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WO2018034680A1 - Mélanges de copolymères de polysiloxane/polyimide et de carbonate de polyester à base de résorcinol pour revêtement de fils électriques - Google Patents

Mélanges de copolymères de polysiloxane/polyimide et de carbonate de polyester à base de résorcinol pour revêtement de fils électriques Download PDF

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Publication number
WO2018034680A1
WO2018034680A1 PCT/US2016/053883 US2016053883W WO2018034680A1 WO 2018034680 A1 WO2018034680 A1 WO 2018034680A1 US 2016053883 W US2016053883 W US 2016053883W WO 2018034680 A1 WO2018034680 A1 WO 2018034680A1
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Prior art keywords
resin composition
mpa
polysiloxane
copolymer
resorcinol
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Inventor
Raghavendra Raj MADDIKERI
Jinfeng ZHUGE
Hariharan Ramalingam
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SABIC Global Technologies BV
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SABIC Global Technologies BV
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C08L69/005—Polyester-carbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/445—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences
    • C08G77/448—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences containing polycarbonate sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/452—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences
    • C08G77/455—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences containing polyamide, polyesteramide or polyimide sequences

Definitions

  • the disclosure concerns polysiloxane/polyimide compositions containing resorcinol based polyester polycarbonate resin compositions with polysiloxane units for use in electric wire coating.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the present disclosure relates to a resin composition
  • 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 present disclosure also relates to a resin composition
  • 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.
  • 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.
  • the present disclosure relates to a method of forming a resin composition
  • 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. %.
  • the present disclosure further relates to a wire coating resin composition
  • 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.
  • the present disclosure relates to an electrical wire coating resin composition
  • an electrical wire coating resin composition comprising a polysiloxane polycarbonate copolymer, a polycarbonate copolymer, and a polysiloxane/polyimide block copolymer.
  • the electrical wire coating resin composition may comprise a polysiloxane/polyimide block copolymer and a resorcinol-based polyester polycarbonate copolymer.
  • polycarbonate or “polycarbonates” as used herein includes copoly carbonates, homopoly carbonates and (co)polyester carbonates.
  • polycarbonate can be further defined as compositions have repeating structural units of the formula (1):
  • each R 1 can be an aromatic group and, more preferably, R 1 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 A 1 and A 2 is a monocyclic divalent aryl radical and Y 1 is a single bond or a bridging group having one or two atoms that separate A 1 from A 2 . In some examples, a single atom separates A 1 from A 2 .
  • each R 1 can be derived from an aromatic dihydroxy compound such as a bisphenol of formula 3):
  • 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(0 2 ) -, -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-i 8 cycloalkylene group, or a group of the formula -B ⁇ Q-B 2 - wherein B 1 and B 2 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):
  • 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
  • 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.
  • 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- ⁇ aryl group, or a halogen substituted C6-10 aryl group, or a halogen substituted C6-10 aryl group, and n is 0 to 4.
  • 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.
  • bisphenol-A 2,2-bis(4-hydrox yphenyl)butane
  • BP A 2,2-bis(4-hydroxyphenyl)octane
  • l,l-bis(4 hydroxyphenyl)propane 1, 1 -bis(4 - hydroxy
  • the resin compositions of the present disclosure can comprise repeating polycarbonate units of the formula (l a):
  • 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.
  • a 1 and A 2 are p-phenylene and Yl is isopropylidene, the repeating units can be referred to as "bisphenol A carbonate units.”
  • the resin compositions of the present disclosure can comprise poly(carbonate-arylate ester) copolymers comprising repeating arylate ester units of formula (6):
  • Ar is a Ce-n hydrocarbyl group containing at least one aromatic group, e.g., a phenyl, naphthalene, anthracene, or the like.
  • Ar 1 is derived from a bisphenol (3), a monoaryl dihydroxy compound (5), or a combination comprising different bisphenol or monoaryl dihydroxy compounds.
  • 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.
  • 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):
  • 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.
  • 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.
  • 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.
  • 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.
  • Specific poly(ester-carbonate)s are those including bisphenol A carbonate units and isophthalate-terephthalate-bisphenol A ester units, also commonly referred to as
  • 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).
  • 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):
  • 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).
  • PCE poly(carbonate-ester)s
  • PPC poly(phthalate-carbonate)s
  • 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)
  • 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- ⁇ aryl group, or a halogen-substituted ⁇ - ⁇ aryl group, and n is 0 to 4.
  • each R h is independently a C1-4 alkyl, and n is 0 to 3, 0 to 1, or 0.
  • R 1 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.
  • 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)
  • 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.
  • the resorcinol based polyester polycarbonate copolymer can include LEXANTM FST-ITR available commercially from SABIC (LEXANTM is a trademark of SABIC IP B. V.).
  • 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.
  • 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).
  • 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)
  • 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.
  • 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):
  • 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.
  • 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.
  • M w weight average molecular weight
  • 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.
  • the poly(carbonate-arylate ester) copolymers further comprise siloxane units (also known as "diorganosiloxane units").
  • these copolymers comprises carbonate units (1) derived from a bisphenol (3), specifically bisphenol-A; monoaryl arylate ester units (7b), and siloxane units.
  • the poly(carbonate-arylate ester) copolymers comprises bisphenol-A carbonate units, ITR ester units (7c), and siloxane units (9).
  • poly(bisphenol-A carbonate)-co- poly(isophthalate-terephthalate-resorcinol ester)-co-poly(siloxane) can be referred to herein as "ITR-PC-siloxane” copolymers.
  • the polysiloxane units can be of formula (10):
  • each R is independently a C 1-13 monovalent hydrocarbyl group.
  • 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- ⁇ aryloxy group, C 7- 13 arylalkyl group, C 7-13 arylalkoxy group, C 7-13 alkylaryl group, or C7-i 3 alkylaryloxy group.
  • the foregoing groups can be fully or partially halogenated with fluorine, chlorine, bromine, or iodine, or a combination thereof.
  • the polysiloxane comprises R groups that have minimal hydrocarbon content.
  • an R group with a minimal hydrocarbon content is a methyl group.
  • 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.
  • E has an average value of 2 to 500, 2 to 200, or 5 to 100, 10 to 100, or 10 to 80.
  • E has an average value of 16 to 50, more specifically 20 to 45, and even more specifically 25 to 45.
  • 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.
  • polysiloxane units can be structural units of formula (10a):
  • 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.
  • the dihydroxy aromatic compound is unsubstituted, or does not contain non-aromatic hydrocarbyl substituents such as alkyl, alkoxy, or alkylene substituents.
  • 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):
  • 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
  • Commercially available polysiloxane/polyetherimides can be obtained from SABIC Innovative Plastics under the brand name SILTEMTM (Trademark of SABIC Innovative Plastics IP B.V.).
  • the polysiloxane/polyimide block copolymers disclosed herein can comprise polysiloxane blocks and polyimide blocks.
  • the number of siloxane units (g) of formula (11) can determine the size of the siloxane block for 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
  • 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.
  • 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.
  • 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.
  • Diamino siloxanes can be of formula (12):
  • R 1"6 and g are defined as above for formula (1).
  • R2-5 are methyl groups and Rl and R6 are alkylene groups.
  • R 1 and R 6 are alkylene groups having 3 to 10 carbons.
  • R 1 and R 6 are the same and in some embodiments R 1 and R 6 are different.
  • Useful dianhydrides in the preparation of extended siloxane oligomers can have the formula (13):
  • 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
  • W is a divalent moiety such as -0-, -S-, -C(O) -, -S0 2 -, -C y H 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
  • 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.
  • 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.
  • dianhydride refers to dianhydrides and their chemical equivalents.
  • the extended siloxane oligomers described above can be further reacted with non-siloxane diamines and additional dianhydrides to make the polysiloxane/polyimide block copolymer.
  • polysiloxane/polyimide block copolymer should be about equal so that the copolymer can polymerize to a high molecule weight.
  • 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.
  • Mn number average molecular weight
  • the additional dianhydride may be the same or different from the dianhydride used to form the extended siloxane oligomer.
  • the non-siloxane polyimide block can comprise repeating units having the general Formula (15):
  • 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).
  • R 10 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):
  • R 9 and R 10 can be the same or can be different.
  • 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.
  • 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.
  • smoke conductivity as judged by the change in Water conductivity can be less than or equal to 1000 microsiemens.
  • the smoke has an acidity, as determined by pH, greater than or equal to 5.
  • the extended siloxane oligomers can be further reacted with non-siloxane diamines and additional dianhydrides to form the polysiloxane/polyimide block copolymer.
  • the non-siloxane polyimide blocks can comprise a polyetherimide block.
  • Polyetherimide blocks can com rise repeating units of formula (18):
  • 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):
  • 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):
  • dianhydrides includes chemical equivalents of dianhydrides.
  • Diamines useful for forming the repeating units of Formula (16) and (18) have the formula H 2 N-R 10 -NH 2 (21) wherein R 10 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.
  • 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.
  • the extended siloxane oligomer is amine terminated and the non- siloxane polyimide oligomer is anhydride terminated.
  • the extended siloxane oligomer is anhydride terminated and the non-siloxane polyimide oligomer is amine terminated.
  • 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.
  • the siloxane content can be less than or equal to 40 wt.
  • 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.
  • 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. %.
  • 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.
  • 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.
  • the polysiloxane/ polyimide copolymer and, in particular, a polyetherimide copolymer can have a glass transition temperature of 240 to 350 °C.
  • 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.
  • ASTM American Society for Testing Materials
  • 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.
  • the resorcinol moiety content 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.
  • 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,
  • 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.
  • the disclosed composition can comprise one or more additional fillers, plasticizers, stabilizers, anti-static agents, impact modifiers, colorant, antioxidant, and/or mold release agents.
  • the resin compositions can comprise an antioxidant.
  • the antioxidants can include either a primary or a secondary antioxidant.
  • 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.
  • the resin composition composition can comprise a mold release agent.
  • 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.
  • heat stabilizer additive can be used.
  • 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;
  • 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.
  • 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.
  • the disclosed composition can comprise antistatic agents.
  • antistatic agents can include, for example, glycerol monostearate, sodium stearyl sulfonate, sodium dodecylbenzenesulfonate or the like, or combinations of the foregoing antistatic agents.
  • 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.
  • 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 (CYASORBTM 531); 2-[4,6-bis(2,4-dimethylphenyl)-l,3,5-triazin-2-yl]- 5-(octyloxy)-phenol (CYASORBTM 1164); 2,2'-(l,4- phenylene)bis(4H-3,l-benzoxazin-4-one) (CYASORBTM 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
  • 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).
  • SAN styrene-acrylonitrile copolymer
  • TSAN styrene-acrylonitrile copolymer
  • TSAN styrene-acrylonitrile copolymer
  • 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.
  • additives to improve flow and other properties may be added to the composition, such as low molecular weight hydrocarbon resins.
  • 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
  • the resin compositions of the present disclosure a can exhibit properties particularly advantageous to use as a wire coating resin.
  • a low flexural modulus can be an essential property for a material to be used as a wire coating.
  • 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.
  • the resin compositions disclosed herein have a flexural modulus of up to about 2500 MPa.
  • 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 LEXANTM FST-ITR, having a flexural modulus of about 2500 MPa can thereby increase the flexural modulus when blended with a SILTEMTM resin such as STM 1700 or STM 1500.
  • a phosphazene FR additive has a lesser effect on the flexural modulus of the resin blends disclosed than the bisphenol A bis-(diphenyl phosphate)
  • the resin compositions disclosed herein can have a tensile elongation of greater than about 80 % elongations.
  • STM 1700 can have a tensile elongation of about 25 %, STM 1600 at about 130 %, and LEXANTM FST-ITR of about 45 % elongation.
  • 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.
  • 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.
  • 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.
  • t-FOT flame out time
  • 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/m 2 to about 205 kw/m 2 peak heat release, from about 80 s to about 180 s time to ignition, from about 0.5 kw/m 2 s to about 1.6 kw/m 2 s fire growth rate, from about 230 m 2 /kg to about 785 m 2 /kg specific extinction area, and from about 0.03 m 2 /s to about 0.09 m 2 /s peak smoke production rate when tested using a cone calorimeter according to ISO5660/ASTM El 354.
  • 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.
  • the compositions disclosed herein may exhibit improved tensile elongation, tear strength, heat release, flame retardance, and flexural modulus.
  • 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.
  • the resin may be a coating for electrical wiring.
  • the resin composition may be formed into electrical wire coating.
  • the resin composition may be extruded onto electrical wire at a desired insulating thickness.
  • the resin composition may be coated onto a copper wire at an insulation thickness of from about 0.1 to about 0.4 mm.
  • the present disclosure can include at least the following aspects.
  • 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. %.
  • Aspect 2 The resin composition of claim 1 , wherein the resin composition further comprises an additive.
  • 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.
  • Aspect 4 The resin composition of claim 2, wherein the additive comprises a flame retardant or a smoke suppressant.
  • 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.
  • 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.
  • 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/m 2 s to about 1.6 kw/m
  • 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.
  • t-FOT flame out time
  • Ds NBS smoke specific optical density
  • 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. %.
  • 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.
  • 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.
  • 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).
  • 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.
  • Aspect 17 The article of claim 16, wherein the article is selected from the group consisting of: electrical connectors, electrical wires, and electrical housings.
  • 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.
  • 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.
  • 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.
  • 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.
  • Blends of polysiloxane/polyimide copolymers (SILTEMTM), polycarbonate polysiloxane copolymer (PC-ST or LEXANTM-ST) were prepared. Resin blends comprising 10 parts by weight (pbw) to 90 pbw SILTEMTM and 10 pbw to 90 pbw LEXANTM 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).
  • SILTEMTM polysiloxane/polyimide copolymers
  • SILTEMTM polycarbonate polysiloxane copolymer
  • PC-ST polycarbonate polysiloxane copolymer
  • PC- 175 polycarbonate derived from bisphenol A units
  • 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 comprised STM 1700.
  • the notched Izod impact (" ⁇ ") 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.
  • STM1700 and 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. % LEXANTM FST-ITR composition and for STM1600 based blends at composition 50 wt. % STM1600 and 50 wt. % LEXANTM 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.
  • additional flame retardants bisphenol A bis-(biphenyl) phosphate BPADP, zinc borate ZB, and phosphazene (SPB-100
  • Bisphenol A bis-(biphenyl) phosphate may include polymers of the structure including its polymers which can include its monomers, oligomers, and other structural polymers.
  • 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.
  • Zinc Borate (ZB) 0 0 0 0 0 5 5 0 0
  • 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 (SILTEMTM STM1700) as comparative sample 1 (CS la), a resorcinol based polyester carbonate copolymer (LEXANTM 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.
  • SILTEMTM STM1700 comparative sample 1
  • LXANTM FST-ITR resorcinol based polyester carbonate copolymer
  • 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 (LEXANTM FST-ITR) resin.
  • SILTEMTM/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.
  • 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.
  • Sample 18 also included a polysiloxane-poly carbonate (LEXANTM 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.
  • LXANTM EXL polysiloxane-poly carbonate
  • 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.
  • LEXANTM FST-ITR resins to SILTEMTM resins increased the tensile strength of blends.
  • the notched impact resistance at room temperature is improved for Samples 14-22 (SILTEMTM/FST-ITR blends), compared to individual constituent resins CSla-,CS lb, and CSlc.
  • the three FR additives reduced the impact strength significantly.
  • BPADP reduced the impact strength moderately, zinc borate significantly while SPB-100 increased the impact resistance significantly.
  • 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.
  • 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.
  • 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 LEXANTM FST-ITR resin to SILTEMTM 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 LEXANTM 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 SILTEMTM resins.
  • MCC Microscale Combustion Calorimetry
  • 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.
  • Peak heat release rate PHRR
  • temperature to Peak heat release rate Tp
  • total heat release TRR
  • 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.
  • 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/m 2 ).
  • 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.
  • 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 l acked 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 LEXANTM 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 LEXANTM FST-ITR and STM1600 (Sample 10) reduced PHRR and THR, probably due to higher siloxane content and hence FI was around 0.92.
  • FIGRA PHRR/time to PHRR
  • SEA average specific extinguish area
  • TTI Time to Ignition
  • Sample 15 has s lesser amount of LEXANTM 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.
  • 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.
  • 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.
  • the SILTEMTM/F S T-ITR blends had much lower average specific extinguish area (SEA).
  • SEA average specific extinguish area
  • 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 SILTEMTM/FST- ITR blends was tested using VW-1 method according to UL1581 standard. Results are presented in Table 7.
  • 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 SILTEMTM/FST- ITR blends robustly pass VW-1 flame test indicating that the flame retardancy of these blends are on par with SILTEMTM resins. A significant improvement in the tear strength was also observed for SILTEMTM/FST-ITR blends compared to individual SILTEMTM resins.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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:
  • 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.
  • weight average molecular weight or “Mw” can be used interchangeably, and are defined by the formula:
  • Mw is measured by gel permeation chromatography. In some cases, Mw can be measured by gel permeation chromatography and calibrated with polycarbonate standards.
  • 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.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition de résine et des articles formés à partir de celle-ci, comprenant un copolymère séquencé polysiloxane/polyimide et un copolymère de polysiloxane-polycarbonate de polyester à base de résorcinol. La composition de résine peut avantageusement comprendre en outre des additifs retardateurs de flamme et suppresseurs de fumée.
PCT/US2016/053883 2016-08-14 2016-09-27 Mélanges de copolymères de polysiloxane/polyimide et de carbonate de polyester à base de résorcinol pour revêtement de fils électriques Ceased WO2018034680A1 (fr)

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IN201611027772 2016-08-14

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109915210A (zh) * 2019-03-16 2019-06-21 管炜 一种煤矿自燃监测报警降温装置及使用方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3972902A (en) 1971-01-20 1976-08-03 General Electric Company 4,4'-Isopropylidene-bis(3- and 4-phenyleneoxyphthalic anhydride)
US4455410A (en) 1982-03-18 1984-06-19 General Electric Company Polyetherimide-polysulfide blends
WO2013148759A1 (fr) * 2012-03-28 2013-10-03 Sabic Innovative Plastics Ip B.V. Mélanges de polyétherimide-polycarbonate
US20140329940A1 (en) * 2013-05-01 2014-11-06 Sabic Innovative Plastics Ip B. V. Interior train components having low smoke and low heat release, and methods of their manufacture
WO2015106208A1 (fr) * 2014-01-10 2015-07-16 Sabic Global Technologies B.V. Compositions compatibilisées, articles à base de celles-ci, et leurs procédés de fabrication

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3972902A (en) 1971-01-20 1976-08-03 General Electric Company 4,4'-Isopropylidene-bis(3- and 4-phenyleneoxyphthalic anhydride)
US4455410A (en) 1982-03-18 1984-06-19 General Electric Company Polyetherimide-polysulfide blends
WO2013148759A1 (fr) * 2012-03-28 2013-10-03 Sabic Innovative Plastics Ip B.V. Mélanges de polyétherimide-polycarbonate
US20140329940A1 (en) * 2013-05-01 2014-11-06 Sabic Innovative Plastics Ip B. V. Interior train components having low smoke and low heat release, and methods of their manufacture
WO2015106208A1 (fr) * 2014-01-10 2015-07-16 Sabic Global Technologies B.V. Compositions compatibilisées, articles à base de celles-ci, et leurs procédés de fabrication

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109915210A (zh) * 2019-03-16 2019-06-21 管炜 一种煤矿自燃监测报警降温装置及使用方法
CN109915210B (zh) * 2019-03-16 2020-09-11 管炜 一种煤矿自燃监测报警降温装置及使用方法

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