WO2018034680A1 - Blends of polysiloxane/polyimide and resorcinol based polyester carbonate copolymers for electrical wire coating - Google Patents

Abstract

A resin composition and articles formed therefrom including a polysiloxane/polyimide block copolymer and a resorcinol based polyester polycarbonate polysiloxane copolymer is disclosed. The resin composition may advantageously further include flame retardant and smoke suppressant additives.

Description

BLENDS OF POLYSILOXANE/POLYIMIDE AND RESORCINOL BASED POLYESTER CARBONATE COPOLYMERS FOR ELECTRICAL WIRE COATING

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of and priority to Indian Patent Application No. 201611027772, filed August 14, 2016, which is hereby incorporated herein by reference in its entirety.

TECHNICAL FIELD

[0002] The disclosure concerns polysiloxane/polyimide compositions containing resorcinol based polyester polycarbonate resin compositions with polysiloxane units for use in electric wire coating.

BACKGROUND

[0003] Blended resins of polyetherimide and resorcinol-based polyester polycarbonate copolymer may exhibit superior properties such as low heat release, excellent impact strength, high temperature resistance and processability. However, polyetherimide and resorcinol-based polyester polycarbonate copolymer blends are inherently stiffer materials (higher modulus). This increased stiffness can limit the use of these blends in applications requiring flexibility along with heat performance, specifically wire and cable applications. Thus, it would be beneficial to provide a blend of resorcinol-based polyester carbonate siloxane copolymers and

polysiloxane/polyimide blends exhibiting properties useful in wire coating applications.

Polysiloxane/polyimide block copolymers are flexible due to functionalized and flexible siloxane monomer in the polyetherimide backbone. As such, blends of polysiloxane/polyimide block polymers and resorcinol-based polyester polycarbonate copolymer would offer flexibility along with other superior mechanical properties, heat performance and processability, which are suitable for wire and cable applications. The inclusion of flame retardant additives and smoke suppressant in these blends advantageously provides a resin that is well-suited for use in electrical wires requiring good flame retardancy while maintaining their expected properties such as heat resistance, mechanical performance, durability and processability.

SUMMARY

[0004] Resorcinol-based polyester carbonate polysiloxane copolymers and

polysiloxane/polyimide copolymer blends have been developed. Such flame retardant blends comprising these copolymers may provide good flexibility with high tensile elongation to break, exceptional impact strength, high softening temperature, good flexural strength, low heat release properties and smoke properties and thus are applicable in wire coating applications.

[0005] The present disclosure relates to a resin composition comprising: from 10 wt. % to about 70 wt. % of a polysiloxane/polyimide block copolymer; from about 20 wt. % to about 90 wt. % of a siloxane-resorcinol based polyester carbonate copolymer; and wherein the combined weight percent value of all components in the resin composition does not exceed about 100 wt. %, and wherein the resin composition has a total siloxane content of from about 3 wt. % to about 25 wt. %.

[0006] The present disclosure also relates to a resin composition comprising: from about 8 wt. % to about 95 wt. % of a polysiloxane/polyimide block copolymer; from about 4 wt. % to about 91 wt. % of a siloxane-resorcinol based polyester carbonate copolymer; and wherein the resin composition has a total siloxane content of from about 3 wt. % to about 25 wt. %; and wherein the combined weight percent value of all components in the resin composition does not exceed about 100 wt. %; wherein the resin composition exhibits a tensile modulus of from about 1900 MPa to about 2600 MPa, a tensile strength of from about 50 MPa to about 80 MPa, a tensile elongation at yield of from about 3% to about 8 %, a flexural modulus of from about 1900 MPa to about 2650 MPa, a flexural strength of from about 80 MPa to about 120 MPa when measured in accordance with ASTM D638 and a glass transition temperature of from about 140 to about 200 °C measured using differential scanning calorimetry at a rate of 20 °C per minute.

[0007] In yet further aspects, the present disclosure relates to a method of forming a resin composition comprising: combining about 8 wt. % to about 95 wt. % of polysiloxane polyimide copolymer and from about 4 wt. % to about 91 wt. % of a resorcinol based polyester carbonate siloxane copolymer; wherein the combined weight percent value of all components in the resin composition does not exceed about 100 wt. %;wherein all weight percent values are based on the total weight of the resin composition; and wherein the resin compositions has a total siloxane content of from about 3 wt. % to about 25 wt. %.

[0008] The present disclosure further relates to a wire coating resin composition comprising a polysiloxane/polyimide copolymer and a resorcinol based polycarbonate copolymer wherein the resin composition exhibits properties favorable for thin-walled electric wire resin coating compositions including improved strength, flame retardance, heat release, and processability.

DETAILED DESCRIPTION [0009] The present disclosure relates to an electrical wire coating resin composition comprising a polysiloxane polycarbonate copolymer, a polycarbonate copolymer, and a polysiloxane/polyimide block copolymer. In some aspects, the electrical wire coating resin composition may comprise a polysiloxane/polyimide block copolymer and a resorcinol-based polyester polycarbonate copolymer.

[0010] The terms "polycarbonate" or "polycarbonates" as used herein includes copoly carbonates, homopoly carbonates and (co)polyester carbonates. The term polycarbonate can be further defined as compositions have repeating structural units of the formula (1):

in which at least 75 percent of the total number of R¹ groups are aromatic organic moieties and the balance thereof are aliphatic, alicyclic, or aromatic groups. In an example, each R¹ can be an aromatic group and, more preferably, R¹ can be derived from a dihydroxy compound of the formula HO-R1-OH, or more specifically a group of formula (2): HO-A -Y -A^OH (2), wherein each of A¹ and A² is a monocyclic divalent aryl radical and Y¹ is a single bond or a bridging group having one or two atoms that separate A¹ from A². In some examples, a single atom separates A¹ from A².

[0011] In further examples, each R¹ can be derived from an aromatic dihydroxy compound such as a bisphenol of formula 3):

where R^a and R^b are each independently a Ci-12 alkyl; and p and q are each independently integers of 0 to 4. It is to be understood that R^a is hydrogen when p has a value of 0, and R^b is hydrogen when q is 0. In a particular embodiment, no halogen is present in the structure. X^a can be a bridging group between the two hydroxy -substituted aromatic groups, where the bridging group and the hydroxy substituent of each C7 arylene group are disposed ortho, meta, or para to each other on the C7 arylene group. Exemplary bridging groups can include, but are not limited to -0-, -S-, -S(O) -, -S(0₂) -, -C(O) -, methylene, cyclohexyl-methylene, 2-[2.2.1]- bicycloheptylidene, ethylidene, isopropylidene, neopentylidene, cycloalkylidenes (such as, for example, cyclohexylidene, cyclopentadecylidene, or cyclododecylidene) adamantylidene, or a Ci-18 group. The bridging CMS group can be cyclic or acyclic, aromatic or non-aromatic and can further comprise heteroatoms such as oxygen, nitrogen, sulfur, silicon, phosphorous, or halogens. Xa can also be a C_1-18 alkylene group, a C3-18 cycloalkylene group, a fused C6-i₈ cycloalkylene group, or a group of the formula -B^Q-B²- wherein B¹ and B² are the same or different C_1-6 alkylene group and Q is a C_3-12 cycloalkylidene group or Ce-16 arylene group. X^a can also be a substituted C_3-18 cycloalkylidene of formula (4):

wherein R^r, R^p, R^q, and R^l are each independently hydrogen, halogen, oxygen, or C_1-12 organic groups; I is a direct bond, a carbon or a divalent oxygen, sulfur, or -N(Z)— where Z is hydrogen, halogen, hydroxy, C_1-12 alkoxy, or C_1-12 acyl; h is 0 to 2, j is 1 or 2, 1 is an integer of 0 or 1, and k is an integer of 0 to 3, with the proviso that at least two of R^r, R^p, R^q, and R^l taken together are a fused cycloaliphatic, aromatic, or heteroaromatic ring.

[0012] Other useful aromatic dihydroxy compounds of the formula HO— R¹— OH include monoaryl dihydroxy compounds of formula (5):

(5)

wherein each R^h is independently a halogen atom, a CMO hydrocarbyl such as Ci-10 alkkyl group, a halogen substituted Ci-10 alkyl group, a Ce-ιο aryl group, or a halogen substituted C6-10 aryl group, or a halogen substituted C6-10 aryl group, and n is 0 to 4. In various examples, the halogen can be bromine. In further examples, no halogen is present. Exemplary bisphenol compounds of formula (3) can include l,l-bis(4-hydroxyphenyl)methane, l,l-bis(4-hy droxyphenyl)ethane, 2,2- bis(4-hydroxyphenyl)propane (hereinafter "bisphenol-A" or "BP A"), 2,2-bis(4-hydrox yphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, l,l-bis(4 hydroxyphenyl)propane, 1, 1 -bis(4 - hydroxyphenyl)n-butane, and 2,2-bis(4 -hydroxy-2 -methylphenyl)propane among others.

[0013] As an example, the resin compositions of the present disclosure can comprise repeating polycarbonate units of the formula (l a):

wherein R^a and R are each independently C_1-12 alkyl, p and 1 are each independently integers of 0 to 4, and X^a is a single bond. In one example, where A¹ and A² are p-phenylene and Yl is isopropylidene, the repeating units can be referred to as "bisphenol A carbonate units."

[0014] In addition to carbonate units (1) and (la), the resin compositions of the present disclosure can comprise poly(carbonate-arylate ester) copolymers comprising repeating arylate ester units of formula (6):

wherein Ar is a Ce-n hydrocarbyl group containing at least one aromatic group, e.g., a phenyl, naphthalene, anthracene, or the like. In an embodiment, Ar¹ is derived from a bisphenol (3), a monoaryl dihydroxy compound (5), or a combination comprising different bisphenol or monoaryl dihydroxy compounds. Thus, arylate ester units (6) can be derived by reaction of isophthalic acid, terephthalic acid, or a combination thereof (referred to herein as a "phthalic acid"), with an aromatic bisphenol (3), a monoaryl dihydroxy compound (5), or a combination thereof. The molar ratio of isophthalate to terephthalate can be 1 :99 to 99: 1 , or 80:20 to 20: 80, or 60:40 to 40:60.

[0015] As an example, the poly(carbonate-arylate ester) copolymers comprising carbonate units (1), specifically bisphenol-A carbonate units, and arylate ester units (6) can be alternating or block copolymers of formula (7):

wherein R¹ and Ar¹ are as defined in formulas (1) and (6), respectively. The copolymers can be block copolymers comprising carbonate blocks and ester blocks wherein the weight ratio of total ester units to total carbonate units in the copolymers can vary broadly.

[0016] Specific ester units can include ethylene terephthalate, n-propylene terephthalate, n-butylene terephthalate, 1,4-cyclohexanedimethylene terephthalate, and ester units derived from isophthalic acid, terephthalic acid, and resorcinol (ITR). The molar ratio of ester units to carbonate units in the copolymers can vary broadly, for example 1 : 99 to 99: 1, specifically 10:90 to 90: 10, more specifically 25:75 to 75:25, or 2:98 to 15:85, depending on the desired properties of the final composition. In some examples, the molar ratio of isophthalate to terephthalate in the ester units of the copolymers can also vary broadly, for example from 0: 100 to 100:0, or from 92:8 to 8:92, more specifically from 98:2 to 45:55, depending on the desired properties of the thermoplastic composition. For example, the weight ratio of total ester units to total carbonate can be 99: 1 to 40:60, or 90: 10 to 50:40, wherein the molar ratio of isophthalate to terephthalate is from 99: 1 to 40:50, more specifically 98:2 to 45:55, depending on the desired properties of the thermoplastic composition.

[0017] Specific poly(ester-carbonate)s are those including bisphenol A carbonate units and isophthalate-terephthalate-bisphenol A ester units, also commonly referred to as

poly(carbonate-ester)s (PCE) poly(phthalate-carbonate)s (PPC) depending on the molar ratio of carbonate units and ester units. A further example can include a poly(carbonate-bisphenol arylate ester) comprising carbonate units (1), specifically bisphenol carbonate units, even more specifically bisphenol-A carbonate units and repeating bisphenolarylate ester units. The bisphenol arylate units can comprise residues of phthalic acid and a bisphenol, for example a bisphenol (3).

[0018] A further specific example of a poly(carbonate-bisphenol arylate ester) is a poly(bisphenol-A carbonate)-copoly(bisphenol-A phthalate ester) of formula (7a):

(7a)

[ wherein y and x represent the weight percent of arylate-bisphenol A ester units and bisphenol A carbonate units, respectively. Generally, the units are present as blocks. In an embodiment, the weight percent of ester units y to carbonate units x in the copolymers is 50:50 to 99: 1, or 55:45 to 90: 10, or 75:25 to 95:5. Copolymers of formula (7a) comprising 35 to 45 wt.% of carbonate units and 55 to 65 wt.% of ester units, wherein the ester units have a molar ratio of isophthalate to terephthalate of 45:55 to 55:45 are often referred to as poly(carbonate-ester)s (PCE) and copolymers comprising 15 wt.% to 25 wt.% of carbonate units and 75 wt.% to 85 wt.% of ester units having a molar ratio of isophthalate to terephthalate from 98:2 to 88: 12 are often referred to as poly(phthalate-carbonate)s (PPC).

[0019] In another aspect, a specific polycarbonate copolymer can be a poly(carbonate)- co-(monoaryl arylate ester) containing carbonate units (1) and repeating monoaryl arylate ester units of formula (6b)

wherein each R^h is independently a halogen atom, a CMO hydrocarbon such as a CMO alkyl group, a halogen-substituted CMO alkyl group, a Ce-ιο aryl group, or a halogen-substituted Οβ-ιο aryl group, and n is 0 to 4. Specifically, each R^h is independently a C1-4 alkyl, and n is 0 to 3, 0 to 1, or 0. These poly(carbonate)-co-(monoaryl arylate ester) copolymers are of formula (7b)

wherein R¹ is as defined in formula (1) and R^h, and n are as defined in formula (7b), and the mole ratio of x:m is 99: 1 to 1 :99, specifically 80:20 to 20: 80, or 60:40 to 40:60.

[0020] Specifically, the monoaryl-arylate ester unit (7b) can be derived from the reaction of a combination of isophthalic and terephthalic diacids (or derivatives thereof) with resorcinol (or reactive derivatives thereof) to provide isophthalate-terephthalate-resorcinol ("ITR" ester units) of formula (7c)

wherein m is 4 to 100, 4 to 90, 5 to 70, more specifically 5 to 50, or still more specifically 10 to 30. The ITR ester units can be present in the polycarbonate copolymer in an amount greater than or equal to 95 mol%, specifically greater than or equal to 99 mol%, and still more specifically greater than or equal to 99.5 mol% based on the total moles of ester units in the copolymer. As an example, the resorcinol based polyester polycarbonate copolymer can include LEXAN™ FST-ITR available commercially from SABIC (LEXAN™ is a trademark of SABIC IP B. V.).

[0021] A resorcinol based polyester carbonate copolymer can include a copolymer comprising resorcinol moieties and resorcinol-based ester linkages and possibly other linkages also such as resorcinol-based polycarbonate linkages. These terms are meant to include both polyesters only containing ester bonds and polyester carbonates in instances where resorcinol- based polycarbonate linkages are present. For example, a resorcinol-based polyaryl ester may comprise both carbonate linkages (e.g., between a resorcinol moiety and a bisphenol A moiety) and ester linkages (e.g., between a resorcinol moiety and a isophthalic acid moiety).

[0022] A specific example of a poly(carbonate)-co-(monoaryl arylate ester) can be a poly(bisphenol A carbonate)-co-(isophthalate-terephthalate-resorcinol ester) of formula (7c)

(7c)

wherein m is 4 to 100, 4 to 90, 5 to 70, more specifically 5 to 50, or still more specifically 10 to 30, and the mole ratio of x:m is 99: 1 to 1 :99, specifically 90: 10 to 10:90. The ITR ester units are present in the poly(carbonate-arylate ester) copolymer in an amount greater than or equal to 95 mol%, specifically greater than or equal to 99 mol%, and still more specifically greater than or equal to 99.5 mol% based on the total moles of ester units. Other carbonate units, other ester units, or a combination thereof can be present, in a total amount of 1 to 20 mole% based on the total moles of units in the copolymers, for example resorcinol carbonate units of formula (8) and bisphenol A phthalate ester units of the formula bisphenol ester units of formula (9):

[0023] In one aspect, poly(bisphenol A carbonate)-co-(isophthalate-terephthalate- resorcinol ester) (7c) can comprise 1 to 20 mol% of bisphenol A carbonate units, 20-98 mol% of isophthalic acid-terephthalic acid-res or cinol ester units, and optionally 1 to 60 mol% of resorcinol carbonate units, isophthalic acid-terephthalic acid-bisphenol A phthalate ester units, or a combination thereof.

[0024] The polycarbonate copolymers comprising arylate ester units can have a weight average molecular weight (M_w) of 2,000 to 100,000 g/mol, specifically 3,000 to 75,000 g/mol, more specifically 4,000 to 50,000 g/mol, more specifically 5,000 to 35,000 g/mol, and still more specifically 17,000 to 30,000 g/mol. Molecular weight determinations are performed using GPC using a cross linked styrene-divinyl benzene column, at a sample concentration of 1 milligram per milliliter, and as calibrated with polycarbonate standards. Samples are eluted at a flow rate of 1.0 ml/min with methylene chloride as the eluent.

[0025] In another example, the poly(carbonate-arylate ester) copolymers further comprise siloxane units (also known as "diorganosiloxane units"). In a specific embodiment these copolymers comprises carbonate units (1) derived from a bisphenol (3), specifically bisphenol-A; monoaryl arylate ester units (7b), and siloxane units. Still more specifically, the poly(carbonate-arylate ester) copolymers comprises bisphenol-A carbonate units, ITR ester units (7c), and siloxane units (9). For convenience, these polymers, poly(bisphenol-A carbonate)-co- poly(isophthalate-terephthalate-resorcinol ester)-co-poly(siloxane), can be referred to herein as "ITR-PC-siloxane" copolymers.

[0026] The polysiloxane units can be of formula (10):

wherein each R is independently a C_1-13 monovalent hydrocarbyl group. For example, each R can independently be a Ci- alkyl group, C_1-13 alkoxy group, C_2-13 alkenyl group, C_2-13 alkenyloxy group, C3-6 cycloalkyl group, C3-6 cycloalkoxy group, C_6-i4 aryl group, Ce-ιο aryloxy group, C_7- 13 arylalkyl group, C_7-13 arylalkoxy group, C_7-13 alkylaryl group, or C7-i₃alkylaryloxy group. The foregoing groups can be fully or partially halogenated with fluorine, chlorine, bromine, or iodine, or a combination thereof. In an embodiment no halogens are present. Combinations of the foregoing R groups can be used in the same copolymer. In one example, the polysiloxane comprises R groups that have minimal hydrocarbon content. In a specific embodiment, an R group with a minimal hydrocarbon content is a methyl group.

[0027] The average value of E in formula (9) can vary widely depending on the type and relative amount of each component in the thermoplastic composition, whether the polymer is linear, branched or a graft copolymer, the desired properties of the composition, and like considerations. As an example, E has an average value of 2 to 500, 2 to 200, or 5 to 100, 10 to 100, or 10 to 80. In a further example, E has an average value of 16 to 50, more specifically 20 to 45, and even more specifically 25 to 45. In another embodiment, E has an average value of 4 to 50, 4 to 15, specifically 5 to 15, more specifically 6 to 15, and still more specifically 7 to 10.

[0028] In an example, the polysiloxane units can be structural units of formula (10a):

wherein E is as defined above; each R can independently be the same or different, and is as defined above; and each Ar can independently be the same or different, and is a substituted or unsubstituted Ce-30 compound containing an aromatic group, wherein the bonds are directly connected to the aromatic moiety. The Ar groups in formula (10a) can be derived from a C_{6- 3}odihydroxy aromatic compound. Combinations comprising at least one of the foregoing dihydroxy aromatic compounds can also be used. Exemplary dihydroxy aromatic compounds are resorcinol (i.e., 1,3-dihydroxybenzene), 4-methyl-l,3-dihydroxybenzene, 5-methyl-l,3- dihydroxybenzene, 4,6-dimethyl-l,3-dihydroxybenzene, 1,4-dihydroxy benzene, l,l-bis(4- hydroxyphenyl)methane, l,l-bis(4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl sulfide), and l,l-bis(4-hydroxy-t-butylphenyl)propane. Combinations comprising at least one of the foregoing dihydroxy compounds can also be used. As an example, the dihydroxy aromatic compound is unsubstituted, or does not contain non-aromatic hydrocarbyl substituents such as alkyl, alkoxy, or alkylene substituents.

[0029] In a specific example, where Ar is derived from resorcinol, the polysiloxane units are of the formula (10a- 1):

or, where Ar is derived from bisphenol-A, the polysiloxane has the formula (10a-2):

or a combination comprising at least one of the foregoing can be used, wherein E has an average value as described above, specifically an average value of 2 to 200. [0030] As disclosed, the resin compositions may comprise polysiloxane /polyimide block copolymers. The polysiloxane/polyimide block copolymers can have a siloxane content of greater or equal to about 20 wt. % based on the total weight of the block copolymer. The block copolymer com rises a siloxane block of formula (10):

wherein R^1"6 are independently at each occurrence selected from the group consisting of substituted or unsubstituted, saturated, unsaturated, or aromatic monocyclic groups having 5 to 30 carbon atoms, substituted or unsubstituted, saturated, unsaturated, or aromatic poly cyclic groups having 5 to 30 carbon atoms, substituted or unsubstituted alkyl groups having 1 to 30 carbon atoms and substituted or unsubstituted alkenyl groups having 2 to 30 carbon atoms, V is a tetravalent linker selected from the group consisting of substituted or unsubstituted, saturated, unsaturated, or aromatic monocyclic and poly cyclic groups having 5 to 50 carbon atoms, substituted or unsubstituted alkyl groups having 1 to 30 carbon atoms, substituted or

unsubstituted alkenyl groups having 2 to 30 carbon atoms and combinations comprising at least one of the foregoing linkers, g equals 1 to 30, and d is 2 to 20. Commercially available polysiloxane/polyetherimides can be obtained from SABIC Innovative Plastics under the brand name SILTEM™ (Trademark of SABIC Innovative Plastics IP B.V.).

[0031] The polysiloxane/polyimide block copolymers disclosed herein can comprise polysiloxane blocks and polyimide blocks. Generally, the number of siloxane units (g) of formula (11) can determine the size of the siloxane block for random polysiloxane/polyimide block copolymers. In some non-random polysiloxane/polyimide block copolymers, the order of the polyimide blocks and polyimide blocks is pre-determined, but the size of the siloxane block is still determined by the number of siloxane units in the monomer. For the

polysiloxane/polyimide block copolymers described herein, the siloxane blocks are extended. That is, two or more silane monomers link together to form an extended silane oligomer which can then be used to form the block copolymer.

[0032] An extended polysiloxane/polyimide block copolymer can be prepared by forming an extended siloxane oligomer and then using the extended siloxane oligomer to make the block copolymer. The extended siloxane oligomer can be prepared from the reaction of a diamino siloxane and a dianhydride wherein either the diamino siloxane or the dianhydride is present in from about 10 % to about 50 % molar excess, or more specifically, from about 10 % to about 20 % molar excess. As used herein, molar excess can refer to the state of one reactant being in excess of another reactant. For example, if the diamino siloxane is present in 10 % molar excess, then for 100 moles of dianhydride present there are 110 moles of diamino siloxane.

[0033] Diamino siloxanes can be of formula (12):

wherein R^1"6 and g are defined as above for formula (1). In one example R2-5 are methyl groups and Rl and R6 are alkylene groups. In one embodiment R¹ and R⁶ are alkylene groups having 3 to 10 carbons. In some embodiments R¹ and R⁶ are the same and in some embodiments R¹ and R⁶ are different.

[0034] Useful dianhydrides in the preparation of extended siloxane oligomers can have the formula (13):

wherein V is a tetravalent linker as described above. Suitable substitutions and/or linkers include, but are not limited to, carbocyclic groups, aryl groups, ethers, sulfones, sulfides amides, esters, and combinations comprising at least one of the foregoing. Exemplary linkers include, but are not li

wherein W is a divalent moiety such as -0-, -S-, -C(O) -, -S0₂-, -C_yH_2y- (y being an integer of 1 to 20), and halogenated derivatives thereof, including perfluoroalkylene groups, or a group of the Formula -0-Z-O- Wherein the divalent bonds of the -O- or the -0-Z-O- group are in the 3,3', 3,4', 4,3', or the 4,4' positions, and wherein Z includes, but is not limited to, divalent

(15)

[0035] Dianhydrides as used herein can comprise aromatic bis(ether anhydride)s as disclosed in, for example, U.S. Pat. Nos., 3,972,902 and 4,455,410. Exemplary bis(ether anhydride)s can include 4,4'-bis(3,4-dicar boxyphenoxy)diphenyl ether dianhydride; 4,4'-bis(3,4 dicarboxyphenoxy)diphenyl sulfide dianhydride; 4,4'-bis(3, 4-dicarboxyphenoxy)benzophenone dianhydride; 4-(2,3-dicarbox yphenoxy)-4'-(3,4-dicarboxyphenoxy)benzophenone dianhydride and 4-(2,3-dicarboxyphenoxy)-4'-(3,4 dicarboxyphenoxy)diphenyl sulfone dianhydride, as well as mixtures comprising at least two of the foregoing. A chemical equivalent to a dianhydride may also be used. Examples of dianhydride chemical equivalents include tetra functional carboxylic acids capable of forming a dianhydride, and ester or partial ester derivatives of the tetra functional carboxylic acids. As used herein, "dianhydride" refers to dianhydrides and their chemical equivalents.

[0036] The extended siloxane oligomers described above can be further reacted with non-siloxane diamines and additional dianhydrides to make the polysiloxane/polyimide block copolymer. The overall molar ratio of the total amount of dianhydride and diamine (the total of both the siloxane and non-siloxane containing diamines) used to make the

polysiloxane/polyimide block copolymer should be about equal so that the copolymer can polymerize to a high molecule weight. In some examples, the polysiloxane/polyimide block copolymer will have a number average molecular weight (Mn) of 5,000 to 50,000 Daltons, or, more specifically, 10,000 to 30,000 Daltons. The additional dianhydride may be the same or different from the dianhydride used to form the extended siloxane oligomer.

[0037] The non-siloxane polyimide block can comprise repeating units having the general Formula (15):

wherein a is more than 1, typically 10 to 1,000 or more, and can specifically be 10 to 500; and wherein U is a tetravalent linker without limitation, as long as the linker does not impede synthesis of the polyimide oligomer. Suitable linkers include, but are not limited to: (a) substituted or unsubstituted, saturated, unsaturated or aromatic monocyclic and poly cyclic groups having 5 to 50 carbon atoms, (b) substituted or unsubstituted, linear or branched, saturated or unsaturated alkyl groups having 1 to 30 carbon atoms, and combinations comprising at least one of the foregoing linkers. Suitable substitutions and/or linkers include, but are not limited to, carbocyclic groups, aryl groups, ethers, sulfones, sulfides amides, esters, and combinations comprising at least one of the foregoing. Exemplary linkers can include, but are not limited to, tetravalent aromatic radicals as listed above for formula (14).

[0038] As an example, V in the polysiloxane block and U in the polyimide block can be the same, or V and U can be different. R¹⁰ in Formula (16) includes, but is not limited to, substituted or unsubstituted divalent organic moieties such as: aromatic hydrocarbon moieties having 6 to 20 carbons and halogenated derivatives thereof; straight or branched chain alkylene moieties having 2 to 20 carbons; cycloalkylene moieties having 3 to 20 carbon atom; or divalent moieties of the general Formula 17):

wherein Q is defined as above. As an example, R⁹ and R¹⁰ can be the same or can be different.

[0039] The polysiloxane or polyimide copolymer can be used alone or in combination with each other and/or other of the disclosed polymeric materials in fabricating the polymeric components of the resin composition. In some examples, only the polysiloxane is used. In further examples, the weight ratio of polysiloxane: polyimide can be from 99: 1 to 50:50.

[0040] The polysiloxane/polyimide block copolymer as disclosed herein can be halogen free. Halogen free is defined as having a halogen content less than or equal to 1000 parts by weight of halogen per million parts by weight of block copolymer (ppm) as determined by ordinary chemical analysis such as atomic absorption. Halogen free polymers can further have combustion products with low smoke corrosivity, for example as determined by DIN 57472 part 813. In some embodiments smoke conductivity, as judged by the change in Water conductivity can be less than or equal to 1000 microsiemens. In some examples, the smoke has an acidity, as determined by pH, greater than or equal to 5.

[0041] As noted herein, the extended siloxane oligomers can be further reacted with non-siloxane diamines and additional dianhydrides to form the polysiloxane/polyimide block copolymer. In an example, the non-siloxane polyimide blocks can comprise a polyetherimide block. Polyetherimide blocks can com rise repeating units of formula (18):

wherein T is 40* or a group of the Formula -0-Z-O- Wherein the divalent bonds of the -O- or the -0-Z-O- group are in the 3,3', 3,4', 4,3', or the 4,4' positions, and wherein Z and RIO are defined as described above. The polyetherimide block can comprise structural units according to Formula (15) Wherein each RIO is independently derived from p-phenylene, m-phenylene, diamino aryl sulfone or a mixture thereof, and T is a divalent moiety of the formula (19):

[0042] The repeating units of Formula (16) and Formula (18) are formed by the reaction of a dianhydride and a diamine. Dianhydrides useful for forming the repeating units have the formula (20):

wherein U is as defined above. As mentioned above the term dianhydrides includes chemical equivalents of dianhydrides. Diamines useful for forming the repeating units of Formula (16) and (18) have the formula H₂N-R¹⁰-NH₂ (21) wherein R¹⁰ is as defined above. Examples of specific organic diamines are disclosed, for example, in US. Pat. Nos. 3,972, 902 and 4,455,410. Exemplary diamines include, but are not limited to, ethylenediamine, propylenediamine, trimethylenediamine, diethylenetriamine, triethylenetertramine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, 1,12-dodecanediamine, 1,18-octadecanediamine, 3-methylheptamethylene diamine.

[0043] When using a polyimide oligomer and an extended siloxane oligomer to form the block copolymer, the stoichiometric ratio of terminal anhydride functionalities to terminal amine functionalities is 0.90 to 1.10, or, more specifically, 0.95 to 1.05. In one example, the extended siloxane oligomer is amine terminated and the non- siloxane polyimide oligomer is anhydride terminated. In another example, the extended siloxane oligomer is anhydride terminated and the non-siloxane polyimide oligomer is amine terminated. In another example, the extended siloxane oligomer and the non-siloxane polyimide oligomer are both amine terminated and they are both reacted with a sufficient amount of dianhydride (as described above) to provide a copolymer of the desired molecular weight. The siloxane content in the block copolymer can be determined by the amount of extended siloxane oligomer used during polymerization. The siloxane content is greater than or equal to 20 wt. %, or, more specifically, greater than or equal to 25 wt. %, based on the total weight of the block copolymer. As a further example, the siloxane content can be less than or equal to 40 wt. %, based on the total weight of the block copolymer. In some examples, two or more polysiloxane/polyimide block copolymers may be combined to achieve the desired siloxane content for use in the blend. The block copolymers may be used in any proportion. For example, when two block copolymers are used the weight ratio of the first block copolymer to the second block copolymer may be 1 to 99. The polysiloxane/polyimide block copolymer is present in an amount of 14 to 75 wt. % based on the total weight of the composition. Within this range the polysiloxane/polyimide block copolymer may be present in an amount greater than or equal to 20 wt. %, or, more specifically, greater than or equal to 25 wt. %. Also within this range the polysiloxane/polyimide block copolymer may be present in an amount less than or equal to 70 wt. %, or, more specifically, less than or equal to 65 wt. %, or, more specifically, less than or equal to 60 wt. %.

[0044] In some examples of the present disclosure, the polysiloxane or polyimide copolymer can have a weight average molecular weight (Mw) of 5,000 to 100,000 grams per mole (g/mole) as measured by gel permeation chromatography (GPC). In some embodiments the Mw can be 10,000 to 80,000. The molecular weights as used herein refer to the absolute weight averaged molecular weight (Mw). The polysiloxane/polyimide copolymer can have an intrinsic viscosity greater than or equal to 0.2 deciliters per gram (dl/g) as measured in m-cresol at 25 °C. Within this range the intrinsic viscosity can be 0.35 to 1.4 dl/g, as measured in m- cresol at 25 °C.

[0045] In further examples, the polysiloxane/polyimide copolymer can have a glass transition temperature of greater than 1 10°C, specifically of 200 °C to 500 °C, as measured using differential scanning calorimetry (DSC) per ASTM test D3418. In some embodiments, the polysiloxane/ polyimide copolymer and, in particular, a polyetherimide copolymer can have a glass transition temperature of 240 to 350 °C.

[0046] The polysiloxane/polyimide copolymer can have a melt index of 0.1 to 50 grams per minute (g/min), as measured by American Society for Testing Materials (ASTM) DI 238 at 340 to 370° C, using a 6.7 kilogram (kg) weight.

[0047] In various examples of the present disclosure, blends of siloxane copolymers, for instance polysiloxane/polyimide (including polyetherimides) or siloxane polycarbonates, with resorcinol derived polyaryl esters can have surprisingly low heat release values. The siloxane copolymers can be very effective in improving flame retardant (FR) performance even when included in such a blend at a very low concentration. This behavior can also be observed when the resorcinol-based aryl polyester is a copolymer containing non-resorcinol-based moieties, for instance a resorcinol— bisphenol-A copolyester carbonate. In certain embodiments, the resorcinol moiety content (RMC) can be greater than about 40 mole % of the total monomer- derived moieties present in the resorcinol-based aryl polyester. In some instances RMC of greater than 50 mole %, such as 60 mole%, 70 mole%, 80 mole%, 90 mole%, or 100 mole % resorcinol moieties may be desired.

ADDITIVES

[0048] To deliver flame retardant and certain fire properties, the resin may comprise a flame retardant additive or a smoke suppressant. The flame retardant additive may comprise a phosphate. Exemplary phosphate flame retardant additives may include bisphenol A bis- (biphenyl phosphate), zinc borate, or phosphazene. Exemplary smoke suppressant additives may include, but are not limited to, metal borate salts for example zinc borate, alkali metal or alkaline earth metal borate or other borate salts. Additionally other boron containing compounds, such as boric acid, borate esters, boron oxides or other oxygen compounds of boron may be useful. Additionally other flame retardant additives, such as aryl phosphates, sulfonate salts and brominated aromatic compounds,

[0049] The resin may further comprise a reinforcing filler. Reinforcing fillers may include but are not limited to mica, clay, feldspar, flue dust, fillite, quartz, quartzite, perlite, tripoli, diatomaceous earth, carbon black, or the like, or combinations including at least one of the foregoing fillers or reinforcing agents. The reinforcing filler can be organic or inorganic. The resin compositions may further include other additives. As such, the disclosed

thermoplastic composition can comprise one or more additives conventionally used in the manufacture of molded thermoplastic parts with the provision that the optional additives do not adversely affect the desired properties of the resulting composition. Mixtures of optional additives can also be used. Such additives can be mixed at a suitable time during the mixing of the components for forming the composite mixture. For example, the disclosed composition can comprise one or more additional fillers, plasticizers, stabilizers, anti-static agents, impact modifiers, colorant, antioxidant, and/or mold release agents.

[0050] The resin compositions can comprise an antioxidant. The antioxidants can include either a primary or a secondary antioxidant. For example, antioxidants can include organophosphites such as tris(nonyl phenyl)phosphite, tris(2,4-di-t-butylphenyl)phosphite, bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite or the like; alkylated monophenols or polyphenols; alkylated reaction products of polyphenols with dienes, or combinations including at least one of the foregoing antioxidants. Antioxidants can generally be used in amounts of from 0.01 to 0.5 parts by weight, based on 100 parts by weight of the total composition, excluding any filler.

[0051] In certain instances, the resin composition composition can comprise a mold release agent. Exemplary mold releasing agents can include for example, metal stearate, stearyl stearate, pentaerythritol tetrastearate, beeswax, montan wax, paraffin wax, or the like, or combinations including at least one of the foregoing mold release agents. Mold releasing agents are generally used in amounts of from about 0.1 to about 1.0 parts by weight, based on 100 parts by weight of the total composition, excluding any filler.

[0052] A heat stabilizer additive can be used. As an example, heat stabilizers can include, for example, organo phosphites such as triphenyl phosphite, tris-(2,6- dimethylphenyl)phosphite, tris-(mixed mono-and di-nonylphenyl)phosphite or the like;

phosphonates such as dimethylbenzene phosphonate or the like, phosphates such as trimethyl phosphate, or the like, or combinations including at least one of the foregoing heat stabilizers. Heat stabilizers can generally be used in amounts of from 0.01 to 0.5 parts by weight based on 100 parts by weight of the total composition, excluding any filler.

[0053] In further aspects, light stabilizers can be present in the thermoplastic composition. Exemplary light stabilizers can include, for example, benzotriazoles such as 2-(2- hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)-benzotriazole and 2- hydroxy-4-n-octoxy benzophenone or the like or combinations including at least one of the foregoing light stabilizers. Light stabilizers can generally be used in amounts of from about 0.1 to about 1.0 parts by weight, based on 100 parts by weight of the total composition, excluding any filler.

[0054] In further aspects, the disclosed composition can comprise antistatic agents. These antistatic agents can include, for example, glycerol monostearate, sodium stearyl sulfonate, sodium dodecylbenzenesulfonate or the like, or combinations of the foregoing antistatic agents. In one aspect, carbon fibers, carbon nanofibers, carbon nanotubes, carbon black, or any combination of the foregoing can be used in a polymeric resin containing chemical antistatic agents to render the composition electrostatically dissipative.

[0055] Ultraviolet (UV) absorbers can also be present in the disclosed thermoplastic composition. Exemplary ultraviolet absorbers can include for example, hydroxybenzophenones; hydroxybenzotriazoles; hydroxybenzotriazines; cyanoacrylates; oxanilides; 2-hydroxy-4-n- octyloxybenzophenone (CYASORB™ 531); 2-[4,6-bis(2,4-dimethylphenyl)-l,3,5-triazin-2-yl]- 5-(octyloxy)-phenol (CYASORB™ 1164); 2,2'-(l,4- phenylene)bis(4H-3,l-benzoxazin-4-one) (CYASORB™ UV- 3638); nano-size inorganic materials such as titanium oxide, cerium oxide, and zinc oxide, all with particle size less than 100 nanometers; or the like, or combinations including at least one of the foregoing UV absorbers. UV absorbers are generally used in amounts of from 0.01 to 3.0 parts by weight, based on 100 parts by weight of the total composition, excluding any filler.

[0056] Anti-drip agents can also be used in the resin, for example a fibril forming or non-fibril forming fluoropolymer such as polytetrafluoroethylene (PTFE). The anti-drip agent can be encapsulated by a rigid copolymer, for example styrene-acrylonitrile copolymer (SAN). PTFE encapsulated in SAN is known as TSAN. In one example, TSAN can comprise 50 wt. % PTFE and 50 wt. % SAN, based on the total weight of the encapsulated fluoropolymer. The SAN can comprise, for example, 75 wt. % styrene and 25 wt. % acrylonitrile based on the total weight of the copolymer. An antidrip agent, such as TSAN, can be used in amounts of 0.1 to 10 parts by weight, based on 100 parts by weight of the total composition, excluding any filler.

[0057] Additionally, additives to improve flow and other properties may be added to the composition, such as low molecular weight hydrocarbon resins. These materials are also known as process aids. Particularly useful classes of low molecular weight hydrocarbon resins are those derived from petroleum C5 to C9 feedstock that are derived from unsaturated C5 to C9 monomers obtained from petroleum cracking. Non-limiting examples include olefins, e.g. pentenes, hexenes, heptenes and the like; diolefins, e.g. pentadienes, hexadienes and the like; cyclic olefins and diolefins, e.g. cyclopentene, cyclopentadiene, cyclohexene, cyclohexadiene, methyl cyclopentadiene and the like; cyclic diolefin dienes, e.g., dicyclopentadiene,

methylcyclopentadiene dimer and the like; and aromatic hydrocarbons, e.g. vinyltoluenes, indenes, methylindenes and the like. The resins can be partially or fully hydrogenated. PROPERTIES

[0058] The resin compositions of the present disclosure a can exhibit properties particularly advantageous to use as a wire coating resin. As one skilled in the art might appreciate, a low flexural modulus can be an essential property for a material to be used as a wire coating. As an example, a low flexural modulus can be up to about 2100 - 2800 MPa. Tensile elongation at break is another mechanical property indicative of applicability for wire resin coating and jacketing purposes. A higher tensile elongation value is indicative that the resin would be advantageous in wire coating. Tensile strength can also gauge applicability for wire resin coating use. The higher the tensile strength, the better for wire coating purposes.

[0059] The resin compositions disclosed herein have a flexural modulus of up to about 2500 MPa. For reference, the polysiloxane/polyetherimide copolymer STM 1700 can have a flexural modulus of about 2150 MPa. Polysiloxane/polyetherimide copolymer STM 1600, a combination of STM 1700 and STM 1500 can have a flexural modulus of about 1250 MPa when assessed according to ASTM x as disclosed herein. The incorporation of LEXAN™ FST-ITR, having a flexural modulus of about 2500 MPa, can thereby increase the flexural modulus when blended with a SILTEM™ resin such as STM 1700 or STM 1500. Furthermore, the addition of an appropriate flame retardant/smoke suppressant agent can also affect flexural modulus. As provided herein, a phosphazene FR additive has a lesser effect on the flexural modulus of the resin blends disclosed than the bisphenol A bis-(diphenyl phosphate)

[0060] In certain instances, the resin compositions disclosed herein can have a tensile elongation of greater than about 80 % elongations. For reference, STM 1700 can have a tensile elongation of about 25 %, STM 1600 at about 130 %, and LEXAN™ FST-ITR of about 45 % elongation. It is noted however that the addition of a flame retardant additive can decrease the tensile elongation of a given resin blend prepared according to the methods disclosed herein. The flame retardant effect on tensile elongation is greater for STM 17600 blends than for STM 1700 blends.

[0061] In further aspects, the resin composition may comprise a 10 wt. % to about 70 wt. % of a polysiloxane/polyimide block copolymer and from about 20 wt. % to about 90 wt. % of a siloxane-resorcinol based polyester carbonate copolymer wherein the resin composition exhibits a glass transition temperature of from about 140 °C to about 165 °C measured using differential scanning calorimetry at a rate of 20 °C per minute, a heat deflection temperature of from about 115 °C to about 145 °C measured at 0.45 MPa, and a heat deflection temperature of from about 105 °C to about 130 °C measured at 1.82 MPa. Further, the resin compositions may exhibit a tensile modulus of from about 1920 MPa to about 2600 MPa, a tensile strength of from about 50 MPa to about 80 MPa, a tensile elongation of from about 15% to about 135%, a flexural modulus of from about 1900 MPa to about 2650 MPa, a flexural strength of from about 80 MPa to about 130 MPa when measured in accordance with ASTM D638, a V0 flame rating at 1 mm measured according to UL 94 (2014) with a flame out time (t-FOT) of from about 10 seconds to 25 seconds, and a NBS smoke density in flaming mode of 190 Ds to about 280 Ds. The resin composition may further exhibit fire properties of from about 150 e/g to about 260 w/g peak release rate, from about 8 kJ/g to about 12 kJ/g total heat release, from about 465 °C to about 515 °C temperature of maximum mass loss rate, and from about 0.8 to 1.6 flame index when tested in accordance with MCC D7309, and from about 70 kw/m² to about 205 kw/m² peak heat release, from about 80 s to about 180 s time to ignition, from about 0.5 kw/m² s to about 1.6 kw/m² s fire growth rate, from about 230 m²/kg to about 785 m²/kg specific extinction area, and from about 0.03 m²/s to about 0.09 m²/s peak smoke production rate when tested using a cone calorimeter according to ISO5660/ASTM El 354.

[0062] As discussed, the advantageous mechanical properties of the resin compositions disclosed herein can make these resins particularly suitable for use in electrical applications, particularly for electrical wiring applications. For example, the compositions disclosed herein may exhibit improved tensile elongation, tear strength, heat release, flame retardance, and flexural modulus.

[0063] In one example, the resin compositions may be used for electrical wire coating. The nature of wire coating requires certain processability characteristics. Properties including improved flame retardance, high tensile elongation, tear strength, high heat stability, and low smoke at ignition are desirable for use in electrical wiring.

[0064] In various further examples, the resin may be a coating for electrical wiring. The resin composition may be formed into electrical wire coating. As an example, the resin composition may be extruded onto electrical wire at a desired insulating thickness. In a further example, the resin composition may be coated onto a copper wire at an insulation thickness of from about 0.1 to about 0.4 mm.

[0065] The present disclosure can include at least the following aspects.

[0066] Aspect 1. A resin composition comprising: from 10 wt. % to about 70 wt. % of a polysiloxane/polyimide block copolymer; from about 20 wt. % to about 90 wt. % of a siloxane- resorcinol based polyester carbonate copolymer; and wherein the combined weight percent value of all components in the resin composition does not exceed about 100 wt. %, and wherein the resin composition has a total siloxane content of from about 3 wt. % to about 25 wt. %.

[0067] Aspect 2. The resin composition of claim 1 , wherein the resin composition further comprises an additive.

[0068] Aspect 3. The resin composition of claim 2, wherein the additive comprises a pigment, a dye, a filler, a plasticizer, a fiber, a flame retardant, an antioxidant, a lubricant, wood, glass, metal, an ultraviolet agent, an anti-static agent, an anti-microbial agent, impact modifier or a combination thereof.

[0069] Aspect 4. The resin composition of claim 2, wherein the additive comprises a flame retardant or a smoke suppressant.

[0070] Aspect 5. The resin composition of claim 4, wherein the flame retardant or smoke suppressant comprises phosphagene, zinc borate, bisphenol A bis-(diphenyl phosphate or combinations thereof.

[0071] Aspect 6. The resin composition of any of the preceding claims, wherein the resin composition comprises a flame retardant or a smoke suppressant or a combination thereof and wherein the resin composition exhibits a tensile modulus of from about 1920 MPa to about 2600 MPa, a tensile strength of from about 50 MPa to about 80 MPa, a tensile elongation of from about 15% to about 135%, a flexural modulus of from about 1900 MPa to about 2650 MPa, a flexural strength of from about 80 MPa to about 130 MPa when measured in accordance with ASTM D638 and a glass transition temperature of from about 140 to about 200 °C measured using differential scanning calorimetry at a rate of 20 °C per minute.

[0072] Aspect 7. The resin composition of any of the preceding claims, wherein the resin composition comprises a flame retardant or a smoke suppressant or a combination thereof and wherein the resin composition exhibits (a) a peak (specific) heat release rate from about 150 W/g to about 260 W/g; (b) a total heat release from about 8 kJ/g to about 14 kJ/g; (c) a temperature of maximum mass loss rate of from about 465 °C to about 515 °C; (d) a flame index of from about 0.8 to 1.6 when tested in accordance with MCC D7309; (e) a peak heat release rate of from about 125 kilowatts per square meter (kw/m2) to about 205 kw/m2, (f) a time to ignition of from about 80 s to about 180 s, (e) a fire growth rate of from about 0.5 kilowatts per square meter per second kw/m² s to about 1.6 kw/m² s, (f) a specific extinction area of from about 230 square meters per kilogram (m²/kg) to about 785 m²/kg, and (g) a peak smoke production rate from about 0.03 square meters per second (m²/s) to about 0.09 m²/s when tested using a cone calorimeter according to ISO5660/ASTM El 354.

[0073] Aspect 8. The resin composition of any of the preceding claims, wherein the resin composition comprises a flame retardant or a smoke suppressant or a combination thereof and wherein the resin composition exhibits a VO flame rating at 1 mm measured according to UL 94 (2014) with a flame out time (t-FOT) of from about 10 s to 25 s; and (g) an NBS smoke specific optical density (Ds) in flaming mode of 190 Ds to about 280 Ds as measured by ASTM E662.

[0074] Aspect 9. The resin composition of any of claims 4-8, wherein the flame retardant or the smoke suppressant is present in the composition in an amount less than about 10 wt. %.

[0075] Aspect 10. The resin composition of any of claims 4-8, further comprising about 5 wt. % of bisphenol A bis-(biphenyl) phosphate and its polymers.

[0076] Aspect 11. The resin composition of any of the preceding claims, wherein the polysiloxane/polyimide copolymer has a molecular weight of from about 20,000 Daltons to about 60,000 Daltons.

[0077] Aspect 12. The resin composition of any of the preceding claims, wherein the polysiloxane/polyimide copolymer has a glass transition temperature of from about 100 °C to about 250 °C.

[0078] Aspect 13. The resin composition of any of the preceding claims, wherein the resorcinol based polyester carbonate siloxane copolymer is an isophthalate-terephthalate- resorcinol)-carbonate copolymer.

[0079] Aspect 14. The resin composition of any of the preceding claims, wherein the resorcinol based polyester carbonate is a poly(bisphenol A carbonate)-co-(isophthalate- terephthalate-resorcinol ester).

[0080] Aspect 15. The resin composition of any of the preceding claims, wherein the resorcinol based polyester carbonate comprises from 1 mole percent to 20 mole percent of bisphenol A carbonate units, from 20 mole percent to 98 mole percent of isophthalic acid- terephthalic acid-resorcinol ester units, and from 0 mole percent to 60 mole percent of resorcinol carbonate units, isophthalic acid-terephthalic acid-bisphenol A phthalate ester units, or a combination thereof.

[0081] Aspect 16. An article comprising the resin composition of any of the preceding claims.

[0082] Aspect 17. The article of claim 16, wherein the article is selected from the group consisting of: electrical connectors, electrical wires, and electrical housings.

[0083] Aspect 18. The article of claim 16, wherein the article is selected from the group consisting of optical fiber cables, data communication cables, rolling stock cables, films, foams, sheets, separator, injection molded articles, profile extruded articles, and tapes.

[0084] Aspect 19. A resin composition comprising: from 8 wt. % to about 95 wt. % of a polysiloxane/polyimide block copolymer; from about 4 wt. % to about 91 wt. % of a

polysiloxane polycarbonate copolymer; wherein the resin composition has a total siloxane content of from about 3 wt. % to about 25 wt. %; and wherein the combined weight percent value of all components in the resin composition does not exceed about 100 wt. %; wherein the resin composition exhibits a tensile modulus of from about 1900 MPa to about 2600 MP a, a tensile strength of from about 50 MPa to about 80 MPa, a tensile elongation at yield of from about 3% to about 8 %, a flexural modulus of from about 1900 MPa to about 2650 MPa, a flexural strength of from about 80 MPa to about 120 MPa when measured in accordance with ASTM D638 and a glass transition temperature of from about 140 to about 200 °C measured using differential scanning calorimetry at a rate of 20 °C per minute.

[0085] Aspect 20. A method of forming a resin composition comprising: combining about 8 wt. % to about 90 wt. % of polysiloxane/polyimide copolymer and from about 8 wt. % to about 90 wt. % of a resorcinol based polyester carbonate siloxane copolymer; wherein the resin composition has a total siloxane content of from about 3 wt. % to about 25 wt. %; wherein the combined weight percent value of all components in the resin composition does not exceed about 100 wt. %, and wherein all weight percent values are based on the total weight of the resin composition.

EXAMPLES

[0086] Detailed embodiments of the present disclosure are disclosed herein; it is to be understood that the disclosed embodiments are merely exemplary of the disclosure that may be embodied in various forms. Therefore, specific structural and functional details disclosed herein are not to be interpreted as limits, but merely as a basis for teaching one skilled in the art to employ the present disclosure. The specific examples below will enable the disclosure to be better understood. However, they are given merely by way of guidance and do not imply any limitation. The following examples are provided to illustrate the compositions, processes, and properties of the present disclosure. The examples are merely illustrative and are not intended to limit the disclosure to the materials, conditions, or process parameters set forth therein.

General Materials and Methods

Example A

[0087] Blends of polysiloxane/polyimide copolymers (SILTEM™), polycarbonate polysiloxane copolymer (PC-ST or LEXAN™-ST) were prepared. Resin blends comprising 10 parts by weight (pbw) to 90 pbw SILTEM™ and 10 pbw to 90 pbw LEXAN™ FST, such that the total resin would be 100% by weight, were formed by extrusion in a 2.5 -inch twin screw, vacuum vented extruder. The extruder was operated at a temperature range of 250 °C to 310 °C at a speed of about 300 rpm under a vacuum atmosphere. The extrudate was cooled, pelletized, and dried at 120 °C. The pellets were injection molded at a temperature range of 280 °C to 310 °C and a mold temperature of 120 °C with a cycle time of 30 seconds (s).

[0088] Combinations (Samples 1 - 5) of polysiloxane/polyimide copolymers

(SILTEM™), polycarbonate polysiloxane copolymer (PC-ST or LEXAN™-ST), and polycarbonate derived from bisphenol A units (PC- 175) were prepared as presented in Table 1. The percent siloxane (% silox.) and the first and second glass transition temperatures (T_gl, T_g2) measured using differential scanning calorimetry at 20 °C per minute are also presented.

Table 1. Compositions of polysiloxane/polyimide and polycarbonate polysiloxane copolymer and their mechanical properties.

Comparative examples

[0089] Molded comparative samples CS1-CS5 were conditioned for at least 48 hours at 50 % relative humidity prior to testing in accordance with the standards presented below.

Comparative sample 1 (CSla) comprised STM 1700. The notched Izod impact ("ΝΠ") test was carried out on 3.1 mm thick bars according to ASTM D256. Data units are J/m. Tensile properties were measured on Tensile Type 1 bars (50 mm x 13 mm) in accordance with ASTM D638 using sample bars prepared in accordance with a Tensile Type 1 bar (50 mm x 13 mm). Tensile strength is reported at yield (Y), percent elongation (% Elong.) and at break (B); B and Y are reported in units of MPa.

[0090] Inventive samples of SILTEM™ and LEXAN™-FST blends were prepared and evaluated for mechanical properties.

Table 2. Mechanical properties of SILTEM™ and LEXAN™-FST blends

Nil (J/m) 150 390 291 151 154 207 392 285 409 562 557

Tg, DSC

202 195 142 196 177 161 149 148 168 147 146 (°C)

Comparative examples

[0091] As shown in Table 2, a significant increase in tensile elongation and notched Izod impact strength was apparent for the blends more so than the individual component comparative samples CSla, CS lb, and CS lc. Further, the flexural modulus slightly increased with the addition of LEXAN™-F S T to the SILTEM™ resins (for example, see Sample 5 compared to Sample 1). Tensile strength also increased with the addition of LEXAN™-FST (for example, see Sample 4 compared to Sample 1)

Example B

[0092] Additional combinations of SILTEM™ and LEXAN™ FST-ITR were prepared including two different SILTEM™ resins: STM1700 and STM1600. STM1600 comprises a blend of STM1700 and STM1500. From Example A, the most favorable values for mechanical properties (tensile elongation) were observed for STM1700 based blends having 25 wt. % STM1700 and 75 wt. % LEXAN™ FST-ITR composition and for STM1600 based blends at composition 50 wt. % STM1600 and 50 wt. % LEXAN™ FST-ITR resin. These combinations with additional flame retardants (bisphenol A bis-(biphenyl) phosphate BPADP, zinc borate ZB, and phosphazene (SPB-100) were evaluated for flame retardance and smoke performance.

Bisphenol A bis-(biphenyl) phosphate may include polymers of the structure including its polymers which can include its monomers, oligomers, and other structural polymers.

[0093] Blends were prepared by extrusion in a 2.5-inch twin screw, vacuum vented extruder with barrel temperature profile ramped from 280 °C to 310 °C at the feed throat and die head respectively. The blends were run at about 300 rpm under vacuum. The extrudate was cooled, pelletized and dried at 120 °C. Test samples were molded on 180-ton injection molding machine with 5.25 ounce barrel set at temperature range of 280 °C to 320 °C and mold temperature of 120 °C using a 30 second cycle time. All formulations were dry blended and tumbled and dried at 120 °C. Formulations are presented in Table 3.

Table 3. Composition of polysiloxane/polyimide (SILTEM™ STM1700 and STM1600) and resorcinol based polyester carbonate polysiloxane copolymer (LEXAN™ FST-ITR) resin blends

STM 1700 25 30 23.7 28.5 23.5 23.7 28.5 23.7 28.5

STM 1600 0 20 0 19 0 0 19 0 19

LEXAN™ FST- ITR 75 50 71.3 47.5 64.5 71.3 47.5 71.3 47.5

LEXAN™ EXL 0 0 0 0 7 0 0 0 0

BPADP 0 0 5 5 5 0 0 0 0

Zinc Borate (ZB) 0 0 0 0 0 5 5 0 0

SPB-100 0 0 0 0 0 0 0 5 5

Amount of

5.8 14.5 5.5 13.8 5.4 5.5 13.8 5.5 13.8 Siloxane (wt %)

[0094] Molded samples of the formulations were conditioned for at least 48 hours at 50% relative humidity prior to testing of physical properties. Molded inventive samples 14-22 were evaluated with polysiloxane/polyimide (SILTEM™ STM1700) as comparative sample 1 (CS la), a resorcinol based polyester carbonate copolymer (LEXAN™ FST-ITR) as comparative sample 2 (CS lb), and a polysiloxane/polyimide blend (STM1600, a blend of 60 wt.% STM1700 and 40 wt. % STM1500) as comparative sample 3 (CSlc), and The properties were measured using ASTM test methods as described in Example A, except as differentiated as follows for impact strength. Nil impact values were measured at room temperature on 3.2 mm thick bars as per ASTM D256.

Table 4. Mechanical properties of Inventive Samples 1-9 and control Samples

15 160 141 126 2170 61 94 2180 100 83

16 143 127 108 2414 70 107 2470 114 127

17 153 130 112 1930 53 22 1950 88 830

^♦Comparative examples.

[0095] As shown in Table 4, each sample 9-16 and control samples CS1-CS3 exhibited a single transition temperature confirming that they are miscible blends. No melting or crystallization transitions were observed demonstrating amorphous nature of the resins. The presence of high glass transition temperatures for CSla (STM1700) and CS lb (STM1600) polymers in the blends increased the softening temperature of the CS lc (LEXAN™ FST-ITR) resin.

[0096] The heat deflection temperature (HDT) of CS 1 a (STM1700) and CS3

(STM1600) were higher than the CSlc (LEXAN™ FST-ITR) resin and hence the

SILTEM™/FST-ITR (14-22) exhibited higher heat deflection temperature for samples 9, 11, 13, 14, and 16. The HDT at 1.82 MPa of for CSla (145 °C) is higher than that of CS2 (120 °C), but for CSlb (80 °C) it is lower. Hence, the STM1700/FST-ITR resins (Samples 9, 11, 13, 14, and 16) exhibited higher HDT than CSlb but Samples 10, 12, 15, and 17 (STM1600/FST-ITR blends) had lower HDT. Samples 11, 12, and 13 included 5 wt. % of liquid flame retardant additive, BPADP. Sample 18 also included a polysiloxane-poly carbonate (LEXAN™ EXL). It was apparent that BPADP reduced the T_g and HDT of Samples 12 and 13. Samples 14 and 15 include inorganic flame retardant additive zinc borate which did not impact the glass transition and HDT temperatures. Samples 16 and 17 include phosphazene oligomer flame retardant additive, which reduced the T_g and HDT of these samples.

[0097] The control samples CSla (STM1700) and CSlb (STM1600) exhibited values for flexural modulus greater than CS lc (LEXAN™ FST-ITR). The results suggested that the addition of LEXAN™ FST-ITR polymer to SILTEM™ resins increases the flexural modulus of blends. A high tensile modulus was also observed. Flexural and tensile modulus was also increased by the addition of the flame retardant additives. The phosphagene SPB-100 appeared to have the least effect on the modulus of the blends while BPADP had the greatest effect. The tensile elongation for break is another important mechanical property for wire and cable insulation materials. For CSla, the tensile elongation to break was 25% while that of CSlb was 45%. The tensile elongation for Sample 9 (STM1700/FST-ITR, 1 :3) was greater than 100% and that Sample 10 (STM1600/FST-ITR) was more than 130%. The addition of FR additives resulted in reduced tensile elongation of blends. Based upon these results, the flame retardant additives BPADP and SPB-100 significantly reduced the tensile elongation to break of STM1600 based blends but very moderately in STM1700 based samples (9, 11, 13, 14, and 16). The zinc borate additive moderately reduced tensile elongation to break of both blends to less than 100%. The tensile strength of CSla and CSlb are 60 MPa and 40 MPa respectively, lower than 70 MPa for CSlc. Thus, the addition of LEXAN™ FST-ITR resins to SILTEM™ resins increased the tensile strength of blends. The notched impact resistance at room temperature is improved for Samples 14-22 (SILTEM™/FST-ITR blends), compared to individual constituent resins CSla-,CS lb, and CSlc. For samples , 11, 13, 14, and 16, the three FR additives reduced the impact strength significantly. In the case of samples 10, 12, 15, and 17 (STM1600/FST-ITR resins), BPADP reduced the impact strength moderately, zinc borate significantly while SPB-100 increased the impact resistance significantly.

Flammability and fire properties

[0098] Flammability and smoke performance properties of Samples 9 to 17 were evaluated according to analyses of Microscale Cone Calorimetry (MCC), Cone Calorimetry, UL 94 flame tests V0 and 5VB, and NBS Smoke Density (ASTM E662). Flammability testing was conducted using the statistical "UL tool" in which 5 bars, at specified thickness (at both 0.8 and 1 mm) were burned using the UL94 test protocol for V and 5VB rating. The samples were rated for V0, VI and V2 according to UL94 V protocol. The UL94 5VB protocol would consider the sample as "PASS" or "FAIL" based on its test criteria. The total flame-out-times in seconds was determined in accordance with bot the V and 5VB flame rating. Smoke density was evaluated for Samples 9 to 17 according to the NBS Smoke Chamber as specified in ASTM E662 and NFPA 258. Samples were formed into 3 inch (in.) by 3 in. by 3 mm thickness. The plaques were exposed to a radiant heat source. Two modes of evaluation were used - flaming and non-flaming (or smoldering) mode. In flaming mode a small flame was provided in addition to radiant source to ignite the sample. In the smoldering or non-flaming mode, the sample was exposed to the radiant heat with no pilot ignition. The smoke generated was collected in a chamber. Light is directed into the chamber and the amount of light transmitted through the sample chamber is measured. The maximum smoke density, Ds(max) generated by the material in flaming mode within the 20 minutes of testing period is reported. Table 5 provides the flammability and smoke testing results.

Table 5. Standard flame and smoke testing results for polysiloxane/polyimide and resorcinol based polyester carbonate polysiloxane copolymer resin samples. NBS Smoke

UL 94 5VB @ Density in

UL 94 VO @ 1mm 1mm Flaming mode

t-FOT t-FOT

Samples Rating (s) Rating (s) Ds (max)

CSla (STM1700)* VO 17 Fail 11 101

CSlb (STM1600)* VO 31 Fail 34 NA

CSlc (LEXAN™ FST- ITR)* NA

9 VO 20 Fail 22 NA

10 VO 13 Fail 15 257

11 VO 15 Fail 9 273

12 VO 14 Fail 14 NA

13 VO 14 Fail 16 NA

14 VO 15 Fail 16 193

15 VO 12 Fail 28 NA

16 VO 14 Fail 10 209

17 VO 11 Fail 13 NA

^♦Comparative examples.

[0100] Each control sample CSla-CSlc and each inventive sample 14-22 exhibited a VO rating for 1 mm thickness flame bars and each failed in UL94 5VB test method. Thus neither flammability method was sufficient to differentiate the flammability of different samples. The total flame out times (t-FOT) of CSla (STM1700) and CS lb (STM1600) by UL94 VO test method were 17 and 31 seconds respectively. Similarly, the t-FOT of CSla and CS lb by UL94 5VB are 11 and 34 seconds respectively. Sample 9 revealed that the incorporation of the LEXAN™ FST-ITR resin to SILTEM™ resins increased the t-FOT of STM1700 to 20 seconds and 22 seconds by UL94 V0 and 5VB test methods respectively. On contrary, the addition of LEXAN™ FST-ITR reduced the t-FOT of STM1600 to 13 and 15 seconds by UL94 V0 and 5VB test methods respectively as shown in Sample 10. The differences in the t-FOT of samples 9 and 10 can be attributed to their compositional differences. On average, samples with flame retardant additives (16-22) had shorter t-FOT times than the commercial SILTEM™ resins. The organic flame retardant additives, BPADP and SPB-100 were more effective in reducing t-FOT than the inorganic flame retardant additive, zinc borate. The maximum smoke density of all samples was less than 300 units, indicating all samples were low-smoke resins. [0101] Microscale Combustion Calorimetry (MCC) was used to further assess the flammability of polymers using only milligrams of the test specimen. In MCC followed herein, 4 milligram (mg) to 5 mg sized samples were first decomposed in a pyrolysis chamber in a nitrogen environment (method A). The samples were then evaluated according to the ASTM D7309 standard. The heating rate was 1 °C per second (°C/s) and the maximum decomposition temperature was 750 °C. The temperature of combustion chamber was maintained at a constant 900 °C while 20 cubic centimeters per minute (cc/min) of oxygen and 80 cc/min of nitrogen were supplied to the equipment during the test.

[0102] Peak heat release rate (PHRR), temperature to Peak heat release rate (Tp) and total heat release (THR) were determined to provide an empirical flammability index (FI).

Lower FI values indicate better resistance to flame or ignition. The SILTEM™ STM1700 (CSla) was used as reference and the FI equation below compares the performance of different resins in comparison to CS 1.

„. PHRR(x) THR (x) 548 ₁

r l =

160 * 12 *——

Tp(x) ( 1 ')

[0103] Cone calorimetry was also used to assess flammability according to the test methods prescribed in ISO5660 and ASTM El 354. Cone calorimetry was also used to indicate the smoke generation of the resins when subjected to fire. The cone calorimetry method observed heat release, mass loss, and smoke generation providing for the assessment of for several fire properties such as: heat release rate (HRR), peak heat release rate (PHRR), time to ignition (TTI), total heat release (THR), mass loss rate (MLR), peak of mass loss (PMLR) and specific extinction area (SEA). The fire growth rate FIGRA (PHRR/time to PHRR) was also derived from cone-calorimetry evaluation. Lower FIGRA values indicated better flame resistance performance. The SEA measures the relative smokiness, or smoke generation, of a given sample. For SEA, the samples were approximately 100 millimeters (mm) by 100 mm by 3 mm and the applied heat flux was 35 kilowatts per square meter (kw/m²). The samples were wrapped in aluminum foil (shiny surface to the sample) with only one surface of the sample horizontally exposed to the applied heat flux. The distance between cone heater and the sample surface was 60 mm. Table 6 provides results for additional fire properties.

Table 6. Results from comprehensive flammability testing by MCC and Cone Calorimetry of polysiloxane/polyimide and resorcinol based polyester carbonate polysiloxane copolymer samples.

Samples | MCC | Cone Calorimetry Flame

Index

PHRR THR Tp (FI) PHRR TTI FIGRA SEA PSPR w/g kJ/S °c (kw s (kw/m².s) (mVs)

STM1700*

(CSla) 160 12 548 1 76 200 0.19 902 0.05

STM1600*

(CSlb) 185 14 525 1.41 88 200 0.18 880 0.04

LEXAN™

FST-ITR*

(CSlc) 196 9.8 502 0.94 140 130 1.03 256 0.05

9 202 12 502 1.38 148 125 1.06 650 0.07

10 155 10.5 505 0.92 152 140 0.89 382 0.06

11 190 10.1 512 1.07 200 140 1.21 480 0.08

12 228 12 504 1.55 157 150 0.92 680 0.08

13 195 11 511 1.20 144 170 0.67 610 0.06

14 251 10.5 478 1.57 137 85 1.49 240 0.05

15 175 11 472 1.16 137 89 1.26 354 0.04

16 184 10.6 508 1.10 151 168 0.69 605 0.07

17 200 11.5 504 1.30 131 135 0.75 777 0.04 comparative examples

[0104] CSla-CSlc and Samples 9 to 17 were tested in pellet form for MCC analyses while molded plaques were used for cone calorimetry testing. CSla lacked tensile elongation and tear strength that are essential for wire and cable application but is inherently flame retardant material. Thus, CSla could be considered as benchmark material for the evaluating the flammability of resins in this studies. CSlb has better mechanicals than CSla i.e. higher tensile elongation and lower flexural modulus, but had reduced flame. The PHRR and THR were higher for CSlb and lower T_p and hence the flame index was around 1.41. CSlc resin had even higher PHRR, lower T_p than CSlb but lower THR and thus the flame index was around 0.94. The combination of LEXAN™ FST-ITR and STM1700 (Sample 9) increased the PHRR significantly and reduced the T_p without affecting the THR. The lower T_p of the blend would make it is easier to ignite and with higher PHRR it would be easier for flame to spread. The combination of LEXAN™ FST-ITR and STM1600 (Sample 10) on the other hand, reduced PHRR and THR, probably due to higher siloxane content and hence FI was around 0.92. For the

SILTEM™1700/FST-ITR based blends, the BPADP of Samples 11 and 13) and the SPB-100 of Sample 16 appeared to reduce the PHRR by 6% and 9% respectively. They also slightly reduced the THR and increased the temperature at PHRR. Thus, BPADP and SPB-100 containing

STM1700/FST-ITR blend exhibited a better flammability resistance than blends without them. On the other hand, for Samples 12, 15, and 17 ( SILTEM™1600/FST-ITR blends), it was apparent that all flame retardants increased the PHRR results. For both Samples 14

(SILTEM™1700/FST-ITR) and 7 (SILTEM™1600/ FST-ITR) with the zinc borate flame retardant additive, the T_p was greatly reduced and PHRR was increased and thus had lower flame resistance. Samples 13 including the LEXAN™ EXL appeared to have slightly poorer MCC performance, possibly due to the relatively inferior performance of LEXAN™ EXL itself.

[0105] The flame performance of the materials was analyzed by cone calorimetry and the fire growth rate or FIGRA (PHRR/time to PHRR), SEA (average specific extinguish area) and TTI (Time to Ignition). A high PHRR and short time to PHRR yield high FIGRA values which indicates that the sample has a higher tendency for fire growth. The PHRR values for SILTEM™ resins CSla-STM1700 and CSlb-STM1600 were low, thus the FIGRA would also be low for both these. The addition of LEXAN™ FST-ITR would result in higher PHRR and a lower time to PHRR and a much higher FIGRA for the blends (samples 9 and 10). Sample 15 has s lesser amount of LEXAN™ FST-ITR in its composition and thus has better FIGRA when compared to sample 9. Samples 11-13 containing BPADP and samples 14 and 15 containing zinc borate either exhibited increased PHRR or reduced time to PHRR. Accordingly, these samples had higher FIGRA than the samples without the additives. Based on samples 16 and 17 containing SPB-100, SPB-100 appeared to be an effective flame retardant additive which either reduced the PHRR or time to PHRR, thus causing much lower FIGRA values. However, for sample 11 the char formation was more noticeable. While sample 11 exhibited the highest PHRR, as long as the char layer forms, the HRR decreased dramatically, and the flame self- extinguished. Removing the char layer, the un-burnt resin was left out, which confirmed that char layer protected the underlying material. The charring results also indicated the limitation of MCC because one would be unable to determine the protection afforded by the char barrier since the sample size is so small. The BPADP and SPB-100 either increased or do not affect the TTI of S ILTEM™/F ST-ITR blends. However, the zinc borate did appear to degrade the LEXAN™ FST-ITR resin and reduce the TTI significantly which was consistent with FIGRA and FI data. Cone calorimetry also provided smoke information. As shown in Table 3, compared to STM 1700 and STM1600, the SILTEM™/F S T-ITR blends had much lower average specific extinguish area (SEA). For SEA, the higher value the more smoke been generated. The result confirmed the low smoke generation from the LEXAN™ FST-ITR resins.

Wire Testing

[0106] Samples 10 and 11 were dried at 105 °C and extruded onto AWG 22 solid copper (preheated to 80 °C) with insulation thickness within the range of 0.2 to 0.3 mm. The extrusion was performed with a tube die and at a 300 °C to 330 °C melt temperature, a 4.5 MPa melt pressure, and a 20-50 m/min line speed. The tensile elongation at break of the wire coatings was evaluated using an Instron testing machine. The flame resistance of the SILTEM™/FST- ITR blends was tested using VW-1 method according to UL1581 standard. Results are presented in Table 7.

Table 7. Properties of the wires of polysiloxane/polyimide (SILTEM™ STM1700 and

STM1600) and Resorcinol based Polyester Carbonate Copolymer (LEXAN™ FST-ITR) Blend.

* comparative examples.

[0107] The blends showed excellent wire coating processability and property performance. The STM1600/FST-ITR blend exhibited a tensile elongation to break more than 150%, which is improved in comparison with STM1700 and STM1600. The SILTEM™/FST- ITR blends robustly pass VW-1 flame test indicating that the flame retardancy of these blends are on par with SILTEM™ resins. A significant improvement in the tear strength was also observed for SILTEM™/FST-ITR blends compared to individual SILTEM™ resins.

[0108] In summary, the addition of LEXAN™ FST-ITR resin to SILTEM™ resins improves their tensile elongation, impact strength, flexural strength, tear strength, smoke generation with moderate increase in flexural modulus. In this studies, the flame retardancy of these blends have been improved by adding three different flame retardant additives. The wire processability and improvement in the mechanicals by these blends when compared to commercial SILTEM™ resins and at the same pass the flammability tests.

[0109] As used herein, the terms "about" and "at or about" mean that the amount or value in question can be the value designated some other value approximately or about the same. It is generally understood, as used herein, that it is the nominal value indicated ±10% variation unless otherwise indicated or inferred. The term is intended to convey that similar values promote equivalent results or effects recited in the claims. That is, it is understood that amounts, sizes, formulations, parameters, and other quantities and characteristics are not and need not be exact, but can be approximate and/or larger or smaller, as desired, reflecting tolerances, conversion factors, rounding off, measurement error and the like, and other factors known to those of skill in the art. In general, an amount, size, formulation, parameter or other quantity or characteristic is "about" or "approximate" whether or not expressly stated to be such. It is understood that where "about" is used before a quantitative value, the parameter also includes the specific quantitative value itself, unless specifically stated otherwise.

[0110] When values are expressed as approximations, by use of the antecedent 'about,' it will be understood that the particular value forms another aspect. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint. It is also understood that there are a number of values disclosed herein, and that each value is also herein disclosed as "about" that particular value in addition to the value itself. For example, if the value " 10" is disclosed, then "about 10" is also disclosed. It is also understood that each unit between two particular units are also disclosed. For example, if 10 and 15 are disclosed, then 11 , 12, 13, and 14 are also disclosed.

[0111] While aspects of the present disclosure can be described and claimed in a particular statutory class, such as the system statutory class, this is for convenience only and one of skill in the art will understand that each aspect of the present invention can be described and claimed in any statutory class. Unless otherwise expressly stated, it is in no way intended that any method or aspect set forth herein be construed as requiring that its steps be performed in a specific order. Accordingly, where a method claim does not specifically state in the claims or descriptions that the steps are to be limited to a specific order, it is no way intended that an order be inferred, in any respect. This holds for any possible non-express basis for interpretation, including matters of logic with respect to arrangement of steps or operational flow, plain meaning derived from grammatical organization or punctuation, or the number or type of aspects described in the specification.

[0112] Moreover, it is to be understood that unless otherwise expressly stated, it is in no way intended that any method set forth herein be construed as requiring that its steps be performed in a specific order. Accordingly, where a method claim does not actually recite an order to be followed by its steps or it is not otherwise specifically stated in the claims or descriptions that the steps are to be limited to a specific order, it is no way intended that an order be inferred, in any respect. This holds for any possible non-express basis for interpretation, including: matters of logic with respect to arrangement of steps or operational flow; plain meaning derived from grammatical organization or punctuation; and the number or type of aspects described in the specification.

[0113] It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting. As used in the specification and in the claims, the term "comprising" may include the aspects "consisting of and "consisting essentially of." Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs.

[0114] As used in the specification and the appended claims, the singular forms "a," "an" and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a polycarbonate" includes mixtures of two or more such polycarbonates. Furthermore, for example, reference to a filler includes mixtures of two or more such fillers.

[0115] Ranges can be expressed herein as from "about" one particular value, and/or to "about" another particular value. When such a range is expressed, another aspect includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent "about," it will be understood that the particular value forms another aspect. A value modified by a term or terms, such as "about" and "substantially," is intended to include the degree of error associated with measurement of the particular quantity based upon the equipment available at the time of filing this application. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint. It is also understood that there are a number of values disclosed herein, and that each value is also herein disclosed as "about" that particular value in addition to the value itself. For example, if the value "10" is disclosed, then "about 10" is also disclosed. It is also understood that each unit between two particular units are also disclosed. For example, if 10 and 15 are disclosed, then 1 1, 12, 13, and 14 are also disclosed.

[0116] As used herein, the terms "optional" or "optionally" mean that the subsequently described event, condition, component, or circumstance may or may not occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.

[0117] Disclosed are component materials to be used to prepare disclosed compositions as well as the compositions themselves to be used within methods disclosed herein. These and other materials are disclosed herein, and it is understood that when combinations, subsets, interactions, groups, etc. of these materials are disclosed that while specific reference of each various individual and collective combinations and permutation of these compounds cannot be explicitly disclosed, each is specifically contemplated and described herein. For example, if a particular compound is disclosed and discussed and a number of modifications that can be made to a number of molecules including the compounds are discussed, specifically contemplated is each and every combination and permutation of the compound and the modifications that are possible unless specifically indicated to the contrary. Thus, if a class of molecules A, B, and C are disclosed as well as a class of molecules D, E, and F and an example of a combination molecule, A-D is disclosed, then even if each is not individually recited each is individually and collectively contemplated meaning combinations, A-E, A-F, B-D, B-E, B-F, C-D, C-E, and C-F are considered disclosed. Likewise, any subset or combination of these is also disclosed. Thus, for example, the sub-group of A-E, B-F, and C-E would be considered disclosed. This concept applies to all aspects of this application including, but not limited to, steps in methods of making and using the compositions of the disclosure. Thus, if there are a variety of additional steps that can be performed it is understood that each of these additional steps can be performed with any specific aspect or combination of aspects of the methods of the disclosure.

[0118] References in the specification and concluding claims to parts by weight, of a particular element or component in a composition or article denotes the weight relationship between the element or component and any other elements or components in the composition or article for which a part by weight is expressed. Thus, in a composition containing 2 parts by weight of component X and 5 parts by weight component Y, X and Y are present at a weight ratio of 2:5, and are present in such ratio regardless of whether additional components are contained in the compound. A weight percent of a component, unless specifically stated to the contrary, is based on the total weight of the formulation or composition in which the component is included.

[0119] Compounds disclosed herein are described using standard nomenclature. For example, any position not substituted by any indicated group is understood to have its valency filled by a bond as indicated, or a hydrogen atom. A dash ("-") that is not between two letters or symbols is used to indicate a point of attachment for a substituent. For example, -CHO is attached through carbon of the carbonyl group. Unless defined otherwise, technical and scientific terms used herein have the same meaning as is commonly understood by one of skill in the art to which this disclosure belongs.

[0120] As used herein, the terms "number average molecular weight" or "Mn" can be used interchangeably, and refer to the statistical average molecular weight of all the polymer chains in the sample and is defined by the formula:

„ . ∑NiMi

Mn = ,

∑Ni

where M; is the molecular weight of a chain and N; is the number of chains of that molecular weight. Mn can be determined for polymers, such as polycarbonate polymers or polycarbonate- polysiloxane copolymers, by methods well known to a person having ordinary skill in the art.

[0121] As used herein, the terms "weight average molecular weight" or "Mw" can be used interchangeably, and are defined by the formula:

„ . ∑NiMi²

Mw = ^ ∑NiMi ,

where Mi is the molecular weight of a chain and Ni is the number of chains of that molecular weight. Compared to Mn, Mw takes into account the molecular weight of a given chain in determining contributions to the molecular weight average. Thus, the greater the molecular weight of a given chain, the more the chain contributes to the Mw. It is to be understood that as used herein, Mw is measured by gel permeation chromatography. In some cases, Mw can be measured by gel permeation chromatography and calibrated with polycarbonate standards. As an example, a polycarbonate of the present disclosure can have a weight average molecular weight of greater than about 5,000 Daltons based on PS standards. As a further example, the polycarbonate can have an Mw of from about 20,000 to about 100,000 Daltons.

Claims

Claimed:

A resin composition comprising:

from 10 wt. % to about 70 wt. % of a polysiloxane/polyimide block copolymer;

from about 20 wt. % to about 90 wt. % of a siloxane-resorcinol based polyester carbonate copolymer; and

wherein the combined weight percent value of all components in the resin composition does not exceed about 100 wt. %, and wherein the resin composition has a total siloxane content of from about 3 wt. % to about 25 wt. %.

The resin composition of claim 1, wherein the resin composition further comprises an additive.

The resin composition of claim 2, wherein the additive comprises a pigment, a dye, a filler, a plasticizer, a fiber, a flame retardant, an antioxidant, a lubricant, wood, glass, metal, an ultraviolet agent, an anti-static agent, an anti-microbial agent, impact modifier or a combination thereof.

The resin composition of claim 2, wherein the additive comprises a flame retardant or a smoke suppressant.

The resin composition of claim 4, wherein the flame retardant or smoke suppressant comprises phosphagene, zinc borate, bisphenol A bis-(diphenyl phosphate or combinations thereof.

The resin composition of any one of the preceding claims, wherein the resin composition comprises a flame retardant or a smoke suppressant or a combination thereof and wherein the resin composition exhibits a tensile modulus of from about 1920 MPa to about 2600 MPa, a tensile strength of from about 50 MPa to about 80 MPa, a tensile elongation of from about 15% to about 135%, a flexural modulus of from about 1900 MPa to about 2650 MPa, a flexural strength of from about 80 MPa to about 130 MPa when measured in accordance with ASTM D638 and a glass transition temperature of from about 140 to about 200 °C measured using differential scanning calorimetry at a rate of 20 °C per minute.

The resin composition of any one of the preceding claims, wherein the resin composition comprises a flame retardant or a smoke suppressant or a combination thereof and wherein the resin composition exhibits (a) a peak heat release rate from about 150 W/g to about 260 W/g; (b) a total heat release from about 8 kJ/g to about 14 kJ/g; (c) a temperature of maximum mass loss rate of from about 465 °C to about 515 °C; and (d) a flame index of from about 0.8 to 1.6 when tested in accordance with MCC D7309; (e) a peak heat release rate of from about 125 kilowatts per square meter (kw/m²) to about 205 kw/m², (f) a time to ignition of from about 80 s to about 180 s, (e) a fire growth rate of from about 0.5 kilowatts per square meter per second kw/m² s to about 1.6 kw/m² s, (f) a specific extinction area of from about 230 square meters per kilogram (m²/kg) to about 785 m²/kg, and (g) a peak smoke production rate from about 0.03 square meters per second (m²/s) to about 0.09 m²/s when tested using a cone calorimeter according to

ISO5660/ASTM E1354.

8. The resin composition of any one of the preceding claims, wherein the resin composition comprises a flame retardant or a smoke suppressant or a combination thereof and wherein the resin composition exhibits a V0 flame rating at 1 mm measured according to UL 94 (2014) with a flame out time (t-FOT) of from about 10 s to 25 s; and (g) an NBS smoke specific optical density (Ds) in flaming mode of 190 Ds to about 280 Ds as measured by ASTM E662.

9. The resin composition of any one of claims 4-8, wherein the flame retardant or the smoke suppressant is present in the composition in an amount less than about 10 wt. %.

10. The resin composition of any one of claims 4-8, further comprising about 5 wt. % of bisphenol A bis-(biphenyl) phosphate and its polymers.

11. The resin composition of any one of the preceding claims, wherein the

polysiloxane/polyimide copolymer has a molecular weight of from about 20,000 Daltons to about 60,000 Daltons.

12. The resin composition of any one of the preceding claims, wherein the

polysiloxane/polyimide has a glass transition temperature of from about 100 °C to about 250 °C.

13. The resin composition of any one of the preceding claims, wherein the resorcinol based polyester carbonate siloxane copolymer is an isophthalate-terephthalate-resorcinol)- carbonate copolymer.

14. The resin composition of any one of the preceding claims, wherein the resorcinol based polyester carbonate is a poly(bisphenol A carbonate)-co-(isophthalate-terephthalate- resorcinol ester).

15. The resin composition of any one of the preceding claims, wherein the resorcinol based polyester carbonate comprises from 1 mole percent to 20 mole percent of bisphenol A carbonate units, from 20 mole percent to 98 mole percent of isophthalic acid-terephthalic acid-resorcinol ester units, and from 0 mole percent to 60 mole percent of resorcinol carbonate units, isophthalic acid-terephthalic acid-bisphenol A phthalate ester units, or a combination thereof.

16. An article comprising the resin composition of any one of the preceding claims.

17. The article of claim 16, wherein the article is selected from the group consisting of:

electrical connectors, electrical wires, and electrical housings.

18. The article of claim 16, wherein the article is selected from the group consisting of

optical fiber cables, data communication cables, rolling stock cables, films, foams, sheets, separator, injection molded articles, profile extruded articles, and tapes.

19. A resin composition comprising:

from 8 wt. % to about 95 wt. % of a polysiloxane/polyimide block copolymer;

from about 4 wt. % to about 91 wt. % of a siloxane-resorcinol based polyester carbonate copolymer; and wherein the resin composition has a total siloxane content of from about 3 wt. % to about 25 wt. %;

wherein the combined weight percent value of all components in the resin composition does not exceed about 100 wt. %; and

wherein the resin composition exhibits a tensile modulus of from about 1900 MPa to about 2600 MPa, a tensile strength of from about 50 MPa to about 80 MPa, a tensile elongation at yield of from about 3% to about 8 %, a flexural modulus of from about 1900 MPa to about 2650 MPa, a flexural strength of from about 80 MPa to about 120 MPa when measured in accordance with ASTM D638 and a glass transition temperature of from about 140 to about 200 °C measured using differential scanning calorimetry at a rate of 20 °C per minute.

20. A method of forming a resin composition comprising: combining about 8 wt. % to about 90 wt. % of polysiloxane polyimide copolymer and from about 8 wt. % to about 90 wt. % of a resorcinol based polyester carbonate siloxane copolymer; and the resin composition has a total siloxane content of from about 3 wt. % to about 25 wt. %; and

wherein the combined weight percent value of all components in the resin composition does not exceed about 100 wt. %, and wherein all weight percent values are based on the total weight of the resin composition.