, or 3.
  • An endcapping agent can be present during imidization, in particular a monofunctional compound that can react with an amine or anhydride.
  • exemplary compounds include monofunctional aromatic anhydrides such as phthalic anhydride, an aliphatic monoanhydride such as maleic anhydride, or monofunctional aldehydes, ketones, esters isocyanates, aromatic monoamines such as aniline, or C 1 -C 18 linear or cyclic aliphatic monoamines.
  • a monofunctional bisphthalimide can also be added before or during imidization.
  • the amount of endcapping agent that can be added depends on the desired amount of chain terminating agent, and can be, for example, more than 0 to 10 mole percent (mol %), or 0.1 to 10 mol %, or 0.1 to 6 mol %, based on the moles of endcapping agent and amine or anhydride reactant.
  • a catalyst can be present during imidization.
  • exemplary catalysts include sodium aryl phosphinates, guanidinium salts, pyridinium salts, imidazolium salts, tetra(C 7-24 arylalkylene) ammonium salts, dialkyl heterocycloaliphatic ammonium salts, bis-alkyl quaternary ammonium salts, (C 7-24 arylalkylene)(C 1-16 alkyl) phosphonium salts, (C 6-24 aryl)(C 1-16 alkyl) phosphonium salts, phosphazenium salts, and combinations thereof.
  • the anionic component of the salt is not particularly limited, and can be, for example, chloride, bromide, iodide, sulfate, phosphate, acetate, maculate, tosylate, and the like.
  • a combination of different anions can be used.
  • a catalytically active amount of the catalyst can be determined by one of skill in the art without undue experimentation, and can be, for example, more than 0 to 5 mol % percent, or 0.01 to 2 mol %, or 0.1 to 1.5 mol %, or 0.2 to 1.0 mol % based on the moles of polyamine (8) or (8′) and organic diamine (10).
  • T can be a group of the formula O—Z—O as described in formula (1a) and (1a′), and G is a C 1-60 hydrocarbon group having a valence of 2, or a C 6-40 aromatic hydrocarbon group, a C 2-20 aliphatic group, or a C 4-8 cycloaliphatic group, and x′′, y′′, z′′, and p′′ each have a value of n as described in formulas (1), (1′), (1a), and (1a′).
  • Polymerization is generally carried out in a solvent, for example relatively non-polar solvents with a boiling point above 100° C., or above 150° C., for example o-dichlorobenzene, dichlorotoluene, 1,2,4-trichlorobenzene, diphenyl sulfone, or a monoalkoxybenzene such as anisole, veratrole, diphenylether, or phenetole.
  • a solvent for example relatively non-polar solvents with a boiling point above 100° C., or above 150° C.
  • o-dichlorobenzene dichlorotoluene, 1,2,4-trichlorobenzene, diphenyl sulfone, or a monoalkoxybenzene such as anisole, veratrole, diphenylether, or phenetole.
  • Ortho-dichlorobenzene and anisole can be particularly mentioned.
  • the polymerization is generally at least 110° C.
  • Atmospheric or super-atmospheric pressures can be used, for example up to 5 atmospheres, to facilitate the use of high temperatures without causing solvent to be lost by evaporation.
  • Effective times depend on the particular reactants and reaction conditions, and can be 0.5 hours to 3 days, for example, generally for 0.5 to 72 hours, preferably 1 to 30 or 1 to 20 hours.
  • the reaction is complete 20 hours or less, preferably 10 hours or less, more preferably 3 hours or less.
  • compositions can be obtained by pre-dissolving the polyamine (8), preferably (8′), and the diamine (10) before adding the dianhydride (9) or (9a), or before adding the diamine/polyamine to the dianhydride.
  • the catalyst can be added any time during the reaction between the polyamine (8), preferably (8′), and organic diamine (10), and the dianhydride (9) or (9a) continuously or in portions during the course of the reaction.
  • the catalyst is added after pre-dissolution the polyamine (8), preferably (8′), and organic diamine (10), with the dianhydride (9) or (9a).
  • the solvent, polyamine (8), preferably (8′), diamine (10), dianhydride (9) or (9a), and optional components (e.g., catalyst and endcapping agent) (i.e., the reaction mixture) can be combined in amounts such that the total solids content the during the reaction to form the branched polyimide are 5 to 70 weight percent (wt %), preferably 10 to 70 wt %, more preferably 20 to 70 wt %.
  • Total solids content expresses the proportion of the reactants as a percentage of the total weight including liquids present in the reaction at any given time.
  • the reaction mixture can comprise 200 parts per million by weight (ppm) or less of water, 100 ppm or less of water, or 50 ppm or less of water, or to 25 ppm or less of water, based on parts by weight of the reaction mixture.
  • ppm parts per million by weight
  • a molar ratio of dianhydride (9) or (9a) to a combination of polyamine (8), preferably (8′), and diamine (10) of 0.9:1 to 1.1:1, or 1:1 can be used. While other ratios can be used, a slight excess of dianhydride or diamine may be desirable.
  • a proper stoichiometric balance between the dianhydride and combination of polyamine (8), preferably (8′), and diamine (10) is maintained to allow for the production of the desired molecular weight of the polymer, or prevent the formation of polymer with significant amounts of amine end groups.
  • imidization proceeds via forming an initial reaction mixture having a targeted initial molar ratio of dianhydride (9) or (9a) to a combination of polyamine (8), preferably (8′), and diamine (10); heating the reaction mixture to a temperature of at least 100° C.
  • the amount can be more than 0 to 10 mol % based on the total amount of dianhydride (9) or (9a). If an anhydride-containing endcapping agent is used, the amount can be in the range of more than 0 to 20 mol %, or 1 to 10 mol % based on the amount of the polyamine (8), preferably (8′), and diamine (10) combined. In general, due to the presence of the polyamines, an anhydride-containing endcapping agent is used to decrease the number of amine end groups in the branched polyimides and polyetherimides. The endcapping agent can be added at any time.
  • the endcapping agents are mixed with or dissolved into reactants having the similar functionality.
  • anhydride-containing endcapping agent can be combined with dianhydride (9) or (9a).
  • dianhydride (9) or (9a) an anhydride-containing endcapping agent
  • the quantity of amine functionality [2 ⁇ diamine moles]+[t ⁇ polyamine, moles wherein t is the number of reactive amino groups]
  • the quantity of amine functionality [2 ⁇ diamine moles]+[t ⁇ polyamine, moles wherein t is the number of reactive amino groups]
  • the stoichiometry condition of the polymerization reaction mixture can be analyzed, and the stoichiometry corrected if needed to provide a stoichiometry within +0.2 mol % of a stoichiometry of 1:1.
  • the branched polyimides can be synthesized by an ether-forming polymerization, which proceeds via an imidization, i.e., reaction of the polyamine of formula (8), preferably (8′), and the diamine of formula (10) with an anhydride of formula (11)
  • the polyamine (8), preferably (8′), can be present in the reaction in an amount of 0.01 to 20 mol %, or 0.1 to 20 mol %, or 0.5 to 10 mol %, or 1.0 to 5 mol %, or 1.5 to 4 mol %, or 0.01 to 2 mol % to achieve increased branching.
  • An optional catalyst or optional monofunctional chain terminating agent as described above can be present during imidization.
  • AM is an alkali metal and Z is as defined above, to provide the branched polyetherimide.
  • Polymerization conditions effective to provide the branched polyimides are generally known, and can be conducted in a solvent as described above. This polymerization can also be conducted in the melt, for example at 250 to 350° C., where a solvent is generally not present.
  • mPD meta-phenylenediamine
  • a polyamine of formula (8′) for example a triamine such as 2,4,4′-triaminodiphenyl ether (TADE) can be reacted with 4Cl-PA to produce a reactive tris-imide branching agent.
  • the reactive tris-imide branching agent can then be reacted with the alkali metal salt of a dihydroxy aromatic compound (13) to provide the branched polyimide.
  • the intermediate bis(phthalimide) of formula (12a) is prepared by reacting Cl-PAMI with BPA, which can then be reacted with the alkali metal salt of a dihydroxy aromatic compound of formula (13) to provide the branched polyimide. This embodiment is shown in Scheme 2b.
  • the branched polyimide can have one or more of the following properties.
  • the branched polyimide can have a T g greater than 100° C., preferably 100 to 395° C., more preferably 180 to 280° C., even more preferably 200 to 250° C.
  • the branched polyimide can have an average branch molecular weight (M b ) of 12,000 to 50,000 grams per mole (g/mol), preferably 15,000 to 40,000 g/mol, more preferably 23,000 to 38,000 g/mol, as determined by size exclusion chromatography or proton nuclear magnetic resonance.
  • the branched polyimide can have a viscosity of greater than 25,000 pascal-seconds at a frequency of 0.1 radians per second.
  • the branched polyimide can have a polydispersity (PDI) of 1.5 to 3.0, as determined by size exclusion chromatography multi-angle light scattering (SEC-MALS).
  • the branched polyimide 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.
  • the branched polyimide can have a weight average molecular weight (M w ) of 1,000 to 150,000 g/mol, or 10,000 to 80,000 g/mol, or 20,000 to 60,000 g/mol, as measured by gel permeation chromatography (GPC), using polystyrene standards, light scattering, and/or triple point detector.
  • M w weight average molecular weight
  • the branched polyimide can have an intrinsic viscosity greater than 0.2 deciliters per gram (dL/g), or, more preferably, 0.35 to 0.7 dL/g, as measured in m-cresol at 25° C.
  • the branched polyimide can have less than 5 wt %, or less than 3 wt %, or less than 1 wt %, or less than 0.5 wt % of a gel.
  • the gel can be observed visually. In an embodiment, no gel is observable.
  • the branched polyimide can have a UL94 rating of V-1 or better, as measured following the procedure of Underwriter's Laboratory Bulletin 94 entitled “Tests for Flammability of Plastic Materials for Parts in Devices and Appliances” (ISBN 0-7629-0082-2), Fifth Edition, Dated Oct. 29, 1996, incorporating revisions through and including Dec. 12, 2003.
  • the branched polyimide has a UL94 rating of V-0 or V-1 at a thickness of 0.2, 0.3, 0.5, 0.6, 0.75, 0.9, 1, 1.2, 1.5, 2, 2.5, or 3 mm.
  • the branched polyimide has a UL94 rating of V-0 at a thickness of 0.3, 0.5, 0.75, 0.9, 1, 1.5, 2, or 3 mm. In a preferred embodiment, the branched polyimide has a UL94 rating of V-0 at a thickness of 0.5 mm or of 1.5 mm. In another preferred embodiment, the branched polyimide can have a flame retardance that is greater than or equal to the same polyimide manufactured without the polyamine (8) or (8′).
  • the polyamines (8), preferably (8′), and diamines (10) are reacted in combination, wherein the polyamine is present in an amount of 0.01 to 20 mol %, or 0.1 to 20 mol %, or 0.5 to 10 mol %, or 1.0 to 5 mol %, or 1.5 to 4 mol %, or 0.01 to 2 mol % to achieve increased branching and increased PDI.
  • both branched and unbranched poly(imides) are formed, to provide a polyimide composition comprising the branched polyimides and a second polyimide that is not the same as the branched polyimide.
  • This second polyimide is generally an unbranched polyimide that comprises more than 1, for example 5 to 1000, or 5 to 500, or 10 to 100, structural units of formula (15)
  • V and R are as described in formula (1) and (1′). It is also possible to combine the branched polyimide or polyimide composition with a second polyimide that is separately manufactured, and contains a different degree of branching or no branching, to obtain the polyimide composition.
  • the polyimide composition includes 1 to 99 wt %, or 10 to 90 wt %, or 0.1 to 20 wt %, or 0.5 to 10 wt %, or 1 to 5 wt % of a branched polyimide and 99 to 1 wt %, or 90 to 10 wt %, or 99.9 to 80 wt %, or 99.5 to 90 wt %, or 99 to 95 wt % of a second polyimide.
  • both branched and unbranched poly(etherimides) can be formed, to provide a polyetherimide composition comprising the branched polyetherimides (1a) or (1a′) and a second polyetherimide that is not the same as the branched polyetherimides.
  • This second polyetherimide is generally an unbranched polyetherimide that comprises more than 1, for example 5 to 1000, or 5 to 500, or 10 to 100, structural units of formula (16)
  • the polyetherimide composition includes 1 to 99 wt %, or 10 to 90 wt %, or 0.1 to 20 wt %, or 0.5 to 10 wt %, or 1 to 5 wt % of a branched polyetherimide (1a) or (1a′) and 99 to 1 wt %, or 90 to 10 wt %, 99.9 to 80 wt %, or 99.5 to 90 wt %, or 99 to 95 wt % of a second polyetherimide.
  • polyimide composition or the polyetherimide compositions can include 1 to 99 wt % of the polyimide or polyetherimide composition and 1 to 99 wt % of the third polymer, or 10 to 90% of the polyimide or polyetherimide composition and 10 to 90 wt % of the third polymer.
  • third polymers include a polyacetal, poly(C 1-6 alkyl)acrylate, polyacrylamide, polyacrylonitrile, polyamide, polyamideimide, polyanhydride, polyarylene ether, polyarylene ether ketone, polyarylene ketone, polyarylene sulfide, polyarylene sulfone, polybenzothiazole, polybenzoxazole, polybenzimidazole, polycarbonate, polyester, poly(C 1-6 alkyl)methacrylate, polymethacrylamide, cyclic olefin polymer, polyolefin, polyoxadiazole, polyoxymethylene, polyphthalide, polysilazane, polysiloxane, polystyrene, polysulfide, polysulfonamide, polysulfonate, polythioester, polytriazine, polyurea, polyurethane, vinyl polymer, or a combination comprising at least one of the foregoing.
  • the branched polyimide, the polyimide composition, the polyetherimide composition, and the polymer composition can include various additives ordinarily incorporated into compositions of this type, with the proviso that any additive is selected so as to not significantly adversely affect the desired properties of the composition.
  • additives include antioxidants, thermal stabilizers, light stabilizers, ultraviolet light (UV) absorbing additives, quenchers, plasticizers, lubricants, mold release agents, antistatic agents, visual effect additives such as dyes, pigments, and light effect additives, flame resistances, anti-drip agents, and radiation stabilizers.
  • additives include carbon nanotubes, exfoliated nanoclays, carbon nanowires, carbon nanospheres, carbon-metal nanospheres, carbon nanorods, carbon-metal nanorods, nanoparticles, or insoluble polymers. Combinations of additives can be used. The foregoing additives can be present individually in an amount from 0.005 to 10 wt %, or combined in an amount from 0.005 to 20 wt %, preferably 0.01 to 10 wt %, based on the total weight of the composition. Particulate fillers and reinforcing fillers can also be present.
  • a wide variety of articles can be manufactured using the branched polyimide, the polyimide compositions, the polyetherimide compositions, and the polymer compositions, for example articles of utility in automotive, telecommunication, aerospace, electrical/electronics, battery manufacturing, wire coatings, transportation, food industry, and healthcare applications.
  • Such articles can include films, fibers, foams (both open- and closed-cell foams), thin sheets, small parts, coatings, fibers, preforms, matrices for polymer composites, or the like.
  • the article is an open- or closed-cell foam, preferably a closed-cell foam.
  • the articles can be extruded or molded, for example injection molded.
  • the articles can be made by an additive manufacturing method, for example three dimensional printing.
  • Components for electronic devices and components for sterilizable medical articles are preferably mentioned.
  • Thin-wall components manufactured by injection molding are also preferred, such as a wall having a thickness from 0.1 to 10 millimeters (mm), or 0.2 to 5 mm, or 0.5 to 2 mm.
  • a film can be manufactured by solution-casting or melt processing the branched polyimide, the polyimide compositions, the polyetherimide compositions, and the polymer compositions described herein.
  • polyimides and polyetherimides are further illustrated by the following non-limiting examples.
  • Table 1 list components that are used in the examples. Unless specifically indicated otherwise, the amount of each component is in weight percent in the following examples, based on the total weight of the composition.
  • Carbon nuclear magnetic resonance ( 13 C NMR) spectroscopy characterization was performed on a Varian Unity 400 at 100 MHz in deuterated chloroform.
  • T g and T m Glass transition temperature (T g ) and melting temperature (T m ) were determined using Differential Scanning Calorimetry (DSC) according to ASTM D3418. The test was performed using a TA Q1000 DSC instrument. In a typical procedure, a polymer sample (10-20 milligrams) was heated from 40 to 400° C. at a rate of 20° C./min, held at 400° C. for 1 minute, cooled to 40° C. at a rate of 20° C./min, then held at 40° C. for 1 minute, and the above heating/cooling cycle was repeated. The second heating cycle is usually used to obtain the T g and T m .
  • DSC Differential Scanning Calorimetry
  • Average branch molecular weight was determined by size exclusion chromatography (SEC) and 1 H NMR spectroscopy.
  • Chloroform size exclusion chromatography (SEC) provided absolute molecular weights using a Waters 1515 Isocratic HPLC Pump and Waters 717 plus Autosampler with Waters 2414 refractive index and Wyatt MiniDAWN MALS detectors (flow rate 1.0 mL min ⁇ 1 ).
  • Weight average molecular weight (M w ) was determined by SEC or determined by GPC using polystyrene standards (or a light scattering detector in combination with a refractive index detector, or a triple detector).
  • Torque was determined using a HaakeTM torque rheometer from Thermo Scientific.
  • 1,1,1-tris(4-hydroxyphenyl) ethane (20 g, 65.3 millimoles (mmol)), potassium carbonate (45.1 g), dimethylacetamide (115 milliliter (mL)), and toluene (58 mL) were charged to a three-necked, 500-mL, round-bottomed flask.
  • a Dean-Stark trap with condenser, glass stir rod with Teflon blade and glass bearing, and rubber septa were attached to each of the three necks, respectively. Purging the whole setup with nitrogen for 20 minutes (min) provided an inert atmosphere.
  • the round-bottomed flask was lowered into a 180° C.
  • Tris((p-nitrophenoxy)phenyl) ethane (60 g, 89.6 mmol), 10 wt % palladium over carbon (10 g), and tetrahydrofuran (200 mL) were charged to a two-necked, round-bottomed, 500 mL flask.
  • the flask was equipped with a condenser and addition funnel and subsequently purged with nitrogen for 20 minutes.
  • a solution of hydrazine (537.6 mmol) in tetrahydrofuran (70 mL) was added to the addition funnel. Under a constant nitrogen purge, the round-bottomed flask was heated to 80° C. Over the course of 1 h, the hydrazine solution was added dropwise to the round-bottomed flask. After addition, the reaction was maintained at 80° C. and reflux for several hours until the reaction was completed (98% yield).
  • TAPB tris(p-aminophenyl)benzene
  • the synthesis of 1,3,5-triphenylbenzene, and related derivatives is by an acid catalyzed cyclotrimerization of acetophenone or a derivative thereof, which provides a one-step method for making a triamine without hydrogenation of a nitro derivative.
  • the trimerization of 4-amino acetophenone to give 1,3,5-tris(4-aminophenyl)benzene in a one-pot reaction is low yielding ( ⁇ 5%) due to the unfavorable side reaction which yields a polyamine. This can be overcome by protecting the amine group during the reaction. Protecting the amine by preparing an ammonium salt results in an increase in product yield.
  • Tris(p-aminophenyl)benzene (TAPB) is synthesized from an ammonium salt of 4-amino acetophenone (4-AA), as shown in Scheme 7.
  • a purified yellow product is obtained after flash column chromatography on silica gel with ethyl acetate and hexanes as eluents (elution gradient of 0-40% ethyl acetate over 25 minutes), to obtain the TAPB ( ⁇ 20% yield).
  • a synthesis of a 45 kg/mol polyetherimide branched with 1 mol % of TAPE follows as an example.
  • TAPE (0.12 g, 0.34 mmol)
  • m-phenylene diamine (5.52 g, 51.0 mmol)
  • o-dichlorobenzene 75 mL
  • the flask was then equipped with a rubber septum, glass stir rod with Teflon blade, and Dean-Stark trap.
  • a condenser completed the set up on the Dean-Stark trap, and the contents purged with nitrogen for 20 minutes.
  • the round-bottomed flask was then heated to 100° C.
  • Example 6 The synthetic procedure of Example 6 was followed to prepare larger batches of long-chain branched polyetherimides. Specifically, a 500 mL, 3-neck round, bottom-flask connected to a stirrer and a Dean-Stark trap was charged with mPD (16.8 g, 155 mmol) and TAPE via an addition funnel. Degassed oDCB (120 mL) was then added and residual solids from the sides of the flask were rinsed into the solution. While stirring, the flask was lowered into an oil bath pre-heated to 80° C. The mixture of amines was stirred for 30 minutes under N 2 , and the temperature was slowly increased to 100° C. over the course of 15 minutes.
  • the polymer media is found to be rich in mPD by 0.5-1 mol %, then an appropriate additional amount of BPA-DA can be added.
  • the temperature is then lowered to 170° C. and after 24 hours of heating, a second stoichiometric analysis is performed to evaluate if stoichiometric conditions are met.
  • the polymer is then let to heat for an additional 24 h if desired.
  • the reaction product is subsequently isolated by precipitation with hexanes (2-3 L) in an industrial blender or in the vessel of a Haake rheometer.
  • Table 2b shows the absolute M w for the same PEIs, as determined by a triple point detector in chloroform.
  • T g glass transition temperature
  • FIG. 4 shows the viscosity profiles of the LCB-PEIs having various branching densities.
  • a second series of LCB-PEIs with varying amounts of TAPE were prepared on a small scale (ca. 4 g). Samples were prepared with 0, 0.3, 0.6, 1.0 and 3.0 mol % of TAPE, and each sample included 3.07 mol % of an endcapping agent. The solutions obtained were homogeneous, with the exception of the LCB-PEI prepared using 3.0 mol % TAPE, which was a dark brown gel-like material a few millimeters wide.
  • Table 5 shows the apparent weight average molecular weight (Apparent M w ), absolute weight average molecular weight (Absolute M w ), polydispersity (PDI), and PDI*, respectively, obtained for the second series of LCB-PEIs prepared with different amounts of TAPE.
  • Table 5 shows an exponential increase in the M w correlated to an increase in the amount of branching agent. This increase is also reflected in the polydispersity index (PDI) and PDI* values, which indicated a broader M w distribution and more branching, respectively, as the amount of TAPE is increased in the samples.
  • PDI polydispersity index
  • PDI* polydispersity index
  • LCB-PEIs with varying amounts of TAPE were prepared on a larger scale (ca. 80 g).
  • LCB-PEIs were prepared with 0, 0.5, and 1.5 mol % TAPE, and each sample included 3.07 mol % of an endcapping agent.
  • the control sample (0 mol % TAPE) was a clear amber solution, while the samples prepared with 0.5 and 1.5 mol % TAPE were dark gels interspersed throughout the solution media. These gels were found to be insoluble even in a 30% hexafluoroisopropanol in methylene chloride solution.
  • the torque was measured after 15 minutes for each of the LCB-PEIs of the third series of samples.
  • the torque increased based on the increase in M w , which in turn was as a result of higher incorporation of TAPE loading ( FIG. 5 ).
  • LCB-PEIs were prepared on a smaller scale (ca. 4 g).
  • the LCB-PEIs each included 1 wt % of TAPE, with variations between the M w for each of the PEIs.
  • Three of the samples were prepared from amines that were pre-dissolved in a heated oDCB solution, whereas the other three samples were prepared by way of a “regular addition”-all reagents were combine in oDCB and then heated with stirring. The appearance of the resulting polymer mixtures after reaching stoichiometric conditions were evaluated and physical properties were identified by GPC. These results are shown in Table 6.
  • the polymer mixtures prepared via the pre-dissolved amines method appeared homogeneous and lighter in color, and gels did not form.
  • the M w of the PEIs prepared by the pre-dissolved amines method were heavier than the PEIs prepared by the regular addition method by 4 to 9 kg/mol.
  • the GPC and torque data are displayed in FIG. 6 .
  • the M w of the LCB-PEIs obtained with 1 mol % TAPE using the pre-dissolved amines method is similar to the data obtained for the LCB-PEIs prepared with 1.5 mol % TAPE using the regular addition method. This further validates that the pre-dissolved amines method provides more efficient branching, which also translated into a decreased amount of gel formation. Pictures of the polymer media at the end of these reactions are shown in FIG. 7 .
  • LCP-PEIs with varying degrees of branching were synthesized at a targeted M w by the incorporation of additional amounts of endcapping agent (phthalic anhydride) to cap the additional endgroups introduced by the TAPE branching agent.
  • endcapping agent phthalic anhydride
  • a series of LCB-PEIs were prepared with 0.3, 0.5, 1.0, and 1.5 mol % TAPE on an 80 g scale by pre-dissolving the amines in hot oDCB followed by the addition of anhydrides. The polymers were heated for 2 days under stoichiometric conditions and then precipitated as white flakes in hexanes in a large industrial blender.
  • M w (g/mol) PDI* PDI 0 54,437 1.597 2.08 0.3 52,087 1.654 2.10 0.5 48,203 1.674 2.11 1.0 55,434 1.857 2.31 1.5 48,770 1.916 2.35
  • M w is from integration of the major GPC trace, and excluding the smaller low M w peaks.
  • GPC data is from stoichiometric films after 1 day of heating.
  • a branched polyimide of formula (1) preferably formula (1′), wherein G is a group having a valence of t, present in an amount of 0.01 to 20 mol %, or 0.1 to 20 mol %, or 0.5 to 10 mol %, or 1.0 to 5 mol %, or 1.5 to 4 mol %, or 0.01 to 2 mol %, each Q is independently the same or different, and is a divalent C 1-60 hydrocarbon group, each M is independently the same or different, and is —O—, —C(O)—, —OC(O)—, —OC(O)O—, —NHC(O), —(O)CNH—, —S—, —S(O)—, or —S(O) 2 —, D is a phenylene, each V is independently the same or different, and is a tetravalent C 4-40 hydrocarbon group, each R is independently the same or different, and is a C 1-20 divalent
  • Aspect 2 The branched polyimide of aspect 1, wherein when t is 2, G is —O—, —C(O)—, —OC(O)—, —(O)CO—, —NHC(O), —(O)CNH—, —S—, —S(O)—, —S(O) 2 —, or —P(R a )(O)— wherein R a is a C 1-8 alkyl or C 6-12 aryl; or when t is 3, G is a nitrogen, phosphorus, or pentavalent P(O); or G is a C 1-60 hydrocarbon group having a valence of t.
  • Aspect 3 The branched polyimide of aspect 1 or 2, wherein G is —O— when m is 0, pentavalent P(O), a C 6-50 hydrocarbon having at least one aromatic group, a C 2-20 aliphatic group, a C 4 -8 cycloaliphatic group, or a C 3-12 heteroarylene, or a polymer moiety.
  • Aspect 4 The branched polyimide of any one or more of aspects 1 to 3, wherein q is 1, Q is a C 6-20 arylene, m is 1, and M is —O—.
  • Aspect 5 The branched polyimide of any one or more of aspects 1 to 4, wherein V is of the formula (2), wherein W is —O—, —S—, —C(O)—, —SO 2 —, —SO—, —P(R a )( ⁇ O)— wherein R a is a 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, or a group of the formula —O—Z—O— wherein Z is an aromatic C 6-24 monocyclic or polycyclic moiety optionally substituted with 1 to 6 C 1-8 alkyl groups, 1 to 8 halogen atoms, or a combination comprising at least one of the foregoing, provided that the valence of Z is not exceeded.
  • Aspect 6 The branched polyimide of any one or more of aspects 1 to 5, wherein the branched polyimide is a branched polyetherimide of formula (1a), preferably (1a′), wherein each Z is independently an aromatic C 6-24 monocyclic or polycyclic moiety optionally substituted with 1 to 6 C 1-8 alkyl groups, 1 to 8 halogen atoms, or a combination comprising at least one of the foregoing, provided that the valence of Z is not exceeded.
  • Aspect 7 The branched polyimide of aspect 6, wherein Z is a divalent group of formula (7a) wherein J is —O—, —S—, —C(O)—, —SO 2 —, —SO—, or —C y H 2y — wherein y is an integer from 1 to 5 or a halogenated derivative thereof and R is m-phenylene, p-phenylene, bis(4,4′-phenylene)sulfone, bis(3,4′-phenylene)sulfone, or bis(3,3′-phenylene)sulfone.
  • Aspect 9 The aspect of aspect 8, further comprising pre-dissolving the polyamine and the diamine in the solvent before adding the dianhydride.
  • a method for the manufacture of the branched polyimide of any one or more of aspects 1 to 7, wherein the branched polyimide is a branched polyetherimide comprising: reacting a polyamine of formula (8) and a diamine of formula (10) with an anhydride of the formula (11) wherein X is a nitro group or halogen, to provide intermediate bis(phthalimide)s of the formulas (12) and (12a); and reacting the bis(phthalimide)s with an alkali metal salt of a dihydroxy aromatic compound of formula (13) wherein AM is an alkali metal, to provide the branched polyetherimide, wherein G, Q, M, D, R, V, q, m, d, p, and t are as defined in any one or more of aspects 1 to 7.
  • Aspect 11 The method of any one or more of aspects 8 to 10, wherein the polyamine is of the formulas (8b), (8k), (8r), (8s), or (8t).
  • Aspect 12 The method of any one or more of aspects 8, 9, or 11, wherein the dianhydride is 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, and the diamine is bis-(4-aminophenyl) sulfone or m-phenylenediamine.
  • the dianhydride is 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride
  • the diamine is bis-(4-aminophenyl) sulfone or m-phenylenediamine.
  • Aspect 14 An article comprising the branched polyimide of any one or more of aspects 1 to 7 or 13, or made by any one or more of the methods of aspects 8 to 12.
  • a polyimide composition comprising 1 to 99 wt %, or 10 to 90 wt %, 0.1 to 20 wt %, or 0.5 to 10 wt %, or 1 to 5 wt % of the branched polyimide of any one or more of aspects 1 to 7 or 13, or made by the method of aspects 8 to 12; and 1 to 99 wt %, or 10 to 90 wt %, or 0.9 to 80 wt %, or 99.5 to 90 wt %, or 99 to 95 wt % of a polyimide a second polyimide that is not the same as the branched polyimide; and wherein each amount is based on the total weight of the branched polyimide and the polyimide.
  • Aspect 16 An article comprising the polyimide composition of aspect 15.
  • a polymer composition comprising the polyimide composition of aspect 14; and a third polymer different from the branched polyimide and the second polyimide.
  • Aspect 18 The polymer composition of aspect 17, wherein the second polymer is a polyacetal, poly(C 1-6 alkyl)acrylate, polyacrylamide, polyacrylonitrile, polyamide, polyamideimide, polyanhydride, polyarylene ether, polyarylene ether ketone, polyarylene ketone, polyarylene sulfide, polyarylene sulfone, polybenzothiazole, polybenzoxazole, polybenzimidazole, polycarbonate, polyester, polyetherimide, polyimide, poly(C 1-6 alkyl)methacrylate, polymethacrylamide, cyclic olefin polymer, polyolefin, polyoxadiazole, polyoxymethylene, polyphthalide, polysilazane, polysiloxane, polystyrene, polysulfide, polysulfonamide, polysulfonate, polythioester, polytriazine, polyurea, polyurethane, vinyl polymer, or
  • Aspect 19 An article comprising the polymer composition of aspect 17 or 18.
  • the article of aspects 16 or 19, wherein the article is a foam, preferably a closed cell foam.
  • compositions, methods, and articles can alternatively comprise, consist of, or consist essentially of, any appropriate components or steps herein disclosed.
  • the compositions, methods, and articles can additionally, or alternatively, be formulated so as to be devoid, or substantially free, of any steps, components, materials, ingredients, adjuvants, or species that are otherwise not necessary to the achievement of the function or objectives of the compositions, methods, and articles.
  • hydrocarbyl and “hydrocarbon” refer broadly to a group comprising carbon and hydrogen, optionally with 1 to 3 heteroatoms, for example, oxygen, nitrogen, halogen, silicon, sulfur, or a combination thereof;
  • aliphatic means a branched or unbranched, saturated or unsaturated group containing carbon and hydrogen, optionally with 1 to 3 heteroatoms, for example, oxygen, nitrogen, halogen, silicon, sulfur, or a combination thereof;
  • cycloaliphatic means a saturated or unsaturated group comprising carbon and hydrogen optionally with 1 to 3 heteroatoms, for example, oxygen, nitrogen, halogen, silicon, sulfur, or a combination thereof;
  • alkyl means a straight or branched chain, saturated monovalent hydrocarbon group;
  • alkylene means a straight or branched chain, saturated, divalent hydrocarbon group;
  • alkylidene means a straight or branched chain, saturated divalent hydrocarbon group, with both valences on a single common carbon
  • each of the foregoing groups can be unsubstituted or substituted, provided that the substitution does not significantly adversely affect synthesis, stability, or use of the compound.
  • substituted means that at least one hydrogen on the designated atom or group is replaced with another group, provided that the designated atom's normal valence is not exceeded.
  • substituent is oxo (i.e., ⁇ O)
  • two hydrogens on the atom are replaced.
  • Exemplary groups that can be present on a “substituted” position include, but are not limited to, cyano; hydroxyl; nitro; alkanoyl (such as a C 2-6 alkanoyl group such as acyl); carboxamido; C 1-6 or C 1-3 alkyl, cycloalkyl, alkenyl, and alkynyl (including groups having at least one unsaturated linkages and from 2 to 8, or 2 to 6 carbon atoms); C 1-6 or C 1-3 alkoxys; C 6-10 aryloxy such as phenoxy; C 1-6 alkylthio; C 1-6 or C 1-3 alkylsulfinyl; C 1-6 or C 1-3 alkylsulfonyl; amino di(C 1-6 or C 1-3 )alkyl; C 6-12 aryl having at least one aromatic rings (e.g., phenyl, biphenyl, naphthyl, or the like); C 7-19 arylalkylene

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