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WO2013134018A1 - Compositions de copolymères à blocs de résine-organosiloxane linéaire - Google Patents

Compositions de copolymères à blocs de résine-organosiloxane linéaire Download PDF

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Publication number
WO2013134018A1
WO2013134018A1 PCT/US2013/027904 US2013027904W WO2013134018A1 WO 2013134018 A1 WO2013134018 A1 WO 2013134018A1 US 2013027904 W US2013027904 W US 2013027904W WO 2013134018 A1 WO2013134018 A1 WO 2013134018A1
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Prior art keywords
mole
organosiloxane
block copolymer
linear
resin
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English (en)
Inventor
John Horstman
Steven Swier
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Dow Silicones Corp
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Dow Corning Corp
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Priority to JP2014560946A priority Critical patent/JP6218757B2/ja
Publication of WO2013134018A1 publication Critical patent/WO2013134018A1/fr
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    • 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
    • C08G77/44—Block-or graft-polymers containing polysiloxane sequences containing only polysiloxane sequences
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • H01L23/296—Organo-silicon compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

Definitions

  • LEDs Light emitting diodes
  • solar panels use an encapsulant coating to protect electronic components from environmental factors.
  • Such protective coatings must be optically clear to ensure maximum efficiency of these devices.
  • these protective coatings must be tough, durable, long lasting, and yet easy to apply.
  • Many of the currently available coatings, however, lack toughness; are not durable; are not long-lasting; and/or are not easy to apply. There is therefore a continuing need to identify protective and/or functional coatings in many areas of emerging technologies.
  • Embodiment 1 relates to an organosiloxane block copolymer comprising:
  • each R1, at each occurrence, is independently a Ci to C30 hydrocarbyl or an Rf group
  • each R 2 is independently a Ci to C20 hydrocarbyl or an Rf group
  • Rf represents a fluorine-containing group, with the proviso that there is at least one Rf group in the organosiloxane block copolymer;
  • disiloxy units [R ⁇ SiC ⁇ l are arranged in linear blocks having an average of from 10 to 400 disiloxy units [RI2S1O2/2] per linear block,
  • the trisiloxy units [R3 ⁇ 4iC>3/2] are arranged in non-linear blocks having a molecular weight of at least 500 g/mole, and at least 30% of the non-linear blocks are crosslinked with each other, each linear block is linked to at least one non-linear block; and the organosiloxane block copolymer has a weight average molecular weight (M w ) of at least 20,000 g/mole.
  • Embodiment 2 relates to the organosiloxane block copolymer of
  • Embodiment 1 wherein R 1 comprises an Rf group.
  • Embodiment 3 relates to the organosiloxane block copolymer of
  • Embodiment 1 or 2 wherein R2 comprises an Rf group.
  • Embodiment 4 relates to the organosiloxane block copolymer of
  • Embodiment 5 relates to the organosiloxane block copolymer of
  • Embodiments 1-4 wherein R2 is phenyl.
  • Embodiment 6 relates to the organosiloxane block copolymer of
  • Embodiments 1-5 wherein is methyl or phenyl.
  • Embodiment 7 relates to the organosiloxane block copolymer of
  • Embodiments 1-6 wherein the disiloxy units have the formula
  • Embodiment 8 relates to a curable composition comprising an organosiloxane block copolymer of Embodiment 1-7.
  • Embodiment 9 relates to a solid film composition comprising the curable composition of Embodiment 8.
  • Embodiment 10 relates to the cured product of the composition of
  • Embodiment 11 relates to the solid film composition of
  • Embodiment 9 wherein the solid composition has an optical transmittance of at least 95%.
  • Embodiment 12 relates to the solid film composition of
  • Embodiment 9 wherein the solid composition has a low refractive index.
  • Embodiment 13 relates to an LED encapsulant comprising an organosiloxane block copolymer of Embodiments 1-12.
  • Embodiment 14 relates to a process for preparing an
  • organosiloxane block copolymer of Embodiment 1 comprising:
  • each R.1 at each occurrence, is independently a C ⁇ to C30 hydrocarbyl or an Rf group,
  • n 10 to 400, q is 0, l , or 2
  • E is a hydrolyzable group containing at least one carbon atom
  • each R ⁇ at each occurrence, is independently a Ci to C20 hydrocarbyl or an Rf group; in c) an organic solvent;
  • step I) wherein the amounts of a) and b) used in step I) are selected to provide the resin-linear organosiloxane block copolymer with 40 to 90 mole % of disiloxy units [RI2S1O2/2] and 10 to 60 mole % of trisiloxy units [R ⁇ Si03/2], and
  • step I) wherein at least 95 weight percent of the linear organosiloxane added in step I) is incorporated into the resin-linear organosiloxane block copolymer;
  • step II reacting the resin-linear organosiloxane block copolymer from step I) to crosslink the trisiloxy units of the resin-linear organosiloxane block copolymer sufficiently to increase the weight average molecular weight (M w ) of the resin-linear organosiloxane block copolymer by at least 50%;
  • Embodiment 15 relates to the process of Embodiment 14, wherein the further processing enhances storage stability and/or optical clarity
  • Embodiment 16 relates to the process of Embodiment 14, wherein
  • Rl comprises an Rf group.
  • Embodiment 17 relates to the process of Embodiment 14 or 16, wherein R ⁇ comprises an Rf group.
  • Embodiment 18 relates to the process of Embodiments 14-17, wherein the Rf group comprises -CH2CH2CF3
  • Embodiment 19 relates to the process of Embodiments 14-18, wherein R ⁇ is phenyl.
  • Embodiment 20 relates to the process of Embodiments 14-19, wherein Rl is methyl, phenyl or combinations thereof.
  • Embodiment 21 relates to the process of Embodiments 14-20, wherein the linear organosiloxane has the formula
  • Embodiment 23 relates to an organosiloxane block copolymer prepared by the process of Embodiments 14-22.
  • Embodiment 24 relates to the organopolyxiloxane block copolymer of Embodiment 23, wherein the organopolysiloxane block copolymer is the reaction product of step II).
  • Embodiment 25 relates to a composition comprising the organopolysiloxane block copolymer of Embodiment 23.
  • Embodiment 26 relates to the composition of Embodiment 25, which is curable.
  • Embodiment 27 relates to the composition of Embodiment 25, which is solid.
  • Embodiment 28 relates to the cured product of the composition of Embodiments 25-27.
  • Embodiment 29 relates to a solid film composition comprising the composition of Embodiments 24-26.
  • Embodiment 30 relates to the solid film composition of
  • Embodiment 29 wherein the solid composition has an optical transmittance of at least 95%.
  • Embodiment 31 relates to an LED encapsulant comprising the compositions of Embodiments 25-30.
  • compositions comprising such fluorinated organosiloxane block copolymers have, in some embodiments, different physical properties relative to non-fluorinated "resin- linear" organosiloxane block copolymers.
  • curable composition of fluorinated "resin-linear" organosiloxane block copolymers of the embodiments described herein may have improved stability, e.g., at higher temperatures.
  • curable composition of fluorinated "resin-linear" organosiloxane block copolymers of the embodiments described herein may be useful in the preparation of low refractive index coatings, e.g. , those having refractive indeces from about 1.3 to about 1.45 or from about 1.35 to about 1.42.
  • the fluorinated "resin-linear" organosiloxane block copolymers comprise:
  • R1 is, at each occurrence, independently a C ⁇ to C30 hydrocarbyl or an Rf group
  • R2 is, at each occurrence, independently a Ci to C20 hydrocarbyl or an Rf group
  • Rf represents a fluorine-containing group, with the proviso that there is at least one Rf group in the organosiloxane block copolymer
  • disiloxy units [R ⁇ SiC ⁇ l are arranged in linear blocks having an average of from 10 to 400 disiloxy units [RI2S1O2/2] per linear block,
  • the trisiloxy units [R3 ⁇ 4iC>3/2] are arranged in non-linear blocks having a molecular weight of at least 500 g/mole, and at least
  • each linear block is linked to at least one non-linear block
  • the organosiloxane block copolymer has a weight average molecular weight (M w ) of at least 20,000 g/mole.
  • Organopolysiloxanes are polymers containing siloxy units independently selected from [R3S1O1 /2],
  • [R2S1O2/2L [RS1O3/2], or [S1O4/2] siloxy units where R may be, e.g. , an organic group. These siloxy units are commonly referred to as M, D, T, and Q units respectively. These siloxy units can be combined in various manners to form cyclic, linear, or branched structures. The chemical and physical properties of the resulting polymeric structures vary depending on the number and type of siloxy units in the organopolysiloxane.
  • linear organopolysiloxanes may contain mostly D, or [R2S1O2/2] siloxy units, which results in polydiorganosiloxanes that are fluids of varying viscosities, depending on the "degree of polymerization” or “dp” as indicated by the number of D units in the polydiorganosiloxane.
  • Linear organopolysiloxanes may have glass transition temperatures (Tg) that are lower than 25°C.
  • Resin" organopolysiloxanes result when a majority of the siloxy units are selected from T or Q siloxy units.
  • T siloxy units When T siloxy units are predominately used to prepare an organopolysiloxane, the resulting organosiloxane is often referred to as a "resin” or a “silsesquioxane resin.” Increasing the amount of T or Q siloxy units in an organopolysiloxane may result in polymers having increasing hardness and/or glass like properties. "Resin" organopolysiloxanes thus have higher Tg values, for example siloxane resins often have Tg values greater than 40°C, e.g., greater than 50°C, greater than 60°C, greater than 70°C, greater than 80°C, greater than 90°C or greater than 100°C.
  • T criteria for siloxane resins is from about 60°C to about 100°C, e.g., from about 60°C to about 80°C, from about 50°C to about 100°C, from about 50°C to about 80°C or from about 70°C to about 100°C.
  • organosiloxane block copolymers or “resin-linear organosiloxane block copolymers” refer to organopolysiloxanes containing "linear” D siloxy units in combination with "resin” T siloxy units.
  • the organosiloxane copolymers are "block” copolymers, as opposed to “random” copolymers.
  • the "resin-linear organosiloxane block copolymers” of the disclosed embodiments refer to organopolysiloxanes containing D and T siloxy units, where the D units (i.e.
  • [RI2S1O2/2] units are primarily bonded together to form polymeric chains having, in some embodiments, an average of from 10 to 400 D units (e.g. , an average of from about 10 to about 400 D units; about 10 to about 300 D units; about 10 to about 200 D units; about 10 to about 100 D units; about 50 to about 400 D units; about 100 to about 400 D units; about 150 to about 400 D units; about 200 to about 400 D units; about 300 to about 400 D units; about 50 to about 300 D units; about 100 to about 300 D units; about 150 to about 300 D units; about 200 to about 300 D units; about 100 to about 150 D units, about 115 to about 125 D units, about 90 to about 170 D units or about 110 to about 140 D units), which are referred herein as "linear blocks.”
  • 10 to 400 D units e.g. , an average of from about 10 to about 400 D units; about 10 to about 300 D units; about 10 to about 200 D units; about 10 to about 100 D units; about 50 to about 400
  • the T units are, in some embodiments, primarily bonded to each other to form branched polymeric chains, which are referred to as "non-linear blocks.”
  • non-linear blocks branched polymeric chains
  • a significant number of these nonlinear blocks may further aggregate to form "nano-domains" when solid forms of the block copolymer are provided.
  • these nano-domains form a phase separate from a phase formed from linear blocks having D units, such that a resin-rich phase forms.
  • the non-linear blocks have a number average molecular weight of at least 500 g/mole, e.g., at least 1000 g/mole, at least 2000 g/mole, at least 3000 g/mole or at least 4000 g/mole; or have a molecular weight of from about 500 g/mole to about 4000 g/mole, from about 500 g/mole to about 3000 g/mole, from about 500 g/mole to about 2000 g/mole, from about 500 g/mole to about 1000 g/mole, from about 1000 g/mole to 2000 g/mole, from about 1000 g/mole to about 1500 g/mole, from about 1000 g/mole to about 1200 g/mole, from about 1000 g/mole to 3000 g/mole, from about 1000 g/mole to about 2500 g/mole, from about 1000 g/mole to about 4000
  • organosiloxane block copolymers e.g., those comprising 40 to 90 mole percent disiloxy units of the formula [Rf 2S1O2/2] and 10 to 60 mole percent trisiloxy units of the formula [R2S1O3/2]
  • the organosiloxane block copolymers may be represented by the formula [Rf 2Si02/2]a[R ⁇ Si03/2lb where the subscripts a and b represent the mole fractions of the siloxy units in the copolymer,
  • a is about 0.4 to about 0.9
  • b is from 0.1 to 0.6
  • Rf is independently a Ci to C30 hydrocarbyl or an Rf group
  • R2 is independently a C ⁇ to C20 hydrocarbyl or an Rf group, where R represents a fluorine-containing group, with the proviso that there is at least one Rf group in the organosiloxane block copolymer.
  • the organosiloxane block copolymers of the embodiments described herein comprise 40 to 90 mole percent disiloxy units of the formula [Rf2Si02/2L e.g., 50 to 90 mole percent disiloxy units of the formula [Rf 2Si02/2l; 60 to 90 mole percent disiloxy units of the formula [Rf 2S1O2/2]; 65 to 90 mole percent disiloxy units of the formula [R 2S1O2/2]; 70 to 90 mole percent disiloxy units of the formula [Rf2Si02/2l; or 80 to 90 mole percent disiloxy units of the formula [Rf2Si02/2l; 40 to 80 mole percent disiloxy units of the formula [Rf 2S1O2/2]; 40 to 70 mole percent disiloxy units of the formula [Rf 2S1O2/2]; 40 to 60 mole percent disiloxy units of the formula [Rf 2S1O2/2]; 40 to 50 mole percent disil
  • the organosiloxane block copolymers of the embodiments described herein comprise 10 to 60 mole percent trisiloxy units of the formula [R3 ⁇ 4i03/2], e.g., 10 to 20 mole percent trisiloxy units of the formula [R2S1O3/2]; 10 to 30 mole percent trisiloxy units of the formula [R2S1O3/2]; 10 to 35 mole percent trisiloxy units of the formula [R2S1O3/2] ; 10 to 40 mole percent trisiloxy units of the formula [R3 ⁇ 4 103/2] ; 10 to 50 mole percent trisiloxy units of the formula [R ⁇ Si03/2] ; 20 to 30 mole percent trisiloxy units of the formula [R3 ⁇ 4 103/2] ; 20 to 35 mole percent trisiloxy units of the formula [R3 ⁇ 4i03/2]; 20 to 40 mole percent trisiloxy units of the formula [R S1O3/2]; 20 to
  • the organosiloxane block copolymers of the embodiments described herein may contain additional siloxy units, such as M siloxy units, Q siloxy units, other unique D or T siloxy units (for example, having organic groups other than R1 or R3 ⁇ 4, provided that the organosiloxane block copolymer contains the mole fractions of the disiloxy and trisiloxy units as described herein.
  • the sum of the mole fractions as designated by subscripts a and b do not necessarily have to sum to one.
  • the sum of a + b may be less than one to account for minor amounts of other siloxy units that may be present in the organosiloxane block copolymer.
  • the sum of a + b is greater than 0.6, alternatively greater than 0.7, alternatively greater than 0.8, or alternatively greater than 0.9.
  • the sum of a + b is from about 0.6 to about 0.9, e.g. , from about 0.6 to about 0.8, from about 0.6 to about 0.7, from about 0.7 to about 0.9, from about 0.7 to about 0.8, or from about 0.8 to about 0.9.
  • the organosiloxane block copolymer consists essentially of the disiloxy units of the formula [RI2S1O2/2] and trisiloxy units of the formula [R2S1O3/2], while also containing 0.5 to 25 mole percent silanol groups [ ⁇ SiOH] (e.g., 0.5 to 5 mole percent, 0.5 to 10 mole percent, 0.5 to 15 mole percent, 0.5 to 20 mole percent, 5 to 10 mole percent, 5 to 15 mole percent, 5 to 20 mole percent, 5 to 25 mole percent, 10 to 15 mole percent 10 to 20 mole percent, 10 to 25 mole percent, 15 to 20 mole percent, 15 to 25 mole percent, or 20 to 25 mole percent), where R1 and R ⁇ are as defined herein.
  • the sum of a + b when using mole fractions to represent the amount of disiloxy and trisiloxy units in the copolymer is greater than 0.95, alternatively greater
  • the resin-linear organosiloxane block copolymers may also contain from 0.5 to 35 mole percent silanol groups [ ⁇ SiOH], alternatively from 2 to 32 mole percent silanol groups [ ⁇ SiOH], and alternatively from 8 to 22 mole percent silanol groups [ ⁇ SiOH].
  • the silanol groups may be present on any siloxy units within the organosiloxane block copolymer.
  • the amount described herein represent the total amount of silanol groups found in the organosiloxane block copolymer. In some embodiments, the majority (e.g., greater than 75%, greater than 80%, greater than 90%; from about 75% to about 90%, from about 80% to about 90%, or from about 75% to about 85%) of the silanol groups will reside on the trisiloxy units, i.e. , the resin component of the block copolymer.
  • each Rl in the above disiloxy unit is independently a Ci to C30 hydrocarbyl or an Rf group, where the hydrocarbyl group may independently be an alkyl, aryl, or alkylaryl group.
  • Each Rl at each occurrence, may independently be a Ci to C30 alkyl group, alternatively, at each occurrence, each Rl may be a Ci to Ci g alkyl group.
  • each Rl at each occurrence, may be a Ci to C5 alkyl group such as methyl, ethyl, propyl, butyl, pentyl, or hexyl.
  • each Rl at each occurrence, may be methyl.
  • each Rl at each occurrence, may be any combination of the aforementioned alkyl, aryl or Rf groups such that, in some embodiments, each disiloxy unit may have two alkyl groups (e.g. , two methyl groups); two aryl groups (e.g.
  • each Rl at each occurrence, is phenyl, methyl or Rf.
  • Each R 2 at each occurrence, in the above trisiloxy unit is independently a Ci to C20 hydrocarbyl or an Rf group, where the hydrocarbyl group may independently be an alkyl, aryl, or alkylaryl group.
  • Each R 2 at each occurrence, may be a Ci to C20 alkyl group, alternatively each R 2 at each occurrence, may be a C ⁇ to Ci g alkyl group.
  • each R 2 at each occurrence may be a C ⁇ to Cg alkyl group such as methyl, ethyl, propyl, butyl, pentyl, or hexyl.
  • each R 2 at each occurrence may be methyl.
  • Each R 2 at each occurrence may be an aryl group, such as phenyl, naphthyl, or an anthryl group.
  • each R 2 at each occurrence may be any combination of the aforementioned alkyl, aryl or Rf groups such that, in some embodiments, each disiloxy unit may have two alkyl groups (e.g. , two methyl groups); two aryl groups (e.g. , two phenyl groups); an alkyl (e.g., methyl) and an aryl group (e.g., phenyl), two Rf groups; one R f group and one alky group (e.g., methyl); or one R f group and one aryl group (e.g.
  • hydrocarbyl also includes substituted hydrocarbyls. "Substituted” as used throughout the specification refers broadly to replacement of one or more of the hydrogen atoms of the group with substituents known to those skilled in the art and resulting in a stable compound as described herein. Examples of suitable substituents include, but are not limited to, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, alkaryl, hydroxy, alkoxy, aryloxy, carboxy (i.e.
  • Substituted hydrocabyl also includes halogen substituted hydrocarbyls, where the halogen may be chlorine, bromine or combinations thereof.
  • the organosiloxane block copolymers of the embodiments described herein comprise at least one group.
  • the group may be present on any siloxy unit within the organosiloxane block copolymer.
  • the Rf group may be present on the linear block disiloxy units; on the non-linear block trisiloxy unit; or on both the linear block disiloxy units and the non-linear block trisiloxy units.
  • the mole percent of R groups on the linear block disiloxy units versus the mole percent of R groups on the non-linear block trisiloxy units should be such that the linear and non-linear blocks are substantially incompatible (e.g.
  • a solid organosiloxane block copolymer as described herein, contains a first phase and an incompatible second phase, the first phase containing predominately the disiloxy units [RI2S1O2/2] as defined herein, the second phase containing predominately the trisiloxy units [R3 ⁇ 4i03/2] as defined herein, the non- linear blocks being sufficiently aggregated into nano-domains which are incompatible with the first phase).
  • R ⁇ represents a fluorine-containing group
  • Rf may be selected from various fluorocarbyls, perfluorocarbyls, or hydrocarbyls containing at least one CF3 group, any of which may be linear or branched.
  • the fluorine-containing group may be selected from various perfluorocarbyls, including, but not limited to CF3-, CF3CF2- CF3(CF2)2", CF 3 (CF 2 )3-, C3F7-, (CF 3 ) 2 CF-, C4F9-, CsFn -CgF ⁇ - groups or the like.
  • the fluorine-containing group may also be hydrocarbyls containing at least one CF3 group including, but not limited to -CH 2 CH 2 CF 3 , - CH 2 CH 2 CH 2 CF3, -CH 2 CH 2 CH 2 CH 2 CF 3 , -CH 2 CH 2 CH 2 CH 2 CH 2 CF 3 , similar hydrocarbyls in the series or the like.
  • Fluorocarbyls include hydrocarbyls where at least one hydrogen atom has been replaced with a fluorine.
  • Fluorocarbyls include, but are not limited to -CHFCH3, -CF 2 CH 3 , -CF 2 CHFCH 3 , -CHFCF 2 CH 3 ,
  • fluorocarbyl encompasses “perfluorocarbyls and "hydrocarbyls containing at least one CF 3 group.”
  • the fluorine-containing group may also be selected from those represented by the formula -CH 2 CH 2 CH 2 (G) a [CR 3 (CF ) 2 ] b where G is a linking group comprising at least one atom selected from C, O or combinations thereof; each is independently selected from F or H; the subscript a has a value of 0 or 1 ; and the subscript b has a value of 1 or 2.
  • the linking group, G is -0-.
  • the linking group, G is an ether group having 2 to 4 carbon atoms, such as 0-CH 2 CH 2 CH 2 -; an alkylene group having 2 to 4 carbon atoms, such as -CH 2 CH 2 CH 2 -; a branched alkylene group having 3 to 5 carbon atoms, such as -CH(CH 2 -) 2; or a fiuorinated alkylene group having 2 to 4 carbon atoms, such as (-CH(CF 3 )CH 2 -) C where c is an integer from 1 to 8.
  • fluorine-containing groups useful herein may include,
  • the fluorine-containing group is fluorine-containing group
  • the number or amount of Rf groups present on the organosiloxane block copolymer may vary, providing there is at least one siloxy unit containing an Rf group.
  • the organosiloxane block copolymer contains from about 20 to about 80 mole%, from about 20 to about 50 mole%, or from about 25 to about 45 mole % siloxy units comprising an Rf group.
  • the disiloxy units of the organosiloxane block copolymer have the formula [(CH3)(CF3CH2CH2)Si02/2]- m some embodiments, the organosiloxane block copolymer contains from about 20 to about 80 mole %, from about 20 to about 50 mole %, or from about 25 to about 45 mole % siloxy units dilsiloxy units the formula [(CH 3 )(CF 3 CH2CH2)Si02/2].
  • the organosiloxane block copolymers of the embodiments described herein have a weight average molecular weight (M w ) of at least
  • the organosiloxane block copolymers of the embodiments described herein have a weight average molecular weight (M w ) of from about 20,000 g/mole to about 250,000 g/mole or from about
  • 100,000 g/mole to about 250,000 g/mole alternatively a weight average molecular weight of from about 40,000 g/mole to about 100,000 g/mole, alternatively a weight average molecular weight of from about 50,000 g/mole to about 100,000 g/mole, alternatively a weight average molecular weight of from about 50,000 g/mole to about 80,000 g/mole, alternatively a weight average molecular weight of from about 50,000 g/mole to about 70,000 g/mole, alternatively a weight average molecular weight of from about 50,000 g/mole to about 60,000 g/mole.
  • the organosiloxane block copolymers of the embodiments described herein have a number average molecular weight (M n ) of from about 15,000 to about 50,000 g/mole; from about 15,000 to about 30,000 g/mole; from about 20,000 to about 30,000 g/mole; or from about 20,000 to about 25,000 g/mole.
  • M n number average molecular weight
  • the average molecular weight may be readily determined using Gel Permeation Chromatography (GPC) techniques.
  • the structural ordering of the disiloxy and trisiloxy units may be further described as follows: the disiloxy units [RI2S1O2/2] sre arranged in linear blocks having an average of from 10 to 400 disiloxy units [R ⁇ SiC ⁇ l P er linear block, and the trisiloxy units [R3 ⁇ 4 103/2] are arranged in non-linear blocks having a molecular weight of at least 500 g/mole. Each linear block is linked to at least one non-linear block in the block copolymer. Furthermore, at least 30% of the non-linear blocks are crosslinked with each other,
  • from about 30% to about 80% of the nonlinear blocks are crosslinked with each other; from about 30% to about 70% of the non-linear blocks are crosslinked with each other; from about 30% to about 60% of the non-linear blocks are crosslinked with each other; from about 30% to about 50% of the non-linear blocks are crosslinked with each other; from about 30% to about 40% of the non-linear blocks are crosslinked with each other; from about 40% to about 80% of the non-linear blocks are crosslinked with each other; from about 40% to about 70% of the non-linear blocks are crosslinked with each other; from about 40% to about 60% of the non-linear blocks are crosslinked with each other; from about 40% to about 50% of the non-linear blocks are crosslinked with each other; from about 50% to about 80% of the non-linear blocks are crosslinked with each other; from about 50% to about 70% of the non-linear blocks are crosslinked with each other; from about 50% to about 60% of the non-linear blocks are crosslinked with each other; from about 60% to
  • the crosslinking of the non-linear blocks may be accomplished via a variety of chemical mechanisms and/or moieties.
  • crosslinking of non-linear blocks within the block copolymer may result from the condensation of residual silanol groups present in the non-linear blocks of the copolymer.
  • Crosslinking of the non-linear blocks within the block copolymer may also occur between "free resin” components and the non- linear blocks. "Free resin" components may be present in the block copolymer compositions as a result of using an excess amount of an organosiloxane resin during the preparation of the block copolymer.
  • the free resin component may crosslink with the non-linear blocks by condensation of the residual silanol groups present on the non-blocks and on the free resin.
  • the free resin may provide crosslinking by reacting with lower molecular weight compounds added as crosslinkers, as described herein.
  • the free resin when present, may be present in an amount of from about 10% to about 20% by weight of the organosiloxane block copolymers of the embodiments described herein, e.g., from about 15% to about 20% by weight organosiloxane block copolymers of the embodiments described herein.
  • certain compounds may be added during the preparation of the block copolymer to, e.g. , crosslink the non-resin blocks.
  • These crosslinking compounds may include an organosilane having the formula R 5 qSiX_L_q, which is added during the formation of the block copolymer (step
  • X is a hydrolyzable group
  • q is 0, 1, or 2.
  • X is any hydrolyzable group, E or, alternatively, X may be an oximo, acetoxy, halogen atom, hydroxyl (OH), or an alkoxy group.
  • the organosilane having the formula qSiX4_q is an alkyltriacetoxysilane, such as methyltriacetoxysilane, ethyltriacetoxysilane, or a combination of both.
  • alkyltriacetoxysilanes include ETS-900 (Dow Corning Corp., Midland, MI).
  • organosilanes useful as crosslinkers include; methyl tris(methylethylketoxime)silane (MTO), methyl triacetoxysilane, ethyl triacetoxysilane, tetraacetoxysilane, tetraoximesilane, dimethyl diacetoxysilane, dimethyl dioximesilane, and methyl tris(methylmethylketo xime) silane .
  • MTO methyl tris(methylethylketoxime)silane
  • the amount of organosilane having the formula R ⁇ qSiX ⁇ q when added during step II) may vary, but, in some embodiments, is based on the amount of organosiloxane resin used in the process.
  • the amount of silane used may provide a molar stoichiometry of 2 to 15 mole % of organosilane/moles of Si in the organosiloxane resin, e.g., 2 to 10 mole % of organosilane/moles of Si in the organosiloxane resin; 5 to 15 mole % of organosilane/moles of Si in the organosiloxane resin; 2 to 5 mole % of organosilane/moles of Si in the organosiloxane resin; 10 to 15 mole % of organosilane/moles of Si in the organosiloxane resin; 5 to 10 mole % of organosilane/moles of Si in
  • the amount of the organosilane having the formula R ⁇ qSiX_L_q added during step II) is, in some embodiments, controlled to ensure a stoichiometry that does not consume all the silanol groups on the organosiloxane block copolymer.
  • the amount of the organosilane used in step II is selected to provide an organosiloxane block copolymer containing 0.5 to 35 mole percent of silanol groups [ ⁇ SiOH].
  • the crosslinks within the block copolymer may primarily be siloxane bonds, ⁇ Si-0-Si ⁇ , resulting from the condensation of silanol groups, as discussed herein.
  • the amount of crosslinking in the block copolymer may be estimated by determining the average molecular weight of the block copolymer, such as with GPC techniques. In some embodiments, crosslinking the block copolymer increases its average molecular weight. Thus, an estimation of the extent of crosslinking may be made, given the average molecular weight of the block copolymer, the selection of the linear siloxy component (that is the chain length as indicated by its degree of polymerization), and the molecular weight of the non-linear block (which is primarily controlled by the selection of the organosiloxane resin used to prepare the block copolymer).
  • organosiloxane block copolymer of the embodiments described herein may be prepared by the methods known in the art, including the methods disclosed in Published PCT Application Nos. WO2012/040302 and WO2012/040305, which are incorporated herein by reference in their entirety.
  • solid compositions which include a resin- linear organosiloxane block copolymer, also contain a superbase catalyst.
  • a superbase catalyst See, e.g. , PCT Appl. No. PCT/US2012/069701 , filed December 14, 2012; and U.S. Provisional Appl. No. 61/570,477, filed December 14, 2012, the entireties of which are incorporated by reference as if fully set forth herein.
  • solid compositions which include a resin- linear organosiloxane block copolymer, also contain a stabilizer.
  • a stabilizer See, e.g. , PCT Appl. No. PCT/US2012/067334, filed November 30, 2012; and U.S. Provisional Appl. No. 61/566,031, filed December 2, 2011, the entireties of which are incorporated by reference as if fully set forth herein.
  • compositions comprising:
  • organosiloxane block copolymers as described herein, in some embodiments in combination with a stabilizer or a superbase as described herein, and
  • the organic solvent is an aromatic solvent, such as benzene, toluene, or xylene.
  • the curable compositions may further contain an organosiloxane resin (e.g. , free resin that is not part of the block copolymer).
  • the organosiloxane resin present in these compositions is, in some embodiments, the same organosiloxane resin used to prepare the organosiloxane block copolymer.
  • the organosiloxane resin may comprise at least 60 mole % of [R3 ⁇ 4i03/2] siloxy units in its formula (e.g. , at least 70 mole % of
  • the organosiloxane resin is a silsesquioxane resin, or alternatively a phenyl silsesquioxane resin.
  • a curable composition may contain:
  • 40 to 80 weight % of the organosiloxane block copolymer as described herein e.g. , 40 to 70 weight %, 40 to 60 weight %, 40 to 50 weight %); 10 to 80 weight % of the organic solvent (e.g. , 10 to 70 weight %, 10 to 60 weight %, 10 to 50 weight %, 10 to 40 weight %, 10 to 30 weight %, 10 to 20 weight %, 20 to 80 weight %, 30 to 80 weight %, 40 to 80 weight %, 50 to 80 weight %, 60 to 80 weight %, or 70 to 80 weight); and
  • 5 to 40 weight % of the organosiloxane resin e.g. , 5 to 30 weight %, 5 to 20 weight %, 5 to 10 weight %, 10 to 40 weight %, 10 to 30 weight %, 10 to 20 weight %, 20 to 40 weight % or 30 to 40 weight %);
  • curable compositions consist essentially of the organosiloxane block copolymer as described herein, the organic solvent, and the organosiloxane resin. In some embodiments, the weight % of these components sum to 100%, or nearly 100%.
  • the curable compositions contain a cure catalyst.
  • the cure catalyst may be selected from any catalyst known in the art to effect condensation cure of organosiloxane s, such as various tin or titanium catalysts.
  • Examples include, but are not limited to basic compounds, such as trimethylbenzylammonium hydroxide, tetramethylammonium hydroxide, n-hexylamine, tributylamine, diazabicycloundecene (DBU) and dicyandiamide; and metal-containing compounds such as tetraisopropyl titanate, tetrabutyl titanate, titanium acetylacetonate, aluminum triisobutoxide, aluminum triisopropoxide, zirconium tetra(acetylacetonato), zirconium tetrabutylate, cobalt octylate, cobalt acetylacetonato, iron acetylacetonato, tin acetylacetonato, dibutyltin octylate, dibutyltin laurate, zinc octylate, zinc bezoate, zinc p-tert-butyl
  • the condensation catalysts include zinc octylate, zinc bezoate, zinc p-tert- butylbenzoate, zinc laurate, zinc stearate, aluminium phosphate, and aluminum triisopropoxide. See, e.g. , U.S. Patent No. 8,193,269, the entire disclosure of which is incorporated by reference as if fully set forth herein.
  • condensation catalysts include, but are not limited to aluminum alkoxides, antimony alkoxides, barium alkoxides, boron alkoxides, calcium alkoxides, cerium alkoxides, erbium alkoxides, gallium alkoxides, silicon alkoxides, germanium alkoxides, hafnium alkoxides, indium alkoxides, iron alkoxides, lanthanum alkoxides, magnesium alkoxides, neodymium alkoxides, samarium alkoxides, strontium alkoxides, tantalum alkoxides, titanium alkoxides, tin alkoxides, vanadium alkoxide oxides, yttrium alkoxides, zinc alkoxides, zirconium alkoxides, titanium or zirconium compounds, especially titanium and zirconium alkoxides, and chelates
  • Double metal alkoxides are alkoxides containing two different metals in a particular ratio.
  • the condensation catalysts include titanium tetraethylate, titanium tetrapropylate, titanium tetraisopropylate, titanium tetrabutylate, titanium tetraisooctylate, titanium isopropylate tristearoylate, titanium truisopropylate stearoylate, titanium diisopropylate distearoylate, zirconium tetrapropylate, zirconium tetraisopropylate, zirconium tetrabutylate. See, e.g., U.S. Patent No.
  • condensation catalysts include titanates, zirconates and hafnates as described in DE 4427528 C2 and EP 0 639 622 Bl , both of which are incorporated by reference as if fully set forth herein.
  • Solid compositions containing the resin-linear organosiloxane block copolymers may be prepared by removing the solvent from curable organosiloxane block copolymer compositions as described herein.
  • the solvent may be removed by any known processing techniques.
  • a film of a curable composition containing the organosiloxane block copolymers is formed, and the solvent is allowed to evaporate from the film. Subjecting the films to elevated temperatures, and/or reduced pressures, will accelerate solvent removal and subsequent formation of the solid curable composition.
  • the curable compositions may be passed through an extruder to remove solvent and provide the solid composition in the form of a ribbon or pellets.
  • Coating operations against a release film could also be used as in slot die coating, knife over roll, rod, or gravure coating. Also, roll-to-roll coating operations could be used to prepare a solid film. In coating operations, a conveyer oven or other means of heating and evacuating the solution can be used to drive off the solvent and obtain the final solid film.
  • the structural ordering of the disiloxy and trisiloxy units in the organosiloxane block copolymer, as described herein, may provide the copolymer with certain unique physical property characteristics when solid compositions of the block copolymer are formed.
  • the structural ordering of the disiloxy and trisiloxy units in the copolymer may provide solid coatings that allow for a high optical transmittance of visible light ⁇ e.g., at least an 85% transmittance; at least a 90% transmittance; at least a 95% transmittance; at least a 99% transmittance; or 100% transmittance at wavelengths above 350 nm).
  • the structural ordering may also allow the organosiloxane block copolymer to flow and cure upon heating, yet remain stable at room temperature. They may also be processed using lamination techniques. These properties are useful to provide coatings for various electronic articles to improve weather resistance and durability, while providing low cost and easy procedures that are energy efficient.
  • the present disclosure further relates to solid forms of the aforementioned organosiloxane block copolymers and solid compositions derived from the curable compositions described herein comprising the organosiloxane block copolymers.
  • organosiloxane block copolymers comprising:
  • each , at each occurrence, is independently a C ⁇ to C30 hydrocarbyl or an Rf group
  • each R2 is independently a C ⁇ to C20 hydrocarbyl or an Rf group
  • Rf represents a fluorine-containing group, with the proviso that there is at least one Rf group in the organosiloxane block copolymer
  • disiloxy units [RI2S1O2/2] are arranged in linear blocks having an average of from 10 to 400 disiloxy units [RI2S1O2/2] per linear block,
  • the trisiloxy units [R3 ⁇ 4iC>3/2] are arranged in non-linear blocks having a molecular weight of at least 500 g/mole, at least 30% of the non-linear blocks are crosslinked with each other and are predominately aggregated together in nano-domains, each linear block is linked to at least one non-linear block; and the organosiloxane block copolymer has a weight average molecular weight of at least 20,000 g/mole, and is a solid at 25°C.
  • the organosiloxane block copolymers contained in the solid forms and solid compositions comprise 40 to 90 mole percent disiloxy units of the formula [RI2S1O2/2L e.g.
  • the organosiloxane block copolymers contained in the solid forms and solid compositions comprise 10 to 60 mole percent trisiloxy units of the formula [R3 ⁇ 4i03/2], e.g. , 10 to 20 mole percent trisiloxy units of the formula [R3 ⁇ 4i03/2l; 10 to 30 mole percent trisiloxy units of the formula [R3 ⁇ 4iC>3/2]; 10 to 35 mole percent trisiloxy units of the formula [R3 ⁇ 4i03/2]; 10 to 40 mole percent trisiloxy units of the formula [R ⁇ Si03/2l; 10 to 50 mole percent trisiloxy units of the formula [R3 ⁇ 4 103/2]; 20 to 30 mole percent trisiloxy units of the formula [R ⁇ Si03/2l; 20 to 35 mole percent trisiloxy units of the formula [R3 ⁇ 4 103 2]; 20 to 40 mole percent trisiloxy units of the formula [R3 ⁇ 4i03/2]; 20
  • the organosiloxane block copolymers contained in the solid forms and solid compositions comprise 0.5 to 25 mole percent silanol groups [ ⁇ SiOH] (e.g., 0.5 to 5 mole percent, 0.5 to 10 mole percent, 0.5 to 15 mole percent, 0.5 to 20 mole percent, 5 to 10 mole percent, 5 to 15 mole percent, 5 to 20 mole percent, 5 to 25 mole percent, 10 to 15 mole percent 10 to 20 mole percent, 10 to 25 mole percent, 15 to 20 mole percent, 15 to 25 mole percent, or 20 to 25 mole percent).
  • silanol groups e.g., 0.5 to 5 mole percent, 0.5 to 10 mole percent, 0.5 to 15 mole percent, 0.5 to 20 mole percent, 5 to 10 mole percent, 5 to 15 mole percent, 5 to 20 mole percent, 5 to 25 mole percent, 10 to 15 mole percent 10 to 20 mole percent, 10 to 25 mole percent, 15 to 20 mole percent, 15 to 25 mole
  • the disiloxy units [R ⁇ SiC ⁇ l m the organosiloxane block copolymers contained in the solid forms and solid compositions are arranged in linear blocks having an average of 10 to 400 disiloxy units, e.g., an average of from about 10 to about 400 disiloxy units; about 10 to about 300 disiloxy units; about 10 to about 200 disiloxy units; about 10 to about 100 disiloxy units; about 50 to about 400 disiloxy units; about 100 to about 400 disiloxy units; about 150 to about 400 disiloxy units; about 200 to about 400 disiloxy units; about 300 to about 400 disiloxy units; about 50 to about 300 disiloxy units; about 100 to about 300 disiloxy units; about 150 to about 300 disiloxy units; about 200 to about 300 disiloxy units; about 100 to about 150 disiloxy units, about 115 to about 125 disiloxy units, about 90 to about 170 disiloxy units or about 110 to about 140 disiloxy units).
  • an average of 10 to 400 disiloxy units e.g
  • the non-linear blocks in the organosiloxane block copolymers contained in the solid forms and solid compositions have a number average molecular weight of at least 500 g/mole, e.g. , at least 1000 g/mole, at least 2000 g/mole, at least 3000 g/mole or at least 4000 g/mole; or have a molecular weight of from about 500 g/mole to about 4000 g/mole, from about 500 g/mole to about 3000 g/mole, from about 500 g/mole to about 2000 g/mole, from about 500 g/mole to about 1000 g/mole, from about 1000 g/mole to 2000 g/mole, from about 1000 g/mole to about 1500 g/mole, from about 1000 g/mole to about 1200 g/mole, from about 1000 g/mole to 3000 g/mole, from about 1000 g//mole,
  • At least 30% of the non-linear blocks in the organosiloxane block copolymers contained in the solid forms and solid compositions are crosslinked with each other, e.g., at least 40% of the non- linear blocks are crosslinked with each other; at least 50% of the non-linear blocks are crosslinked with each other; at least 60% of the non-linear blocks are crosslinked with each other; at least 70% of the non-linear blocks are crosslinked with each other; or at least 80% of the non-linear blocks are crosslinked with each other.
  • from about 30% to about 80% of the non-linear blocks are crosslinked with each other; from about 30% to about 70% of the non-linear blocks are crosslinked with each other; from about 30% to about 60% of the non-linear blocks are crosslinked with each other; from about 30% to about 50% of the non-linear blocks are crosslinked with each other; from about 30% to about 40% of the non-linear blocks are crosslinked with each other; from about 40% to about 80% of the non-linear blocks are crosslinked with each other; from about 40% to about 70% of the non-linear blocks are crosslinked with each other; from about 40% to about 60% of the non-linear blocks are crosslinked with each other; from about 40% to about 50% of the non-linear blocks are crosslinked with each other; from about 50% to about 80% of the non-linear blocks are crosslinked with each other; from about 50% to about 70% of the non-linear blocks are crosslinked with each other; from about 55% to about 70% of the non-linear blocks are crosslinked with each other; from about 50% to about 60%
  • the organosiloxane block copolymers contained in the solid forms and solid compositions have a weight average molecular weight (M w ) of at least 20,000 g/mole, alternatively a weight average molecular weight of at least 40,000 g/mole, alternatively a weight average molecular weight of at least 50,000 g/mole, alternatively a weight average molecular weight of at least 60,000 g/mole, alternatively a weight average molecular weight of at least 70,000 g/mole, or alternatively a weight average molecular weight of at least 80,000 g/mole.
  • the organosiloxane block copolymers contained in the solid forms and solid compositions have a weight average molecular weight (M w ) of from about
  • the organosiloxane block copolymers of the embodiments described herein have a number average molecular weight (M n ) of from about
  • the aforementioned organosiloxane block copolymers are isolated in a solid form, for example by casting films of a solution of the block copolymer in an organic solvent (e.g. , benzene, toluene, xylene or combinations thereof) and allowing the solvent to evaporate.
  • an organic solvent e.g. , benzene, toluene, xylene or combinations thereof
  • the aforementioned organosiloxane block copolymers can be provided as solutions in an organic solvent containing from about 50 wt % to about 80 wt % solids, e.g.
  • the solvent is toluene.
  • such solutions will have a viscosity of from about 1500 cSt to about 4000 cSt at 25 ° C, e.g., from about 1500 cSt to about 3000 cSt, from about 2000 cSt to about 4000 cSt or from about 2000 cSt to about 3000 cSt at 25 ° C.
  • the non-linear blocks of the block copolymer Upon drying or forming a solid, the non-linear blocks of the block copolymer further aggregate together to form "nano-domains.”
  • “predominately aggregated” means the majority (e.g. , greater than 50%; greater than 60%; greater than 75%, greater than 80%, greater than 90%; from about 75% to about 90%, from about 80% to about 90%, or from about 75% to about 85%) of the non-linear blocks of the organosiloxane block copolymer are found in certain regions of the solid composition, described herein as "nano-domains.”
  • “nano-domains” refers to those phase regions within the solid block copolymer compositions that are phase separated within the solid block copolymer compositions and possess at least one dimension sized from 1 to 100 nanometers.
  • the nano-domains may vary in shape, providing at least one dimension of the nano-domain is sized from 1 to 100 nanometers.
  • the nano-domains may be regular or irregularly shaped.
  • the nano-domains may be spherically shaped, tubular shaped, and, in some instances, lamellar shaped.
  • the solid organosiloxane block copolymers as described herein contain a first phase and an incompatible second phase, the first phase containing predominately the disiloxy units [RI2S1O2/2] as defined herein, the second phase containing predominately the trisiloxy units [R 2 Si0 3/2 ] as defined herein, the non-linear blocks being sufficiently aggregated into nano-domains which are incompatible with the first phase.
  • the organosiloxane block copolymer which may also contain an organosiloxane resin, as described herein, the organosiloxane resin also predominately aggregates within the nano-domains.
  • the structural ordering of the disiloxy and trisiloxy units in the solid block copolymers of the present disclosure, and characterization of the nano-domains, may be determined explicitly using certain analytical techniques such as Transmission Electron Microscopic (TEM) techniques, Atomic Force Microscopy (AFM), Small Angle Neutron Scattering, Small Angle X-Ray Scattering, and Scanning Electron Microscopy.
  • TEM Transmission Electron Microscopic
  • AFM Atomic Force Microscopy
  • Small Angle Neutron Scattering Small Angle Neutron Scattering
  • Small Angle X-Ray Scattering Small Angle X-Ray Scattering
  • Scanning Electron Microscopy Scanning Electron Microscopy.
  • the structural ordering of the disiloxy and trisiloxy units in the block copolymer, and formation of nano-domains may be implied by characterizing certain physical properties of coatings resulting from the present organosiloxane block copolymers.
  • the present organosiloxane copolymers may provide coatings that have an optical transmittance of visible light greater than 95%.
  • optical clarity is possible (other than refractive index matching of the two phases) only when visible light is able to pass through such a medium and not be diffracted by particles (or domains as used herein) having a size greater than 150 nanometers. As the particle size, or domains further decreases, the optical clarity may be further improved.
  • coatings derived from the present organosiloxane copolymers may have an optical transmittance of visible light of at least 95%, e.g., at least 96%; at least 97%; at least 98%; at least 99%; or 100% transmittance of visible light.
  • visible light includes light with wavelengths above 350 nm.
  • One advantage of the present resin-linear organopolysiloxanes block copolymers is that they can be processed several times, because the processing temperature (Tp j - Q cess jjj g) is less than the temperature required to finally cure (T cure ) the organosiloxane block copolymer, i.e., Tp rocessm g ⁇ T cure .
  • the organosiloxane copolymer will cure and achieve high temperature stability when Tp rocess n g is taken above T cure .
  • the present resin-linear organopolysiloxanes block copolymers offer a significant advantage of being "re- processable" in conjunction with the benefits that may be associated with silicones, such as; hydrophobicity, high temperature stability, moisture/UV resistance.
  • the solid compositions of the organosiloxane block copolymers may be considered as "melt processable.”
  • the solid compositions such as a coating formed from a film of a solution containing the organosiloxane block copolymers, exhibit fluid behavior at elevated temperatures, that is upon “melting.”
  • the "melt processable" features of the solid compositions of the organosiloxane block copolymers may be monitored by measuring the "melt flow temperature" of the solid compositions, that is when the solid composition demonstrates liquid behavior.
  • the melt flow temperature may specifically be determined by measuring the storage modulus (G'), loss modulus (G") and tan delta (tan ⁇ ) as a function of temperature storage using commercially available instruments.
  • a commercial rheometer such as TA Instruments' ARES-RDA with 2KSTD standard fiexular pivot spring transducer, with forced convection oven
  • Test specimens e.g., 8 mm wide, 1 mm thick
  • the flow onset may be calculated as the inflection temperature in the G' drop (labeled FLOW), the viscosity at 120°C is reported as a measure for melt processability and the cure onset is calculated as the onset temperature in the G' rise (labeled CURE).
  • FLOW of the solid compositions will also correlate to the glass transition temperature of the nonlinear segments (i.e. , the resin component) in the organosiloxane block copolymer.
  • the solid compositions may be characterized as having a melt flow temperature ranging from 25°C to 200°C, alternatively from 25°C to 160°C, or alternatively from 50°C to 160°C.
  • melt processability benefits enables the reflow of solid compositions of the organosiloxane block copolymers around device architectures at temperatures below T cure , after an initial coating or solid is formed on the device. This feature is very beneficial to encapsulated various electronic devices.
  • the solid compositions of the organosiloxane block copolymers may be considered as "curable.”
  • the solid compositions such as a coating formed from a film of a solution containing the organosiloxane block copolymers, may undergo further physical property changes by further curing the block copolymer.
  • the present organosiloxane block copolymers contain a certain amount of silanol groups. It is possible that the presence of these silanol groups on the block copolymer permit further reactivity, e.g. , a cure mechanism. Upon curing, the physical properties of solid compositions may be further altered.
  • the "melt processability" the extent of cure and/or the rate of cure of the solid compositions of the organosiloxane block copolymers may be determined by rheological measurements at various temperatures.
  • the solid compositions containing the organosiloxane block copolymers may have a storage modulus (C) at 25°C ranging from 0.01 MPa to 500 MPa and a loss modulus (G") ranging from 0.001 MPa to 250 MPa, alternatively a storage modulus (G') at 25°C ranging from 0.1 MPa to 250 MPa and a loss modulus (G") ranging from 0.01 MPa to 125 MPa, alternatively a storage modulus (G') at 25 °C ranging from 0.1 MPa to 200 MPa and a loss modulus (G") ranging from 0.01 MPa to 100 MPa.
  • C storage modulus
  • G loss modulus
  • the solid compositions containing the organosiloxane block copolymers may have a storage modulus (G') at 120°C ranging from 10 Pa to 500,000 Pa and a loss modulus (G") ranging from 10 Pa to 500,000 Pa, alternatively a storage modulus (G') at 120°C ranging from 20 Pa to 250,000 Pa and a loss modulus (G") ranging from 20 Pa to 250,000 Pa, alternatively a storage modulus (G') at 120°C ranging from 30 Pa to 200,000 Pa and a loss modulus (G' ') ranging from 30 Pa to 200,000 Pa.
  • G' storage modulus
  • G' loss modulus
  • the solid compositions containing the organosiloxane block copolymers may have a storage modulus (G') at 200°C ranging from 10 Pa to 100,000 Pa and a loss modulus (G") ranging from 5 Pa to 80,000 Pa, alternatively a storage modulus (G') at 200°C ranging from 20 Pa to 75,000 Pa and a loss modulus (G") ranging from 10 Pa to 65,000 Pa, alternatively a storage modulus (G') at 200°C ranging from 30 Pa to 50,000 Pa and a loss modulus (G") ranging from 15 Pa to 40,000 Pa.
  • G' storage modulus
  • G loss modulus
  • the solid compositions may be further characterized by certain physical properties such as tensile strength and % elongation at break.
  • the present solid compositions derived from the aforementioned organosiloxane block copolymers may have an initial tensile strength greater than 0.1 MPa, alternatively greater than 0.5 MPa, alternatively greater than 1.5 MPa, or alternatively greater than 2 MPa.
  • the solid compositions may have an initial tensile strength from about 0.1 MPa to about 10 MPa, e.g., from about 0.5 to about 10 MPa, from about 1.5 MPa to about 10 MPa, from about 2 MPa to about 10 MPa, from about 5 MPa to about 10 MPa or from about 7 MPa to about 10 MPa.
  • the present solid compositions derived from the aforementioned organosiloxane block copolymers may have an initial % elongation at break (or rupture) greater than 40%, alternatively greater than 50%, or alternatively greater than 75%.
  • the solid compositions may have a % elongation at break (or rupture) of from about 20% to about 90%, e.g. , from about 25% to about 50%, from about 20% to about 60%, from about 40% to about 60%, from about 40% to about 50%, or from about 75% to about 90%.
  • tensile strength and % elongation at break are measured according to ASTM D412.
  • the aforementioned resin-linear organosiloxane block copolymers may be prepared by a process comprising:
  • each R1 at each occurrence, is independently a Ci to
  • n 10 to 400, q is 0, l , or 2
  • E is a hydrolyzable group containing at least one carbon atom
  • organosiloxane resin comprising at least 60 mole % of [R3 ⁇ 4iC>3/2] siloxy units in its formula, wherein each R ⁇ , at each occurrence, is independently a Ci to C20 hydrocarbyl or an Rf group, in c) an organic solvent;
  • step I) wherein the amounts of a) and b) used in step I) are selected to provide the resin-linear organosiloxane block copolymer with 40 to 90 mole % of disiloxy units [RI2S1O2/2] an d 10 to 60 mole % of trisiloxy units [R ⁇ Si03/2], and
  • step II reacting the resin-linear organosiloxane block copolymer from step I) to crosslink the trisiloxy units of the resin-linear organosiloxane block copolymer sufficiently to increase the weight average molecular weight (M w ) of the resin-linear organosiloxane block copolymer by at least 50%;
  • step III) optionally further processing the resin-linear organosiloxane block copolymer from step II) to enhance storage stability and/or optical clarity and/or optionally adding to the resin-linear organosiloxane block copolymer from step II) a stabilizer or a superbase;
  • Step I) in the process comprises reacting:
  • R 1 q(E)(3-q)SiO(Rl 2 Si02/2)nSi(E)(3-q) R ⁇ , wherein each R1, at each occurrence, is independently a C ⁇ to
  • n 10 to 400, q is 0, l, or 2
  • E is a hydrolyzable group containing at least one carbon atom
  • organosiloxane resin comprising at least 60 mole % of [R3 ⁇ 4iC>3/2] siloxy units in its formula, wherein each R ⁇ , at each occurrence, is independently a Ci to C20 hydrocarbyl or an Rf group, in c) an organic solvent;
  • step I) wherein the amounts of a) and b) used in step I) are selected to provide the resin-linear organosiloxane block copolymer with 40 to 90 mole % of disiloxy units [RI2S1O2/2] an d 10 to 60 mole % of trisiloxy units [R3 ⁇ 4i03/2], and
  • step I) wherein at least 95 weight percent of the linear organosiloxane added in step I) is incorporated into the resin-linear organosiloxane block copolymer.
  • reaction of step I) of the process may be represented generally according to the following schematic:
  • step I) may be considered as a condensation reaction between the organosiloxane resin and the linear organosiloxane.
  • Component a) in step I) of the process is a linear organosiloxane having the formula R q(E)(3_q)SiO(Rl2Si02/2)nSi(E)(3_q) R ⁇ q> where each R1 is independently a C ⁇ to C30 hydrocarbyl, an Rf group, or combinations thereof; the subscript "n” may be considered as the degree of polymerization (dp) of the linear organosiloxane and may vary from 10 to 400 ⁇ e.g., an average of from about 10 to about 400 D units; about 10 to about 300 D units; about 10 to about 200 D units; about 10 to about 100 D units; about 50 to about 400 D units; about 100 to about 400 D units; about 150 to about 400 D units; about 200 to about 400 D units; about 300 to about 400 D units; about 50 to about 300 D units; about 100 to about 300 D units; about 150 to about 300 D units; about 200 to about 300 D units; about 100 to about 150 D units,
  • R ⁇ q(E)(3-q)SiO(Rl2Si02/2)nSi(E)(3-q) R ⁇ q> one skilled in the art recognizes small amount of alternative siloxy units, such a T (RIS1O3/2) siloxy units, may be incorporated into the linear organosiloxane of component a).
  • the organosiloxane may be considered as being "predominately" linear by having a majority of D (RI2S1O2/2) siloxy units.
  • the linear organosiloxane used as component a) may be a combination of several linear organosiloxane s.
  • the linear organosiloxane used as component a) may comprise silanol groups.
  • the linear organosiloxane used as component a) comprises from about 0.5 to about 5 mole % silanol groups, e.g., from about 1 mole % to about 3 mole %; from about 1 mole % to about 2 mole % or from about 1 mole % to about 1.5 mole % silanol groups.
  • each in the above linear organosiloxane formula is independently a C ⁇ to C30 hydrocarbyl or an Rf group, where the hydrocarbyl group may independently be an alkyl, aryl, or alkylaryl group.
  • Rl at each occurrence, may independently be a C] to C30 alkyl group, alternatively, at each occurrence, each Rl may be a C ⁇ to C j g alkyl group. Alternatively each Rl , at each occurrence, may be a C ⁇ to C5 alkyl group such as methyl, ethyl, propyl, butyl, pentyl, or hexyl. Alternatively each Rl, at each occurrence, may be methyl. Each Rl , at each occurrence, may be an aryl group, such as phenyl, naphthyl, or an anthryl group.
  • each Rl at each occurrence, may be any combination of the aforementioned alkyl, aryl or Rf groups such that, in some embodiments, each disiloxy unit may have two alkyl groups ⁇ e.g. , two methyl groups); two aryl groups ⁇ e.g. , two phenyl groups); an alkyl ⁇ e.g. , methyl) and an aryl group ⁇ e.g., phenyl), two Rf groups; one Rf group and one alky group ⁇ e.g. , methyl); or one R f group and one aryl group ⁇ e.g. , phenyl).
  • each Rl, at each occurrence is phenyl, methyl or Rf.
  • E may be selected from any hydrolyzable group containing at least one carbon atom ⁇ e.g. , from one to ten carbon atoms; from one to five carbon atoms; from one to four carbon atoms; or from one to three carbon atoms).
  • E is selected from an oximo, epoxy, carboxy, amino, amido group or combinations thereof.
  • the linear organosiloxane has the formula
  • the linear organosiloxane has the formula (CH3) q (E) ( 3. q) SiO[(CF3CH2CH2)(C 6 H5)Si02/2)]nSi(E)(3-q)(CH 3 ) q , where E, n, and q are as defined herein.
  • a silanol terminated polydiorganosiloxane is reacted with an "endblocking" compound such as an alkyltriacetoxysilane or a dialkylketoxime.
  • an "endblocking" compound such as an alkyltriacetoxysilane or a dialkylketoxime.
  • the stoichiometry of the endblocking reaction is typically adjusted such that a sufficient amount of the endblocking compound is added to react with all the silanol groups on the polydiorganosiloxane.
  • a mole of the endblocking compound may be used per mole of silanol on the polydiorganosiloxane.
  • the reaction is, in some embodiments, conducted under anhydrous conditions to minimize condensation reactions of the silanol polydiorganosiloxane.
  • the silanol ended polydiorganosiloxane and the endblocking compound may be dissolved in an organic solvent under anhydrous conditions, and allowed to react at room temperature, or at elevated temperatures (up to the boiling point of the solvent).
  • Component b) in the present process is an organosiloxane resin comprising at least 60 mole % of [R ⁇ Si03 2] siloxy units in its formula, where each R 2 , at each occurrence, is independently a C ⁇ to C20 hydrocarbyl, an Rf group or combinations thereof.
  • the organosiloxane resin may contain any amount and combination of other M, D, and Q siloxy units, provided the organosiloxane resin contains at least 70 mole % of [R ⁇ Si03/2] siloxy units, alternatively the organosiloxane resin contains at least 80 mole % of [R3 ⁇ 4iC>3/2] siloxy units, alternatively the organosiloxane resin contains at least 90 mole % of [R3 ⁇ 4i03/2] siloxy units, or alternatively the organosiloxane resin contains at least 95 mole % of [R3 ⁇ 4i03/2] siloxy units.
  • the organosiloxane resin contains from about 70 to about 100 mole % of [R3 ⁇ 4iC>3/2] siloxy units, e.g. , from about 70 to about 95 mole % of [R ⁇ Si03/2] siloxy units, from about 80 to about 95 mole % of [R3 ⁇ 4i03/2] siloxy units or from about 90 to about 95 mole % of [R 2 Si03/2] siloxy units.
  • Organosiloxane resins useful as component b) include those known as "silsesquioxane" resins.
  • Each R 2 at each occurrence, in the above trisiloxy unit is independently a C ⁇ to C20 hydrocarbyl or an Rf group, where the hydrocarbyl group may independently be an alkyl, aryl, or alkylaryl group.
  • Each R 2 at each occurrence may be a C ⁇ to C20 alkyl group, alternatively each R 2 at each occurrence, may be a C ⁇ to Cj g alkyl group.
  • each R 2 at each occurrence, may be a C ⁇ to C5 alkyl group such as methyl, ethyl, propyl, butyl, pentyl, or hexyl.
  • each R 2 at each occurrence may be methyl.
  • Each R 2 may be an aryl group, such as phenyl, naphthyl, or an anthryl group.
  • each R 2 at each occurrence, may be any combination of the aforementioned alkyl, aryl or Rf groups such that, in some embodiments, each disiloxy unit may have two alkyl groups (e.g. , two methyl groups); two aryl groups (e.g. , two phenyl groups); an alkyl (e.g., methyl) and an aryl group (e.g., phenyl), two Rf groups; one R group and one alky group (e.g., methyl); or one R group and one aryl group (e.g. , phenyl).
  • each disiloxy unit may have two alkyl groups (e.g. , two methyl groups); two aryl groups (e.g. , two phenyl groups); an alkyl (e.g., methyl) and an aryl group (e.g
  • R 2 at each occurrence, is phenyl, methyl or Rf.
  • the weight average molecular weight (M w ) of the organosiloxane resin is not limiting, but, in some embodiments, ranges from 1000 to 10000, or alternatively 1500 to 5000 g/mole.
  • [R 2 Si03 2] siloxy units and methods for preparing them, are known in the art. They are typically prepared by hydrolyzing an organosilane having three hydrolyzable groups on the silicon atom, such as a halogen or alkoxy group in an organic solvent.
  • An organosilane having three hydrolyzable groups on the silicon atom such as a halogen or alkoxy group in an organic solvent.
  • a representative example for the preparation of a silsesquioxane resin may be found in U.S. Patent No. 5 ,075, 103.
  • organosiloxane resins are available commercially and sold either as a solid (flake or powder), or dissolved in an organic solvent.
  • organosiloxane resins useful as component b) include; Dow Corning® 217 Flake Resin, 233 Flake, 220 Flake, 249 Flake, 255 Flake, Z- 6018 Flake (Dow Corning Corporation, Midland MI). [0113]
  • organosiloxane resins containing such high amounts of [R3 ⁇ 4i03 2] siloxy units may have a certain concentration of Si-OZ where Z may be hydrogen (i.e. , silanol), an alkyl group (so that OZ is an alkoxy group), or alternatively OZ may also be any of the "E" hydrolyzable groups as described herein.
  • the Si-OZ content as a mole percentage of all siloxy groups present on the organosiloxane resin may be readily determined by ⁇ Si NMR.
  • concentration of the OZ groups present on the organosiloxane resin will vary, as dependent on the mode of preparation, and subsequent treatment of the resin.
  • the silanol (Si- OH) content of organosiloxane resins suitable for use in the present process will have a silanol content of at least 5 mole %, alternatively of at least 10 mole %, alternatively 25 mole %, alternatively 40 mole %, or alternatively 50 mole %.
  • the silanol content is from about 5 mole % to about 60 mole %, e.g. , from about 10 mole % to about 60 mole %, from about 25 mole % to about 60 mole %, from about 40 mole % to about 60 mole %, from about 25 mole % to about 40 mole % or from about 25 mole % to about 50 mole %.
  • organosiloxane resins containing such high amounts of [R ⁇ Si03 2] siloxy units and silanol contents may also retain water molecules, especially in high humidity conditions. Thus, it is often beneficial to remove excess water present on the resin by "drying" the organosiloxane resin prior to reacting in step I). This may be achieved by dissolving the organosiloxane resin in an organic solvent, heating to reflux, and removing water by separation techniques (for example Dean Stark trap or equivalent process).
  • step I) The amounts of a) and b) used in the reaction of step I) are selected to provide the resin-linear organosiloxane block copolymer with 40 to
  • the mole % of dilsiloxy and trisiloxy units present in components a) and b) may be readily determined using ⁇ Si NMR techniques. The starting mole % then determines the mass amounts of components a) and b) used in step I). [0116] In some embodiments, the amount of components a) and b) may be selected to ensure there is a molar excess of the silanol groups on the organosiloxane resin versus the amount of linear organosiloxane added. Thus, a sufficient amount of the organosiloxane resin may, in some embodiments, be added to potentially react with all the linear organosiloxane used in step I). As such, a molar excess of the organosiloxane resin may be used. The amounts used may be determined by accounting for the moles of the organosiloxane resin used per mole of the linear organosiloxane.
  • the reaction effected in step I) is a condensation reaction between the hydrolyzable groups of linear organosiloxane with the silanol groups on the organosiloxane resin.
  • a sufficient amount of silanol groups remains on the resin component of the formed resin-linear organosiloxane copolymer to further react in step II) of the present process.
  • at least 10 mole %, alternatively at least 20 mole %, or alternatively at least 30 mole % silanol remains on the trisiloxy units of the resin-linear organosiloxane copolymer as produced in step I) of the present process.
  • from about 10 mole % to about 60 mole % e.g. , from about 20 mole % to about 60 mole %, or from about 30 mole % to about 60 mole %, remains on the trisiloxy units of the resin- linear organosiloxane copolymer as produced in step I) of the present process.
  • reaction conditions for reacting the aforementioned (a) linear organosiloxane with the (b) organosiloxane resin are not limited. In some embodiments, reaction conditions are selected to effect a condensation type reaction between the a) linear organosiloxane and b) organosiloxane resin. Various non-limiting embodiments, and reaction conditions, are described in the Examples herein.
  • the (a) linear organosiloxane and the (b) organosiloxane resin are reacted at room temperature. In other embodiments, (a) and (b) are reacted at temperatures that exceed room temperature and that range up to about 50, 75, 100, or even up to 150°C.
  • (a) and (b) can be reacted together at reflux of the solvent.
  • (a) and (b) are reacted at temperatures that are below room temperature by 5, 10, or even more than 10°C.
  • (a) and (b) react for times of 1, 5, 10, 30, 60, 120, or 180 minutes, or even longer.
  • (a) and (b) are reacted under an inert atmosphere, such as nitrogen or a noble gas.
  • (a) and (b) may be reacted under an atmosphere that includes some water vapor and/or oxygen.
  • (a) and (b) may be reacted in any size vessel and using any equipment including mixers, vortexers, stirrers, heaters, etc.
  • (a) and (b) are reacted in one or more organic solvents which may be polar or non-polar.
  • organic solvents which may be polar or non-polar.
  • aromatic solvents such as toluene, xylene, benzene, and the like are utilized.
  • the amount of the organosiloxane resin dissolved in the organic solvent may vary, but may be an amount that minimizes the chain extension of the linear organosiloxane or premature condensation of the organosiloxane resin.
  • the order of addition of components a) and b) may vary.
  • the linear organosiloxane is added to a solution of the organosiloxane resin dissolved in the organic solvent. This order of addition may enhance the condensation of the hydrolyzable groups on the linear organosiloxane with the silanol groups on organosiloxane resin, while minimizing chain extension of the linear organosiloxane or premature condensation of the organosiloxane resin.
  • the organosiloxane resin is added to a solution of the linear organosiloxane dissolved in the organic solvent.
  • the progress of the reaction in step I), and the formation of the resin-linear organosiloxane block copolymer may be monitored by various analytical techniques, such as GPC, IR, or ⁇ Si NMR.
  • the reaction in step I) is allowed to continue until at least 95 weight percent (e.g. , at least 96%, at least 97%, at least 98%, at least 99% or 100%) of the linear organosiloxane used in step I) is incorporated into the resin-linear organosiloxane block copolymer.
  • Step II) of the present process involves further reacting the resin- linear organosiloxane block copolymer from step I) to crosslink the trisiloxy units of the resin-linear organosiloxane block copolymer to increase the molecular weight of the resin-linear organosiloxane block copolymer by at least 50%, alternatively by at least 60%, alternatively by 70%, alternatively by at least 80%, alternatively by at least 90%, or alternatively by at least 100%.
  • step II) of the present process involves further reacting the resin- linear organosiloxane block copolymer from step I) to crosslink the trisiloxy units of the resin-linear organosiloxane block copolymer to increase the molecular weight of the resin-linear organosiloxane block copolymer from about 50% to about 100%, e.g. , from about 60% to about 100%, from about 70% to about 100%, from about 80% to about 100 % or from about 90% to about 100%.
  • reaction of step II) of the process may be represented
  • step II crosslinks the trisiloxy blocks of the resin-linear organosiloxane block copolymer formed in step I), which will increase the average molecular weight of the block copolymer.
  • the crosslinking of the trisiloxy blocks provides the block copolymer with an aggregated concentration of trisiloxy blocks, which ultimately may help to form "nano-domains" in solid compositions of the block copolymer. In other words, this aggregated concentration of trisiloxy blocks may phase separate when the block copolymer is isolated in a solid form such as a film or cured coating.
  • the aggregated concentration of trisiloxy block within the block copolymer and subsequent formation of "nano-domains" in the solid compositions containing the block copolymer may provide for enhanced optical clarity of these compositions as well as the other physical property benefits associated with these materials.
  • the crosslinking reaction in step II) may be accomplished via a variety of chemical mechanisms and/or moieties.
  • crosslinking of non-linear blocks within the block copolymer may result from the condensation of residual silanol groups present in the non-linear blocks of the copolymer.
  • Crosslinking of the non-linear blocks within the block copolymer may also occur between "free resin” components and the non-linear blocks.
  • "Free resin” components may be present in the block copolymer compositions as a result of using an excess amount of an organosiloxane resin in step I) of the preparation of the block copolymer.
  • the free resin component may crosslink with the nonlinear blocks by condensation of the residual silanol groups present on the non- linear blocks and on the free resin.
  • the free resin may provide crosslinking by reacting with lower molecular weight compounds added as crosslinkers, as described herein.
  • Step II) of the process may occur simultaneous upon formation of the resin-linear organosiloxane of step I), or involve a separate reaction in which conditions have been modified to effect the step II) reaction.
  • the step II) reaction may occur in the same conditions as step I. In this situation, the step II) reaction proceeds as the resin-linear organosiloxane copolymer is formed.
  • the reaction conditions used for step I) are extended to further the step II) reaction.
  • the reaction conditions may be changed, or additional ingredients added to effect the step II) reaction.
  • the step II) reaction conditions may depend on the selection of the hydrolyzable group (E) used in the starting linear organosiloxane.
  • (E) in the linear organosiloxane is an oxime group
  • the step II) reaction it is possible for the step II) reaction to occur under the same reaction conditions as step I). That is, as the resin-linear organosiloxane copolymer is formed in step I), it will continue to react via condensation of the silanol groups present on the resin component to further increase the molecular weight of the resin-linear organosiloxane copolymer.
  • step II) reaction may proceed simultaneously under the same conditions for step I).
  • the resin-linear organosiloxane copolymer is formed in step I), it may further react under the same reaction conditions to further increase its molecular weight via a condensation reaction of the silanol groups present on the resin component of the copolymer.
  • step II) reaction may be enhanced with a further component to effect condensation of the resin components of the resin-linear organosiloxane copolymer, as described herein.
  • an organosilane having the formula S1X4 is added during step II), where is a C ⁇ to Cg hydrocarbyl or a C ⁇ to Cg halogen-substituted hydrocarbyl, X is a hydrolyzable group, and q is 0, 1, or 2.
  • X is any hydrolyzable group, alternatively X may be E, as defined herein, a halogen atom, hydro xyl (OH), or an alkoxy group.
  • the organosilane is an alkyltriacetoxysilane, such as methyltriacetoxysilane, ethyltriacetoxysilane, or a combination of both.
  • Commercially available representative alkyltriacetoxysilanes include ETS-900 (Dow Corning Corp., Midland, MI).
  • organosilanes useful in some embodiments include; methyl tris(methylethylketoxime)silane (MTO), methyl triacetoxysilane, ethyl triacetoxysilane, tetraacetoxysilane, tetraoximesilane, dimethyl diacetoxysilane, dimethyl dioximesilane, methyl tris(methylmethylketo xime) silane .
  • the amount of organosilane having the formula R ⁇ qSiX_L_q when added during step II) varies and may be based on the amount of organosiloxane resin used in the process.
  • the amount of silane used should provide a molar stoichiometry of 2 to 15 mole % of organosilane per moles of Si on the organosiloxane resin, e.g.
  • organosilane/moles of Si on the organosiloxane resin 2 to 10 mole % of organosilane/moles of Si on the organosiloxane resin; 5 to 15 mole % of organosilane/moles of Si on the organosiloxane resin; 2 to 5 mole % of organosilane/moles of Si on the organosiloxane resin; 10 to 15 mole % of organosilane/moles of Si on the organosiloxane resin; 5 to 10 mole % of organosilane/moles of Si on the organosiloxane resin; or 2 to 12 mole % of organosilane/moles of Si on the organosiloxane resin.
  • the amount of the organosilane having the formula R ⁇ qSiX ⁇ q added during step II) may be controlled, in some embodiments, to ensure a stoichiometry that does not consume all the silanol groups on the organosiloxane block copolymer.
  • the amount of the organosilane used in step II) may be selected to provide an organosiloxane block copolymer containing 0.5 to 35 mole percent of silanol groups [ ⁇ SiOH].
  • Step III) in the process is optional, and involves further processing the resin-linear organosiloxane block copolymer. Further processing includes, but is not limited to further processing the resin-linear organosiloxane block copolymer to enhance its storage stability and/or optical clarity.
  • further processing refers broadly to any further reaction or treatment of the formed resin-linear organosiloxane copolymer to, among other things, enhance its storage stability, and/or optical clarity.
  • the resin-linear organosiloxane copolymer as produced in step II) may, for example, still contain a significant amount of reactive "OZ" groups (that is ⁇ SiOZ groups, where Z is as defined herein), and/or X groups (where X is introduced into the block copolymer when the organosilane having the formula R ⁇ qSiX ⁇ q is used in step II).
  • the OZ groups present on the resin-linear organosiloxane copolymer at this stage may be silanol groups that were originally present on the resin component, or alternatively may result from the reaction of the organosilane having the formula R ⁇ qSiX ⁇ q with silanol groups, when the organosilane is used in step II).
  • step III) may be performed to further react OZ or X present on the organosiloxane block copolymer produced in step II) to improve storage stability and/or optical clarity.
  • the conditions for step III) may vary, depending on the selection of the linear and resin components, their amounts, and the endcapping compounds used.
  • step III) is performed by reacting the resin-linear organosiloxane from step II) with water and removing any small molecular compounds formed in the process, such as acetic acid.
  • the resin-linear organosiloxane copolymer may be produced from a linear organosiloxane where E is an acetoxy group, and/or an acetoxy silane is used in step II).
  • the resin-linear organosiloxane formed in step II) contains a significant quantity of hydrolyzable Si-0-C(0)CH3 groups, which may limit the storage stability of the resin-linear organosiloxane copolymer.
  • water may be added to the resin-linear organosiloxane copolymer formed from step II), which may hydrolyze a substantial amount of Si-0-C(0)CH3 groups to further crosslink the trisiloxy units, and eliminate acetic acid.
  • the formed acetic acid, and any excess water may be removed by known separation techniques.
  • the amount of water added in some embodiments may vary. In some embodiments, the amount of water added may be 10 weight %, or alternatively 5 weight % is added per total solids (as based on resin-linear organosiloxane copolymer in the reaction medium).
  • step III) is performed by reacting the resin-linear organosiloxane from step II) with an endcapping compound, including endcapping compounds selected from an alcohol, oxime, or trialkylsiloxy compound.
  • the resin-linear organosiloxane copolymer may be produced from a linear organosiloxane where E is an oxime group.
  • the endcapping compound may be a Cj-C20 alcohol (e.g.,
  • the endcapping compound may also be a trialkylsiloxy compound, such as trimethylmethoxysilane or trimethylethoxysilane. The amount of endcapping compound may vary.
  • it is between 3 and 15 wt % (e.g., 3 to 10 wt %, 5 to 15 wt %, 3 to 5 wt %, 10 to 15 wt %, 5 to 10 wt %, or 3 to 12 wt %) with respect to the resin linear organosiloxane block copolymer solids in the reaction medium.
  • Optional step III) in the process may, in addition to, or in place of
  • “further processing,” involve contacting the resin-linear organosiloxane block copolymer from step II) with a stabilizer or a superbase.
  • Step IV) of the present process is optional, and involves removing the organic solvent used in the reactions of steps I) and II).
  • the organic solvent may be removed by any known techniques.
  • the organic solvent may be removed by heating the resin-linear organosiloxane copolymer compositions at elevated temperature, either at atmospheric conditions or under reduced pressures. In some embodiments, not all of the solvent is removed. In some embodiments, at least 20%, at least 30%, at least 40%, or at least 50% of the solvent is removed, e.g. , at least 60%, at least 70%, at least 75%, at least 80% or at least 90% of the solvent is removed. In some embodiments, less than 20% of the solvent is removed, e.g.
  • less than 15%, less than 10%, less than 5% or 0% of the solvent is removed.
  • from about 20% to about 100% of the solvent is removed, e.g. , from about 30% to about 90%, from about 20% to about 80%, from about 30 to about 60%, from about 50 to about 60%, from about 70 to about 80% or from about 50% to about 90% of the solvent is removed.
  • Some of the embodiments of the present invention relate to optical assemblies and articles comprising the compositions described herein such as those described in PCT/US2012/071011, filed December 20, 2012; PCT/US2013/021707, filed January 16, 2013 ; and PCT/US2013/025126, filed February 7, 2013, all of which are incorporated by reference as if fully set forth herein. Accordingly, some embodiments of the present invention relate to an LED encapsulant comprising an organosiloxane block copolymer described herein.
  • NMR samples of resin linear products were prepared, e.g. , by weighing ⁇ 3 grams of solvent free resin linear (prepared by drying sample overnight at room temperature), 1 g of CDCI3, and 4 grams of 0.04 M Cr(acac)3 solution in CDCI3 into a vial and mixing thoroughly Samples were then transferred into a silicon-free NMR tube. Spectra were acquired using a Varian Mercury 400 MHz NMR. NMR samples of other materials such as 217 Flake and silanol terminated PDMS were prepared by diluting 4 g of sample into 4 grams of 0.04 M Cr(acac)3 solution in CDCI3
  • 13 C NMR experiments were performed, e.g. , by placing samples into 16 mm glass NMR tubes. A 5 mm NMR tube was placed inside the 16 mm tube and filled with lock solvent, l ⁇ C DEPT NMR was acquired in 12 or 20 minute signal averaging blocks. Data was acquired on a Varian Inova NMR spectrometer with a 1 H operational frequency of 400 MHz.
  • Samples were prepared, e.g., in certified THF at 0.5% w/v concentration, filtered with a 0.45 ⁇ PTFE syringe filter, and analyzed against polystyrene standards.
  • the relative calibration (3 r ⁇ order fit) used for molecular weight determination was based on 16 polystyrene standards ranging in molecular weights from 580 to 2,320,000 Daltons.
  • the chromatographic equipment consisted of a Waters 2695 Separations Module equipped with a vacuum degasser, a Waters 2410 differential refractometer and two (300 mm x 7.5 mm) Polymer Laboratories Mixed C columns (molecular weight separation range of 200 to 3,000,000) preceded by a guard column.
  • the separation was performed using certified grade THF programmed to flow at 1.0 mL/min., injection volume was set at 100 ⁇ L and columns and detector were heated to 35°C. Data collection was 25 minutes and processing was performed using Atlas/Cirrus software.
  • the flow onset was calculated as the inflection temperature in the G' drop (labeled FLOW), the viscosity at 120°C will be reported as a measure for melt processability and the cure onset was calculated as the inflection temperature in the G' rise (labeled CURE).
  • Optical clarity was evaluated as the % transmission of light at wavelengths from about 350-1000 nanometers, measured through 1 mm thick samples of cast sheets of the present compositions. Samples having a % transmittance of at least 95% were considered to be optically clear.
  • Example 1 (reference): Preparation of an OH- terminated trifluoropropylmethyl siloxane with a dp of 99
  • the polymer was stripped on a thin film evaporator at 235°C, stir speed setting of 40, -0.3 mm Hg, for 1 hour 40 min. Isolated yield: 131.1 g.
  • the polymer was dissolved in 4- chlorobenzotrifiuoride at 65 wt % polymer. The solution had a light haze, so it was filtered through a 0.22 ⁇ filter. The resulting product had a dp of 99 with an OH content of 2.02 mole %.
  • Example 2 (reference): Preparation of D Me2 o.ioT Me o.80 TPh 0.10 TMe resin for use in the synthesis of low RI resin linear compositions
  • the reaction mixture was allowed to stir for 5 minutes with ice-water bath removed. The temperature dropped to 44°C during this time. The aqueous layer was removed in a 2 L separatory funnel. The organic layer was washed three times at room temperature using the 2 L separatory funnel with 58.5 g of DI water for each wash. The following process was repeated several times until the final wash water had a pH of 4.0.
  • the organic phase was transferred to a 1 L 3-neck flask and DI water (58.5 g; 58.5g is 10% of [theoretical yield (110.8 g) + MIBK (474.6 g)]) was added. The reaction mixture was heated at 60°C for 15 minutes. The aqueous phase was then removed. Residual water was removed by heating to reflux via azeotropic distillation. Pressure filtered through a 1.2 ⁇ filter the following day.
  • Example 3 Preparation of a resin-linear having 45 wt % methyl-T resin and 55 wt % 99 dp TFP siloxane
  • a 500 mL 4-neck round bottom flask was loaded with 4- chlorobenzotrifiuoride (CBTF; 120.38 g) and the methyl-T resin from Example 2 (45.0 g, 0.582 moles Si).
  • the flask was equipped with a thermometer, teflon stir paddle, and a Dean Stark apparatus attached to a water-cooled condenser. A nitrogen blanket was applied; the Dean Stark apparatus was prefilled with CBTF; and a heating mantle was used for heating.
  • the reaction mixture was heated at reflux (141 ° C) for 30 minutes.
  • the reaction mixture was cooled to 138 ° C (pot temperature).
  • MTA methyl triacetoxy silane
  • ETA ethyl triacetoxy silane
  • a solution of the capped silanol terminated TFP siloxane was added to the resin solution quickly at 138 ° C.
  • the reaction mixture turned very hazy.
  • To this reaction mixture were added 83.3 g of CBTF to reduce the solids content to approximately 30% solids.
  • the reaction mixture was still hazy.
  • Another 66.7 g of CBTF were added to further reduce the solids content to about 25% solids. Reaction mixture now only had a light haze.

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Abstract

L'invention concerne des copolymères à blocs d'organosiloxane contenant au moins un groupe Rf contenant du fluor, des compositions durcissables et des compositions solides dérivées de ces copolymères à blocs.
PCT/US2013/027904 2012-03-09 2013-02-27 Compositions de copolymères à blocs de résine-organosiloxane linéaire Ceased WO2013134018A1 (fr)

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Cited By (5)

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Publication number Priority date Publication date Assignee Title
WO2017019179A1 (fr) 2015-07-28 2017-02-02 Dow Corning Corporation Matériaux optiques à puce, formulations, procédés, utilisations, articles et dispositifs
US9705056B2 (en) 2012-02-09 2017-07-11 Dow Corning Corporation Gradient polymer structures and methods
WO2019218336A1 (fr) 2018-05-18 2019-11-21 Rohm And Haas Electronic Materials Llc Procédé de production de del par stratification de films en une étape
WO2025170712A1 (fr) 2024-02-07 2025-08-14 Dow Silicones Corporation Copolymère de polyorganosiloxane linéaire-résine à fonction époxy, composition contenant le copolymère, et procédés pour leur préparation et leur utilisation
WO2025178717A1 (fr) 2024-02-20 2025-08-28 Dow Silicones Corporation Copolymère séquencé de polyorganosiloxane linéaire – résine fonctionnelle – ester d'alcényle, composition contenant le copolymère, et leurs procédés de préparation et d'utilisation

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EP0639622B1 (fr) 1993-08-17 1999-10-06 Dow Corning Corporation Caoutchouc de silicone auto-adhésif au verre et métal
DE4427528C2 (de) 1994-08-04 1999-05-20 Ge Bayer Silicones Gmbh & Co Siliconmassen mit Titanaten, Zirkonaten und Hafnaten
US7005460B2 (en) 2001-01-25 2006-02-28 Kettenbach Gmbh & Co. Kg Two-step curable mixer-suitable materials
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9705056B2 (en) 2012-02-09 2017-07-11 Dow Corning Corporation Gradient polymer structures and methods
WO2017019179A1 (fr) 2015-07-28 2017-02-02 Dow Corning Corporation Matériaux optiques à puce, formulations, procédés, utilisations, articles et dispositifs
US10175510B2 (en) 2015-07-28 2019-01-08 Dow Corning Corporation Smart optical materials, formulations, methods, uses, articles, and devices
WO2019218336A1 (fr) 2018-05-18 2019-11-21 Rohm And Haas Electronic Materials Llc Procédé de production de del par stratification de films en une étape
WO2025170712A1 (fr) 2024-02-07 2025-08-14 Dow Silicones Corporation Copolymère de polyorganosiloxane linéaire-résine à fonction époxy, composition contenant le copolymère, et procédés pour leur préparation et leur utilisation
WO2025178717A1 (fr) 2024-02-20 2025-08-28 Dow Silicones Corporation Copolymère séquencé de polyorganosiloxane linéaire – résine fonctionnelle – ester d'alcényle, composition contenant le copolymère, et leurs procédés de préparation et d'utilisation

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JP2015513600A (ja) 2015-05-14

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